CN1071182A - Heat-sensitive colour-changing ink - Google Patents
Heat-sensitive colour-changing ink Download PDFInfo
- Publication number
- CN1071182A CN1071182A CN 91109163 CN91109163A CN1071182A CN 1071182 A CN1071182 A CN 1071182A CN 91109163 CN91109163 CN 91109163 CN 91109163 A CN91109163 A CN 91109163A CN 1071182 A CN1071182 A CN 1071182A
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- coordination thing
- heat
- thing
- ink
- colour
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- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The present invention relates to a kind of heat-sensitive colour-changing ink, particularly be used in the antiforge trade mark, packing box for example, wrapping paper, anti-false trademark on the packaging film and false proof pressure-sensitive adhesive trade mark and plastic wrapping and all prints that need take false proof measure, comprise low-melting ink vehicle, filler, pigment in the printing ink is a kind of in the following coordination thing or two or more arbitrary combination: copper (1) is or/and coordination thing or divalent transition metal and 3 of the derivative of the coordination thing of silver (1) and the iodide of mercury or itself and dithiocarboxylic acid, the coordination thing of 3 dimethyl tetramethylenediamines or quadrol or hexamethylenetetramine or pyridine, whole coordination thing weight account for 5～30% of total weight.Heat-sensitive colour-changing ink of the present invention is cheap, and is convenient and practical.
Description
The present invention relates to a kind of heat-sensitive colour-changing ink, particularly be used in the antiforge trade mark, for example the packing closes, anti-false trademark on the wrapping paper, packing book film and false proof pressure-sensitive adhesive trade mark and plastic wrapping and need take the heat-sensitive colour-changing ink of all prints of false proof measure.
Along with going deep into and expanding economy of China's reform and opening-up, the proportion of market economy is with increasing, the kind of light industrial goods is more and more, quality is also more and more higher, people are after pleasantly surprised, found that but another problem-fake products is also more and more, and the technology that appearance is imitated is also more and more higher, increasing of fake products, increased fear for people's work and life, although TV, news medias such as newspaper often remind this to belong to illegal activities, but because the legal system of China is not well established, and the also lighter book of people's sense of legal system, counterfeit product is to have to prohibit not have to end the name cigarette, the name cigarette, famous brand of wine, change the shape product, audio-visual product, pharmaceuticals and invigorant etc. are palmed off the object that factory falls over each other to imitate especially, even make the counterfeit drug product, murder for one's money, make false agricultural chemicals, false chemical fertilizer causes the crops underproduction or the particle in 1 year not to be received, the hole state hole people, fake products has seriously been upset market, has damaged consumers in general's interests.
At this illegal activities of disregarding prohibitions, domestic many producers all stick on the laser hologram sign of a small area on the packing of own product, and laser hologram sign cost height, and be difficult to directly be printed in the whole commodity packaging, add that it also can copy, the human consumer is difficult to again distinguish then and there and differentiates.
The object of the present invention is to provide a kind of cheap, convenient and practical heat-sensitive colour-changing ink.The various prints that this printing ink is printed, the human consumer can very easily distinguish then and there and differentiate, can effectively stop and hit counterfeit commodity and print.
Analysis-by-synthesis is the characteristics of existing various anti-counterfeiting packing materials both at home and abroad, and a good anti-false sign should have following characteristics:
A) can have tangible physical condition to change, best this variation is a reversible;
B) changing should be rich and varied;
C) human consumer detects simple, the convenience of variation means of this physical condition;
D) do not destroy the glassine paper of original packing, particularly outer packaging as far as possible;
E) make this packing as far as possible simply, conveniently, preferably adopt the mode of printing;
F) imitation should be compared difficulty, and antifalse effect is good;
G) cheap.
Heat-sensitive colour-changing ink of the present invention comprises low-melting ink vehicle, and filler, the pigment in the printing ink are a kind of in the following coordination thing or two or more arbitrary combination:
1) the coordination thing of the iodide of copper (I) and mercury;
2) the coordination thing of the iodide of silver (I) and mercury;
3) the coordination thing of the derivative of the iodide of copper (I) and mercury and dithiocarboxylic acid;
4) the coordination thing of the derivative of the iodide of silver (I) and mercury and dithiocarboxylic acid;
5) the coordination thing of the derivative of the iodide of copper (I) and silver (I) and mercury and dithiocarboxylic acid;
6) the coordination thing of divalent transition metal and 3,3 dimethyl tetramethylenediamines;
7) the coordination thing of divalent transition metal and quadrol;
8) the coordination thing of divalent transition metal and hexamethylenetetramine;
9) the coordination thing of divalent transition metal and pyridine;
Whole coordination thing weight accounts for the 5-30% of total weight.
Above-mentioned divalent transition metal can be copper or cobalt or nickel or manganese, wherein is best with the cobalt.
Anionic radical in the above-mentioned divalent transition metal can be Cl
-Or Br
-Or I
-Or No
- 3Or So
2- 4Or ClO
- 4Or BF
- 4
Low-melting ink vehicle in the above-mentioned printing ink can adopt various low-melting ink vehicle of the prior art, to adapt to the requirement of various printing ink, for example tin printing ink, ink used for plastic or the like, inventive point of the present invention does not lie in low-melting ink vehicle, and is to adopt the heat-sensitive variable colour ligand to substitute or part substitutes pigment in the printing ink of prior art.
These meet certain requirements as the thermosensitive chromotropic material of the pigment in the printing ink, can be following several:
Cu
2Hg I
4Discoloring temperature be 67 ℃, its colour-change is for purple from red stain;
Ag
2Hg I
4Discoloring temperature be 50 ℃, its colour-change is to be pink from xanthochromia;
CuIAuIHgI
2Discoloring temperature be 70 ℃, its colour-change is to become redness from yellow orange;
CoCl
22(CH
2)
6N
410H
2The discoloring temperature of O is 35 ℃, and its colour-change is from the pink blueness that becomes;
CoBr
22(CH
2)
6N
410H
2The discoloring temperature of O is 40 ℃, and its colour-change is from the pink blueness that becomes;
CoI
22(CH
2)
6N
410H
2The discoloring temperature of O is 50 ℃, and its colour-change is from the pink green that becomes;
Co(CNS)
22(CH
2)
6N
410H
2The discoloring temperature of O is 60 ℃, and its colour-change is from the pink cyan that becomes;
Co(No
3)
22(CH
2)
6N
410H
2The discoloring temperature of O is 75 ℃, and its colour-change is to be red-violet colour from red stain;
CoSo
42(CH
2)
6N
410H
2The discoloring temperature of O is 60 ℃, and its colour-change is from the pink purple that becomes;
NiBr
22(CH
2)
6N
410H
2The discoloring temperature of O is 60 ℃, its colour-change be become from pale green light blue;
NiCl
22(CH
2)
6N
410H
2The discoloring temperature of O is 60 ℃, and its colour-change is to become purple from pale green;
Ni(No
3)
22(CH
2)
6N
410H
2The discoloring temperature of O is 60 ℃, and its colour-change is from the pink red-violet colour that becomes;
Co(AsO
4)
2C
6H
5N8H
2The discoloring temperature of O is 50 ℃, and its colour-change is from the sky blue green that becomes;
Co(CNS)
2(C
6H
5N)
2Discoloring temperature be 90 ℃, its colour-change is from the pake purpke blueness that becomes.
Above-mentioned various off-color materials can combine dexterously, and low-melting ink vehicle, filler with forming printing ink constitute the askew kind of better heat-sensitive colour-changing ink of performance, because selection is different with ratio, will influence change in color, therefore make anti-fake mark more be difficult to copy.
In theory, the reversible colour-change can take place in some material under heat effect, and this phenomenon is called thermochromism.The color that has been found that some coordination thing can be with temperature generation obvious variation, and this thermochromism causes owing to the relevant stereochemical change of the heat of chromophoric group that normally it depends on the central ion of coordination thing and the character of ligand.
Transition metal (as Cu, Co, Ni) waits the complex compound of some diamines to show thermal discoloration, central ion ligand and negatively charged ion difference, and each is variant for the thermo-color performance, and the obvious degree of variable color etc. all is subjected to the influence of above-mentioned factor.Central ion and the ligand identical, and negatively charged ion difference, then change in color difference as having of some complex compound.Some is to change suddenly, and some is a continually varying.And when changing ligand, then can obtain the thermal discoloration compound of a step or two step variable colors.Can also change discoloring temperature as required.Change the electrochromic substance that central ion can obtain different colours.This metal complex with d-d absorption band, although the detailed mechanism of its thermochromism is also disputable, but the lever effect is universally recognized mechanism, promptly along with variation of temperature, variation has taken place in the chemical environment of central ion, thereby make the configuration of central ion that distortion take place, thereby changed the break-up energy of d-d track, absorption spectrum is changed.To the complex compound of Cu, Co, Ni and diamines, along with the increase of temperature, be in central ion and ligating atom planar reactive force and reduce, and the reactive force of negatively charged ion and central ion to be strengthened, distance shortens, thereby the minimizing of d-d break-up energy, and absorption band shifts.
By the thermosensitive chromotropic material that meets certain requirements as the pigment in the printing ink, with low-melting ink vehicle, the filler of forming printing ink, can make heat-sensitive colour-changing ink of the present invention, particularly be used in antiforge trade mark and plastic wrapping and all prints that need take false proof measure, thermosensitive chromotropic material in the printing ink can be in the above-mentioned coordination thing a kind of, in the above-mentioned coordination thing any all is to change reversible to change, the weight of whole coordination things accounts for 5～30% of total weight, and this heat-sensitive colour-changing ink can directly print various anti-counterfeit packages with fork-like farm tool used in ancient China.When the human consumer had the commodity of this anti-counterfeit package in purchase, only with hand was pinned or is heated the anti-fake mark certain hour of printing with cigarette end, as colour-change takes place, and after cooling, color is got back to original color again, is genuine piece, and this can satisfy the false proof requirement of general commodity.
Perhaps will have different colours changes, different discoloring temperatures, the off-color material of different variable color speed combines dexterously, with the low-melting ink vehicle of forming printing ink, filler together, because selection is different with ratio, to influence change in color, and therefore make anti-fake mark more be difficult to copy, can be used for some high-grade goods, as two kinds of material mixing are used, become blue look after wherein a kind of being heated, become original color after the cooling immediately again, become yellow after another kind is heated, but just can return very slowly, like this, after mixing by a certain percentage, under the situation of being heated, mark becomes green, cooling back mark becomes yellow, then just gets back to original color very slowly, thereby reaches better imitative pseudo-purpose.
Heat-sensitive colour-changing ink is mainly used in the antiforge trade mark, the change in color fork-like farm tool used in ancient China was judged the true and false of trade mark or packing before and after utilization was heated, because changing, the front and back of color relate to concrete prescription, primary colors and variable color and discoloring temperature can be as the foundations of judging, in prescription, design several transformation temperatures and color especially, the prescription of the coloured and coloured bleach of especially comprehensive colourless change, antifalse effect is extraordinary.
Owing to adopt the mode of printing, can also adopt chromaticity printing, first kind is adopted above-mentioned array mode with second kind of heat-sensitive colour-changing ink, can also comprehensive reversible color and irreversible off-color material, the thermosensitive chromotropic material in the printing ink can be two or more the arbitrary combination in the above-mentioned coordination thing, certainly, the color kind that changes is a lot, amplitude is changeable, as long as prescription changes promptly variable your the well-content color of sening as an envoy to.
This heat-sensitive colour-changing ink can also increase the popularity of product in false proof.Now range of product much needless to say, same series products (as beer) also has different manufacturers, the differentiation of different trade marks, want in these numerous like products, to improve the popularity of oneself, attract more customers, when advertising, if can somewhat distinguished thing, that really is further strengthened, and off-color material has catered to people's curiosity just, because curious, more people can talk about, buy your commodity, virtually, improved the popularity of product.
This heat-sensitive colour-changing ink can be used for the industry and the temperature indicating of civilian well heater, for example is used for the warning temperature indicating of electric food warmer, electric iron, can represent charging degree when being used in the outer packaging of rechargeable battery, also can be used for the toy industry, its discoloring temperature scope is very big, from-80 ℃～1300 ℃
This heat-sensitive colour-changing ink can be used on arbitrary mode of printings such as relief printing plate, lithographic plate, intaglio plate, silk screen, and do not influence the technology of printing, than the anti-false trademark (as the SUN crispy rice) of hologram 70-100 unit/square metre manufacturing cost, and the printing cost of anti-false trademark of the present invention than the only high 1-1.5 of original common printed cost unit/square metre, be cost 10-20 unit/square metre, therefore, have very big magnetism on the price, have very big market potential.
Heat-sensitive colour-changing ink of the present invention is cheap, convenient and practical, the various prints that this printing ink is printed, for example the packing closes, anti-false trademark on the wrapping paper, packing book film and false proof pressure-sensitive adhesive trade mark and plastic wrapping and need take all prints of false proof measure, very easy the differentiation then and there of human consumer differentiated, can effectively stop and hit counterfeit commodity and print.
Claims (3)
1, a kind of heat-sensitive colour-changing ink comprises low-melting ink vehicle, and filler is characterized in that, the pigment in the printing ink is a kind of in the following coordination thing or two or more arbitrary combination:
1) the coordination thing of the iodide of copper (I) and mercury;
2) the coordination thing of the iodide of silver (I) and mercury;
3) the coordination thing of the derivative of the iodide of copper (I) and mercury and dithiocarboxylic acid;
4) the coordination thing of the derivative of the iodide of silver (I) and mercury and dithiocarboxylic acid;
5) the coordination thing of the derivative of the iodide of copper (I) and silver (I) and mercury and dithiocarboxylic acid;
6) the coordination thing of divalent transition metal and 3,3 dimethyl tetramethylenediamines;
7) the coordination thing of divalent transition metal and quadrol;
8) the coordination thing of divalent transition metal and hexamethylenetetramine;
9) the coordination thing of divalent transition metal and pyridine;
Whole coordination thing weight account for 5～30% of total weight.
2, said according to claim 1, it is characterized in that divalent transition metal is copper or cobalt or nickel or manganese, wherein be best with the cobalt.
3, said according to claim 1, it is characterized in that the anionic radical in the divalent transition metal is Cl
-Or Br
-Or I
-Or No
- 3Or So
2- 4Or ClO
- 4Or BF
- 4
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91109163 CN1071182A (en) | 1991-09-28 | 1991-09-28 | Heat-sensitive colour-changing ink |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91109163 CN1071182A (en) | 1991-09-28 | 1991-09-28 | Heat-sensitive colour-changing ink |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1071182A true CN1071182A (en) | 1993-04-21 |
Family
ID=4909679
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91109163 Pending CN1071182A (en) | 1991-09-28 | 1991-09-28 | Heat-sensitive colour-changing ink |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1071182A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016197234A1 (en) | 2015-06-11 | 2016-12-15 | National Research Council Of Canada | Preparation of high conductivity copper films |
| US11472980B2 (en) | 2017-02-08 | 2022-10-18 | National Research Council Of Canada | Molecular ink with improved thermal stability |
| US11746246B2 (en) | 2017-02-08 | 2023-09-05 | National Research Council Of Canada | Silver molecular ink with low viscosity and low processing temperature |
-
1991
- 1991-09-28 CN CN 91109163 patent/CN1071182A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016197234A1 (en) | 2015-06-11 | 2016-12-15 | National Research Council Of Canada | Preparation of high conductivity copper films |
| US10954406B2 (en) | 2015-06-11 | 2021-03-23 | National Research Council Of Canada | Preparation of high conductivity copper films |
| US11472980B2 (en) | 2017-02-08 | 2022-10-18 | National Research Council Of Canada | Molecular ink with improved thermal stability |
| US11746246B2 (en) | 2017-02-08 | 2023-09-05 | National Research Council Of Canada | Silver molecular ink with low viscosity and low processing temperature |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |