JP5760468B2 - Anti-counterfeit printed matter - Google Patents

Description

  The present invention relates to an anti-counterfeit printed matter, and more particularly to an anti-counterfeit printed matter having a layer containing a material that emits light by stress and a layer containing a material that changes color by heat.

  Securities are securities that represent property rights, and the transfer or exercise of the rights represented by these securities is defined as bills, checks, stock certificates, corporate bonds, and various securities that are transferred by the securities. Securities include gift certificates, book coupons, transportation tickets, admission tickets for paid facilities and events, lottery tickets, winning tickets for public competitions, etc. in addition to the above stipulated in the Commercial Code. It is. Not only the above-mentioned securities but also printed materials that require prevention of counterfeiting such as passports, identification cards, and various commercial printed materials, that is, anti-counterfeiting printed materials are frequently used.

  In recent years, along with the spread of electronic devices such as printers and scanners, unauthorized duplication of securities, etc. has been rampant, but this is considered an illegal act even if it is not used in public, and it is malicious Cases are subject to criminal punishment. The damage of counterfeiting due to unauthorized copying described above has become a social problem, and anti-counterfeiting technology is becoming more sophisticated, so the development of advanced anti-counterfeiting technology is urgently needed.

  For example, as disclosed in Patent Document 1, there is a printed matter using a hologram as an advanced anti-counterfeiting technique, but the manufacturing cost is high, causing a practical problem. Further, as disclosed in Patent Document 2, there has been proposed a printed fluorescent ink that cannot be viewed with visible light and emits fluorescence with light of a certain wavelength other than visible light. However, in the case of printing of this fluorescent ink, the forgery technique has progressed and has been widely known due to the obsolescence of the technique, and there is a problem that the effect of preventing forgery is weak.

JP-A-6-278396 JP-A-6-297888

  Therefore, an object of the present invention is to provide an anti-counterfeit printed matter that has an anti-counterfeit technology that is not present in the past and that has no trouble in manufacturing.

The above object is achieved by the present invention described below. That is, the present invention is characterized in that at least one layer containing a material that emits light by stress and a layer containing a thermochromic material that changes to a transparent state by heat are laminated in this order on one surface of the substrate. The anti-counterfeit printed matter is configured .

According to the above configuration, in the state where stress such as pressure is applied without applying heat to the anti-counterfeit printed matter, only the stress-luminescent material-containing layer emits light. For example, when the discoloration material-containing layer is covered in an opaque and colored state, light emission of the stress-stimulated luminescent material-containing layer is not visible.

Further , according to the above configuration, in the state where heat is applied without applying pressure or other stress to the forgery-preventing printed matter, only the thermochromic material-containing layer is discolored, for example, it is made transparent from an opaque colored state. Thus, no light is emitted from the layer containing the stress-stimulated luminescent material located below.
Further, according to the above configuration, by adding both energy due to temperature change and energy due to stress , the thermochromic material-containing layer changes color and becomes transparent, and light emission from the layer containing the stress-luminescent material is recognized .

  A forgery-preventing printed matter is characterized in that a printed layer is provided between the substrate and a layer containing a material that emits light by stress. As a result, when both energy due to temperature change and energy due to stress are applied to the anti-counterfeit printed matter, the content layer of the thermochromic material is discolored and becomes transparent, for example, and the light emission of the content layer of the stress luminescent material is further printed. A layer is seen and the anti-counterfeiting property is further enhanced.

According to the present invention , the layer containing the thermochromic material changes color and becomes transparent only under specific conditions in which both heat and stress are applied to the anti-counterfeit printed matter, and the layer containing the stress luminescent material emits light. since it is recognized, that very thing as Do effect of anti-counterfeiting is high.

It is sectional drawing which shows one embodiment which is a forgery prevention printed matter of this invention. It is sectional drawing which shows other embodiment which is a forgery prevention printed matter of this invention. It is sectional drawing which shows other embodiment which is a forgery prevention printed matter of this invention.

Next, embodiments of the present invention will be described in detail.
In FIG. 1, one embodiment which is the forgery prevention printed matter 1 of this invention is shown. This is a forgery-preventing printed matter 1 having a structure in which a stress-luminescent material-containing layer 3 and a thermochromic material-containing layer 4 are laminated on one surface of a substrate 2.

  FIG. 2 is a cross-sectional view showing another embodiment of the anti-counterfeit printed matter 1 of the present invention. On one surface of the substrate 2, a stress-luminescent material containing layer 3 and a thermochromic material containing layer 4 are provided. The print layer 5 is provided between the base material 2 and the stress light emitting material containing layer 3, and both the energy due to temperature change and the energy due to stress are added to the anti-counterfeit printed matter 1. In this case, the content layer of the thermochromic material is discolored to be transparent, and the light emission of the content layer of the stress luminescent material and the printed layer can be seen.

  FIG. 3 is a cross-sectional view showing another embodiment of the anti-counterfeit printed matter 1 of the present invention. The printed layer 5, the stress-luminescent material-containing layer 3, and the thermochromic material are formed on one surface of the substrate 2. In the configuration in which the content layer 4 is laminated, the printing layer 5 includes a portion covered with the stress light emitting material content layer 3 and the thermochromic material content layer 4, and a portion not covered and exposed on the surface. There is. When both the energy due to temperature change and the energy due to stress are applied to the anti-counterfeit printed matter 1, the content layer of the thermochromic material changes color and becomes transparent, and the light emission of the content layer of the stress luminescent material is further observed. And the exposed portion of the printed layer that is not covered with anything can be observed.

  Although not shown in FIGS. 1 to 3, for example, printing of character information, a background pattern, or the like is performed on the surface opposite to the surface of the base material 2 on which the stress-luminescent material-containing layer 3 and the thermochromic material-containing layer 4 are provided. Can also be applied. Further, an adhesive layer may be provided on the surface opposite to the surface of the substrate 2 on which the stress-luminescent material-containing layer 3 and the thermochromic material-containing layer 4 are provided, and used as a seal.

Below, the element which comprises the forgery prevention printed matter of this invention is demonstrated in detail.
(Base material)
Examples of the base material 2 of the anti-counterfeit printed material include paper such as high-quality paper, art paper, coated paper, cast coated paper, synthetic resin or emulsion-impregnated paper, synthetic rubber latex-impregnated paper, synthetic resin internal paper, and cellulose fiber paper , Plastic sheets of various synthetic resins such as polyolefin (polyethylene, polypropylene, etc.), polystyrene, polycarbonate, polyethylene terephthalate, polyvinyl chloride, polymethacrylate, etc., and white films formed by adding white pigments and fillers to these synthetic resins An opaque film or a film (so-called synthetic paper) having fine voids inside the substrate can be used.

  However, it is preferably used by rubbing the thermochromic material-containing layer located on the surface of the anti-counterfeit printed matter and applying heat due to stress and friction at the same time. In this case, the thermochromic material-containing layer is discolored. Thus, the base material is preferably opaque so that light emission from the content layer of the stress luminescent material is easily recognized. The thickness of the substrate is usually about 3 to 300 μm. In the present invention, it is preferable to use a substrate having a thickness of about 20 to 175 μm in consideration of handling suitability and the like.

(Layer containing material that emits light by stress)
The layer 3 containing a material that emits light due to stress (stressed luminescent material containing layer) can be formed by printing ink composed of a binder (bonding agent), a stress luminescent material, an additive, a solvent, and the like. A material that emits light by stress, that is, a stress-stimulated luminescent material, has a property that the material itself emits light by strain energy applied from the outside, and has a property that light emission intensity is changed in proportion to the strain energy. The stress luminescent material is, for example, a material (ceramics) in which an element serving as a luminescent center is added to an inorganic crystal skeleton whose structure is highly controlled, and is obtained in the form of powder particles. Materials that emit light at various wavelengths from ultraviolet to visible to infrared have been obtained by selecting the kind of inorganic material or emission center. The printed part containing such a stress-stimulated luminescent material can be read visually or by a machine.

Since the anti-counterfeit printed matter of the present invention is provided with a stress-stimulated luminescent material-containing layer, it is possible to easily cause the stress-stimulated luminescent material-containing layer to emit light by applying an external force by scratching or rubbing the surface. it can. The stress-stimulated luminescent material can be divided into a stress-stimulated luminescent material and a stress-stimulated phosphorescent material according to the decay time of luminescence due to given energy. Examples of fluorescent materials include strontium aluminate with europium added as the emission center (SrAl ₂ O ₄ : Eu, green emission), zinc sulfide with manganese emission center (ZnS: Mn, emission in yellow green) ) And the like. These stress luminescent materials are present as particles in the printing ink, and the ink is printed to form a layer containing the stress luminescent material. In particular, it is possible to adjust the printing ink using a material in which a stress light emitting material is dispersed in a highly transparent polymer resin in the form of a so-called nanoparticle having a particle diameter of about 10 to 200 nm. This is preferably carried out because it can be improved and stabilized. Examples of the polymer resin in which the above-described stress-luminescent material of nanoparticles is dispersed include polymethyl methacrylate (PMMA) and epoxy resin.

  The ink used to form the layer containing the stress-stimulated luminescent material has a binder (bonding agent), a stress-stimulated luminescent material, and an additive so that the ink characteristics according to the printing method can be obtained and the required luminescence intensity can be obtained. The blending ratio of the agent, solvent, etc. is determined. For printing for forming a layer containing a stress-stimulated luminescent material, generally known methods such as intaglio, letterpress, offset, screen, gravure, flexographic printing, ink jet printing, spray printing or coating can be employed.

(Layer containing material that changes color by heat)
The layer 4 containing the material that changes color by heat (the layer containing the thermochromic material) colors (1) the electron donating colorable organic compound and (2) the electron donating colorable organic compound. A layer containing a color change material by heat comprising three components: a developer that is an electron-accepting compound, and (3) a medium compound having a polar group that controls the temperature at which the color reaction of both occurs. . It is preferable that the homogeneous solution made of the thermochromic material is encapsulated in a microcapsule to form a capsule pigment, and the capsule pigment is dispersed in an ink vehicle to adjust the ink.

  As the electron-donating color-forming organic compound, a so-called leuco dye group that is colored by a compound having a phenolic hydroxyl group is applied. , Phenylindolylphthalides, phenylindolylazaphthalides, styrylquinolines and the like.

  Further, the color developer for coloring the electron donating color-forming organic compound includes monohydric phenol, dihydric phenol and polyhydric phenol as a compound having a phenolic hydroxyl group, and further, as a substituent on the benzene ring. There are an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, a carboxy group and its ester or amide group, a halogen-containing group, a bis-type, a tris-type phenol, and the like.

  Examples of the medium compound having a polar group that controls the temperature at which the coloration reaction of both the electron-donating color-forming organic compound and the electron-accepting compound that colors the compound occur are alcohols, esters, and ketones. Or a compound selected from either carboxylic acids.

  As the encapsulation method, a known encapsulation method such as an interfacial polymerization method, an interfacial polycondensation method, an in situ method, a coacervate method, or the like can be applied, and the capsule size is 0.5 μm in average particle size. About 10 μm is used, and in the case of ink for offset printing, a finer capsule is used due to the transferability of the ink from the blanket cylinder, etc., and the particle diameter is set in the range of 1 to several μm. It is desirable.

  The above-mentioned thermochromic material can adjust the temperature at which the color changes depending on the kind and content ratio of the above three components. The temperature is raised from room temperature (20 ° C.) to about 27 to 40 ° C. It is preferable to change from a colored opaque state such as blue to a transparent state. Further, from the transparent state, the anti-counterfeit printed matter can be cooled to about −6 to 15 ° C. to obtain a colored opaque state. The change between the opaque state and the transparent state can be reversibly and repeatedly changed.

  The layer containing the thermochromic material is composed of a medium compound having the above-mentioned electron-donating color-forming organic compound, a color developer that is an electron-accepting compound, and a polar group that controls the temperature at which the color reaction of both occurs. The material that changes color due to the heat of the three components is microencapsulated and dispersed in the ink vehicle to prepare the ink. However, the ink is prepared by selecting a vehicle, an additive, a solvent and the like according to the printing method to be applied. For printing for forming the layer containing the thermochromic material, generally known methods such as intaglio, letterpress, offset, screen, gravure, flexographic printing, ink jet printing, spray printing or coating can be employed.

(Print layer 5)
The printing layer 5 provided on the substrate is printed with intaglio, letterpress, offset, screen, gravure, flexographic or ink jet printing, spray printing, using commonly used color pigments or printing inks using fluorescent materials. Or the like. The fluorescent material can be either an ultraviolet light emitting type or an infrared light emitting type.

  As the ultraviolet light-emitting fluorescent substance, known ultraviolet fluorescent dyes and commercially available inorganic and organic ultraviolet fluorescent pigments are used. Examples of the ultraviolet fluorescent dye include fluorescein, coumarin, oxazole, pyrazoline, thiadiazole, spiropyran, pyrenesulfonic acid, benzimidazole, and diaminostilbene dyes.

  Examples of organic ultraviolet fluorescent pigments include fluorescein, eosin, rhodamine 6G, rhodamine B, basic yellow HG and the like, such as polyvinyl chloride resin, alkyd resin, polymethacrylate resin, urea resin, melamine resin. Those obtained by uniformly dissolving and pulverizing the dye are used.

Inorganic ultraviolet fluorescent pigments include zinc sulfide activated with copper, silver, manganese, etc., zinc silicate activated with manganese, zinc sulfide activated with silver, copper, etc., cadmium, bismuth, etc. Zn ₂ GeO activated with activated calcium sulfide, strontium sulfide activated with samarium, cerium, etc., calcium tungstate activated with lead, etc., Sr ₅ (PO ₄ ) ₃ Cl activated with europium, etc., manganese, etc. ₂ , Y ₂ O ₂ S activated with europium or the like, Y ₂ O ₃ activated with europium or the like is used.

Known infrared fluorescent dyes and commercially available inorganic and organic infrared fluorescent pigments are used as the infrared light emitting fluorescent material. For example, rare earth phosphors using Yb ³⁺ , Er ³⁺ , and Ho ³⁺ as activators are used. YF ₃ and Yb + Er are colored green and red when irradiated with infrared rays, and YF ₃ and Yb + Tm are infrared rays. Colors blue when irradiated.

  The anti-counterfeit printed matter of the present invention is compatible with both the discoloration of the thermochromic material and the light emission of the stress luminescent material only under the specified conditions of applying both heat and stress, but by using a fluorescent substance in the printed layer, The anti-counterfeiting property can be further enhanced by combining the fluorescence of the printed layer and the fluorescence of the content layer of the stress luminescent material.

Example 1
As the base material 2, high-quality paper (DSK135kg / 46) manufactured by Daishowa Paper Co., Ltd. was prepared, and on one side thereof, with an offset ink using a fluorescent material that emits green light by ultraviolet rays, as shown in FIG. The print layer 5 was formed by offset printing. On the printed layer 5, a layer 3 containing a material that emits light by stress was formed by gravure printing using an ink containing the following stress luminescent material.

As an ink containing a stress-stimulated luminescent material, nanoparticles of strontium aluminate (SrAl ₂ O ₄ : Eu, luminescent in green) added with europium as the luminescent center were used. Polymethylmethacrylate (PMMA) The gravure ink was prepared by adding the material dispersed in the molecular resin and other vehicles and additives.

  The forgery of Example 1 is carried out by forming the layer 4 containing the material that changes color by heat by using the ink containing the following thermochromic material on the containing layer 3 of the stress luminescent material. A prevention print was made.

  Using UV-TRONIC DRY OFFSET THERMOCHROMIC GREEN, UV-TRONIC DRY OFFSET THERMOCHROMIC BLUE, and UV-TRONIC DRY OFFSET THERMOCROMIC RED made by SICPA Inktec) was added in an amount of 1% by mass, and three types of ink containing a thermochromic material containing a fluorescent substance were prepared. The above-mentioned thermochromic material made of SICPA becomes transparent when it becomes 27 ° C. or higher from a colored opaque state at room temperature.

  In the anti-counterfeit printed matter of Example 1 obtained above, when it was prepared and allowed to stand at room temperature (20 ° C.), only the thermochromic material containing layer 4 was recognized, but it was reciprocated about 10 times with a finger. When the layer containing the thermochromic material is rubbed strongly (under the condition that both heat and stress are applied), the colored opaque state of the thermochromic material containing layer changes to a transparent state and is exposed to ultraviolet rays. Both the green fluorescent light emission of the stress light emitting material containing layer and the green fluorescent light emission of the printed layer were recognized, and the anti-counterfeiting property was very high.

  In addition, the anti-counterfeit printed matter of Example 1 does not apply stress such as pressure, and in a state where heat is applied, only the content layer of the thermochromic material is discolored and becomes transparent from an opaque colored state, Although the underlying layer containing the stress-stimulated luminescent material is observed, no fluorescence is observed. Further, in the state where stress such as pressure is applied without applying heat to the anti-counterfeit printed matter of Example 1, only the stress-luminescent material-containing layer emits light, but thermal discoloration occurs on the stress-luminescent material-containing layer. Since the material-containing layer is covered in an opaque and colored state, the fluorescence emission of the stress-stimulated luminescent material-containing layer is invisible, and only under specific conditions where both heat and stress are applied, thermal discoloration occurs. The discoloration of the material and the light emission of the stress-stimulated luminescent material are both compatible, and the effect of preventing forgery is extremely high.

DESCRIPTION OF SYMBOLS 1 Anti-counterfeit printed matter 2 Base material 3 Layer containing the material light-emitted by stress (Contained layer of stress luminescent material)
4 Layer containing a material that changes color by heat (Content layer of thermochromic material)
5 Print layer

Claims (2)

An anti-counterfeit printed matter, wherein at least a layer containing a material that emits light by stress and a layer containing a thermochromic material that changes to a transparent state by heat are laminated in this order on one surface of the substrate. The forgery-preventing printed matter according to claim 1, wherein a printed layer is provided between the base material and a layer containing a material that emits light by stress.

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