JP2007238898A - Acoustic illuminant and anti-falsification medium using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an illuminant that uses a material hardly available in markets, is difficult to falsificate, emits light at a dark place, which is easily discriminable by visual observation and an anti-falsification medium using the illuminant. <P>SOLUTION: The acoustic illuminant 1 is obtained by sealing a solution containing a luminescent substance to exhibit an acoustic luminous reaction in a microcapsule. The anti-falsification medium 10 is obtained by dispersing the acoustic illuminant 1 into a printing ink binder to obtain ink and forming an ink layer 22 composed of the acoustic luminous ink on a specific part of a material 20 to be printed. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a luminescent material that exhibits an acoustic luminescence reaction and an anti-counterfeit medium that has been converted into an ink and printed on a specific portion such as securities.

  Conventionally, for the purpose of making counterfeiting difficult, there is an anti-counterfeit medium in which an ink containing a high-brightness pigment such as titanium coating mica (such as pearl ink) is printed on a specific part of the base surface of securities or cards ( For example, see Patent Documents 1 and 2.)

  The anti-counterfeit medium of the present invention is superior in that it is not easily counterfeited and does not require a special authenticity determination device, but has a problem of forgery due to similar commercially available materials.

  In addition, there is a method of manufacturing a forgery prevention medium that uses special fluorescent ink and prints a mark or the like on a specific portion of a base material surface of securities or cards (see, for example, Patent Documents 1 and 2).

  According to the method for producing an anti-counterfeit medium of the invention described above, since the mark by the fluorescent ink is concealed in a normal state, it is excellent in that it is not noticed by the user. May be difficult to distinguish, and in addition, a black light irradiation device is required for authenticity determination. These authenticity determination techniques have a problem that many years have passed since they were technically established, and when they are generally recognized and publicized, they are more likely to be counterfeited. .

The above prior art documents are shown below.
JP 2000-272240 A JP 2001-162955 A

  The present invention solves the problems of the prior art, and the problem is that it is difficult to counterfeit using a material that is difficult to obtain on the market, and it is easy to visually observe the light emission in the dark. It is an object of the present invention to provide an illuminant that can be discriminated and an anti-counterfeit medium used for securities and the like using the illuminant.

  In order to achieve the above object in the present invention, first, in the invention of claim 1, an acoustic illuminant in which a solution containing a chemiluminescent substance or a bioluminescent substance exhibiting an acoustic luminescence reaction is enclosed in a microcapsule. An acoustic luminescent material, wherein a positive catalyst for light emission of the chemiluminescent material and the bioluminescent material or a photosensitizer that generates active oxygen by acoustic luminescence is added to the solution. is there.

  According to a second aspect of the present invention, there is provided an acoustic light emitter according to the first aspect, wherein a phosphor that is excited by a light wave of acoustic light emission to emit light is added to the solution.

The invention of claim 3 is characterized in that at least one light emitting material of phosphor, phosphor, or phosphorescent material that emits light by ultraviolet rays or infrared rays is added to the solution. Any one of the acoustic light emitters described above is provided.

  According to a fourth aspect of the present invention, the acoustic luminescent material according to any one of the first to third aspects is printed on a specific portion of the substrate using the acoustic luminescent ink dispersed in a printing ink binder. This is a medium for preventing forgery.

  Since this invention is the above structure, there exist the following effects.

  That is, according to the first aspect of the present invention, a solution containing a chemiluminescent substance or a bioluminescent substance exhibiting an acoustic luminescence reaction is used as an acoustic luminescent material enclosed in a microcapsule, and the chemiluminescence is added to the solution. The addition of a photocatalyst for the emission of substances and bioluminescent substances or a photosensitizer that generates active oxygen by acoustic emission increases the amount of emitted light, resulting in a brighter and easier-to-see acoustic emitter. be able to.

  According to the second aspect of the present invention, the phosphor that is excited by the light wave of the acoustic emission to emit light is added to the solution containing the chemiluminescent substance or the bioluminescent substance that exhibits the acoustic emission reaction. Further, since the light emission intensity and the light emission time are improved and the light emission in a specific wavelength region (specific color) and the waveform of a specific light emission spectrum are provided, an acoustic light emitter having a more anti-counterfeit effect can be obtained.

  According to the third aspect of the present invention, the solution containing a chemiluminescent substance or bioluminescent substance exhibiting an acoustic luminescence reaction is provided with at least one of phosphor, phosphor, and phosphorescent substance that emits ultraviolet or infrared light. By adding the light emitting material, there is an improvement in sustainability of light emission and light emission luminance, and an acoustic light emitter with higher visibility can be obtained.

  Furthermore, according to the invention according to claim 4, the acoustic luminescent material according to any one of claims 1 to 3 is dispersed in a printing ink binder to obtain an acoustic luminescent ink, and the ink is used. By printing (applying) on specific parts of printed materials such as securities, it is difficult to counterfeit because materials that are difficult to obtain on the market are used, and specific sound (ultrasonic waves, etc.) in the dark ) Irradiation can be used as an anti-counterfeit medium that can be easily discriminated visually (determination of authenticity).

  Hereinafter, the best mode for carrying out the present invention will be described in detail with reference to the drawings.

  FIG. 1 shows an embodiment of an acoustic luminescent material of the present invention. In this example, a solution (11) containing a chemiluminescent substance exhibiting an acoustic luminescence reaction is enclosed in a microcapsule (12). FIG. 2 is a schematic diagram showing an acoustic luminescent ink (5) in which the acoustic luminescent material (1) is dispersed in a printing binder (14). is there.

  FIG. 3 shows an embodiment of the anti-counterfeit medium according to the present invention. In this example, an ink layer (22) printed with the above-described acoustic light-emitting ink on a specific portion on the substrate (20). ) Is provided with an anti-counterfeit medium (10).

  In the following, the mechanism of acoustic luminescence and the chemiluminescent substance or bioluminescent substance that exhibits an acoustic luminescence reaction and constitutes the luminescent material will be described in more detail.

The acoustic illuminant of the present invention directly or indirectly utilizes luminescence obtained by sonoluminescence (acoustic luminescence phenomenon) generated when ultrasonic waves are applied, and is luminescent for anti-counterfeit medium having high visibility. Is the body.

  Regarding the sonoluminescence (acoustic luminescence phenomenon), when a liquid is irradiated with ultrasonic waves, bubbles (cavitation) are generated inside the liquid, and when the generated bubbles are broken, heat, pressure, and the like are locally generated. For this reason, the water vapor in the bubbles causes a chemical reaction to generate OH radicals, hydrogen peroxide, and the like. It is known that radicals such as OH radicals emit light having a wavelength range of 300 to 600 nm when they transition from an excited state to a ground state or recombine (for example, “Sonochemistry”, KS Suslick, Science, Vol. 247, pages 1439-1445, 1990).

  Luminescence can be obtained by causing a chemical reaction with the generated hydrogen peroxide, singlet oxygen, etc. and dissolving a chemiluminescent substance or bioluminescent substance that emits light in a solution in advance. The light in this case emits light having a specific wavelength depending on the luminescent substance, and this light emission is also generally called sonoluminescence (acoustic light emission phenomenon).

  In the present invention, the latter mechanism is used in order to obtain light emission with high visibility, and in order to obtain light emission with high visibility by this mechanism, cavitation is efficiently generated and a high light emission amount is obtained. In order to obtain it, it is necessary to select or combine luminescent substances.

  There are several states that can cause this cavitation efficiently, one of which is to lower the threshold for cavitation generation, and the other is the intensity of ultrasonic waves.

  The threshold for the occurrence of cavitation is known to depend on the air content in the aqueous solution and the hydrostatic pressure, and needs to be optimized depending on the solution used and the enclosure. In particular, regarding the air content, since noble gases other than air act on this light emission, argon gas or the like may be used.

  On the other hand, the intensity of the ultrasonic wave includes a change in cavitation state depending on the frequency. In general, the cavitation threshold is lower at lower frequencies. For example, ultrasonic cleaners and the like use 20 to 40 kilohertz, and sonoluminescence (acoustic luminescence phenomenon) that can be visually confirmed even at such a frequency has been confirmed.

  The acoustic luminescent material is not particularly limited as the chemiluminescent material or bioluminescent material as described below, and known materials can be used, for example, luminol, isoluminol, N-ethylisoluminol, N -(4-aminobutyl) -N-ethylisoluminol hemisuccimide, N- (6-aminohexyl) -N-ethylisoluminol, lophine, lucigenin, acridinium salt, peroxalate, xanthene dye, firefly luciferin , Sea firefly luciferin and the like. Any of these illuminants can be selected and adopted. As described above, it emits light by reaction with hydrogen peroxide or singlet oxygen generated by cavitation, and a high light emission amount can be obtained. In addition, luminols and sea firefly luciferins are preferable in view of the fact that the sound luminescence is stable over time and that repeated sound luminescence is obtained.

Further, the positive catalyst and photosensitizer for light emission constituting the acoustic light emitter of the present invention will be described in more detail. As the positive catalyst for the light emission, for example, in the light emission mechanism of luminol, K ₂ S ₂ O ₈ K, NaClO, FeII salt, MnII salt, NH ₃ —Cu ⁺⁺ , K ₃ Fe (CN) ₆ , cobalt (III) Ammine complex salts, hemoglobin, hemin and the like can be mentioned. In addition, the dependency of the amount of emitted light by pH is known. Thus, it is necessary to select an effective catalyst depending on the light emitting mechanism of the light emitting material.

  As the photosensitizer, any photosensitizer can be used as long as it can generate active oxygen by sonoluminescence, and specifically, various porphyrin derivatives, water-soluble substances can be used. In addition to fullerene complexed with polymer, acridine, rose bengal, acridine orange, berberine sulfate, fluorescein, tetracycline, eosin Y, NTS, psoralen, bonorin, pheoformimide, chlorin, which are conventionally used as photosensitizers Various photosensitizers such as e6, mesotetra (hydroxyphenyl) chlorine, phthalocyanine, purpurine, 5-aminolaebric acid (ALA), HAT-DO1 (magnesium chlorine-chlorine dimer) can be used. Examples of porphyrin derivatives include porfimer sodium (photofurin (registered trademark)), hematoporphyrin, metalloporphyrin, tetraphenylporphyrin sulfate, protoporphyrin, uroporphyrin, coproporphyrin, dihematoporphyrin ether (DHE), benzoporphyrin (BPS) ATX-70 (gallium-profylline complex), ATX-S10 (four-formyloximethylidene-3-hydroxy-2-vinyl-deuterioporphynyl (IX) -6-7-bisasparticacid) and the like. Among various porphyrin derivatives, porfimer sodium can be particularly preferably used.

Hereinafter, the phosphor, phosphor and phosphorescent material constituting the acoustic light emitter will be described in more detail. This phosphor emits light in the vicinity of the visible range by external stimulation (excitation). In general, the phosphor and the phosphor are sometimes collectively referred to as a phosphor, but when distinguishing between the phosphor and the phosphor, a phosphor having a relatively long afterglow is often referred to as a phosphor. . In particular, in many cases, the phosphor generally refers to a phosphor whose afterglow lasts longer than the degree perceived by the eye after the excitation is stopped (approximately 0.1 sec). In addition, the phosphorescent material generally has a long afterglow that lasts for a long time. The following are mentioned as an example of a fluorescent substance. Ultraviolet-emitting fluorescent agents are those that are excited by ultraviolet rays and have spectral peaks in the blue, green, red, etc. wavelength range when returning to lower energy levels. After a trace amount of metal (copper, silver, manganese, bismuth, lead, etc.) is added as an activator in order to enhance the emission of light to a high-purity phosphor of sulfide, it can be obtained by high-temperature firing. These can adjust the hue, brightness, and degree of color attenuation by the combination of the base crystal and the activator. In addition, there are infrared emitting fluorescent agents, which are excited by infrared rays and emit light in the visible wavelength range (referred to as infrared visible conversion fluorescent agents), and excited by infrared rays. Some emit light in a longer wavelength range. The former infrared-visible conversion fluorescent agent is a phosphor having a very special excitation mechanism, and excites visible light emission by using a plurality of low-energy infrared photons. There are two types of light emission mechanisms of these (the infrared visible conversion fluorescent agent and those that emit light in a longer wavelength region when excited by infrared rays), one of which is based on multi-stage excitation of activator ions, On the other hand, a plurality of resonance energy transmissions from the sensitizer enable high excitation, respectively. The former type is observed in many host crystals that use Er ³⁺ or Ho ³⁺ as an activator, and the latter type absorbs infrared rays by the sensitizer Yb ³⁺ and emits light by multistage energy transfer. Of Er ³⁺ , Tm ³⁺ , Ho ³⁺ , etc. are excited to a high level. In addition, a semiconducting substance having a high electron mobility such as sulfide (ZnS, CdS) or oxysulfide (Y ₂ O ₂ S) as a base crystal and having photoconductivity is used as an electron beam-excited phosphor. It is possible to use.

  In the present invention, the emission intensity and emission time can be increased by adding one or more phosphors, phosphors, and phosphors that are excited by light waves emitted by the acoustic emission phenomenon to emit light in the vicinity of the visible region. It is possible to obtain a light emitter that is more difficult to counterfeit by improving light emission, having light emission in a specific wavelength region (specific color), or having a waveform of a specific emission spectrum. These phosphors, phosphors and phosphors may be added to the solution inside the phosphor or mixed, contained or coated on the surface of the material constituting the sealed container.

Hereinafter, the acoustic light emitter ink using the acoustic light emitter will be described in more detail. The ink for dispersing the acoustic luminescent material may be either aqueous or non-aqueous, and is not particularly limited.

  Specific examples of the binder resin for printing include natural resins such as albumin, gelatin, casein, starch, gum arabic, and sodium alginate, cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose, polyamide, polyacrylamide, and polyhydroxyethyl methacrylate. , Polyphenylacetoacetal, Polyethyleneimine, Polyvinylpyrrolidone, Polyvinylpyridium halide, Melamine resin, Polyurethane, Polyvinyl alcohol and its derivatives, Polyester, Polyacrylic acid soda, Acrylic acid ester copolymer, Synthetic resin, Dimethylamine / Epichlorohydrin Polycondensate, acrylamide / diallylamine copolymer, polyvinylamine copolymer, dicyandiamide, dimethyl Compound mainly containing diallyl ammonium chloride or ink using a cationic resin, such as a mixture of two or more thereof can be mentioned.

In addition, there are electron beam curable inks and ultraviolet curable inks, and anionic resins such as rosin-modified maleic acid having anionic groups such as sulfonic acid groups, carboxyl groups, sulfate ester groups, and phosphate ester groups are also required. Can be used as required. Examples of the photopolymerizable monomer of these inks include unsaturated carboxylic acids such as acrylic acid and methacrylic acid or esters thereof such as alkyl-, cycloalkyl-, halogenated alkyl-, alkoxyalkyl-, hydroxyalkyl-, aminoalkyl- Tetrahydrofurfuryl-, allyl-, glycidyl-, benzyl-, phenoxy-acrylate and methacrylate, alkylene glycol, polyoxyalkylene glycol mono- or diacrylate and methacrylate, trimethylolpropane triacrylate and methacrylate, pentaerythritol tetraacrylate and Acrylamide, methacrylamide, or derivatives thereof such as methacrylates, such as alkyls mono- or di-substituted with alkyl or hydroxyalkyl groups. Ruamido and methacrylamide, diacetone acrylamide and methacrylamide, N, etc. N'- alkylene-bis acrylamide and methacrylamide, allyl compounds such as allyl alcohol, allyl isocyanate, diallyl phthalate, and the like triallyl isocyanurate. Further, in the case of applications where curing shrinkage is an obstacle, for example, isobornyl acrylate or methacrylate, norbornyl acrylate or methacrylate, dicyclopentenoxyethyl acrylate or methacrylate, dicyclopentenoxypropyl acrylate or methacrylate, Dicyclopentenyl cinnamate, dicyclopentenoxyethyl cinnamate, such as acrylic ester or methacrylic ester of diethylene glycol dicyclopentenyl monoether, acrylic ester or methacrylic ester of polyoxyethylene or polypropylene glycol dicyclopentenyl monoether 3,9-bis (1,1-bismethyl-2-oxyethyl), such as dicyclopentenoxyethyl monofumarate or difumarate ) -Spiro [5,5] undecane, 3,9-bis (1,1-bismethyl-2-oxyethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-bis Mono-, diacrylates such as (2-oxyethyl) -spiro [5,5] undecane, 3,9-bis (2-oxyethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane or Mono-, dimethacrylate, or mono-, diacrylate, or mono-, dimethacrylate, or methyl ether of the monoacrylate or methacrylate, 1-azabicyclo [2 , 2,2] -3-octenyl acrylate or methacrylate, bicyclo [2,2,1] -5 Use a photopolymerizable monomer such as heptene-2,3-dicarboxyl monoallyl ester such as dicyclopentadienyl acrylate or methacrylate, dicyclopentadienyloxyethyl acrylate or methacrylate, dihydrodicyclopentadienyl acrylate or methacrylate be able to. These photopolymerizable monomers may be used alone or in combination of two or more. Examples of the acrylic photopolymerizable oligomer include epoxy resin acrylic acid esters such as diglycidyl ether diacrylate of bisphenol A, reaction products of epoxy resin, acrylic acid and methyltetrahydrophthalic anhydride, epoxy resin and 2- Reaction product with hydroxyethyl acrylate, ring-opening copolymerization ester of glycidyl diacrylate and phthalic anhydride, ester of methacrylic acid dimer and polyol, polyester obtained from acrylic acid, phthalic anhydride and propylene oxide, polyvinyl Unsaturated polyester-based prepolymers such as reaction products of alcohol and N-methylolacrylamide, reaction products of polyethylene glycol, maleic anhydride and glycidyl methacrylate, and anhydrous polyvinyl alcohol Polyester obtained by esterification with succinic acid followed by addition of glycidyl methacrylate and the like, a reaction product of methyl vinyl ether-maleic anhydride copolymer and 2-hydroxyethyl acrylate, or glycidyl Polyacrylic acid or maleic acid copolymer prepolymers such as those reacted with methacrylate, etc. In addition, polyoxyalkylene segments and / or saturated polyester segments are connected via urethane bonds, and acryloyl groups or methacryloyl groups are connected to both ends. Examples thereof include a urethane prepolymer having a group. These acrylic photopolymerizable oligomers suitably have a weight average molecular weight in the range of about 2,000 to 30,000.

  The photopolymerization initiator for the electron beam curable ink and ultraviolet curable ink may be a conventionally known photopolymerization initiator such as 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1- Phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1-bis (2,6-dimethoxybenzoyl) -2,4,4 -Trimethyl-pentylphosphine oxide-bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and the like. These photopolymerization initiators may be used alone or in combination of two or more. The content is usually preferably selected in the range of 5 to 15 parts by mass per 100 parts by mass of the vehicle. The dispersion amount of the acoustic illuminant is not particularly limited as long as it is a dispersion amount that can be stably maintained. The dispersion method and apparatus are not particularly limited, and known ones can be used.

In the acoustic luminescent ink of the present invention, known fillers such as silica, alumina, mica, carbon powder, pigments, dyes, polymerization inhibitors, thickeners, thixotropic agents, precipitation inhibitors, as long as the effects of the present invention are not impaired. Antioxidants, dispersants, surfactants and the like can be added.
The luminescent ink of the present invention is, for example, brush coating, roll coating method, kiss coat, wheeler coat, spray method, curtain coating method, dipping method, electrostatic coating method, gravure coater, dilitho coater, flexo, air knife coater, bar coater. Apply to a predetermined part or all of the surface of the object by coating means such as letterpress printing, intaglio printing, silk screen printing, etc., and dry and cure as necessary to form a coating film in close contact with the object The acoustic emission ink thus obtained is printed on a security medium such as a security medium, thereby providing an anti-counterfeit medium that can be easily distinguished visually in the dark. Therefore, it is possible to establish a true / false determination technique using acoustic emission. Further, by combining with existing authenticity determination means, it is possible to provide an anti-counterfeit medium having a further anti-counterfeit effect.

The present invention will be described below with reference to experimental examples, but the present invention is not limited to these experimental examples <Experimental Example 1>
A 10% aqueous sodium hydroxide solution containing 0.1% luminol is prepared, and the aqueous solution is 5 ×.
An acoustic illuminant was obtained by enclosing in a 10 × 45 mm ³ glass cell.

  As a result of irradiating the acoustic illuminant with ultrasonic waves in an ultrasonic cleaning machine of 40 kilohertz, light emission due to acoustic luminescence could be visually confirmed in a dark place.

It is a schematic diagram which shows an example of the acoustic light-emitting body of this invention. It is a schematic diagram which shows an example of the acoustic luminescent ink which made the acoustic luminescent material of this invention into ink. An example of an anti-counterfeit medium using an acoustic illuminant according to the present invention will be described. (A) is a plan view thereof, and (b) is a cross-sectional view showing a BB plane of (a). is there.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Acoustic luminescent body 5 ... Acoustic luminescent ink 10 ... Anti-counterfeit medium 11 ... Solution containing luminescent substance which exhibits acoustic luminescence reaction 12 ... Microcapsule 14 ... Binder for printing ink 20 ... Printed material 22 ... Ink layer made of acoustic luminescent ink

Claims (4)

  A solution containing a chemiluminescent substance or a bioluminescent substance exhibiting an acoustic luminescence reaction, which is an acoustic luminescent material enclosed in a microcapsule, and is a positive catalyst for issuing the chemiluminescent substance and the bioluminescent substance in the solution, or An acoustic luminescent material, wherein a photosensitizer that generates active oxygen by acoustic emission is added.   2. The acoustic illuminant according to claim 1, wherein a phosphor that emits light by being excited by a light wave of acoustic luminescence is added to the solution.   The light emitting material of at least 1 sort (s) or 2 or more types of the fluorescent substance, phosphorescent body, and phosphorescent substance which light-emits with an ultraviolet-ray or infrared rays is added to the said solution. Acoustic illuminant.   An anti-counterfeit medium characterized by being printed on a specific portion of a printing medium using the acoustic luminescent ink in which the acoustic luminescent material according to any one of claims 1 to 3 is dispersed in a printing ink binder.

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