CN106221547B - Random distribution has the transferable coating of fiber and the antifalsification label containing the coating - Google Patents

Random distribution has the transferable coating of fiber and the antifalsification label containing the coating Download PDF

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Publication number
CN106221547B
CN106221547B CN201610688524.3A CN201610688524A CN106221547B CN 106221547 B CN106221547 B CN 106221547B CN 201610688524 A CN201610688524 A CN 201610688524A CN 106221547 B CN106221547 B CN 106221547B
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coating
fiber
emulsion
transferable
water
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CN106221547A (en
Inventor
王俊博
胡俊
吴跟新
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CHANGFENG CHEMICALS INTERNATIONAL Ltd
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CHANGFENG CHEMICALS INTERNATIONAL Ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D175/00Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04Polyurethanes
    • C09D175/06Polyurethanes from polyesters
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02Monomers containing only one unsaturated aliphatic radical
    • C08F212/04Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06Hydrocarbons
    • C08F212/08Styrene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/34Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348Hydroxycarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/42Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/46Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
    • C08G18/4676Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing sulfur
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633Compounds of group C08G18/42
    • C08G18/6659Compounds of group C08G18/42 with compounds of group C08G18/34
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/30Camouflage paints
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/334Applications of adhesives in processes or use of adhesives in the form of films or foils as a label
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2475/00Presence of polyurethane
    • C09J2475/005Presence of polyurethane in the release coating

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

There is fiber the invention provides a kind of random distribution and there is anti-fraud functional transferable coating, the coating includes the aqueous polyurethane emulsion that components by weight percent is 45 50%, 30% 35% water-and acrylate emulsion, 5% 8% false proof debris, 0.05 0.2% defoamer, 0.1 0.5% mould inhibitor and 1 10% deionized water;Aqueous polyurethane emulsion is that to use toluene di-isocyanate(TDI) and sulfonated polyester polyol be raw material, polymerize by hydrophilic chain extender of dimethylolpropionic acid and be made;Water-and acrylate emulsion is to use methyl methacrylate, butyl methacrylate, styrene, Isooctyl acrylate monomer and isobornyl methacrylate to be made for monomer by way of emulsion polymerization;A diameter of 0.04 0.06mm of false proof debris, length are 2 3mm.The coating of the present invention, can easily be peeled off without release layer from carrier film, and can at utmost ensure the integrality of coating fiber when transfer and carrier film are peeled off, the false proof layer particularly suitable as antifalsification label.Present invention also offers a kind of antifalsification label containing above-mentioned coating.

Description

Random distribution has the transferable coating of fiber and the antifalsification label containing the coating
Technical field
The present invention relates to a kind of coating, more particularly to one kind can be stripped out from carrier film and be transferred on other stocks Coating, specifically relating to a kind of random distribution has fiber and has anti-fraud functional transferable coating.The invention further relates to A kind of antifalsification label containing above-mentioned transferable coating.
Background technology
The development of modern communicationses and scanning technique, conveniently provided for us with the distribution characteristics for recording and checking fiber To carry out false proof method.The existing anti-fake identification mark made using random fibers, its structure and discriminating fashion are usually to carry Body film(PET film)Upper coated with adhesive layers, then dispense a number of fiber at random over the binder layer, then by this carry with Being pasted after the marker numbering of machine distributed fibers on packing material, the random distribution characteristic information of fiber is collected, with reference to The sequence number of marker is collectively stored in the computer Antiforge inquiry system database of access telephone network or/and internet, for big Crowd's examination true and false;Because random fibers are fixed on together by adhesive on packing material with carrier film, compare when taking packaging apart Difficulty is torn up, and adhesive is generally PUR, and fake producer can make adhesive lose viscous force by hot blast, completely by whole mark Thing transfer sticking is passed a fake product off as a genuine one on fake products, causes anti-counterfeiting mark into the amulet of fake products;In view of this, originally The technical staff in field developed a kind of false proof blocking film made using random fibers in recent years, and the blocking film includes carrier Film, release layer, adhesive phase, random distribution have the fibrous layer and adhesive layer of fiber, using the method for transfer by false proof blocking film It is fixed on packing material, then carrier film is peeled off, the fibrous layer that leaving release layer, adhesive phase, random distribution has fiber is wrapping Fill on thing, the characteristic information of fiber random distribution is gathered and stored in advance in fibrous layer, although this structure can avoid faking The problem of person shifts whole anti-fake identification mark, but this false proof blocking film complex process, long flow path, and each functional layer is superimposed upon Together, it is survivable to tear up.
The content of the invention
To solve the problem present on, it is an object of the invention to provide the transferable painting that a kind of random distribution has fiber Layer, the coating are small and frangible with carrier film adhesive force.
It is a further object of the present invention to provide a kind of antifalsification label containing above-mentioned transferable coating, the antifalsification label makes Technique is simple, Making programme is short.
To realize object above, random distribution of the invention has the transferable coating of fiber, including components by weight percent is 45- 50% aqueous polyurethane emulsion, 30%-35% water-and acrylate emulsion, 5%-8% false proof debris, 0.05-0.2% disappear Infusion, 0.1-0.5% mould inhibitor and 1 ~ 10% deionized water;Wherein aqueous polyurethane emulsion is to use toluene di-isocyanate(TDI) It is raw material with sulfonated polyester polyol, by hydrophilic chain extender of dimethylolpropionic acid, polymerization is made;Water-and acrylate emulsion is Methyl methacrylate, butyl methacrylate, styrene, Isooctyl acrylate monomer and isobornyl methacrylate are used to be single Body is made by way of emulsion polymerization;A diameter of 0.04-0.06mm, the length 2-3mm of false proof debris.
In order to more preferably improve the stripping ability of transferable coating, above-mentioned transferable coating also includes 5-10% organosilicon Auxiliary agent.
The preparation of above-mentioned transferable coating is first to add aqueous polyurethane emulsion, water-and acrylate emulsion and deionized water It is added in the rustless steel container with high speed agitator, low whipping speed is that 0.5-1 hours are stirred under 800-1500 revs/min, Filter bag filtering through 300 mesh, then organosilicon auxiliary agent, defoamer, mould inhibitor and false proof debris are sequentially added in filtrate, will Mixing speed brings up to 2000-2500 revs/min, stirs 10-30 minutes, and by way of three roller gluings and comma scraper is coated with shape Into.
Above-mentioned aqueous polyurethane emulsion is by toluene di-isocyanate(TDI), the 13%-15% including components by weight percent for 8%-10% Sulfonated polyester polyol, 7%-8% dimethylolpropionic acid, 6%-7% triethylamine, 25%-27% acetone and 36%-48% go from Sub- water is polymerized.
Above-mentioned water-and acrylate emulsion is by butyl methacrylate, the 3%-4% including components by weight percent for 8%-10% Isooctyl acrylate monomer, 14%-16% styrene, 5%-6% methyl methacrylate, 3%-4% isobornyl methacrylate, 2.5%-4.8% emulsifying agent, 0.5%-1.2% ammoniacal liquor, 0.5%-0.9% thickener, 0.05%-0.2% defoamer, 0.1%- 0.5% bactericide and 54%-63% deionized water are synthesized into.
The preferred 0.1-0.15mm of thickness of above-mentioned transferable coating.
The present invention also provides a kind of antifalsification label containing above-mentioned transferable coating, and the label includes carrier film, carrier film It is upper be coated with any of the above-described transferable coating, glue-line is coated with transferable coating, on glue-line covered with separate paper.
The above-mentioned preferred non-drying glue layer of glue-line.
The random distribution of the present invention has the transferable coating of fiber and the antifalsification label containing the coating, has as follows excellent Point:
1st, the water paint that the present invention is mixed to prepare using the good aqueous polyurethane of matching and aqueous acrylic emulsion, Ensure without release layer with regard in the case of peelable, solid content can accomplish 35%-40%, it is reachable that it dries the coating layer thickness formed 0.1-0.15mm, can be fully wrapped around wherein by random fibers, at utmost ensure that fine when coating transfer and carrier film are peeled off The integrality of dimension.False proof layer particularly suitable as antifalsification label.
2nd, water paint of the invention is a kind of non-newtonian fluid, can be in the case where ensureing that solid content is certain by viscosity Accomplish the rotating speed of 4000-5000cp/3 rotors/12(Rotation viscometer, sample temperature is at 25 DEG C), in the state of static, The viscosity allows fiber is dispersed to be suspended in coating enough, and in the presence of high speed rotating speed cutting power, it presents a kind of false Plastic fluid phenomenon, as shearing force increases, viscosity declines, and can more preferably control the thickness of coating.
3rd, transferable coating of the invention has more soft characteristic compared to the release coating of oiliness, can make coating stripping more Add smoothly, and its good film-forming property also makes it be more prone to be applied at various packaging cornerite Kaifeng or in all kinds of special-shaped packagings.
4th, because fiber is wrapped around in aqueous coating, label destroy after or make the remaining leftover pieces of label, Ke Yitong Cross water-washing method to recycle fiber recovery, not only environmental protection but also economized on resources.
5th, antifalsification label of the invention, its anti-fake identification mark are free of carrier film, irrecoverable once destroying, and compared to existing False proof blocking film, eliminate release layer and adhesive phase, simple in construction, Making programme is short, and security coating is easy to destruction and torn up.
Brief description of the drawings
Fig. 1 is the structural representation for the transferable coating that random distribution of the present invention has fiber.
Fig. 2 is the structural representation of antifalsification label of the present invention.
Embodiment
First, embodiment
1st, the preparation of aqueous polyurethane emulsion
Formula:
Prepare:
(1)Toluene di-isocyanate(TDI) and sulfonated polyester polyol are added in the reactor by above-mentioned formula ratio, gradually heating To 80 DEG C, react 2 hours, cool to 40 DEG C;
(2)Dimethylolpropionic acid solution is added dropwise into reactor, is added dropwise, is warming up to 70 DEG C;
(3)The performed polymer that reaction obtains is cooled to 40 DEG C, acetone dilution is added, is quickly stirred, obtains intermediate;
(4)Deionized water is slowly added into intermediate, while high-speed stirred emulsifies, and triethylamine regulation system is added dropwise PH value is 6-7, and vacuum sloughs acetone and obtains aqueous polyurethane emulsion.
2nd, the preparation of water-and acrylate emulsion
Formula:
Prepare:
(1)Prepare pre-emulsion:The lauryl sodium sulfate emulsifying agent of 90% amount is dispersed in water by formula(With 1:30 ratios Example), then by methyl methacrylate, butyl methacrylate, styrene, methyl methacrylate, the different ice of methacrylic acid The monomers such as piece ester add in the case where opening stirring, and high-speed stirred 30 minutes is fully emulsified, obtains pre-emulsion;
(2)Deionized water is added after ammonium persulfate is mixed with potassium peroxydisulfate and obtains initiator solution(With 1:12 ratios Example);
(3)Bottom, which is fitted over, by formula ratio adds remaining water and lauryl sodium sulfate emulsifying agent, sodium acid carbonate and 20%- 30% pre-emulsion, 72 DEG C are warming up to, add 30% initiator solution, after being warming up to 80 DEG C, be incubated about 20-30 minutes, obtain seed Emulsion, remaining pre-emulsion is uniformly then dripped off in about 3-4 hours, while remaining initiator solution is added dropwise, residue triggers The agent aqueous solution postpones to drip off for 20 minutes, and whole reaction temperature is maintained at 80 DEG C, after reaction terminates, and is warming up to 90 DEG C, insulation 1 is small When;
(3)Then 70 DEG C are cooled to, initiator solution is eliminated after addition(Rongalite and tert-butyl hydroperoxide Hydrogen), 1 hour is incubated, then less than 40 DEG C are cooled to, defoamer, bactericide and ammoniacal liquor regulation pH to 7-8.5 are added, passes through thickening Agent and ammoniacal liquor regulation viscosity, viscosity is the numerical value for using rotation viscometer to be measured under 25 DEG C, No. 3 rotors, 12 rotating speeds for 4500- 5500cp, filtered, discharged using 300 mesh filter bags.
3rd, random dispersion has the preparation of the transferable coating fluid of fiber
Formula:
Prepare:Aqueous polyurethane, water-and acrylate emulsion and deionized water are added to high speed agitator successively Rustless steel container in, open stirring, mixing speed be 800-1500 revs/min, keep 0.5-1 hours, the filtering through 300 mesh Bag filtering, then sequentially adds organosilicon auxiliary agent, defoamer, mould inhibitor and false proof debris, then mixing speed is brought up to 2000-2500 revs/min, stir 10-30 minutes, be made the water-based peelable coating fluid of random fibers, control thereon machine viscosity be The numerical value that rotation viscometer measures under 25 DEG C, No. 3 rotors, 12 rotating speeds is used as 4000-5000cp.
4th, the preparation of antifalsification label
(1)Above-mentioned coating fluid is imported into trough of coating machine, from 16-22um PET film 1, using three rollers glue mode and Comma scraper is coated on PET film and is coated, and forms transferable coating 2, drying, machine speed with oven temperature regard actual conditions and Fixed, by taking 5 section drying tunnels as an example, machine speed is 40-60m/min, and it is 80 DEG C/100 DEG C/140 DEG C/135 DEG C/90 DEG C often to save temperature;
(2)The PET film that drying finishes is passed through into non-setting adhesive cement 3 and white board 4 with the side coated with transferable coating Carry out compound, obtain the label coil paper with random fibers, as shown in Figure 1, 2;
(3)Label coil paper is cut into serialized antifalsification label one by one.
2nd, apply
After the antifalsification label of the present invention is bought by producer, the white board on antifalsification label is torn by producer, is affixed on packing material Sealing part, while by this it is transfer coated on fiber random distribution characteristic information gathering get off, with reference to the sequence number one of marker Storage is played into the Antiforge inquiry system database of producer's computer.It is specific by being installed on mobile phone when user buys commodity APP takes pictures to the antifalsification label of commodity sealing part, the fiber that image collects in advance by internet and line server Random distribution characteristic information is compared, and comparison result is back to the APP at user mobile phone end, then can show certified products or palm off Product, if certified products, packaging is opened after user's purchase, now frangible mark will be destroyed, and random fibers will not revival;If Counterfeit, user can select that counterfeit report and the information such as uploading pictures and geographical position is to producer, treat that producer does Further checking and follow-up processing.

Claims (6)

1. a kind of random distribution has a transferable coating of fiber, including aqueous polyurethane emulsion that components by weight percent is 45-50%, 30%-35% water-and acrylate emulsion, 5%-8% false proof debris, 0.05-0.2% defoamer, 0.1-0.5% it is mould proof Agent and 1-10% deionized water;Wherein aqueous polyurethane emulsion is by the toluene diisocynate including components by weight percent for 8%-10% Ester, 13%-15% sulfonated polyester polyol, 7%-8% dimethylolpropionic acid, 6%-7% triethylamine, 25%-27% acetone and 36%-48% deionized water is polymerized;Water-and acrylate emulsion is by the metering system including components by weight percent for 8%-10% Acid butyl ester, 3%-4% Isooctyl acrylate monomer, 14%-16% styrene, 5%-6% methyl methacrylate, 3%-4% methyl Isobornyl acrylate, 2.5%-4.8% emulsifying agent, 0.5%-1.2% ammoniacal liquor, 0.5%-0.9% thickener, 0.05%-0.2% Defoamer, 0.1%-0.5% bactericide and 54%-63% deionized water be made by way of emulsion polymerization;False proof broken fibre A diameter of 0.04-0.06mm, the length 2-3mm of dimension.
2. random distribution according to claim 1 has the transferable coating of fiber, it is characterised in that:The transferable coating Also include 5-10% organosilicon auxiliary agent.
3. random distribution according to claim 1 or 2 has the transferable coating of fiber, it is characterised in that:It is described transferable The preparation of coating is that first aqueous polyurethane emulsion, water-and acrylate emulsion and deionized water are added to high speed agitator Rustless steel container in, low whipping speed be 800-1500 revs/min under stir 0.5-1 hours, the filter bag mistake through 300 mesh Filter, then organosilicon auxiliary agent, defoamer, mould inhibitor and false proof debris are sequentially added in filtrate, mixing speed is brought up to 2000-2500 revs/min, 10-30 minutes are stirred, is coated with and to be formed with comma scraper by way of three roller gluings.
4. random distribution according to claim 3 has the transferable coating of fiber, it is characterised in that:The transferable coating Thickness be 0.1-0.15mm.
5. a kind of antifalsification label, including carrier film, it is characterised in that:Any institutes of claim 1-4 are coated with the carrier film State transferable coating, on transferable coating coated with glue-line, glue-line covered with separate paper.
6. antifalsification label according to claim 5, it is characterised in that:The glue-line is non-drying glue layer.
CN201610688524.3A 2016-08-19 2016-08-19 Random distribution has the transferable coating of fiber and the antifalsification label containing the coating Active CN106221547B (en)

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CN111171737A (en) * 2020-02-27 2020-05-19 广东九佛新材料科技有限公司 Protective film and preparation method thereof
WO2022036496A1 (en) * 2020-08-17 2022-02-24 福建华峰运动用品科技有限公司 Waste-cloth-containing recycled fiber coating slurry, coating and preparation method therefor

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CN101403206B (en) * 2008-09-23 2011-04-27 东莞市天盛特种纸制品有限公司 Fibre false-proof production method of paper
CN101923804A (en) * 2009-06-11 2010-12-22 湖北中烟工业有限责任公司 Anti-counterfeiting fragile self-adhesive paper and preparation method thereof
RU2539342C1 (en) * 2010-10-27 2015-01-20 Ханьнань Ппк Нетворк Текнолоджи Ко. Лтд Printing material with protection against forgery with thermally transferred pattern, special foil for thermal transfer and manufacturing method of such material
KR101450614B1 (en) * 2012-04-19 2014-10-17 한국조폐공사 Security Paper Having Security Element of Discoloration by Chemical and Method for Manufacturing the same

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