WO2015068291A1

WO2015068291A1 - Printed article

Info

Publication number: WO2015068291A1
Application number: PCT/JP2013/080345
Authority: WO
Inventors: 文人小林; 芝岡　良昭; 博昭島根; 渉吉住; 正太川▲崎▼
Original assignee: 共同印刷株式会社
Priority date: 2013-11-08
Filing date: 2013-11-08
Publication date: 2015-05-14

Abstract

Provided is a printed article in which a printed layer (A) and a printed layer (B) are disposed on a base material. The printed layer (A) is disposed outside an area in which the printed layer (B) is disposed. The infrared absorbance of the printed layer (A) and the infrared absorbance of the printed layer (B) are different. The printed layer (A) and/or the printed layer (B) include antimony-doped tin oxide. The antimony-doped tin oxide includes tin oxide and antimony oxide, and satisfies (a) and/or (b): (a) the half-value width (∆2θ) of a peak in the vicinity of 2θ=27˚ obtained from an X-ray diffraction measurement is not more than 0.30; and/or (b) the antimony oxide content is 0.5-10.0 wt% using the weight of the antimony-doped tin oxide as a reference, and the degree of crystallization, i.e. a value obtained by dividing, by the half-value width (∆2θ), the peak value of the peak in the vicinity of 2θ=27˚ obtained from the X-ray diffraction measurement, is at least 58427.

Description

Printed matter

The present invention relates to a printed matter, and particularly to an infrared absorbing printed matter for preventing counterfeiting.

Conventionally, for the purpose of preventing forgery of printed matter such as securities or determining the authenticity, a method of providing a region that absorbs infrared rays on the printed matter has been used.

In this printed matter, the area of the infrared absorbing ink is visually observed in the same manner as the area of the general ink (infrared non-absorbing ink). On the other hand, when the printed matter is confirmed in the infrared region, the region of the infrared absorbing ink can be confirmed while the region of the general ink is not observed.

Therefore, when part of the print design is formed with infrared absorbing ink and the remaining part is formed with infrared non-absorbing ink to obtain a printed matter, only the infrared absorbing ink portion is confirmed by checking the printed matter with an infrared detector. Can be confirmed.

As 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.

For example, Patent Document 1 describes that a printed matter is obtained using an infrared absorbing ink containing carbon black as an infrared absorbing material.

Patent Document 2 discloses a printed matter in which an infrared absorbing printing layer containing a conventional antimony-doped tin oxide and an infrared reflecting (infrared non-absorbing) printing layer are arranged on a base material in a state in which the colors are matched. Is described.

JP 2005-219356 A JP 2009-6528 A

However, an infrared absorbing printing layer containing an infrared absorbing organic material as an infrared absorber can exhibit various colors because of the variety of colors of this material, but the problem of low weather resistance has been pointed out. .

On the other hand, the infrared absorbing printing layer formed with an infrared absorbing ink containing carbon black as an infrared absorbing inorganic material is superior to the ink containing the infrared absorbing organic material in weather resistance, but the carbon black has a dark color tone. Since it is a pigment which has, the color of the printing layer was restricted to the thing of a black type or a low brightness. For this reason, when carbon black was used as the infrared absorbing inorganic material, it was not possible to obtain an infrared absorbing printing layer having a variety of colors by mixing with pigments or dyes having other colors. In particular, it was impossible to obtain a light-colored, particularly light-colored, light-colored infrared absorbing printing layer. Even if a white pigment such as titanium oxide or zinc oxide is added to this layer in order to increase the brightness of the infrared absorption printing layer containing carbon black, the white pigment has the property of reflecting infrared rays, so the printing layer Infrared absorptivity is inhibited, and the function as a printed matter for preventing counterfeiting is adversely affected.

Also, an infrared absorbing printing layer containing a metal oxide such as tungsten oxide or lead oxide as an infrared absorbing inorganic material has a problem that the infrared absorbing effect is low although the transparency is high.

Among metal oxides, indium tin oxide (ITO) is known for its relatively high absorption effect. However, since indium is a rare metal, the cost of ITO is high.

Among metal oxides, antimony tin oxide (ATO) 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.

In this connection, there was room for study on the amount of antimony oxide contained in the conventional antimony-doped tin oxide. Moreover, the infrared rays absorption printing layer containing the conventional antimony dope tin oxide has not been examined in detail about the aspect of arrangement | positioning on a base material.

Accordingly, an object of the present invention is to provide a printed matter that is excellent in infrared absorptivity, transparency, weather resistance, safety and cost, and can exhibit a variety of colors by including colorants of various colors. To do.

In order to solve the above problems, the present invention adopts the following solutions:
[1] A printed matter in which the printing layer (A) and the printing layer (B) are arranged on a substrate,
The printed layer (A) is disposed outside the range in which the printed layer (B) is disposed,
The infrared absorption rate of the printing layer (A) and the printing layer (B) is different,
The printing layer (A) and / or the printing layer (B) contains antimony-doped tin oxide, and the antimony-doped tin oxide contains tin oxide and antimony oxide, and the following (a) and / or (b Meet):
(A) The half width (Δ2θ) of a peak around 2θ = 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 2θ = 27 ° obtained by X-ray diffraction measurement by the half-value width (Δ2θ), based on the weight of tin oxide, from 0.5 to 10.0% by weight. The degree of crystallinity is 58427 or more.
Printed matter.
[2] The printed matter according to [1], which is for forgery prevention.
[3] The printed matter according to [1] or [2], wherein, in (a), the full width at half maximum (Δ2θ) is 0.21 or less.
[4] In (b), the content of the antimony oxide is 2.8 to 9.3 wt% based on the weight of the antimony-doped tin oxide, according to [1] or [2] Printed matter.
[5] The printed material according to [1] or [2], wherein the crystallinity is 78020 or more.
[6] The printed matter according to any one of [1] to [5], wherein the antimony-doped tin oxide has an average particle size of 200 μm or less.
[7] The printing layer (A) and the printing layer (B) contain the antimony-doped tin oxide, and the content of the antimony-doped tin oxide in the printing layer (A) and the printing layer (B) is The printed matter according to any one of [1] to [6], which is different.
[8] The range in which the print layer (A) is disposed and the range in which the print layer (B) is disposed are adjacent to or separated from each other. The printed matter according to claim 1.
[9] The printed material according to any one of [1] to [8], wherein another layer is disposed below the printed layer (A) and / or the printed layer (B).
[10] The printed material according to any one of [1] to [9], wherein the substrate has a flat surface, a curved surface, or unevenness.
[11] The printed matter according to any one of [1] to [10], wherein the printed layer (A) and the printed layer (B) are formed on the substrate by partial printing.
[12] The printing layer (A) is formed by at least one selected from the group consisting of offset printing, flexographic printing, letterpress printing, intaglio printing, gravure printing, screen printing, and inkjet printing. ] To [11].
[13] The printing layer (B) is formed by at least one selected from the group consisting of offset printing, flexographic printing, letterpress printing, intaglio printing, gravure printing, screen printing, and inkjet printing. ] To [12].
[14] The printing layer (A) and / or the printing layer (B) further includes at least one selected from the group consisting of a chromic material, a magnetic pigment, an ultraviolet absorber, an optical variable material, and a pearl pigment. The printed material according to any one of [1] to [13].
[15] A method for producing a printed material, in which the printed layer (A) and the printed layer (B) are formed on a substrate by printing,
The printed layer (A) is disposed outside the range in which the printed layer (B) is disposed,
The infrared absorption rate of the printing layer (A) and the printing layer (B) is different,
The printing layer (A) and / or the printing layer (B) contains antimony-doped tin oxide, and the antimony-doped tin oxide contains tin oxide and antimony oxide, and the following (a) and / or (b Meet):
(A) The half width (Δ2θ) of a peak around 2θ = 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 2θ = 27 ° obtained by X-ray diffraction measurement by the half-value width (Δ2θ), based on the weight of tin oxide, from 0.5 to 10.0% by weight. The degree of crystallinity is 58427 or more.
Manufacturing method of printed matter.

The antimony-doped tin oxide pigment used in the present invention is an inorganic pigment and hardly deteriorates due to light such as ultraviolet rays. Therefore, according to the present invention, the antimony-doped tin oxide pigment includes an infrared absorption printing layer having high weather resistance and infrared absorption. A printed matter is obtained.

In addition, since the printed matter of the present invention has a lightness and a light white color of the antimony-doped tin oxide pigment, various colors, particularly bright colors, are provided by mixing the antimony-doped tin oxide pigment with other colorants. can do. Therefore, according to the present invention, it is possible to provide printed matter such as banknotes, securities, and cards that are excellent in forgery prevention effect and design.

Moreover, the production cost of antimony-doped tin oxide pigments is 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 a conventional antimony-doped tin oxide pigment can be used in a printed matter. Therefore, according to the present invention, it is possible to provide an anti-counterfeit printed matter excellent in economy while complying with safety regulations regarding the amount of antimony used in a wide range of industries.

FIG. 1 is a process diagram showing one embodiment of a method for producing antimony-doped tin oxide. FIG. 2 (A) is a diagram showing the results of X-ray diffraction of antimony-doped tin oxide of Example 1 (antimony oxide content: 0.7% by weight, with aerated firing / cooling), and FIG. 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. 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. 4 (B) 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. 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. FIG. 13 is a schematic diagram illustrating a detection pattern when the printed material according to the embodiment of the present invention is observed, and FIG. 13A illustrates the detection pattern when the printed material is observed visually or with a visible light detector. FIG. 13B shows a detection pattern when the printed material is observed with an infrared light detector.

<Printed matter>
The printed matter of the present invention includes a substrate, a printed layer (A), and a printed layer (B). Moreover, the infrared absorption factor of a printing layer (A) and a printing layer (B) differs. Furthermore, on the base material, the printing layer (A) is disposed outside the range in which the printing layer (B) is disposed. Therefore, the printing layer (A) and the printing layer (B) are arranged on the substrate so as not to overlap each other.

In the printed matter of the present invention, at least one of the printing layer (A) and the printing layer (B) contains antimony-doped tin oxide. Since antimony-doped tin oxide has infrared absorptivity, at least one of the printed layer (A) and the printed layer (B) is an infrared absorbing printed layer. The printed matter of the present invention can be for anti-counterfeit due to the infrared absorptivity of the infrared absorbing printing layer. In addition, the antimony dope tin oxide used by embodiment of this invention is mentioned later.

The substrate, the printing layer (A) and the printing layer (B) will be described below.

<Base material>
A base material is a component holding a printing layer (A) and a printing layer (B). Further, the substrate may be a substrate to be printed on the printing layer (A) and the printing layer (B).

Furthermore, the substrate may be planar or three-dimensional. For example, the base material may be in the form of a sheet, a film, a sphere, a rectangular parallelepiped, a cube, or the like. Therefore, the substrate may have a flat surface, a curved surface, or irregularities depending on the desired form of the printed material.

Examples of the substrate include paper, carton board, metal plate, resin film, fabric, clothing, glass, wallpaper, flooring, card, label, and seal.

<Print layer (A) and print layer (B)>
The printing layer (A) can have one or a plurality of regions. When the print layer (A) has a plurality of regions, the infrared absorption rates of the plurality of regions may be the same or different.

The printing layer (B) can have a single region or a plurality of regions. When the print layer (B) has a plurality of regions, the infrared absorption rates of the plurality of regions may be the same or different.

For example, when the print layer (A) or the print layer (B) is formed as a number pattern “12”, the infrared absorption rate in the pattern “1” region and the pattern “2” region may be the same. And may be different.

The infrared absorption rate of the printing layer (A) and the printing layer (B) is different. Therefore, the infrared absorptivity of the printing layer (A) and the printing layer (B) is also different.

For example, one of the print layer (A) and the print layer (B) may have a specific infrared absorption rate, while the other may have an infrared absorption rate different from the infrared absorption rate. Further, if one of the print layer (A) and the print layer (B) has a positive infrared absorption rate, the other infrared absorption rate may be 0.

The printing layer (A) is disposed outside the range where the printing layer (B) is disposed. Moreover, the range in which the printing layer (A) is disposed and the range in which the printing layer (B) is disposed may be adjacent to each other or may be separated from each other. Therefore, when the printed material is observed from a direction perpendicular to the printing surface of the printed material, the range in which the printed layer (A) is arranged and the range in which the printed layer (B) are arranged do not overlap.

If the range in which the print layer (A) is arranged and the range in which the print layer (B) are arranged do not overlap, layers other than the print layer (A) and the print layer (B) It may be arranged on the substrate, under the printing layer (A) or under the printing layer (B). Moreover, the other infrared non-absorbing layer may be arrange | positioned on the printing layer (A) or the printing layer (B).

The printing layer (A) and the printing layer (B) are obtained by partially printing ink on a substrate. Here, partial printing is printed as a pattern such as a character, a picture, a pattern, a background pattern, or a line drawing on a part or the entire surface of the substrate, or the entire surface (a part of the substrate is covered with ink ( Solid) Refers to printing. For example, the printing layer (A) and the printing layer (B) can be formed as a pattern such as a character, a picture, a pattern, a background pattern, and a line drawing. Moreover, the printing layer (A) and the printing layer (B) may be arranged in a donut shape so as not to overlap each other.

Since at least one of the printing layer (A) and the printing layer (B) contains antimony-doped tin oxide, it is an infrared absorption printing layer. In this connection, when the printing layer (A) and the printing layer (B) contain antimony-doped tin oxide, the printing layer (A) and the printing layer (B) are infrared absorbing printing layers, but different infrared absorptions. Therefore, the content of antimony-doped tin oxide in the print layer (A) and the print layer (B) is different. The printed layer (A) and / or the printed layer (B) may contain an infrared absorbing material other than antimony-doped tin oxide as long as the printed layer (A) and / or the printed layer (B) have different infrared absorption rates.

Further, one of the printing layer (A) and the printing layer (B) may not contain antimony-doped tin oxide. In that case, the layer not containing antimony-doped tin oxide becomes an infrared non-absorbing print layer if it does not contain other infrared absorbing materials.

Furthermore, as long as the printed layer (A) and the printed layer (B) have different infrared absorption rates, they may have the same color tone when observed visually or with a visible light detector. Therefore, the printing layer (A) and the printing layer (B) can be formed in a color-matched state.

Since the printing layer (A) and the printing layer (B) can be formed by printing ink on a substrate, the ink will be described below.

<Ink>
In the embodiment of the present invention, an ink containing antimony-doped tin oxide is used in order to give the printed layer (A) and / or the printed layer (B) infrared absorption. In that case, since the antimony-doped tin oxide has infrared absorptivity, the ink is an infrared absorbing ink. This infrared absorbing ink can be used to prevent forgery of printed matter by utilizing the infrared absorbing property of antimony-doped tin oxide.

Further, the content of the infrared absorbing material such as antimony-doped tin oxide in the ink or the presence or absence of the infrared absorbing material in the ink so that the printing layer (A) and the printing layer (B) have different infrared absorption rates. Is preferably determined.

Also, in order to make one of the printing layer (A) and the printing layer (B) an infrared non-absorbing printing layer, an ink that does not contain an infrared absorbing material such as antimony-doped tin oxide can be used. In that case, the ink may be an infrared non-absorbing ink.

Further, in order to impart properties other than infrared absorption to the printing layer (A), the printing layer (B), or other printing layers other than the printing layer (A) and the printing layer (B), infrared absorption is performed. An ink containing a functional material other than the material may be used. For example, a chromic material can be included in the ink as a functional material.

In an embodiment of the present invention, the ink includes antimony-doped tin oxide and / or a colorant and a vehicle. The ink may also contain adjuvants as well as antimony-doped tin oxide, colorants and vehicles.

In general, the ink can be used as an oxidation polymerization ink, an ultraviolet curable ink, an oxidation polymerization / ultraviolet curable ink, or a solvent-containing ink depending on the type of vehicle component.

Here, 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. In general, oil-based inks contain a resin, a crosslinking agent or a gelling agent, a drying oil or a semi-drying oil, a solvent and the like as a vehicle component.

UV curable ink (hereinafter abbreviated as “UV ink”) is an ink that can be cured by photopolymerization of a vehicle component. In general, a UV ink contains a photopolymerizable resin, a photopolymerization initiator, and the like as a vehicle component, but may not contain a volatile component such as a solvent.

The oil-based / ultraviolet-curing combined ink (hereinafter abbreviated as “oil-based / UV combined ink”) is an ink having curing characteristics of both oil-based ink and UV ink.

The solvent-containing ink is an ink containing a solvent and antimony-doped tin oxide and / or a colorant. The solvent-containing ink can fix the antimony-doped tin oxide and / or the colorant to the substrate by evaporation of the solvent or penetration of the solvent into the printing medium. In general, the solvent-containing ink is preferably used as an aqueous ink containing water as a main solvent or an organic solvent-containing ink containing an organic solvent as a main solvent.

Here, the water-based ink is an ink containing water as a main solvent, but may contain an organic solvent. Furthermore, the water-based ink is preferable because it can contain various resins such as a water-soluble resin, a colloidal dispersion resin, and an emulsion resin in addition to water.

On the other hand, the organic solvent-containing ink is an ink containing an organic solvent as a main solvent, but does not need to contain water substantially. “Substantially free of water” means that the content of water in the ink is 0% by mass, or that the ink inevitably contains 1% by mass or less of water.

Antimony-doped tin oxide, vehicle, auxiliary agent and coloring agent will be described below.

[Antimony-doped tin oxide]
Antimony-doped tin oxide is a substance in which tin oxide is doped with antimony. The antimony-doped tin oxide may be in the form of a pigment containing tin oxide and antimony oxide.

The antimony-doped tin oxide used in the present invention contains tin oxide and antimony oxide. The content of antimony oxide is about 0.5% by weight or more, about 1.0% by weight or more, about 1.5% by weight or more, about 2.0% by weight or more based on the weight of antimony-doped tin oxide. The content is preferably 2.5% by weight or more, or about 2.8% by weight or more, and the content thereof is about 10.0% by weight or less, about 9.5% by weight or less, and about 9.3% by weight. Or less, about 8.0% or less, about 7.0% or less, about 6.0% or less, about 5.5% or less, about 5.0% or less, about 4.0% or less, It is preferably about 3.5% by weight or less, or about 3.0% by weight or less. The content of antimony oxide is about 2.5 to about 9.3 wt%, about 2.8 to about 9.3 wt%, and about 2.8 to about 5 based on the weight of antimony-doped tin oxide. More preferably, it is 0.5 wt%, or about 2.8 to about 3.5 wt%.

Conventional antimony-doped tin oxide needs to contain more than 10% by weight of antimony oxide in order to obtain a transparent conductive material having sufficient conductivity. On the other hand, the antimony dope tin oxide used for this invention can reduce the usage-amount of antimony oxide compared with the conventional antimony dope tin oxide as above-mentioned.

However, 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.

Therefore, the antimony-doped tin oxide used in the present invention has a half-value width (Δ2θ) in the vicinity of 2θ = 27 ° obtained by X-ray diffraction measurement of 0.35 or less in order to suppress a decrease in infrared absorption effect. And / or the crystallinity, which is a value obtained by dividing the peak value of the peak around 2θ = 27 ° obtained by X-ray diffraction measurement by the half-value width (Δ2θ), is 18092 or more.

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.

Therefore, when antimony oxide is appropriately solid-solved in the crystal lattice of tin oxide, the antimony-doped tin oxide used in the present invention is oxidized in the antimony-doped tin oxide by maintaining the crystal structure appropriately. Even if the antimony content is very small (for example, at least 0.5% by weight), the infrared absorption effect can be exhibited. At this time, for example, in the X-ray diffraction measurement, a sharp peak is observed in the vicinity of 2θ = 27 °.

On the other hand, for example, when 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.

In this case, the portion of antimony oxide that does not contribute to the infrared absorption effect remains as a waste material (impurity). For this reason, when manufacturing antimony dope tin oxide, 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 (Δ2θ) of antimony-doped tin oxide is wide and / or the crystallinity (the crystallization of the whole material when the material is crystallized). When the ratio of the portion is low, antimony oxide as an impurity increases. On the other hand, when the half width (Δ2θ) is narrow and / or the degree of crystallinity is high, antimony oxide as an impurity decreases. I found it.

In addition, 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.

Therefore, the present invention provides an antimony-doped tin oxide having a narrowed half width (Δ2θ) and / or an increased crystallinity in order to minimize the amount of antimony oxide used. In this respect, when the half width (Δ2θ) 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. .

Therefore, in the X-ray diffraction measurement, by adjusting the half width (Δ2θ) near 2θ = 27 ° to 0.35 or less and / or adjusting the crystallinity near 2θ = 27 ° to 18092 or more, Even if the amount of antimony used is suppressed, a sufficient infrared absorption effect can be exhibited.

In this specification, when measuring X-ray diffraction, a commercially available X-ray diffractometer may be used to select an arbitrary scan speed, but the number of integrations is set to one.

In the antimony-doped tin oxide used in the present invention, the half-value width (Δ2θ) near 2θ = 27 ° is 0.30 in order to sufficiently exhibit the infrared absorption effect while reducing the amount of antimony oxide used. Hereinafter, it is preferably 0.25 or less, 0.21 or less, 0.20 or less, or 0.19 or less.

Further, the antimony-doped tin oxide used in the present invention preferably has a crystallinity of around 2427 = 27 °, 58427 or more, particularly 78020 or more.

When 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 μm and about 11.6% by weight. When 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.

In this connection, if the value obtained by subtracting the average reflectance in the wavelength region of 780 to 1100 nm from the average reflectance in the wavelength region of 380 to 780 nm is 3.00% or more, the antimony-doped tin oxide Visible light absorption is relatively low, that is, the visible light transparency of antimony-doped tin oxide is relatively high. Therefore, antimony-doped tin oxide can be used in a wide range of applications without being restricted by the color exhibited by antimony-doped tin oxide.

The value obtained by subtracting the average reflectance in the wavelength range of 780 to 1100 nm from the average reflectance in the wavelength range of 380 to 780 nm is about 4.80% or more, or about 4.85% or more. And more preferably about 99% or less, about 90% or less, or about 80% or less.

The infrared absorbing material used in the present invention may be an infrared absorbing pigment made of the above antimony-doped tin oxide.

According to the infrared absorbing material used in the present invention, the action and effect of the antimony-doped tin oxide described above can be realized by the infrared absorbing material. For this reason, while reducing the usage-amount of antimony oxide, the infrared absorption effect can fully be exhibited, and the high quality infrared absorption material which followed the predetermined safety standard etc. can be provided.

When the solid matter weight ratio of antimony-doped tin oxide contained in the infrared absorption printing layer is 11.6% by weight, the printed matter of the present invention has a peak reflectance value of 28.776 in the infrared wavelength region of 780 to 1100 nm. % Or less is preferable.

Thus, by using an infrared absorbing printing layer having a low infrared reflectance, antimony oxide contained in the infrared absorbing printing layer can be reduced, and the infrared absorbing effect can be sufficiently exhibited.

The antimony-doped tin oxide used in the present invention can be produced, for example, by the following method.

[Method for producing antimony-doped tin oxide]
The method for producing antimony-doped tin oxide used in the present invention includes an aeration firing step of firing the antimony-doped tin oxide raw material under ventilation.

In the present invention, aeration firing or cooling is performed not only by firing or cooling while circulating a firing or cooling atmosphere, but also by firing or cooling in an open space (hereinafter also referred to as “open system”) that does not block outside air. Including.

The method for producing antimony-doped tin oxide used in the present invention can make the half-value width of antimony-doped tin oxide narrower than that of the conventional product and / or increase the crystallinity of antimony-doped tin oxide than that of the conventional product.

The method for producing antimony-doped tin oxide used in the present invention includes an antimony-doped tin oxide that can sufficiently exhibit an infrared absorption effect while reducing the amount of antimony oxide used by including an aeration firing step. Can be manufactured.

In the present specification, the “antimony-doped tin oxide raw material” is a raw material that becomes the antimony-doped tin oxide of the present invention by aeration firing, for example, a raw material that satisfies at least one of the following (i) to (v):
(I) a mixture of a tin compound and an antimony compound;
(Ii) a product obtained by firing the mixture of (i) above in a closed system (closed space that blocks outside air);
(Iii) a product obtained by cooling the product of (ii) above in a closed system;
(Iv) a crude antimony-doped tin oxide obtained by a coprecipitation firing method using a tin compound and an antimony compound as raw materials; and (v) a half width (Δ2θ) near 2θ = 27 ° obtained by X-ray diffraction measurement, The crystallinity, which is a value exceeding 0.35 and / or the peak value of the peak around 2θ = 27 ° obtained by X-ray diffraction measurement, divided by the half width (Δ2θ) is less than 18092 Some crude antimony-doped tin oxide.

As apparent from the above (ii) and (iii), since the firing process and the cooling process are conventionally performed in a closed system, in the conventional antimony-doped tin oxide, antimony oxide that is not solid-solved in the crystal lattice of tin oxide is present. Despite being present as an impurity and not contributing to the infrared absorption effect, it was antimony-doped tin oxide with a large amount of antimony oxide.

Therefore, the inventors of the present invention have found that the removal of excess antimony oxide can be achieved by performing an aeration firing process and a subsequent cooling process. And the antimony dope tin oxide obtained by the said manufacturing method has a narrow half value width and / or a high crystallinity degree, It is thought that this originates in there being few antimony oxides of an impurity. On the other hand, if 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.

In the present specification, 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”.

In addition, for antimony oxide dissolved in the crystal lattice, the above-described manufacturing method can maintain the crystal structure appropriately while removing a part thereof by the aeration firing process, so that a high infrared absorption effect Can be maintained. For this reason, a high infrared absorption effect can be obtained while reducing the amount of antimony oxide used by passing through the aeration firing step.

Examples of the “tin compound” include metastannic acid, sodium stannate trihydrate, niobium tritin, fenbutane oxide, tin oxide, and tin hydride.

Examples of the “antimony compound” include antimony oxide, indium antimonide, and stibine.

If desired, the method for producing antimony-doped tin oxide used in the present invention may include the following steps after the aeration firing step:
A ventilation cooling step of cooling the obtained antimony-doped tin oxide under ventilation; and / or a cooling step of cooling the obtained antimony-doped tin oxide at a cooling rate of 200 [° C./hour] or more.

The aeration cooling process can be performed, for example, by sending air into the furnace (specifically, it is possible to set the number of hours and how many times it is cooled by setting the cooling device).

If the time required for the hermetic cooling process (so-called natural cooling) is 10 hours, 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.

In the ventilation cooling process or the simple cooling process, the cooling rate is preferably 200 [° C./hour] or more, 215 [° C./hour] or more, or 216 [° C./hour] or more.

Moreover, it is preferable that the manufacturing method of the antimony dope tin oxide used for this invention includes the following mixing processes and closed baking processes before a ventilation baking process:
A mixing step of mixing a tin compound and an antimony compound to obtain a mixture; and a closed baking step of firing the mixture in a closed system to obtain an antimony-doped tin oxide raw material.

Furthermore, it is preferable that the manufacturing method of the antimony dope tin oxide used for this invention includes the closed cooling process which cools an antimony dope tin oxide raw material by a closed system between a closed baking process and an aeration baking process.

The antimony-doped tin oxide raw material satisfying the above (i) to (iii) can be obtained by the mixing step, the closed firing step, and the closed cooling step, respectively.

Each process of the manufacturing method of the antimony dope tin oxide which concerns on one Embodiment of this invention is demonstrated below with reference to FIG.

[Raw material mixing step: Step S100]
In this step, a tin compound and an antimony compound as raw materials for antimony-doped tin oxide are mixed. Specifically, powdered metastannic acid (H ₂ SnO ₃ ) and powdered antimony trioxide (Sb ₂ O ₃ ) are mixed. The proportions of blending were “metastannic acid (H ₂ SnO ₃ ) = 90 wt%, antimony trioxide (Sb ₂ O ₃ ) = 10 wt%”, and pulverized and mixed with a ball mill using water as a medium. The content of antimony trioxide is preferably 10% by weight, but may be about 5 to 20% by weight.

[First drying step: 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.

[First grinding step: Step S104]
In this step, 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.

[Closed firing process: Step S106]
In this step, 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.

[Closed cooling process: Step S107]
In this step, 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.

[First fine grinding step: Step S108]
If desired, this step may be performed to pulverize the material cooled in the previous closed cooling step (step S107). Specifically, 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. 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.).

[Second drying step: Step S110]
If desired, this step may be performed, and 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. 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.).

[Second grinding step: Step S112]
If desired, 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.).

[Ventilation firing process: Step S114]
In this step, 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). In this step, 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. In this step, 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. By this aeration firing process, the antimony-doped tin oxide raw material produced by the closed firing process is fired again under ventilation. Further, in the aeration firing process, since the firing is performed under ventilation, excess antimony oxide in tin oxide (SnO ₂ ) can be vaporized and eliminated. The final content of antimony oxide (solid solution ratio) is about 0.5 to 10.0% by weight.

[Ventilation cooling step: Step S116]
In this step, the antimony-doped tin oxide fired in the previous aeration firing step (step S114) is cooled under ventilation.

Specifically, 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.

In addition, when performing the vaporization refinement | purification method in embodiment, an aeration cooling process (step S116) can be performed after an aeration baking process (step S114).

[Second fine grinding step: Step S118]
In this process, 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.

[Washing process: Step S120]
In this step, 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.

[Third drying step: Step S122]
In this step, 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 | cleaning material by the previous washing | cleaning process (step S120), the material after washing | cleaning can be dried.

[Finish grinding process: Step S124]
In this step, 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 μm.

And antimony dope tin oxide used for this invention is manufactured by passing through each said process.

[Vehicle]
The vehicle is a medium in which antimony-doped tin oxide and / or colorant is dispersed and adhered to the substrate. The ink may contain known vehicle components used in printing. Since the ink can be formed as oil-based ink, UV ink, oil-based / UV combined ink, or solvent-containing ink, vehicles suitable for each ink will be described below.

(Vehicle suitable for oil-based ink)
As a vehicle suitable for the oil-based ink, for example, a resin, an oxidation polymerization catalyst, a solvent, or the like can be used alone or in combination. The resin, the oxidation polymerization catalyst, and the solvent will be described below.

〔resin〕
Resins contained in oil-based inks include linseed oil, tung oil and other drying oils, soybean oil, rapeseed oil and other semi-drying oils, alkyd resins produced by modification from semi-drying oils, and other modified alkyd resins, especially Use phenol-modified alkyd resin, epoxy-modified alkyd resin, urethane-modified alkyd resin, silicone-modified alkyd resin, acrylic-modified alkyd resin, vinyl-modified alkyd resin, neutralized acid alkyd resin, etc. Can do.

[Oxidation polymerization catalyst]
As the oxidation polymerization catalyst, a metal compound such as cobalt, vanadium, manganese, zirconium, lead, iron, cerium, or a salt of a long chain fatty acid may be used alone or in combination of two or more. Examples of the oxidation polymerization catalyst include cobalt borate, cobalt octylate, manganese octylate, zircon octylate, cobalt naphthenate, lead monoxide and the like.

〔solvent〕
A known solvent used for the ink may be selected in consideration of the boiling point of the solvent, the compatibility between the solvent and the resin, the drying property of the ink, the permeability to the printing material, and the like. Examples of the solvent include mineral oil; aromatic oil such as toluene and xylene; ester such as ethyl acetate; ketone such as methyl ethyl ketone; alcohol such as isopropyl alcohol; glycol such as ethylene glycol, diethylene glycol and triethylene glycol; cellulose solvent; and high boiling mineral oil such as n-dodecane mineral oil.

(Vehicle suitable for UV ink)
Examples of the vehicle suitable for the UV ink include photopolymerizable resins such as monomers, oligomers and binder polymers; photopolymerization initiators and the like. The photopolymerizable resin and the photopolymerization initiator will be described below.

[Monomer / Oligomer]
Photopolymerizable resins include epoxy acrylate, urethane acrylate, polyester acrylate, silicone acrylate, acrylated amine, acrylic saturated resin and acrylic acrylate, bisphenol A type epoxy acrylate acid anhydride addition acrylate, phenol novolac epoxy acrylate acid Carboxylic acid acrylates with hydroxyl anhydrides added to hydroxylated acrylates such as anhydride added acrylates, acid anhydride added acrylates of dipentaerythritol pentaacrylate, and carboxyls with acid anhydrides added to urethane acrylates with hydroxyl groups Group-containing acrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, polyglycerin epoxy Relate, water-soluble acrylates such as polyglycerol acrylate, monomers and oligomers such as acryloyl morpholine, may be used in combination either alone or two or more.

The oligomer is a resin that governs the basic physical properties of the UV ink, and the monomer mainly acts as a diluent and affects the curability and adhesiveness as well as the viscosity adjustment of the ink.

(Photopolymerization initiator)
The photopolymerization initiator is a compound that generates radicals such as active oxygen when irradiated with ultraviolet rays. The UV ink may contain a known photopolymerization initiator used for printing.

Examples of the photopolymerization initiator include, but are not limited to, acetophenone, α-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, benzoin ethyl ether, benzoin-n-propyl ether, beizoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin dimethyl ketal, benzoin per Benzoins such as oxides; acyl phosphine oxides such as 2,4,6-trimethoxybenzoin diphenylphosphine oxide; benzyl and methylphenyl-glyoxyesters; benzophenone, methyl-4-phenylbenzophenone, o-benzoylbenzoate, 2 -Chlorobenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyls Benzophenones such as luffide, acrylic-benzophenone, 3,3'4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 3,3'-dimethyl-4-methoxybenzophenone; 2-methylthioxanthone, 2-isopropylthioxanthone Thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone; aminobenzophenones such as Michler ketone, 4,4′-diethylaminobenzophenone; tetramethylthiuram mono Sulfide; Azobisisobutyronitrile; Di-tert-butyl peroxide; 10-butyl-2-chloroacridone; 2-ethylanthraquinone; 9,10-phenanthrenequinone; Such as quinone, and the like.

Further, a photopolymerization initiation assistant such as ethyl 4-dimethylaminobenzoate or isoamyl 4-dimethylaminobenzoate may be used in combination with the photopolymerization initiator.

(Vehicle suitable for oil-based and UV combined ink)
In the embodiment of the present invention, an oil-based ink and a UV ink may be used in combination to form an oil-based / UV combined ink. In that case, antimony-doped tin oxide is added to a vehicle for oil-based inks other than the solvent, and optionally a solvent comprising a vegetable oil component, a radically polymerizable monomer and / or oligomer, or a pigment dispersant is added to the bead mill or three-roll mill. An ink mill base is obtained by dispersing the kneaded meat with a dispersing machine such as the above. Furthermore, a photopolymerization initiator is added to the mill base for the ink, and if desired, other materials can be added to obtain an oil-based / UV combined ink.

The oil-based ink vehicle is obtained by dissolving the components described above as a vehicle suitable for oil-based inks, and the UV ink vehicle is prepared by dissolving the components described above as vehicles suitable for UV ink. Is. Further, a colorant may be added to the oil-based / UV combined ink.

(Vehicle suitable for solvent-containing ink)
Suitable vehicles for solvent-containing inks include at least a solvent. For example, a suitable vehicle for water-based ink includes water. The vehicle suitable for the water-based ink may contain an organic solvent, a resin, or the like alone or in combination. On the other hand, vehicles suitable for organic solvent-containing inks contain organic solvents and are substantially free of water. Further, the vehicle suitable for the organic solvent-containing ink may contain a resin.

As the resin contained in the solvent-containing ink, a resin described as a vehicle suitable for the oil-based ink or the UV ink may be used. The resin contained in the water-based ink is preferably in the form of a water-soluble resin, a colloidal dispersion resin, or an emulsion resin.

As the organic solvent contained in the solvent-containing ink, a solvent described as a vehicle suitable for the oil-based ink may be used.

[Adjuvant]
In an embodiment of the present invention, the ink may contain known adjuvants used in printing. Examples of auxiliary agents include extender pigments, waxes, antifoaming agents, dispersants, plasticizers, crosslinking agents, leveling agents, conductivity imparting agents, penetrating agents, pH adjusting agents, preservatives or fungicides, and oxygen scavengers. And other additives. These adjuvants will be described below.

Extender pigments are frequently used when the viscosity of the ink is high and it is difficult to wipe the ink from the intaglio plate. As the extender pigment, for example, barium sulfate, calcium carbonate, calcium sulfate, kaolin, talc, silica, corn starch, titanium dioxide, or a mixture thereof can be used.

The wax is an additive for imparting properties such as friction resistance, anti-blocking property, slipperiness and anti-scratch properties to the ink, and examples thereof include polyethylene wax and fluorinated wax.

The defoaming agent is an auxiliary agent used to suppress the generation of bubbles in the ink or reduce the bubbles generated in the ink. As the antifoaming agent, for example, silicone compounds, polysiloxanes, polyglycols, polyalkoxy compounds and the like can be used alone or in combination. Specifically, examples of the antifoaming agent include BYK (registered trademark) -019, BYK (registered trademark) -022, BYK (registered trademark) -024, and BYK (registered trademark) -065 manufactured by Byk-Chemie. , And BYK (registered trademark) -088.

The dispersant is an auxiliary agent for improving the leveling property, stability and dispersibility of the ink. Specifically, the dispersant improves the wetting of the antimony-doped tin oxide or colorant by the vehicle component, or adsorbs the antimony-doped tin oxide or colorant to the vehicle component and / or is dispersed in the ink. It can be used to prevent reagglomeration of the antimony doped tin oxide or colorant.

Examples of the dispersant include a low molecular dispersant, a polymer dispersant, a pigment derivative, and a coupling agent.

Examples of the low molecular weight dispersant include soap, α-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.

As the polymer dispersant, a polymer having a portion corresponding to an anchor group and a barrier group may be arbitrarily used. For example, it is preferable to use 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. 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. For example, dialkylaminomethylene copper phthalocyanine, amine salt copper phthalocyanine, and the like are used to form flexographic printing inks that contain phthalocyanine as a colorant.

The coupling agent is a material that adsorbs to the surface of the antimony-doped tin oxide or the colorant or chemically bonds to improve the adhesion between the antimony-doped tin oxide or the colorant and the vehicle. Examples of the coupling agent include a silane coupling agent and a titanate coupling agent.

The plasticizer is an auxiliary agent for adjusting the film formability of the ink or the flexibility of the ink coating film. Examples of plasticizers include aliphatic hydrocarbon oils such as naphthene oil and paraffin oil; liquid polydienes such as liquid polybutadiene and liquid polyisoprene; polystyrene; poly-α-methylstyrene; α-methylstyrene-vinylstyrene copolymer Hydrogenated rosin pentaerythritol ester; polyterpene resin; ester resin and the like.

The crosslinking agent is an auxiliary agent necessary for chemically bonding a plurality of substances, and is also called a gelling agent or a curing agent. Examples of the crosslinking agent include isocyanate compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, tetramethylxylylene diisocyanate, polymethylene polyphenyl polyisocyanate; trimethylolpropane-tris-β-N-aziridini Aziridine compounds such as lupropionate and pentaerythritol propane-tris-β-N-aziridinylpropionate; epoxy compounds such as glycerol polyglycidyl ether and trimethylolpropane polyglycidyl ether; aluminum triisopropoxide, mono- sec-Butoxyaluminum diisopropoxide, Aluminum tri-sec-butoxide, Ethyl acetoacetate Aluminum alcoholates such as aluminum diisopropoxide and aluminum trisethyl acetoacetate; aluminum chelate compounds; metal soaps such as aluminum stearate and aluminum octoate; oligomers or chelate compounds of metal soaps; bentonite and the like.

A leveling agent is an additive that, when added to an ink, lowers the surface tension of the ink and improves the surface smoothness of the coating film. Examples of the leveling agent include silicone polymers, polyacrylate polymers, and polyvinyl ether polymers.

Specifically, as the leveling agent, for example, “BYK-310”, “BYK-323”, “BYK-320”, “BYK-377”, “BYK-UV3510”, “BYK-Silclean 3700”, “BYK” -UV3500 "and" BYK-UV3570 "" (both manufactured by Big Chemie Japan).

The conductivity imparting agent is an additive that imparts conductivity to the ink. The conductivity imparting agent is preferably used in continuous ink jet printing.

Examples of the conductivity imparting agent include alkali metal salts such as lithium, sodium and potassium; alkaline earth metal salts such as magnesium and calcium; and simple ammonium salts or quaternary ammonium salts. These salts are halogenated compounds (eg chloride, bromide, iodide, fluoride, etc.), perchlorate, nitrate, thiocyanate, formate, acetate, sulfate, sulfonate, propionate , Trifluoroacetate, triflate (trifluoro-methanesulfonate), hexafluorophosphate (eg potassium hexafluorophosphate), hexafluoro-antimonate, tetrafluoroborate, picrate and It may be a carboxylate or the like.

The penetrating agent is an additive for penetrating and fixing the ink to the printing medium. Examples of the penetrant include potassium hydroxide, ethanol, isopropanol and the like.

The pH adjuster is an additive for controlling the pH of the ink within a predetermined range. Examples of the pH adjuster include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as acetic acid and benzoic acid; hydroxides such as sodium hydroxide and potassium hydroxide; halides such as ammonium chloride; sodium sulfate and the like. Sulfate such as potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, etc .; phosphates such as sodium hydrogen phosphate and sodium dihydrogen phosphate; organic acid salts such as ammonium acetate and sodium benzoate; tributylamine, And organic amines such as triethanolamine.

Preservatives or fungicides are additives for suppressing the generation or growth of microorganisms in the ink. Examples of the antiseptic or fungicide include sodium benzoate, potassium sorbitanate, thiabendazole, benzimidazole, siabendazole, thiazosulfamide, pyridinethiol oxide, and the like. Further, it is preferable to contain a preservative or a fungicide in the water-based ink.

The oxygen scavenger is an additive used to remove dissolved oxygen in the ink. Examples of the oxygen scavenger include organic oxygen scavengers such as ascorbic acid, catechol, erythorbic acid, pyrogallol, hydroquinone, reducing sugars, and tannic acid; and organic acid salts such as sodium ascorbate.

In the ink used in the present invention, a polymerization inhibitor such as phenothiazine and t-butylhydroxytoluene; a sensitizer; a thermal stabilizer; an ultraviolet absorber; a light stabilizer; a light absorber; Anti-skinning agent; Antistatic agent; Conductive agent; Flame retardant; Transferability improver; Liquid repellent; Dry retarder; Antioxidant; Anti-set-off agent; or Nonionic surfactant An activator or the like may be included.

The adjuvants listed above can be used alone or in combination of two or more.

[Colorant]
The colorant is a component that adds color to the ink. The ink used in the present invention may contain a known colorant used for printing. Examples of the colorant include inorganic pigments, organic pigments, dyes, organic pigments for toners, and the like.

Examples of 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.

Examples of organic pigments include soluble azo pigments such as β-naphthol pigments, β-oxynaphthoic acid pigments, β-oxynaphthoic acid anilide pigments, acetoacetate anilide pigments, and pyrazolone pigments; β-naphthol pigments Insoluble azo pigments such as pigments, β-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, flavantron, thioindigo, anthraquinone , Perinone, perylene, etc.), isoindolinone pigments, metal complex pigments, polycyclic or heterocyclic pigments such as quinophthalone pigments.

Examples of the dye include azo dyes, complex salts of azo dyes and chromium, anthraquinone dyes, indigo dyes, phthalocyanine dyes, xanthene dyes, thiazine dyes, and the like.

Here, the organic pigment includes a lake pigment. In general, 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. Examples of 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. As the organic pigment for toner, a dye or an organic pigment may be used, but a dye is preferred from the viewpoint of transparency and coloring power.

Also, the colorant can be used to adjust the color tone of the printing layer (A) and the printing layer (B). In that case, it is preferable to use a color matching dye as the colorant. Examples of color matching dyes include "Microlith (registered trademark) red" manufactured by Sakuramiya Chemical Co., Ltd., "Microlith (registered trademark) blue" manufactured by Sakuramiya Chemical Co., Ltd., and "Microlith (registered trademark) yellow" manufactured by Sakuramiya Chemical Co., Ltd. Etc.

Furthermore, in addition to the colorant described above, other functional materials such as functional pigments and functional dyes may be blended in the ink used in the present invention. Here, the functional material may be inorganic or organic, and may be an additive that imparts functionality to the ink.

Examples of functional materials include chromic materials, magnetic pigments, ultraviolet absorbers, optically variable materials, pearl pigments, and the like. In general, 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. Examples of 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.

<Combination ratio of contents in ink>
When the ink contains antimony-doped tin oxide, the blending ratio of each component contained in the ink is preferably about 0 to 20% by weight of the colorant when the viscosity of the ink is adjusted to about 50 to 1000 poise. The vehicle is preferably about 10 to 90% by weight, the adjuvant is preferably 0 to about 10% by weight, and the antimony-doped tin oxide is preferably about 1 to 50% by weight. .

On the other hand, when the ink does not contain antimony-doped tin oxide, the blending ratio of each component contained in the ink is about 1 to 50% by weight of the colorant when the viscosity of the ink is adjusted to about 50 to 1000 poise. Preferably, the vehicle is about 10-90% by weight and the adjuvant is preferably 0-about 10% by weight.

The viscosity of the ink can be arbitrarily adjusted as long as it is within the viscosity range suitable for the printing method used.

<Ink production method>
Infrared absorbing inks are obtained by dispersing antimony-doped tin oxide and / or colorants in a vehicle, optionally with auxiliary colorants. For example, using a mixer such as a single-screw mixer or a twin-screw mixer; a two-roller mill, a three-roller mill, a bead mill, a ball mill, a sand grinder, an attritor, or the like, an antimony-doped tin oxide and The colorant can be dispersed in the vehicle.

<Particle size of antimony-doped tin oxide in ink>
When the ink contains antimony-doped tin oxide, the average particle diameter of the antimony-doped tin oxide in the ink is 200 μm or less, 150 μm or less, 100 μm or less, 80 μm or less, 60 μm or less, 40 μm or less, 20 μm or less, 15 μm or less, 10 μm or less, It may be 5 μm or less, 2.5 μm or less, 1 μm or less, 0.5 μm or less, 0.1 μm or less, 0.05 μm or less, or 0.025 μm or less, and the average particle diameter is 0.001 μm or more, 0 It may be 0.01 μm or more, or 0.015 μm or more. The average particle diameter refers to the median diameter of the laser diffraction / scattering method.

Means for adjusting the average particle size of the antimony-doped tin oxide in the ink to a range of 0.001 μm to 200 μm is not limited, but means for pulverizing the antimony-doped tin oxide during the production of the antimony-doped tin oxide; It is considered to be a combination with means for dispersing antimony-doped tin oxide in the vehicle during the production of the ink. For example, the antimony-doped tin oxide is sufficiently pulverized by the step S118 or S124. Further, as described above, the antimony-doped tin oxide is sufficiently dispersed in the vehicle by a mixer or a meat grinder.

<Printing method>
In the printed matter of the present invention, a printing layer (A) and a printing layer (B) are formed by printing ink on a substrate by a known printing method, and the printing layer (A) is disposed on the printing layer (B). It is obtained by arranging outside the range.

Also, the printing layer (A) and the printing layer (B) can be formed on the substrate by the same or different printing methods. Furthermore, the printing layer (A) can be formed by printing before, during, or after the formation of the printing layer (B).

In the embodiment of the present invention, the printing method may be plate printing or non-plate printing.

As the plate printing, for example, relief printing such as flexographic printing and letterpress printing; lithographic printing such as offset printing; gravure printing; intaglio printing such as direct printing plate printing and etching printing; stencil printing such as screen printing; Is mentioned.

Here, flexographic printing is a printing method in which ink is adhered to a roll having a concave portion, the ink in the concave portion is transferred to the convex portion of the relief cylinder, and then the ink on the convex portion is transferred to the printing medium.

Typographical printing is a printing method that prints using letterpress. The letterpress is a plate obtained by forming or assembling line drawing parts such as type letters, ruled lines, patterns, and photographs as convex parts.

Offset printing is a printing method in which the ink attached to the plate is transferred to a transfer body, and then the ink attached to the transfer body is transferred to a substrate. Further, a rubber blanket is generally used as the transfer body.

Gravure printing is a printing method in which cells with recesses are formed in a plate cylinder, ink is put into the cells, and excess ink on the surface of the plate cylinder is scraped off with a doctor blade while the ink in the cells is transferred to the substrate. It is.

Intaglio printing (intaglio printing) forms depressions on the plate surface by line printing or etching, deposits ink on the entire plate, wipes ink adhering to the plate surface other than the depressions, and In this printing method, the printing medium is pressed against the printing medium, and the ink in the recesses is transferred to the printing medium. The plate may be not only a flat plate but also a body plate.

In intaglio printing, the recesses formed on the printing plate correspond to the line drawing part, and the line drawing part is composed of a line drawing recessed from the surroundings. Further, a portion other than the concave portion on the printing plate is called a non-line drawing portion. Therefore, the cells used for gravure printing are not formed on the intaglio plate surface.

Screen printing is a printing method in which ink is put on a screen plate and ink is pushed out from the screen plate by sliding of a squeezee. The screen plate is formed by applying a screen to the frame and providing an image area and a non-image area on the image by a resist method. Generally, the non-image area is closed with a resin or the like by a resist method.

Examples of plateless printing include inkjet printing; other plateless printing such as electrophotography, thermal printing, and thermal transfer printing.

Inkjet printing is a printing method in which ink is ejected as ink droplets from a nozzle and deposited on a substrate. Inkjet printing does not use a plate, does not apply pressure to the substrate, and the nozzle and the substrate do not contact each other, so printing is faster without damaging the substrate compared to printing methods that use plates. It can be performed.

Generally, in an ink jet printer, the method of ejecting ink from a nozzle is roughly divided into a continuous method and an on-demand method.

The continuous method is a method for electrically controlling the flight trajectory of the ink liquid by continuously discharging the ink liquid. On the other hand, the on-demand method is a method for ejecting a necessary amount of ink during printing. In general, the on-demand method is roughly classified into a piezo method, a thermal method, and an electrostatic induction method, depending on a method in which ink is pressurized and ejected.

The printed matter of the present invention can be obtained by using a single or a combination of the printing methods described above.

<Judgment method>
In the printed matter of the present invention, since the printing layer (A) and / or the printing layer (B) contains the antimony-doped tin oxide, the printing layer (A) and / or the printing layer (B) is an infrared absorption printing layer. . Therefore, when one of the printing layer (A) and the printing layer (B) is an infrared absorbing printing layer and the other is an infrared non-absorbing printing layer, the printed matter is observed with an infrared detector, and the infrared absorbing printing layer A pattern is seen.

For example, as shown in FIG. 13A, the printed matter (1) in which the infrared non-absorbing printing layer (3) and the infrared absorbing printing layer (4) are arranged side by side on the substrate (2) is visually observed. Or when it observes with a visible light detector, the pattern of an infrared non-absorption printing layer (3) and an infrared absorption printing layer (4) is seen. On the other hand, as shown in FIG. 13B, when the printed matter (1) is observed with an infrared light detector such as an infrared camera, a pattern of the infrared absorbing printed layer (3) is seen.

Moreover, when the printing layer (A) and the printing layer (B) contain antimony-doped tin oxide, both layers become infrared absorption printing layers, but the antimony-doped oxidation in the printing layer (A) and the printing layer (B). The tin content is different. In that case, when the printed matter of the present invention is observed with an infrared detector, the density of the detection pattern varies depending on the range in which the print layer (A) or the print layer (B) is disposed.

As described above, the authenticity of the printed matter can be determined using the presence or absence of the infrared absorption pattern or the density gradient of the infrared absorption pattern.

Further, another determination method may be combined with the determination method based on the presence or absence of the infrared absorption pattern or the density of the infrared absorption pattern. Other determination methods include, for example, other functional materials such as chromic materials, magnetic pigments, ultraviolet absorbers, optical variable materials, and pearl pigments described above in the infrared non-absorbing print layer and / or infrared absorbing print layer. The method of making it contain and utilizing the functionality of a functional material is mentioned.

<Preparation of antimony-doped tin oxide>
The materials used are as follows:
Metastannic acid: Metastannic acid manufactured by Nippon Chemical Industry Co., Ltd. Antimony trioxide: PATOX-CF (registered trademark; manufactured by Nippon Seiko Co., Ltd.)
Antimony-doped tin oxide raw material (commercially available): ELCOM (registered trademark) P-specialized product manufactured by JGC Catalysts & Chemicals Co., Ltd. (antimony oxide content: 9.9% by weight, no air firing, no air cooling)

The used firing furnace is a shuttle-type firing furnace with a cooling device (manufactured by Tsuji Electric Furnace).

[Example 1]
Steps 100-124 were performed as described in FIG. 1 using 118.8 g of metastannic acid and 1 g of antimony trioxide.

Specifically, as described in Table 1 below, a method including a mixing step (S100), a closed firing step (S106), a closed cooling step (S107), an aeration firing step (S114), and an aeration cooling step (S116). Thus, antimony-doped tin oxide having an antimony oxide content of 0.7% by weight was obtained.

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]
Examples 2 to 7 and Comparative Examples 1 and 2 were performed as described in Table 1 below. For Examples 2 to 4, 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.

On the other hand, in Comparative Example 2, the mixing step (S100), the closed firing step (S106), and the closed cooling step (S107) were performed in the same manner as in Example 1, but the aeration firing step (S114) and the aeration cooling step (S116). ), A product having the same antimony oxide content as in Example 2 was obtained.

In Comparative Example 1, a commercially available antimony-doped tin oxide raw material was prepared. On the other hand, in 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.

In 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).

[Method for measuring content of antimony oxide in product]
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.

[X-ray diffraction measurement of product]
And X-ray diffraction was performed about each product of the Example and the comparative example, and the value of crystallinity was computed from the measurement result.

As shown in Table 1, FIGS. 2 to 5 are diagrams showing the results of X-ray diffraction by the antimony-doped tin oxide of the example, and FIG. 6 is a diagram showing the results of X-ray diffraction of the comparative example. In each figure, the vertical axis indicates “intensity (CPS)” of reflected light when X-rays are irradiated, and the horizontal axis indicates “2θ (deg)”.

[CPS]
Here, “CPS (Count Per Second)” indicates the amount of reflected photons per second when the measurement object is irradiated with X-rays, and can also be regarded as the intensity (level) of reflected light. .

[2θ]
Further, “2θ” indicates an irradiation angle when the measurement object is irradiated with X-rays. The reason for “2θ” is that if the angle (incident angle) for irradiating X-rays is θ, the reflection angle is also θ, and the sum of the incident angle and the reflection angle is 2θ. It is.

[Calculation method of crystallinity]
The degree of crystallinity is calculated based on the measurement result of X-ray diffraction (XRD). The equipment used and the measurement conditions are as follows.
(1) Equipment used: Rigaku Corporation MultiFlex (X-ray diffractometer)
(2) Measurement conditions:
Scan speed: 4.0 ° / min.
Radiation source: 40 kV, 30 mA
Integration count: 1 time

For example, the graph of FIG. 2 (B) is a graph showing the result of X-ray diffraction by antimony-doped tin oxide of Example 2. In the antimony-doped tin oxide of Example 2, points where the intensity of reflected light greatly increases (points where the waveform rises) are generated at a plurality of locations.

Specifically, a point near “2θ = 27 °”, a point near “2θ = 34 °”, a point near “2θ = 38 °”, a point near “2θ = 52 °”, “2θ = 55 ° ”And a point near“ 2θ = 58 ° ”.
Then, the crystallinity is calculated using the measured values of 2θ (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. The point where the intensity of reflected light is the highest in antimony-doped tin oxide is a point near “2θ = 27 °”.

FIG. 7 is a conceptual diagram schematically showing a method for calculating the crystallinity.
The crystallinity indicates the ratio of the crystallized portion with respect to the entire material when the material is crystallized, and is defined here as crystallinity = CPS / Δ2θ (half-value width). That is, the crystallinity is defined by a numerical value at a point near 2θ = 27 °. Thereby, the crystallinity can be calculated from the measurement result of X-ray diffraction (XRD). In the illustrated graph, the peak of the waveform is larger and the tip of the waveform becomes sharper as the crystal structure is regular and there are no impurities.

[CPS]
Since CPS is the intensity (level) of reflected light, it has a waveform height in the illustrated example.

[Δ2θ]
Further, Δ2θ 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).

For this reason, the larger the CPS value (the higher the peak of the waveform), the larger the crystallinity value. Further, the smaller the value of Δ2θ (the narrower the half width), the larger the crystallinity value.

Here, when X-rays are applied to the material to be inspected, there are an angle at which the reflected light is generated and an angle at which the reflected light is not generated depending on the angle at which the X-ray is applied. The angle at which the reflected light is generated is constant depending on the material. If the material is the same, the rising or falling tendency of the waveform is almost the same. In the present embodiment, since antimony-doped tin oxide, which is the same material, is used in each example and each comparative example, the position of 2θ at which the CPS value is maximum is unified as “2θ = 27 °”. .

For Examples 1 to 7 and Comparative Examples 1 and 2, the full width at half maximum (Δ2θ) near 2θ = 27 °, the intensity (CPS) near 2θ = 27 °, the crystallinity (CPS / Δ2θ), and the X-ray diffraction graph The drawing numbers are shown in Table 1 below.

2A is a graph showing the result of X-ray diffraction by the antimony-doped tin oxide of Example 1. FIG. The antimony-doped tin oxide of Example 1 has the highest reflected light intensity at a point near “2θ = 27 °”, and the maximum value of CPS is about 12,000. Also regarding Δ2θ, the width of the bottom part of the waveform where the CPS value reaches a peak is almost the same as that in Examples 2 to 4 described above. Therefore, Example 1 is considered to have sufficient crystallinity as antimony-doped tin oxide. However, since the content of antimony oxide is 0.7% by weight and the amount of antimony oxide dissolved in the crystal lattice of tin oxide is small, the infrared absorption effect is considered to be lower than those of Examples 2 to 4. It is done.

3 (A) and 3 (B) are graphs showing the results of X-ray diffraction using antimony-doped tin oxide of Examples 3 and 4, respectively. Even in the antimony-doped tin oxides of Examples 3 and 4, the point where the intensity of the reflected light is the highest is a point near “2θ = 27 °”.

4A and 4B are graphs showing the results of X-ray diffraction by antimony-doped tin oxide of Examples 5 and 6, respectively, and the graph of FIG. 5 is the antimony of Example 7. It is a graph which shows the result of the X-ray diffraction by dope tin oxide. Even in the antimony-doped tin oxides of Examples 5 to 7, the point where the intensity of the reflected light is the highest is a point in the vicinity of “2θ = 27 °”.

In each of the antimony-doped tin oxides of Examples 2 to 4, 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. In the commercially available product of Comparative Example 1, the intensity of reflected light is highest at a point in the vicinity of “2θ = 27 °”, but the CPS value is extremely small compared to those of Examples 1 to 7 above ( About 2000). As for Δ2θ, 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. In the product of Comparative Example 2, the intensity of reflected light is highest at a point in the vicinity of “2θ = 27 °”, but the CPS value is smaller than those in Examples 1 to 7 (CPS = 6860.0). As for Δ2θ, 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.

[Measurement of infrared absorption effect]
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.

(1) Equipment used: Spectrophotometer V570 manufactured by JASCO Corporation
(2) Sample preparation conditions: 95 parts of acrylic / silicone varnish (Aqueous Cefcote # 800 Clear manufactured by Urethane Giken Co., Ltd.) is added with 5 parts of the infrared absorbing pigments of Examples and Comparative Examples, and a planetary dispersion mill is used. Infrared absorbing ink is prepared by dispersing and coated on a 200 μm thick PET film with a film applicator and dried to form a printed part with a film thickness of 70 μm in a dry state. It was created.
(3) Measuring method: A standard white plate was attached to the back of the coated film, and the reflectance in the wavelength range of 200 to 2500 nm was measured. In addition, about 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 | require the solar reflectance of a coating film". Moreover, about the solid content weight ratio (pigment ratio) of the infrared rays absorption pigment contained in a printing part, it calculates as follows. 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. Since 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.

For Examples 1 to 7 and Comparative Examples 1 and 2, the relationship between the wavelength of 200 nm to 2500 nm and the reflectance is shown in FIGS. 8 to 11, and the average reflectance in the wavelength range of 380 nm to 780 nm and / or 780 to 1100 nm, Table 1 below shows the maximum reflectivity and the wavelength indicating the maximum reflectivity.

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.

In the near infrared region (wavelength region of 780 to 1100 nm) used for general authenticity determination, it is desirable that 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. When 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. In this connection, as shown in FIG. 8, 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.

From FIG. 9, even if it has an antimony oxide content of 2.7 to 2.8% by weight, 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.

Further, Examples 5 and 6 were performed under substantially the same conditions except for the cooling rate in the aeration cooling step (S116). However, as shown 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 (Δ2θ) is narrow and the degree of crystallinity is high. In this connection, even if a small amount of antimony oxide dissolved in the crystal lattice is removed together with excess antimony oxide not dissolved in the crystal lattice of tin oxide by aeration baking, By actively cooling after firing, it is expected that the crystal lattice will be maintained. Therefore, it is considered that 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.

From FIG. 10, even if it is a commercially available antimony-doped tin oxide pigment (Comparative Example 1) having an antimony oxide content of 9.9% by weight, a sufficient infrared absorption effect can be obtained through the aeration firing process. It can be seen that the antimony-doped tin oxide (Example 5) has an antimony oxide content of 2.7% by weight. That is, excess antimony oxide that is not dissolved in the crystal lattice (that is, impurities that do not contribute to the infrared absorption effect) can be removed by the aeration firing process.

From FIG. 11, even if the closed firing step and the closed cooling step are omitted, that is, only the mixing step, the aeration firing step and the aeration cooling step are performed, an antimony-doped tin oxide having a sufficient infrared absorption effect can be obtained. I understand.

Here, when comparing Examples 1 to 7 with respect to Table 1 below, 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. .

Therefore, by producing antimony-doped tin oxide using an aerated firing process, 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.

In addition, 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.

<Preparation of infrared absorbing ink>
The following materials were stirred with a mixer and dissolved uniformly, followed by filtration to obtain an infrared absorbing ink:
Infrared absorbing pigment: 3 g of the infrared absorbing pigment of Example 2;
Resin: Mixture of vinyl chloride-vinyl acetate copolymer and polyester resin (weight ratio 1: 1) 30 g;
Solvent: 15 g of a mixture of methyl ethyl ketone (MEK) and toluene (weight ratio 1: 1); and colorant for color matching: “Microlith (registered trademark) blue” (diluted 1/100) by Sakuramiya Chemical Co., Ltd. 4 g

<Production of infrared non-absorbing ink>
The following materials were stirred to dissolve uniformly and then filtered to obtain an infrared non-absorbing ink:
Dye: “Microlith (registered trademark) red” (1/100 diluted product) 0.39 g manufactured by Sakuramiya Chemical Co., Ltd. “Microlith (registered trademark) blue” (1/100 diluted product) 0.16 g manufactured by Sakuramiya Chemical Co., Ltd. A mixture with 0.76 g of “Microlith (registered trademark) yellow” (1/100 diluted product) manufactured by Sakuramiya Chemical Co., Ltd. 1.31 g;
Resin: Mixture of vinyl chloride-vinyl acetate copolymer and polyester resin (weight ratio 1: 1) 30 g;
Solvent: 15 g of a mixture of methyl ethyl ketone (MEK) and toluene (weight ratio 1: 1); and colorant for color matching: “Microlith (registered trademark) blue” (diluted 1/100) by Sakuramiya Chemical Co., Ltd. 4 g

[Infrared absorption effect of printed matter]
The infrared absorbing ink and the infrared non-absorbing ink so that the infrared absorbing printing layer formed of the infrared absorbing ink and the infrared non-absorbing printing layer formed of the infrared non-absorbing ink are arranged side by side. Was printed on fine paper (Nippon Paper Shiraoi fine paper) with a gravure printing machine (K Printing Proofer, Matsuo Sangyo Co., Ltd.) and dried to obtain a printed matter.

When the printed matter was observed using an infrared camera (Dino-Lite Pro manufactured by ANMO), the printed surface of the infrared absorbing printing layer appeared black because it absorbed infrared light, whereas infrared non-absorbing printing. The printed surface of the layer appeared white because it transmitted or reflected infrared radiation.

[Relationship between color tone of infrared absorbing printing layer and infrared absorptivity]
The following substrates and inks were prepared:
Base material: General paper (OK Prince fine quality 90 kg)
Process ink (3 colors):
Indigo (C): Super Tech GT Series Indigo (T & K TOKA Co., Ltd.)
Crimson (M): Super Tech GT Series Crimson (T & K TOKA Co., Ltd.)
Yellow (Y): Super Tech GT Series Yellow (manufactured by T & K TOKA Corporation)

According to the following print sample preparation conditions, the above three color process inks were respectively printed on the substrate to obtain three types of print samples:
(Print sample preparation conditions)
Printing machine: Offset printing machine RI tester Ink volume: 0.125cc
Ink film thickness: about 1 μm

The light reflectance of three types of printed samples was measured according to the following measurement conditions:
(Measurement condition)
Measuring device: UV-visible spectrophotometer U-4000 (manufactured by Hitachi, Ltd.)
Measurement item: Reflectance (%)
Measurement wavelength: 350-2500 nm

FIG. 12 shows the reflectance in the wavelength range of 350 to 1500 nm for the indigo (C), red (M), and yellow (Y) process inks.

FIG. 12 is a graph showing the reflectance of a printed matter obtained by offset printing of CMY process inks. In addition, as long as the colorant concentration, film thickness, and measurement conditions are uniform, the reflectance of the printed matter obtained by gravure printing, flexographic printing, screen printing, or inkjet printing is the same as the reflectance of the printed matter obtained by offset printing. it is conceivable that. Therefore, by combining the reflectance graph of the CMY process ink shown in FIG. 12 and the reflectance graphs of Examples 1 to 7 shown in FIGS. 8 to 11, various infrared absorbing printing layers are formed in the printed matter of the present invention. The relationship between color tone and infrared absorptivity when formed by a printing method can be expected.

For example, in FIG. 12, the red and yellow process inks do not absorb light in the infrared wavelength region (780 to 1100 nm). On the other hand, in the reflectance graphs of Examples 1 to 7 shown in FIGS. 8 to 11, since the average reflectance in the infrared wavelength region is lower than the average reflectance in the visible light wavelength region (380 nm to 780 nm), it is higher than that of visible light. Infrared light is also considered to be absorbed. Therefore, if the antimony-doped tin oxide used in the present invention is contained in red or yellow ink, or if the infrared absorbing ink used in the present invention is used as red or yellow ink, the color tone of red or yellow is affected. It can be seen that the ink can be provided with infrared absorptivity.

Further, from FIG. 12, it can be considered that the indigo process ink slightly absorbs light in the infrared wavelength region (780 to 1100 nm). However, in FIGS. 8 to 11, compared with the ratio of the infrared absorbing inks of Examples 1 to 7 to absorb infrared light, 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 antimony-doped tin oxide used in the present invention is contained in the indigo ink, or the infrared absorbing ink used in the present invention is used as the indigo ink, without affecting the color tone of the indigo color, It can be seen that infrared absorptivity can be imparted to the ink.

Furthermore, 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. In this connection, the infrared-absorbing ink containing antimony-doped tin oxide obtained in Examples 1 to 7 and containing no colorant has high brightness and a light white color. The effect on the color tone of yellow ink is considered to be small. Therefore, the infrared absorbing ink containing antimony-doped tin oxide obtained in Examples 1 to 7 and containing no colorant can be grasped as a special color ink or functional ink suitable for various printing methods. In that case, the reflectance graphs of Examples 1 to 7 shown in FIGS. 8 to 11 can be regarded as graphs representing the light reflection characteristics of the special color ink used in the present invention.

The present invention can be implemented with various modifications or replacements without being limited to the above-described embodiments and examples. In addition, it should be understood that any of the configurations and materials described in the above-described embodiments and examples are preferable examples and can be implemented by appropriately modifying them.

DESCRIPTION OF SYMBOLS 1 Printed material 2 Base material 3 Infrared absorption printing layer 4 Infrared non-absorption printing layer

Claims

A printed matter in which the printed layer (A) and the printed layer (B) are arranged on a substrate,
The printed layer (A) is disposed outside the range in which the printed layer (B) is disposed,
The infrared absorption rate of the printing layer (A) and the printing layer (B) is different,
The printing layer (A) and / or the printing layer (B) contains antimony-doped tin oxide, and the antimony-doped tin oxide contains tin oxide and antimony oxide, and the following (a) and / or (b Meet):
(A) The half width (Δ2θ) of a peak around 2θ = 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 2θ = 27 ° obtained by X-ray diffraction measurement by the half-value width (Δ2θ), based on the weight of tin oxide, from 0.5 to 10.0% by weight. The degree of crystallinity is 58427 or more.
Printed matter.
The printed matter according to claim 1, which is used for preventing forgery.
The printed matter according to claim 1 or 2, wherein, in (a), the half width (Δ2θ) is 0.21 or less.
3. The printed matter according to claim 1, wherein 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.
The printed matter according to claim 1 or 2, wherein the crystallinity is 78020 or more.
The printed matter according to any one of claims 1 to 5, wherein the antimony-doped tin oxide has an average particle size of 200 µm or less.
The printed layer (A) and the printed layer (B) contain the antimony-doped tin oxide, and the content of the antimony-doped tin oxide in the printed layer (A) and the printed layer (B) is different. The printed material according to any one of claims 1 to 6.
The range in which the print layer (A) is disposed and the range in which the print layer (B) is disposed are adjacent to each other or spaced apart from each other. Prints.
The printed material according to any one of claims 1 to 8, wherein another layer is disposed under the printing layer (A) and / or the printing layer (B).
The printed material according to any one of claims 1 to 9, wherein the substrate has a flat surface, a curved surface, or irregularities.
The printed matter according to any one of claims 1 to 10, wherein the printing layer (A) and the printing layer (B) are formed on the substrate by partial printing.
The printing layer (A) is formed by at least one selected from the group consisting of offset printing, flexographic printing, letterpress printing, intaglio printing, gravure printing, screen printing, and inkjet printing. The printed matter according to any one of the above.
The printing layer (B) is formed by at least one selected from the group consisting of offset printing, flexographic printing, letterpress printing, intaglio printing, gravure printing, screen printing, and inkjet printing. The printed matter according to any one of the above.
The print layer (A) and / or the print layer (B) further includes at least one selected from the group consisting of a chromic material, a magnetic pigment, an ultraviolet absorber, an optical variable material, and a pearl pigment. 14. The printed material according to any one of 1 to 13.
A method for producing a printed material in which a printed layer (A) and a printed layer (B) are formed on a substrate by printing,
The printed layer (A) is disposed outside the range in which the printed layer (B) is disposed,
The infrared absorption rate of the printing layer (A) and the printing layer (B) is different,
The printing layer (A) and / or the printing layer (B) contains antimony-doped tin oxide, and the antimony-doped tin oxide contains tin oxide and antimony oxide, and the following (a) and / or (b Meet):
(A) The half width (Δ2θ) of a peak around 2θ = 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 2θ = 27 ° obtained by X-ray diffraction measurement by the half-value width (Δ2θ), based on the weight of tin oxide, from 0.5 to 10.0% by weight. The degree of crystallinity is 58427 or more.
Manufacturing method of printed matter.