Tamper-resistant paint for color inkjet printing


(57) Abstract:

The invention relates to the development of counterfeit-protected inks for inkjet printing methods that can be used to make important business documents. Describes tamper paint for color ink jet printing containing microcapsules soluble pigment and microcapsules protective compounds, each in an amount of 1.1-1.3 wt.%, moreover, the pigment and protective compound adsorbed on ultramatic particles of silver chloride in the form of microcapsules with a shell of structured polyethylenimine melamine-formaldehyde resin. The paint also contains surfactant OP-7 in the amount of 3.0 to 3.2 wt.% and OS-20 - 1.5 to 1.7 wt. %, thiourea - 4,5-4.7 wt.%, vegetable oil - 1,0-1,2 wt.% and distilled water - the rest. The paint provides a high degree of reliability of printed products against forgery, simplicity and efficiency authenticate and has excellent printing characteristics.

The invention relates to printing inks and ink, and more particularly to tamper-resistant inks for inkjet printing methods. The main area of ispolzovat important business documents.

Known compositions of the inks for ink jet printing containing a binder, the dye in dispersion, surfactant and solvent, usually water /U.S. patent N 5395431, MKI C 09 D 11/02, NCI 106-20 P, 1994; Japan's bid N 8612223, MKI C 09 D 11/18, 1996; Japan's bid N 6013653, MKI C 09 D 11/00, 1994/. Inkjet inks are strictly balanced systems. Introduction to the composition of any additional substances in order to give them special properties leads to the destabilization and destruction of the variance. Therefore tamper inkjet ink is barely known. Of the many patents relating to inkjet inks, as a prototype of the proposed technical solution selected U.S. patent N 5395432 A MKI C 09 D 11/00, NCI 106-21 A, 1993 (prototype), in which the proposed structure cannot be fake ink for inkjet printing method. According to the patent, the ink contains a binder resin soluble in alcohol - polyamide, polyketone, acrylic and other denatured ethyl alcohol, nonionic surfactant, deionized water and technological additives defoamers. As a protective compounds in the paint composition is administered zinc chloride or ferric chloride in amounts of from 0.5 d which is only by the action of the sealed section of special chemicals (token).

The disadvantages of the proposed prototype composition should include the fact that it is not possible to print a visible tamper information or image, and requires application to the visualization of additional funds. In addition, the inkjet ink is not waterproof and printed image made it when wet, blurred, which is unacceptable for important business documents.

The technical problem on which this invention is directed, is to determine the composition of water-resistant, tamper-resistant inks for inkjet printing methods. While the paint on the prints should be protected by known chemical compounds, for example, phosphors, optical brighteners, fotogrammi, etc. It should also provide the ability to create not only hidden, but visible printed image.

A positive result is achieved by the fact that the proposed ink-jet ink contains soluble organic pigment and a protective compound in the form of microcapsules with a size of 0.1 - 0.2 μm. Themselves microcapsules consist of a kernel - ultramega particles of silver chloride which precipitated organic pigment or a protective connection is ski injected a mixture of surfactants OP 7 (monoalkylphenols ether of polyethylene glycol, containing 7-8 ethoxylated groups) and OS-20 (polietilenglikolya a fatty acid ester, C18-20), thiourea and vegetable oil. Finish paint is a water dispersion and has the following ratio of ingredients, %:

Microcapsules with soluble organic pigment - 1,1 - 1,3

Microcapsules with a protective compound is 1,1 - 1,3


OP-7 - 3,0 - 3,2

OS-20 - 1,5 - 1,7

Thiourea - 4,5 - 4,7

Vegetable oil - 1,0 - 1,2

Distilled water - the Rest

The use in inkjet inks the coloring matter and protective compounds in the form of microcapsules with a size of 0.1 - 0.2 μm, and a mixture of two surfactants having different chemical and conformational structure of thiourea as a regulator of rheology of disperse systems provide using an inkjet printing is protected from a fake hidden (if the system has to exclude microcapsules with pigment) and the visible image on the paper.

Comparative analysis of the prototype allows to conclude that the claimed anti-forgery ink-jet ink is different from the known as on the chemical nature of the main ingr the p composition of ingredients of the paint gives the printed sheets new properties moisture resistance, totoproject, provides the ability to obtain and protect against forgery color images, which allows to draw conclusions on the conformity of the proposed solutions to the criterion of "significant differences".

Information confirming the possibility of carrying out the invention.

Tamper-resistant paint for color inkjet printing, proposed in this invention can be used for applying visible or hidden text and artistic images on porous substrates, mainly for paper and cardboard. Authenticity executed prints can be checked using a conventional quartz-analytical lamp.

For compositions of paint pre-microcapsules were prepared with organic pigments and protective compounds in the form of their dispersions in water.

Of different groups soluble organic pigments to obtain triad in relation to the subtractive method of color reproduction, implemented using an inkjet printer, were selected pigments, high purity color tone:

- purple color component Hostaperm - Rosa E Efal 305 firm Hoechst (Germany);

- R>
with the blue color component of PV - Echtblau BG DJHL 502 firm Clariant GmbH (Germany) or Neozapon Blau 807 BASF AG (Germany).

As protective compounds used:

- phosphor - Luminor yellow-green 540 T (TU 6-09-477-76, chem. plant them. Exam, Moscow);

optical bleach uvitex OB 45420 "Ciba-Geigy (Switzerland);

UV - absorber - Advastab 46 company "Advance" (Germany) 2-Hydroxy-4-octyloxybenzophenone or Tinuvin P 2-(2'-Hydroxy-5'-methylbenzotriazole company "Ciba-Geigu" (Switzerland); organic photochrom - 61-thermo-1,3 .3m1-trimethylspiro-[(2H1-11- benzopyran)-2,21indolin], thermochromic compound - 61,81-dichloro-1,3 .3m1-trimethylspiro-[(2H1-11-benzopyran)-2,21indolin] .

These pigments are capsulerebel substances. For each of them prepared a mixture consisting of a, g: capsuleneo substance - 0,9; thiourea - 2,1; surfactants - OP-7 - 1,4; OS-20 - 0,7; sunflower oil is 0.5. The mixture was dissolved with stirring in 20 ml of ethanol to the formation of homogeneous solution. Then the alcohol was evaporated at 75-80oC in a water bath. The obtained paste was dissolved in 33 g of distilled water and subjected to SUP> at a frequency of 20 MHz for 1 h during ultrasonic impact every 15 min to the mixture was sequentially added 2.5 wt.% aqueous solutions of polyethylenimine (mol. m 10000) - 2 g of silver nitrate and 1.5 g of hydrochloric acid to 2.5 wt.% an aqueous solution of melamine-formaldehyde resin (pH 1,42) - 3, were obtained by the Sol capsulerebel substances in an aqueous medium containing a surfactant, thiourea and sunflower oil. As a result of interaction of silver nitrate and hydrochloric acid was accompanied by the formation of microparticles of silver chloride, which was adsorbing from a mixture of primarily Sol capsulerebel substances, and then melamine-formaldehyde resin. The latter was graded by polyethylenimine. In this way the reaction mixture was obtained microcapsules consisting of microparticles of silver chloride with adsorbed on them by Sol capsulerebel substances and shell of the melamine-formaldehyde resin, structured (stitched) polyethylenimine. The size of the microcapsules was 0.1 to 0.2 microns with a distribution of 98%. Surfactants, thiourea and sunflower oil in the composition of the microcapsules are not included. They provide the possibility of emulsification process, the RM mixture are water dispersion, containing microcapsules with organic pigments, and can be used as paints for colour inkjet printing. Dispersion of microcapsules with a protective compounds used for printing concealed images observed only upon irradiation with filtered UV light.

With the aim of obtaining counterfeit ink for color inkjet printing each of the dispersions of microcapsules with Magenta, yellow, and blue pigments were mixed with an equal quantity of the dispersion of microcapsules with one of the protective compounds. Thus, the formulation is protected from a fake colors for color inkjet printing includes, g (%):

Microcapsules with an organic pigment (Magenta, yellow, or blue) - 1,1 (1,2)

Microcapsules with one of the protective compounds - 1,1 (1,2)

Surfactant - OP-7 - 2,8 (3,1)

OS-20 - 1,4 (1,6)

Thiourea - - 4,2 (4,6)

Sunflower oil - 1,0 (1,1)

Distilled water - 79,0 (87,2).

According to this formulation was prepared by the triad of protected colors - Magenta, yellow, and blue.

For applying the printed image on the writing paper of the type "the Seagull" used inkjet printer model 690 print cartridge HP 51629 company "Hewlett Packard" (USA), sochineniy the est program contained color text and artistic images.

The color of the printed image produced by triad containing microcapsules with phosphor or optical bleach when exposed to UV light (a = 365 nm), fluoresce intensely. When used in a paint composition UV-adsorber printed image looks dark on the total light background paper. The presence in the paint organic photochrome gives the printed image effect photochromism - under irradiation of UV light (a = 365 nm) the intensity of the luminescence of the dye in the visible region gradually within 1-3 min increases to 7-8 times. Luminescence colour varies from pink to bright crimson. In daytime lighting conditions within 3-5 min color is initial.

In the case of the use of microcapsules with a thermochromic substance - colorful printed image when heated print on special thermostate (you can use any electric appliance with a sheathed heating element), 120oC changes the color from slightly red to intense blue. At day light the paint gradually regains its color.

The presence of the listed effects on printed materials or decorated using an inkjet printerproperties dyes and protective compounds are water resistant, have high printing technical characteristics. Paint penetrate deep into the paper 30-40 μm when the thickness of the paper 80-90 μm. Penetration of paint on the reverse side of the paper was not observed.

Test prints after 45 min after printing has shown that the hydration colorful image is not blurred and does not have a halo, and a day later reprints withstand even a short immersion in hot (60-80oC) water.

Use a paint composition microencapsulated substances is a kind of technological protection executed documentation, as are virtually impossible for counterfeiters technical difficulties.

Thus, the application of the proposed inkjet inks provides in comparison with the known paint the following benefits:

- high reliability printed products against forgery;

the simplicity and efficiency of the authentication as it does not require the use of special activators;

- process control and authentication samples do not undergo irreversible changes and suitable for further use.


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