CN100559426C - Titanium dioxide nano sol-polyurethane complex media transparent laser holographic false proof film - Google Patents
Titanium dioxide nano sol-polyurethane complex media transparent laser holographic false proof film Download PDFInfo
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- CN100559426C CN100559426C CNB2003101092816A CN200310109281A CN100559426C CN 100559426 C CN100559426 C CN 100559426C CN B2003101092816 A CNB2003101092816 A CN B2003101092816A CN 200310109281 A CN200310109281 A CN 200310109281A CN 100559426 C CN100559426 C CN 100559426C
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- false proof
- laser holographic
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- colloidal sol
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 26
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 26
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000004408 titanium dioxide Substances 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- 238000000576 coating method Methods 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 239000010408 film Substances 0.000 claims description 39
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 19
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 15
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 10
- 238000005516 engineering process Methods 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- 239000012948 isocyanate Substances 0.000 claims description 6
- 150000002513 isocyanates Chemical class 0.000 claims description 6
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 claims description 5
- RNQYDRPQWNFRAZ-UHFFFAOYSA-N CC=CC1=CC=CC=C1.N=C=O Chemical class CC=CC1=CC=CC=C1.N=C=O RNQYDRPQWNFRAZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 239000002671 adjuvant Substances 0.000 claims description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 5
- -1 hydrofluorite Substances 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- DQFBYFPFKXHELB-UHFFFAOYSA-N Chalcone Natural products C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 3
- XTUVJUMINZSXGF-UHFFFAOYSA-N N-methylcyclohexylamine Chemical compound CNC1CCCCC1 XTUVJUMINZSXGF-UHFFFAOYSA-N 0.000 claims description 3
- PAMIQIKDUOTOBW-UHFFFAOYSA-N N-methylcyclohexylamine Natural products CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- GTTSNKDQDACYLV-UHFFFAOYSA-N Trihydroxybutane Chemical compound CCCC(O)(O)O GTTSNKDQDACYLV-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004359 castor oil Substances 0.000 claims description 3
- 235000019438 castor oil Nutrition 0.000 claims description 3
- 235000005513 chalcones Nutrition 0.000 claims description 3
- 229960002887 deanol Drugs 0.000 claims description 3
- 125000005442 diisocyanate group Chemical group 0.000 claims description 3
- 239000012972 dimethylethanolamine Substances 0.000 claims description 3
- 150000002009 diols Chemical class 0.000 claims description 3
- 239000000835 fiber Substances 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
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 229960002725 isoflurane Drugs 0.000 claims description 3
- GIWKOZXJDKMGQC-UHFFFAOYSA-L lead(2+);naphthalene-2-carboxylate Chemical compound [Pb+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 GIWKOZXJDKMGQC-UHFFFAOYSA-L 0.000 claims description 3
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- KFBXUKHERGLHLG-UHFFFAOYSA-N 2,4-Nonanedione Chemical compound CCCCCC(=O)CC(C)=O KFBXUKHERGLHLG-UHFFFAOYSA-N 0.000 claims description 2
- 229920002799 BoPET Polymers 0.000 claims description 2
- 239000005041 Mylar™ Substances 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 230000002457 bidirectional effect Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 239000003925 fat Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000002372 labelling Methods 0.000 abstract description 3
- 235000019504 cigarettes Nutrition 0.000 abstract description 2
- 238000012856 packing Methods 0.000 abstract description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 210000002469 basement membrane Anatomy 0.000 description 2
- 239000012973 diazabicyclooctane Substances 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 210000004379 membrane Anatomy 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000005269 aluminizing Methods 0.000 description 1
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 1
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005489 elastic deformation Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000013028 medium composition Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
Images
Landscapes
- Laminated Bodies (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
A kind of transparent laser holographic false proof film relates to the composition and the preparation of film.It is by organic film and the individual layer high index of refraction titania (TiO that applies on it
2) the antiforge laser holographic image that is pressed into of Nano sol-polyurethane complex media and this medium patrix forms.The complex media coating combines firmly with organic film, and equipment is simple, and production cost is low, has broad application prospects, can be directly used in cigarette, drinks, etc. the disposable integral external packing of commodity; Also can be used as the labeling of commodity and the false proof sheath film of certificate and document.
Description
Technical field
The invention belongs to field of anti-counterfeit technology, it relates to a kind of transparent counterfeiting film and preparation method thereof, and more specifically, it relates to a kind of titanium dioxide nano sol-polyurethane complex media transparent laser holographic false proof film and preparation method thereof.
Background technology
Use the labeling of extremely wide different band adhesive sticker in the present false proof field, its stock is a kind of reflective laser holographic film of aluminizing, and begins to use (CN87205139) from the middle and later periods eighties, is subjected to great welcome.The very fast maturation of the manufacture craft of this product under the catalysis rapidly of market heavy demand, technology is very fast to be popularized, and following, antiforge function day by day descends, and is close to forfeiture until now.This in addition anti false film has covered products to be packaged, uses to have certain limitation.In light of this situation, select the new material of high-tech content, develop transparent anti-fake material and be suitable for characteristic and enlarge the effective way that usable range becomes developing anti-counterfeiting technology and field to increase.
Transparent laser holographic anti-counterfeiting film film forming has several different methods (CN2226328), (CN2234640Y), mostly is physics or chemical vapor deposition greatly, thus the big preparation of equipment investment, complex process, efficient is low, and the cost height can only be limited to small size and use; For reducing cost, there is the people that hologram image is directly molded into polypropylene film, make transparent laser holographic false proof film (CN1075909), because the problem of the elastic deformation of material and masterplate coupling causes that hologram image is difficult for distinguishing, antifalse effect is relatively poor.Also once had employing inorganic sol (CN2300965Y) to make transparent laser holographic false proof film as reflecting medium, because the adhesion problem of organic film and inorganic coating, the result of final practical application is not ideal enough.
Summary of the invention
The purpose of this invention is to provide a kind of be difficult to counterfeit, but easy to make, low production cost; Transparent laser holographic false proof film of the clear difficult drop-off again of hologram image, wearing and tearing and preparation method thereof.
The transparent laser holographic false proof film that the present invention proposes is by organic plastics film and the individual layer high index of refraction carbon dioxide (TiO that is coated with on it
2) Nano sol-polyurethane colloidal sol complex media composition, the antiforge laser holographic image or the literal that have mold pressing to make on this complex media.Here the used masterplate of mold pressing can be clapped into hologram with needed image by the laser hologram photography technology, copies to above the metallograph with the form of grating and makes.
Among the present invention, TiO
2The each component weight proportion of Nano sol-polyurethane colloidal sol is a nano-TiO
2Colloidal sol: polyurethane colloidal sol: solvent is: 1: (0.8-1.2): (2.5-3.5).Solvent for use can be ethyl acetate.
Among the present invention, described TiO
2Nano sol each component proportioning is as follows: butyl titanate: water: solvent: adjuvant=(1.0～10.0): (1～5): (10.0～150.0): (0.02～2.0) (mol ratio), and wherein, solvent is absolute ethyl alcohol, acetone; Described adjuvant is hydrochloric acid, nitric acid, hydrofluorite, acetic acid, ammoniacal liquor, hexanoyl acetone.
Among the present invention, the component weight proportion of described polyurethane colloidal sol is as follows: the A component: B component: solvent: catalyzer is 1: (0.8-1.2): (8-12): (0.08-0.12); Wherein, the A component is by the ratio addition in NCO: OH＞2: 1 of isocyanates and low molecular weight diol.The isocyanates here is toluene diisocyanate (TDI), '-diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), isoflurane chalcone diisocyanate (IPDI), dicyclohexyl methyl hydride diisocyanate (H12MDI), tetramethylxylylene diisocyanate (TMXDI), at least a in methyl styrene isocyanates (TMI) and/or diisocyanate (TDI) and trihydroxy methyl propane (TMP) addition product;
The B component be contain hydroxyl in advance or the polymkeric substance of branched chain type, be polyester (ether) polyvalent alcohol, at least a in castor oil, the fiber derivative;
Catalyzer is a triethylamine, triethylenediamine (DABCO), methyldiethanolamine, dimethylethanolamine, triethylenediamine, N, N-methylcyclohexylamine, N-methylmorpholine, dibutyl tin laurate (DBTDL), dibutyltin diacetate, stannous octoate, zinc naphthenate, cobalt naphthenate, at least a in lead naphthenate and/or the sad inferior zinc;
The colloidal sol solvent is an acetone, aniline, benzene, butanone, phenixin, methenyl choloride, butyl acetate, ethanol, triethylamine, methyl second acetone, at least a in cyclohexanone and/or the N-Methyl pyrrolidone.
Among the present invention, used organic plastics transparent membrane can be bidirectional stretching polypropylene film, mylar or polyvinyl chloride film etc.
The preparation method of the transparent laser holographic false proof film that the present invention proposes is as follows:
1, preparation TiO
2Nano sol.With above-mentioned TiO
2The each component of Nano sol mixes in molar ratio, at room temperature stirs, and makes it to mix, and sealing then at room temperature through hydrolysis in 5-30 days and aging, forms TiO
2Nano sol.
2, preparation polyurethane solutions.The each component (A component, B component, solvent, catalyzer) of above-mentioned polyurethane is mixed by aforementioned weight proportion, at room temperature stirring reaction 2-5 hour, promptly form polyurethane colloidal sol.
3, preparation compound medium layer.Adopt the coating filming technology, with above-mentioned TiO
2Coat after Nano sol, polyurethane colloidal sol and solvent mix by weight ratio on the above-mentioned organic plastics transparent membrane, obtain compound medium layer.Described coating process is to adopt colloidal sol on the cable roll on the coating machine, and finishes curing and moulding in drying tunnel.
4, mold pressing anti-counterfeiting image.Anti-counterfeiting image is made on the compound medium layer by mould pressing technology.
The present invention has the following advantages:
1. adopt titania (TiO
2) Nano sol-polyurethane colloidal sol complex media does coating and have three-dimensional nanometer network structure, combine closely with the plastic sheeting of doing base material simultaneously.It is not only firm that hologram image is embedded in the network structure, and the stereoeffect of image is also demonstrated fully.
2. owing to adopt chemistry coating filming technology, need not expensive equipment input, base material is a common plastic film, and dielectric layer is used also mostly is common industrial chemicals, thereby cost of manufacture is low, and the production efficiency height has good application prospects.
3. have the high grade of transparency and phototropic effect concurrently.Hologram image on the anti false film is along with the angle generation light and shade of incident light changes (light becomes effect such as Fig. 2), and have does not simultaneously influence its transparent characteristic at all.Can know by this film and to see or cover the original looks of object that angle changing can clearly be seen the holographic false proof image simultaneously packaged.
4. easy to use, of many uses.Can be used as the whole anti-counterfeit package of object, also can be cut into fritter and do anti-fake label, also can be used for the false proof sheath of certificate and plastic encapsulation material etc.This film has strong artistic effect, also can be used as ornament materials.
This laser holographic anti-counterfeiting film, the complex media coating combines firmly with organic film, equipment is simple, production cost is low, has broad application prospects, can be directly used in cigarette, drinks, etc. the disposable integral external packing of commodity; Also can be used as the labeling of commodity and the false proof sheath film of certificate and document.
Description of drawings
Fig. 1 is a transparent laser holographic false proof film microstructure synoptic diagram.Wherein 1 is basilar memebrane, and 2 is compound medium layer.
Fig. 2 is the influence (550nm) of the incident angle of light to the pattern reflectivity.
Embodiment
The invention is further illustrated by the following examples, but be not limited to this embodiment.
Titania (TiO
2) preparation of Nano sol: at first press butyl titanate: water: ethanol: diacetone and acetic acid=1.0: 2.0: 50: 0.3 mixed in molar ratio, through fully stirring, mix, then mixed liquor is placed closed container, at room temperature aging 14 days, can obtain stable TiO
2Nano sol.
The preparation of polyurethane colloidal sol
Get 20 parts of polyurethane A components, 20 parts of B components, 200 parts of solvents, 2 parts of catalyzer, adding has in the reactor of magnetic stirring apparatus, thermometer, condenser pipe one by one, stirs, and reacts 2～5 hours under 30 ℃ of temperature, forms polyurethane colloidal sol.
Above-mentioned polyurethane Sol A component is by the ratio addition in NCO: OH＞2: 1 of isocyanates and low molecular weight diol.Isocyanates wherein is toluene diisocyanate (TDI), '-diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), isoflurane chalcone diisocyanate (IPDI), dicyclohexyl methyl hydride diisocyanate (H12MDI), tetramethylxylylene diisocyanate (TMXDI), at least a in methyl styrene isocyanates (TMI) and/or diisocyanate (TDI) and trihydroxy methyl propane (TMP) addition product.
The B component be contain hydroxyl in advance or the polymkeric substance of branched chain type, be polyester (ether) polyvalent alcohol, at least a in castor oil, the fiber derivative.
Catalyzer is a triethylamine, triethylenediamine (DABCO), methyldiethanolamine, dimethylethanolamine, triethylenediamine, N, N-methylcyclohexylamine, N-methylmorpholine, dibutyl tin laurate (DBTDL), dibutyltin diacetate, stannous octoate, zinc naphthenate, cobalt naphthenate, at least a in lead naphthenate and/or the sad inferior zinc.
Above-mentioned polyurethane colloidal sol solvent is an acetone, aniline, benzene, butanone, phenixin, methenyl choloride, butyl acetate, ethanol, triethylamine, methyl second acetone, at least a in cyclohexanone and/or the N-Methyl pyrrolidone.
Embodiment 3.
Titania (TiO
2) preparation of Nano sol-polyurethane colloidal sol complex media colloidal sol
With titania (TiO
2) Nano sol and polyurethane colloidal sol successively pours container in the ratio of 1: 1 (volume ratio).At room temperature, make it to become the solution that is evenly distributed through being not less than the stirring of 30min.
Embodiment 4.
Utilize the coating machine of band cable roll to go up coating complex media colloidal sol at plastic sheeting (PET or BOPP etc.).Line density is that the cable roll of 200 lines takes up colloidal sol in rotation and is coated with 60m/min speed, is sent into baking oven together with coating and basement membrane with same speed then and dries.The process of oven dry also is to finish the process of gel.The temperature of oven dry remains on 80～100 ℃, and the compound medium layer that the process of oven dry is about about such one the 2 μ m of 1-2min. has formed on basement membrane.
Embodiment 5.
The work masterplate is installed on the version roller of special-purpose two roller die press, the film that has compound medium layer passes between version roller and pressure roller.The version roller need be heated to about 100 ℃, adjusts the pressure (2～4kg/cm of two rollers
2) and transmit the speed (25～40m/min) of film.Grating fringe on masterplate under the acting in conjunction of temperature and pressure has been copied to compound medium layer, forms the transparent laser holographic film.This film that has a recording laser hologram image grating can or be gone up adhesive sticker and base stock is made anti-fake label according to the actual demand of product, or directly being compounded in product becomes false-proof film outward.
Claims (9)
1. transparent laser holographic false proof film is characterized in that: by organic film, with apply the antiforge laser holographic image that individual layer high index of refraction titanium dioxide nano sol-polyurethane colloidal sol compound medium layer on it and this compound medium layer patrix be pressed into and form.
2. transparent laser holographic false proof film according to claim 1 is characterized in that: described TiO
2The proportioning that the Nano sol each component is pressed molal quantity is as follows: butyl titanate: water: solvent: adjuvant=(1.0～10.0): (1～5): (10.0～150.0): (0.02～2.0), and wherein, solvent is absolute ethyl alcohol or acetone; Described adjuvant is hydrochloric acid, nitric acid, hydrofluorite, acetic acid, ammoniacal liquor or hexanoyl acetone.
3. transparent laser holographic false proof film according to claim 1 is characterized in that: the component weight proportion of described polyurethane colloidal sol the following is: the A component: B component: solvent: catalyzer is 1: (0.8-1.2): (8-12): (0.08-0.12); Wherein, the A component is by the ratio addition in NCO: OH＞2: 1 of isocyanates and low molecular weight diol, the isocyanates here is a toluene diisocyanate, '-diphenylmethane diisocyanate, hexamethylene diisocyanate, isoflurane chalcone diisocyanate, dicyclohexyl methyl hydride diisocyanate, tetramethylxylylene diisocyanate, at least a in methyl styrene isocyanates and/or diisocyanate and the trihydroxy methyl propane addition product;
The B component be contain hydroxyl in advance or the polymkeric substance of branched chain type, be polyester (ether) polyvalent alcohol, at least a in castor oil, the fiber derivative;
Catalyzer is a triethylamine, triethylenediamine, methyldiethanolamine, dimethylethanolamine, triethylenediamine, N, N-methylcyclohexylamine, N-methylmorpholine, dibutyl tin laurate, dibutyltin diacetate, stannous octoate, zinc naphthenate, cobalt naphthenate, at least a in lead naphthenate and/or the sad inferior zinc;
The colloidal sol solvent is an acetone, aniline, benzene, butanone, phenixin, methenyl choloride, butyl acetate, ethanol, triethylamine, methyl second acetone, at least a in cyclohexanone and/or the N-Methyl pyrrolidone.
4. transparent laser holographic false proof film according to claim 1 is characterized in that: described TiO
2Nano sol and polyurethane colloidal sol reach and the part by weight of solvent is: 1: (0.8-1.2): (2.5-3.5), solvent is an ethyl acetate.
5. transparent laser holographic false proof film according to claim 1 is characterized in that: described organic film is bidirectional stretching polypropylene film, mylar or polyvinyl chloride film.
6. the preparation method as the described transparent laser holographic false proof of claim 1-5 film is characterized in that concrete steps are as follows: the preparation titanium dioxide nano sol; Preparation polyurethane colloidal sol; The preparation compound medium layer; The mold pressing anti-counterfeiting image.
7. preparation method according to claim 6 is characterized in that: described TiO
2Nano sol prepares by following technology: metatitanic acid fourth fat, water, solvent, adjuvant are pressed (1.0～10.0): (1～5): (10.0～150.0): (0.02～2.0) mixed in molar ratio, at room temperature stir, mix, sealing then, at room temperature, form Nano sol through hydrolysis in 5～30 days and aging.
8. preparation method according to claim 6 is characterized in that: described polyurethane colloidal sol mixes each component in proportion by following technology preparation, at room temperature even stirring reaction 2-5 hour, forms polyurethane colloidal sol.
9. preparation method according to claim 6 is characterized in that: described coating processes is to adopt colloidal sol on the cable roll on the coating machine, and finishes curing and moulding in drying tunnel.
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| CNB2003101092816A CN100559426C (en) | 2003-12-11 | 2003-12-11 | Titanium dioxide nano sol-polyurethane complex media transparent laser holographic false proof film |
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| CNB2003101092816A CN100559426C (en) | 2003-12-11 | 2003-12-11 | Titanium dioxide nano sol-polyurethane complex media transparent laser holographic false proof film |
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| CN100559426C true CN100559426C (en) | 2009-11-11 |
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| US10280506B2 (en) | 2014-03-18 | 2019-05-07 | 3D-Oxides | Deposition process based on stencil mask and application to the fabrication of tags supporting multi-functional traceable codes |
| CN106965583A (en) * | 2017-01-23 | 2017-07-21 | 浙江亚欣包装材料有限公司 | A kind of secondary mould pressing technique |
| CN108706629B (en) * | 2018-05-24 | 2020-11-13 | 武汉华工图像技术开发有限公司 | Laser holographic anti-counterfeiting film TiO2Method for producing a layer |
| CN113442627B (en) * | 2021-07-05 | 2022-04-19 | 安徽顺彤包装材料有限公司 | Laser holographic anti-counterfeiting film and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1075909A (en) * | 1993-03-15 | 1993-09-08 | 张旭 | The application of polypropylene screen hologram mould pressing technology and this film |
| CN2226328Y (en) * | 1995-04-11 | 1996-05-01 | 深圳启恒特殊印刷有限公司 | Transparent holographic anti-forging trade mark |
| CN2234640Y (en) * | 1995-12-22 | 1996-09-04 | 电子科技大学 | Laser holographic watermark card protecting film |
| CN2300965Y (en) * | 1997-07-23 | 1998-12-16 | 同济大学 | Transparent laser holographic anti-counterfeit film |
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2003
- 2003-12-11 CN CNB2003101092816A patent/CN100559426C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1075909A (en) * | 1993-03-15 | 1993-09-08 | 张旭 | The application of polypropylene screen hologram mould pressing technology and this film |
| CN2226328Y (en) * | 1995-04-11 | 1996-05-01 | 深圳启恒特殊印刷有限公司 | Transparent holographic anti-forging trade mark |
| CN2234640Y (en) * | 1995-12-22 | 1996-09-04 | 电子科技大学 | Laser holographic watermark card protecting film |
| CN2300965Y (en) * | 1997-07-23 | 1998-12-16 | 同济大学 | Transparent laser holographic anti-counterfeit film |
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