CN103436093B - Anti-counterfeiting stamp-pad ink and preparation method thereof - Google Patents
Anti-counterfeiting stamp-pad ink and preparation method thereof Download PDFInfo
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- CN103436093B CN103436093B CN201310377475.8A CN201310377475A CN103436093B CN 103436093 B CN103436093 B CN 103436093B CN 201310377475 A CN201310377475 A CN 201310377475A CN 103436093 B CN103436093 B CN 103436093B
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Abstract
The invention relates to anti-counterfeiting stamp-pad ink and a preparation method thereof. The invention aims at providing environmentally-friendly anti-counterfeiting stamp-pad ink suitable for long-term use for anti-counterfeiting, which has good weather fastness and corrosion resistance and a preparation method thereof. The anti-counterfeiting stamp-pad ink comprises solvents, resin and an anti-counterfeiting material. The preparation method comprises the following steps: uniformly mixing and stirring the solvents to obtain a mixed solvent; adding 1/2 mixed solvent into a reaction kettle, heating, maintaining a constant temperature, adding the resin, continuing to stir after the resin is completely dissolved, cooling the mixture to the room temperature to obtain a resin solution; uniformly mixing a part of resin solution with the mixed solvent, adding the anti-counterfeiting material, pigment or dope in the mixed solution, and injecting the mixture into a grinding machine for grinding to obtain color sizing; and adding the rest resin solution, the rest mixed solution and other additives into the color sizing, stirring and standing to obtain a product. The product prepared by the invention can be printed on various materials, the formed film is uniform, unlikely to drop, excellent in acid and alkali resistance and weather fastness and short in drying time, thereby being suitable for long-term anti-counterfeiting, particularly suitable for anti-counterfeiting of precious painting.
Description
Technical field
The present invention relates to a kind of anti-counterfeiting stamp ink and preparation method thereof.
Background technology
In order to accurately authenticity of products can be differentiated, make product not easily be imitated and copy, multiple anti-counterfeiting technology is used in industrial production: digital false-proof technology, bar codes technique, planar bar code technology, Laser Holographic Counterfeit-proof Technique, latent image anti-counterfeiting technology, security version line technology, micro anti-counterfeiting technology, refractive power latent-image anti-counterfeiting technology, by stages decryption technology, RF identification anti-counterfeiting technology, chemical ink anti-counterfeiting technology, biological anti-counterfeiting technology, nuclear track anti-counterfeit technology, texture anti-fake technology, code anti-fake technology.And chemical ink technology is one of of paramount importance technology in anti-counterfeiting technology, its application surface is extremely wide, has the aspect application such as banknote is false proof, invoice anticounterfeiting.It is simple to operate, with low cost, good concealment, can have multiple color, is suitable for various entity products, is particularly useful for the product false proof of the thinner thickness of paper.
Following seven classes are mainly divided into according to the different ink of anti-fake material are false proof:
1, ultraviolet excited fluorescence is false proof: in stamp-pad ink, add the visible fluorescence compound having ultraviolet and excite;
2, Infrared fluorescence is false proof: add the visible fluorescence compound with infrared excitation in stamp-pad ink;
3, temperature discoloring is false proof: the pigment of use temperature variable color or dyestuff, and stamp-pad ink color varies with temperature and changes.
4, magnetic anti-counterfeit: add magnetic substance in stamp-pad ink, as ferric oxide etc.
5, visual angle color-changing anti-counterfeit: color adopts the broken film of multi-coated interference optics.
6, anti-correction is false proof: in stamp-pad ink, add the material to being coated with the chemical substance of using instead and having chromogenic chemical reaction.
7, wet sensitive colour changing is false proof: add the compound with humidity change in stamp-pad ink.
The corresponding solvent dispersion of these false proof chemical substances, the false proof body surface of needs is coated in by the technology of ink-jet or transfer printing, under special light or temperature, there is special visual effect, or can anti-counterfeiting signal be sent in special detector, thus play anti-fake effect.But because security coating thickness is thin, the phenomenons such as the paper security coating under long-term wet environment or open-air atmosphere coating security coating can come off, cracking, and anti-forgery ink is coated on paper because of its time of drying of longer easy diffusion, not only affect attractive in appearance, for famous and precious painting and calligraphy, also there is certain destruction.
Summary of the invention
The object of the present invention is to provide a kind of weathering resistance, good corrosion resistance, be applicable to anti-counterfeiting stamp ink of the environmental protection of long-term false proof use and preparation method thereof.
For achieving the above object, the technical solution used in the present invention is: a kind of anti-counterfeiting stamp ink comprises following component: solvent, resin, anti-fake material, and its mass ratio is (12-13): (2-3): (3-4);
Described resin is by Resin A, resin B, resin C, resin D in mass ratio (4-6): (4-6): (5-10): (1-3) forms;
Wherein: Resin A is at least one in ethyl cellulose, Nitrocellulose;
Resin B is at least one in polyvinyl alcohol resin, polyvinyl butyral resin;
Resin C is at least one in acrylic resin, Synolac;
Resin D is at least one in urethane resin, aminoresin.
Synolac is the low molecular weight polyester resin all containing ester group in master chain structure, is usually prepared by glycerine or tetramethylolmethane, Tetra hydro Phthalic anhydride, fatty acid response.Aminoresin is by the general name of the resin obtained through polycondensation containing amino compound and formaldehyde, as urea-formaldehyde resin, terpolycyantoamino-formaldehyde resin, Polyamide-Polyamsne-Epichlorohydrin etc.
In Resin A, two kinds of celluosic resins contain great amount of hydroxy group, and the sticking power on paper is fine, stability might as well, and fast light, water-fast, weathering resistance is all good; The good weatherability of resin B, acid and alkali-resistance, dispersed, anti-oxidant, elasticity etc. is all very good, and UV resistant performance is excellent; Resin D sticking power, good dispersity are all good to the sticking power of paper, metal, glass, plastics.Four kinds of resins all have good sticking power and the dispersiveness to pigment and anti-counterfeiting substances, can long-term storage after four resinoids are miscible, its stable in properties after film, and anti-counterfeiting substances wherein can be made also to be attached on article for a long time, reach object false proof for a long time, be especially applicable to the Application in Anti-counterfeiting of valuables as famous and precious painting and calligraphy.
Anti-counterfeiting stamp ink of the present invention can also comprise the component such as painted pigment or dyestuff, raising system dispersing uniformity tensio-active agent, the oxidation inhibitor preventing component to be oxidized, the sanitas preventing component degradation.
Further preferred, described resin by Resin A, resin B, resin C, resin D in mass ratio 5:5:8:2 form.
Further, described solvent is made up of solvent orange 2 A, solvent B, solvent C, solvent D;
Wherein: solvent orange 2 A is at least one in ethanol, propyl alcohol, butanols, phenylcarbinol, Virahol;
Solvent B is at least one in butanone, N-ethyl pyrrolidone;
Solvent C is at least one in ethyl acetate, butylacetate, acetic acid penta fat, propylene glycol, propylene glycol monomethyl ether acetic acid fat;
Solvent D is at least one in glycol ether, triglycol ether.
Preferred further, the mass ratio of described solvent orange 2 A, solvent B, solvent C, solvent D is (6-8): (4-8): (4-6): (1-3).
Preferred further, the mass ratio of described solvent orange 2 A, solvent B, solvent C, solvent D is 7:6:5:2.
Further, described anti-fake material is at least one in ultraviolet fluorescent material, infrared fluorescent material, magneticsubstance, temperature change material, visual angle off-color material.Ultraviolet fluorescent material is material that can be luminous under ultraviolet excitation, comprises the organic compound containing rare earth elements europium, terbium, as terbium-para-amino benzoic acid fluorescent agent, europium-α-thenoyltrifluoroacetone-phenanthroline ternary coordination compound etc.; Infrared fluorescent material is material that can be luminous under Infrared irradiation, comprises colored cyanines class, boron fluoride complexing two pyrroles methine class material; Magneticsubstance is the magnetic material of tool, as mixed the materials such as cobalt in ferric oxide, ferric oxide; Temperature becomes material namely along with envrionment temperature change can react the material making the color of material itself change, as the iodide of Ag, Hg, Cu tri-kinds of metals, complex compound or double salt, 3,6-diethoxy fluorane, benzoyl leucomethylene blue, 1,3,3-tri-methyl indole quinoline-7-chloro-β-naphtho-spiro-pyrans etc.; Namely visual angle off-color material is the reflection utilizing the anisotropy of liquid crystal to make rayed on material is also anisotropy, thus when observing material from different perspectives, it can present various color to reach false proof object, mainly cholesteric liquid crystal class material.
Further, described anti-counterfeiting stamp ink also comprises 2,6 di tert butyl 4 methyl phenol.2,6 di tert butyl 4 methyl phenol and antioxidant BHT, it can prevent polymkeric substance from causing rotten because of oxidation, increases the work-ing life of stamp-pad ink.
Further, described anti-counterfeiting stamp ink also comprises organic-silicon-modified tensio-active agent.Tensio-active agent is that existing oleophilic group has again hydrophilic group organism, the lipophilic group of organic silicon surfactant is then siliceous, as full methyl polysiloxane, its some surface active property is better than common tensio-active agent, all kinds of SOLVENTS in formula and resin, anti-fake material can be made to dissolve and be uniformly dispersed.
Further, described anti-counterfeiting stamp ink also comprises environmental-friendly pigment or environment-friendly dye.So-called environmental-friendly pigment or environment-friendly dye are for meeting EN71-3(2000) pigment of environmental protection standard and European Union RoHS standard or environment-friendly dye, as pthalocyanine blue, azophloxine, iron oxide red, von Muller's indicator 156, ACID BROWN 75, orange GGL, sun green N-B etc.Also pigment or dyestuff can not be added, during as made transparent counterfeiting stamp-pad ink in certain stamp-pad ink.
The preparation method of described anti-counterfeiting stamp ink, is characterized in that: comprise step:
A. the solvent orange 2 A of calculated amount, solvent B, solvent C and solvent D mixing and stirring are obtained mixed solvent;
B. getting 1/2 mixed solvent adds in reactor, is heated to 55-65 DEG C of constant temperature, under agitation adds in reactor by the Resin A of calculated amount, resin B, resin C and resin D, treats that it dissolves completely, continues to stir 2-5h, be cooled to room temperature and obtain resin solution;
C. get 1/10 resin solution to mix with 1/4 mixed solvent, anti-fake material, pigment or dyestuff are added in mixed solution in the shredder that reinjects and grinds 1-2h, obtain mill base;
D. remaining resin liquid, remaining mixed solvent, 2,6 di tert butyl 4 methyl phenol, organic-silicon-modified tensio-active agent are added in mill base, stir 2-3h, leave standstill more than 24h, obtain product.
In technique scheme, the consumption of each component is the optimum feed stock ratio participating in reaction, but those skilled in the art can carry out according to instruction of the present invention the change that is equal to.Such as: because the Parameters variation that the error of industrial production itself causes is equal to technical scheme of the present invention, on formula basis of the present invention, composite other is assisted and be equal to technical scheme of the present invention with agent.
Product prepared by the present invention can be printed on various material, film forming is even, strong adhesion, resistance to acids and bases, excellent weather resistance and hard, very applicable long-term false proof use, product prepared by the present invention is coated on paper or other material only needs several seconds time just dry, can not occur in diffusion phenomena, especially be applicable to the security purposes of famous and precious painting and calligraphy.
Embodiment
For making those skilled in the art clearly and technical scheme clearly of the present invention, spy provides preferred embodiment below, but technological thought of the present invention is not limited to following examples.
Embodiment one
A. 8.75kg butanols, 7.5kg butanone, 6.25kg propylene glycol methyl ether acetate, 2.5kg triglycol ether mixing and stirring are obtained mixed solvent, stand-by;
B. 12.5kg mixed solvent is added in reactor, be heated to 60 DEG C of constant temperature, be under agitation the 1.25kg ethyl cellulose of 4000-9000 by molecular weight, 1.25kg polyvinyl butyral resin, 2kg Synolac, 0.5kg urethane resin add in reactor successively, treat that it dissolves completely, continue constant temperature and stir 2.5h, be cooled to room temperature and obtain resin solution;
C. get resin solution quality 1/10 mixes with 6.25kg mixed solvent, 7kg infrared fluorescent material, 1kg iron oxide red is added in mixed solution in the shredder that reinjects and grinds 1.5h, obtain mill base;
D. remaining resin liquid, remaining mixed solvent, 0.05kg2,6-di-tert-butyl-4-methy phenol, the organic-silicon-modified tensio-active agent of 0.5kg are added in mill base, stir 2.5h, leave standstill 48h, obtain product.
Embodiment two
A. 10.4kg Virahol, 6.5kgN-ethyl pyrrolidone, 5.2kg ethyl acetate, 3.9kg glycol ether mixing and stirring are obtained mixed solvent;
B. 13kg mixed solvent is added in reactor, be heated to 55 DEG C of constant temperature, be under agitation the 1.2kg ethyl cellulose of 4000-9000 by molecular weight, 1kg polyvinyl butyral resin, 1.2kg Synolac, 0.6kg urethane resin add in reactor, treat that it dissolves completely, continue to stir 4h, be cooled to room temperature and obtain resin solution;
C. get resin solution quality 1/10 mixes with 6.5kg mixed solvent, is added in mixed solution in the shredder that reinjects by 6kg ultraviolet fluorescent material and grinds 2h, obtain mill base;
D. remaining resin liquid, remaining mixed solvent, 0.04kg2,6-di-tert-butyl-4-methy phenol, the organic-silicon-modified tensio-active agent of 0.6kg are added in mill base, stir 3h, leave standstill 60h, obtain product.
Embodiment three
A. 7.2kg propyl alcohol, 8.4kgN-ethyl pyrrolidone, 7.2kg acetic acid penta fat, 1.2kg triglycol ether mixing and stirring are obtained mixed solvent;
B. getting 12kg mixed solvent adds in reactor, be heated to 65 DEG C of constant temperature, be under agitation that the 1.2kg Nitrocellulose of 4000-9000,1.8kg polyvinyl alcohol resin, 2.7kg acrylic resin and 0.3kg urethane resin add in reactor by molecular weight, treat that it dissolves completely, continue to stir 3h, be cooled to room temperature and obtain resin solution;
C. get resin solution quality 1/10 mixes with 6kg mixed solvent, 8kg visual angle off-color material, 0.5kg orange GGL is added in mixed solution in the shredder that reinjects and grinds 1h, obtain mill base;
D. remaining resin liquid, remaining mixed solvent, 0.06kg2,6-di-tert-butyl-4-methy phenol, the organic-silicon-modified tensio-active agent of 0.5kg are added in mill base, stir 2h, leave standstill 72h, obtain product.
Product prepared by embodiment one to three loads in sealed vessel, successively places respectively after 48 hours at temperature 55 DEG C and-25 DEG C, and product does not occur that solid is separated out or demixing phenomenon occurs, and liquid viscosity is also unchanged, and the mobility of product is very stable.
Application examples one
Anti-counterfeiting stamp ink prepared by embodiment one to three is added ink pad, is printed on two groups of plain papers by seal, dry after at room temperature placing 2-3s, recording coating thickness is 60 ± 10 microns.
Paper after drying first group is placed in ultraviolet accelerated ageing testing box and carries out burn-in test: light source is hernia lamp, and UV-light peak averaging wavelength is 335nm, average lamp intensity 56W/m
2, lamp tube wall is 30mm to the closest range of specimen surface, and irradiation time is 1000h.The phenomenons such as test result is film without coming off, ftracture, bubble.
Paper after another group being dried is placed in the neutral salt fog chamber 1000h continuously meeting GB/T2423.17-2008 " electric and electronic product Elementary Procedure test Ka: salt-fog test method ".The phenomenons such as test result is film without coming off, ftracture, bubble.
Still anti-fake effect can have been given play under the false proof light-illuminating of each leisure of film after two groups of tests.
Application examples two
Anti-counterfeiting stamp ink prepared by embodiment one to three is added ink pad, is printed on three plain papers respectively by seal, dry after at room temperature placing 2-3s, recording coating thickness is 60 ± 10 microns.The paper printing anti-counterfeiting stamp ink is lain against upward on clean platform, the counterweight cotton of 500g is wrapped, get suitable alcohols and soak cotton, with the speed of the 40-60 beat/min paper surface back and forth wiping 300 time of this cotton at stamp-pad ink anti-counterfeiting stamp ink, each stroke is about 20mm.Test terminates, and stamp-pad ink does not find phenomenon of revealing the exact details, and by the stamp-pad ink thickness average out to 52 microns after wiping, still can give play to anti-fake effect under the false proof light-illuminating of each leisure of the film after having tested.
Application examples three
Anti-counterfeiting stamp ink prepared by embodiment one to three is added ink pad, is printed on PVC plastic flitch, on stainless steel plate, on sheet glass and on plank respectively by seal, dry after at room temperature placing 2-3s, recording coating thickness is 60 ± 10 microns.Burn-in test, the test of neutral salt fog chamber and sticking power test is carried out according to the testing method in application examples one and application examples two, the phenomenons such as front two test results are film without coming off, ftracture, bubble, sticking power test result is by the stamp-pad ink thickness average out to 54 microns after wiping.
Application examples four
Anti-counterfeiting stamp ink prepared by embodiment one to three is added ink pad, is printed on respectively on cotton by seal, dry after at room temperature placing 2-3s, recording coating thickness is 50 ± 10 microns, and stamp-pad ink does not have diffusion phenomena on cotton.
Claims (10)
1. an anti-counterfeiting stamp ink printed by seal, and it is characterized in that: comprise following component: solvent, resin, anti-fake material, its mass ratio is (12-13): (2-3): (3-4);
Described resin is by Resin A, resin B, resin C, resin D in mass ratio (4-6): (4-6): (5-10): (1-3) forms;
Wherein: Resin A is at least one in ethyl cellulose, Nitrocellulose;
Resin B is at least one in polyvinyl alcohol resin, polyvinyl butyral resin;
Resin C is at least one in acrylic resin, Synolac;
Resin D is urethane resin.
2. anti-counterfeiting stamp ink according to claim 1, is characterized in that: described resin by Resin A, resin B, resin C, resin D in mass ratio 5:5:8:2 form.
3. anti-counterfeiting stamp ink according to claim 1, is characterized in that: described solvent is made up of solvent orange 2 A, solvent B, solvent C, solvent D;
Wherein: solvent orange 2 A is at least one in ethanol, propyl alcohol, butanols, phenylcarbinol, Virahol;
Solvent B is at least one in butanone, N-ethyl pyrrolidone;
Solvent C is at least one in ethyl acetate, butylacetate, pentyl acetate, propylene glycol, propylene glycol methyl ether acetate;
Solvent D is at least one in glycol ether, triglycol ether.
4. anti-counterfeiting stamp ink according to claim 3, is characterized in that: the mass ratio of described solvent orange 2 A, solvent B, solvent C, solvent D is (6-8): (4-8): (4-6): (1-3).
5. anti-counterfeiting stamp ink according to claim 3, is characterized in that: the mass ratio of described solvent orange 2 A, solvent B, solvent C, solvent D is 7:6:5:2.
6. anti-counterfeiting stamp ink according to claim 1, is characterized in that: described anti-fake material is at least one in ultraviolet fluorescent material, infrared fluorescent material, magneticsubstance, temperature change material, visual angle off-color material.
7. anti-counterfeiting stamp ink according to claim 1, is characterized in that: described anti-counterfeiting stamp ink also comprises 2,6 di tert butyl 4 methyl phenol.
8. anti-counterfeiting stamp ink according to claim 1, is characterized in that: described anti-counterfeiting stamp ink also comprises organic-silicon-modified tensio-active agent.
9. anti-counterfeiting stamp ink according to claim 1, it is characterized in that: described anti-counterfeiting stamp ink also comprises environmental-friendly pigment or environment-friendly dye, described environmental-friendly pigment or environment-friendly dye are for meeting EN71-3(2000) pigment of environmental protection standard and European Union RoHS standard or environment-friendly dye are pthalocyanine blue, azophloxine, iron oxide red, von Muller's indicator 156, ACID BROWN 75, orange GGL or sun green N-B.
10. the purposes of the anti-counterfeiting stamp ink described in the arbitrary claim of claim 1-9 in seal is printed.
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| CN106046925A (en) * | 2016-06-29 | 2016-10-26 | 农杰 | Processing technique of printing ink |
| CN106009913A (en) * | 2016-06-29 | 2016-10-12 | 农杰 | Preparation method of stamp-pad ink with forgery prevention function |
| CN106147384A (en) * | 2016-06-29 | 2016-11-23 | 农杰 | The preparation method of stamp-pad ink |
| CN106009912A (en) * | 2016-06-29 | 2016-10-12 | 农杰 | Preparation method of anti-counterfeiting stamp-pad ink |
| CN106046941A (en) * | 2016-06-29 | 2016-10-26 | 农杰 | Processing technique of forgery prevention printing ink |
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| CN108912843A (en) * | 2018-08-15 | 2018-11-30 | 芜湖扬展新材料科技服务有限公司 | Infrared or Fluorescent Falsification-resistant Ink of one kind and preparation method thereof |
| CN110105812A (en) * | 2018-10-24 | 2019-08-09 | 重庆理工大学 | A kind of no ink ink-jet ink and its preparation method and application |
| CN109504180A (en) * | 2018-12-05 | 2019-03-22 | 赵晓锐 | A kind of ink paste and preparation method thereof |
| CN111709507B (en) * | 2020-06-14 | 2021-09-28 | 北京化工大学 | Multilayer color code micro-marker capable of coding information and preparation method thereof |
| CN111739408B (en) * | 2020-07-02 | 2022-03-25 | 深圳市深大极光科技有限公司 | Anti-counterfeit label |
| CN112342695A (en) * | 2020-12-08 | 2021-02-09 | 常州科旭纺织有限公司 | Application of short fiber filament composite yarn in fabric |
| CN112778839B (en) * | 2021-03-24 | 2022-04-26 | 湖北中烟工业有限责任公司 | Magnetic color-changing ink and preparation method thereof |
| CN114591728B (en) * | 2022-01-20 | 2023-12-26 | 华南理工大学 | Anti-counterfeiting pigment and preparation method and application thereof |
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| JP5787317B2 (en) * | 2011-12-08 | 2015-09-30 | 独立行政法人 国立印刷局 | An ultraviolet curable glitter ink composition for screen printing. |
| CN103242700B (en) * | 2012-10-24 | 2014-12-24 | 北京印刷学院 | Ultraviolet excited blue fluorescent inkjet ink for printing and imaging by additive method and preparation method |
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Effective date of registration: 20171206 Address after: 510000 Guangdong city of Guangzhou province Tianhe District high Pulu Kingfa Park No. 38 building 105 Patentee after: Shi Julin Address before: Haizhuqu District Guangzhou city of Guangdong Province, 510000 Industrial Road No. 270 Building No. 1 by East building six floor room 06 Patentee before: Sun Baolin |