JP2017114095A - Forgery-proof printed matter, light emission ink for printing the same, and authenticity determination method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a printed matter for which it is not easily discovered whether anti-forgery measures are taken or not, so that the printed matter is proof against forgery.SOLUTION: This invention relates to a printed matter (10) having a light emission printed layer (1) comprising a fluorescent material and a mechano-luminescent material on a base material (2).SELECTED DRAWING: Figure 1

Description

  The present invention relates to an anti-counterfeit printed matter, a luminescent ink for printing the same, and an authenticity determination method using the same. In particular, the present invention relates to an anti-counterfeit printed matter that emits fluorescence when irradiated with ultraviolet rays and emits light when stress is applied to the place, a luminescent ink for printing the same, and an authenticity determination method using the same. .

  Mechanoluminescence materials that emit light upon receiving mechanical stimuli such as stress are known. Mechanoluminescence materials are being studied for application in anti-counterfeiting-related fields as well as application to stress measurement systems and the like.

  For example, Patent Literature 1 discloses a stress light emitting structure for preventing forgery using a specific mechanoluminescence material. Further, Patent Document 2 discloses a sheet-like printed matter that emits light when a ticket is separated by forming a region including a mechanoluminescence material at the perforation of a separation portion of a ticket or the like.

  Patent Document 3 discloses a forgery-preventing printed matter comprising a printing part A containing a material that emits fluorescence when irradiated with light and a printing part B containing a material that emits light by stress. According to this printed matter, the authenticity is determined by the printing part A that emits fluorescence by light irradiation, and the authenticity can be determined also in the printing part B by applying stress. Examples of fluorescent materials include fluorescent pigments that emit fluorescent light when irradiated with ultraviolet rays.

JP 2007-55144 A JP 2010-188669 A JP 2012-131095 A

  In the printed matter described in Patent Document 3, since the printing unit including the fluorescent material and the printing unit including the mechanoluminescence material are provided separately, whether or not forgery prevention measures are taken because each can be easily recognized. Can be understood immediately. On the other hand, in recent years, fluorescent materials and mechanoluminescent materials have been used in various fields, and are thus relatively easy to obtain. That is, the printed matter described in Patent Document 3 is forged relatively easily when there is a person who wants to forge.

  In view of the above, an object of the present invention is to provide a printed matter that is difficult to understand whether or not counterfeiting measures have been taken, thereby making it difficult to counterfeit.

The present invention can include the following aspects:
<< Aspect 1 >>
An anti-counterfeit printed matter having a light-emitting printed layer containing a fluorescent material and a mechanoluminescent material on a substrate.
<< Aspect 2 >>
The printed matter according to aspect 1, wherein the color of light emitted from the printed layer when irradiated with light is different from the color of light emitted from the printed layer when subjected to mechanical stimulation.
<< Aspect 3 >>
The printed matter according to aspect 1 or 2, wherein the fluorescent material emits visible light when irradiated with ultraviolet rays.
<< Aspect 4 >>
When the printed layer is irradiated with light, it emits light in any one of red, yellow, green, cyan, blue, and magenta areas, and red when mechanically stimulated. The printed matter according to any one of aspects 1 to 3, wherein light of a region different from a region of light emitted when irradiated with the light among the regions of yellow, green, cyan, blue, and magenta is emitted.
<< Aspect 5 >>
The fluorescent material emits red light when irradiated with light, and emits green light when the mechanoluminescent material receives mechanical stimulation. The printed matter described.
<< Aspect 6 >>
The printed matter according to any one of aspects 1 to 5, wherein the ratio of the mass of the fluorescent material to the mass of the mechanoluminescent material contained in the light-emitting printed layer is 0.25 or more and 10 or less. .
<< Aspect 7 >>
The printed matter according to any one of aspects 1 to 6, which is a bill, a securities, a public document, a ticket, a cash voucher, a card, or a seal for authenticity determination.
<< Aspect 8 >>
A luminescent ink comprising a vehicle, a mechanoluminescent material, and a fluorescent material.
<< Aspect 9 >>
The luminescent ink according to aspect 8, wherein the ratio of the mass of the fluorescent material to the mass of the mechanoluminescent material is 0.25 or more and 10 or less.
<< Aspect 10 >>
A step of irradiating the printed material according to any one of aspects 1 to 7 with light to cause the fluorescent material to emit light; and / or a step of applying a mechanical stimulus to the printed material to cause the mechanoluminescent material to emit light. A method for determining the authenticity of a printed matter.

  According to the present invention, it is difficult to determine whether or not counterfeit measures are taken, and thereby it is possible to provide a printed matter that is difficult to counterfeit.

FIG. 1 shows how the printed light-emitting layer of the printed material according to one embodiment of the present invention appears when irradiated with ultraviolet rays and how it appears when a mechanical stimulus is applied. FIG. 2 shows how the light emitting printed layer of the printed material according to another embodiment of the present invention looks when irradiated with ultraviolet rays and how it looks when a mechanical stimulus is applied. FIG. 3 shows an XYZ color system diagram divided into six regions. FIG. 4 shows the coordinates of the fluorescence color when the light emitting printed layers of the printed materials of Examples 7 to 12 are irradiated with ultraviolet rays, plotted on an XYZ color system diagram.

《Printed matter》
The printed matter of the present invention has a light-emitting printed layer containing a fluorescent material and a mechanoluminescent material on a substrate. The fluorescent material emits light by irradiating the light emitting printed layer of the printed matter of the present invention with ultraviolet rays, and the mechanoluminescent material emits light by applying mechanical stimulation to the light emitting printed layer.

  In the authenticity determination using only the fluorescent material, the authenticity determination person determines the authenticity according to the presence or absence of the fluorescence by irradiating the print layer containing the fluorescent material with ultraviolet rays. However, since there is only one type of anti-counterfeiting means, there is a possibility that the presence of the anti-counterfeiting means can be easily discovered by those who intend to forge. Moreover, since the fluorescent material is relatively easy to obtain, forgery countermeasures using only the fluorescent material may be easily avoided.

  In authenticity determination using only the mechanoluminescent material, the authenticity determination person determines authenticity according to the presence or absence of light emission by giving a mechanical stimulus to the print layer containing the mechanoluminescent material. However, since there is only one type of anti-counterfeiting means, there is a possibility that the presence of the anti-counterfeiting means can be easily discovered by those who intend to forge. In addition, since mechanoluminescence materials are relatively easily available, counterfeiting measures using only mechanoluminescence materials may be easily avoided.

  On the other hand, in the printed matter of the present invention that includes the fluorescent material and the mechanoluminescent material in the same light emitting printed layer, when the ultraviolet light is irradiated, the observer can derive the light emission of the light emitting printed layer from the fluorescent material. It is not usually recognized that mechanoluminescent material is included in the printed layer. That is, by setting it as such an aspect, presence of a mechanoluminescent material can be substantially concealed.

  Therefore, the authenticity judge can observe the light emission of the fluorescent material by irradiating ultraviolet rays, and then determine the authenticity by observing the light emission of the mechanoluminescent material by applying a mechanical stimulus, For those who do not know that such counterfeit measures are taken, even if they can recognize that the fluorescent material is present in the luminescent printed layer, it is not possible to recognize that there is a mechanoluminescent material. Have difficulty.

  Even in authenticity determination using only a mechanoluminescent material, it is necessary to excite the mechanoluminescent material by irradiating the printed layer containing the mechanoluminescent material with ultraviolet rays or the like, so the printed matter of the present invention was used. In this case, the authenticity determination person can perform the authenticity determination with the same effort as the authenticity determination of the printed matter using only the mechanoluminescence material.

  The printed matter of the present invention is very useful for printed matter that should be subjected to counterfeit prevention measures such as banknotes, securities, official documents, tickets, cash vouchers, cards, or authenticity determination seals.

<Light emitting printing layer>
The light-emitting printed layer used in the printed material of the present invention is not formed by laminating a printing layer containing only a fluorescent material and a printing layer containing only a mechanoluminescent material on the same place, but in the same place. The luminescent material is included in the same layer. In the light emitting printed layer formed in this way, the fluorescent material and the mechanoluminescent material are dispersed in the light emitting printed layer, so that the light emitted from the fluorescent material and the mechanoluminescent material is relatively strong. If the layers are formed on the upper and lower sides, the light of the layer located below becomes weak.

  The light emitting printing layer used in the present invention is preferably different in color of light emitted when irradiated with ultraviolet rays and color of light emitted when subjected to mechanical stimulation. In general, the mechanoluminescence material also emits light when it is irradiated with ultraviolet rays, and the color of light emission when light is irradiated is the same as the color of light emission when a mechanical stimulus is applied. However, in the above-described aspect, it is possible to provide a novel light-emitting printing layer in which the color of light emitted when irradiated with ultraviolet light is different from the color of light emitted when mechanical stimulation is applied. It becomes.

  Preferably, the luminescent printed layer emits red light when subjected to ultraviolet irradiation and emits green light when subjected to mechanical stimulation. In addition, the fluorescent material used in that case emits red light when irradiated with ultraviolet rays, and the mechanoluminescent material emits green light when subjected to mechanical stimulation. In such a mode, it is easy to distinguish the difference in light emission between the fluorescent material and the mechanoluminescent material.

  As shown in FIG. 1, in one embodiment of the present invention, the printed matter (10) of the present invention has a printed layer (1) of a character string “genuine”. Includes fluorescent materials and mechanoluminescent materials. In this case, when the character string is irradiated with ultraviolet rays, all characters emit light in the same color, and when a mechanical stimulus is applied to the character string, all characters emit light in the same color.

  As shown in FIG. 2, in one embodiment of the present invention, the printed matter (10) has a light-emitting printed layer (1) having a character string “genuine” on a substrate (2). The printed layers of the letters “g”, “n”, “i” and “e” located in the odd-numbered rows of the column contain only the fluorescent material, and “e”, “u” and “n” located in the even-numbered rows The luminescent printed layer of the letter comprises a fluorescent material and a mechanoluminescent material. In this case, all characters of the character string “geneuine” irradiated with ultraviolet rays emit light, but when mechanical stimulation is applied, only the characters “e”, “u”, and “n” emit light. .

  Since mechanoluminescent materials generally emit light even when irradiated with ultraviolet rays, odd-numbered character strings containing only fluorescent materials and even-numbered character strings containing fluorescent materials and mechanoluminescent materials are: Some color differences may appear when exposed to ultraviolet light. However, by appropriately selecting the type and amount of the fluorescent material and the mechanoluminescent material, all the characters in the character string “genuine” can emit light with substantially the same color when irradiated with ultraviolet rays. .

  FIG. 3 shows an XYZ color system diagram (chromaticity diagram) defined in JIS Z8701 in order to express the light emission color of the fluorescent material and the mechanoluminescent material. Here, the color system region is divided into three primary colors of red, green, and blue (R, G, and B) and three colors of cyan (C), magenta (M), and yellow (Y).

Here, the range of G (G _x , G _y ) is
_{-1.020G y +0.674 <G x <0.348G} y +0.217
1/3 <G _y
It was. However, G _x and G _y are within the range of the XYZ color system diagram.

Here, the range of Y (Y _x , Y _y ) is
1/3 <Y _x
0.663Y _x +0.112 <Y _y <2.870 Y _x −0.623
It was. However, _{Y x} and _{Y y} is in the range of the XYZ color system diagram.

Here, the range of R (R _x , R _y ) is
R _x <1/3
−0.741R _x +0.580 <R _y <0.663R _x +0.112
It was. However, R _x and R _y are within the range of the XYZ color system diagram.

Here, the range of M (M _x , M _y ) is
−1.350 M _y +0.783 <M _y <0.583 M _x +0.139
M _y <1/3
It was. However, _{M x} and _{M y} is in the range of the XYZ color system diagram.

Here, the range of B (B _x , B _y ) is
B _x <1/3
-0.991B _x +0.0029 <B _y <1.7146 + 0.238
It was. However, _{B x} and _{B y} are within the scope of the XYZ color system diagram.

Here, the range of C (C _x , C _y ) is
C _x <1/3
−0.991C _x +0.0029 <C _y <−0.979 C _x +0.656
It was. However, _Cx and _Cy are within the range of the XYZ color system diagram.

  When selecting fluorescent materials and mechanoluminescent materials, their emission colors can be selected to be different from the six regions of G / Y / R / M / B / C. , Preferably in areas that are not adjacent.

  For example, the fluorescent material may emit in the red region and the mechanoluminescent material may emit in the yellow, green, cyan, blue or magenta region, preferably emitting in the green, cyan or blue region. The fluorescent material may emit in the yellow region and the mechanoluminescent material may emit in the red, green, cyan, blue or magenta region, preferably in the cyan, blue or magenta region. The fluorescent material may emit in the green region and the mechanoluminescent material may emit in the red, yellow, cyan, blue or magenta region, preferably in the red, blue or magenta region. The fluorescent material emits light in the cyan region, and the mechanoluminescent material is red, yellow, green, Luminous or magenta light may be emitted, preferably red, yellow or magenta light may be emitted; the fluorescent material may emit light in the blue region, and the mechanoluminescent material may be red, yellow or green. May emit in the cyan or magenta region, preferably in the red, yellow or green region; the fluorescent material emits in the blue region and the mechanoluminescent material may be red, yellow, It may emit in the green, cyan or magenta region, preferably in the red, yellow or green region; the fluorescent material emits in the magenta region and the mechanoluminescent material is red, yellow. May emit in the green, cyan or blue region, preferably in the yellow, green or cyan region. It may be. Even if light is emitted from coordinates located in these areas, the color of the area may be different from that of the area. That is, the light may be emitted from the red region, may be orange light, or may be white light.

In this specification, the color difference means that in the XYZ color system, the coordinates of the color of light emitted from the fluorescent material (X1, Y1) and the coordinates of the color of light emitted from the mechanoluminescent material (X2, Y2). the distance ^{d (= {(X1-X2} ) 2 + (Y1-Y2) 2} 1/2) is 0.05 or more, 0.10 or more, 0.20 or more, 0.30 or more, 0.40 or more, Or the case of 0.50 or more.

  The coordinates of the color of light emitted from the fluorescent material and the mechanoluminescent material are given only under the condition that the fluorescent material and the mechanoluminescent material emit light, for example, by irradiating with light such as ultraviolet rays in a dark room. (CS-100A, Konica Minolta Co., Ltd.) can be measured and determined.

  Although the thickness of the light emitting printing layer depends on the printing method, it may be, for example, 1.0 μm or more, 2.0 μm or more, 3.0 μm or more, or 4.0 μm or more, 20 μm or less, 15 μm or less, 10 μm or less, It may be 8.0 μm or less, or 5.0 μm or less.

<Light emitting printing layer-fluorescent material>
The fluorescent material is not particularly limited as long as it is a material that emits visible light fluorescence when irradiated with light such as ultraviolet rays and infrared rays. However, since the mechanoluminescence material described later can be excited simultaneously, it is irradiated with ultraviolet rays. A material that emits fluorescence is preferred. However, in this specification, the fluorescent material is a material different from the mechanoluminescence material, and is a material that does not emit visible light even when mechanically stimulated. In particular, the fluorescent material is a material that does not emit light that can be seen in the dark when a 1 μm-thick light-emitting printed layer containing 10% by mass of the fluorescent material is irradiated with ultraviolet rays and scratched by hand after 5 seconds.

  The fluorescent material may be an organic material or an inorganic material, and may be a fluorescent dye or a fluorescent pigment. Examples of the organic fluorescent material include rhodamine, cyanine, naphthalimide, perylene, coumarin, and quinacridone compounds. Examples of the inorganic fluorescent material include various oxide-based, nitride-based, oxynitride-based, sulfide-based, and oxysulfide-based phosphors.

  The fluorescent material may be contained in the light emitting printing layer at 1.0% by mass or more, 3.0% by mass or more, 5% by mass or more, 10% by mass or more, 15% by mass or more, or 20% by mass or more, 60 mass% or less, 50 mass% or less, 40 mass% or less, 30 mass% or less, 20 mass% or less, or 15 mass% or less may be contained. The fluorescent material is preferably used at a blending ratio that emits light more strongly than the mechanoluminescent material. In such an aspect, when the fluorescent material and the mechanoluminescent material emit light in different colors, the visibility of the difference in the luminescent color of the luminescent printed layer when irradiated with ultraviolet light and when mechanical stimulation is applied is improved. This is useful as a printed matter for preventing forgery.

  The mass ratio of the fluorescent material to the mechanoluminescent material (fluorescent material / mechanoluminescent material) contained in the same luminescent printed layer is 0.10 or more, 0.20 or more, 0.30 or more, 0.50 or more, and 1. It may be 0 or more, or 1.5 or more, and may be 10 or less, 5.0 or less, 3.0 or less, 2.0 or less, or 1.0 or less.

<Light emitting printing layer-Mechanoluminescence material>
The mechanoluminescent material used in the present invention is a material that emits light that can be visually recognized at least in the dark by receiving a mechanical stimulus after being excited by irradiation with light including ultraviolet rays. In general, this mechanoluminescent material emits light of the same color as light emitted in response to mechanical stimulation, even if it is not subjected to mechanical stimulation, during irradiation with light such as ultraviolet rays. However, in this specification, the mechanoluminescent material is a material different from the above-described fluorescent material.

  The mechanoluminescence material has a basic structure in which alkali metal ions and / or alkaline earth metal ions are inserted in a space of a matrix structure having a plurality of polyhedral structures, and the alkali metal ions inserted in the spaces and Part of the alkaline earth metal ion is substituted with at least one metal ion selected from the group consisting of rare earth metal ions, transition metal ions, group III metal ions and group IV metal ions Materials can be mentioned.

Specifically, as a mechanoluminescence material, a material obtained by adding Eu or Nd as an activator to an Al ₂ O _6- like structure in which Sr or Ca described in Japanese Patent No. 2999631 is inserted, Japanese Patent No. 3421736 Examples include Y ₂ SiO ₅ to which Eu or Ce is added, BaSi ₂ O ₅ to which Pb is added, Ba ₃ MgSi ₂ O ₈ to which Eu is added, and materials described in Japanese Patent No. 3511083. be able to.

  As such a mechanoluminescence material, for example, commercially available materials such as N nightlight G series, N nightlight GLL series, N nightlight BG series, N nightlight BGL series (Nemoto Lumimaterial Co., Ltd.) can be used. .

In addition, some mechanoluminescent materials have a phosphorescent property such that afterglow can be recognized with the naked eye for a considerable length of time (several tens of minutes to several hours) after the irradiation is stopped after ultraviolet irradiation. There are also things. Examples of such a material include materials disclosed in Japanese Patent No. 4628957. Here, a phosphorescent material containing Al ₂ O ₄ like structure with strontium inserted, europium (Eu), which is a rare earth metal as an activator, and dysprodium (Dy), which is a rare earth element, is disclosed as a coactivator .

  The mechanoluminescence material may be contained in the light emitting printing layer at 1.0 mass% or more, 3.0 mass% or more, 5 mass% or more, 10 mass% or more, 15 mass% or more, or 20 mass% or more. It may be contained in 60 mass% or less, 50 mass% or less, 40 mass% or less, 30 mass% or less, 20 mass% or less, or 15 mass% or less. Since the light emitted from the mechanoluminescent material often disappears in a short time after receiving a mechanical stimulus, it is preferable to set the light emission to 10% by mass or more for easy confirmation of the light emission.

<Light emitting printing layer-Others>
The light emitting printing layer may contain a binder resin for binding the fluorescent material and the mechanoluminescent material to the substrate. Such a binder resin may be a natural resin or a synthetic resin, and may be a homopolymer or a copolymer.

  Examples of natural resins include rosin, cocoon, shellac, and gilsonite. Synthetic resins include, for example, polyamide resin, two-component urethane resin, epoxy resin, acrylic resin, vinyl chloride resin, butyral resin, vinylidene chloride resin, styrene resin, rosin, phenol resin, modified alkyd resin, polyester resin, chlorine And maleic resins such as fluorinated polypropylene, petroleum resin, rosin-modified maleic resin, cyclized rubber, chlorinated rubber, and other synthetic resins and copolymers.

  Moreover, nitrocellulose and its derivative can also be mentioned as resin. Nitrocellulose is a nitrate ester of cellulose obtained by treating cellulose with a mixture of nitric acid and sulfuric acid, and is also called nitrified cotton or nitric acid fibrin. Nitrocellulose has different solubility in a solvent depending on the degree of nitrification, and has a different melt viscosity depending on the degree of polymerization.

  The binder resin may be contained in the light emitting printing layer in an amount of 10% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, or 50% by mass or more, and 98% by mass or less and 90% by mass or less. 80 mass% or less, 70 mass% or less, or 60 mass% or less.

<Base material>
The substrate used in the printed material of the present invention is not particularly limited as long as it is a material capable of forming a layer by printing.

  Specifically, as the base material, a paper base material such as fine paper, coated paper, art paper, cast coated paper, foil paper, recycled paper, impregnated paper, variable information paper, etc .; film base material such as polyester A film, a polyolefin film, a polystyrene film, a vinyl chloride film, a polyimide film, a film for variable information, etc .; or a cloth substrate such as a woven cloth or a non-woven cloth may be used.

<Method for producing printed matter>
The method for producing a printed material according to the present invention includes a step of preparing a base material; a luminescent printing layer containing the fluorescent material and the mechanoluminescent material is formed on the base material using a luminescent ink containing the fluorescent material and the mechanoluminescent material. The process of carrying out is included.

  As the substrate, the above-described printing substrate can be used. A pattern layer, an anchor coat layer, or the like may be formed on the substrate by a known method before printing the light emitting print layer.

  The light emitting printing layer can be formed by printing. The printing method is not particularly limited, and silk screen printing, gravure printing, intaglio printing, offset printing, letterpress printing, ink jet printing, flexographic printing, and the like can be used.

《Luminescent ink》
The luminescent ink of the present invention contains a fluorescent material and a mechanoluminescent material. Furthermore, the luminescent ink of the present invention contains a vehicle and may further contain auxiliary agents, colorants and the like.

  The luminescent ink of the present invention is an oxidation polymerization type ink (hereinafter referred to as “oil-based ink”), an ultraviolet curable ink (hereinafter referred to as “UV ink”), or an oil-based / ultraviolet curable ink, depending on the type of vehicle component. As a mold combined ink (hereinafter referred to as “oil-based / UV combined ink”), it can be used in various printing methods.

  Oil-based inks are inks that can be cured by oxidative polymerization of vehicle components. In general, the oil-based ink includes a resin, a crosslinking agent or a drying accelerator, a drying oil or a semi-drying oil, a solvent, and the like.

  UV inks are inks that can be cured by photopolymerization of vehicle components. In general, the UV ink contains a resin, a photopolymerizable monomer or oligomer, a photopolymerization initiator and the like as a vehicle component, but does not contain a volatile component such as a solvent.

  The oil-based / UV combined ink is an ink having curing characteristics of both oil-based ink and UV ink.

  The luminescent ink of the present invention can also be used as a water-based ink containing water as a main solvent or a solvent ink containing an organic solvent as a main solvent, depending on the type of solvent that can be used as a vehicle.

  The water-based ink is an ink containing water as a main solvent, but may contain an organic solvent. The solvent ink is an ink containing an organic solvent as a main solvent, but may be substantially free of water. “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.

  The luminescent ink of the present invention is used as a general printing ink, for example, silk screen printing ink, gravure printing ink, intaglio printing ink, offset printing ink, letterpress printing ink, inkjet printing ink, flexographic printing ink, etc. Can do. The intaglio printing ink can be used for press printing using a direct printing plate surface or an etching plate surface.

  The content of the fluorescent material and the mechanoluminescent material in the luminescent ink is respectively solid so that the printed matter including the luminescent printed layer printed with the luminescent ink of the present invention easily exhibits the above effects. 1.0% by mass or more, 3.0% by mass or more, 5% by mass or more, 10% by mass or more, or 20% by mass or more, or 80% by mass or less, 70% by mass, % Or less, 60 mass% or less, 50 mass% or less, 40 mass% or less, 30 mass% or less, 20 mass% or less, or 15 mass% or less.

  The luminescent ink of the present invention can be obtained by mixing and dispersing optional components such as an auxiliary agent and a colorant in addition to a fluorescent material, a mechanoluminescent material, and a vehicle. The mixing and dispersion of each component can be performed by a mixer such as a single-screw mixer and a twin-screw mixer; an ink mill, such as a three-roll mill, a ball mill, a sand grinder, and an attritor.

<Vehicle>
The vehicle used in the luminescent ink of the present invention is a medium for transferring the fluorescent material and the mechanoluminescent material to the base material and fixing the fluorescent material and the mechanoluminescent material to the base material after printing. The vehicle used in the present invention may contain a known vehicle component used for printing, for example, the above-mentioned binder resin, solvent, photopolymerization component and the like.

  The solid content contained in the vehicle varies depending on the printing method, but may be, for example, 10% by mass or more, 15% by mass or more, or 20% by mass or more, and is 80% by mass or less, 60% by mass or less, and 50% by mass. Or 30% by mass or less.

  In an embodiment of the present invention, a known binder resin used for printing may be included as a vehicle. For example, you may use said binder resin. Examples of the solvent include known organic solvents, drying oils, semi-drying oils, mineral oils, and water. Examples of the photopolymerization component include known photopolymerizable monomers or oligomers, photopolymerization initiators, and the like.

<Auxiliary agent>
The luminescent ink of the present invention contains known adjuvants used in printing, such as dispersants, crosslinking agents, drying accelerators, waxes, extender pigments, antifoaming agents, leveling agents and other additives. It's okay.

《Authenticity Judgment Method》
The authenticity determination method of the present invention includes a step of irradiating the printed matter with light to cause the fluorescent material to emit light; and / or a step of applying mechanical stimulation to the printed matter that has been irradiated with ultraviolet light to cause the mechanoluminescent material to emit light. Including.

  Here, ultraviolet rays are preferably used in the step of irradiating light. By irradiating with ultraviolet rays, the fluorescent material is caused to emit light, and at the same time, the mechanoluminescent material can be excited to cause the mechanoluminescent material to emit light strongly in a later step.

  In the step of applying a mechanical stimulus, the mechanical stimulus can be given by rubbing, bending, scratching or the like of the printed material. In addition, the step of applying mechanical stimulation is preferably performed without irradiating light, separately from the above-described light irradiation step, so as to improve the visibility of the mechanoluminescent material.

  The present invention will be described more specifically with reference to the following examples, but the present invention is not limited thereto.

<Sample preparation>
<Example 1>
As a mechanoluminescence material, Eu and Dy were added as activators and coactivators to an Al ₂ O ₄ like structure in which strontium was inserted, and SrAl ₂ O ₄ : Eu, Dy (GLL-300FFS, Nemoto Corporation) Lumi material) was used. This is a mechanoluminescent material having a phosphorescent property, and the coordinates in the XYZ color system of light emitted when irradiating ultraviolet rays and applying a mechanical stimulus thereafter are x = 0.254; y = 0.438 (G region in FIG. 3).

As the fluorescent material, yttrium vanadate (YVO ₄ : Eu, Bi) containing bismuth (Bi) and Eu as an activator was used. The coordinates in the XYZ color system of light emitted when irradiating ultraviolet rays were x = 0.610; y = 0.337 (R region in FIG. 3).

  Addition of 30 parts by mass of xylene-containing solvent (vinyl standard solvent, Jujo Chemical Co., Ltd.) to 67 parts by mass of varnish containing vinyl resin (vinyl ink H-type halftone, Jujo Chemical Co., Ltd., solid content: 30% by mass) And mixed using a stirrer. Thereto, 3 parts by mass of a mixture of a silicone-based antifoaming agent (JA-750X, Jujo Chemical Co., Ltd.) and a silicone-based leveling agent (JA-200, Jujo Chemical Co., Ltd.) was added to obtain a silk screen printing vehicle.

  80 parts by mass of the obtained silk screen printing vehicle, 10 parts by mass of the mechanoluminescent material, and 10 parts by mass of the fluorescent material were mixed to prepare a luminescent ink. Using this ink, printing was performed on a paper substrate (OK Prince Quality, Oji Paper Co., Ltd.) by silk screen printing so that the printed film thickness was 20 μm, and the printed matter of Example 1 was obtained.

<Example 2>
A printed matter of Example 2 was obtained in the same manner as Example 1 except that Eu-activated barium magnesium aluminate was used as the fluorescent material. In the fluorescent material used here, the coordinates in the XYZ color system of light emitted when irradiating ultraviolet rays were x = 0.144; y = 0.065 (B region in FIG. 3).

<Example 3>
A printed matter of Example 3 was obtained in the same manner as Example 1 except that Lumilux (trademark) Green CD163 (Honeywell) was used as the fluorescent material. In the fluorescent material used here, the coordinates in the XYZ color system of light emitted when irradiating ultraviolet rays were x = 0.164; y = 0.583 (G region in FIG. 3).

<Example 4>
A printed matter of Example 4 was obtained in the same manner as Example 1 except that Lumilux (trademark) Yellow CD782 (Honeywell) was used as the fluorescent material. In the fluorescent material used here, the coordinates in the XYZ color system of the light emitted when irradiating ultraviolet rays were x = 0.594; y = 0.532 (Y region in FIG. 3).

<Example 5>
A printed material of Example 5 was obtained in the same manner as Example 4 except that Sr ₄ Al ₁₄ O ₂₅ : Eu, Dy (BGL-300FFS, Nemoto Lumi Material Co., Ltd.) was used as the mechanoluminescent material. The mechanoluminescent material used here has coordinates in the XYZ color system of light emitted when ultraviolet light is irradiated and when mechanical stimulation is applied thereafter, x = 0.164; y = 0.196. (C region in FIG. 3).

<Example 6>
A printed matter of Example 6 was obtained in the same manner as Example 2 except that Sr ₄ Al ₁₄ O ₂₅ : Eu, Dy (BGL-300FFS, Nemoto Lumi Material Co., Ltd.) was used as the mechanoluminescent material. The mechanoluminescent material used here has coordinates in the XYZ color system of light emitted when ultraviolet light is irradiated and when mechanical stimulation is applied thereafter, x = 0.164; y = 0.196. (C region in FIG. 3).

<Examples 7 to 12>
The mass ratio of the silk screen printing vehicle, mechanoluminescent material and fluorescent material used in obtaining the printed material described in Example 1 was changed as described in Table 2 to obtain printed materials of Examples 7-12. It was.

<Evaluation>
About the printed matter obtained as mentioned above, the printed layer was made to emit light by irradiating with ultraviolet rays, and this was visually observed. Thereafter, the irradiation of ultraviolet rays was stopped, and the printed layer was mechanically stimulated by scratching with a nail in a dark room to cause mechanoluminescence, and this was visually observed.

  If there is a large difference between the color of light emitted when irradiated with UV light and the color of light emitted when mechanical stimulation is applied, the difference can be clearly identified. When there is a difference between the color of light and the color of luminescence when a mechanical stimulus is applied, and the difference can be confirmed, there is a difference. When the color of luminescence and a mechanical stimulus are applied when irradiated with ultraviolet light When it was difficult to confirm the difference in the luminescent color, “no difference” was evaluated.

  About Examples 7-12, the color of the light emission when irradiating an ultraviolet-ray was measured with the color luminance meter (CS-100A, Konica Minolta Co., Ltd.), and the XY coordinate of the XYZ color system was also measured.

"result"
The results are shown in Tables 1 and 2 below. Moreover, the figure which plotted the XY coordinate of the XYZ color system of the color of the light emission when each single ultraviolet-ray of the printed matter of Examples 7-12 and a mechanoluminescent material and a fluorescent material was irradiated is shown in FIG.

DESCRIPTION OF SYMBOLS 1 Light emitting printing layer 2 Base material 10 Printed matter

Claims (10)

  An anti-counterfeit printed matter having a light-emitting printed layer containing a fluorescent material and a mechanoluminescent material on a substrate.   The printed matter according to claim 1, wherein a color of light emitted from the printed layer when irradiated with light is different from a color of light emitted from the printed layer when subjected to mechanical stimulation.   The printed matter according to claim 1, wherein the fluorescent material emits visible light when irradiated with ultraviolet rays.   When the printed layer is irradiated with light, it emits light in any one of red, yellow, green, cyan, blue, and magenta areas, and red when mechanically stimulated. The printed matter according to any one of claims 1 to 3, which emits light in a region different from a region of light emitted when irradiated with the light among regions of yellow, green, cyan, blue, and magenta. .   The fluorescent material emits red light when irradiated with light, and emits green light when the mechanoluminescent material is mechanically stimulated. Printed matter described in 1.   The ratio of the mass of the fluorescent material to the mass of the mechanoluminescent material contained in the light emitting printing layer is 0.25 or more and 10 or less, according to any one of claims 1 to 5. Printed matter.   The printed matter according to any one of claims 1 to 6, which is a bill, a securities, a public document, a ticket, a cash voucher, a card, or a seal for authenticity determination.   A luminescent ink comprising a vehicle, a mechanoluminescent material, and a fluorescent material.   The luminescent ink according to claim 8, wherein a ratio of a mass of the fluorescent material to a mass of the mechanoluminescent material is 0.25 or more and 10 or less.   A step of irradiating the printed material according to any one of claims 1 to 7 with light to cause the fluorescent material to emit light; and / or applying a mechanical stimulus to the printed material to cause the mechanoluminescent material to emit light. A method for determining the authenticity of printed matter, including a process.