CN1095734A - Photochromism anti-forging printing-ink and manufacture method thereof - Google Patents
Photochromism anti-forging printing-ink and manufacture method thereof Download PDFInfo
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- CN1095734A CN1095734A CN 93106107 CN93106107A CN1095734A CN 1095734 A CN1095734 A CN 1095734A CN 93106107 CN93106107 CN 93106107 CN 93106107 A CN93106107 A CN 93106107A CN 1095734 A CN1095734 A CN 1095734A
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- printing
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- photochromism
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- forging printing
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Abstract
The invention discloses a kind of photochromism anti-forging printing-ink and preparation method thereof, photochromism anti-forging printing ink of the present invention mainly comprises spiral shell indoline Nai Bing oxazine class photochromic dyes, benzene fourth block copolymerized resin, thiobis phenol type antioxidant and other ancillary component, wherein the chemical structural formula of spiral shell indoline naphthalene and oxazine class dyestuff is a following formula.
The present invention is applicable to the anti-fake mark printing of famous-brand and high-quality goods marks and important bill certificate, the present invention can make color change (colourless-blueness) under ultraviolet ray or irradiation of sunlight, and it is fast to have variable color speed, and the variable color process is reversible, long service life, characteristics such as printing effect is good.
Description
The present invention relates to a kind of anti-counterfeit printing material and manufacture method thereof, particularly a kind of photochromism anti-forging printing-ink and manufacture method thereof.
Photochromic material is a kind of material that can change color under UV-light or other radiation exposure rapidly, and indoline spiro-pyrans class is the photochromic compound of fully studying, and such material is very limited on the purposes owing to the resistance to fatigue deficiency.The Luo oxazine is another kind of photochromic organism.Recently studies show that this type organic has superior chemical stability and resistance to fatigue than spiro-pyrans, so application potential is very big.Several patents (day disclosure special permission communique 87-172,075 are arranged; 88-196,673; 88-305,181; 90-20,576; 91-81,378) relate to and utilize the Luo oxazine to make pen or garden pearl board pen ink, or the heat transfer printing that is used for textiles is when being used for the printing of paper, because the influence of factors such as viscosity, flowability, meeting generation inadaptability photochromic compound more or less is used to make the anti-counterfeit printing material also report (EP279,600; WO88-01,288; CN1,044,860A), but used dyestuff is a fulgides, preparation process is many, processed complex, printing is still needed special light sources could variable color.
The purpose of this invention is to provide a kind of photochromism anti-forging printing-ink and manufacture method thereof, can overcome the deficiencies in the prior art part, make not only changeable colour under ultraviolet ray or other radiation exposure of printed pattern, and under common sunlight also changeable colour.
Implementation procedure of the present invention:
1, photochromism anti-forging printing-ink provided by the invention mainly is made up of photochromic dyes, low-melting ink vehicle and ancillary component thereof
1. photochromic dyes of the present invention is the key component of anti-counterfeit printing printing ink, and it belongs to spiral shell indoline Nai Bing oxazine compounds, and its chemical structural formula is:
R wherein
1Be C
1-C
18Alkyl, aralkyl ， oxazine alkyl; R
2, R
3Be methyl; R
4Be hydrogen, methyl or methoxy; R
5Be hydrogen or ethoxycarbonyl; R
6Be hydrogen hydroxyl, chlorine or bromine.Such dyestuff is low-melting white or faint yellow solid, to light, heat, air-stable, but weak acid resistant or weakly alkaline environment.Its solution changes blueness or bluish voilet rapidly under UV-light or direct sunlight, when removing ultraviolet source or breaking away from direct sunlight, restore to the original state again, and above variable color process can be carried out repeatedly, does not lose efficacy for a long time.
2. low-melting ink vehicle of the present invention is the main component of anti-counterfeit printing printing ink, and it belongs to polyolefin resin, as if the multipolymer of polyethylene, polypropylene, polystyrene and vinylbenzene and divinyl.For adapting to requirement of the present invention, several resins can be used with certain proportioning sometimes.Wherein as low-melting ink vehicle of the present invention best be styrene-butadiene block copolymer.This resin appearance colorless is transparent, and good film-forming property is good with above-mentioned dyestuff intermiscibility, and in order to make anti-forgery ink, these resins need to be dissolved earlier as low-melting ink vehicle.Solvent commonly used has aromatic hydrocarbons, as benzene,toluene,xylene or chlorobenzene; The ester class is as ethyl acetate, butylacetate, pentyl acetate or phthalic acid ester class; Also have paraffin hydro carbons, ethers and ketone in addition.All be to form mixed solvent as a rule, to satisfy the requirement of solvability and volatility coupling with several organism.
3. auxiliary composition of the present invention has tensio-active agent, photostabilizer and filler etc., and commonly used tensio-active agent is a non-ionic type, as sorbester p17, polysorbate40, peregal 0 etc.; Photostabilizer is thiobisphenol and nickel complex thereof, steric hindrance amine; Filler is the vitriol of calcium, magnesium or the oxide compound of carbonate and some metal etc.
2, in manufacture craft of the present invention, at first be that dyestuff and photostabilizer are mixed with dissolved low-melting ink vehicle with above-mentioned solvent solution-forming, add other ancillary component again and process.Dye dosage is the 0.1-1.0% of low-melting ink vehicle weight, and the consumption of tensio-active agent and photostabilizer and dyestuff quite or slightly lack in the ancillary component, and the add-on of filler requires to decide according to the viscosity of printing ink.Each ancillary component should be even with dyestuff, low-melting ink vehicle thorough mixing, preferably grinds on three-roller or ball mill, so far can obtain photochromism anti-forging printing-ink of the present invention.
Anti-forgery ink provided by the invention is applicable to the printing of various stocks, enamelled paper, newsprinting paper, gelatine printing paper as different size, and polyethylene film and textiles etc., be most convenient with the screen printing mode, be mainly used in the false proof of trade mark, security and vital document.When differentiating the true and false of these printed matters, as long as the pattern secret mark that will utilize the present invention to print places under common sunlight or the UV-light, as rapid generation variable color, very fast again recovery when leaving illumination then is a genuine piece, then is counterfeit as above-mentioned phenomenon not occurring.
Advantage of the present invention is: 1. use the pattern secret mark of ink printing of the present invention not only under specific light source such as UV-light, can develop the color, and under sunlight also changeable colour; 2. its variable color process is a reversible, and variable color speed is fast, long service life, and printed matter can be preserved more than 1 year; 3. the fastness of printed matter, sharpness etc. all can make the user satisfied; 4. starting material required for the present invention are easy to get, and the photochromic dyes manufacture method is simple, and the printing ink manufacturing is also more convenient.
The invention will be further described below by example:
Example 1, with 10 parts of benzene fourth block resin＜research institute of Lan Hua company products〉be dissolved in 20 parts of mixed solvents and (be lower than 250 ℃ ink oil 8 by boiling point, dimethylbenzene 6,1 part of composition of diethyl phthalate 5 and paraffin wax) in, obtains water white transparency heavy-gravity low-melting ink vehicle (A) with R among the dyestuff SP-0-5(formula @
1-4Be CH
3-, R
5-6Be H), photostabilizer (thiobisphenol type) and peregal 0 each portion are dissolved in the suitable N-BUTYL ACETATE jointly, obtain the transparent liquid of oyster (B).To fully grind below 30 ℃ in A and B and 5 parts of Place grinding machines of light calcium carbonate, get white uniform jelly, anti-forgery ink promptly of the present invention.The pattern secret mark that obtains with silk screen printing is difficult for differentiating, but when placing under ultraviolet lamp or the sunlight, just demonstrates the blue marking of analysing clearly immediately.Leave light source, color disappears in can be in several seconds.Printing was preserved under usual condition more than 1 year, and its painted and colour killing performance does not have considerable change.
Example 2, not existing together with example 1 is that dyestuff is R in the BSP-O(formula
2-3Be CH
3-, R
4-6Be H, R
1Wei the oxazine butyl, consumption is 0.5% of an amount of resin, and with N-BUTYL ACETATE/dimethylbenzene (1: 1) dissolving with preparation B.The performance of gained printing ink and printing is consistent with example 1.
Example 3, with example 1 difference be the resin polystyrene, dyestuff is with R among the SP-0-16(formula @
1=C
16H
33, R
2-3=CH
3, R
4-6=H), dye dosage is 1% of a resin, gained printing ink is consistent with example 1 with the printing performance.
Claims (6)
1, a kind of photochromism anti-forging printing-ink and manufacture method thereof is characterized in that printing ink mainly is made up of spiral shell indoline naphthalene and oxazine class dyestuff, polyethylene resin low-melting ink vehicle and other auxiliary composition.
2, photochromism anti-forging printing-ink according to claim 1 is characterized in that photochromic compound is a spiral shell indoline Nai Bing oxazine class, and its chemical structural formula is:
R wherein
1Be C
1-C
18Alkyl, aralkyl ， oxazine alkyl; R
2, R
3Be methyl; R
4Be hydrogen, methyl or methoxy; R
5Be hydrogen or ethoxycarbonyl; R
6Be hydrogen, hydroxyl, chlorine or bromine
3, photochromism anti-forging printing-ink according to claim 1, it is characterized in that as the macromolecule compound of low-melting ink vehicle best be styrene-butadiene block copolymer
4, photochromism anti-forging printing-ink according to claim 1 is characterized in that tensio-active agent in the ancillary component is a non-ionic type, and photostabilizer is thiobisphenol and nickel complex thereof, and filler is the vitriol or the carbonate of calcium, magnesium
5, a kind of photochromism anti-forging printing-ink and manufacture method thereof, it is characterized in that at first the low-melting ink vehicle styrene-butadiene block copolymer being dissolved with mixing solutions, again dyestuff-spiral shell indoline Nai Bing oxazine and photostabilizer are dissolved with another kind of solvent, then with these two kinds of component mixings, add tensio-active agent and filler again, put into jointly on three-roller or the ball mill and grind.
6, photochromism anti-forging printing-ink according to claim 5 is characterized in that mainly being suitable for the silk screen printing of paper, and the printing stable performance can be used for the false proof of trade mark, security and vital document.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93106107 CN1039649C (en) | 1993-05-22 | 1993-05-22 | Photochromism anti-forging printing ink and its prodn. method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93106107 CN1039649C (en) | 1993-05-22 | 1993-05-22 | Photochromism anti-forging printing ink and its prodn. method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1095734A true CN1095734A (en) | 1994-11-30 |
| CN1039649C CN1039649C (en) | 1998-09-02 |
Family
ID=4986073
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93106107 Expired - Fee Related CN1039649C (en) | 1993-05-22 | 1993-05-22 | Photochromism anti-forging printing ink and its prodn. method |
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| Country | Link |
|---|---|
| CN (1) | CN1039649C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1064046C (en) * | 1997-11-12 | 2001-04-04 | 南开大学戈德防伪技术公司 | Photochromic spiro-compound and its preparation |
| CN1315555C (en) * | 2002-10-30 | 2007-05-16 | 百乐墨水株式会社 | Method of alternatively dioplaying photochromic action of memory color in toy assembly, and photochromic toy having alternatively color memory |
| US7238460B2 (en) * | 2002-09-04 | 2007-07-03 | National Institute Of Advanced Industrial Science And Technology | Optical recording medium, production method thereof and method of using same |
| CN103911877A (en) * | 2014-04-17 | 2014-07-09 | 傅科杰 | Color-changing agent applicable to textile fabrics |
| CN106046241A (en) * | 2016-06-01 | 2016-10-26 | 何国雄 | Preparation method of double-pyran thiophene photochromic polymer and color-changing anti-counterfeiting printing ink thereof |
| CN110698923A (en) * | 2019-07-12 | 2020-01-17 | 湖北中北工贸有限责任公司 | Optically variable ink |
| CN112208237A (en) * | 2020-10-14 | 2021-01-12 | 深圳市深龙杰科技有限公司 | Method for printing multicolor pattern by adopting photochromic principle |
| CN114561124A (en) * | 2022-04-11 | 2022-05-31 | 辽宁大学 | Anti-counterfeiting ink with controllable color development time and anti-counterfeiting printed matter containing anti-counterfeiting ink |
-
1993
- 1993-05-22 CN CN 93106107 patent/CN1039649C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1064046C (en) * | 1997-11-12 | 2001-04-04 | 南开大学戈德防伪技术公司 | Photochromic spiro-compound and its preparation |
| US7238460B2 (en) * | 2002-09-04 | 2007-07-03 | National Institute Of Advanced Industrial Science And Technology | Optical recording medium, production method thereof and method of using same |
| CN1315555C (en) * | 2002-10-30 | 2007-05-16 | 百乐墨水株式会社 | Method of alternatively dioplaying photochromic action of memory color in toy assembly, and photochromic toy having alternatively color memory |
| CN103911877A (en) * | 2014-04-17 | 2014-07-09 | 傅科杰 | Color-changing agent applicable to textile fabrics |
| CN106046241A (en) * | 2016-06-01 | 2016-10-26 | 何国雄 | Preparation method of double-pyran thiophene photochromic polymer and color-changing anti-counterfeiting printing ink thereof |
| CN110698923A (en) * | 2019-07-12 | 2020-01-17 | 湖北中北工贸有限责任公司 | Optically variable ink |
| CN112208237A (en) * | 2020-10-14 | 2021-01-12 | 深圳市深龙杰科技有限公司 | Method for printing multicolor pattern by adopting photochromic principle |
| CN114561124A (en) * | 2022-04-11 | 2022-05-31 | 辽宁大学 | Anti-counterfeiting ink with controllable color development time and anti-counterfeiting printed matter containing anti-counterfeiting ink |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1039649C (en) | 1998-09-02 |
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