CN102911661A - Temperature-resistant anti-counterfeiting compound and method for producing same - Google Patents
Temperature-resistant anti-counterfeiting compound and method for producing same Download PDFInfo
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- CN102911661A CN102911661A CN2012103995205A CN201210399520A CN102911661A CN 102911661 A CN102911661 A CN 102911661A CN 2012103995205 A CN2012103995205 A CN 2012103995205A CN 201210399520 A CN201210399520 A CN 201210399520A CN 102911661 A CN102911661 A CN 102911661A
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- powder
- resistant anti
- high temperature
- counterfeiting
- temperature resistant
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Abstract
The invention provides a temperature-resistant anti-counterfeiting compound. The temperature-resistant anti-counterfeiting compound consists of 10%-70% of aluminate fluorescent powder and 30%-90% of glass flux by mass percent; the chemical formula of the aluminate fluorescent powder is Ba(1-x)MgAl10O17:xEu<2+>, wherein 0.01<=x<=0.2; and the glass flux comprises the following components by mass percent: 30%-50% of SiO2, 0-10% of Al2O3, 5%-35% of B2O3, 0%-15% of ZnO, 1%-10% of alkali metal and 0%-10% of alkaline earth metal. The temperature-resistant anti-counterfeiting compound provided by the invention has wide materials supply, no pollution and high temperature resistance, and can satisfy the requirements of ceramic and glass decorating firing and the like; a fluorescent pattern can be shown after irradiating an anti-counterfeiting pattern through ultraviolet of 220-365 nanometers; and the temperature-resistant anti-counterfeiting compound cannot be imitated, has a good anti-counterfeiting effect and is durable and wear-resistant.
Description
Technical field
The present invention relates to a kind of anti-counterfeiting combination, relate in particular to a kind of high temperature resistant anti-counterfeiting combination and preparation method thereof.
Background technology
Anti-counterfeiting technology is varied, has a wide range of applications in a lot of fields.Fluorescence falsification preventing is applied to the aspects such as important ticket, currency, commodity sign as one of false proof means, but existing fluorescence falsification preventing technology only limits to normal temperature or be lower than under 300 ℃ the condition use.Be 200610035687.8 a kind of anti-counterfeit container and manufacture method and shaped device such as the patent No., a kind of anti-counterfeit container and manufacture method thereof and shaped device have been described, described anti-counterfeit container comprises the blow-molded container body of plastic extrusion or injection moulding, at least one sidewall on the wherein said container body or bottom one are extruded or injection moulding go out to have at least one have can be under sun exposure stealthy and under UV-irradiation, can show the anti-counterfeiting mark part of special gloss.Owing to adopting fluorescent anti-counterfeiting mark is shaped in method in the container body, antifalse effect is better, but the temperature of its moulding is lower than 300 ℃.
In pottery, the glass technology field, owing to need through barbecue, and the barbecue temperature often is higher than 300 ℃, therefore, existing fluorescence falsification preventing technology can't adapt to the requirements such as decoration firing of pottery, glass, fluorescent anti-counterfeiting mark can't be shaped in pottery, the glass.If pottery, glass finished-product after the barbecue are carried out such as the normal temperature of organic oil ink print etc. false proof, then antifalse effect is poor, is unfavorable for the protection of certified products.
Summary of the invention
The problem that exists for solving prior art, the contriver is carrying out a large amount of explorations aspect the selection of fluorescent substance, high temperature resistance solvent and the false proof process, against expectation find, the anti-counterfeiting combination that obtains after aluminate fluorescent powder provided by the invention and glass earth flux mixed in certain proportion, can adapt to the requirements such as decoration firing of pottery, glass, later stage can't copy again, and the security pattern antifalse effect of preparation is good and wear-resisting lastingly, thereby finishes the present invention.
An aspect the invention provides a kind of high temperature resistant anti-counterfeiting combination, is comprised of the aluminate fluorescent powder of 10% ~ 70% mass percent and the glass earth flux of 30% ~ 90% mass percent; The chemical formula of described aluminate fluorescent powder is
Ba
1-xMgAl
10O
17: xEu
2+, 0.01≤x≤0.2 wherein; Described glass earth flux comprises following composition and mass percent thereof: 30% ~ 50% SiO
2, 0 ~ 10% Al
2O
3, 5% ~ 35% B
2O
3, 0 ~ 15% ZnO, 1% ~ 10% basic metal, 0 ~ 10% alkaline-earth metal.
Adopt technique scheme, the high temperature resistant anti-counterfeiting combination that obtains after aluminate fluorescent powder and glass earth flux are mixed in certain proportion, raw material sources are extensive, and are pollution-free, and resistance to elevated temperatures is good, can adapt to the requirements such as decoration firing of pottery, glass; High temperature resistant anti-counterfeiting combination is imprinted on security pattern on the marble paper by silk screen printing with the printing ink that obtains after stand linseed oil mixes, turn again note to pottery or on glass, put into decorating firing kiln after 600 ~ 900 ℃ of lower grillings, security pattern can manifest phosphor pattern with 220 ~ 365nm UV-irradiation; Later stage can't copy again, and the security pattern antifalse effect of preparation is good and wear-resisting lastingly.
As a further improvement on the present invention, described basic metal is selected from Na
2O, K
2O and Li
2One or more of O.
As a further improvement on the present invention, described alkaline-earth metal is selected from one or more of CaO, BaO, MgO and SrO.
As a further improvement on the present invention, described x is 0.08.
On the other hand, the present invention also provides a kind of preparation method of high temperature resistant anti-counterfeiting combination, comprises the steps:
A) preparation of aluminate fluorescent powder: according to Ba
1-xMgAl
10O
17: xEu
2+Stoichiometric ratio, take by weighing respectively aluminum oxide, acetic acid europium, magnesiumcarbonate, barium carbonate, add alcohol and grind and to obtain the raw material mixed powder; After this raw material mixed powder oven dry, 1200 ~ 1400 ℃ of calcinings in passing into the environment of hydrogen, the powder after obtaining calcining; Powder after this calcining is ground, washs, dries, sieves, make aluminate fluorescent powder, wherein 0.01≤x≤0.2;
B) preparation of glass earth flux: the composition that takes by weighing following mass percent: 25% ~ 35% silica powder, 10% ~ 20% feldspar in powder, 15% ~ 25% borax, 15% ~ 25% boric acid, 0 ~ 10% ZnO, 1% ~ 10% M
2CO
3, 0 ~ 10% NCO
3, after mixing, 1200 ~ 1400 ℃ of fusings, put into the cold water shrend and make frit; With frit pack into levigate in the ball mill after, dewater, dry, pulverize, sieve, make the glass solvent, wherein M is selected from one or more of Li, Na and K, N is selected from one or more of Ca, Ba, Mg and Sr;
C) aluminate fluorescent powder that makes and the glass earth flux that the makes mass ratio with 10 ~ 70:30 ~ 90 is mixed, make high temperature resistant anti-counterfeiting combination.
As a further improvement on the present invention, the preparation method of high temperature resistant anti-counterfeiting combination provided by the invention comprises the steps:
A) preparation of aluminate fluorescent powder: according to Ba
1-xMgAl
10O
17: xEu
2+Stoichiometric ratio, take by weighing respectively aluminum oxide, acetic acid europium, magnesiumcarbonate, barium carbonate, add alcohol and grind and to obtain the raw material mixed powder; After this raw material mixed powder oven dry, 1400 ℃ of calcinings in passing into the environment of hydrogen, the powder after obtaining calcining; Powder after this calcining is ground, washs, dries, sieves, make aluminate fluorescent powder, wherein x is 0.08;
B) preparation of glass earth flux: the composition that takes by weighing following mass percent: 25% silica powder, 20% feldspar in powder, 17% borax, 23% boric acid, 8% ZnO, 3% Li
2CO
3, 2% CaCO
3, 2% MgCO
3, after mixing, 1250 ℃ of fusings, put into the cold water shrend and make frit; With frit pack into levigate in the ball mill after, dewater, dry, pulverize, sieve, make the glass solvent;
C) aluminate fluorescent powder that makes and the glass earth flux that the makes mass ratio with 40:60 is mixed, make high temperature resistant anti-counterfeiting combination.
Compared with prior art, the invention has the beneficial effects as follows: high temperature resistant anti-counterfeiting combination provided by the invention, raw material sources are extensive, and are pollution-free, and resistance to elevated temperatures is good, can adapt to the requirements such as decoration firing of pottery, glass; High temperature resistant anti-counterfeiting combination is imprinted on security pattern on the marble paper by silk screen printing with the printing ink that obtains after stand linseed oil mixes, turn again note to pottery or on glass, put into decorating firing kiln after 600 ~ 900 ℃ of lower grillings, security pattern can manifest phosphor pattern with 220 ~ 365nm UV-irradiation; Later stage can't copy again, and the security pattern antifalse effect of preparation is good and wear-resisting lastingly.
Embodiment
The present invention is described in further detail below by specific embodiment.
Embodiment one high temperature resistant anti-counterfeiting combination.
According to Ba
0.92MgAl
10O
17: 0.08Eu
2+Stoichiometric ratio, take by weighing respectively the aluminum oxide of 5 moL, the acetic acid europium of 0.08 moL, the magnesiumcarbonate of 1 moL, the barium carbonate of 0.92 moL, add alcohol and grind and to obtain the raw material mixed powder; After this raw material mixed powder oven dry, 1400 ℃ of calcinings in passing into the environment of hydrogen, the powder after obtaining calcining; Powder after this calcining is ground, washs, dries, crosses 400 mesh sieves, make aluminate fluorescent powder.Take by weighing respectively silica powder (200 order), the feldspar in powder (200 order) of 20 parts by weight, the borax of 17 parts by weight, the boric acid of 23 parts by weight, the ZnO of 8 parts by weight, the Li of 3 parts by weight of 25 parts by weight
2CO
3, 2 parts by weight CaCO
3, 2 parts by weight MgCO
3, after mixing, 1250 ℃ of fusings, put into the cold water shrend and make frit; With frit pack into levigate in the ball mill after, dehydration, oven dry, pulverize, cross 400 mesh sieves, make the glass solvent.
The aluminate fluorescent powder that makes and the glass earth flux that the makes mass ratio with 40:60 is mixed, make high temperature resistant anti-counterfeiting combination.Stand linseed oil kind with high temperature resistant anti-counterfeiting combination is used with the mass ratio adding printing ceramic marble paper of 1:1 rolls into printing ink with three-roll grinder after mixing; The security pattern of design is made half tone, security pattern is imprinted on the marble paper by silk screen printing with above-mentioned printing ink, perhaps cover is imprinted on the marble paper that is printed on the marble paper pattern, upper front cover oil after dry, then the marble paper that is printed on anti-forgery ink is posted on the pottery, put into decorating firing kiln 850 ℃ of lower grillings 10 minutes, after the grilling, security pattern can manifest blue phosphor pattern with the 365nm UV-irradiation.
Embodiment two high temperature resistant anti-counterfeiting combination.
The aluminate fluorescent powder that makes among the embodiment one and the glass earth flux that the makes mass ratio with 60:40 is mixed, make high temperature resistant anti-counterfeiting combination.Stand linseed oil kind with high temperature resistant anti-counterfeiting combination is used with the mass ratio adding printing ceramic marble paper of 1:1 rolls into printing ink with three-roll grinder after mixing; The security pattern of design is made half tone, security pattern is imprinted on the marble paper by silk screen printing with above-mentioned printing ink, perhaps cover is imprinted on the marble paper that is printed on the marble paper pattern, upper front cover oil after dry, then the marble paper that is printed on anti-forgery ink is posted on the pottery, put into decorating firing kiln 850 ℃ of lower grillings 10 minutes, after the grilling, security pattern can manifest blue phosphor pattern with the 254nm UV-irradiation.
Embodiment three high temperature resistant anti-counterfeiting combination.
According to Ba
0.8MgAl
10O
17: 0.2Eu
2+Stoichiometric ratio, take by weighing respectively the aluminum oxide of 5 moL, the acetic acid europium of 0.2 moL, the magnesiumcarbonate of 1 moL, the barium carbonate of 0.8 moL, add alcohol and grind and to obtain the raw material mixed powder; After this raw material mixed powder oven dry, 1300 ℃ of calcinings in passing into the environment of hydrogen, the powder after obtaining calcining; Powder after this calcining is ground, washs, dries, crosses 400 mesh sieves, make aluminate fluorescent powder.Take by weighing respectively silica powder (200 order), the feldspar in powder (200 order) of 15 parts by weight, the borax of 20 parts by weight, the boric acid of 20 parts by weight, the ZnO of 5 parts by weight, the Na of 5 parts by weight of 30 parts by weight
2CO
3, 2 parts by weight BaCO
3, 3 parts by weight MgCO
3, after mixing, 1350 ℃ of fusings, put into the cold water shrend and make frit; With frit pack into levigate in the ball mill after, dehydration, oven dry, pulverize, cross 400 mesh sieves, make the glass solvent.
The aluminate fluorescent powder that makes and the glass earth flux that the makes mass ratio with 30:70 is mixed, make high temperature resistant anti-counterfeiting combination.Stand linseed oil kind with high temperature resistant anti-counterfeiting combination is used with the mass ratio adding printing ceramic marble paper of 1:1 rolls into printing ink with three-roll grinder after mixing; The security pattern of design is made half tone, security pattern is imprinted on the marble paper by silk screen printing with above-mentioned printing ink, perhaps cover is imprinted on the marble paper that is printed on the marble paper pattern, upper front cover oil after dry, then the marble paper that is printed on anti-forgery ink is posted on the pottery, put into decorating firing kiln 800 ℃ of lower grillings 10 minutes, after the grilling, security pattern can manifest blue phosphor pattern with the 365nm UV-irradiation.
Embodiment four high temperature resistant anti-counterfeiting combination.
The aluminate fluorescent powder that makes among the embodiment three and the glass earth flux that the makes mass ratio with 60:40 is mixed, make high temperature resistant anti-counterfeiting combination.Stand linseed oil kind with high temperature resistant anti-counterfeiting combination is used with the mass ratio adding printing ceramic marble paper of 1:1 rolls into printing ink with three-roll grinder after mixing; The security pattern of design is made half tone, security pattern is imprinted on the marble paper by silk screen printing with above-mentioned printing ink, perhaps cover is imprinted on the marble paper that is printed on the marble paper pattern, upper front cover oil after dry, then the marble paper that is printed on anti-forgery ink is posted on the pottery, put into decorating firing kiln 800 ℃ of lower grillings 10 minutes, after the grilling, security pattern can manifest blue phosphor pattern with the 254nm UV-irradiation.
Above content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that implementation of the present invention is confined to these explanations.For the general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, can also make some simple deduction or replace, all should be considered as belonging to protection scope of the present invention.
Claims (6)
1. a high temperature resistant anti-counterfeiting combination is characterized in that: be comprised of the aluminate fluorescent powder of 10% ~ 70% mass percent and the glass earth flux of 30% ~ 90% mass percent; The chemical formula of described aluminate fluorescent powder is Ba
1-xMgAl
10O
17: xEu
2+, 0.01≤x≤0.2 wherein; Described glass earth flux comprises following composition and mass percent thereof: 30% ~ 50% SiO
2, 0 ~ 10% Al
2O
3, 5% ~ 35% B
2O
3, 0 ~ 15% ZnO, 1% ~ 10% basic metal, 0 ~ 10% alkaline-earth metal.
2. high temperature resistant anti-counterfeiting combination according to claim 1, it is characterized in that: described basic metal is selected from Na
2O, K
2O and Li
2One or more of O.
3. high temperature resistant anti-counterfeiting combination according to claim 1, it is characterized in that: described alkaline-earth metal is selected from one or more of CaO, BaO, MgO and SrO.
4. high temperature resistant anti-counterfeiting combination according to claim 1, it is characterized in that: described x is 0.08.
5. the preparation method of a high temperature resistant anti-counterfeiting combination is characterized in that: comprise the steps:
A) preparation of aluminate fluorescent powder: according to Ba
1-xMgAl
10O
17: xEu
2+Stoichiometric ratio, take by weighing respectively aluminum oxide, acetic acid europium, magnesiumcarbonate, barium carbonate, add alcohol and grind and to obtain the raw material mixed powder; After this raw material mixed powder oven dry, 1200 ~ 1400 ℃ of calcinings in passing into the environment of hydrogen, the powder after obtaining calcining; Powder after this calcining is ground, washs, dries, sieves, make aluminate fluorescent powder, wherein 0.01≤x≤0.2;
B) preparation of glass earth flux: the composition that takes by weighing following mass percent: 25% ~ 35% silica powder, 10% ~ 20% feldspar in powder, 15% ~ 25% borax, 15% ~ 25% boric acid, 0 ~ 10% ZnO, 1% ~ 10% M
2CO
3, 0 ~ 10% NCO
3, after mixing, 1200 ~ 1400 ℃ of fusings, put into the cold water shrend and make frit; With frit pack into levigate in the ball mill after, dewater, dry, pulverize, sieve, make the glass solvent, wherein M is selected from one or more of Li, Na and K, N is selected from one or more of Ca, Ba, Mg and Sr;
C) aluminate fluorescent powder that makes and the glass earth flux that the makes mass ratio with 10 ~ 70:30 ~ 90 is mixed, make high temperature resistant anti-counterfeiting combination.
6. the preparation method of high temperature resistant anti-counterfeiting combination according to claim 5 is characterized in that: comprise the steps:
A) preparation of aluminate fluorescent powder: according to Ba
1-xMgAl
10O
17: xEu
2+Stoichiometric ratio, take by weighing respectively aluminum oxide, acetic acid europium, magnesiumcarbonate, barium carbonate, add alcohol and grind and to obtain the raw material mixed powder; After this raw material mixed powder oven dry, 1400 ℃ of calcinings in passing into the environment of hydrogen, the powder after obtaining calcining; Powder after this calcining is ground, washs, dries, sieves, make aluminate fluorescent powder, wherein x is 0.08;
B) preparation of glass earth flux: the composition that takes by weighing following mass percent: 25% silica powder, 20% feldspar in powder, 17% borax, 23% boric acid, 8% ZnO, 3% Li
2CO
3, 2% CaCO
3, 2% MgCO
3, after mixing, 1250 ℃ of fusings, put into the cold water shrend and make frit; With frit pack into levigate in the ball mill after, dewater, dry, pulverize, sieve, make the glass solvent;
C) aluminate fluorescent powder that makes and the glass earth flux that the makes mass ratio with 40:60 is mixed, make high temperature resistant anti-counterfeiting combination.
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| CN2012103995205A CN102911661A (en) | 2012-10-19 | 2012-10-19 | Temperature-resistant anti-counterfeiting compound and method for producing same |
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| CN2012103995205A CN102911661A (en) | 2012-10-19 | 2012-10-19 | Temperature-resistant anti-counterfeiting compound and method for producing same |
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Cited By (3)
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| CN111574062A (en) * | 2020-03-31 | 2020-08-25 | 温州大学 | Nitride red-light glass and application thereof |
| CN112979169A (en) * | 2020-10-14 | 2021-06-18 | 温州大学 | One kind of Ce: YAGG composite glass material and preparation and application thereof |
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| CN105439644B (en) * | 2015-11-22 | 2018-03-06 | 湖南嘉盛电陶新材料股份有限公司 | A kind of protective layer of super-low expansion surface of ceramic body magnetic conductive film |
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| CN112979169A (en) * | 2020-10-14 | 2021-06-18 | 温州大学 | One kind of Ce: YAGG composite glass material and preparation and application thereof |
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Address after: 518000 Guangdong City, Longhua New District view Lake Street, Yongfeng Industrial Zone, the source of the concept of road, the south side of the road 2 Applicant after: SHENZHEN GUOCI YONGFENGYUAN CERAMICS CO., LTD. Address before: 518000 Yongfeng, Baoan District Guanlan Town, Shenzhen Industrial Park, the source of the concept of road, the south side of the road, the world's 2 Applicant before: Shenzhen Yongfengyuan Porcelain Co.,Ltd. |
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Application publication date: 20130206 |