JP2006276722A - Material for detecting unauthorized heating history - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a simple material for detecting unauthorized heating history with high production efficiency, which can accurately detect unauthorized heating of itself and indicates it as an obvious change in the tone without degrading functions of a label showing stripping history. <P>SOLUTION: The material for detecting unauthorized heating history detects unauthorized heating history on a heat-softening adhesive layer applied on a label showing stripping history, and has a temperature-sensitive ink layer applied on a substrate. The temperature-sensitive ink layer contains a granular or powdery hot-melt substance having a melting point equal to or lower than the heat-softening temperature of the adhesive layer, a granular or powdery dye having diffusing property by dispersion or dissolution into the molten substance, and an ink vehicle capable of diffusing the molten substance. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a fraudulent heating history detection material that detects improper heating of a label that displays a peeling history and indicates a change in color tone.

  Confidential documents sealed in envelopes have been illegally opened and have not been viewed or altered, or products such as packaged software recording media or electronic devices have been illegally unwound and duplicated or altered In order to confirm that there is not, a peeling history display label is affixed to a seal such as an envelope.

  Known peeling history display labels include those in which a fragile label base material is broken when it is peeled off and a peeling history is displayed, and holograms that cannot be duplicated.

  Further, Patent Document 1 discloses a peeling history display label in which a release agent coating layer is partially formed on one side of a film substrate, and a vapor deposition film and an adhesive coating film are entirely formed covering the release coating layer. ing. When this label attached to the envelope is peeled off through the adhesive coating film, a partial release agent coating layer remains unevenly on the envelope, and a peeling history is displayed.

  When these peeling history display labels are improperly heated, the pressure sensitive adhesive softens and reduces its adhesive strength, so that it can be peeled cleanly without leaving a peeling history. When this is applied again, it is mistaken that it has not yet been peeled off.

  Patent Document 2 discloses a label having a brittle substrate and an adhesive layer containing a thermal foaming agent. When the label is peeled off, the brittle substrate tears unevenly and displays a history of peeling. On the other hand, when heated, the label displays a history of incorrect heating due to colorless bubbles generated from the thermal foaming agent.

  A fraudulent heating history detection material that can detect fraudulent heating accurately with a simpler structure than conventional labels, can be displayed with clear color change, and can handle various labels with different peel history display principles. It was desired.

Japanese Utility Model Publication No.59-001077 JP 2000-293108 A

  The present invention was made in order to solve the above-mentioned problems, and without deteriorating the function of the peeling history display label, it is possible to accurately detect improper heating on it and indicate it with a clear change in color tone, An object of the present invention is to provide an unauthorized heating history detection material that is simple and has high production efficiency.

  The unauthorized heating history detection material according to claim 1, which has been made to achieve the above object, detects an unauthorized heating history to the heat-softening adhesive layer attached to the peeling history display label. A granular or powdery hot-melt material having a melting point equal to or lower than the heat softening temperature of the adhesive layer, and a granular or powdery pigment having diffusibility by dispersion or dissolution in the hot-melted material A temperature-sensitive ink layer containing an ink vehicle having a diffusibility of the heat-melted substance is coated on the substrate.

  When the fraudulent heating history detecting material is heated, the hot melted material diffuses and irreversibly changes its color clearly. Even if it is cooled, it remains discolored for a long period of time.

  The unauthorized heating history detection material according to claim 2 is characterized in that the substrate has a heat non-peelable adhesive layer.

  The unauthorized heating history detecting material may be bonded to the front side surface or the back side surface of the peeling history display label through a heat non-peeling adhesive layer. Further, the unauthorized heating history detection material may be bonded to the envelope of the envelope via a heat non-peelable adhesive layer, and a peeling history display label may be attached to cover the unauthorized heating history detection material. The base material of the unauthorized heating history detection material may also serve as a peeling history display label base material.

  Since the heat non-peelable adhesive layer is present, it is not possible to peel only the detection material from the peel history display label or the envelope of the envelope. For this reason, the unauthorized heating history cannot be hidden after being heated illegally.

  Similarly, the peeling history display label according to claim 3 is a peeling history display label base material with at least one of a weakened portion that is broken by peeling or a colored layer that is irreversibly transferred, a hologram, a fluorescent ink layer, and an identification symbol. The unauthorized heating history detection material according to claim 1 is attached.

  By attaching a fraudulent heating history detection material while avoiding such a flaking history display location of the label, it is possible to accurately detect fraudulent heating on the label without impairing the flaking history display function.

  For example, the peeling history display label is obtained by adhering an unauthorized heating history detection material in an arbitrary shape, for example, a disc shape having a diameter of 0.1 mm or more, to a peeling history display label substrate. It is preferable that the fraudulent heating history detecting material is adhered to the vicinity of the periphery of the peeling history display label base material which starts to peel off the peeling history display label.

  The unauthorized heating history detection material discolors irreversibly by heating and can be stored for a long time while being discolored, so that it can be left as evidence of unauthorized heating history on the peeling history display label.

  Further, the unauthorized heating history detection material can be used by being freely bonded to any position of various peeling history display labels having different principles and structures, and therefore has versatility.

  Even if the peeling history display label to which the fraudulent heating history detection material is bonded is peeled off at room temperature, the peeling history is displayed, and even if heated and peeled off, the heating history is displayed. Thereby, since any peeling of a peeling history display label can be detected, the presence or absence of unauthorized opening can be confirmed accurately and simply visually.

  Therefore, the peeling history display label provided with the unauthorized heating history detection material can improve the security of a sealed confidential document and the like, and is useful for preventing unauthorized opening.

  Examples of the present invention will be described in detail below, but the scope of the present invention is not limited to these examples. The unauthorized heating history detection material and the peeling history display label attached thereto are produced as follows.

  First, a granular or powdery hot-melt material having a melting point equal to or lower than the heat-softening temperature of the heat-softening pressure-sensitive adhesive layer attached to the peeling history display label, and particles that are diffusible due to dispersion or dissolution in the heat-melted material. Alternatively, a temperature-sensitive ink is prepared by kneading a powdered dye, a thermally diffusible ink vehicle of the substance, and a solvent. On the back side surface of the base material for the unauthorized heating history detection material, an adhesive layer to be adhered to the peeling history display label is attached. It prints with a temperature-sensitive ink on the surface side of this base material. This base material is cut into an appropriate shape and size as necessary to obtain an unauthorized heating history detection material.

  Next, a thermosoftening adhesive layer is attached to the back side surface of the peeling history display label base material having a fragile portion such as a perforation. When the unauthorized heating history detection material is adhered to the vicinity of the periphery on the front side of the peeling history display label substrate, a peeling history display label is obtained.

  The heat-softening pressure-sensitive adhesive layer of the peel history display label contains, for example, a thermoplastic resin as the pressure-sensitive adhesive, and the heat softening temperature is preferably 70 to 150 ° C.

  The heat-meltable substance is a component that determines the discoloration temperature, has a melting point that is not higher than the heat softening temperature of the adhesive layer, and is heated and melted when heated above the melting point to change from granular or powder to liquid. It is a substance. This hot-melt material preferably has a diameter of 0.01 μm to 5 mm.

  The hot-melt material is preferably a fatty acid derivative, alcohol derivative, ether derivative, aldehyde derivative, ketone derivative, amine derivative, amide derivative, nitrile derivative, hydrocarbon derivative, thiol derivative, or sulfide derivative.

More specifically, the hot-melt material is myristic acid, palmitic acid, adipic acid, octanoic acid, tricosanoic acid, tetratriacontanoic acid, 2,3-dimethylnonanoic acid, 23-methyltetracosanoic acid, 2-hexenoic acid. , Brassic acid, 2-methyl-2-dodecenoic acid, β-eleostearic acid, behenolic acid, cis-9,10-methyleneoctadecanoic acid, sorghumulinic acid, 3,3′-thiodipropionic acid-n- Dodecyl, trilaurin, palmitic acid anilide, stearic acid amide, zinc stearate, salicylic acid anilide, N-acetyl-L-glutamic acid, caproic acid-β-naphthylamide, enanthic acid phenylhydrazide, arachidic acid-p-chlorophenacyl formate, cholesteryl formate, 1-aceto-2,3-distearin, thiolauric acid-n Examples include pentadecyl, stearic acid chloride, palmitic anhydride, stearic acid-acetic anhydride, succinic acid, benzylammonium sebacate, 2-bromovaleric acid, α-sulfostearic acid methyl sodium salt, and 2-fluoroarachidic acid. Fatty acid derivatives obtained;
Octadecyl alcohol, cholesterol, D-mannitol, galactitol, heptatriacontanol, hexadecan-2-ol, 1-trans-2-octadecenol, β-eleostearyl alcohol, cycloeicosanol, d (+) cellobiose , P, p′-biphenol, riboflavin, 4-chloro-2-methylphenol, alcohol derivatives such as 2-bromo-1-indanol;
Ether derivatives such as dihexadecyl ether, dioctadecyl ether, cytidine, adenosine, sodium phenoxyacetate, 1,3-bis (4-hydroxyphenoxy) benzene, aluminum triethoxide;
Aldehyde derivatives such as stearaldehyde, paralaurylaldehyde, parasteaaldehyde, naphthaldehyde, p-chlorobenzaldehyde, phthalaldehyde, 4-nitrobenzaldehyde;
Ketone derivatives such as stearone, docosan-2-one, phenylheptadecyl ketone, cyclononadecane, vinyl heptadecyl ketone, 4,4-bisdimethylaminobenzophenone, bis (2,4-pentanedionite) calcium, 1-chloroanthraquinone ;
Tricosylamine, dioctadecylamine, N, N-dimethyloctylamine, heptadecamethyleneimine, naphthylamine, ethyl p-aminobenzoate, o-trithiourea, sulfamethazine, guanidine nitrate, p-chloroaniline, propylamine hydrochloride Amine derivatives obtained;
Amide derivatives such as hexylamide, octacosylamide, N-methyldodecylamide, N-methylheptacosylamide, α-cyanoacetamide, salicylamide, dicyandiamide, 2-nitrobenzamide, N-bromoacetamide;
Nitrile derivatives such as pentadecanenitrile, margaronitrile, 2-naphthonitrile, o-nitrophenoxyacetic acid, 3-bromobenzonitrile, 3-cyanopyridine, 4-cyanophenol;
Hexadecane, 1-nonatriacontene, trans-n-2-octadecene, hexatriacontylbenzene, 2-methylnaphthalene, bicene, cyanuric chloride, 1-fluorononadecane, 1-chloroeicosane, 1-iodopentadecane, 1 -Hydrocarbon derivatives such as bromoheptadecane, 1,2,4,5-tetrakis (bromomethyl) benzene;
Thiol derivatives such as pentadecanethiol, eicosanethiol, 2-naphthalenethiol, 2-mercaptoethyl ether, 2-nitrobenzenesulfenyl chloride;
Sulfide derivatives such as 1,3-diatine, 2,11-dithia [3,3] paracyclophane, bis (4-hydroxy-3-methylphenyl) sulfide, 4,4-dipyridyl sulfide, 4-methylmercaptophenol Is used. These may be used alone or in combination.

  The heat-sensitive ink preferably contains 10 to 70% by weight of a heat-meltable substance. If it is less than 10% by weight, the change in color tone is unclear. On the other hand, if it is more than 70% by weight, the fixing force is reduced and application to a substrate or printing cannot be performed.

  It is preferable to select a hot-melt material having a melting point in the vicinity of the range so that the color change temperature of the unauthorized heating history detection material is 40 to 140 ° C. When the heat softening temperature of the heat softening pressure-sensitive adhesive layer is 70 to 150 ° C, it is more preferable that the heat melting material is selected so that the discoloration temperature of the unauthorized heating history detection material is 40 to 70 ° C.

  The coloring matter is contained in the temperature-sensitive ink in the form of particles or powder, and diffuses by being dispersed or dissolved in a hot-melt material. Further, the pigment may be one in which the particle surface or powder surface of the pigment is wetted by the heat-melted substance. Examples of pigments include direct dyes, acid dyes, basic dyes, dispersible dyes, reactive dyes, oil-soluble dyes, vat dyes, mordant dyes, azoic dyes, dyes exemplified by sulfur dyes, organic pigments and inorganic pigments. A wide range of pigments can be used. These pigments may be used as a mixture of two or more.

  This dye preferably has a diameter of 0.001 μm to 5 mm. In the temperature-sensitive ink, the pigment is preferably contained in a ratio of 0.001 to 100 parts by weight with respect to 100 parts by weight of the hot-melt material.

Specifically, the dyes are CI Direct Orange 39, CI Direct Brown 2, CI Acid Yellow 73, CI Acid Red 52, CI Acid Red. Violet 49, CI Basic Yellow 11, CI Basic Red 38, Cation Red SGLH, Cation Red GTLH, Cation Red 4GH, Cation Red 7BNH (manufactured by Hodogaya Chemical Co., Ltd.), C.I Mordant Red 7, C.I. Mordant Black 38, C.I. Azoic Blue 9, C.I. Azoic Diazo Component 11, C.I. Sulfur Black 1, C.I. Sulfur Red 5, CI Bat Green 9, CI Bat Violet 2, CI Disperse Blue 3, Discharge Red BB (Mitsui Toatsu Dye) CI Reactive Blue 19, CI Reactive Blue 15, Remazol Br Blue R-KN (Mitsubishi), CI Solvent Orange 2, CI Solvent Dyes including Blue 25, CI Acid Green 1, Flavianic Azido Disodium Salt, Primulin Sulfonic Acid;
4,10-dibromoanthanthrone, dibenzoanthrone, cochineal lake, CI pigment yellow 1, CI pigment red 38, CI pigment blue 15, CI pigment red 209 CI Pigment Yellow 109, CI Pigment Green 10, CI Basic Red 1-Lake, CI Acid Red 87-Lake, CI Pigment Blue 6, CI Pigment Red 179, CI Pigment Red 88, Alizarin Lake, CI Pigment Violet 23, CI Pigment Green 8, C.I. Pigment Red 53, C.I. Pigment Yellow 23-Lake, Tannic Acid / Gallic Acid / Iron Lake, CI Pigment Yellow 34, CI Pigment Yellow 35 Organic pigments that;
Inorganic pigments such as kaolin, bitumen, strontium sulfate, titanium dioxide, aluminum hydroxide, calcium silicate, and carbon black are used. The C.I. is an abbreviation for color index.

  The ink vehicle does not dissolve and diffuse the hot-melt substance and the dye at room temperature, but can diffuse the hot-melt substance in which the dye is dispersed or dissolved by hot melting. The ink vehicle is, for example, phenol resin; nylon; ethyl cellulose; hydroxy cellulose; polyvinyl alcohol; carboxymethyl cellulose; silica, epoxy, amino, urethane, urethane acrylate, epoxy acrylate, ether acrylate, alkyd, vinyl acetal. , Acrylic or acrylic polyester ultraviolet curable resin. Commercially available ink vehicles, PAS800 medium (trade name, manufactured by Jujo Kako Co., Ltd.), High Set Matt Medium (trade name, manufactured by Mino Group), Dicure AK (manufactured by Dainippon Ink & Chemicals, Inc.), FDS New (Toyo Ink) Manufacture Co., Ltd.), Reicure TU4400 (manufactured by Jujo Chemical Co., Ltd.), UVSPA Clear (manufactured by Teikoku Ink Manufacturing Co., Ltd.), and UV8418 (manufactured by Seiko Advance Co., Ltd.).

  The temperature-sensitive ink may contain a solvent that does not dissolve the hot-melt material and the dye but dissolves the ink vehicle. Such solvents include, for example, water, ethanol, butanol, ethyl acetate, isoamyl acetate, methyl ethyl ketone, methyl isobutyl ketone, xylene, diethylbenzene, toluene, butyl cellosolve, ethyl cellosolve, mineral spirit, and UV curable resin. The monomer of the photosensitive resin is mentioned.

  Furthermore, the temperature-sensitive ink may contain a dispersant exemplified by talc, magnesium carbonate, and silica so that the color change can be made clear by dispersing the pigment. For temperature-sensitive inks, direct dyes, acid dyes, basic dyes, disperse dyes, reactive dyes, oil-soluble dyes, architectural dyes, mordant dyes, azoic dyes, sulfur dyes are exemplified to amplify color change. In addition, any of organic pigments and inorganic pigments may be included, and an auxiliary colorant exhibiting a color tone and a contrasting color of the coloring matter may be included. Further, the temperature-sensitive ink may contain a wax or a surfactant that adjusts the fluidity and drying property of the ink.

  The base material is paper exemplified by plain paper, Japanese paper, Kent paper; synthetic paper; wood slab exemplified by straw; plastic exemplified by polypropylene, polyethylene terephthalate, acrylonitrile-butadiene-styrene resin, polycarbonate, acrylic resin Slabs are mentioned.

  The substrate preferably has an adhesive layer on the back surface, and may be a card-like, sheet-like, or rod-like label.

  The thermal ink is printed on the substrate by, for example, flexographic printing, screen printing, offset printing, gravure printing, coater printing, or brush coating.

  The ink layer formed by printing this thermal ink may be covered with a transparent or translucent laminate material. Laminating materials include, for example, polypropylene, polyethylene terephthalate, acrylonitrile-butadiene-styrene resin, polycarbonate, acrylic film exemplified by plastic film; acrylic resin, nylon, phenol resin, urethane resin, silica exemplified laminate printing Examples include medium.

  When an ultraviolet curable resin is used as the ink vehicle, an ink layer having equivalent environmental resistance can be obtained without being covered with a laminate material.

  The peeling history display label to which the unauthorized heating history detection material is bonded is used as follows.

  The peeling history display label is affixed to the sealed envelope of the sealed envelope through the heat softening adhesive layer on the back side surface.

  At this time, the improper heating history detecting material has a granular or powdery hot-melt substance and a granular or powdery dye in a mixed state, and the dye is concealed by the hot-melt substance.

  If the peeling history display label is heated improperly, the thermosoftening adhesive layer is softened. The peeling history display label can be peeled off cleanly without damaging the fragile portion.

  The fraudulent heating history detection material is also heated at the same time, and the hot-melt material is heated to the melting point or higher and melted. Dye is dispersed or dissolved in a hot-melt material that has been melted and diffused, and the granular or powdery surface of the pigment is wetted by this material that has been melted hot. The peeling history display label is irreversibly discolored and displayed while being adhered to the history display label. Since the diffusion of the dye into the heat-melting substance is irreversible, the temperature of the fraudulent heating history detection material is lowered after the color change and does not return to the color tone before the color change even if the heat-melting substance is solidified.

  Even if the peeling history display label is affixed to the envelope seal again, it is possible to detect improper heating.

  On the other hand, if the peeling history display label is peeled off at room temperature, it can be detected that the fragile portion is torn unevenly and opened illegally.

  Example 1 shows an example in which a fraudulent heating history detection material to which the present invention is applied using a temperature-sensitive ink is prototyped and a peeling history display label is prototyped using the material. An example of a peeling history display label to which the present invention is not applied is shown in Comparative Example 1.

Example 1
A composition of 100 parts by weight of behenic acid, 20 parts by weight of ethyl cellulose, 200 parts by weight of xylene and 1 part by weight of CI Reactive Blue 19 was kneaded for 3 days to prepare a temperature-sensitive ink. A temperature-sensitive ink was printed on the front side of a high-quality paper with a tack on the back side, and a seal-like fraudulent heating history detection material having a diameter of several mm was produced.

  Use a tamper-proof peel proof label (trade name, manufactured by Nihon Brady Co., Ltd.) as a base material, and leave this improper heating history detection material on it. Obtained.

(Comparative Example 1)
A tamper-proof peel proof label (manufactured by Nippon Brady Co., Ltd .; trade name) was used as a test piece for the peel history display label of Comparative Example 1.

(Evaluation test of peel history display label)
The test piece of the peeling history display label of Example 1 was attached to the seals of the two envelopes. When the peel history display label of one envelope was peeled together with the substrate at room temperature and the envelope of the envelope was opened, the mark of the peel history display label remained on the envelope, and the peel history was displayed. When the other envelope was heated to 90 ° C with a dryer, the release history display label was peeled off together with the base material, and the envelope of the envelope was opened, the base material of the release history display label was not damaged, but it was affixed to it The unauthorized heating history detection material turned from white to blue, and the history of unauthorized heating was detected and displayed clearly.

  On the other hand, the test piece of the peeling history display label of Comparative Example 1 was attached to the seals of the two envelopes. Similar to the above, when the envelope seal was opened at room temperature, the peel history display label remained on the envelope, and the peel history was displayed. When the other envelope was heated in the same manner as described above and the envelope of the envelope was opened, the base material of the peel history display label was not damaged, and the history of incorrect heating was not displayed. When it was affixed again, it had the same appearance as the original, and it was mistaken as if neither the peeling history nor the incorrect heating history had passed.

  The unauthorized heating history detection material of the present invention can be attached to various peeling history display labels and used for confirmation of unauthorized opening and prevention thereof. By appropriately selecting the hot-melt material, the color change temperature can be freely set from a low temperature to a high temperature.

  This unauthorized heating history detecting material has an irreversible change in color tone, and can be stored for a long time without fading in the color tone after the color change.

  The peeling history display label of the present invention is used to detect an unauthorized opening of a sealed confidential document or a product such as a packaged electronic medium.

Claims (3)

  A material for detecting the history of unauthorized heating to the heat-softening adhesive layer attached to the peeling history display label, a granular or powdery heat-meltable substance having a melting point equal to or lower than the heat-softening temperature of the adhesive layer; A temperature-sensitive ink layer containing a diffusible granular or powdery dye by dispersion or dissolution in the hot-melted material and a diffusible ink vehicle of the hot-melted material is formed on the substrate. An unauthorized heating history detection material characterized by being applied.   The unauthorized heating history detection material according to claim 1, wherein the base material has a heat non-peelable adhesive layer.   At least one of a weakened portion that breaks when peeled off or a irreversibly colored layer, a hologram, a fluorescent ink layer, and an identification symbol on the peeling history display label substrate, and the unauthorized heating history detecting material according to claim 1 Is a peeling history display label characterized by being attached.