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WO2015068281A1 - Encre pour sérigraphie à absorption dans l'infrarouge - Google Patents

Encre pour sérigraphie à absorption dans l'infrarouge Download PDF

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Publication number
WO2015068281A1
WO2015068281A1 PCT/JP2013/080313 JP2013080313W WO2015068281A1 WO 2015068281 A1 WO2015068281 A1 WO 2015068281A1 JP 2013080313 W JP2013080313 W JP 2013080313W WO 2015068281 A1 WO2015068281 A1 WO 2015068281A1
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WO
WIPO (PCT)
Prior art keywords
antimony
ink
tin oxide
oil
resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2013/080313
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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▼
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kyodo Printing Co Ltd
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Kyodo Printing Co Ltd
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Filing date
Publication date
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Priority to PCT/JP2013/080313 priority Critical patent/WO2015068281A1/fr
Publication of WO2015068281A1 publication Critical patent/WO2015068281A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • 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
    • 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
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution

Definitions

  • the present invention relates to an infrared absorbing screen printing ink, and more particularly to an infrared absorbing screen printing ink for preventing counterfeiting.
  • infrared absorbing screen printing ink It has been studied to partially screen print bills, securities, etc. using infrared absorbing screen printing ink. Further, screen printing using infrared absorbing screen printing ink is desired for non-paper members such as fabric tags, automobile meters, plastic sheets, and blue-ray discs.
  • Infrared absorbing screen printing ink is configured by adding an infrared absorbing agent to commonly used screen 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 screen printing ink containing a phthalocyanine compound as an infrared absorber.
  • Patent Document 3 describes an anti-counterfeit infrared absorbing ink containing antimony-doped tin oxide as an infrared absorber.
  • screen 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.
  • screen printing inks using carbon black as an infrared absorbing inorganic material have better weather resistance than inks containing infrared absorbing organic materials, 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 an infrared absorbing inorganic material, it was not possible to prepare a screen printing ink having a variety of colors by mixing with a pigment or dye having another color. In particular, it was impossible to prepare light screen printing inks of light colors, particularly light colors.
  • the white pigment Even if a white pigment such as titanium oxide or zinc oxide is added to increase the brightness of the screen printing ink containing carbon black, the white pigment has the property of reflecting infrared rays, so the infrared absorption of the ink is low. As a result, the function as an anti-counterfeit ink is adversely affected.
  • screen printing inks containing metal oxides such as tungsten oxide and lead oxide as infrared absorbing inorganic materials have high transparency but weak infrared absorbing effect, and 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 screen printing ink that is excellent in infrared absorptivity, transparency, weather resistance, safety and cost, and can exhibit a variety of colors in combination with colorants of various colors.
  • the purpose is to do.
  • the present invention adopts the following solutions: [1] An infrared-absorbing screen 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.
  • Screen printing ink [2] The infrared absorbing screen printing ink according to [1], which is for counterfeiting. [3] The infrared-absorbing screen 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 screen printing ink. [5] The infrared absorbing screen printing ink according to [1] or [2], wherein the crystallinity is 78020 or more.
  • 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, a screen printing ink having high weather resistance and infrared absorption is obtained. Can do.
  • the screen printing ink of the present invention containing an antimony-doped tin oxide pigment has a high lightness 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 screen printing ink that could not be realized with a conventional infrared-absorbing inorganic material such as carbon black. Printed matter such as banknotes, securities, and cards can be produced.
  • antimony-doped tin oxide pigments are lower than that of tin-doped indium oxide pigments. Furthermore, according to the present invention, an antimony-doped tin oxide pigment having a lower content of antimony oxide than conventional antimony-doped tin oxide pigments can be used in screen printing inks. Therefore, according to the present invention, anti-counterfeiting screen printing ink excellent in economic efficiency can be provided in a wide range of industries while complying with safety regulations regarding the amount of antimony used.
  • 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 is suitable for any drying method used for screen printing.
  • the drying method of screen printing ink is roughly divided into drying by permeation, drying by evaporation, and drying by polymerization. These drying methods can be used alone or in combination at the time of screen printing.
  • Drying by penetrating means that the low viscosity vehicle component in the ink penetrates into the printing material, which increases the viscosity of the ink and causes the ink to dry apparently.
  • Highly absorbent printed materials such as paper and nonwoven fabric Used for screen printing. Immediately after the ink has transferred to the superabsorbent substrate, the ink penetrates the substrate, for example by capillary action. Therefore, in order to promote drying by permeation, it is preferable to select a vehicle component according to the surface characteristics and internal structure of the printing medium.
  • Drying by evaporation means that the ink is dried by evaporation of the solvent contained in the vehicle, and is used for screen printing using a solvent as the vehicle.
  • the drying by evaporation include spontaneous evaporation of the solvent from the ink film; external drying of the ink by normal temperature blowing, hot air blowing, etc .; electromagnetic wave heating of the ink by infrared rays and the like.
  • 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 about 250 ° C. is used for hot air drying of the ink.
  • Drying by polymerization means that the ink is dried by polymerization of vehicle components in the ink.
  • Examples of the drying by polymerization include drying by oxidative polymerization of the vehicle component, curing of the vehicle component by light or electron beam polymerization, and drying by thermal polymerization of the vehicle component.
  • the ink of the present invention can be prepared as an oxidation polymerization type ink, an ultraviolet curable ink, or an oxidation polymerization type / ultraviolet curable ink.
  • the oxidation polymerization type ink (hereinafter abbreviated as “oil-based ink”) is an ink that can be cured by oxidative polymerization of a vehicle component.
  • the oil-based ink includes a resin, a crosslinking agent or a drying accelerator, a drying oil or a semi-drying oil, a solvent, and the like.
  • UV curable ink is an ink that can be cured by photopolymerization of a vehicle component.
  • UV ink contains a photopolymerizable resin, a photopolymerization initiator, and the like.
  • Oxidation polymerization type / ultraviolet curable ink (hereinafter abbreviated as “oil-based / UV combined ink”) is an ink having curing characteristics of both oil-based ink and UV ink.
  • the ink of the present invention may contain not only antimony-doped tin oxide and vehicle but also auxiliary agents and / or colorants.
  • auxiliary agents and / or colorants By adjusting the type and content of the vehicle and / or auxiliary agent in the ink, the above drying methods can be properly used or combined during screen printing.
  • 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 solvent, or the like can be used alone or in combination.
  • the resin and solvent will be described below.
  • the oil-based inks may contain known resins used for printing.
  • the following resins (I) to (XVI) can be contained in the oil-based ink.
  • Acrylic resin is a polymer having a repeating unit derived from acrylic acid, methacrylic acid, acrylic ester or methacrylic ester.
  • the acrylic resin is excellent in weather resistance, adhesion and fluidity, and is particularly suitable for gloss finishing ink.
  • the acrylic resin can be used for screen printing on a plastic substrate such as an acrylic molded article, vinyl chloride, or polycarbonate.
  • Acrylic resins are divided into thermoplastic resins and thermosetting resins.
  • Thermoplastic acrylic resin is resin which has acrylic acid ester or methacrylic acid ester as a main component.
  • the thermosetting acrylic resin has a reactive functional group introduced into a side chain of a thermoplastic acrylic resin, and can be cured by reaction with a melamine resin, an epoxy resin, or the like.
  • Examples of the monomer for obtaining the acrylic resin include acrylic acid, methacrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2- Examples include ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, naphthyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. It is done.
  • “(meth) acrylate” means acrylate or methacrylate.
  • Vinyl resin is a resin obtained by polymerizing a monomer having a terminal double bond such as a vinyl group CH 2 ⁇ CH— or a vinylidene group CH 2 ⁇ C ⁇ , or a modified resin thereof, or of these monomers. It is a copolymer.
  • the vinyl resin can improve the weather resistance and printability of the ink in screen printing when the printing medium is formed of vinyl chloride.
  • vinyl resins are used as matte or semi-matte finish inks.
  • vinyl resin examples include vinyl chloride resin, vinyl acetate resin, vinylidene chloride resin, polyvinyl alcohol, polyvinyl acetal, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinylidene chloride copolymer, and the like.
  • polyester resin is a polycondensate of a polyvalent carboxylic acid and a polyalcohol. Since the polyester resin is excellent in adhesiveness and weather resistance, for example, it can be used for printing using a polyester film, a membrane switch, a direction indicator curtain for transportation, or the like as a printing material.
  • polyester resin examples include polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate.
  • Nitrified cotton is a nitrate ester of cellulose obtained by treating cellulose with a mixture of nitric acid and sulfuric acid, and is also called nitric acid fibrin. Nitrified cotton has different solubility in a solvent depending on the degree of nitrification, and has a different melt viscosity depending on the degree of polymerization.
  • examples of the fiber derivative include cellulose, ethyl cellulose, cellulose acetobutyrate, cellulose acetopropionate, cellulose acetate, and ethyl cellulose.
  • nitrified cotton and fibrin derivatives improve the printability and drying properties of the ink, they can be used, for example, in screen printing inks for paper or plastics.
  • Epoxy resin is a thermosetting resin having an epoxy group in the molecule.
  • An epoxy resin can be hardened by bridge
  • the epoxy resin curing method include a method in which an epoxy resin is thermally cured at a high temperature in combination with a melamine resin or a phenol resin, and a curing agent such as an amine compound, polyamide, or acid anhydride is added to the epoxy resin and cured at a low temperature. The method of making it, etc. are mentioned.
  • epoxy resins are excellent in weather resistance and chemical resistance, and therefore can be applied to printing using a metal, glass, a coated plate, a printed board or the like as a printing medium.
  • Examples of the epoxy resin include a copolymer of bisphenol A or F and epichlorohydrin, a polyfunctional epoxy resin obtained by further reacting epichlorohydrin with phenol novolak, which is a reaction product of phenol and formaldehyde, and o-cresol and formaldehyde.
  • Examples thereof include a polyfunctional epoxy resin obtained by further reacting a reaction product cresol novolak with epichlorohydrin.
  • Natural resins and derivatives thereof include pine oil, straw, shellac, and gilsonite. Generally, natural resins contain a resin acid as a non-volatile component. Examples of 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, petroleum resin, rosin modified maleic acid 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 ink, but 100% phenolic resin or modified phenolic resin is preferable in consideration of vehicle resistance.
  • a 100% phenol resin is a resin obtained by condensing an alkylphenol and formaldehyde in the presence of an acid or an alkali catalyst. 100% phenolic resin can form a dry film having water resistance, friction resistance and chemical resistance.
  • 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.
  • the modified phenolic resin can control the solubility and softening point of the resin or the resistance of the coating depending on the type or amount of the modified component.
  • a modified phenol resin using rosin as a modifying component is preferable.
  • 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 for screen printing using a metal, glass, a coated plate or the like as a printing medium.
  • 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.
  • Petroleum resin is a resin obtained by polymerizing an unsaturated olefin having 5 or more carbon atoms. Petroleum resins have a softening point of 80 to 130 ° C., and are excellent in solubility in petroleum solvents or drying oils, 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.
  • a polyamide resin is a thermoplastic resin obtained by condensation polymerization of a polymerized fatty acid and a polyamine. Generally, a polyamide resin is excellent in adhesiveness, flexibility, blocking resistance, and gloss.
  • Chlorinated rubber is a resin powder obtained by chlorinating natural rubber or synthetic rubber. Generally, chlorinated rubber contains about 64% by mass or more of chlorine, is easily soluble in aromatic hydrocarbon solvents such as toluene, is stable to acids and alkalis, and is wettable with pigments, color developability, and quick-drying properties. Excellent heat resistance.
  • Chlorinated polypropylene is a solvent-soluble resin obtained by chlorinating polypropylene.
  • chlorinated polypropylene containing about 66% by mass or more of chlorine is a powder and has properties similar to chlorinated rubber, so that it can be used together with an aromatic hydrocarbon solvent such as toluene.
  • chlorinated polypropylene containing about 45% by mass or less of chlorine is liquid and has excellent adhesion to untreated polypropylene.
  • it is used in combination with biaxially oriented polypropylene, ethylene-vinyl acetate copolymer, etc. Can be used in screen printing inks.
  • the urethane resin is a mixture of a polyisocyanate compound and a polyol compound, or a polymer having a urethane bond by a condensation reaction of the polyisocyanate compound and the polyol compound.
  • the prepolymer before the condensation reaction of the polyisocyanate compound and the polyol compound is also included in the “urethane resin”. Therefore, one of the polyisocyanate compound and the polyol compound may be contained in the ink of the present invention, and the other may be added to the ink before printing.
  • polyisocyanate compound examples include aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, and aliphatic diisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate.
  • polyol compound examples include polyether polyol, polymer polyol, and polyester polyol.
  • polyether polyol examples include propylene glycol, ethylene glycol, glycerin, trimethylolpropane, triethanolamine, pentaerythritol, ethylenediamine, aromatic diamine, diethylenetriamine, sorbitol, sucrose, and polyoxypropylenetriol.
  • the polymer polyol is obtained, for example, by copolymerizing acrylonitrile or styrene in a polyether polyol.
  • the polyester polyol can be obtained, for example, by dehydrating condensation of a carboxylic acid such as adipic acid or phthalic acid and a polyhydric alcohol such as ethylene glycol, 1,4-butanediol, or 1,6-hexanediol.
  • a carboxylic acid such as adipic acid or phthalic acid
  • a polyhydric alcohol such as ethylene glycol, 1,4-butanediol, or 1,6-hexanediol.
  • Butyral resin is a resin obtained by reacting polyvinyl alcohol and butyraldehyde.
  • the butyral resin not only forms a tough film, but also has excellent flexibility and adhesion to glass or metal.
  • styrenic resin is a polymer containing a styrene skeleton as a repeating unit.
  • the styrene resin is soluble in benzene, toluene, methyl ethyl ketone, acetate ester, and the like, while insoluble in water, alcohol, aliphatic hydrocarbons, and the like.
  • the styrenic resin is stable to acids and alkalis and has excellent melt fluidity, it can be used as a vehicle suitable for organic solvent-containing inks.
  • Examples of the monomer for forming the styrene resin include styrene, ⁇ -methylstyrene, vinyltoluene and the like.
  • the styrene resin not only a polymer of these monomers but also a styrene-butadiene copolymer, a styrene-acrylonitrile copolymer, a styrene-butadiene-acrylonitrile copolymer, or the like may be used.
  • maleic resin is a polymer having a repeating unit derived from maleic acid, maleic anhydride or maleic ester.
  • Maleic resin improves solubility in organic solvents or ink penetrability by adjusting the ratio of repeating units derived from maleic acid, maleic anhydride or maleic ester Can be made. Therefore, the maleic acid resin is a highly versatile resin in oil-based ink.
  • Examples of the monomer for forming the maleic resin include, for example, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monopropyl maleate, monobutyl maleate, monohexyl maleate, monooctyl maleate, maleic acid Examples thereof include mono-2-ethylhexyl, monolauryl maleate, monostearyl maleate, dimethyl maleate, diethyl maleate, and dibutyl maleate.
  • resins suitable for oil-based inks include, for example, acrylamide, methacrylamide, crotonic acid and its ester compounds, itaconic acid and its ester compounds, citraconic acid and its ester compounds, Polymers of unsaturated bond-containing compounds such as acrylonitrile; ionomer resins; high-density polyethylene resins; polypropylene resins; epoxy acrylate resins; phenol resins; polyester resins such as unsaturated polyester resins; phenol-modified alkyd resins, epoxy-modified alkyd resins, Examples include alkyd resins such as styrene-modified alkyd resin, acrylic-modified alkyd resin, and amino alkyd resin; polycarbonate resin; polyketone; polyvinyl acetate;
  • (XV) Other Copolymers The monomers for forming the resins represented by the above (I) to (XIV) can be copolymerized in any combination.
  • suitable copolymers for oil-based inks include vinyl chloride-maleic acid copolymers, vinyl chloride-vinyl acetate-maleic acid copolymers, styrene-acrylic acid copolymers, and acrylic acid-acrylic acid ester copolymers.
  • Styrene-maleic acid copolymer Styrene-maleic acid copolymer, soptylene-maleic anhydride copolymer, acrylonitrile-acrylic styrene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, acrylonitrile chlorinated polyethylene-styrene copolymer Coalescence etc.
  • soptylene-maleic anhydride copolymer acrylonitrile-acrylic styrene copolymer
  • acrylonitrile-styrene copolymer acrylonitrile-styrene copolymer
  • acrylonitrile-butadiene-styrene copolymer acrylonitrile chlorinated polyethylene-styrene copolymer Coalescence etc.
  • (XVI) Resin for water-based ink When water is used as a solvent, it is preferable to contain a resin for water-based ink in the ink. Depending on the desired ink properties such as adhesion to the substrate, drying properties, heat resistance, and glossiness, the water-based ink may contain a known water-based ink resin used for printing.
  • the acid value of the water-based ink resin is preferably 100 mgKOH / g or more, or 130 mgKOH / g or more in order to ensure the solubility of the resin in the water-based ink. In order to ensure the water resistance of the coating film, it is preferably 300 mgKOH / g or less, or 250 mgKOH / g or less.
  • the resin contained in the water-based ink plays different roles during printing and after printing. Specifically, the resin contained in the water-based ink disperses the antimony-doped tin oxide in water during printing, whereas after printing, the antimony-doped tin oxide is fixed to the printed material and eluted into water. prevent. Therefore, 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. These forms will be described below.
  • Water-soluble resin is a resin that can be dissolved in water to form an aqueous solution. Therefore, the structure of the water-soluble resin is preferably designed so as to have a hydrophilic portion.
  • the resin having a hydrophilic portion is a nonionic resin having a hydrophilic group such as a hydroxyl group, an ether group or an amide group; a hydrophilic group such as a carboxyl group, a sulfonic acid group or a phosphate ester group is an alkaline substance.
  • the alkaline substance used for neutralization volatilizes with water, so that the resin before neutralization remains in the dried coating film.
  • the alkaline substance include inorganic alkali compounds such as sodium hydroxide and ammonium hydroxide; organic amine compounds such as butylamine, dibutylamine, triethylamine, tributylamine, monoethanolamine, and triethanolamine.
  • the acid used for neutralization volatilizes with water, so that the resin before neutralization remains in the dried coating film.
  • the resin when the above-listed resins have low water solubility, the resin may be water-solubilized by incorporating a hydrophilic portion so that the resin becomes a nonionic, anionic or cationic resin. .
  • an aqueous dispersion of a water-solubilized resin is transparent.
  • the colloidal dispersion resin is a resin dispersion in which the resin is dispersed in a colloidal form in water.
  • a colloidal dispersion resin is a so-called semi-dissolved state in which a lipophilic portion of the resin is surrounded by a hydrophilic portion in water. Therefore, the resin in the colloidal dispersion is stably dispersed by Brownian motion.
  • colloidal dispersion resins have a resin particle size of about 0.01 ⁇ m to about 0.1 ⁇ m.
  • the colloidal dispersion resin has an intermediate property between the water-soluble resin and the emulsion resin, and therefore has an excellent balance between printability and physical properties of the coating film.
  • a colloidal dispersion resin is obtained by ionizing a part of a resin in the same manner as an anionic or cationic resin when polymerization is performed in an aqueous solution containing an emulsifier such as a surfactant. It is also preferable to obtain a colloidal dispersion resin by using alcohol together with water during polymerization.
  • colloidal dispersion resin for example, an aqueous dispersion of the above-listed resins and emulsifiers can be used.
  • Emulsion resin is a resin dispersion obtained by polymerization in an aqueous solution in which an emulsifier such as a surfactant is present.
  • the resin in the dispersion is generally in the form of particles, and is stably dispersed in the aqueous solution by electrical repulsion between the particles.
  • an emulsion resin has a resin particle size of about 0.1 ⁇ m to about 1 ⁇ m in water when emulsion polymerization is employed, and has a resin particle size of about 1 ⁇ m to about 10 ⁇ m in water when suspension polymerization is employed.
  • the emulsion resin is generally cloudy.
  • an emulsion resin can increase the solid content of an ink as compared with a water-soluble resin, so that it is easy to control drying properties and physical properties of a coating film.
  • the water dispersion of the resin enumerated above and an emulsifier can be used, for example.
  • the resins listed in (I) to (XVI) can be used alone or in combination of two or more. Moreover, you may contain the monomer for forming resin enumerated above in the ink of this invention as a prepolymer. Furthermore, the ink of the present invention may contain a resin other than the resins listed above.
  • 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 petroleum solvents such as mineral oil; aromatic solvents such as toluene, xylene and solvent naphtha; esters such as ethyl acetate; ethers such as n-butyl ether and dioxane; methyl ethyl ketone, methyl isobutyl ketone and diacetone.
  • Ketones such as alcohol, cyclohexanone and isophorone; alcohols such as ethanol and isopropyl alcohol; glycols such as ethylene glycol, diethylene glycol and triethylene glycol; ethyl cellosolve, butyl cellosolve, cellosolve acetate, butyl cellosolve, butyl carbitol; trichloroethylene, o-dichlorobenzene And halogen solvents such as cellulose solvent, water and the like.
  • 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.
  • Mineral oil includes spindle oil, machine oil, white kerosene, non-aromatic petroleum solvent and the like.
  • 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 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).
  • Water is an essential component of water-based ink.
  • Water can form an aqueous dispersion with antimony-doped tin oxide, resins, monomers, organic solvents, colorants, adjuvants, and the like.
  • water used as a solvent for water-based ink include pure water, deionized water, distilled water, drinking water, tap water, seawater, groundwater, agricultural water, industrial water, soft water, hard water, light water, and heavy water. It is done.
  • 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 waxes, dispersants, lubricants, antifoaming agents, leveling agents, plasticizers, crosslinking agents, water-soluble agents, drying oils and semi-drying oils, drying accelerators, extender pigments, oxidation polymerization catalysts, Other additives may be mentioned. These adjuvants will be described below.
  • ⁇ 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 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.
  • the low molecular weight dispersant is a low molecular weight substance having a portion having high orientation or adsorptivity to antimony-doped tin oxide or a colorant and a portion having high affinity with a vehicle, and is also called a surfactant or a wetting 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.
  • the polymer dispersant is a high molecular weight substance having an anchor group adsorbed on the surface of antimony-doped tin oxide or a colorant and a barrier group that exhibits a steric hindrance effect in the vehicle.
  • the polymer dispersant can be adsorbed at multiple points with antimony-doped tin oxide or a colorant.
  • the polymer dispersant has a higher barrier group than the low molecular dispersant, the dispersion stability of the antimony-doped tin oxide or the colorant is improved.
  • 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 of the present invention.
  • dialkylaminomethylene copper phthalocyanine, amine salt copper phthalocyanine, and the like are used to form 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 silane coupling agent is an organosilicon compound having in its molecule an organic functional group that reacts with an organic material and a hydrolyzable group that reacts with an inorganic material.
  • organic functional group include a vinyl group, an epoxy group, a methacryloxy group, and an amino group
  • hydrolyzable group include an alkoxy group, a chloro group, and an acetoxy group.
  • the silane coupling agent is an antimony-doped tin oxide or the colorant and the vehicle. Adhesiveness with a component can be improved.
  • the hydrolyzable group is an alkoxy group such as a methoxy group or an ethoxy group
  • a silanol group obtained by hydrolysis of the alkoxy group self-condenses or reacts with a hydroxyl group of a component other than a silane coupling agent.
  • the silane coupling agent is preferably used for improving the dispersibility of a colorant having a hydroxyl group on the surface (for example, an inorganic pigment containing glass, silica, alumina, etc.).
  • examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3 -Glycidoxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane , 3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, and the like.
  • the titanate coupling agent is an organic titanium compound having in its molecule an organic functional group that reacts with an organic material and a hydrolyzable group that reacts with an inorganic material. Also, the organic functional groups and hydrolyzable groups described for the silane coupling agent can be incorporated into the titanate coupling agent.
  • the titanate coupling agent since the titanate coupling agent has low solubility in water, it is preferable to use the titanate coupling agent by dissolving it in an organic solvent.
  • the lubricant is an auxiliary agent for lubricating the coating surface. For example, when a lubricant is added to the ink, generation of frictional heat can be prevented during screen printing, and wear of the squeegee, screen plate, or printing medium can be prevented.
  • the ink of the present invention may contain a known lubricant used for printing.
  • the lubricant include lubricating oil, grease, and solid lubricant. It is also preferable to use the above wax and a lubricant in combination.
  • the lubricating oil, grease and solid lubricant will be described below.
  • oils other than the above wax may be used.
  • spindle oil machine oil, engine oil, white kerosene, non-aromatic petroleum solvent, castor oil, etc. may be used.
  • Grease is obtained by distributing non-soap substances such as calcium, sodium, lithium, aluminum soap, or bentonite to the lubricating oil. If desired, polytetrafluoroethylene, calcium oxide, silicone resin or the like may be added to the grease.
  • solid lubricant for example, graphite, molybdenum disulfide, polytetrafluoroethylene, silver, lead or the like can be used.
  • the solid lubricant may be in the form of a block, powder, granule or the like.
  • An antifoaming agent is an auxiliary agent used to suppress the generation of bubbles in the ink or reduce the bubbles generated in the ink.
  • antifoaming agents can be used during ink production, storage, circulation, transfer or printing.
  • a vehicle suitable for water-based ink is more likely to foam than a vehicle suitable for ink containing an organic solvent. Therefore, it is preferable to add an antifoaming agent to the water-based ink in order to suppress foaming of the water-based ink.
  • 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®-088; Surfinol DF-37, Surfinol DF-75, Surfinol DF-110D, and Surfinol DF-210 manufactured by Nissin Chemical Industry; US Air Products and Examples include EnviroGem (registered trademark) AE03 manufactured by Chemicals, Inc., and FAMEX 835 commercially available from Evonik-Tego-Chemie, Germany.
  • a leveling agent is an additive which, when added to an ink, reduces 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. Any polymer can be used to improve the leveling properties of the ink.
  • a leveling agent having a plurality of double bonds in its structure is preferably used for UV ink.
  • a silicone-based polymer having at least one double bond for example, 2, 3, or 4 double bonds in the structure as a leveling agent.
  • a leveling agent having a surfactant structure in its structure is preferably used for water-based ink.
  • “having a surfactant structure” means that the leveling agent has both a hydrophobic portion and a hydrophilic portion.
  • the leveling agent has a surfactant structure.
  • examples of the silicone polymer include dimethylpolysiloxane, methylphenylpolysiloxane, and organically modified polysiloxane introduced with polyether, polyester, aralkyl and the like.
  • examples of polyalkyl acrylate etc. are mentioned as a polyacrylate type polymer.
  • examples of the polyvinyl ether polymer include polyalkyl vinyl ether.
  • the leveling agent for example, Surflon “S-381”, “S-382”, “SC-101”, “SC-102”, “SC-103” and “SC-104” (whichever Asahi Glass Co., Ltd.); Fluorad “FC-430”, “FC-431” and “FC-173” (all manufactured by Sumitomo 3M); F-top “EF352”, “EF301” and “EF303” (all (Manufactured by Shin-Akita Chemical Co., Ltd.); “BYK-310”, “BYK-323”, “BYK-320”, “BYK-377”, “BYK-UV3510”, “BYK-Silclean3700”, “BYK-UV3500” and “BYK-UV3570” (all manufactured by Big Chemie Japan) and the like.
  • the plasticizer is an auxiliary agent for adjusting the film formability of the ink or the flexibility of the ink coating film.
  • the plasticizer is in liquid form.
  • the weight average molecular weight of the plasticizer may be about 30,000 or less, or about 5000 or less, and the weight average molecular weight may be about 200 or more, or about 300 or more.
  • the weight average molecular weight is a value in terms of polystyrene.
  • 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.
  • 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 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.
  • a gelling agent for cross-linking, the chain polymer changes to a shaded structure; the formation of a urethane bond by the reaction of an isocyanate group and a hydroxyl group; the formation of a secondary amine by the reaction of a primary amine and an epoxy group, followed by a secondary amine And reaction of epoxy group.
  • a crosslinking agent a polyisocyanate compound, a polyol compound, an epoxy compound, an amine compound, an oxazoline compound, a formalin compound, a divinyl compound, a melamine compound, or the like can be used alone or in combination.
  • isocyanate compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, tetramethylxylylene diisocyanate, polymethylene polyphenyl polyisocyanate; trimethylolpropane-tris- ⁇ -Aziridine compounds such as N-aziridinylpropionate and pentaerythritol propane-tris- ⁇ -N-aziridinylpropionate; epoxy compounds such as glycerol polyglycidyl ether and trimethylolpropane polyglycidyl ether; aluminum triiso Propoxide, mono-sec-butoxyaluminum diisopropoxide, aluminum tri-sec-butoxide, ethyl acetate
  • Aluminum alcoholates such as cetoacetate aluminum diisopropoxide and aluminum trisethylacetoacetate
  • the water-solubilizing agent is an auxiliary agent for making the antimony-doped tin oxide, the colorant, or the vehicle component water-soluble, and is generally used in the production of water-based inks.
  • a water-soluble agent suitable for antimony-doped tin oxide or colorant among the above-mentioned dispersants, a portion having high orientation or adsorptivity to antimony-doped tin oxide or colorant in the molecule, and affinity with water Those having a high portion may be used.
  • the water-solubilizing agent for making the vehicle component water-soluble may be an emulsifier such as a surfactant as described for the colloidal dispersion resin or the emulsion resin.
  • 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 in order to improve the fluidity of the ink at low temperatures or the transferability to the substrate.
  • 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 drying accelerator is an auxiliary agent that accelerates drying by oxidative polymerization of resin for oil-based ink, 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.
  • 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 a resin for oil-based ink, a dry oil and / or a semi-dry 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.
  • the ink of the present invention may contain a surfactant such as a pigment dispersant, a drying retarder, an antioxidant, an anti-set-off agent, or a nonionic surfactant.
  • a surfactant such as a pigment dispersant, a drying retarder, an antioxidant, an anti-set-off agent, or a nonionic surfactant.
  • 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.
  • composition and viscosity of infrared absorbing screen printing ink When the viscosity of the oil-based ink is adjusted to about 10 to 1000 poise, the colorant is 0 to about 35% by weight and the vehicle is about 50 to 75%. % By weight, adjuvant from 0 to about 5% by weight and antimony-doped tin oxide from about 0.3 to 30% by weight.
  • the weight ratio of the solvent to the resin contained in the vehicle of the oil-based ink may be about 1.7 or more, or about 2 or more. , About 10 or less, or about 4 or less.
  • the colorant is 0 to about 50% by weight, and the vehicle is about 10 to 85%. % By weight, adjuvant from 0 to about 5% by weight and antimony-doped tin oxide from about 0.3 to 30% by weight.
  • the weight ratio of the photopolymerization initiator to the resin contained in the UV ink vehicle may be about 0.05 or more, or about 0.1 or more.
  • the weight ratio may be about 0.3 or less, about 0.2 or less, or about 0.15 or less.
  • an oil-based ink and a UV ink may be used in combination to form an oil-based / UV combined ink.
  • a vehicle suitable for oil-based ink and a vehicle suitable for UV ink are blended.
  • an antimony-doped tin oxide and / or a colorant is added to an oil-based ink vehicle other than a solvent, and if desired, an oil component such as vegetable oil or mineral oil, and further a radical polymerizable monomer and / or oligomer, or a pigment dispersant
  • the mill base for ink is obtained by dispersing the meat by a dispersing machine such as a bead mill or a three-roll mill.
  • 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 such that when the viscosity of the oil-based / UV combined ink is adjusted to about 10 to 1000 poise, the oil-based ink vehicle is about 30 to 50% by weight, and the UV ink vehicle Is about 30 to 50% by weight, the adjuvant is 0 to about 5% by weight, and the antimony-doped tin oxide is about 0.3 to 30% by weight.
  • the oil-based ink vehicle is described above as a vehicle suitable for oil-based ink
  • the UV ink vehicle is described above as a vehicle suitable for UV ink.
  • a colorant may be added to the oil-based / UV combined ink.
  • the viscosity of the oil-based ink, UV ink, or oil-based / UV combined ink of the present invention is about 1000 mPa ⁇ s or more, about 2000 mPa ⁇ s or more, about 3000 mPa ⁇ s or more, about 4000 mPa ⁇ s or more at a temperature of about 5 to 35 ° C. Or about 5000 mPa ⁇ s or more, and the viscosity may be about 100 Pa ⁇ s or less, about 50 Pa ⁇ s or less, about 25 Pa ⁇ s or less, about 10 Pa ⁇ s or less, or about 7 Pa ⁇ s or less. Furthermore, this viscosity is preferably about 5000 mPa ⁇ s or more, and preferably about 7 Pa ⁇ s or less.
  • 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, using a mixer such as a dissolver, a single screw mixer, or a twin screw mixer.
  • a mixer such as a dissolver, a single screw mixer, or a twin screw mixer.
  • 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 a relatively low viscosity 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). Further, when preparing an ink containing antimony-doped tin oxide and not containing a colorant, 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.
  • screen printing inks such as oil-based inks, UV inks, and oil-based / UV combined inks can be produced.
  • oil-based inks such as oil-based inks, UV inks, and oil-based / UV combined inks
  • both the oil-based vehicle and the UV vehicle can be used as the vehicle
  • 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 diameter of the antimony-doped tin oxide in the infrared absorbing screen printing ink is 200 ⁇ m or less, 150 ⁇ m or less, 100 ⁇ m or less, 75 ⁇ m or less, 50 ⁇ m or less, 25 ⁇ m or less, 20 ⁇ m or less in consideration of the suitability of the ink for screen printing. 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, 0.1 ⁇ m or less, 0.05 ⁇ m or less, or 0.025 ⁇ m or less. , 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 0.01 ⁇ 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 screen 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).
  • a printed matter can be obtained by screen printing using the ink of the present invention.
  • Screen printing is a printing method in which ink is placed 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.
  • the frame can be formed of, for example, metal (for example, aluminum, hollow aluminum, etc.), wood, or the like.
  • the size of the frame may be determined according to the size of the desired printed material, but may be, for example, 20 mm ⁇ 30 mm, 50 mm ⁇ 100 mm, 100 mm ⁇ 200 mm, 2 m ⁇ 4 m, or the like.
  • the scissors can be formed of, for example, tetron, nylon, stainless steel or the like.
  • the heel is attached to the frame via an adhesive.
  • the tension of the heel stretched on the frame is preferably about 8 to 10 kg / cm 2 when the heel is Tetron or nylon, and is about 10 to 13 kg / cm 2 when the heel is stainless steel. preferable.
  • the wrinkles are preferably 60 mesh or more, 100 mesh or more, 150 mesh or more, 200 mesh or more, or 225 mesh or more, and on the other hand, 500 mesh or less, 400 mesh or less, or 300 mesh or less. preferable.
  • the “mesh” is the number of yarns per inch (about 2.54 cm).
  • the amount of transfer of the screen printing ink of the present invention to the printing medium can be controlled by adjusting the length and ratio of the opening of the screen plate.
  • the screen plate may have an opening “M” (opening length) of about 292 ⁇ m and an opening area “O” (ratio of opening to the screen plate) of about 65%. It's okay.
  • a resin containing polyvinyl alcohol (PVA) may be used as the resist resin.
  • a squeegee is an instrument for transferring ink from a plate to a printing medium by sliding while pressing the plate surface in screen printing.
  • a squeegee can be created by, for example, fixing a rubber piece (for example, urethane rubber piece) having a thickness of about 10 mm with a metal material or wood.
  • the rubber piece is preferably formed of a soft rubber so as to withstand a solvent and not damage the screen plate.
  • the shore height of the rubber piece may be about 60 ° -80 °.
  • the squeegee can be formed as a flat squeegee, a prismatic squeegee or a sword squeegee depending on the shape of the rubber piece.
  • the substrate to be printed may be formed of, for example, paper, fabric, glass, metal, resin, ceramic, and the like, and has a three-dimensional curved surface such as a clock, a display panel of an instrument, a bottle, or a bill, a card, a plate, etc. It may be a form having a two-dimensional curved surface.
  • screen printing can be used for, for example, textile printing, perfume printing, and printed wiring board formation in addition to the formation of printed matter.
  • the screen plate and the printing medium are set so that the distance between the screen plate and the printing medium is about 5 to 10 mm. It is preferable to arrange the body.
  • the ink ejection amount is generally determined by multiplying the thickness of the screen plate by the area of the opening area “O”.
  • the ink film thickness is about 5 ⁇ m or more or about 10 or more, and the film thickness is about 200 ⁇ m or less, about 150 ⁇ m or less, about 100 ⁇ m or less, about 50 ⁇ m or less, or about 30 ⁇ m or less.
  • ink is easily foamed because there is a wrinkle by blocking the transferred ink layer.
  • the smoothness of the printed surface that is, the leveling property
  • screen printing has a simple plate making process and printing process compared to other printing methods, and has a wide range of ink compositions and properties, so that it can be applied to various uses and small lot printing. Can do.
  • the ink of the present invention can be printed not only by conventional screen printing but also by rotary screen printing.
  • 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.
  • UV curable varnish 95 parts by weight of the ultraviolet curable varnish was mixed with 5 parts by weight of the infrared absorbing pigment of Example 2, and then stirred with a mixer (Pony Mixer, manufactured by Inoue Seisakusho Co., Ltd.) to prepare a UV ink.
  • 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.
  • FIG. 12 is a graph showing the reflectance of a printed matter obtained by offset printing of CMY process ink.
  • the reflectance of the printed matter obtained by screen printing is considered to be the same as the reflectance of the printed matter obtained by offset printing. 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, the screen printing ink of the present invention is used as a general color ink. The relationship between the color tone and infrared absorptivity 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.
  • 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 screen printing ink of the present invention is used as the indigo ink, the ink does not affect the color tone of the indigo color. It turns out that an 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 screen 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.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

La présente invention concerne une encre pour sérigraphie à absorption dans l'infrarouge comprenant de l'oxyde d'étain dopé à l'antimoine et un véhicule. L'oxyde d'étain dopé à l'antimoine comprend de l'oxyde d'étain et de l'oxyde d'antimoine, et satisfait (a) et/ou (b) : (a) la largeur à mi-hauteur (∆2θ) d'un pic dans le voisinage de 2θ=27˚obtenue à partir d'une mesure de diffraction de 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 à l'aide du poids de l'oxyde d'étain dopé à l'antimoine comme référence, et le degré de cristallisation, à savoir une valeur obtenue en divisant, par la largeur à mi-hauteur (∆2θ), la valeur maximale du pic dans le voisinage de 2θ=27˚ obtenue à partir d'une mesure de diffraction de rayons X, est d'au moins 58427.
PCT/JP2013/080313 2013-11-08 2013-11-08 Encre pour sérigraphie à absorption dans l'infrarouge Ceased WO2015068281A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021161430A1 (fr) * 2020-02-12 2021-08-19 共同印刷株式会社 Encre uv absorbant le rayonnement infrarouge, et procédé de fabrication de celle-ci
JP2021126896A (ja) * 2019-09-03 2021-09-02 東レ株式会社 印刷物の製造方法

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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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JP2009057441A (ja) * 2007-08-31 2009-03-19 Kyodo Printing Co Ltd インキ組成物
JP2009114298A (ja) * 2007-11-06 2009-05-28 Brother Ind Ltd 水系インクジェット記録用赤外吸収インク、インクジェット記録方法及びインクジェット記録装置
JP2010006999A (ja) * 2008-06-29 2010-01-14 Kyodo Printing Co Ltd 偽造防止用赤外線吸収インキ
JP2010084079A (ja) * 2008-10-01 2010-04-15 Kyodo Printing Co Ltd 偽造防止用赤外線吸収インキ及び印刷物
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
WO2013146937A1 (fr) * 2012-03-28 2013-10-03 共同印刷株式会社 Support d'impression filigrané pour prévention des contrefaçons
WO2013147029A1 (fr) * 2012-03-29 2013-10-03 三菱マテリアル株式会社 Poudre d'oxyde d'étain dopée à l'antimoine et son procédé de fabrication
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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Publication number Priority date Publication date Assignee Title
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
JP2005531661A (ja) * 2002-06-28 2005-10-20 メルク　パテント　ゲゼルシャフト　ミット　ベシュレンクテル　ハフトング 表面コーティング系および印刷インクの硬化および乾燥
JP2009057441A (ja) * 2007-08-31 2009-03-19 Kyodo Printing Co Ltd インキ組成物
JP2009114298A (ja) * 2007-11-06 2009-05-28 Brother Ind Ltd 水系インクジェット記録用赤外吸収インク、インクジェット記録方法及びインクジェット記録装置
JP2010006999A (ja) * 2008-06-29 2010-01-14 Kyodo Printing Co Ltd 偽造防止用赤外線吸収インキ
JP2010084079A (ja) * 2008-10-01 2010-04-15 Kyodo Printing Co Ltd 偽造防止用赤外線吸収インキ及び印刷物
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
WO2013147029A1 (fr) * 2012-03-29 2013-10-03 三菱マテリアル株式会社 Poudre d'oxyde d'étain dopée à l'antimoine et son procédé de fabrication
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

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021126896A (ja) * 2019-09-03 2021-09-02 東レ株式会社 印刷物の製造方法
JP7501243B2 (ja) 2019-09-03 2024-06-18 東レ株式会社 印刷物の製造方法
WO2021161430A1 (fr) * 2020-02-12 2021-08-19 共同印刷株式会社 Encre uv absorbant le rayonnement infrarouge, et procédé de fabrication de celle-ci

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