WO2013168812A1 - アンチモンドープ酸化錫、赤外線吸収顔料、赤外線吸収インキ、印刷物及びアンチモンドープ酸化錫の製造方法 - Google Patents
アンチモンドープ酸化錫、赤外線吸収顔料、赤外線吸収インキ、印刷物及びアンチモンドープ酸化錫の製造方法 Download PDFInfo
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- WO2013168812A1 WO2013168812A1 PCT/JP2013/063220 JP2013063220W WO2013168812A1 WO 2013168812 A1 WO2013168812 A1 WO 2013168812A1 JP 2013063220 W JP2013063220 W JP 2013063220W WO 2013168812 A1 WO2013168812 A1 WO 2013168812A1
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- Prior art keywords
- antimony
- tin oxide
- doped tin
- oxide
- cooling
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- 229910001887 tin oxide Inorganic materials 0.000 title claims abstract description 178
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 176
- 239000000049 pigment Substances 0.000 title claims description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 229910000410 antimony oxide Inorganic materials 0.000 claims abstract description 86
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims abstract description 86
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 38
- 238000001816 cooling Methods 0.000 claims description 81
- 238000000034 method Methods 0.000 claims description 81
- 238000010304 firing Methods 0.000 claims description 74
- 238000005273 aeration Methods 0.000 claims description 43
- 239000002994 raw material Substances 0.000 claims description 25
- 238000009423 ventilation Methods 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 150000001463 antimony compounds Chemical class 0.000 claims description 9
- 150000003606 tin compounds Chemical class 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 229920001296 polysiloxane Polymers 0.000 claims description 7
- 238000007639 printing Methods 0.000 claims description 7
- 239000002966 varnish Substances 0.000 claims description 7
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 description 43
- 230000000694 effects Effects 0.000 description 42
- 239000000463 material Substances 0.000 description 36
- 230000000052 comparative effect Effects 0.000 description 23
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 18
- 239000013078 crystal Substances 0.000 description 18
- 239000012535 impurity Substances 0.000 description 18
- 229910052787 antimony Inorganic materials 0.000 description 14
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 14
- 238000005259 measurement Methods 0.000 description 12
- AUYOHNUMSAGWQZ-UHFFFAOYSA-L dihydroxy(oxo)tin Chemical compound O[Sn](O)=O AUYOHNUMSAGWQZ-UHFFFAOYSA-L 0.000 description 10
- 238000010586 diagram Methods 0.000 description 9
- 238000010298 pulverizing process Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000000227 grinding Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 238000000790 scattering method Methods 0.000 description 5
- 238000009834 vaporization Methods 0.000 description 5
- 230000008016 vaporization Effects 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- -1 dried Substances 0.000 description 3
- 239000011324 bead Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000013014 purified material Substances 0.000 description 2
- 238000002310 reflectometry Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- HFYPIIWISGZGRF-UHFFFAOYSA-N [Nb].[Sn].[Sn].[Sn] Chemical compound [Nb].[Sn].[Sn].[Sn] HFYPIIWISGZGRF-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 229910000074 antimony hydride Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011538 cleaning material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- SFXJSNATBHJIDS-UHFFFAOYSA-N disodium;dioxido(oxo)tin;trihydrate Chemical compound O.O.O.[Na+].[Na+].[O-][Sn]([O-])=O SFXJSNATBHJIDS-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- WPYVAWXEWQSOGY-UHFFFAOYSA-N indium antimonide Chemical compound [Sb]#[In] WPYVAWXEWQSOGY-UHFFFAOYSA-N 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- WMHSAFDEIXKKMV-UHFFFAOYSA-N oxoantimony;oxotin Chemical compound [Sn]=O.[Sb]=O WMHSAFDEIXKKMV-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- KXCAEQNNTZANTK-UHFFFAOYSA-N stannane Chemical compound [SnH4] KXCAEQNNTZANTK-UHFFFAOYSA-N 0.000 description 1
- OUULRIDHGPHMNQ-UHFFFAOYSA-N stibane Chemical compound [SbH3] OUULRIDHGPHMNQ-UHFFFAOYSA-N 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 229910000083 tin tetrahydride Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/48—Stabilisers against degradation by oxygen, light or heat
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G30/00—Compounds of antimony
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/32—Radiation-absorbing paints
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2231—Oxides; Hydroxides of metals of tin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K3/2279—Oxides; Hydroxides of metals of antimony
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24893—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material
- Y10T428/24901—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material including coloring matter
Definitions
- the present invention relates to an antimony-doped tin oxide that absorbs infrared rays, an infrared-absorbing pigment, an infrared-absorbing ink, a printed matter, and a method for producing antimony-doped tin oxide.
- Antimony-doped tin oxide is a tin oxide containing a small amount of antimony
- the conventional general production method is a coprecipitation firing method using a hydrolyzable tin compound and an antimony compound as raw materials. there were.
- tin and antimony hydrated oxides are co-precipitated by simultaneously hydrolyzing (eg, neutralizing) tin and antimony compounds in the same solution.
- the coprecipitate is recovered, washed to remove the adhering salt, and then dehydrated to an oxide by baking at 400 ° C. or higher to obtain ATO.
- firing is performed in a closed system in order to reduce energy consumption.
- antimony-doped tin oxide (ATO) has been used as a transparent conductive material.
- the content of antimony oxide needs to be about 10% by weight.
- antimony oxide is added in an amount of 3 to 30% by weight, preferably 5 to 20% by weight, based on tin oxide.
- the fine powder obtained by the method contains 5% by weight or 10% by weight of antimony oxide.
- antimony-doped tin oxide also has an infrared absorption effect and can be used as a security material (see, for example, Patent Document 3).
- Patent Document 3 an infrared-absorbing ink having high transparency can be produced by adding antimony-doped tin oxide to the ink.
- Patent Document 3 it is considered that an infrared absorbing ink exhibiting a variety of colors can be manufactured in combination with pigments of various colors. Moreover, since antimony dope tin oxide is an inorganic pigment, it is thought that the infrared rays absorption ink excellent in light resistance can be provided.
- Antimony-doped tin oxide is produced by adding antimony oxide to tin oxide, which is the main component.
- the principle that antimony-doped tin oxide exhibits an infrared absorption effect is that a crystal structure that absorbs infrared rays is formed when antimony oxide is dissolved (enters) into the crystal lattice of tin oxide, which is the main component. It is possible.
- antimony oxide is listed as a target substance in the chemical substance release and transfer notification system (PRTR) or toy safety standards. Therefore, it is desirable that the amount of antimony oxide used be as small as possible.
- antimony oxide is considered to exhibit the 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. There is a problem of end up.
- an object of the present invention is to provide a technique that can sufficiently exhibit the infrared absorption effect 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 of the antimony-doped tin oxide having a thickness of 70 ⁇ m and 11.6% by weight.
- the coating film having a ratio is formed and the solar reflectance of the coating film is measured in accordance with JIS K5602, 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 antimony-doped tin oxide according to [1], wherein the value obtained by the step is 3.00% or more.
- a printed matter comprising a printing part printed with the infrared absorbing ink according to [8].
- the peak value of the reflectance in the infrared wavelength region of 780 to 1100 nm is 28.776% or less.
- a method for producing antimony-doped tin oxide comprising a ventilation firing step of firing an antimony-doped tin oxide raw material under ventilation.
- the method according to [11] including a cooling step of cooling the antimony-doped tin oxide at a cooling rate of 200 [° C./hour] or more.
- [13] Before the ventilation firing step, [11] or [12], comprising a mixing step of mixing a tin compound and an antimony compound to obtain a mixture, and a closed firing step of firing the mixture in a closed system to obtain the antimony-doped tin oxide raw material. the method of.
- the method according to [13] including a closed cooling step of cooling the antimony-doped tin oxide raw material in a closed system.
- the infrared absorption effect can be improved by improving the crystallinity of antimony-doped tin oxide, the infrared absorption effect can be sufficiently exerted even if the amount of antimony oxide used is reduced. Can do.
- 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.
- 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 of the present invention is 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 infrared absorbing ink of the present invention is an infrared absorbing ink containing the above infrared absorbing pigment.
- the action and effect of the infrared absorbing pigment can be realized by the infrared absorbing ink. For this reason, while reducing the usage-amount of antimony oxide, while being able to fully exhibit the infrared absorption effect, the high quality infrared absorption ink 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 powder by a high-speed 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 high-speed 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 baked at 1000 to 1300 ° C. for 1 to 12 hours under ventilation (a state in which ventilation is maintained inside the furnace).
- the antimony-doped tin oxide raw material produced by the closed firing process is fired again under ventilation.
- excess antimony oxide (Sb) in the tin oxide (SnO 2 ) can be vaporized and eliminated.
- the final antimony oxide content (solid solution ratio) is about 0.5 to 9.3 wt%.
- 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 finished and pulverized with a high-speed pulverizer so that the particle diameter (median diameter by the 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 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 aeration cooling step contributes to improvement of 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.
Abstract
Description
[1] 酸化錫と酸化アンチモンを含有するアンチモンドープ酸化錫であって、下記(a)及び/又は(b)を満たすアンチモンドープ酸化錫:
(a)X線回折測定により得られた2θ=27°付近の半値幅(Δ2θ)が、0.35以下である;及び/又は
(b)前記酸化アンチモンの含有量が、前記アンチモンドープ酸化錫の重量を基準として、0.5~10.0重量%であり、かつ、X線回折測定により得られた2θ=27°付近のピークのピーク値を半値幅(Δ2θ)で除算した値である結晶化度が、18092以上である。
[2] 前記(a)において、前記半値幅(Δ2θ)は、0.21以下である、[1]に記載のアンチモンドープ酸化錫。
[3] 前記(b)において、前記酸化アンチモンの含有量は、前記アンチモンドープ酸化錫の重量を基準として、2.8~9.3重量%である、[1]に記載のアンチモンドープ酸化錫。
[4] 前記結晶化度が58427以上である、[1]に記載のアンチモンドープ酸化錫。
[5] 前記結晶化度が78020以上である、[1]に記載のアンチモンドープ酸化錫。
[6] 前記アンチモンドープ酸化錫を、アクリルポリマー及びシリコーンを含むワニスに溶解させ、基材に塗布し、乾燥し、70μmの厚さ及び11.6重量%の前記アンチモンドープ酸化錫の固形分重量比を有する塗膜を形成して、JIS K5602に従って前記塗膜の日射反射率を測定したときに、380~780nmの波長域における平均反射率から780~1100nmの波長域における平均反射率を引くことにより得られた値が、3.00%以上である、[1]に記載のアンチモンドープ酸化錫。
[7] [1]~[6]のいずれか1項に記載のアンチモンドープ酸化錫からなる赤外線吸収顔料。
[8] [7]に記載の赤外線吸収顔料を含む赤外線吸収インキ。
[9] [8]に記載の赤外線吸収インキにより印刷された印刷部を備える印刷物。
[10] 前記印刷部に含有されるアンチモンドープ酸化錫の固形分重量比が11.6重量%である場合、780~1100nmの赤外線波長域における反射率のピーク値が28.776%以下である、[9]に記載の印刷物。
[11] アンチモンドープ酸化錫原料を通気下で焼成する通気焼成工程を含む、アンチモンドープ酸化錫の製造方法。
[12] 前記通気焼成工程の後に、
200[℃/時間]以上の冷却速度で前記アンチモンドープ酸化錫を冷却する冷却工程
を含む、[11]に記載の方法。
[13] 前記通気焼成工程の前に、
錫化合物とアンチモン化合物を混合して、混合物を得る混合工程、及び
前記混合物を閉鎖系で焼成して、前記アンチモンドープ酸化錫原料を得る閉鎖焼成工程
を含む、[11]又は[12]に記載の方法。
[14] 前記閉鎖焼成工程と前記通気焼成工程の間に、
前記アンチモンドープ酸化錫原料を閉鎖系で冷却する閉鎖冷却工程
を含む、[13]に記載の方法。
本発明のアンチモンドープ酸化錫の製造方法は、アンチモンドープ酸化錫原料を通気下で焼成する通気焼成工程を含む。
(i)錫化合物とアンチモン化合物の混合物;
(ii)上記(i)の混合物を閉鎖系(外気を遮断する密閉空間)で焼成することにより得られる生成物;
(iii)上記(ii)の生成物を閉鎖系で冷却することにより得られる生成物;
(iv)錫化合物及びアンチモン化合物を原料として用いる共沈焼成法により得られる粗アンチモンドープ酸化錫;及び
(v)X線回折測定により得られた2θ=27°付近の半値幅(Δ2θ)が、0.35を超えており、かつ/又は、X線回折測定により得られた2θ=27°付近のピークのピーク値を半値幅(Δ2θ)で除算した値である結晶化度が、18092未満である粗アンチモンドープ酸化錫。
得られたアンチモンドープ酸化錫を、通気下で冷却する通気冷却工程;及び/又は
得られたアンチモンドープ酸化錫を200[℃/時間]以上の冷却速度で冷却する冷却工程。
錫化合物とアンチモン化合物を混合して、混合物を得る混合工程;及び
混合物を閉鎖系で焼成して、アンチモンドープ酸化錫原料を得る閉鎖焼成工程。
この工程では、アンチモンドープ酸化錫の原料となる錫化合物とアンチモン化合物と混合する。具体的には、粉末状のメタ錫酸(H2SnO3)と粉末状の三酸化アンチモン(Sb2O3)とを混合する。配合の割合は、「メタ錫酸(H2SnO3)=90重量%、三酸化アンチモン(Sb2O3)=10重量%」の割合とし、水を媒体としてボールミルで砕混合を行う。なお、三酸化アンチモンの含有量は、10重量%が好ましいが、5~20重量%程度であってもよい。
この工程では、先の原料混合工程(ステップS100)で混合された材料を320℃にて乾燥させる。これにより、先の原料混合工程(ステップS100)にて材料を混合する際に使用した水を除去することができる。
この工程では、先の第1乾燥工程(ステップS102)にて乾燥された材料を粉砕する。具体的には、乾燥された材料を高遠粉砕機で粉末状に粉砕する。
この工程では、先の第1粉砕工程(ステップS104)にて粉砕された材料を焼成する。具体的には、先の第1粉砕工程(ステップS104)にて粉砕された材料を閉鎖系にて1000~1300℃で1時間以上焼成する。閉鎖焼成工程では、閉鎖系にて焼成しているため、酸化アンチモンの含有率(固溶比率)は、10重量%程度に維持される。
この工程では、先の閉鎖焼成工程(ステップS106)で焼成された材料を冷却する。具体的には、閉鎖焼成工程の終了と同時に冷却を開始して、焼成された材料を閉鎖系で冷却する。これにより、錫(Sn)とアンチモン(Sb)とを複合させたアンチモンドープ酸化錫原料が生成される。アンチモンドープ酸化錫原料は、閉鎖焼成工程(ステップS106)及び閉鎖冷却工程(ステップS107)を経て生成される。なお、冷却は自然冷却でもよいが、後述する通気冷却工程と同様に、焼成された材料を通気下で冷却してもよい。
所望により、この工程を行なって、先の閉鎖冷却工程(ステップS107)にて冷却された材料を粉砕してよい。具体的には、水を媒体としつつ、ビーズミルを用いて、焼成後の材料を粒径(レーザー回折散乱法でのメディアン径)が100nm程度になるまで粉砕することができる。なお、この工程を省略する場合には、この工程より前の工程(例えば、ステップS106、ステップS107など)で使用された装置内において、連続的に後の工程に進んでよい。
所望により、この工程を行なって、先の第1微粉砕工程(ステップS108)で粉砕された材料を、320℃に加熱することにより乾燥させてよい。これにより、先の第1微粉砕工程(ステップS108)にて材料を粉砕する際に使用した水を除去することができる。なお、この工程を省略する場合には、この工程より前の工程(例えば、ステップS106、ステップS107など)で使用された装置内において、連続的に後の工程に進んでよい。
所望により、この工程を行なって、先の第2乾燥工程(ステップS110)にて乾燥された材料を粉砕してよい。具体的には、乾燥された材料を高遠粉砕機で粉末状に粉砕することができる。なお、この工程を省略する場合には、この工程より前の工程(例えば、ステップS106、ステップS107など)で使用された装置内において、連続的に後の工程に進んでよい。
この工程では、先の第2粉砕工程(ステップS112)にて粉砕された材料を焼成する。具体的には、先の第2粉砕工程(ステップS112)にて粉砕された材料を通気下(炉内部に通気を保った状態)にて1000~1300℃で1~12時間焼成する。この通気焼成工程により、閉鎖焼成工程により生成されたアンチモンドープ酸化錫原料を通気下で再び焼成することになる。また、通気焼成工程では、通気下にて焼成しているため、酸化錫(SnO2)中の余分な酸化アンチモン(Sb)を気化させて消失させることができる。そして、最終的な酸化アンチモンの含有量(固溶比率)は、0.5~9.3重量%程度になる。
この工程では、先の通気焼成工程(ステップS114)で焼成されたアンチモンドープ酸化錫を、通気下にて冷却する。
この工程では、先の通気冷却工程(ステップS116)にて冷却された精製後の材料を粉砕する。具体的には、水を媒体としつつ、ビーズミルを用いて、精製後の材料を粒径(レーザー回折散乱法でのメディアン径)が100nm程度になるまで粉砕する。
この工程では、先の第2微粉砕工程(ステップS118)にて粒度調整された材料の不純物を水洗により除去する。不純物は、原材料に含まれる微量の電解質(例えば、ナトリウム(Na)、カリウム(K)など)であり、不純物が十分に除去されたか否かは、導電率で確認することができる。
この工程では、先の洗浄工程(ステップS120)で洗浄された材料を145℃に加熱することにより乾燥させる。これにより、先の洗浄工程(ステップS120)にて材料を洗浄する際に使用した水を除去することができるとともに、洗浄後の材料を乾燥させることができる。
この工程では、先の第3乾燥工程(ステップS122)にて乾燥された材料を粉砕する。具体的には、乾燥された材料を高遠粉砕機で、粒径(レーザー回折散乱法でのメディアン径)が数10nm~100μm程度になるように仕上粉砕する。
使用した材料は、以下の通りである:
メタ錫酸:日本化学産業株式会社製のメタ錫酸
三酸化アンチモン:PATOX-CF(登録商標;日本精鉱株式会社製)
アンチモンドープ酸化錫原料(市販品):日揮触媒化成株式会社製のELCOM(登録商標) P-特殊品(酸化アンチモンの含有量:9.9重量%、通気焼成なし、通気冷却なし)
118.8gのメタ錫酸及び1gの三酸化アンチモンを用いて、図1に記載の通りに、ステップ100~ステップ124を行なった。
下記表1に記載の通りに、実施例2~7並びに比較例1及び2を行なった。実施例2~4については、メタ錫酸及び三酸化アンチモンの重量、及び/又は通気焼成工程(S114)の時間を変化させることによって、得られたアンチモンドープ酸化錫中の酸化アンチモン含有量を変化させた。
生成物中の酸化アンチモン含有量の測定は、蛍光X線分析装置RIX-1000(株式会社リガク製)のオーダー分析法にて行っている。また、測定条件としては、アンチモンドープ酸化錫を粉末にして測定を行っている。粉末は、粒径(レーザー回折散乱法でのメディアン径)が120nmの条件で測定を行っている。
そして、実施例及び比較例の各生成物についてX線回折を行い、その測定結果から結晶化度の値を算出した。
ここで、「CPS(Count Per Second)」とは、測定対象物にX線を照射した際の1秒あたりの光子の反射量を示しており、反射光の強度(レベル)として捉えることもできる。
また、「2θ」は、測定対象物にX線を照射する際の照射角度を示している。なお、「2θ」としている理由は、X線を照射する角度(入射角)がθであれば、反射角もθとなるため、この入射角と反射角とを合計した角度は2θとなるからである。
結晶化度は、X線回折(XRD)の測定結果に基づいて算出している。使用機器及び測定条件は、以下の通りである。
(1)使用機器:株式会社リガク製 MultiFlex(X線回折装置)
(2)測定条件:
スキャン速度:4.0°/min.
線源:40kV、30mA
積算回数:1回
そして、反射光の強度が上昇する地点のうち、反射光の強度が最も高い地点での2θ(deg)と強度(CPS)の測定値を用いて結晶化度を算出する。アンチモンドープ酸化錫で反射光の強度が最も高い地点は、「2θ=27°」付近の地点である。
結晶化度は、物質が結晶化した際の物質全体に対する結晶化部分の割合を示しており、ここでは、結晶化度=CPS/Δ2θ(半値幅)と定義している。すなわち、結晶化度は、2θ=27°付近の地点における数値で定義している。これにより、X線回折(XRD)の測定結果から結晶化度を算出することができる。また、図示のグラフにおいて、規則正しい結晶構造を持ち、不純物がない程、波形のピークは大きく、波形の先端がシャープになる。
CPSは、反射光の強度(レベル)であるため、図示の例では波形の高さとなる。
また、Δ2θは、X線回折測定により得られたCPSの最大値(ピーク値)の半分の値に対応する半値幅の広さとなる(図7において、長さA1と、長さA2とは同じ長さである)。
赤外線吸収効果の測定は、分光光度計を用いて光反射率を測定することによって行った。使用機器、測定条件、及び測定方法は、以下の通りである。
(2)試料作成条件:アクリル/シリコーン系ワニス(ウレタン技研工業株式会社製 水性セフコート #800 クリアー)95部に、実施例及び比較例の赤外線吸収顔料5部を添加し、遊星式分散ミルを用いて分散させて赤外線吸収インキを作成し、厚さ200μmのPETフィルム上にフィルムアプリケーターで塗工して、乾燥させ、乾燥状態で膜厚70μmの印刷部を形成し、塗工フィルム(試料印刷物)を作成した。
(3)測定方法:塗工フィルムの背面に標準白色板を装着し、200~2500nmの波長範囲での反射率を測定した。なお、実施例及び比較例の赤外線吸収顔料については、いずれも粒径(レーザー回折散乱法でのメディアン径)を120nmにして測定している。
また、標準白色板の反射率を、約100%の標準値として設定した。
なお、上記測定方法は「JISK5602 塗膜の日射反射率の求め方」に準拠している。また、印刷部に含有される赤外線吸収顔料の固形分重量比(顔料比)については、次のように計算する。上記(2)記載のアクリル/シリコーン系ワニスには樹脂等の固形分のほか、乾燥時に揮発して消失する溶剤等が含まれる。アクリル/シリコーン系ワニスの固形分重量比が40重量%であるため、アクリル/シリコーン系ワニスの固形分が38部、赤外線吸収顔料が5部となり、赤外線吸収顔料の固形分重量比は11.6重量%である。なお、残りの88.4重量%は、樹脂及び/又はその他の添加剤である。
Claims (14)
- 酸化錫と酸化アンチモンを含有するアンチモンドープ酸化錫であって、下記(a)及び/又は(b)を満たすアンチモンドープ酸化錫:
(a)X線回折測定により得られた2θ=27°付近の半値幅(Δ2θ)が、0.35以下である;及び/又は
(b)前記酸化アンチモンの含有量が、前記アンチモンドープ酸化錫の重量を基準として、0.5~10.0重量%であり、かつ、X線回折測定により得られた2θ=27°付近のピークのピーク値を半値幅(Δ2θ)で除算した値である結晶化度が、18092以上である。 - 前記(a)において、前記半値幅(Δ2θ)は、0.21以下である、請求項1に記載のアンチモンドープ酸化錫。
- 前記(b)において、前記酸化アンチモンの含有量は、前記アンチモンドープ酸化錫の重量を基準として、2.8~9.3重量%である、請求項1に記載のアンチモンドープ酸化錫。
- 前記結晶化度が58427以上である、請求項1に記載のアンチモンドープ酸化錫。
- 前記結晶化度が78020以上である、請求項1に記載のアンチモンドープ酸化錫。
- 前記アンチモンドープ酸化錫を、アクリルポリマー及びシリコーンを含むワニスに溶解させ、基材に塗布し、乾燥し、70μmの厚さ及び11.6重量%の前記アンチモンドープ酸化錫の固形分重量比を有する塗膜を形成して、JIS K5602に従って前記塗膜の日射反射率を測定したときに、380~780nmの波長域における平均反射率から780~1100nmの波長域における平均反射率を引くことにより得られた値が、3.00%以上である、請求項1に記載のアンチモンドープ酸化錫。
- 請求項1~6のいずれか1項に記載のアンチモンドープ酸化錫からなる赤外線吸収顔料。
- 請求項7に記載の赤外線吸収顔料を含む赤外線吸収インキ。
- 請求項8に記載の赤外線吸収インキにより印刷された印刷部を備える印刷物。
- 前記印刷部に含有されるアンチモンドープ酸化錫の固形分重量比が11.6重量%である場合、780~1100nmの赤外線波長域における反射率のピーク値が28.776%以下である、請求項9に記載の印刷物。
- アンチモンドープ酸化錫原料を通気下で焼成する通気焼成工程を含む、アンチモンドープ酸化錫の製造方法。
- 前記通気焼成工程の後に、
200[℃/時間]以上の冷却速度で前記アンチモンドープ酸化錫を冷却する冷却工程
を含む、請求項11に記載の方法。 - 前記通気焼成工程の前に、
錫化合物とアンチモン化合物を混合して、混合物を得る混合工程、及び
前記混合物を閉鎖系で焼成して、前記アンチモンドープ酸化錫原料を得る閉鎖焼成工程
を含む、請求項11又は12に記載の方法。 - 前記閉鎖焼成工程と前記通気焼成工程の間に、
前記アンチモンドープ酸化錫原料を閉鎖系で冷却する閉鎖冷却工程
を含む、請求項13に記載の方法。
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WO2015068290A1 (ja) * | 2013-11-08 | 2015-05-14 | 共同印刷株式会社 | 赤外線吸収性凹版印刷インキ |
WO2015068283A1 (ja) * | 2013-11-08 | 2015-05-14 | 共同印刷株式会社 | 赤外線吸収性オフセット印刷インキ |
WO2015068276A1 (ja) * | 2013-11-08 | 2015-05-14 | 共同印刷株式会社 | 赤外線吸収性フレキソ印刷インキ |
WO2015068282A1 (ja) * | 2013-11-08 | 2015-05-14 | 共同印刷株式会社 | 赤外線吸収性インクジェット印刷インク |
WO2015068291A1 (ja) * | 2013-11-08 | 2015-05-14 | 共同印刷株式会社 | 印刷物 |
WO2015068292A1 (ja) * | 2013-11-08 | 2015-05-14 | 共同印刷株式会社 | 印刷物 |
WO2015068289A1 (ja) * | 2013-11-08 | 2015-05-14 | 共同印刷株式会社 | 赤外線吸収性活版印刷インキ |
WO2015068280A1 (ja) * | 2013-11-08 | 2015-05-14 | 共同印刷株式会社 | 赤外線吸収性グラビア印刷インキ |
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JP6172389B2 (ja) | 2015-03-31 | 2017-08-02 | 東洋紡株式会社 | 透明導電性フィルム |
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US20220348034A1 (en) * | 2019-09-13 | 2022-11-03 | Kyodo Printing Co., Ltd. | Printed object |
FR3105663B1 (fr) | 2019-12-23 | 2022-09-09 | St Microelectronics Rousset | Configuration d'une transaction dans un dispositif électronique sans contact |
FR3105662B1 (fr) * | 2019-12-23 | 2021-11-26 | St Microelectronics Rousset | Configuration d'une transaction dans un dispositif électronique sans contact |
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JP5646114B2 (ja) | 2014-12-24 |
KR20150010763A (ko) | 2015-01-28 |
AU2013260538A1 (en) | 2014-11-20 |
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