Title of Invention	A REDISPERSIBLE PIGMENTED PRINTING INK COMPOSITION AND PROCESS FOR PREPARING THE SAME
Abstract	This invention relates to a redispersible pigmented printing ink composition for the continuous ink-jet printing process, said ink composition having a viscosity in the range of between 2 and 10 mPas, said ink composition comprising at least one solvent selected from the group consisting of water and organic solvents of the group of alcohols, ketones and esters, a binder system in an amount between 0.5 and 20% by weight of the total ink, which comprises at least one polymer compound selected from the group consisting of thermoplastic resins, and at least one inorganic luminescent pigment selected from the group consisting of crystalline compounds comprising activator-doped zinc sulfides; oxysulfides, vanadates, fluorides, oxides and oxyfluorides of yttrium or the rare-earths elements of the periodic table; or mixtures thereof, said pigments having a particle size of greater than 300 nm, conductivity control agents, at least one flocculating agent forming a re-dispersible sediment of said pigment in said composition, wherein said flocculating agent is selected from the group con¬sisting of inorganic salts of aluminum, calcium and iron (III), and of organic polymers carrying functional groups able to interact with and bind to the surface of said pigment particles, and wherein said flocculating agent is present in a concentration range of 0.01 to 20% of the inorganic pigment weight.

Title of Invention

A REDISPERSIBLE PIGMENTED PRINTING INK COMPOSITION AND PROCESS FOR PREPARING THE SAME

Abstract

This invention relates to a redispersible pigmented printing ink composition for the continuous ink-jet printing process, said ink composition having a viscosity in the range of between 2 and 10 mPas, said ink composition comprising at least one solvent selected from the group consisting of water and organic solvents of the group of alcohols, ketones and esters, a binder system in an amount between 0.5 and 20% by weight of the total ink, which comprises at least one polymer compound selected from the group consisting of thermoplastic resins, and at least one inorganic luminescent pigment selected from the group consisting of crystalline compounds comprising activator-doped zinc sulfides; oxysulfides, vanadates, fluorides, oxides and oxyfluorides of yttrium or the rare-earths elements of the periodic table; or mixtures thereof, said pigments having a particle size of greater than 300 nm, conductivity control agents, at least one flocculating agent forming a re-dispersible sediment of said pigment in said composition, wherein said flocculating agent is selected from the group con¬sisting of inorganic salts of aluminum, calcium and iron (III), and of organic polymers carrying functional groups able to interact with and bind to the surface of said pigment particles, and wherein said flocculating agent is present in a concentration range of 0.01 to 20% of the inorganic pigment weight.

Full Text	Field of invention The invention is in the field of inks preferably inks for the continuous-ink-jet printing. It concerns in particular pigmented security ink-jet ink formulations, containing inorganic luminescent pigments, which are easy to put into homogeneous dispersion condition (i.e. which have a good redispersibility) upon startup of the printing equipment, which remain homogeneously dispersed during printing operation, which avoid obstruction (clogging) of the printer nozzles, and which furthermore result in printed features of excellent contrast, adherence, as well as resistance against light, humidity, bleach and other adverse environmental influences. Background of the invention In the technique of continuous-ink-jet printing, such as first described in US 3,369,252, a stream of liquid ink is sObdivided into a sequence of small droplets by a piezoelectric resonator, vibrating at a frequency of the order of 50 kHz or more. The droplets are projected out of a nozzle towards the substrate. The electric potential against ground of said nozzle, and thus the electric charge of the resulting ink droplets, is controlled by an addressing electrode. Two deflector (electrodes, arranged along the projection path of said ink droplets, are held on predefined, constant electric potentials. They deflect the ink droplets according to their electric charge and make them impact on different locations on the substrate. By applying a corresponding electric pulse of appropriate voltage and duration to the addressing electrode, a single ink droplet can be addressed and directed to a specific location on the substrate. In the absence of an addressing voltage, the projected ink droplets are collected by a small collecting funnel, from where they are recycled to an ink reservoir. Refinements to the described printing method and equipment include the use of uncharged or slightly opposite charged guard drops between the printing droplets, such as first proposed in US 3,562,757, in order to minimize the effects of the mutual repulsion between droplets having the same electric charge. Further refinements to the printing method are proposed in US 3,828,354; US 3,833,910; US 3,846,800; US 4,688,048; as well as in many other publications. Inks for the continuous-ink-jet printing are normally of the soluble-dye type, in order to provide for the necessary homogeneity, and thus, an easy runnability on the printing machine. The inks may furthermore be fonnulated as solvent-based or water-based liquids. The later option is increasingly preferred, due to the ever growing environmental restrictions which apply to the use of organic solvents. However, printings made with such inks lack in general resistance against environmental influence, and they are also affected by solvents and/or water. Waterfast inks in particular are highly desirable for the production of permanent indicia or images. Pigmented inks for the continuous-ink-jet printing are known in the art and first described in US 4,365,'035. More recent publications include EP 751,194 and EP 853,106. Particular technical problems arise from the heterogeneous nature of the ink, which must be solved through the use of particular dispersing additives, and, principally, through a continuous stirring and circulating of the ink during printing operation. Pigment particles for ink-jet printing are preferably smaller than 1 micrometer, more preferably even smaller than 300 nanometers. However, the presence of some particles as large as 5 micrometers can be tolerated in an ink-jet formulation. In particular, ink-jet inks are generally passed through a filter of 10 micrometer pore size, in order to eliminate pigment fractions or agglomerates larger than this, which could obstruct the printing nozzles. Existing solutions to maintain the pigmented ink dispersed during printing operation, and to prevent hard settling of the pigment between printing operations, include the following approaches: • In US 6,062,682 the ink cartridge is moved along a carrier shaft such as to stir the pigment, and in US 5,451,987 the ink- and recovery-reservoirs are equipped with means, such as a magnetic stirrer, for agitating the ink. • US 5,650,802 suggests the use of a vibrating piezo element to prevent the pigment suspension from settling outside the printing periods. • Alternatively, a re-circulation of the ink in the system at regular frequency has also been successfully used to maintain the ink in an appropriate state of dispersion. Such a system is currently exploited in the OPAQUE DOMINO CIJ printers. In the field of security printing, it would be highly desirable to have available ink-jet inks which resist to the influence of light and to commonly available chemical agents, such as household bleach or solvents of the most various kind. Such inks could noteworthy serve for the rapid and reliable on-line numbering of security documents, such as banknotes, identity documents, lottery tickets, warranty labels and the like. A particular type of waterfast security inks for the ink-jet numbering of lottery tickets has been disclosed in US 5,498,283. However, the disclosed inks do merely contain an organic dye which has improved resistance to bleach; formulations containing inorganic luminescents are not disclosed. To provide for an appropriate intensity of the luminescence response, inorganic security pigments have generally a particle size of greater than 300 nm. Example of such pigments can be found in the disclosures of US 5,891,361; US 6,132,642 and WO 00/63317. Below said particle size, the surface-to-volume ratio of the particles, and thus the influence of the surface defects responsible for luminescence quenching, becomes too important, resulting in a strong drop of the luminescence quantum yield. The addition, to a continuous ink jet ink, of inorganic luminescents of said mentioned types noteworthy presents a couple of particular problems, which are due to the relatively high specific weight of said inorganic compounds, as compared to that of the printing liquid, to the required pigment size, as well as to the very low viscosity of the printing fluid. This results in a strongly increased tendency of the pigment to sediment, forming furthermore relatively dense deposits which are difficult to redisperse. After a stop and restart of the printing operations, not all pigment is thus necessarily redispersed; some of it remaining settled in the corners of the ink reservoir. Moreover, hard sedimentation of the inorganic pigment, when occurring between printing operations or during prolonged storage periods, is very difficult to redisperse and requires high shear mixing forces to put the pigment back into suspension. Hard sedimentation results in a change in concentration of the active ingredient with time, which is not compatible with the stringent standards of security printing. The combination of a particularly enhanced stirring and circulating of the printing liquid during operation, together with the use of an ink formulation according to the present invention, are efficiently used to remedy this problem. Summary of the invention The shortcomings of the inks according to the prior art are avoided by using an ink composition of the present invention. The inventors surprisingly found that a partial flocculation (destabilization) of the ink suspension turned out to be beneficial to its overall properties. The redispersion of a partially flocculated ink suspension turned out to be significantly improved, without perturbing the print-ability of the ink. The printing ink composition comprises at least one solvent, a binder system, optional defoaming, humectant and conductivity control agents, and at least one pigment; the composition being characterized in that it additionally comprises at least one flocculating agent, which flocculating agent is capable of forming a re-dispersible sediment of said pigment in said composition. The solvent is preferably selected from the group comprising water, alcohols (such as methanol, ethanol, etc.), ketones (such as acetone, methyl-ethyl-ketone, etc.) and esters (such as 6 methyl acetate, ethyl acetate, methyl propionate, etc.) or mixtures thereof. The binder system comprises at least one polymer compound suitable for ink-jet ink applications. Mixtures of different polymer compounds are usable as well. The polymer compounds are preferably chosen among the thermoplastic resins and are furthermore chosen such as to be compatible with the solvent. For aqueous ink formulations, the binder system is preferably, but not exclusively, chosen from the group comprising water-soluble resins, such as vinylpyrrolidone polymers and copolymers, water soluble polyesters, salts of acrylic and maleic anhydride polymers and copolymers, polyvinyl alcohol, cellulose derivatives, polyethyleneimides, etc., or from the group of film forming emulsions of fine polymer particles ( For solvent especially organic solvent based systems, solvent soluble thermoplastic resins are preferred, such as acrylic resins, e.g. poly (methylmethacrylate) , vinylic resins, e.g. vinyl acetate / vinyl chloride copolymers, polyvinylbutyral resins, cellulose resins, e.g. nitrocellulose, acetylcellulose etc., polyurethane resins, polyester resins, or polyamine resins. Alternatively phenolic and epoxy resins can be used as well. Depending on tne mole weight (Mw) of the binder resin, different amounts of resin are incorporated into the inkjet ink formulation, in order to reach a viscosity in the range of between 2 and 10 mPa.s (at 25°C), preferably of between 3 and 7 mPa.s (at 25°C). Preferable amounts of binder lie between 0.5 and 20 % and more preferably between 2 % and 15 % by weight of the ink's total weight. The pigments used in an ink composition of the invention are preferably security pigments, i.e. pigments which are not otherwise used in commercial printing processes, and may be selected either from organic or from inorganic pigments. Preferably, luminescent pigments are used. Organic luminescent pigments may include appropriate derivatives of phthalocyanine, naphthalocyanine, perylene and other polycyclic aromatic hydrocarbons, quinazolinone, oxazole, quinone, napthalimide, etc., or mixtures thereof. Preferably inorganic luminescent pigments are selected, chosen from the class of activator-doped crystalline solid-state compounds, such as activator-doped zinc sulfides, oxysulfides, vanadates, fluorides, oxides and oxyfluorides of yttrium and the rare-earths, or mixtures thereof. In order to stabilize or disperse the pigment in the ink composition preferably a dispersing agent is added to the ink composition. This dispersing agent allows to distribute the pigments homogeneously throughout the ink composition and further helps to ensure a continuous good printability' of the ink composition, even after a prolonged storage period. By adding an appropriate amount of a flocculating agent to a pigmented ink-jet ink, a partial destabilisation of the printing fluid suspension was obtained, through a reversible, controlled, weak flocculation of the pigment. Said partial destabilisation resulted on one hand in a faster settling of the pigment, but on the other hand yielded a much softer sediment, which was very easily redispersed upon the application of a small mechanical movement (stirring or shaking). In particular, sedimented inks could be completely redispersed using a simple magnetic stirrer at 200 rpm for a duration of two minutes. 8 Flocculation is a technique known to the one skilled in the art, which is used to render fine suspensions, being otherwise difficult to filter or to decant, coarser through the action of particle agglomeration. In the field of printing, in particular, two different types of flocculation processes are distinguished, i.e. a "controlled" or "slow" flocculation, resulting in a "soft" deposit, and an "uncontrolled" or "rapid" flocculation, resulting in a "hard" deposit. Their definitions are given in Rompp's Lexikon "Lacke und Druckfarben" (p. 240, 1998), as well as in. Ullmanns "Encyclopadie der Technischen Chemie" (Vol. 11, p, 581-586, 4^ edition, 1976) and the content of these definitions is included within the application. The "controlled flocculation" is thus described as a slow sedimentation of the suspended particles, preventing the creation of densly packed and difficult to redisperse sediments. "Controlled flocculating agents" are thus chemical compounds which, upon addition to a suspension, allow to obtain a "soft sediment"^ The resulting flocculated product is generally redispersible, but it flocculates again upon removal of the agitation. This is due to the ease of formation and breaking of the chemical hydrogen bonds, coordination bonds, or Van-der-Waals forces, which are associating the flocculated particles. A flocculating agent as used according to the invention is selected from these types of "controlled" flocculating agents which are capable of forming redispersable "soft" sediments in such a way as described above. Provided that the amount of flocculating agent is properly dosed as a function of pigment nature, amount and particle size, the extent of flocculation can be adjusted to fall between the two non-workable extremes, as found by our experimental work : (i) A too strong flocculation (large amount of added flocculating agent) resulted in a very fast total sedimentation ( (ii) A too weak flocculation (too small or zero amount of added flocculating agent) resulted in a very slow sedimentation (> 48 h) ; the resulting ink had a very good print-ability but was impossible to redisperse without applying high shear mixing forces after standing for some days. The selection of the flocculating agent used in a composition according to the invention is dependent on the specific properties of the solvent, the binder system or further required compounds of the composition, thus the flocculating agent or its interactions with the components has to be "compatible" with these components of the ink composition; a person skilled in the art will be able to make the correct selection. For water based liquids, flocculating agents (flocculents) can be of two types: i) inorganic flocculating agents comprising inorganic salts, especially salts of aluminum, calcium or iron(III) cations, for example aluminum sulfate or iron(III) chloride, calcium chloride, etc.. These cations hydrolyze to form inorganic hydroxy-polymers at the pH value of the solution. The fine particles, suspended in the liquid containing the flocculent, chemically bind to the hydrolyzed metal salt via the action of hydrogen bridges; i.e. the particles get covered with a thin layer of metal hydroxide. It is the interaction between the so coated surfaces of the particles, which makes them associate, forming larger aggregates which eventually precipitate. 10 ii) organic flocculating agents comprising organic polymers carrying functional groups which are able to interact with and bind to the surface of the particles. The flocculation mechanism is the same as in the case of hydrolyzing metal salts. Examples of such polymers are polyacrylates, hydrolyzed polyacrylamide, polysulfonate, polyphosphates and polyphosphonates (anionic), polyimines, quaternized polyamines (cationic), polyacrylamide (nonionic), etc.. Combinations of anionic and cationic flocculents can also be employed to enhance the flocculation effect. For organic-solvent based liquids, the controlled flocculating agents are principally but not exclusively of polymeric nature. They bind to the particles and act by building "bridges" between single pigment particles through remaining free chemical functional groups, resulting in a three-dimensional network implying said particles. Examples of such polymers are : polycarboxylic acids or salts of polycarboxylic acids, alkylammonium salts of polycarboxylic acids, polyamines or salts of polyamines, polycarboxylic acid salts of a polyamine amide, polyamides, alkylolammonium salts of an unsaturated fatty acid, low molecular weight unsaturated polycarboxylic acid polyesters, carboxylic acids or phosphonic acids having formula RiP03(R2)2 (with Ri = H, alkyl; R2 = H, alkyl or aryl) and their salts, etc. or mixtures thereof. Controlled flocculating agents are also known as stabilizing additives for solvent-based paint systems. Such systems are generally high in pigment content, i.e. they have a solid content of the order of 30% by weight. Addition of said stabilizing additives leads to a controlled flocculation of the solids, i.e. "bridges" are formed between the single suspended pigment particles, causing an "airy" 3-dimensional structure to 11 develop, which fills up the entire volume of the liquid. Paints obtained through so controlled flocculation of the pigment show marked thixotropy and a less compact specific weight of the flocculated precipitate than that resulting from mere pigment sedimentation in the absence of the flocculating agent. In particular, by choosing appropriate conditions, the flocculated precipitate occupies the entire volume of the paint, and flooding ,floating, settling and sagging of the pigment are completely avoided. The ink composition according to the invention can be applied for printing methods which use liquid inks. Such liquid printing inks used may be for example drop-on-demand inks, gravure inks, helio-flexo inks, screen-printing inks, ink-jet inks etc.. Preferably a composition according to the invention may be used for ink-jet printing applications. Coating additives to achieve controlled flocculation are known to the skilled in the art and are commercially available. In particular, the "Anti-Terra®^' and "Bykumen®^' products of BYK Chemie GmbH, Wesel, Germany are well known staQsilizing' agents which are recommended for solvent based paint system. They act precisely as controlled flocculating agents which stabilize the pigment dispersion by forming a loose 3-dimensional network between the individual pigment particles. Noteworthy, Anti-Terra®-203 is a solution of an alkyl-ammoniura salt of a polycarboxylic acid; Anti-Terra®-204/205 are solutiotis of a polycarboxylic acid salt of polyamine amides; Anti-Terra®-206 is a solution of an alkylolammonium salt of an unsaturated fatty acid; and Bykumen® is a solution of a lower molecular weight unsaturated acidic polycarboxylic acid polyester. Similar products are also available from other suppliers (for example EFKA, the 5xxx range of products). 12 Initially it was tried to "stabilize" an ink-jet ink in a similar way as the one recommended for stabilizing paints. However, because the solid content of an ink-jet ink is only of the order of 3% of the inks total weight, e.g. about ten times less than the solid content of a paint, the addition of Anti-Terra® to the suspension of pigments did not result in preventing pigment settling, as it was first expected, but, in contrary, it was strongly accelerating the pigment settling process. Surprisingly, we found that the Anti-Terra® flocculated pigment formed a soft sediment,-which was easy to redisperse, and which could be printed after redispersion without any clogging of the printer nozzles. To all evidence, the admixture of such additives to pigmented ink-jet inks acted upon the suspension of solids in a very similar way as in paints by forming reversible three-dimensional agglomerates. Contrary to what happens in paints, the three-dimensional agglomerate formed from pigmented ink-jet inks has not a sufficient volume to occupy on one hand the whole space of the liquid; thus, precipitation is observed. On the other hand, surprisingly, the se'diment formed in such a way is by far not as compact as the sediment formed in the absence of said flocculating additive; the flocculated sediment remains redispersible, and the redispersed liquid remains ink-jet printable. The concentration of the flocculating agent must be chosen such as to properly interact with the available particle surface. Useful concentrations are in the range of 0.01 to 20 % of the inorganic pigment weight depending on the nature and the mole weight of the flocculent, on the polarity of the solvent in the fluid, as well as on the available particle surface. A too low 13 concentration of flocculating agent will result in an insufficient agglomeration (the particles are only partly covered with flocculent); too high concentrations will result in a good flocculation effect, but with excessive flocculent available which leads to unwanted secondary effects. Further, additional compounds like dispersing agents (such as myristic acid, Gantrez AN, Zephrym etc.), defoamers (such as BYK®-022 (polyglycols), BYK®-024 (polysiloxane), humectants (such as glycols, glycols ethers, N-methyl-pyrrolidone, etc.), conductivity agent (electrolytes such as LiNOa, tetrabutyl ammonium chloride, sodium p-toluensulfonate, etc. ), plasticisers (e.g. citroflex, phtalates, etc.), adhesion promoters (silanes, titanium organates, etc.) and biocides, can be added to the ink-jet ink composition. Exemplary embodiments A first embodiment of the invention concerns an ink-jet ink comprising an erbium/ytterbium activated up-converting yttrium oxysulfide luminescent of the formula Y202S:Er,Yb. The luminescent product has a mean particle size of the order of one micrometer. The ink comprises further a polymeric thermoplastic binder (Polyvinylbutyral resin) dissolved in a solvent (Ethanol), a surfactant to support the dispersion of the pigment, a salt to ensure electrical conductivity of the ink, a humectant to pjrevent printer nozzle clogging and the controlled flocculating agent Anti-Terra®-204 (or EFKA 5054). Good printability and good redisperseability were obtained for this embodiment. A good redisperseability of the pigmented continuous-ink-jet printing ink can also be obtained, according to the present 14 invention for an aqueous suspension of the inorganic pigment, applying the same principle of controlled flocculation. A second embodiment of the invention concerns an ink-jet ink comprising a down-converting luminescent pigment (a copper-activated zinc sulphide), having a mean particle size of 300 nanometers. It also comprises a dispersant/binder (polycarboxylic acid sodium salt) and water as the solvent. The stable suspension could be reversibly flocculated upon the addition of a polymeric flocculating agent of the said types. Alternatively, reversible flocculation could also be induced by the addition of sodium hydroxyde, FeCla or by the use of a flocculating agent acting on the electrostatic stability of the suspension (ZetaG). The resulting meta-stable .suspension is partially sedimented (soft sedimentation) over 24 hours but is readily redispersed upon the application of a small mechanical movement. Moreover the printability and luminescence signal of the prints are not affected by the-addition of the "flocculating" agent. A good redispersability of the pigmented continuous-ink-jet printing ink can also be obtained, according to"the present invention, by providing the pigment in two different states; part of the pigment having a soft sedimentation behavior (controlled weak flocculation), and part of the pigment having a harder sedimentation behavior. The mixture of the two types of suspension results in a fractional sedimentation effect as can be seen in the third embodiment. A third embodiment of the invention concerns thus an ink-jet ink formulation comprising an erbium/ytterbium activated up-converting yttrium oxysulfide luminescent of the formula Y202S:Er,yb. The luminescent product has a mean particle size 15 around one micrometer. The formulation also comprises a polymeric thermoplastic resin, dissolved in a solvent (Ethanol/Methyl-Ethyl-Ketone, MEK) , a surfactant to support the dispersion of the pigment, a salt to ensure electrical conductivity of the ink, a humectant to prevent printer nozzle clogging and the controlled flocculating agent, Anti-Terra® (or EFKA) as additives. As described in the first embodiment, a first part of the pigment suspension (fluid A) is flocculated by using a polymeric flocculating agent in the milling process. The obtained suspension (fluid A) is then added to a second part of the pigment suspension (fluid B) , which is free of flocculating agent, and mixed thoroughly, to result in a printing liquid exhibiting a differential sedimentation effect. The weight ratio of the flocculated suspension (fluid A) to the non flocculated suspension (fluid B) can vary between 0.4 to 2.5 in the overall formulation. Therefore if the hard sedimentation of the non flocculated part of the pigment occurs later in time than the soft sedimentation of the flocculated part of the pigment, the whole sediment can be very easily redispersed. This is because its bottom consists of "soft sediment" which is easy to redisperse and which takes as well the overlayer of hard sediment into dispersion. Moreover, the printability of the ink is not affected by the presence of the partially flocculated pigment; as soon as the ink is stirred and circulated, the flocculated agglomerates break up again into individual particles. The pigment used as a redispersion help must not necessarily be of the same type as the luminescent security pigment, as shown in the next embodiment: 16 A fourth embodiment of the invention concerns an ink-jet ink, comprising an erbium/ytterbium activated up-converting yttrium oxysulfide luminescent pigment of the formula Y202S:Er,yb, as a first pigment which has a mean particle size around one micrometer. Said first pigment is dispersed in a fluid A, comprising a polymeric binder (vinyl chloride copolymer), a solvent (MEK), a surfactant to disperse the pigment, a humectant (Dowanol DPM), and a salt to impart electrical conductivity to the ink. The second pigment is a down-converting luminescent (a copper-activated zinc sulfide), having a mean particle size of 300 nanometers, which is dispersed in fluid B. Fluid B also comprises a polymeric binder (vinyl chloride copolymer), a solvent (MEK), a surfactant to disperse the pigment, a humectant (Dowanol DPM), a salt and a controlled flocculating agent. By mixing fluid A and fluid B, in proportions A:B varying between 0.4 and 2.5 of weight ratio a printing liquid is obtained, exhibiting a differential sedimentation effect, producing a bottom layer of soft sediment, covered by a layer of hard sediment. The whole sediment is easily redispersed. Moreover this printing fluid has both, good printability imparted by fluid A, and good redispersion properties imparted by fluid B. The invention will be further outlined by the following formulation examples, which are intended to be purely illustrative of the invention and which are in no way limiting its scope: 17 Example 1 This example illustrates the preparation of an embodiment of the present invention wherein the total amount of inorganic security pigment was dispersed in the presence of the controlled flocculating agent, Anti-Terra®, forming a meta-stable suspension ink. Appropriate dosing of the controlled flocculating agent in a weight ratio between 0.1 and 10 %, preferably of 0.5 to 3 %, of the inorganic pigment's weight (depending on the nature and particle size of the pigment and on the polarity of the solvent), is used to produce soft sediments which are easily redispersed and whose dispersion is stable enough under stirring and ink circulation to offer a good printability of the ink. At higher weight ratio, the flocculation is too fast, leading to an unstable ink which sediments very quickly and results in a poor printability. At lower weight ratio, the stable suspension settles too slowly, producing a hard sediment which requires high shear rate mixing to redisperse it. The following ingredients were employed in the indicated weight amounts. Ingredients for the millbase 1 Parts Ethanol 240 Pioloform BL 18 (Wacker Chemie) 80 Zephrym PD 7000 (ICI) 10 Anti-Terra 2 04 (Byk Chemie) 0.4 Yttrium oxysulfide luminescent Y202S:Er,Yb 40 The inorganic pigment was first pre-dispersed in the above millbase using a high shear rate mixer for about 15 minutes. Remaining pigment agglomerates in the millbase were then broken up by a bead milling passage (ZrOa beads, 2mm diameter) 18 Ingredients for the ink 1 Parts Millbase 1 370 LiN03 (Fluka) * 15 Ethanol 595 Dowanol DPM {T^ow) 20 * providing electric conductivity The ingredients were mixed together to yield the ink-jet ink according to the present invention. Example 2 This example illustrates the preparation of another embodiment of the present invention wherein the total of the inorganic security pigment present was dispersed in a solvent (water) in the presence of a polycarboxylic sodium salt dispersant, thus forming a stable suspension. The controlled flocculating agent was introduced after the milling step into the stable "^" suspension, partially destabilising the ink and favoring its redispersion. The following ingredients were thus employed in the indicated weight amounts. Ingredients for the Millbase 2 Parts Water 106 Sodium Hydroxide (Fluka) 4 Gantrez AN BF 119 (ISP) 8 Copper-activated zinc sulphide pigment 42 19 The inorganic pigment was first pre-dispersed in the above millbase using a high shear rate mixer for about 15 minutes. Remaining pigment agglomerates in the millbase were subsequently-broken up by a bead milling passage (Zr02 beads, 2mm diameter). The NaOH serves in this context as a neutralizing agent for the binder component. Ingredients for the ink 2 Parts Millbase 2 160 Water 800 ZETAG 712 5 (Ciba SC) 4 Dowanol DPM (Dow) 20 The ingredients were mixed together to yield the ink-jet ink 2 according to the present invention. Example 3 This example illustrates the preparation of an embodiment of the present invention wherein only part of the inorganic security pigment present was dispersed in the presence of the controlled flocculating agent, Anti-Terra®-203, to form a meta-stable suspension ink (ink 3A) . The remaining part of the pigment was dispersed in the absence of controlled flocculating agent, forming a stable suspension ink (ink 3B) . Finally the two inks parts were mixed in an appropriate ratio, to produce an ink showing a fractional sedimentation effect (i.e. a rapidly falling out soft sediment, covered by a slowly falling out hard sediment) , which has both, good redispersability and good printability. 20 Appropriate dosing of the controlled flocculating agent in ink A in a ratio between 0.1 and 10 %, by weight, of the inorganic pigment produces a soft sediment which is easily redispersible but whose dispersion is stable enough to offer good printability. The weight ratio of flocculating agent to inorganic pigment more preferably lies between 0.5 to 3 % to provide optimum redispersion properties to the ink of example 3. At higher ratio the flocculation is too fast, leading to an unstable ink which sediments very quickly and has poor printability. At lower ratio, the stable suspension settles too slowly, producing a hard sediment which requires high shear-force mixing to redisperse. The following ingredients were employed in the indicated amounts. Ingredients for the millbase 3A Parts Methyl Ethyl Ketone 100 Paraloid DM-55 (Rohm & Haas) 30 Ethanol 120 Pioloform BL 18 (Wacker Chemie) 4 0 Myristic acid (Fluka) 5 Anti-Terra 203 (Byk Chemie) 1 Yttrium oxysulfide luminescent Y202S:Er,Yb 40 Ingredients for the millbase 33 Parts Methyl Ethyl Ketone 100 Paraloid DM-55 (Rohm & Haas) 3 0 Ethanol 12 0 Pioloform BL 18 (Wacker Chemie) 50 Myristic acid (Fluka) 10 Yttrium oxysulfide luminescent Y202S:Er,Yb 40 21 The inorganic pigments were first pre-dispersed in the above millbases using a high shear force mixer for about 15 minutes. Remaindng pigment agglomerates in the millbase were then broken up by a bead milling passage (ZrOa beads, 2mm diameter). Ingredients £or the ink 3A Parts Millbase 3A Tetrabutylammonium chloride (Fluka) * Ethanol Dowanol DPM (Dow) 310 10 660 20 Ingredients for the ink 3A Parts Millbase 3B Tetrabutylammonium chloride (Fluka) * Ethanol Dowanol DPM (Dow) 310 10 660 20 ■ providing electric conductivity Ingredients for the ink 3 Parts Ink 3A Ink 3B 500 500 The ingredients were mixed together to yield the ink-jet ink according to the present invention. 22 Example 4 This example illustrates the preparation of an embodiment of the present invention, comprising two inorganic security pigments, wherein only one of said two inorganic security pigment was dispersed in the presence of a suitable surfactant and then reversible flocculation was obtained upon the addition of the conductivity agent (electrostatic destabilisation). The meta-stable suspension ink (ink 4A) was therefore the result of the combined action of the dispersing surfactant and of the electrostatic destabilizing conductivity agent. The other of said security pigments was dispersed in the absence of any flocculation, forming a stable suspension ink (ink 4B) . Finally to prevent hard settling of ink 4B, the two inks were mixed in an appropriate ratio to produce an ink showing a fractional sedimentation effect, (i.e. a rapidly falling out soft sediment, covered by a slowly falling out hard sediment) , which has both, good redispersability and good printability. Appropriate dosage of the surfactant which acts in the presence of the present metal salt as a controlled flocculating agent in ink 4A was given by a weight ratio between 0.1 and 10 % of the inorganic pigment, to create a soft sediment which was easily redispersed but whose dispersion was stable enough to offer good printability. The more preferred weight ratio of flocculating agent to inorganic pigment was found to lie between 2 to 8 %, to provide for optimurh redispersion of the ink of example 4A. At higher ratio the flocculation is too fast, leading to an unstable ink which sediments very quickly and has a poor printability. At lower ratio, the stable suspension settles too slowly producing a hard sediment which requires high shear force mixing to redisperse. The following ingredients were employed in the indicated amounts. 23 Ingredients for the millbase 4A Parts Methyl Ethyl Ketone UCAR VMCA vinylic resin (Dow) Octylphosphonic acid copper-activated zinc sulfide pigment 250 130 6 100 Ingredients for the millbase 4B Parts Methyl Ethyl Ketone UCAR VMCA vinylic resin (Dow) UCAR VROH vinylic resin (Dow) Myristic acid Yttrium oxysulfide luminescent Y202S:Er,Yb 250 100 30 50 100 The inorganic pigments were first pre-dispersed in the above millbases using a high shear force mixer for about 15 minutes. Remaining pigment agglomerates in the millbase were then broken up by a bead milling passage (Zr02 beads, 2mm diameter). Ingredients for the ink 4A Parts Millbase 4A Methyl Ethyl Ketone Tetrabutylammonium chloride l(Fluka) * Dowanol DPM (Dow) 500 470 10 20 24 Ingredients for the ink 4B Parts Millbase 4B Methyl Ethyl Ketone Tetrabutylammonium chloride (Fluka) * Dowanol DPM (Dow) 470 500 10 20 *** providing electric conductivity Ingredients for the ink 4 Parts Ink 4A Ink 4B 500 500 The ingredients were mixed together to yield the ink-jet in] vvt ULAIM: A redispersible pigmented printing ink composition for the continuous ink-jet printing process, said ink composition having a viscosity in the range of between 2 and 10 mPas, said ink composition comprising at least one solvent selected from the group consisting of water and organic solvents of the group of alcohols, ketones and esters, a binder system in an amount between 0.5 and 20% by weight of the total ink, which comprises at least one polymer compound selected from the group consisting of thermoplastic resins, and at least one inorganic luminescent pigment selected from the group consisting of crystalline compounds comprising activator-doped zinc sulfides; okysulfides, vanadates, fluorides, oxides and oxyfluorides of yttrium or the rare-earths elements of the periodic table; or mixtures thereof, said pigment* having a particle size of greater than 300 nm, conductivity control agents, at least one flocculating agent forming a re-dispersible sediment of said pigment in said composition, wherein said flocculating agent is selected from the group con¬sisting of inorganic salts of aluminum, calcium and iron (III), and of organic polymers carrying functional groups able to interact with and bind to the surface of said pigment particles, and wherein said flocculating agent is present in a concentration range of 0.01 to 20% of the inorganic pigment weight. 26 2 . The printing ink composition as claimed in claim 1, comprising defoaming, and humectant agents. 3. The printing ink composition as claimed in claim 1, comprising at least one dispersing agent. 4 . The printing ink composition as claimed in claim 1, wherein said flocculating agent is an organic flocculating agent se¬lected from the group consisting of polycarboxylic acids or salts of a polycarboxylic acid, polyamines or salts of a polyamine, polycarboxylic acid salts of a polyamine amide, polyamides, alkylolammonium salts of an unsaturated fatty acid, polyacrylates, hydrolyzed polyacrylamide, polyimines, (poly)phosphates, (poly)phosphonates, quaternized poly¬amines, and polyacrylamides or mixtures thereof. 5. The printing ink composition as claimed in claim 1, wherein said solvent is water, and said thermoplastic resin is se¬lected from the group consisting of water-soluble resins comprising vinylpyrrolidone polymers and copolymers, water-soluble polyesters, salts of acrylic and maleic anhydride polymers and copolymers, polyvinylalcoholm cellulose deriva¬tives, and polyethyleneimides. 6. The printing ink composition as claimed in claim 1, wherein said solvent is an organic solvent of the group of alcohols, ketones and esters, and said thermoplastic resin is selected from the group consisting of acrylic resins, vinylic resins, polyvinylbutyral resins, cellulose resins, polyurethane res¬ins, polyester resins, polyamine resins, phenolic resins and epoxy resins. 27 7. A process for printing security documents or articles, comprising the steps of providing the printing ink composition as claimed in claim 1 and printing therewith said security documents or articles by means of a continuous ink-jet printer. 8. The process as claimed in claim 7, wherein said security docu¬ment is selected from the group consisting of banknotes, identity dociiments, lottery tickets, and warranty labels. 9. A method for enhancing the redispersibility of pigment sedi¬ments in a pigmented printing ink composition as claimed in claim 1 for the continuous ink-jet printing process, said ink composition having a viscosity in the range of between 2 and 10 mPas, said method comprising the steps of a) providing a printing ink composition comprising at least one solvent selected from the group consisting of water and organic solvents of the group of alcohols, ketones and esters; a binder system in an amount between 0.5 and 20% by weight of the total ink, which comprises at least one polymer compound selected from the group consisting of thermoplastic resins; at least one inorganic luminescent pigment selected from the group consisting of crystalline compounds comprising activator-doped zinc sulfides; oxy-sulfides, vanadates, fluorides, oxides and oxyfluorides of yttrium or the rare-earths elements of the periodic table; or mixtures thereof, said pigments- having a particle size of greater than 300 nm; and conductivity control agents; b) adding at least one flocculating agent forming a re-dispersible sediment of said pigment in said composition, wherein said flocculating agent is selected from the group consisting of inorganic salts of aluminum, calcium and iron (III), and of organic polymers carrying functional 28 groups able to interact with and bind to the surface of said pigment particles, and wherein said flocculating agent is present in a concentration range of 0.01 to 20% of the inorganic pigment weight. 10. A method of manufacturing a pigmented printing ink composi¬tion as claimed in claim 1 for the continuous ink-jet print¬ing process, said ink composition having a viscosity in the range of between 2 and 10 mPas, said method comprising the steps of: (a) providing a printing ink composition comprising at least one solvent selected from the group consisting of water and organic solvents of the group of alcohols, ketones and esters; a binder system in an amount between 0.5 and 20% by weight of the total ink, which comprises at least one polymer compound selected from the group consisting of thermoplastic resins; and conductivity control agents; (b) at least one inorganic luminescent pigment selected from the group consisting of crystalline compounds comprising activator-doped zinc sulfides; oxysulfides, vanadates, fluorides, oxides and oxyfluorides of yttrium or the rare-earths elements of the periodic table; or mixtures thereof, said pigment* having a particle size of greater than 300 nm in the mixture of step (a); (c) adding further solvent to the mixture of step (b); and (d) adding at least one flocculating agent, either to the mixture of step (a) or to the mixture of step (c), wherein said flocculating agent forms a re-dispersible sediment of said pigment in said composition, wherein said flocculating agent is selected from the group con¬sisting of inorganic salts of aluminum, calcium and iron (III), and of organic polymers carrying functional 29 groups able to interact with and bind to the surface of said pigment particles, and wherein said flocculating agent is present in a concentration range of 0.01 to 20% of the inorganic pigment weight. 11. The method as claimed in claim 10, wherein in step a) dispersing, defoaming, and humectant agents are provided.

Full Text

Field of invention
The invention is in the field of inks preferably inks for the continuous-ink-jet printing. It concerns in particular pigmented security ink-jet ink formulations, containing inorganic luminescent pigments, which are easy to put into homogeneous dispersion condition (i.e. which have a good redispersibility) upon startup of the printing equipment, which remain homogeneously dispersed during printing operation, which avoid obstruction (clogging) of the printer nozzles, and which furthermore result in printed features of excellent contrast, adherence, as well as resistance against light, humidity, bleach and other adverse environmental influences.
Background of the invention
In the technique of continuous-ink-jet printing, such as first described in US 3,369,252, a stream of liquid ink is sObdivided into a sequence of small droplets by a piezoelectric resonator, vibrating at a frequency of the order of 50 kHz or more. The droplets are projected out of a nozzle towards the substrate. The electric potential against ground of said nozzle, and thus the electric charge of the resulting ink droplets, is controlled by an addressing electrode. Two deflector (electrodes, arranged along the projection path of said ink droplets, are held on predefined, constant electric potentials. They deflect the ink droplets according to their electric charge and make them impact on different locations on the substrate. By applying a corresponding electric pulse of appropriate voltage and duration to the addressing electrode, a single ink droplet can be

addressed and directed to a specific location on the substrate. In the absence of an addressing voltage, the projected ink droplets are collected by a small collecting funnel, from where they are recycled to an ink reservoir. Refinements to the described printing method and equipment include the use of uncharged or slightly opposite charged guard drops between the printing droplets, such as first proposed in US 3,562,757, in order to minimize the effects of the mutual repulsion between droplets having the same electric charge. Further refinements to the printing method are proposed in US 3,828,354; US 3,833,910; US 3,846,800; US 4,688,048; as well as in many other publications.
Inks for the continuous-ink-jet printing are normally of the soluble-dye type, in order to provide for the necessary homogeneity, and thus, an easy runnability on the printing machine. The inks may furthermore be fonnulated as solvent-based or water-based liquids. The later option is increasingly preferred, due to the ever growing environmental restrictions which apply to the use of organic solvents. However, printings made with such inks lack in general resistance against environmental influence, and they are also affected by solvents and/or water. Waterfast inks in particular are highly desirable for the production of permanent indicia or images.
Pigmented inks for the continuous-ink-jet printing are known in the art and first described in US 4,365,'035. More recent publications include EP 751,194 and EP 853,106. Particular technical problems arise from the heterogeneous nature of the ink, which must be solved through the use of particular dispersing additives, and, principally, through a continuous stirring and circulating of the ink during printing operation.

Pigment particles for ink-jet printing are preferably smaller than 1 micrometer, more preferably even smaller than 300 nanometers. However, the presence of some particles as large as 5 micrometers can be tolerated in an ink-jet formulation. In particular, ink-jet inks are generally passed through a filter of 10 micrometer pore size, in order to eliminate pigment fractions or agglomerates larger than this, which could obstruct the printing nozzles.
Existing solutions to maintain the pigmented ink dispersed during printing operation, and to prevent hard settling of the pigment between printing operations, include the following approaches:
• In US 6,062,682 the ink cartridge is moved along a carrier shaft such as to stir the pigment, and in US 5,451,987 the ink- and recovery-reservoirs are equipped with means, such as a magnetic stirrer, for agitating the ink.
• US 5,650,802 suggests the use of a vibrating piezo element to prevent the pigment suspension from settling outside the printing periods.
• Alternatively, a re-circulation of the ink in the system at regular frequency has also been successfully used to maintain the ink in an appropriate state of dispersion. Such a system is currently exploited in the OPAQUE DOMINO CIJ printers.
In the field of security printing, it would be highly desirable to have available ink-jet inks which resist to the influence of light and to commonly available chemical agents, such as household bleach or solvents of the most various kind. Such inks could noteworthy serve for the rapid and reliable on-line numbering of security documents, such as banknotes, identity documents, lottery tickets, warranty labels and the like.

A particular type of waterfast security inks for the ink-jet numbering of lottery tickets has been disclosed in US 5,498,283. However, the disclosed inks do merely contain an organic dye which has improved resistance to bleach; formulations containing inorganic luminescents are not disclosed.
To provide for an appropriate intensity of the luminescence response, inorganic security pigments have generally a particle size of greater than 300 nm. Example of such pigments can be found in the disclosures of US 5,891,361; US 6,132,642 and WO 00/63317. Below said particle size, the surface-to-volume ratio of the particles, and thus the influence of the surface defects responsible for luminescence quenching, becomes too important, resulting in a strong drop of the luminescence quantum yield.
The addition, to a continuous ink jet ink, of inorganic luminescents of said mentioned types noteworthy presents a couple of particular problems, which are due to the relatively high specific weight of said inorganic compounds, as compared to that of the printing liquid, to the required pigment size, as well as to the very low viscosity of the printing fluid. This results in a strongly increased tendency of the pigment to sediment, forming furthermore relatively dense deposits which are difficult to redisperse. After a stop and restart of the printing operations, not all pigment is thus necessarily redispersed; some of it remaining settled in the corners of the ink reservoir. Moreover, hard sedimentation of the inorganic pigment, when occurring between printing operations or during prolonged storage periods, is very difficult to redisperse and requires high shear mixing forces to put the pigment back into suspension.

Hard sedimentation results in a change in concentration of the active ingredient with time, which is not compatible with the stringent standards of security printing.
The combination of a particularly enhanced stirring and circulating of the printing liquid during operation, together with the use of an ink formulation according to the present invention, are efficiently used to remedy this problem.
Summary of the invention
The shortcomings of the inks according to the prior art are avoided by using an ink composition of the present invention.
The inventors surprisingly found that a partial flocculation (destabilization) of the ink suspension turned out to be beneficial to its overall properties. The redispersion of a partially flocculated ink suspension turned out to be significantly improved, without perturbing the print-ability of the ink.
The printing ink composition comprises at least one solvent, a binder system, optional defoaming, humectant and conductivity control agents, and at least one pigment; the composition being characterized in that it additionally comprises at least one flocculating agent, which flocculating agent is capable of forming a re-dispersible sediment of said pigment in said composition.
The solvent is preferably selected from the group comprising water, alcohols (such as methanol, ethanol, etc.), ketones (such as acetone, methyl-ethyl-ketone, etc.) and esters (such as
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methyl acetate, ethyl acetate, methyl propionate, etc.) or mixtures thereof.
The binder system comprises at least one polymer compound suitable for ink-jet ink applications. Mixtures of different polymer compounds are usable as well. The polymer compounds are preferably chosen among the thermoplastic resins and are furthermore chosen such as to be compatible with the solvent. For aqueous ink formulations, the binder system is preferably, but not exclusively, chosen from the group comprising water-soluble resins, such as vinylpyrrolidone polymers and copolymers, water soluble polyesters, salts of acrylic and maleic anhydride polymers and copolymers, polyvinyl alcohol, cellulose derivatives, polyethyleneimides, etc., or from the group of film forming emulsions of fine polymer particles ( For solvent especially organic solvent based systems, solvent soluble thermoplastic resins are preferred, such as acrylic resins, e.g. poly (methylmethacrylate) , vinylic resins, e.g. vinyl acetate / vinyl chloride copolymers, polyvinylbutyral resins, cellulose resins, e.g. nitrocellulose, acetylcellulose etc., polyurethane resins, polyester resins, or polyamine resins. Alternatively phenolic and epoxy resins can be used as well.
Depending on tne mole weight (Mw) of the binder resin, different amounts of resin are incorporated into the inkjet ink formulation, in order to reach a viscosity in the range of between 2 and 10 mPa.s (at 25°C), preferably of between 3 and 7 mPa.s (at 25°C). Preferable amounts of binder lie between 0.5 and 20 % and more preferably between 2 % and 15 % by weight of the ink's total weight.

The pigments used in an ink composition of the invention are preferably security pigments, i.e. pigments which are not otherwise used in commercial printing processes, and may be selected either from organic or from inorganic pigments. Preferably, luminescent pigments are used. Organic luminescent pigments may include appropriate derivatives of phthalocyanine, naphthalocyanine, perylene and other polycyclic aromatic hydrocarbons, quinazolinone, oxazole, quinone, napthalimide, etc., or mixtures thereof. Preferably inorganic luminescent pigments are selected, chosen from the class of activator-doped crystalline solid-state compounds, such as activator-doped zinc sulfides, oxysulfides, vanadates, fluorides, oxides and oxyfluorides of yttrium and the rare-earths, or mixtures thereof.
In order to stabilize or disperse the pigment in the ink composition preferably a dispersing agent is added to the ink composition. This dispersing agent allows to distribute the pigments homogeneously throughout the ink composition and further helps to ensure a continuous good printability' of the ink composition, even after a prolonged storage period.
By adding an appropriate amount of a flocculating agent to a pigmented ink-jet ink, a partial destabilisation of the printing fluid suspension was obtained, through a reversible, controlled, weak flocculation of the pigment. Said partial destabilisation resulted on one hand in a faster settling of the pigment, but on the other hand yielded a much softer sediment, which was very easily redispersed upon the application of a small mechanical movement (stirring or shaking). In particular, sedimented inks could be completely redispersed using a simple magnetic stirrer at 200 rpm for a duration of two minutes.
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Flocculation is a technique known to the one skilled in the art, which is used to render fine suspensions, being otherwise difficult to filter or to decant, coarser through the action of particle agglomeration. In the field of printing, in particular, two different types of flocculation processes are distinguished, i.e. a "controlled" or "slow" flocculation, resulting in a "soft" deposit, and an "uncontrolled" or "rapid" flocculation, resulting in a "hard" deposit. Their definitions are given in Rompp's Lexikon "Lacke und Druckfarben" (p. 240, 1998), as well as in. Ullmanns "Encyclopadie der Technischen Chemie" (Vol. 11, p, 581-586, 4^** edition, 1976) and the content of these definitions is included within the application. The "controlled flocculation" is thus described as a slow sedimentation of the suspended particles, preventing the creation of densly packed and difficult to redisperse sediments. "Controlled flocculating agents" are thus chemical compounds which, upon addition to a suspension, allow to obtain a "soft sediment"^ The resulting flocculated product is generally redispersible, but it flocculates again upon removal of the agitation. This is due to the ease of formation and breaking of the chemical hydrogen bonds, coordination bonds, or Van-der-Waals forces, which are associating the flocculated particles. A flocculating agent as used according to the invention is selected from these types of "controlled" flocculating agents which are capable of forming redispersable "soft" sediments in such a way as described above.
Provided that the amount of flocculating agent is properly dosed as a function of pigment nature, amount and particle size, the extent of flocculation can be adjusted to fall between the two non-workable extremes, as found by our experimental work :

(i) A too strong flocculation (large amount of added flocculating agent) resulted in a very fast total sedimentation ( (ii) A too weak flocculation (too small or zero amount of added flocculating agent) resulted in a very slow sedimentation (> 48 h) ; the resulting ink had a very good print-ability but was impossible to redisperse without applying high shear mixing forces after standing for some days.
The selection of the flocculating agent used in a composition according to the invention is dependent on the specific properties of the solvent, the binder system or further required compounds of the composition, thus the flocculating agent or its interactions with the components has to be "compatible" with these components of the ink composition; a person skilled in the art will be able to make the correct selection.
For water based liquids, flocculating agents (flocculents) can
be of two types:
i) inorganic flocculating agents comprising inorganic salts,
especially salts of aluminum, calcium or iron(III) cations, for example aluminum sulfate or iron(III) chloride, calcium chloride, etc.. These cations hydrolyze to form inorganic hydroxy-polymers at the pH value of the solution. The fine particles, suspended in the liquid containing the flocculent, chemically bind to the hydrolyzed metal salt via the action of hydrogen bridges; i.e. the particles get covered with a thin layer of metal hydroxide. It is the interaction between the so coated surfaces of the particles, which makes them associate, forming larger aggregates which eventually precipitate.
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ii) organic flocculating agents comprising organic polymers
carrying functional groups which are able to interact with and bind to the surface of the particles. The flocculation mechanism is the same as in the case of hydrolyzing metal salts. Examples of such polymers are polyacrylates, hydrolyzed polyacrylamide, polysulfonate, polyphosphates and polyphosphonates (anionic), polyimines, quaternized polyamines (cationic), polyacrylamide (nonionic), etc.. Combinations of anionic and cationic flocculents can also be employed to enhance the flocculation effect.
For organic-solvent based liquids, the controlled flocculating agents are principally but not exclusively of polymeric nature. They bind to the particles and act by building "bridges" between single pigment particles through remaining free chemical functional groups, resulting in a three-dimensional network implying said particles. Examples of such polymers are : polycarboxylic acids or salts of polycarboxylic acids, alkylammonium salts of polycarboxylic acids, polyamines or salts of polyamines, polycarboxylic acid salts of a polyamine amide, polyamides, alkylolammonium salts of an unsaturated fatty acid, low molecular weight unsaturated polycarboxylic acid polyesters, carboxylic acids or phosphonic acids having formula RiP03(R2)2 (with Ri = H, alkyl; R2 = H, alkyl or aryl) and their salts, etc. or mixtures thereof.
Controlled flocculating agents are also known as stabilizing additives for solvent-based paint systems. Such systems are generally high in pigment content, i.e. they have a solid content of the order of 30% by weight. Addition of said stabilizing additives leads to a controlled flocculation of the solids, i.e. "bridges" are formed between the single suspended pigment particles, causing an "airy" 3-dimensional structure to
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develop, which fills up the entire volume of the liquid. Paints obtained through so controlled flocculation of the pigment show marked thixotropy and a less compact specific weight of the flocculated precipitate than that resulting from mere pigment sedimentation in the absence of the flocculating agent. In particular, by choosing appropriate conditions, the flocculated precipitate occupies the entire volume of the paint, and flooding ,floating, settling and sagging of the pigment are completely avoided.
The ink composition according to the invention can be applied for printing methods which use liquid inks. Such liquid printing inks used may be for example drop-on-demand inks, gravure inks, helio-flexo inks, screen-printing inks, ink-jet inks etc.. Preferably a composition according to the invention may be used for ink-jet printing applications.
Coating additives to achieve controlled flocculation are known to the skilled in the art and are commercially available. In particular, the "Anti-Terra®^' and "Bykumen®^' products of BYK Chemie GmbH, Wesel, Germany are well known staQsilizing' agents which are recommended for solvent based paint system. They act precisely as controlled flocculating agents which stabilize the pigment dispersion by forming a loose 3-dimensional network between the individual pigment particles. Noteworthy, Anti-Terra®-203 is a solution of an alkyl-ammoniura salt of a polycarboxylic acid; Anti-Terra®-204/205 are solutiotis of a polycarboxylic acid salt of polyamine amides; Anti-Terra®-206 is a solution of an alkylolammonium salt of an unsaturated fatty acid; and Bykumen® is a solution of a lower molecular weight unsaturated acidic polycarboxylic acid polyester. Similar products are also available from other suppliers (for example EFKA, the 5xxx range of products).
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Initially it was tried to "stabilize" an ink-jet ink in a similar way as the one recommended for stabilizing paints. However, because the solid content of an ink-jet ink is only of the order of 3% of the inks total weight, e.g. about ten times less than the solid content of a paint, the addition of Anti-Terra® to the suspension of pigments did not result in preventing pigment settling, as it was first expected, but, in contrary, it was strongly accelerating the pigment settling process.
Surprisingly, we found that the Anti-Terra® flocculated pigment formed a soft sediment,-which was easy to redisperse, and which could be printed after redispersion without any clogging of the printer nozzles. To all evidence, the admixture of such additives to pigmented ink-jet inks acted upon the suspension of solids in a very similar way as in paints by forming reversible three-dimensional agglomerates. Contrary to what happens in paints, the three-dimensional agglomerate formed from pigmented ink-jet inks has not a sufficient volume to occupy on one hand the whole space of the liquid; thus, precipitation is observed. On the other hand, surprisingly, the se'diment formed in such a way is by far not as compact as the sediment formed in the absence of said flocculating additive; the flocculated sediment remains redispersible, and the redispersed liquid remains ink-jet printable.
The concentration of the flocculating agent must be chosen such as to properly interact with the available particle surface. Useful concentrations are in the range of 0.01 to 20 % of the inorganic pigment weight depending on the nature and the mole weight of the flocculent, on the polarity of the solvent in the fluid, as well as on the available particle surface. A too low
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concentration of flocculating agent will result in an insufficient agglomeration (the particles are only partly covered with flocculent); too high concentrations will result in a good flocculation effect, but with excessive flocculent available which leads to unwanted secondary effects.
Further, additional compounds like dispersing agents (such as myristic acid, Gantrez AN, Zephrym etc.), defoamers (such as BYK®-022 (polyglycols), BYK®-024 (polysiloxane), humectants (such as glycols, glycols ethers, N-methyl-pyrrolidone, etc.), conductivity agent (electrolytes such as LiNOa, tetrabutyl ammonium chloride, sodium p-toluensulfonate, etc. ), plasticisers (e.g. citroflex, phtalates, etc.), adhesion promoters (silanes, titanium organates, etc.) and biocides, can be added to the ink-jet ink composition.
Exemplary embodiments
A first embodiment of the invention concerns an ink-jet ink comprising an erbium/ytterbium activated up-converting yttrium oxysulfide luminescent of the formula Y202S:Er,Yb. The luminescent product has a mean particle size of the order of one micrometer. The ink comprises further a polymeric thermoplastic binder (Polyvinylbutyral resin) dissolved in a solvent (Ethanol), a surfactant to support the dispersion of the pigment, a salt to ensure electrical conductivity of the ink, a humectant to pjrevent printer nozzle clogging and the controlled flocculating agent Anti-Terra®-204 (or EFKA 5054). Good printability and good redisperseability were obtained for this embodiment.
A good redisperseability of the pigmented continuous-ink-jet printing ink can also be obtained, according to the present
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invention for an aqueous suspension of the inorganic pigment, applying the same principle of controlled flocculation.
A second embodiment of the invention concerns an ink-jet ink comprising a down-converting luminescent pigment (a copper-activated zinc sulphide), having a mean particle size of 300 nanometers. It also comprises a dispersant/binder (polycarboxylic acid sodium salt) and water as the solvent. The stable suspension could be reversibly flocculated upon the addition of a polymeric flocculating agent of the said types. Alternatively, reversible flocculation could also be induced by the addition of sodium hydroxyde, FeCla or by the use of a flocculating agent acting on the electrostatic stability of the suspension (ZetaG). The resulting meta-stable .suspension is partially sedimented (soft sedimentation) over 24 hours but is readily redispersed upon the application of a small mechanical movement. Moreover the printability and luminescence signal of the prints are not affected by the-addition of the "flocculating" agent.
A good redispersability of the pigmented continuous-ink-jet printing ink can also be obtained, according to"the present invention, by providing the pigment in two different states; part of the pigment having a soft sedimentation behavior (controlled weak flocculation), and part of the pigment having a harder sedimentation behavior. The mixture of the two types of suspension results in a fractional sedimentation effect as can be seen in the third embodiment.
A third embodiment of the invention concerns thus an ink-jet ink formulation comprising an erbium/ytterbium activated up-converting yttrium oxysulfide luminescent of the formula Y202S:Er,yb. The luminescent product has a mean particle size
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around one micrometer. The formulation also comprises a polymeric thermoplastic resin, dissolved in a solvent (Ethanol/Methyl-Ethyl-Ketone, MEK) , a surfactant to support the dispersion of the pigment, a salt to ensure electrical conductivity of the ink, a humectant to prevent printer nozzle clogging and the controlled flocculating agent, Anti-Terra® (or EFKA) as additives.
As described in the first embodiment, a first part of the pigment suspension (fluid A) is flocculated by using a polymeric flocculating agent in the milling process. The obtained suspension (fluid A) is then added to a second part of the pigment suspension (fluid B) , which is free of flocculating agent, and mixed thoroughly, to result in a printing liquid exhibiting a differential sedimentation effect. The weight ratio of the flocculated suspension (fluid A) to the non flocculated suspension (fluid B) can vary between 0.4 to 2.5 in the overall formulation.
Therefore if the hard sedimentation of the non flocculated part of the pigment occurs later in time than the soft sedimentation of the flocculated part of the pigment, the whole sediment can be very easily redispersed. This is because its bottom consists of "soft sediment" which is easy to redisperse and which takes as well the overlayer of hard sediment into dispersion. Moreover, the printability of the ink is not affected by the presence of the partially flocculated pigment; as soon as the ink is stirred and circulated, the flocculated agglomerates break up again into individual particles.
The pigment used as a redispersion help must not necessarily be of the same type as the luminescent security pigment, as shown in the next embodiment:
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A fourth embodiment of the invention concerns an ink-jet ink, comprising an erbium/ytterbium activated up-converting yttrium oxysulfide luminescent pigment of the formula Y202S:Er,yb, as a first pigment which has a mean particle size around one micrometer. Said first pigment is dispersed in a fluid A, comprising a polymeric binder (vinyl chloride copolymer), a solvent (MEK), a surfactant to disperse the pigment, a humectant (Dowanol DPM), and a salt to impart electrical conductivity to the ink. The second pigment is a down-converting luminescent (a copper-activated zinc sulfide), having a mean particle size of 300 nanometers, which is dispersed in fluid B. Fluid B also comprises a polymeric binder (vinyl chloride copolymer), a solvent (MEK), a surfactant to disperse the pigment, a humectant (Dowanol DPM), a salt and a controlled flocculating agent.
By mixing fluid A and fluid B, in proportions A:B varying between 0.4 and 2.5 of weight ratio a printing liquid is obtained, exhibiting a differential sedimentation effect, producing a bottom layer of soft sediment, covered by a layer of hard sediment. The whole sediment is easily redispersed. Moreover this printing fluid has both, good printability imparted by fluid A, and good redispersion properties imparted by fluid B.
The invention will be further outlined by the following formulation examples, which are intended to be purely illustrative of the invention and which are in no way limiting its scope:
17

Example 1
This example illustrates the preparation of an embodiment of the present invention wherein the total amount of inorganic security pigment was dispersed in the presence of the controlled flocculating agent, Anti-Terra®, forming a meta-stable suspension ink. Appropriate dosing of the controlled flocculating agent in a weight ratio between 0.1 and 10 %, preferably of 0.5 to 3 %, of the inorganic pigment's weight (depending on the nature and particle size of the pigment and on the polarity of the solvent), is used to produce soft sediments which are easily redispersed and whose dispersion is stable enough under stirring and ink circulation to offer a good printability of the ink. At higher weight ratio, the flocculation is too fast, leading to an unstable ink which sediments very quickly and results in a poor printability. At lower weight ratio, the stable suspension settles too slowly, producing a hard sediment which requires high shear rate mixing to redisperse it. The following ingredients were employed in the indicated weight amounts.
Ingredients for the millbase 1 Parts
Ethanol 240
Pioloform BL 18 (Wacker Chemie) 80
Zephrym PD 7000 (ICI) 10
Anti-Terra 2 04 (Byk Chemie) 0.4
Yttrium oxysulfide luminescent Y202S:Er,Yb 40
The inorganic pigment was first pre-dispersed in the above millbase using a high shear rate mixer for about 15 minutes. Remaining pigment agglomerates in the millbase were then broken up by a bead milling passage (ZrOa beads, 2mm diameter)
18

Ingredients for the ink 1 Parts
Millbase 1 370
LiN03 (Fluka) *** 15
Ethanol 595
Dowanol DPM {T^ow) 20
*** providing electric conductivity
The ingredients were mixed together to yield the ink-jet ink according to the present invention.
Example 2
This example illustrates the preparation of another embodiment
of the present invention wherein the total of the inorganic
security pigment present was dispersed in a solvent (water) in
the presence of a polycarboxylic sodium salt dispersant, thus
forming a stable suspension. The controlled flocculating agent
was introduced after the milling step into the stable "^"
suspension, partially destabilising the ink and favoring its redispersion. The following ingredients were thus employed in the indicated weight amounts.
Ingredients for the Millbase 2 Parts
Water 106
Sodium Hydroxide (Fluka) 4
Gantrez AN BF 119 (ISP) 8
Copper-activated zinc sulphide pigment 42
19

The inorganic pigment was first pre-dispersed in the above millbase using a high shear rate mixer for about 15 minutes. Remaining pigment agglomerates in the millbase were subsequently-broken up by a bead milling passage (Zr02 beads, 2mm diameter). The NaOH serves in this context as a neutralizing agent for the binder component.
Ingredients for the ink 2 Parts
Millbase 2 160
Water 800
ZETAG 712 5 (Ciba SC) 4
Dowanol DPM (Dow) 20
The ingredients were mixed together to yield the ink-jet ink 2 according to the present invention.
Example 3
This example illustrates the preparation of an embodiment of the present invention wherein only part of the inorganic security pigment present was dispersed in the presence of the controlled flocculating agent, Anti-Terra®-203, to form a meta-stable suspension ink (ink 3A) . The remaining part of the pigment was dispersed in the absence of controlled flocculating agent, forming a stable suspension ink (ink 3B) . Finally the two inks parts were mixed in an appropriate ratio, to produce an ink showing a fractional sedimentation effect (i.e. a rapidly falling out soft sediment, covered by a slowly falling out hard sediment) , which has both, good redispersability and good printability.
20

Appropriate dosing of the controlled flocculating agent in ink A in a ratio between 0.1 and 10 %, by weight, of the inorganic pigment produces a soft sediment which is easily redispersible but whose dispersion is stable enough to offer good printability. The weight ratio of flocculating agent to inorganic pigment more preferably lies between 0.5 to 3 % to provide optimum redispersion properties to the ink of example 3. At higher ratio the flocculation is too fast, leading to an unstable ink which sediments very quickly and has poor printability. At lower ratio, the stable suspension settles too slowly, producing a hard sediment which requires high shear-force mixing to redisperse. The following ingredients were employed in the indicated amounts.
Ingredients for the millbase 3A Parts
Methyl Ethyl Ketone 100
Paraloid DM-55 (Rohm & Haas) 30
Ethanol 120
Pioloform BL 18 (Wacker Chemie) 4 0
Myristic acid (Fluka) 5
Anti-Terra 203 (Byk Chemie) 1
Yttrium oxysulfide luminescent Y202S:Er,Yb 40
Ingredients for the millbase 33 Parts
Methyl Ethyl Ketone 100
Paraloid DM-55 (Rohm & Haas) 3 0
Ethanol 12 0
Pioloform BL 18 (Wacker Chemie) 50
Myristic acid (Fluka) 10
Yttrium oxysulfide luminescent Y202S:Er,Yb 40
21

The inorganic pigments were first pre-dispersed in the above millbases using a high shear force mixer for about 15 minutes. Remaindng pigment agglomerates in the millbase were then broken up by a bead milling passage (ZrOa beads, 2mm diameter).

Ingredients £or the ink 3A

Parts

Millbase 3A
Tetrabutylammonium chloride (Fluka) ***
Ethanol
Dowanol DPM (Dow)

310 10
660 20

Ingredients for the ink 3A

Parts

Millbase 3B
Tetrabutylammonium chloride (Fluka) ***
Ethanol
Dowanol DPM (Dow)

310 10
660 20

■** providing electric conductivity

Ingredients for the ink 3

Parts

Ink 3A Ink 3B

500 500

The ingredients were mixed together to yield the ink-jet ink according to the present invention.
22

Example 4
This example illustrates the preparation of an embodiment of the present invention, comprising two inorganic security pigments, wherein only one of said two inorganic security pigment was dispersed in the presence of a suitable surfactant and then reversible flocculation was obtained upon the addition of the conductivity agent (electrostatic destabilisation). The meta-stable suspension ink (ink 4A) was therefore the result of the combined action of the dispersing surfactant and of the electrostatic destabilizing conductivity agent. The other of said security pigments was dispersed in the absence of any flocculation, forming a stable suspension ink (ink 4B) . Finally to prevent hard settling of ink 4B, the two inks were mixed in an appropriate ratio to produce an ink showing a fractional sedimentation effect, (i.e. a rapidly falling out soft sediment, covered by a slowly falling out hard sediment) , which has both, good redispersability and good printability.
Appropriate dosage of the surfactant which acts in the presence of the present metal salt as a controlled flocculating agent in ink 4A was given by a weight ratio between 0.1 and 10 % of the inorganic pigment, to create a soft sediment which was easily redispersed but whose dispersion was stable enough to offer good printability. The more preferred weight ratio of flocculating agent to inorganic pigment was found to lie between 2 to 8 %, to provide for optimurh redispersion of the ink of example 4A. At higher ratio the flocculation is too fast, leading to an unstable ink which sediments very quickly and has a poor printability. At lower ratio, the stable suspension settles too slowly producing a hard sediment which requires high shear force mixing to redisperse. The following ingredients were employed in the indicated amounts.
23

Ingredients for the millbase 4A

Parts

Methyl Ethyl Ketone UCAR VMCA vinylic resin (Dow) Octylphosphonic acid copper-activated zinc sulfide pigment

250
130
6
100

Ingredients for the millbase 4B

Parts

Methyl Ethyl Ketone
UCAR VMCA vinylic resin (Dow)
UCAR VROH vinylic resin (Dow)
Myristic acid
Yttrium oxysulfide luminescent Y202S:Er,Yb

250
100
30
50
100

The inorganic pigments were first pre-dispersed in the above millbases using a high shear force mixer for about 15 minutes. Remaining pigment agglomerates in the millbase were then broken up by a bead milling passage (Zr02 beads, 2mm diameter).

Ingredients for the ink 4A

Parts

Millbase 4A
Methyl Ethyl Ketone
Tetrabutylammonium chloride l(Fluka) ***
Dowanol DPM (Dow)

500
470
10
20

24

Ingredients for the ink 4B

Parts

Millbase 4B
Methyl Ethyl Ketone
Tetrabutylammonium chloride (Fluka) ***
Dowanol DPM (Dow)

470
500
10
20

*** providing electric conductivity

Ingredients for the ink 4

Parts

Ink 4A Ink 4B

500 500

The ingredients were mixed together to yield the ink-jet in]

vvt ULAIM:
A redispersible pigmented printing ink composition for the continuous ink-jet printing process, said ink composition having a viscosity in the range of between 2 and 10 mPas, said ink composition comprising
at least one solvent selected from the group consisting of water and organic solvents of the group of alcohols, ketones and esters,
a binder system in an amount between 0.5 and 20% by weight of the total ink, which comprises at least one polymer compound selected from the group consisting of thermoplastic resins, and
at least one inorganic luminescent pigment selected from the group consisting of crystalline compounds comprising activator-doped zinc sulfides; okysulfides, vanadates, fluorides, oxides and oxyfluorides of yttrium or the rare-earths elements of the periodic table; or mixtures thereof, said pigment* having a particle size of greater than 300 nm,
conductivity control agents,
at least one flocculating agent forming a re-dispersible sediment of said pigment in said composition, wherein said flocculating agent is selected from the group con¬sisting of inorganic salts of aluminum, calcium and iron (III), and of organic polymers carrying functional groups able to interact with and bind to the surface of said pigment particles, and wherein said flocculating agent is present in a concentration range of 0.01 to 20% of the inorganic pigment weight.
26

2 . The printing ink composition as claimed in claim 1,
comprising defoaming, and humectant agents.
3. The printing ink composition as claimed in claim 1,
comprising at least one dispersing agent.
4 . The printing ink composition as claimed in claim 1, wherein
said flocculating agent is an organic flocculating agent se¬lected from the group consisting of polycarboxylic acids or salts of a polycarboxylic acid, polyamines or salts of a polyamine, polycarboxylic acid salts of a polyamine amide, polyamides, alkylolammonium salts of an unsaturated fatty acid, polyacrylates, hydrolyzed polyacrylamide, polyimines, (poly)phosphates, (poly)phosphonates, quaternized poly¬amines, and polyacrylamides or mixtures thereof.
5. The printing ink composition as claimed in claim 1, wherein
said solvent is water, and said thermoplastic resin is se¬lected from the group consisting of water-soluble resins comprising vinylpyrrolidone polymers and copolymers, water-soluble polyesters, salts of acrylic and maleic anhydride polymers and copolymers, polyvinylalcoholm cellulose deriva¬tives, and polyethyleneimides.
6. The printing ink composition as claimed in claim 1, wherein
said solvent is an organic solvent of the group of alcohols, ketones and esters, and said thermoplastic resin is selected from the group consisting of acrylic resins, vinylic resins, polyvinylbutyral resins, cellulose resins, polyurethane res¬ins, polyester resins, polyamine resins, phenolic resins and epoxy resins.
27

7. A process for printing security documents or articles, comprising
the steps of providing the printing ink composition as claimed
in claim 1 and printing therewith said security documents or articles by means of a continuous ink-jet printer.
8. The process as claimed in claim 7, wherein said security docu¬ment is selected from the group consisting of banknotes, identity dociiments, lottery tickets, and warranty labels.
9. A method for enhancing the redispersibility of pigment sedi¬ments in a pigmented printing ink composition as claimed in claim 1 for the continuous ink-jet printing process, said ink composition having a viscosity in the range of between 2 and 10 mPas, said method comprising the steps of

a) providing a printing ink composition comprising at least one solvent selected from the group consisting of water and organic solvents of the group of alcohols, ketones and esters; a binder system in an amount between 0.5 and 20% by weight of the total ink, which comprises at least one polymer compound selected from the group consisting of thermoplastic resins; at least one inorganic luminescent pigment selected from the group consisting of crystalline compounds comprising activator-doped zinc sulfides; oxy-sulfides, vanadates, fluorides, oxides and oxyfluorides of yttrium or the rare-earths elements of the periodic table; or mixtures thereof, said pigments- having a particle size of greater than 300 nm; and conductivity control agents;
b) adding at least one flocculating agent forming a re-dispersible sediment of said pigment in said composition, wherein said flocculating agent is selected from the group consisting of inorganic salts of aluminum, calcium and iron (III), and of organic polymers carrying functional
28

groups able to interact with and bind to the surface of said pigment particles, and wherein said flocculating agent is present in a concentration range of 0.01 to 20% of the inorganic pigment weight.
10. A method of manufacturing a pigmented printing ink composi¬tion as claimed in claim 1 for the continuous ink-jet print¬ing process, said ink composition having a viscosity in the range of between 2 and 10 mPas, said method comprising the steps of:
(a) providing a printing ink composition comprising at least one solvent selected from the group consisting of water and organic solvents of the group of alcohols, ketones and esters; a binder system in an amount between 0.5 and 20% by weight of the total ink, which comprises at least one polymer compound selected from the group consisting of thermoplastic resins; and conductivity control agents;
(b) at least one inorganic luminescent pigment selected from the group consisting of crystalline compounds comprising activator-doped zinc sulfides; oxysulfides, vanadates, fluorides, oxides and oxyfluorides of yttrium or the rare-earths elements of the periodic table; or mixtures thereof, said pigment* having a particle size of greater than 300 nm in the mixture of step (a);
(c) adding further solvent to the mixture of step (b); and
(d) adding at least one flocculating agent, either to the mixture of step (a) or to the mixture of step (c), wherein said flocculating agent forms a re-dispersible sediment of said pigment in said composition, wherein said flocculating agent is selected from the group con¬sisting of inorganic salts of aluminum, calcium and iron (III), and of organic polymers carrying functional
29

groups able to interact with and bind to the surface of said pigment particles, and wherein said flocculating agent is present in a concentration range of 0.01 to 20% of the inorganic pigment weight.
11. The method as claimed in claim 10, wherein in step a)
dispersing, defoaming, and humectant agents are provided.

Documents:

1118-chenp-2004 form-2.pdf

1118-chenp-2004 abstract.pdf

1118-chenp-2004 claims.pdf

1118-chenp-2004 form-1.pdf

1118-chenp-2004 form-18.pdf

1118-chenp-2004 form-3.pdf

1118-chenp-2004 form-5.pdf

1118-chenp-2004 others.pdf

1118-chenp-2004 power of attorney.pdf

1118-chenp-2004 correspondence others.pdf

1118-chenp-2004 correspondence po.pdf

1118-chenp-2004 pct search report.pdf

1118-chenp-2004 pct.pdf

1118-chenp-2004 petition.pdf

1118-chenp-2004 complete specification as granted.pdf

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Patent Number

234656

Indian Patent Application Number

1118/CHENP/2004

PG Journal Number

29/2009

Publication Date

17-Jul-2009

Grant Date

10-Jun-2009

Date of Filing

19-May-2004

Name of Patentee

SICPA HOLDING S.A

Applicant Address

AVENUE DE4 FLORISSANT 41, CH-1008 PRILLY

Inventors:

#	Inventor's Name	Inventor's Address
1	MARGUERETTAZ, XAVIER	R. DU GUERCET 93, CH-1920 MARTIGNY
2	TILLER, THOMAS	CHEMIN DU CEDRE 21, CH-1030 BUSSIGNY
3	MULLER EDGAR	RUE P.-A DE FAUCIGNY 7, CH-1700 FRIBOURG
4	GERMAUD, FREDERIC	PLACES DERRIERES, CH-1664 EPAGNY
5	JAQUIER, SYLVAIN	GRAND-RUE 25, CH-1623 SEMSALES

PCT International Classification Number

C09D11/00

PCT International Application Number

PCT/EP02/12041

PCT International Filing date

2002-10-29

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	01127907.2	2001-11-23	EUROPEAN UNION