WATER BASED MAGNETIC INK CHARACTER RECOGNITION INK JET INK BASED ON DISPERSION OF FUNCTIONALIZED NANOPARTICULATE MAGNETIC FERRITE

Abstract

The present invention describes a method to obtain magnetic aqueous ink composition for MICR (Magnetic Ink Character Recognition) ink jet printing comprising an aqueous dispersion of functionalized magnetic nanoparticles, humectant agents, solvents, biocide and water. It also allows obtaining stable inks for long periods with extremely high concentrations of magnetic nanoparticles with loading between 15% and 40% by mass and magnetic signals varying from 80 to 200%. Through the use and special combination of humectant agents, the present inventions increase the print head protection, by decreasing abrasiveness and increasing fluidity. The resulting ink has superior printing quality and increased service life of the printing system.

Claims

1-12. (canceled)

13. A method of making a magnetic ink character recognition inkjet ink composition, comprising: providing a mixture of a solvent comprising at least one of a polyol and an humectant; homogenizing the solvent mixture to provide a homogenized aqueous ink base; adding a stabilized aqueous dispersion of functionalized magnetic ferrite nanoparticles to the homogenized aqueous ink base to provide an ink mixture; mixing the ink mixture to provide a magnetic ink character recognition inkjet ink composition.

14. The method of claim 13, further comprising making the stabilized aqueous dispersion of functionalized magnetic ferrite nanoparticles, prior to adding the stabilized dispersion of functionalized magnetic ferrite nanoparticles to the homogenized aqueous ink base.

15. The method of claim 14, wherein making the stabilized aqueous dispersion of functionalized magnetic ferrite nanoparticles comprises: (a) treating a surface of magnetic ferrite nanoparticles with a solution of a mineral acid to provide acid-treated magnetic ferrite nanoparticles; (b) washing the acid-treated magnetic ferrite nanoparticles with a first washing fluid to remove ions and salts from the acid-treated magnetic ferrite nanoparticles; (c) functionalizing the acid-treated magnetic ferrite nanoparticles with oxalic acid, citric acid, tartaric acid, amino acid, or a combination thereof to provide functionalized magnetic ferrite nanoparticles; (d) adjusting a pH of the functionalized magnetic ferrite nanoparticles to about pH 5.0 to 8.0; (e) washing the functionalized magnetic ferrite nanoparticles with a second washing fluid, using filtration, dialysis, decantation mixing water and organic solvents, or a combination thereof, to provide the stabilized aqueous dispersion of functionalized magnetic ferrite nanoparticles.

16. The method of claim 15, wherein making the stabilized aqueous dispersion of functionalized magnetic ferrite nanoparticles further comprises ultrasonication of the stabilized aqueous dispersion of functionalized magnetic ferrite nanoparticles.

17. The method of claim 13, wherein the at least one of a polyol and an humectant is selected from glycerin, diethylene glycol, polyethylene glycol, ethylene glycol monoethyl ether, sorbitol, mannitol, glycereth, bis-(cyanoethyl)-dihydropropylamine, bis-(2-hydroxyethyl) glycolamide, bis-(hydroxyethyl)-lactamide, bis-(hydroxyethyl)-lactamide, bis(hydroxyethyl) dimethyl hydantoin, and any combination thereof.

18. The method of claim 13, further comprising adding a wetting agent to the ink mixture.

19. The method of claim 13, further comprising adding a biocide to the ink mixture.

20. The method of claim 13, further comprising filtering the magnetic ink character recognition inkjet ink composition.

21. The method of claim 13, wherein the magnetic ink character recognition inkjet ink composition comprises from 15 wt % to 40 wt % of functionalized magnetic ferrite nanoparticles.

22. The method of claim 13, wherein the magnetic ink character recognition inkjet ink has a viscosity of up to 18 cP.

23. The method of claim 13, wherein the magnetic ink character recognition inkjet ink has a density between 1.2 and 1.7 g/cm.sup.3.

24. The method of claim 13, wherein the magnetic ink character recognition inkjet ink has surface tension between 25 and 55 dyne.

25. The method of claim 13, wherein the magnetic ink character recognition inkjet ink has conductivity between 500 and 1000 μS cm.sup.−1.

26. The method of claim 13, wherein the magnetic ink character recognition inkjet ink has pH of about 7.0.

27. The method of claim 13, wherein the size of the functionalized magnetic ferrite nanoparticle is less than 200 nm.

28. The method of claim 13, wherein the magnetic ink character recognition inkjet has magnetization between 80% and 200%.

29. A magnetic ink character recognition inkjet ink composition, made by the method according to claim 13.

Description

DESCRIPTION OF THE DRAWINGS

[0020] FIG. 1: hydrodynamic size distribution of particles, by the technique of Dynamic Light Scattering (DLS) of Nanumadit NA-0701 additive.

DETAILED DESCRIPTION OF THE INVENTION

[0021] To obtain aqueous MICR inks for inkjet printing starts from aqueous dispersion of functionalized nano-sized magnetic ferrite produced according to the process described in U.S. Pat. No. 8,815,393 B2. Nanometrics, simple or compound magnetic ferrites are chemically synthesized by co-precipitation where their physical and magnetic characteristics can be adjusted as needed. These adjustments are possible by modifying the composition of the metal oxide according to the following criteria for simple ferrite (MFe2O4 or MFel2O19) or for compound ferrites (NxM(1-x)Fe2O4 or N(1-y)Mx+YFe(2-x)O4, for example) where M and N can be metal atoms such as Sm, La, Bi, Ba, Mo, Sr, Ni, Co, Fe, Mn, Cr, etc. These ferrites exhibit a particle size distribution ranging from 15 to 300 nm, preferably between 15 and 120 nm, as shown in FIG. 1 below, with a surface area between 10 and 120 m2/g, preferably between 25 and 90 m2/g. Presenting also magnetic saturation between 05 and 80 emu/g, magnetic remanence ranging from 1 to 60 emu/g magnetic coercivity of from 10 to 3000 Oe, a magnetic saturation, preferably between 30 to 80 emu/g, magnetic remanence from 10 to 30 emu/g, and magnetic coercivity between 200 and 800 Oe.

[0022] The following Table 1 shows some practical results:

TABLE-US-00001 TABLE 1 Magnetic properties of the additives used in the MICR ink production. Hc Mr Ms Nanumadit (Oe) (emu/g) (emu/g) Composition NA-2601 34 3 55 Manganese, Boron ferrite NA-2701 724 4 15 Barium, Cobalt ferrite NA-2801 553 15 41 Cobalt. Cerium ferrite NA-0701 347 19 62 Manganese, Cobalt ferrite NA-2901 238 14 54 Manganese, Gadolinium, Cobalt ferrite NA-3001 1201 25 42 Barium ferrite Hc: coercive field, Mr: remnant magnetization, Ms: saturation magnetization

[0023] After this co-precipitation process, a surface treatment of the particles occurs with the addition of a strong acid or base solution, followed by a first wash, thereby preparing the material for functionalization. The functionalization for aqueous base can be accomplished with a functionalizer, or a combination thereof, chosen from oxalic acid, citric acid, tartaric acid and amino acids. The material obtained by the functionalization with adjusted pH is then washed again. This second wash may occur by filtration, dialysis and/or decantation mixing water and organic solvents. So far all follow the procedures set forth in U.S. Pat. No. 8,815,393 B2 and the resultant ferrofluid with solids concentration between 35% and 55%, preferably 50%, is directed to the manufacture of ink without the necessity of transformation into a powder. Some weak agglomeration may occur at this time, particularly if the ferrofluid is stored for a long period, and in this case, a physical deagglomeration action can occur, such as a gentle grinding to not damage the particle/I functionalizing system. Preferably the deagglomeration is done by ultrasound. In general, the ferrofluid, the standard dispersion to produce MICR ink for inkjet printing has the following characteristics: viscosity between 40 and 400 cP for a suspension of 50% m/m and a pH between 5 and 8. In Table 2, below shows practical results of these Nanum dispersions that are already in the market.

TABLE-US-00002 TABLE 2 Physical and chemical properties of magnetic additives used in MICR ink production. Nanumadit Viscosity (cP) pH NA-0701 150-200 6.5-7.0 NA-0716 350-400 7.0-8.0 NA-2701 300-380 6.5-7.0 NA-2801 250-350 6.5-7.0

[0024] In general, the requirements for an adequate MICR ink is to have good print quality, stability, do not cause printhead clogging, good magnetic reading, low kogation, and longprinting decap time. The quality of ink printing includes good definition of the printed characters, driven mainly by the physicochemical characteristics of it, such as viscosity and surface tension. The stability of the ink is closely linked to the stability of the dispersion and the dispersion with the mixing of other solvents, thus other solvents which comprises the ink cannot destabilize the initial dispersion. The ink destabilization leads to clogging of the of the printhead nozzles. Another cause of clogging of these orifices is any failure in the process that allows, for example, contamination by dust or other materials. Typically, all the ink undergoes a final filtration process with filter elements of 0.2 microns to guarantee this does not cause clogging.

[0025] In addition, another major cause of clogging and printing failure is the drying of ink or the deposition of decomposed inkthrough the nozzles (kogation). It is necessary to balance the ink drying time in such a way that as soon as the inkjet exits the nozzles, ink blots and scattering does not occur in the already printed substrate and this variable also depends on the printer technology and printing speed. Thus, it is common to use specific and adapted inks to the various printheads and inkjet technologies (thermal, piezoelectric, etc.). This need for fast ink drying on the substrate also leads to the drying of the ink at the edge of the print nozzles when printing stops. In the return of the activities the dry film should be quickly and completely eliminated to avoid compromising the next print quality, so get a good printing decap time is also key. To analyze and monitor the behavior of the ink decap time and kogation 25 cm solid-fill printing evaluations are performed on the time of the cartridge filling and then after resting for 5 minutes, 30 minutes, 1 day, 7 days and 30 days with no external device that stimulates jetting. In none of these cases the print quality may be compromised.

[0026] With the dispersions based on functionalized nanoparticles, key feature of this technology presented here, the stability of the ink is not a problem and all eyes are basically focused on print quality, drying time, kogation and decap time.

[0027] The production of the MICR ink starts by the manipulation of other solvents (such as—pyrrolidone, n-methyl-pyrrolidone, butyldiglycol, etc) that comprise the aqueous base and will receive the generated or previously acquired magnetic dispersion. The solvents on this technology contain polyols and other humectants which influence the drying time, penetration of the ink into paper or other substrate, and decap time. From the large amount of existing polyols and other humectants compounds which exhibit excellent performance for this technology the preferred are glycerin, diethylene glycol, polyethylene glycol, etilenoglicolmonoetileter, sorbitol, mannitol, glicereth bis-(cyanoethyl)-dihydroxypropylamine (known as “C-1”), bis-(2-hydroxyethyl) glycolamide (known as “BHEGA”), bis-(hydroxyethyl)-lactamide (known as “BHELA”) and bis-(hydroxyethyl) dimethyl hydantoin (referred to as “DANTOCOL EHD”).

[0028] Immediately after homogenizing the aqueous ink base it is added a sufficient amount of the magnetic dispersion (Nanumadit) and new mixing is processed. Depending on the print head and jet firing technology, wetting agents are added to adjust the surface tension, as well as biocides. The ink is then filtered and is ready for storage, supply cartridges, shipment, etc.

[0029] In general, the MICR inks are characterized by viscosity up to 18 cPs, a density between 1.2 and 1.7 g/cm.sup.3, surface tension between 25 and 55 dyne, conductivity between 500 and 1000 μS.Math.cm-1, neutral pH (˜7), particle size smaller than 200 nm and magnetization between 80% and 200% as measured, for example, using the MICR Qualifier equipment from the ROM Corporation.

[0030] Following are examples of the process and products claimed:

Example 1

[0031] The formula is manipulated by homogenization of components forming the basis of the ink which is aqueous. To ensure humectation, decap time and printing head protection diethylene glycol (2%), glycerin (1%) and Dantocol DHE (3%) are added plus 2-pyrrolidone (5%) and butyldiglycol (1%) for drying. Besides influencing the drying time, 2-pyrrolidone improves print quality and butyldiglycol allows greater penetration of the ink into the paper. Water completes the base formulation with 28%. The rest 60% is the ferrofluid Nanumadit NA-0701, synthesized such as described in U.S. Pat. No. 8,815,393 B2 and added in a second step. In this formulation ferrofluid contains 50% of solids and is comprised of a cobalt and manganese ferrite functionalized with citric acid using water as the carrier. The ink base plus the ferrofluid is now homogenised for 60 minutes at 230 rpm without heating. biocide was added to control the growth of microorganisms. This ink has for example printed using HP122 cartridge reaching average magnetization of 110% using IDAutomationSCMC7 source; size 12; and paper weights of 120 g/m.sup.2.

Example II

[0032] In this other formulation, also aqueous, it is added glycerin (7%), BHELA (5%) and polyethylene glycol 6000 (2.5%). Water completes the base formulation with 21.5%. After homogenization the base is added to the magnetic loading (64%)—Nanumadit 0701. Mixing is carried out for 60 minutes more at 230 rpm without heating. The ink is then filtered through 0.5 μm absolute filter. Wetting agents and biocide were added to adjust the surface tension of the cartridge in the acceptable range and control the growth of microorganisms. This formulation has been developed for high-speed printers with piezo printhead, such as Kyocera KJB4 printhead.

Example III

[0033] Another formulation was developed using now Nanumadit NA-0716 additive. It was mixed for humectation diethylene glycol (2%), glycerin (2%) and C-1 (5%) and 2-pyrrolidone (10%) for drying, and print quality. Water is added (26%) to complete the base formulation. In a second step it was added the magnetic loading (55%)—0716 Nanumadit synthesized according to U.S. Pat. No. 8,815,393 B2. In this formulation the ferrofluid contains 50% solids and is comprised of a cobalt and manganese ferrite functionalized with histidine using water as the carrier medium. Homogenization is carried out for 60 minutes at 230 rpm without heating. Wetting agents and biocide were added to adjust surface tension and control the growth of microorganisms. This ink was printed using HP45 cartridge reaching average magnetization of 150% using IDAutomationSCMC7 source; size 12; and paper weights 90 g/m.sup.2.

Example IV

[0034] This aqueous base formulation was prepared with the additive Nanumadit NA-2701. For the base of the ink were mixed glycerol (7%), Dantocol DHE (5%), 2-pyrrolidinone (7%), Cab-o-jet 300 (10%) and water (11%). In a second step it was added the magnetic loading (60%)—2701 Nanumadit synthesized as described in U.S. Pat. No. 8,815,393 B2. In this formulation ferrofluid contains 50% solids and is comprised of a cobalt ferrite and barium functionalized with citric acid using water as the carrier medium. The homogenization was performed during 60 minutes at 230 rpm without heating. The ink was filtered through 0.2 μm absolute filter. Wetting agents and biocide were added to adjust surface tension and control the growth of microorganisms. This formulation was developed for high-speed printers with piezo print head, such as the Ricoh Gen4 head.

Example V

[0035] Another aqueous formulation was prepared using the additive Nanumadit NA-2801. Diethylene glycol (1%), glycerin (1%), polyethylene glycol 600 (1.5%), Dantocol DHE (3%), 2-pyrrolidone (5%), butyl diglycol (0.5%) and water (38%) were mixed to form the base of the ink. In a second step was added the magnetic loading (50%)—Nanumadit 2801, synthesized as disclosed in U.S. Pat. No. 8,815,393 B2. In this formulation ferrofluid contains 50% solids and is comprised of a cobalt and cerium ferrite functionalized with citric acid using water as the carrier medium. Homogenization is carried out for 60 minutes at 230 rpm without heating. Wetting agents and biocide were added to adjust surface tension and control the growth of microorganisms. This ink was printed using HP45 cartridge reaching average magnetization of 100% using IDAutomationSCMC7 source; size 12; and paper weights 140 g/m.sup.2.

Example VI

[0036] For the base of this ink formulation were mixed diethylene glycol (1%), glycerin (2%), BHELA (4%), n-methylpyrrolidone (8%) and water (25%). In a second step the magnetic loading was added (60%)—2812 Nanumadit synthesized as described in U.S. Pat. No. 8,815,393 B2. In this formulation ferrofluid contains 50% solids and is comprised of a cobalt and cerium ferrite functionalized with tartaric acid using water as the carrier medium. The homogenization was performed during 60 minutes at 230 rpm without heating. The ink was first filtered through a 1.0 m nominal filter and an absolute filter followed by 0.5 μm. Wetting agents and biocide were added to adjust surface tension and control the growth of microorganisms. This ink was printed using HP45 cartridge reaching average magnetization of 120% using IDAutomationSCMC7 source; size 12; and paper weights 90 g/m.sup.2.