WO2015068283A1 - Encre pour impression offset absorbant dans l'infrarouge - Google Patents

Encre pour impression offset absorbant dans l'infrarouge Download PDF

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Publication number
WO2015068283A1
WO2015068283A1 PCT/JP2013/080333 JP2013080333W WO2015068283A1 WO 2015068283 A1 WO2015068283 A1 WO 2015068283A1 JP 2013080333 W JP2013080333 W JP 2013080333W WO 2015068283 A1 WO2015068283 A1 WO 2015068283A1
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Prior art keywords
antimony
ink
tin oxide
oil
infrared
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PCT/JP2013/080333
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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▼
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共同印刷株式会社
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Priority to PCT/JP2013/080333 priority Critical patent/WO2015068283A1/fr
Publication of WO2015068283A1 publication Critical patent/WO2015068283A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G30/00—Compounds of antimony
    • C01G30/004—Oxides; Hydroxides; Oxyacids
    • C01G30/005—Oxides
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C01P2002/54—Solid solutions containing elements as dopants one element only
    • 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
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values

Definitions

  • the present invention relates to an infrared absorbing offset printing ink, and more particularly to an infrared absorbing offset printing ink for preventing counterfeiting.
  • the offset printing ink having infrared absorptivity is constituted by adding an infrared absorber to commonly used offset printing ink.
  • 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 discloses infrared absorbing organic materials such as polymethine compounds, cyanine compounds, phthalocyanine compounds, counterion conjugates of benzenedithiol metal complex anions and cyanine dye cations as infrared absorbers; and Infrared absorbing inorganic materials such as composite tungsten oxide, tin oxide, indium oxide, indium tin oxide (ITO) have been described.
  • organic materials such as polymethine compounds, cyanine compounds, phthalocyanine compounds, counterion conjugates of benzenedithiol metal complex anions and cyanine dye cations
  • ITO indium tin oxide
  • Patent Document 2 describes a lithographic offset printing ink containing a thiol nickel complex salt as an infrared absorber.
  • Patent Document 3 describes an anti-counterfeit infrared absorbing ink containing antimony-doped tin oxide as an infrared absorber.
  • offset printing inks containing infrared absorbing organic materials as infrared absorbers can be prepared in various colors because of the variety of colors of these materials, but the problem is that the weather resistance of the ink is low. Has been pointed out.
  • offset printing inks using carbon black as an infrared absorbing inorganic material have better weather resistance than infrared absorbing organic material-containing inks, but carbon black is a pigment having a dark color tone.
  • the color of was limited to black or low brightness.
  • carbon black was used as the infrared absorbing inorganic material, it was not possible to prepare an offset printing ink having a variety of colors by mixing with a pigment or dye having another color. In particular, it has been impossible to prepare light-colored, especially light-colored light-colored offset printing inks.
  • the white pigments Even if white pigments such as titanium oxide and zinc oxide are added to increase the brightness of offset printing inks containing carbon black, the white pigments have the property of reflecting infrared rays, so that the ink absorbs infrared rays. As a result, the function as an anti-counterfeit ink is adversely affected.
  • offset printing inks containing metal oxides such as tungsten oxide and lead oxide as infrared absorbing inorganic materials have high transparency, but have a weak infrared absorbing effect, and a sufficient infrared absorbing effect is obtained when ink or printed matter is formed. There is a problem that can not be.
  • 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
  • the present invention provides an anti-counterfeit offset printing ink that is excellent in infrared absorption, transparency, weather resistance, safety and cost, and can exhibit a variety of colors in combination with various colorants.
  • the purpose is to do.
  • the present invention adopts the following solutions: [1] An infrared-absorbing offset printing ink containing antimony-doped tin oxide and a vehicle,
  • the antimony-doped tin oxide contains tin oxide and antimony oxide and satisfies the following (a) and / or (b):
  • (A) The half width ( ⁇ 2 ⁇ ) of a peak around 2 ⁇ 27 ° obtained by X-ray diffraction measurement is 0.30 or less; and / or (b) the content of the antimony oxide is the antimony dope
  • a value obtained by dividing the peak value of the peak around 2 ⁇ 27 ° obtained by X-ray diffraction measurement by the half-value width ( ⁇ 2 ⁇ ), based on the weight of tin oxide, from 0.5 to 10.0% by weight.
  • the degree of crystallinity is 58427 or more.
  • Infrared absorbing offset printing ink [2] The infrared-absorbing offset printing ink according to [1], which is used for preventing forgery. [3] The infrared-absorbing offset printing ink according to [1] or [2], wherein, in (a), the half width ( ⁇ 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] Infrared absorbing offset printing ink.
  • 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, an offset printing ink having high weather resistance and infrared absorption can be obtained according to the present invention. Can do.
  • the offset printing ink of the present invention containing antimony-doped tin oxide pigment has high brightness and a light white color, so that it can be mixed with other colorants to provide various colors, particularly bright colors. Can do. That is, according to the present invention, it is possible to produce a light-colored infrared-absorbing offset printing ink that could not be realized by a conventional infrared-absorbing inorganic material such as carbon black. Printed matter such as banknotes, securities, and cards can be produced.
  • 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 conventional antimony-doped tin oxide pigments can be used in offset printing ink. Therefore, according to the present invention, it is possible to provide an anti-counterfeit offset printing ink 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 the method of the present invention 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
  • 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
  • the ink of the present invention includes antimony-doped tin oxide and a vehicle. Further, the ink of the present invention can be used to prevent forgery of printed matter by utilizing the infrared absorptivity of antimony-doped tin oxide.
  • the ink of the present invention may contain not only antimony-doped tin oxide and vehicle but also auxiliary agents and / or colorants.
  • the ink of the present invention is suitable for any drying method used for offset printing.
  • the drying method of offset printing ink is roughly divided into drying by polymerization, drying by permeation, and drying by evaporation. These drying methods can be used alone or in combination at the time of offset printing.
  • Drying by polymerization means that the ink is dried by polymerization of a vehicle component in the ink, and is used for drying high-viscosity paste-like ink such as offset printing ink.
  • drying by polymerization include drying by oxidative polymerization of a drying oil and / or semi-drying oil, drying by thermal polymerization of a vehicle component, curing of the vehicle component by light or electron beam polymerization, and the like.
  • Drying by penetrating means that the low viscosity vehicle component in the ink penetrates into the printing medium, which increases the viscosity of the ink and causes the ink to appear to dry.
  • Offset of highly absorbent printing materials such as paper Used for printing.
  • drying by permeation include permeation drying of offset rotary ink for newspaper printing, and gelation by permeation of quick set ink in flat printing.
  • the quick set ink can be dried by both gelation by permeation and drying by oxidative polymerization.
  • Drying by evaporation means that the ink is dried by evaporation of the solvent contained in the vehicle, and is used for offset printing using a solvent as the vehicle.
  • drying by evaporation include spontaneous evaporation of the solvent from the ink film and hot air drying of the heat set ink.
  • a low boiling point solvent that evaporates at room temperature is used for spontaneous evaporation of the solvent from the ink film.
  • a high boiling point solvent that evaporates at about 200 ° C. to 250 ° C. is used for hot air drying of heat set ink.
  • the above drying methods can be used properly or combined during offset printing.
  • the ink of the present invention can be used as an oil-based ink, an ultraviolet curable ink, or an oil-based / ultraviolet curable 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.
  • antimony-doped tin oxide, vehicle, auxiliary agent and colorant contained in the ink of the present invention 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 of 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 of this invention can reduce the usage-amount of an 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.
  • 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 pigment 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 pigment. 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 pigment which followed the predetermined safety standard etc. can be provided.
  • the printed matter of the present invention is a printed matter having a printing part printed with the above infrared absorbing ink.
  • the printed matter of the present invention since the above-described infrared absorbing ink is provided with a printing portion on which characters, figures, and the like are printed, the printed matter has a sufficient effect of absorbing infrared rays while reducing the amount of antimony oxide used. be able to. In addition to providing high-quality printed materials, it is possible to provide printed materials that are environmentally friendly.
  • the printed matter of the present invention has a peak reflectance value of 28.776% or less in the infrared wavelength region of 780 to 1100 nm when the solid content weight ratio of the antimony-doped tin oxide contained in the printed part is 11.6% by weight. It is preferable that
  • the antimony-doped tin oxide of the present invention can be produced, for example, by the following method.
  • the method for producing antimony-doped tin oxide of the present invention includes an aeration firing step of firing the antimony-doped tin oxide raw material under aeration.
  • 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 of the present invention can narrow the half-value width of antimony-doped tin oxide from 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 of the present invention comprises producing an antimony-doped tin oxide capable of sufficiently exhibiting the infrared absorption effect while reducing the amount of antimony oxide used by including an aeration firing step. Can do.
  • the antimony-doped tin oxide obtained by the production method of the present invention has a narrow half-value width and / or a high crystallinity, which is considered to be caused by a small amount of impurity antimony oxide. .
  • 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 production method of the present invention can appropriately maintain the crystal structure while removing a part thereof by the aeration firing step, so that a high infrared ray 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 of 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 of this invention includes the following mixing processes and a closed baking process 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 method for producing antimony-doped tin oxide of the present invention preferably includes a closed cooling step of cooling the antimony-doped tin oxide raw material in a closed system between the closed baking step and the aeration baking step.
  • 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 of this invention is manufactured by passing through each said process.
  • the vehicle is a medium in which antimony-doped tin oxide and / or a colorant is dispersed and adhered to a substrate.
  • the ink of the present invention may contain known vehicle components used for printing. Since the ink of the present invention can be formed as an oil-based ink, a UV ink, or an oil-based / UV combined ink, a vehicle suitable for the oil-based ink and a vehicle suitable for the UV ink will be described below.
  • Vehicle suitable for oil-based ink for example, a resin, a crosslinking agent, a gelling agent, a drying oil, a semi-drying oil, a solvent, a mineral oil, or the like can be used alone or in combination.
  • the resin, crosslinking agent and gelling agent, drying oil and semi-drying oil, solvent, and mineral oil will be described below.
  • the resin contained in the oil-based ink may be a natural resin or a synthetic resin. Moreover, in order to ensure the viscosity of ink, it is preferable that resin is solid.
  • natural resins include pine oil, straw, shellac, and gilsonite.
  • natural resins contain a resin acid as a non-volatile component.
  • the resin acid include abietic acid, neoabietic acid, ballastric acid, pimaric acid, isopimaric acid, dehydroabietic acid, chelolic acid, and aloyritic acid.
  • Examples of the synthetic resin include rosin, phenol resin, modified alkyd resin, polyester resin, petroleum resin, rosin modified maleic resin, and cyclized rubber.
  • Rosin is obtained by refining pine oil and is roughly divided into three types: gum rosin, wood rosin and tall oil rosin. In general, rosin has a softening point of 70-80 ° C. and an acid number of 170-180. In order to improve the strength of the ink film, rosin is preferably used in combination with other synthetic resins.
  • Phenolic resins are resins obtained by condensation of phenol and aldehyde, and are roughly classified into four types: novolac type resin, resol type resin, 100% phenol resin and modified phenol resin. These four types of resins may be included in the offset printing ink, but considering the resistance of the vehicle, 100% phenol resin or modified phenol resin is preferable.
  • a 100% phenol resin is a resin obtained by condensing an alkylphenol and formaldehyde in the presence of an acid or an alkali catalyst. Since 100% phenol resin can form a dry film having water resistance, friction resistance and chemical resistance, it is preferably used for lithographic or letterpress printing inks.
  • the modified phenolic resin is a resin obtained by reacting a condensate of phenol and formalin with a modifying component such as rosin, rosin ester or drying oil. Since the solubility and softening point of the resin or the resistance of the coating can be controlled according to the type or amount of the modifying component, the modified phenolic resin is preferably used for lithographic or letterpress printing inks. In particular, a modified phenolic resin using rosin as a modifying component is called a rosin-modified phenolic resin and is generally used for offset printing ink.
  • the rosin-modified phenolic resin preferably has an acid value of 5 to 40 and / or a softening point of 130 to 190 ° C.
  • the modified alkyd resin is a resin obtained by reacting a condensate of a polybasic acid and a polyhydric alcohol with a modified component such as fatty acid, rosin, drying oil or semi-drying oil. Since the modified alkyd resin is excellent in the wettability, drying property and emulsification resistance of the pigment, it is preferably used in a lithographic or relief printing ink.
  • Examples of the polybasic acid include phthalic anhydride and isophthalic acid.
  • Examples of the polyhydric alcohol include glycerin and pentaerythritol.
  • Examples of fatty acids include linseed oil, dehydrated castor oil, soybean oil, and the like. The drying oil will be described later.
  • modified alkyd resin examples include 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, and the like.
  • Polyester resin is a polycondensate of polyvalent carboxylic acid and polyalcohol.
  • examples of the polyester resin include unsaturated polyester resin and polyethylene terephthalate. Polyester resins can be used in offset printing inks with or without solvents.
  • Petroleum resin is a resin obtained by polymerizing an unsaturated olefin having 5 or more carbon atoms. Petroleum resins are preferably used in offset printing inks because they have a softening point of 80 to 130 ° C. and are excellent in solubility in petroleum solvents or drying oil, emulsification resistance and cost.
  • the rosin-modified maleic resin is a resin obtained by reacting rosin, maleic anhydride and a polyhydric alcohol. By adjusting the amount of maleic anhydride or the type or amount of polyhydric alcohol, the softening point and acid value of the rosin-modified maleic resin can be controlled. Examples of the polyhydric alcohol include glycerin and pentaerythritol.
  • the rosin-modified maleic resin preferably has a softening point of 80 to 140 ° C. and / or an acid value of 15 to 200.
  • Cyclized rubber is a resin obtained by treating natural rubber with tin chloride.
  • the cyclized rubber has a softening point of 120 to 140 ° C. and is excellent in solubility in a drying oil or a solvent.
  • the cyclized rubber is preferably used in combination with a rosin-modified phenol resin.
  • One or more of the resins listed above may be included in the ink of the present invention.
  • a rosin-modified phenol resin or a rosin-modified maleic acid resin having a softening point of 130 ° C. or higher is preferable from the viewpoint of appropriately controlling the molecular weight of the solid resin and improving the printability of ink.
  • Crosslinking agent and gelling agent A crosslinking agent or gelling agent can be added to the vehicle to crosslink or gel the resin.
  • crosslinking agent examples 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, Ethyl acetoacetate Examples include aluminum alcoholates such as trialuminum diisopropoxide and aluminum trisethyl acetoacetate
  • the gelling agent examples include metal soaps such as aluminum stearate and aluminum octoate; oligomers or chelate compounds of metal soap; bentonite and the like.
  • cross-linking agents or gelling agents listed above can be used alone or in combination of two or more.
  • Dry oil and semi-dry oil are oil-based materials that are polymerized and hardened by air oxidation. Dry oil refers to vegetable oil or a component derived from vegetable oil having an iodine value of 130 or more. Semi-drying oil refers to a vegetable oil or vegetable oil-derived component having an iodine value of 100 to 130.
  • drying oils examples include vegetable oils such as linseed oil, tung oil (paulownia oil), poppy oil, perilla oil, walnut oil, oily oil (boiled oil), safflower oil, sunflower oil, and the like; Maleated oil obtained by adding maleic acid; Fatty acid esters of these vegetable oils; Polymerized oil obtained from these vegetable oils as raw materials; Dehydrated castor oil; Petroleum systems such as olefins and diolefins that can be extracted during petroleum refining Synthetic oil etc. are mentioned.
  • semi-drying oils examples include vegetable oils such as soybean oil, rapeseed oil, cottonseed oil, corn oil and sesame oil; fatty acid esters of these vegetable oils; and polymerized oils obtained using these vegetable oils as raw materials.
  • Other vegetable oils that can be used as drying oil and semi-drying oil include, for example, Asa seed oil, Eucommia oil, olive oil, cacao oil, kapok oil, kaya oil, mustard oil, kyounin oil, kukui oil, radish seed oil, Daifushi beef Examples include oils (massage oil), camellia oil, niger oil, nutka oil, palm oil, castor oil, grape seed oil, gentian oil, pine seed oil, coconut oil, peanut oil (peanut oil) and the like.
  • Linseed oil is a faint yellow oil obtained from flax seeds and has an iodine number of 175-195 and a saponification number of 189-195.
  • Kiri oil is an oil obtained from the seeds of Brassica plants, and has an iodine value of 160 to 173 and a saponification value of 190 to 196.
  • Soybean oil is oil obtained from soybeans and has an iodine number of 123-142 and a saponification number of 188-195.
  • the fatty acid ester of vegetable oil is an ester compound of vegetable oil and fatty acid.
  • Examples of fatty acid esters of vegetable oils include fatty acid monoalkyl ester compounds.
  • the fatty acid for forming the fatty acid ester is preferably a saturated or unsaturated fatty acid having 16 to 20 carbon atoms, such as stearic acid, isostearic acid, hydroxystearic acid, oleic acid, linoleic acid, linolenic acid, eleostearic acid. Etc.
  • the alkyl group derived from the alcohol for forming the fatty acid ester is preferably an alkyl group having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, 2 -Ethylhexyl and the like.
  • Examples of the polymer oil obtained using vegetable oil as a raw material include a stand oil and a copolymer of two or more kinds of vegetable oils.
  • Stand oil is oil obtained by polymerizing vegetable oil at a high temperature to increase the viscosity.
  • the stand oil is preferably linseed oil stand oil.
  • Linseed oil stand oil is obtained by polymerizing linseed oil at a high temperature around 300 ° C. Linseed oil stand oil may be used to improve the flowability of the offset printing ink at a low temperature or transfer to a transfer body such as a blanket.
  • copolymer of two or more kinds of vegetable oils examples include copolymers of soybean oil and tung oil, linseed oil and tung oil, and the like. Further, as the copolymer oil, styrene oil obtained by reacting styrene with one or more vegetable oils, cyclopentadiene copolymer oil obtained by reacting cyclopentadiene with one or more vegetable oils, or the like may be used.
  • the dry oil or semi-dry oil listed above can be used alone or in combination of two or more.
  • the solvent used in the ink of the present invention 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 oils; aromatic oils such as toluene and xylene; esters such as ethyl acetate; ketones such as methyl ethyl ketone; alcohols such as isopropyl alcohol; glycols such as ethylene glycol, diethylene glycol, and triethylene glycol; cellulose solvents Is mentioned.
  • oil-based inks petroleum oil solvents having a boiling point of 180 ° C. or higher, preferably 200 ° C. or higher are used.
  • Mineral oil is preferred as the petroleum oil-based solvent. The mineral oil is described in detail below.
  • the mineral oil examples include spindle oil, machine oil, white kerosene, and non-aromatic petroleum solvent.
  • the mineral oil is preferably a non-aromatic petroleum solvent that is incompatible with water and has a boiling point of 180 ° C. or higher.
  • the non-aromatic petroleum solvent examples include n-dodecane mineral oil.
  • Specific examples of non-aromatic petroleum solvents include No. 0 Solvent, AF Solvent No. 5, AF Solvent No. 6, AF Solvent No. 7 (all manufactured by Nippon Oil Corporation).
  • the solvents listed above can be used alone or in combination of two or more.
  • Vehicle suitable for UV ink examples include photopolymerizable resins such as monomers, oligomers and binder polymers; photopolymerization initiators and the like. A monomer and an oligomer, a binder polymer, and a photoinitiator are demonstrated below.
  • the monomer may be a compound having an ethylenically unsaturated bond conventionally used for photopolymerization. Moreover, an oligomer is obtained by oligomerizing the compound which has an ethylenically unsaturated bond.
  • Oligomers are resins that govern the basic physical properties of UV ink.
  • the monomer mainly acts as a diluent and can be used to adjust properties such as ink viscosity, curability and adhesion.
  • Examples of compounds having an ethylenically unsaturated bond include (meth) acrylic acid compounds; maleic acid compounds; urethane-based, epoxy-based, polyester-based, polyol-based, vegetable oil-based compounds and the like. Examples include compounds having a heavy bond.
  • examples of the compound having an ethylenically unsaturated bond include epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, silicone (meth) acrylate, acrylated amine, and acrylic saturation.
  • Resin and acrylic acrylate acid anhydride addition acrylate of bisphenol A type epoxy (meth) acrylate, acid anhydride addition acrylate of phenol novolac epoxy (meth) acrylate, acid addition addition of dipentaerythritol pentaacrylate or dipentaerythritol hexaacrylate
  • Acrylates having a hexyl group polyethylene glycol diacrylate, polypropylene glycol diacrylate, polyglycerol epoxy acrylates, water-soluble acrylates such as polyglycerol acrylate, and acryloyl morpholine.
  • a compound having an ethylenically unsaturated bond that is compatible with the binder polymer and has a high lipophilicity is preferable, for example, a compound having an ethylenically unsaturated bond having a long-chain alkyl group having 6 to 24 carbon atoms.
  • a compound having an ethylenically unsaturated bond modified with polybutylene glycol, a compound having an ethylenically unsaturated bond modified with vegetable oil, and the like are preferable.
  • the binder polymer is a resin that can fix the colorant to the printing material.
  • the weight average molecular weight of the binder polymer is preferably about 1000 to about 3,000,000.
  • binder polymer examples include polyester, diallyl phthalate polymer, poly (meth) acrylic acid, poly (meth) acrylic ester, polyester-melamine polymer, styrene- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid- Alkyl (meth) acrylate copolymer, styrene-maleic acid copolymer, styrene-maleic acid-alkyl (meth) acrylate copolymer, styrene-maleic acid half ester copolymer, vinylnaphthalene- (meth) acrylic acid copolymer, vinylnaphthalene-maleic acid copolymer, And salts thereof.
  • the monomers, oligomers and binder polymers listed above can be used alone or in combination of two or more.
  • the photopolymerization initiator is a compound that generates radicals such as active oxygen when irradiated with ultraviolet rays.
  • the UV ink of the present invention 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.
  • the ink of the present invention may contain known auxiliary agents used for printing.
  • auxiliary agents include drying accelerators, waxes, extender pigments, oxidation polymerization catalysts, and other additives. These adjuvants will be described below.
  • the drying accelerator is an auxiliary agent that accelerates drying by oxidative polymerization of drying oil and / or semi-drying oil. Specifically, the drying accelerator can promote curing of the surface and the inside of the ink film. Examples of the drying accelerator include a metal salt of a fatty acid, a metal salt of an organic carboxylic acid, a metal salt of an inorganic acid, etc. contained in a drying oil or a semi-drying oil.
  • the drying accelerator can be used in the form of a liquid dryer or a paste dryer.
  • the liquid dryer is a liquid in which a drying accelerator is dissolved in a high boiling point solvent.
  • a paste dryer is a paste obtained by kneading a drying accelerator and extender pigment together with a vehicle. Moreover, you may add both a liquid dryer and a paste dryer to oil-based ink.
  • Examples of the organic carboxylic acid for forming the drying accelerator include acetic acid, propionic acid, butyric acid, isopentanoic acid, hexanoic acid, 2-ethylbutyric acid, naphthenic acid, octylic acid, nonanoic acid, decanoic acid, and 2-ethylhexane.
  • isooctanoic acid isononanoic acid
  • lauric acid palmitic acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, versatic acid, secanoic acid, tall oil fatty acid, linseed oil fatty acid, soybean oil fatty acid, dimethylhexanoic acid, Examples include 3,5,5-trimethylhexanoic acid and dimethyloctanoic acid.
  • the organic carboxylic acid is preferably a fatty acid contained in a drying oil or a semi-drying oil.
  • the organic carboxylic acid is preferably naphthenic acid.
  • the organic carboxylic acid is preferably acetic acid.
  • inorganic acids examples include hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, boric acid, hydrofluoric acid, and the like.
  • the drying accelerator is used as a paste dryer, the inorganic acid is preferably boric acid.
  • Examples of the metal for forming the metal salt of the acid include calcium, cobalt, lead, iron, manganese, zinc, vanadium, cerium, zirconium, sodium and the like.
  • cobalt and manganese are preferred, while in order to promote the internal drying of the ink coating, calcium and zinc are preferred. Therefore, it is also preferable to use cobalt or manganese in combination with calcium or zinc.
  • ⁇ wax ⁇ Wax is an auxiliary agent for preventing the printed surface from being scratched.
  • the wax can impart properties such as friction resistance, anti-blocking properties, slipperiness, and anti-scratch properties to the surface of the ink coating.
  • the ink of the present invention may contain a known wax used for printing.
  • waxes examples include natural waxes such as carnauba wax, wax, lanolin, montan wax, paraffin wax, and microcrystalline wax; Fischer Trops wax, polyethylene wax, polypropylene wax, polytetrafluoroethylene wax, polyamide wax, silicone compound Synthetic waxes such as; fluorinated products of synthetic waxes.
  • the wax is preferably a polytetrafluoroethylene wax when added to the heatset ink.
  • the extender pigment is a pigment used for adjusting the viscosity of the ink, and has a low refractive index and a low coloring power. Accordingly, extender pigments are preferably used when the viscosity of the ink is high and wiping is difficult.
  • the ink of the present invention may contain a known extender pigment used for printing.
  • extender pigments examples include barium sulfate, calcium carbonate, calcium sulfate, kaolin, talc, silica, corn starch, titanium dioxide, and mixtures thereof.
  • the oxidative polymerization catalyst is an auxiliary agent that catalyzes the oxidative polymerization of drying oil and / or semi-drying oil. Moreover, you may use a gelling agent or a drying accelerator as an oxidation polymerization catalyst.
  • examples of the oxidation polymerization catalyst include metal compounds such as cobalt borate, cobalt octylate, manganese octylate, zircon octylate, cobalt naphthenate, and lead monoxide; 1,10-phenanthroline, 5-methyl-phenanthroline, and the like. And 2,2′-dipyridyl and the like.
  • a polymerization inhibitor such as phenothiazine and t-butylhydroxytoluene
  • a pigment dispersant such as phenothiazine and t-butylhydroxytoluene
  • a drying retarder such as phenothiazine and t-butylhydroxytoluene
  • a surfactant such as an activator 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 of 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 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 colorant is preferably a pigment.
  • a coloring agent is an inorganic pigment from a viewpoint of the weather resistance of printed matter.
  • the viscosity of the UV ink is adjusted to about 50 to 1000 poise, the colorant is about 10 to 20% by weight, and the vehicle is about 10 to 90% by weight.
  • the adjuvant is 0 to about 25% by weight and the antimony doped tin oxide is about 1 to 50% by weight.
  • the content of the photopolymerizable resin in the UV ink is about 10% by weight or more, or about 20% by weight based on the weight of the finally obtained UV ink, including the amount added later if necessary. % Or more, and the content is preferably about 80% by weight or less, or about 60% by weight or less.
  • an oil-based ink and a UV ink may be used in combination to form an oil-based / UV combined ink.
  • a colorant is added to the 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 vehicle such as a bead mill or a three-roll mill.
  • the mill base for ink is obtained by dispersing the kneaded meat with a disperser.
  • the oil-based / UV combined ink of the present invention can be obtained by adding a photopolymerization initiator to the mill base for ink and adding other materials as desired.
  • the blending ratio of each component contained in the oil-based UV combined ink is about 30 to 50% by weight of the oil-based ink vehicle when the viscosity of the oil-based UV combined ink is adjusted to several thousand poises.
  • 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.
  • the ink of the present invention can be obtained by dispersing antimony-doped tin oxide in a vehicle together with auxiliary agents and / or colorants as desired.
  • One embodiment of the method for producing the ink of the present invention includes the following steps: (1a) a blending step of blending antimony-doped tin oxide and / or colorant with a vehicle, optionally with adjuvant, to obtain a blend; (1b) a premixing step of premixing the formulation to obtain a mill base; (1c) Kneading step of kneading the mill base to obtain a rough ink; (1d) an adjusting step of adding an antimony-doped tin oxide, a colorant, a vehicle and / or an auxiliary agent to the crude ink to obtain an ink; (1e) Polishing step of kneading the ink again to finish the ink; and (1f) Filling step of filling the container with the ink.
  • Step (1a) can be performed by mixing antimony-doped tin oxide and / or colorant into the vehicle in a container such as a mixing tank.
  • a container such as a mixing tank.
  • the antimony-doped tin oxide or colorant is a dried solid or powder, the scattering of the antimony-doped tin oxide or colorant can be prevented by step (1a).
  • Step (1b) is performed to uniformly pulverize the antimony-doped tin oxide and / or colorant, wet it with the vehicle and uniformly disperse it in the vehicle before kneading the formulation.
  • step (1b) may be omitted, if step (1b) is performed, subsequent step (1c) can be efficiently advanced.
  • Step (1b) can be performed by a mixer such as a single screw mixer or a twin screw mixer.
  • Step (1c) is performed to achieve a higher degree of wetting and dispersion of antimony-doped tin oxide and / or colorant compared to step (1b). Further, the particle diameter of the dispersed material in the vehicle can be made uniform by the step (1c).
  • Step (1c) can be performed by a kneading machine (ink mill) such as a three roller mill, a bead mill, a ball mill, a sand grinder, or an attritor.
  • a kneading machine such as a three roller mill, a bead mill, a ball mill, a sand grinder, or an attritor.
  • a three-roller mill when a three-roller mill is used, the mill base becomes a thin film when passing through the roll, so that the coarse ink can be degassed.
  • coarse particles remain on the first roller, so that the dispersed substance can be classified.
  • the bead mill is suitable for producing ink having a relatively low viscosity, such as offset rotary ink.
  • Step (1d) is performed to add antimony-doped tin oxide, colorant, vehicle and / or adjuvant to the crude ink to adjust the final composition, viscosity, color tone or dryness of the ink.
  • Step (1d) can be performed by a mixer such as a single screw mixer or a twin screw mixer. Note that step (1d) may be omitted.
  • each component contained in the ink of the present invention can be finally adjusted to a desired blending ratio by steps (1a) and / or (1d). Therefore, antimony-doped tin oxide may be added to the vehicle in at least one of steps (1a) and (1d). Moreover, when preparing the special color ink or functional ink containing antimony dope tin oxide, it is not necessary to use a colorant in step (1a) or (1d).
  • Step (1e) is performed to remove bubbles or foreign matters from the ink so that the ink can be used.
  • Step (1e) can be performed with a meat mill such as a two-roller mill or a three-roller mill.
  • Step (1f) is performed to fill a container such as a can, a bottle, or a packaging bag with ink.
  • step (1f) can be performed by a metering and filling device provided in the grinder.
  • oil-based inks, UV inks, and oil-based / UV combined inks can be produced.
  • both the oil-based vehicle and the UV vehicle can be used as the vehicle, and both the oil-based ink auxiliary agent and the UV ink auxiliary agent can be used as the auxiliary agent.
  • Another embodiment of the method for producing the ink of the present invention comprises the following steps: (2a) a flushing step to flash the colorant and vehicle and optionally antimony-doped tin oxide and adjuvants to obtain a mill base; (2b) a kneading step for kneading the mill base to obtain a crude ink; (2c) an adjusting step of adding an antimony-doped tin oxide, a colorant, a vehicle and / or an auxiliary agent to the crude ink to obtain an ink; (2d) Polishing step of kneading the ink again to finish the ink; and (2e) Filling step of filling the container with the ink.
  • Step (2a) is performed to omit the step of drying the colorant and the above steps (1a) and (1b) when the colorant contains water.
  • flushing refers to an operation of transferring the colorant from the aqueous phase to the vehicle phase by kneading the water-containing colorant with the vehicle.
  • Step (2a) can be performed by a flasher such as a kneader.
  • Steps (2b) to (2e) can be performed in the same manner as steps (1c) to (1f), respectively.
  • the average particle size of the antimony-doped tin oxide in the anti-counterfeit offset printing ink having infrared absorptivity is 20 ⁇ m or less, 15 ⁇ m or less, 10 ⁇ m or less, 5 ⁇ m or less, 2.5 ⁇ m or less, 1 ⁇ m or less, 0.5 ⁇ m or less, 0. It may be 1 ⁇ m or less, 0.05 ⁇ m or less, or 0.025 ⁇ m or less, and the average particle size 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 offset printing ink is not limited, but means for pulverizing the antimony-doped tin oxide during the production of the antimony-doped tin oxide And a means for dispersing antimony-doped tin oxide in the vehicle during the production of the offset printing 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 the above steps (1b), (1c), (2a) or (2b).
  • Offset printing is a printing method in which ink attached to a plate is transferred to a transfer body, and then ink attached to the transfer body is transferred to a substrate.
  • the plate can be formed of a metal such as aluminum, copper, zinc, or magnesium.
  • a rubber blanket is generally used as the transfer body.
  • the printed material include paper, a carton board, a metal plate, a resin film, and a card.
  • the plate used for offset printing is a flat plate.
  • the surface of the lithographic plate is provided with a lipophilic image area and a hydrophilic non-image area by a photoresist method, a chemical etching method, or the like. Dampening water is supplied to the surface of the lithographic plate, a film of fountain solution is formed on the non-image area, and then the ink of the present invention is supplied to the surface of the lithographic plate, thereby depositing the ink on the image area. Can be made.
  • Examples of the fountain solution include water and a mixture of water and isopropyl alcohol. Since antimony-doped tin oxide used in the present invention is hydrophilic or has low solubility in water, it is difficult to cause emulsification with dampening water or bleeding into dampening water. Therefore, it is considered that the ink of the present invention has high selectivity to the image area on the plate.
  • offset printing is performed by an offset rotary printing press or an offset sheet-fed printing press.
  • the ink of the present invention can be printed using either an offset rotary printing press or an offset sheet-fed printing press.
  • the ink of the present invention may be used as any color ink, but according to the above order of overprinting, it is formed as red ink, yellow ink or special color ink, or red process ink or yellow process ink. It is preferable to be mixed with.
  • Examples of attempts to solve problems such as emulsification and stains related to the interaction between ink and dampening water include dry lithographic printing and letterpress dry offset.
  • Dry lithographic printing is also called waterless offset printing, and is a printing method in which dampening water on a lithographic plate is replaced with silicone.
  • the relief printing dry offset is a printing method in which a relief printing plate is used as a printing plate, and ink on the relief printing plate is transferred to a transfer body without using dampening water.
  • the ink of the present invention can be printed by any printing method of dry planographic printing or relief printing dry offset.
  • the ink of the present invention has infrared absorptivity. Therefore, when a printed matter obtained by printing the ink of the present invention on a substrate is observed with an infrared light detector such as an infrared camera, the portion on which the ink of the present invention is printed absorbs infrared rays, Since it is displayed blacker than the portion of, the infrared absorption contrast can be detected. For example, the authenticity of the printed matter can be determined by comparing a predetermined infrared absorption contrast with an infrared absorption contrast of the observation target.
  • 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.
  • Example 2 Into 80 parts by weight of the vehicle, 20 parts by weight of the infrared absorbing pigment of Example 2 was mixed and kneaded with a three roller mill to obtain a UV ink having infrared absorptivity.
  • a photopolymerizable resin vegetable oil-modified acrylate
  • a photopolymerization initiator ⁇ -aminoacetophenone
  • the printed surface of the infrared absorbing ink appeared black because it absorbed infrared light, whereas infrared absorbing.
  • the non-ink-printed surface eg, the base paper portion, the general process ink print portion, etc. appeared white because it transmitted or reflected infrared radiation.
  • Printing machine Offset printing machine RI tester (manufactured by IHI Machine System Co., Ltd.) Ink filling amount: 0.125 cc 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.
  • the offset printing ink of the present invention is used as a general color ink 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. The relationship between color tone and infrared absorptivity can be predicted.
  • 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.
  • the antimony-doped tin oxide used in the present invention is contained in red or yellow ink, or the offset printing ink of the present invention is used as a red or yellow ink, without affecting the color tone of red or yellow, It can be seen that infrared absorptivity can be imparted to the ink.
  • 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. Therefore, even if the antimony-doped tin oxide used in the present invention is contained in the indigo ink or the offset printing ink of the present invention is used as the indigo ink, it does not affect the color tone of the indigo color. It turns out that absorptivity can be provided.
  • 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 offset printing. 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 of the present invention.

Abstract

La présente invention concerne une encre pour impression offset absorbant dans l'infrarouge comprenant de l'oxyde d'étain dopé à l'antimoine, et un vecteur. L'oxyde d'étain dopé à l'antimoine comprend de l'oxyde d'étain et de l'oxyde d'antimoine, et satisfait à (a) et/ou à (b) : (a) la largeur de demi-absorption (∆2θ) d'un pic à proximité de 2θ = 27˚ obtenu à partir d'une mesure de diffraction aux rayons X est inférieure ou égale à 0,30 ; et/ou (b) la teneur en oxyde d'antimoine est comprise entre 0,5 et 10,0 % en poids, le poids de l'oxyde d'étain dopé à l'antimoine étant utilisé comme référence, et le degré de cristallisation, c'est-à-dire la valeur obtenue par division, par la largeur de demi-absorption (∆2θ), de la valeur de pic dudit pic à proximité de 2θ = 27˚ obtenu à partir de la mesure de diffraction aux rayons X, est supérieur ou égal à 58 427.
PCT/JP2013/080333 2013-11-08 2013-11-08 Encre pour impression offset absorbant dans l'infrarouge WO2015068283A1 (fr)

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JP2017149877A (ja) * 2016-02-25 2017-08-31 東洋インキＳｃホールディングス株式会社 平版印刷インキ
WO2020162039A1 (fr) * 2019-02-07 2020-08-13 サカタインクス株式会社 Composition d'encre durcissable par rayonnement d'énergie active et procédé de fabrication de matière imprimée l'utilisant

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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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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
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JP2017149877A (ja) * 2016-02-25 2017-08-31 東洋インキＳｃホールディングス株式会社 平版印刷インキ
WO2020162039A1 (fr) * 2019-02-07 2020-08-13 サカタインクス株式会社 Composition d'encre durcissable par rayonnement d'énergie active et procédé de fabrication de matière imprimée l'utilisant
JP2020128467A (ja) * 2019-02-07 2020-08-27 サカタインクス株式会社 活性エネルギー線硬化型インキ組成物、及びそれを用いた印刷物の製造方法
JP7292891B2 (ja) 2019-02-07 2023-06-19 サカタインクス株式会社 活性エネルギー線硬化型インキ組成物、及びそれを用いた印刷物の製造方法
US11932767B2 (en) 2019-02-07 2024-03-19 Sakata Inx Corporation Active energy ray curable ink composition and method for manufacturing printed matter using same

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