CN114913763B - Color-changing anti-counterfeiting label - Google Patents
Color-changing anti-counterfeiting label Download PDFInfo
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- CN114913763B CN114913763B CN202210627569.5A CN202210627569A CN114913763B CN 114913763 B CN114913763 B CN 114913763B CN 202210627569 A CN202210627569 A CN 202210627569A CN 114913763 B CN114913763 B CN 114913763B
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- Prior art keywords
- color
- changing
- layer
- substrate layer
- organic solvent
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Links
- 239000000463 material Substances 0.000 claims abstract description 94
- 239000003495 polar organic solvent Substances 0.000 claims abstract description 70
- 239000000758 substrate Substances 0.000 claims abstract description 42
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 31
- 239000011630 iodine Substances 0.000 claims abstract description 31
- 239000000126 substance Substances 0.000 claims abstract description 30
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 17
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims abstract description 11
- 238000007789 sealing Methods 0.000 claims abstract description 5
- 239000010410 layer Substances 0.000 claims description 149
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 15
- 229930195729 fatty acid Natural products 0.000 claims description 15
- 239000000194 fatty acid Substances 0.000 claims description 15
- 239000012790 adhesive layer Substances 0.000 claims description 12
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 8
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 claims description 8
- -1 fatty acid ester Chemical class 0.000 claims description 8
- 150000004665 fatty acids Chemical class 0.000 claims description 8
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 7
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 claims description 6
- 235000021314 Palmitic acid Nutrition 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- MVLVMROFTAUDAG-UHFFFAOYSA-N ethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC MVLVMROFTAUDAG-UHFFFAOYSA-N 0.000 claims description 6
- 235000019197 fats Nutrition 0.000 claims description 6
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 claims description 6
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 6
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 5
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 5
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 5
- 239000005639 Lauric acid Substances 0.000 claims description 5
- 239000005642 Oleic acid Substances 0.000 claims description 5
- 235000021355 Stearic acid Nutrition 0.000 claims description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 5
- 239000008117 stearic acid Substances 0.000 claims description 5
- 239000003925 fat Substances 0.000 claims description 4
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 3
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 3
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 claims description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 3
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000004359 castor oil Substances 0.000 claims description 3
- 235000019438 castor oil Nutrition 0.000 claims description 3
- WZWSOGGTVQXXSN-UHFFFAOYSA-N cyclohexanone;toluene Chemical compound CC1=CC=CC=C1.O=C1CCCCC1 WZWSOGGTVQXXSN-UHFFFAOYSA-N 0.000 claims description 3
- 229940117389 dichlorobenzene Drugs 0.000 claims description 3
- CAMHHLOGFDZBBG-UHFFFAOYSA-N epoxidized methyl oleate Natural products CCCCCCCCC1OC1CCCCCCCC(=O)OC CAMHHLOGFDZBBG-UHFFFAOYSA-N 0.000 claims description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 3
- 229940075529 glyceryl stearate Drugs 0.000 claims description 3
- IPCSVZSSVZVIGE-UHFFFAOYSA-M hexadecanoate Chemical compound CCCCCCCCCCCCCCCC([O-])=O IPCSVZSSVZVIGE-UHFFFAOYSA-M 0.000 claims description 3
- 239000000944 linseed oil Substances 0.000 claims description 3
- 235000021388 linseed oil Nutrition 0.000 claims description 3
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 3
- 235000021313 oleic acid Nutrition 0.000 claims description 3
- 229940090181 propyl acetate Drugs 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 claims description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 3
- 239000002383 tung oil Substances 0.000 claims description 3
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012780 transparent material Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 10
- 230000004913 activation Effects 0.000 abstract 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 125000000524 functional group Chemical group 0.000 description 13
- 239000000976 ink Substances 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 230000008859 change Effects 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000012795 verification Methods 0.000 description 4
- 241000607473 Edwardsiella <enterobacteria> Species 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 230000000149 penetrating effect Effects 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 125000002243 cyclohexanonyl group Chemical group *C1(*)C(=O)C(*)(*)C(*)(*)C(*)(*)C1(*)* 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
- G09F3/02—Forms or constructions
- G09F3/0291—Labels or tickets undergoing a change under particular conditions, e.g. heat, radiation, passage of time
- G09F3/0294—Labels or tickets undergoing a change under particular conditions, e.g. heat, radiation, passage of time where the change is not permanent, e.g. labels only readable under a special light, temperature indicating labels and the like
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/50—Sympathetic, colour changing or similar inks
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Theoretical Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Inspection Of Paper Currency And Valuable Securities (AREA)
- Printing Methods (AREA)
Abstract
The invention relates to a color-changing anti-counterfeiting label, which comprises: a substrate layer made of a dense material; the substrate layer is made of compact materials, is arranged above the base layer in a stacked mode, the edge of the substrate layer is connected with the edge of the base layer in a sealing mode, and a containing space is formed between the base layer and the substrate layer; the color-changing layer is arranged in the accommodating space and is formed by printing anti-counterfeiting color-changing ink, and the anti-counterfeiting color-changing ink comprises: 20 to 40 parts of host material, 5 to 10 parts of auxiliary material, 1 to 10 parts of guest molecule and 0.5 to 3 parts of polar organic solvent; wherein the host material is polyvinyl butyral, the auxiliary material contains carboxyl, and the guest molecule is iodine simple substance. Before the color-changing anti-counterfeiting label is used, the color-changing layer presents a first color; after activation, the color-changing layer gradually changes into a second color, and then gradually changes back to the first color again, and the color-changing layer has a time-delay reciprocating color-changing function after activation and has a higher anti-counterfeiting effect.
Description
Technical Field
The invention relates to the technical field of anti-counterfeiting, in particular to an anti-counterfeiting label.
Background
The anti-fake color-changing label in the prior art is mostly realized by printing anti-fake color-changing ink, and the color-changing effect of the anti-fake color-changing ink in the prior art is mostly stable, namely the color-changing effect is reproducible, which inevitably causes problems: the anti-counterfeit color-changing label cannot be prevented from being reused.
Disclosure of Invention
Based on this, it is necessary to provide a disposable color-changing anti-counterfeit label.
A color-changing security tag comprising:
a substrate layer made of a dense material;
The substrate layer is made of compact materials, is arranged above the base layer in a stacked mode, the edge of the substrate layer is connected with the edge of the base layer in a sealing mode, and a containing space is formed between the base layer and the substrate layer;
The color-changing layer is arranged in the accommodating space, the color-changing layer is formed by printing anti-counterfeiting color-changing ink, and the anti-counterfeiting color-changing ink comprises: 20 to 40 parts of host material, 5 to 10 parts of auxiliary material, 1 to 10 parts of guest molecule and 0.5 to 3 parts of polar organic solvent;
the host material is polyvinyl butyral, the auxiliary material contains carboxyl, and the guest molecule is iodine simple substance.
In one embodiment, the polar organic solvent is contained in an amount of 0.5 to 0.8 parts.
In one embodiment, the auxiliary material is selected from at least one of a fat, a fatty acid or a fatty acid ester.
In one embodiment, the auxiliary material has 11 to 17 carbon atoms.
In one embodiment, the auxiliary material is selected from: at least one of tung oil, linseed oil, oleic acid, elaidic acid, castor oil, palmitic acid, palmitate, lauric acid, myristic acid, stearic acid, palmitic acid, glyceryl stearate, methyl stearate, ethyl stearate, arachidic acid and rosin resin.
In one embodiment, the polar solvent is selected from the group consisting of: at least one of cyclohexanone, toluene cyclohexanone, chlorobenzene, dichlorobenzene, dichloromethane, methanol, ethanol, isopropanol, diethyl ether, propylene oxide, methyl acetate, ethyl acetate, propyl acetate, acetone, methyl butanone, methyl isobutyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, acetonitrile, pyridine, phenol.
In one embodiment, the edge of the substrate layer is sealingly connected to the edge of the base layer by a removable adhesive.
In one embodiment, the side of the base layer away from the substrate layer is further provided with a second adhesive layer.
In one embodiment, a release layer is further disposed on a side of the second adhesive layer away from the substrate layer.
In one embodiment, the substrate layer is a transparent material.
The color-changing anti-counterfeiting label comprises 20-40 parts of host material, 5-10 parts of auxiliary material, 1-10 parts of guest molecule and 0.5-3 parts of polar organic solvent. The host material contains tetragonal plane oxygen-containing functional groups, the auxiliary material contains carboxyl groups, the tetragonal plane oxygen-containing functional groups of the host material and the carboxyl groups in the auxiliary material form O-H …:O hydrogen bonds, and the tetragonal plane oxygen-containing functional groups and the carboxyl groups in the auxiliary material form a local cage-shaped three-dimensional host structure, so that the host material has the capacity of containing guest molecules. On the one hand, the color-changing layer is in a solid state, but is not completely dried, and can be independently attached to the basal layer, so that adhesion with the substrate layer can be avoided; on the other hand, due to the existence of a small amount of polar organic solvent, nonpolar iodine simple substance is polarized under the action of the polar organic solvent, and a combination body of the iodine simple substance and the organic polar organic solvent can be formed through electronic cloud adsorption, so that the volume is increased, the iodine simple substance and a local cage-shaped three-dimensional main body structure can not be combined to form a colored inclusion compound, and the color-changing layer presents a first color colorless; when the polar organic solvent volatilizes, the iodine simple substance restores the original volume, at the moment, the iodine simple substance can enter the local cage-shaped three-dimensional main body structure to form a colored inclusion compound, a second color is dark green, and then, along with the escape of the iodine simple substance to the outside along with overcoming the constraint of Edwardsiella force, the ink again presents the first color to be colorless, and the color-changing layer has a time-delay reciprocating color-changing function after being activated and has a higher anti-counterfeiting effect.
Drawings
FIG. 1 is a schematic diagram of a color-changing anti-counterfeit label according to an embodiment;
fig. 2 is a schematic structural diagram of a color-changing anti-counterfeit label according to another embodiment.
Detailed Description
The following describes in further detail the embodiments of the present invention with reference to the drawings and examples. The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
In the description of the present invention, it should be noted that the terms "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", and the like indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, merely to facilitate description of the present invention and simplify the description, and do not indicate or imply that the apparatus or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present invention.
In the description of the present invention, it should be understood that the terms "connected," "fixed," and the like are used in the present invention in a broad sense, and for example, may be fixedly connected, detachably connected, or integrated; the mechanical connection can be realized, and the welding connection can be realized; either directly or indirectly, through intermediaries, or both, may be in communication with each other or in interaction with each other, unless expressly defined otherwise. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
In this context, unless otherwise specified, parts of the respective raw materials refer to parts by weight.
Referring to fig. 1, a color-changing anti-counterfeit label according to an embodiment includes: a base layer 10, a base layer 20 and a color-changing layer 30.
The base layer 10 is used for carrying the color-changing layer 30 and the substrate layer 20, and the base layer 10 is made of a dense material, so that polar organic solvent molecules and iodine simple substance molecules can be prevented from penetrating and escaping.
Optionally, materials for preparing the substrate layer 10 include, but are not limited to: aluminum foil, PET film and PVC film.
The substrate layer 20 is disposed above the base layer 10, and the substrate layer 20 is made of a dense material, so as to prevent polar organic solvent molecules and iodine molecules from penetrating and escaping.
Optionally, materials for preparing the substrate layer 20 include, but are not limited to: aluminum foil, PET film and PVC film.
Preferably, the substrate layer 20 is made of a transparent dense material, so that, on one hand, the user can see the color condition of the color-changing layer 30 through the substrate layer 20, and on the other hand, the polar organic solvent molecules and iodine molecules can be prevented from penetrating and escaping.
Specifically, the edge of the substrate layer 20 is connected with the base layer 10 in a sealing manner, so that a containing space 12 is formed between the substrate layer 20 and the base layer 10, and the containing space 12 is used for containing the color-changing layer 30.
In the present embodiment, the first adhesive layer 11 is provided on the edge of the base layer 20 on the side close to the base layer, and the base layer 20 and the base layer 10 are hermetically connected by the first adhesive layer 11.
Optionally, the first adhesive layer 11 is a removable adhesive, and when using the color-changing security label, the user may conveniently peel off the substrate layer 20, thereby activating the color-changing layer 30.
The color-changing layer 30 is arranged in the accommodating space 12, the color-changing layer 30 is formed by printing anti-counterfeiting color-changing ink and drying the anti-counterfeiting color-changing ink to a certain extent, and the color-changing layer 30 has a time-delay reciprocating color-changing function.
Specifically, the color-changing layer 30 includes 20 to 40 parts of a host material, 5 to 10 parts of an auxiliary material, 1 to 10 parts of a guest molecule, and 0.5 to 3 parts of a polar organic solvent.
The host material is soluble in a polar organic solvent, is in a free state under the condition of solution, and has the capability of containing guest molecules by weakening molecular kinetic energy along with volatilization of the polar organic solvent in a drying process, and an oxygen-containing functional group on the four-side plane can form O-H …:O hydrogen bonds with carboxyl groups in the auxiliary material so as to form a local cage-shaped three-dimensional host structure.
In this embodiment, the host material is polyvinyl butyral, and on the one hand, polyvinyl butyral is used as the host material and can form a local cage-shaped three-dimensional host structure with the auxiliary material through hydrogen bonds; on the other hand, polyvinyl butyral has a good film-forming effect, and can firmly adhere the color-changing layer 30 to the base layer 10.
The auxiliary material contains carboxyl which is soluble in a polar organic solvent, and the molecular kinetic energy of the auxiliary material is weakened along with the volatilization of the polar organic solvent in the drying process, and the carboxyl can form O-H …:O hydrogen bonds with tetragonal plane oxygen-containing functional groups in the host material, so that a local cage-shaped three-dimensional host structure is formed, and the auxiliary material has the capacity of containing guest molecules.
Specifically, the auxiliary material is at least one of fat, fatty acid or fatty acid ester, and the auxiliary material can be pure substance of any one of fat, fatty acid or fatty acid ester, or can be mixture of various kinds of fat, fatty acid or fatty acid ester.
Optionally, the auxiliary material is a grease, which is typically a fat, a fatty acid or a mixture of fatty acid esters, wherein the carboxyl groups can form O-H …: O hydrogen bonds with the tetragonal planar oxygen-containing functional groups in the host material.
Further, the auxiliary material is a fatty acid, fatty acid or fatty acid ester having 11 to 17 carbon atoms. When the carbon number is lower than 11, the auxiliary material has over-strong hydrophilicity and low surface activity, and the carboxyl of the auxiliary material is difficult to form O-H … O hydrogen bonds with the square plane oxygen-containing functional groups of the hydrophobic polyvinyl butyral; when the number of carbon atoms is higher than 17, the solubility of the modified epoxy resin in a polar organic solvent is too low, and the number of O-H … O hydrogen bonds formed by carboxyl and oxygen-containing functional groups in the tetragonal plane in the main material is low, so that the color change effect is not obvious; when the carbon number is 11-17, on one hand, the auxiliary material has good surface activity and good affinity with the hydrophobic main material, so that the carboxyl can form O-H …:O hydrogen bonds with the tetragonal plane oxygen-containing functional groups in the main material, and on the other hand, the auxiliary material can be dissolved and dispersed in the polar organic solvent, thereby creating conditions for the carboxyl to form O-H …:O hydrogen bonds with the tetragonal plane oxygen-containing functional groups in the main material.
Further, the auxiliary material is at least one selected from tung oil, linseed oil, oleic acid, elaidic acid, castor oil, palmitic acid, palmitate, lauric acid, myristic acid, stearic acid, palmitic acid, glyceryl stearate, methyl stearate, ethyl stearate, arachidic acid and rosin resin.
The guest molecules are iodine simple substances and can be dissolved in a polar organic solvent, when the guest molecules are dissolved, nonpolar iodine simple substances are polarized under the action of the polar organic solvent, and a combination of the iodine simple substances and the polar organic solvent can be formed through electron cloud adsorption, so that the volume is increased, the iodine simple substance molecules cannot enter a local cage-shaped three-dimensional host structure to form a colored inclusion compound, and the color-changing ink is colorless in a first color; when the polar organic solvent volatilizes, the iodine simple substance restores the original volume, at the moment, the iodine simple substance can enter the local cage-shaped three-dimensional main body structure to form a colored inclusion compound, so that a second color dark green is generated, and then, the iodine simple substance escapes to the outside along with overcoming the constraint of Edwardsiella force, so that the ink again presents a first color colorless. The color change has a time delay function because of the volatilization of the polar organic solvent and the escape of the iodine simple substance.
The polar organic solvent is used for dissolving the host material, the auxiliary material and the guest molecules, and can polarize the guest molecules, so that the guest molecules and the polar organic solvent molecules form a larger-volume combination through electron cloud adsorption. The content of the polar organic solvent in the color-changing layer 30 can be controlled by controlling the drying time and drying temperature after the color-changing ink is printed so that the content of the polar organic solvent is 0.5 to 3 parts.
Specifically, when the content of the polar organic solvent is greater than 3 parts, the color-changing layer 30 has insufficient bonding fastness due to insufficient drying on the one hand, and is easy to adhere or smear with the substrate layer 20 on the other hand, after the color-changing anti-counterfeit label is activated, the time for changing the first color of the color-changing layer 30 from the first color to the second color is greatly prolonged, so that the anti-counterfeit verification significance is reduced. When the content of the polar organic solvent is 0.5-3 parts, on one hand, the color-changing layer 30 has enough bonding fastness, and can not be adhered or smeared with the substrate layer 20, so that the color-changing layer 30 has stronger stability, and on the other hand, as the color-changing layer 30 contains a small amount of polar organic solvent, the guest molecules still form a combination body with the polar organic solvent through electronic cloud adsorption, and as the volume of the combination body is larger, the guest molecules can not enter the local cage-shaped three-dimensional main body structure, so that the anti-counterfeiting color-changing ink presents a first color colorless. When the content of the polar organic solvent is less than 0.5 part, the polar organic solvent is too low, a combination body formed by the polar organic solvent and the guest molecules starts to disintegrate, part of the guest molecules are in a monomer form, enter into a local cage-shaped three-dimensional main body structure to form a colored inclusion compound, and present weak second color, so that the color change range generated after the color-changing anti-counterfeit label is activated is reduced, and the significance of anti-counterfeit verification is reduced.
Preferably, the content of the polar organic solvent is 0.5 to 0.8 parts, and in the content range, part of the polar organic solvent is volatilized and then exists in the accommodating space 12 in the form of steam, and dynamic balance of volatilization and combination is achieved in the accommodating space 12, at this time, the guest molecules in the color-changing layer 30 and the local cage-shaped three-dimensional host structure are located on the color-changing critical point, when the substrate layer 20 is uncovered by a user, the volatilization speed of the polar organic solvent is increased due to the reduction of the vapor pressure in the accommodating space 12, and the guest molecules can be quickly combined with the local cage-shaped three-dimensional host structure to form a colored inclusion compound along with the volatilization of the polar organic solvent, so that the color-changing layer 30 can generate obvious color change in a very short time, and the significance of anti-counterfeiting verification is further enhanced.
Alternatively, the polar organic solvent is selected from: at least one of cyclohexanone, toluene cyclohexanone, chlorobenzene, dichlorobenzene, dichloromethane, methanol, ethanol, isopropanol, diethyl ether, propylene oxide, methyl acetate, ethyl acetate, propyl acetate, acetone, methyl butanone, methyl isobutyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, acetonitrile, pyridine, phenol.
In another embodiment, referring to fig. 2, a second adhesive layer 40 is further disposed on a side of the base layer 10 away from the substrate layer 20, and the second adhesive layer 40 is used for attaching the color-changing security tag to an object.
In the embodiment shown in fig. 2, the side of the second adhesive layer 40 away from the substrate layer 10 is further provided with a release layer 50, and the release layer 50 is used for protecting the second adhesive layer 40 to prevent the second adhesive layer 40 from being unnecessarily adhered to an object.
The color-changing anti-counterfeiting label comprises 20-40 parts of host material, 5-10 parts of auxiliary material, 1-10 parts of guest molecule and 0.5-3 parts of polar organic solvent. The host material contains tetragonal plane oxygen-containing functional groups, the auxiliary material contains carboxyl groups, the tetragonal plane oxygen-containing functional groups of the host material and the carboxyl groups in the auxiliary material form O-H …:O hydrogen bonds, and the tetragonal plane oxygen-containing functional groups and the carboxyl groups in the auxiliary material form a local cage-shaped three-dimensional host structure, so that the host material has the capacity of containing guest molecules. At this time, on the one hand, the color-changing layer 30 is in a solid state, but is not completely dried, and can be independently attached to the base layer 10, so that adhesion with the substrate layer 20 is avoided; on the other hand, due to the existence of a small amount of polar organic solvent, nonpolar iodine simple substance is polarized under the action of the polar organic solvent, and a combination body of the iodine simple substance and the organic polar organic solvent can be formed through electronic cloud adsorption, so that the volume is increased, the iodine simple substance and a local cage-shaped three-dimensional main body structure can not be combined to form a colored inclusion compound, and the color-changing layer presents a first color colorless; when the polar organic solvent volatilizes, the iodine simple substance restores the original volume, at the moment, the iodine simple substance can enter the local cage-shaped three-dimensional main body structure to form a colored inclusion compound, a second color is dark green, and then, along with the escape of the iodine simple substance to the outside along with overcoming the constraint of Edwardsiella force, the ink again presents the first color to be colorless, and the color-changing layer has a time-delay reciprocating color-changing function after being activated and has a higher anti-counterfeiting effect.
The following are specific examples.
Example 1
The embodiment provides a color-changing anti-counterfeiting label, which comprises a basal layer 10, a base material layer 20 and a color-changing layer 30. The substrate layer 10 is made of aluminum foil, the substrate layer 20 is made of a transparent compact material PVC film, the edge of the substrate layer 20 is connected with the edge of the substrate layer 10 in a sealing way, the middle position forms a containing space 12, the color-changing layer 30 is arranged in the containing space 12, the color-changing layer 30 comprises 20 parts of main material polyvinyl butyral, 5 parts of auxiliary material, 1 part of guest molecule iodine simple substance and 0.5 part of polar organic solvent, in the embodiment, the auxiliary material is stearic acid, and the polar organic solvent is isopropanol.
Before the color-changing anti-counterfeiting label is used, the color-changing layer 30 of the color-changing anti-counterfeiting label is colorless, after the base material layer 20 is uncovered, the color-changing layer 30 is exposed to the air, the polar organic solvent is quickly volatilized, the color-changing layer 30 can be quickly changed from the first color to the second color from the dark green in 10 seconds, then the color-changing layer is gradually changed from the second color to the first color from the dark green in 3 minutes, the low-delay reciprocating color-changing function is obvious, and the color-changing anti-counterfeiting label has an excellent anti-counterfeiting function.
Example 2
The color-changing anti-counterfeiting label provided by the embodiment is similar to the color-changing anti-counterfeiting label of the embodiment 1, and is different in that: the mass fraction of the polar organic solvent is 0.8 part.
Before the color-changing anti-counterfeiting label is used, the color-changing layer 30 of the color-changing anti-counterfeiting label is colorless in a first color, after the base material layer 20 is uncovered, the color-changing layer 30 is exposed to air, the polar organic solvent is quickly volatilized, the color-changing layer 30 is quickly changed from the first color to the second color to be dark green within 15 seconds, then the color-changing layer is gradually changed from the second color to the first color to be colorless within 3 minutes, the low-delay reciprocating color-changing function is obvious, and the color-changing anti-counterfeiting label has an excellent anti-counterfeiting function.
Example 3
The color-changing anti-counterfeiting label provided by the embodiment is similar to the color-changing anti-counterfeiting label of the embodiment 1, and is different in that: the mass fraction of the polar organic solvent is 1.0 part.
Before the color-changing anti-counterfeiting label is used, the color-changing layer 30 of the color-changing anti-counterfeiting label is colorless in a first color, after the base material layer 20 is uncovered, the color-changing layer 30 is exposed to air, the polar organic solvent is volatilized rapidly, the color-changing layer 30 is gradually changed from the first color to the second color to be dark green within 60 seconds, then the color-changing layer is gradually changed from the second color to the first color to be colorless within 3 minutes, the time-delay reciprocating color-changing function is obvious, and the color-changing anti-counterfeiting label has a better anti-counterfeiting function.
Example 4
The color-changing anti-counterfeiting label provided by the embodiment is similar to the color-changing anti-counterfeiting label of the embodiment 1, and is different in that: (1) The mass part of the main material (polyvinyl butyral) is 30 parts; (2) oleic acid serving as an auxiliary material, wherein the mass part of the oleic acid is 7; (3) 2 parts of guest molecules (iodine simple substance); (4) The polar organic solvent is ethanol, and the mass fraction of the polar organic solvent is 1.5.
Before the color-changing anti-counterfeiting label is used, the color-changing layer 30 of the color-changing anti-counterfeiting label is colorless in a first color, after the base material layer 20 is uncovered, the color-changing layer 30 is exposed to air, the polar organic solvent is volatilized rapidly, the color-changing layer 30 is gradually changed from the first color to the second color to be dark green within 100 seconds, then the color-changing layer is gradually changed from the second color to the first color to be colorless within 10 minutes, the time-delay reciprocating color-changing function is obvious, and the color-changing anti-counterfeiting label has a better anti-counterfeiting function.
Example 5
The color-changing anti-counterfeiting label provided by the embodiment is similar to the color-changing anti-counterfeiting label of the embodiment 1, and is different in that: (1) The mass part of the main material (polyvinyl butyral) is 35 parts; (2) lauric acid is used as an auxiliary material, and the weight part of the lauric acid is 9 parts; (3) 3.5 parts of guest molecules (iodine simple substance); (4) The polar organic solvent is acetone, and the mass fraction of the polar organic solvent is 2.5 parts.
Before the color-changing anti-counterfeiting label is used, the color-changing layer 30 of the color-changing anti-counterfeiting label is colorless in a first color, after the base material layer 20 is uncovered, the color-changing layer 30 is exposed to air, the polar organic solvent is volatilized rapidly, the color-changing layer 30 is gradually changed from the first color to a second color dark green within 120 seconds, then the color-changing layer is gradually changed from the second color dark green to the first color colorless within 15 minutes, the time-delay reciprocating color-changing function is obvious, and the color-changing anti-counterfeiting label has a better anti-counterfeiting function.
Example 6
The color-changing anti-counterfeiting label provided by the embodiment is similar to the color-changing anti-counterfeiting label of the embodiment 1, and is different in that: (1) The mass part of the main material (polyvinyl butyral) is 40 parts; (2) stearic acid as an auxiliary material, wherein the mass part of the auxiliary material is 10; (3) 5 parts of guest molecules (iodine simple substance); (4) The polar organic solvent is cyclohexanone, and the mass portion of the polar organic solvent is 3 portions.
Before the color-changing anti-counterfeiting label is used, the color-changing layer 30 of the color-changing anti-counterfeiting label is colorless in a first color, after the base material layer 20 is uncovered, the color-changing layer 30 is exposed to air, the polar organic solvent is volatilized rapidly, the color-changing layer 30 is gradually changed from the first color to the second color to be dark green within 150 seconds, then the color-changing layer is gradually changed from the second color to the first color to be colorless within 18 minutes, the time-delay reciprocating color-changing function is obvious, and the color-changing anti-counterfeiting label has a certain anti-counterfeiting function.
Comparative example 1
The color-changing anti-counterfeiting label provided by the embodiment is similar to the color-changing anti-counterfeiting label of the embodiment 1, and is different in that: the polar organic solvent (1) is 0.3 part by mass.
Before the color-changing anti-counterfeiting label is used, the color-changing layer 30 of the color-changing anti-counterfeiting label is light green with a weak second color, after the base material layer 20 is uncovered, the color-changing layer 30 is exposed to air, the polar organic solvent is volatilized rapidly, the color-changing layer 30 is gradually changed from the light green with the weak second color to the dark green with the second color within 8 seconds, and then the color-changing layer is gradually changed from the dark green with the second color to the colorless with the first color within 3 minutes. However, the visual change is not obvious in the process of changing the color-changing layer 30 from the weak second color to the dark second color, so that the anti-counterfeiting effect is weak.
Comparative example 2
The color-changing anti-counterfeiting label provided by the embodiment is similar to the color-changing anti-counterfeiting label of the embodiment 1, and is different in that: the polar organic solvent (1) is 5 parts by mass.
Before the color-changing anti-counterfeiting label is used, the color-changing layer 30 of the color-changing anti-counterfeiting label is colorless in a first color, after the base material layer 20 is uncovered, 30% of the color-changing layer 30 of the color-changing anti-counterfeiting label is adhered to the base material layer 20 to cause falling, 70% of the color-changing layer 30 of the color-changing anti-counterfeiting label is gradually changed from the first color to the second color to be dark green within 180 seconds, and then the color of the color-changing layer 30 is gradually changed from the second color to the first color to be colorless within 3 minutes. Therefore, the color-changing anti-counterfeiting label provided by the embodiment has obvious quality problems.
As can be seen from the above embodiments, the initial state of the color-changing layer 30 of the color-changing anti-counterfeit label in each embodiment is colorless in a first color, after the substrate layer 20 is uncovered, the guest molecules are combined with the local cage-shaped three-dimensional host structure to form a colored inclusion compound along with the volatilization of the polar organic solvent, the color-changing layer 30 is dark green in a second color, and finally, the color-changing layer 30 is finally colorless in the first color along with the escape of the iodine simple substance. When the mass fraction of the polar organic solvent is less than 0.3 part, the characteristic of the color-changing layer from the first color to the second color is not significant enough. When the polar organic solvent is 0.5 to 0.8 parts by mass, the color-changing layer 30 can be changed from the first color to the second color in a short time, and the low-delay reciprocating color-changing function is remarkable. When the mass fraction of the polar organic solvent is 0.8 to 3 parts, the time for the color-changing layer 30 to change from the first color to the second color is greatly increased, thereby reducing the remarkable characteristics of the anti-counterfeit verification. When the mass fraction of the polar organic solvent is more than 3 parts, the color-changing anti-counterfeiting label has obvious quality problems.
The formulations of the color-changing inks of examples 1 to 6 and comparative examples 1 to 2 are shown in the following table.
Table 1 comparative table of color change layer formulations for each example
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (6)
1. A color-changing security tag, comprising:
a substrate layer made of a dense material;
The substrate layer is made of compact materials, is arranged above the base layer in a stacked mode, the edge of the substrate layer is connected with the edge of the base layer in a sealing mode, and a containing space is formed between the base layer and the substrate layer;
The color-changing layer is arranged in the accommodating space, the color-changing layer is formed by printing anti-counterfeiting color-changing ink, and the anti-counterfeiting color-changing ink comprises: 20 to 40 parts of host material, 5 to 10 parts of auxiliary material, 1 to 10 parts of guest molecule and 0.5 to 0.8 part of polar organic solvent;
The host material is polyvinyl butyral, the auxiliary material contains carboxyl, the guest molecule is iodine simple substance, the auxiliary material is selected from at least one of fat, fatty acid or fatty acid ester, the carbon number of the auxiliary material is 11-17, and the polar organic solvent is selected from the following materials: at least one of cyclohexanone, toluene cyclohexanone, chlorobenzene, dichlorobenzene, dichloromethane, methanol, ethanol, isopropanol, diethyl ether, propylene oxide, methyl acetate, ethyl acetate, propyl acetate, acetone, methyl butanone, methyl isobutyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, acetonitrile, pyridine, phenol.
2. The color-changing security tag of claim 1 wherein said auxiliary material is selected from the group consisting of: at least one of tung oil, linseed oil, oleic acid, elaidic acid, castor oil, palmitic acid, palmitate, lauric acid, myristic acid, stearic acid, palmitic acid, glyceryl stearate, methyl stearate, ethyl stearate, arachidic acid and rosin resin.
3. The color-changing security tag of claim 1 wherein the edge of the substrate layer is sealingly connected to the edge of the base layer by a removable adhesive.
4. A color-changing security label according to any one of claims 1-3, wherein the side of the base layer remote from the substrate layer is further provided with a second adhesive layer.
5. The color-changing anti-counterfeit label according to claim 4, wherein a release layer is further arranged on one side of the second adhesive layer away from the substrate layer.
6. The color-changing security tag of claim 1 wherein said substrate layer is a transparent material.
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| CN109796813A (en) * | 2019-01-16 | 2019-05-24 | 深圳九星印刷包装集团有限公司 | Color shifting ink and preparation method thereof and its application |
| CN113570961A (en) * | 2021-08-03 | 2021-10-29 | 深圳九星印刷包装集团有限公司 | Anti-counterfeit label |
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| GB1055807A (en) * | 1964-01-10 | 1967-01-18 | Riegel Paper Corp | Heat-sealable,moistureproof coating composition and coated packaging material incorporating same |
| WO2005068566A1 (en) * | 2004-01-20 | 2005-07-28 | Ciba Specialty Chemicals Holding Inc. | Organic solvent-based printing inks |
| EP1854851B1 (en) * | 2006-05-11 | 2009-01-21 | Agfa Graphics N.V. | Method for manufacturing pigmented inks |
| CN102858111B (en) * | 2012-09-24 | 2015-04-29 | 上海蓝沛新材料科技股份有限公司 | Novel electronic housing with antenna function and manufacturing method of novel electronic housing |
| CN111440568A (en) * | 2020-04-16 | 2020-07-24 | 深圳九星印刷包装集团有限公司 | Color-changing glue, color-changing glue film and preparation method of color-changing glue film |
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| CN109796813A (en) * | 2019-01-16 | 2019-05-24 | 深圳九星印刷包装集团有限公司 | Color shifting ink and preparation method thereof and its application |
| CN113570961A (en) * | 2021-08-03 | 2021-10-29 | 深圳九星印刷包装集团有限公司 | Anti-counterfeit label |
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