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    • 专利摘要:
    single-pass inkjet printing method. a single-pass inkjet printing method that includes the steps of: a) providing a radiation-curable inkjet ink set that contains at least one first and a second radiation-curable inkjet ink having a voltage of dynamic surface of not more than 30 nm / m measured maximum bubble pressure tensiometry under a surface age of 50 ms and under 25 <198> c; b) blasting a first radiation-curable inkjet ink into an inkjet ink receiver that moves at a printing speed of at least 35 m / min; c) at least partially cure the first inkjet ink in the ink receiver within the range of 40 to 500 ms after the first inkjet ink has been discharged into the ink receiver; d) blasting a second radiation-curable inkjet ink on the first at least partially cured inkjet ink; and e) at least partially curing the second inkjet ink within a range of 40 to 500 ms after the second inkjet ink has been discharged into the first inkjet ink. a single pass inkjet printer is also revealed.
    公开号:BR112012013314B1
    申请号:R112012013314
    申请日:2010-12-20
    公开日:2020-06-09
    发明作者:Tilemans David；Van Dyck Geert；Van Garsse Joris；Bracke Peter；De Meutter Stefaan
    申请人:Agfa Graphics Nv；Agfa Nv；
    IPC主号:
    专利说明:

    SINGLE-PASS INK JET PRINTING METHOD Technical Field
    The present invention relates to high speed single pass inkjet printing methods that exhibit high quality image.
    Prior Art
    In inkjet printing, tiny drops of fluid are projected directly onto an ink receiving surface without physical contact between the printing device and the ink receiver. The printing device stores the print data electronically and controls a mechanism to eject the droplets towards the image. Printing is performed by moving a printhead through the ink receiver or vice versa or both.
    In a single-pass printing process, inkjet printheads usually cover the entire width of the ink receiver and thus can remain stationary while the ink receiving surface is transported under the jet printheads. of ink. This allows for high speed printing if high image quality can be achieved on a wide variety of ink receivers.
    The composition of the inkjet ink is dependent on the inkjet printing method used and the nature of the ink receiver to be printed. UV-curable inks are more suitable for non-absorbent ink receptors than, for example, water-based or solvent-based inkjet inks. Nevertheless, it has been observed that the behavior and interaction of a UV-curable ink in a substantially non-absorbent ink receiver is largely complicated compared to water and solvent based inks in the ink receiver
    2/50 absorbent. In particular, a good and controlled spread of the ink in the ink receiver is problematic.
    EP 1199181 A (TOYO INK), discloses a method for printing by means of inkjet on a surface of a synthetic resin substrate that comprises the steps of:
    1. conduct a surface treatment for the surface in order to provide the surface with a specific surface energy of 65 to 72 mJ / m 2 ;
    2. provide a paint curable by activation energy beam with a surface tension of 25 to 40 mN / m;
    3. discharging the ink onto the surface which has the specific surface free energy with an inkjet printing device thereby forming printed parts of the ink on the surface; and
    4. project a beam of activation energy on the printed parts.
    EP 1199181 A method (TOYO INK) appears to teach that the surface energy of the ink receiving surface should be greater than the surface energy of the ink. Still in the examples, although the surface energy of the four untreated synthetic resin substrates (ABS, PBT, PE and PS) was higher than the surface energy of the four different inks, good image quality was not observed, that is, good spread of the paint. The surface treatments used in the examples to increase the free surface energy of the ink receiver were crown treatments and plasma treatments. Since the life span of these surface treatments is more limited, it is best to incorporate the surface treatment equipment into the printer instead.
    3/50 inkjet, which makes the printer more complex and expensive.
    EP 2053104 A (AGFA GRAPHICS) discloses a radiation-curable inkjet printing method for producing printed plastic bags using a single-pass printer in which a prepared polymeric substrate has S SU b surface energy which is at least 4 mN / m less than the S Liq surface tension of the non-aqueous radiation-curable inkjet liquid.
    Generally speaking, the surface tension used to characterize an inkjet ink is its static surface tension. Nevertheless, inkjet printing is a dynamic process in which the surface tension changes dramatically over a time scale measured in tens of milliseconds. The active surface molecules spread and orient themselves on the newly formed surfaces at different speeds. Depending on the type of molecule and the surrounding environment, they reduce surface tension at different rates. These newly formed surfaces include not only the surface of the ink droplet exiting the nozzle of a printhead, but also the surface of the ink droplet that is discharged into the ink receiver. Maximum bubble pressure tensiometry is the only technology that makes it possible to measure the dynamic surface voltages of surfactant solutions in a short time less than milliseconds. A traditional ring or plate tensiometer cannot measure these rapid changes.
    EP 1645605 A (TETENAL) exposes an inkjet ink susceptible to radiation hardening in which the dynamic surface tension within the first second
    4/50 must drop at least 4 mN / m in order to improve adhesion on a wide variety of substrates. According to paragraph [0026], the dynamic surface tension of the paint measured by maximum bubble pressure tensiometry was 37 mN / m under a surface age of 10 ms and 30 mN / m under a surface age of 1000 ms.
    The spread of a UV-curable inkjet ink in an ink receiver can be additionally controlled by means of a partial cure or stuck cure treatment, in which the ink drop is fixed, that is, immobilized and there is no another spread. For example, WO 2004/002746 (INCA) discloses a jet printing method for printing an area of a substrate in a plurality of passages using curable ink, wherein the method comprises depositing a first ink pass in the area; partially cure the ink deposited on the first pass; deposit a second ink pass in the area; and fully cure the paint in the area.
    WO 03/074619 (DOTRIX / SERICOL) discloses a single-pass inkjet printing process comprising the steps of applying a first ink drop to a substrate and subsequently applying a second ink drop to the first ink drop without intermediate solidification of the first ink drop, in which the first and second ink drops have different viscosities, surface tensions or curing speeds. In the examples, the use of a high-speed single-pass inkjet printer to print UV-curable inks on a PVC substrate by a wet-to-wet printing process, in which the first ink drop and the subsequent treatment are not cured, that is, they are not irradiated before the
    5/50 next ink. In this way, an increase in ink spread can be achieved due to the increased ink volume of the combined ink droplets on the substrate. Nevertheless, although the spread of the ink can be increased in this way, the neighboring drops in the ink receiver tend to coalesce and mix with each other, especially in the non-absorbent ink receptors which are endowed with diminished surface energy.
    Problems with gloss homogeneity are observed when the printing speed increases, such as, for example, in single pass inkjet printing. EP 1930169 A (AGFA GRAPHICS) discloses a UV-curable inkjet printing method that uses a first set of print passes during which a partial cure occurs, followed by a second set of passages during which no partial curing to improve gloss homogeneity.
    For this reason, it is desirable to be able to provide inkjet image printing, especially on a non-absorbent ink receiver having diminished surface energy, by means of single-pass inkjet printing that exhibits sufficient ink spread without it requires a surface treatment such as crown treatment and at the same time it does not present problems of coalescence, runoff and homogeneity of brightness.
    Summary of the invention
    It was surprisingly revealed that single-pass inkjet printed images were obtained that exhibited excellent image quality without requiring a surface treatment, such as a crown, even in non-absorbent ink receivers having diminished surface energy, for example. control of the β / 50 dynamic surface tension of the ink in combination with an at least partial curing treatment in a very short period of time after the drop has been discharged into the ink receiver.
    For the purpose in if overcome the problems described previously, preferred modalities of gift invention provide one method of printing a jet of pass-through paint only such as is found defined by claim 1Other advantages and modalities of this invention will be highlighted The from description Following.Definitions
    The term “radiation curable ink means that the ink is susceptible to being cured by UV radiation or by means of an electron beam.
    The term "substantially non-absorbent inkjet ink receiver means any inkjet ink receiver that meets at least one of the following two criteria:
    1) No ink penetration into the inkjet receiver deeper than 2 pm;
    2) No more than 20% of a 100 pL drop blasted onto the inkjet ink receiver surface will disappear into the inkjet ink receiver in 5 seconds. If one or more coated layers are present, the dry thickness should be less than 5 pm.
    Standard analytical methods by one skilled in the art may be used to determine whether an ink receiver falls under either one or both of the aforementioned criteria of a substantially non-absorbent ink receiver. For example, after sandblasting
    7/50 on the surface of the ink receiver, a piece of the ink receiver can be harvested and examined using transmission electron microscopy to determine if the ink penetration depth is greater than 2 pm. Additional information regarding the appropriate analytical methods can be found in the article: DESIE, G, et al. Influence of Substrate Properties in Drop on Demand Printing. Proceedings of Imaging Science and Technology’s 18th International Conference on Non Impact Printing. 2002, p. 360-365.
    The term alkyl means all possible variants for each number of carbon atoms in the alkyl group, that is, for three carbon atoms: n-propyl and isopropyl; for four carbon atoms: n-butyl, isobutyl and tert-butyl; for five carbon atoms: n-pentyl, 1,1-dimethyl-propyl, 2,2-dimethyl-propyl and 2-methyl-butyl, etc.
    Single-pass inkjet printing methods
    The single-pass inkjet printing method according to the present invention includes the steps of:
    a) providing a radiation-curable inkjet ink set containing at least one first and a second radiation-curable inkjet ink that have a measured dynamic surface tension of no more than 30 mN / m by means of maximum bubble pressure tensiometry under a surface age of 50 ms and under 25 ° C;
    b) blasting a first radiation-curable inkjet ink into an inkjet ink receiver that moves at a printing speed of at least 35 m / min;
    8/50
    c) at least partially cure the first inkjet ink in the ink receiver within the range of 40 to 500 ms after the first inkjet ink is discharged into the ink receiver;
    d) blasting a second radiation-curable inkjet ink on the first at least partially cured inkjet ink; and
    e) at least partially cure the ink from the second inkjet within the range of 40 to 500 ms after the ink from the second inkjet is discharged into the ink from the first inkjet.
    In a preferred embodiment of the single-pass inkjet printing method, the inkjet ink receiver is a substantially non-absorbent inkjet ink receiver.
    In a preferred embodiment of the single-pass inkjet printing method, the ink receiver moves at a printing speed of at least 50 m / min.
    In a preferred embodiment of the single-pass inkjet printing method, the ink of the first and / or second inkjet is cured at least partially within the range of 40 to 420 ms, more preferably within the range of 50 to 200 ms.
    In a preferred embodiment of the single-pass inkjet printing method, at least partial curing treatment of the first and / or second inkjet ink begins after at least 100 ms.
    In a preferred embodiment of the single pass inkjet printing method, the first and second partially cured inkjet ink receives a final curing treatment within 2.5 s, more preferably within 2.0 s.
    9/50
    In a preferred embodiment of the single-pass inkjet printing method, the ink receiver surface has a specific surface free energy of no more than 30 mJ / m 2 .
    Inkjet Printers
    A suitable single-pass inkjet printer according to the present invention is an apparatus configured to carry out the aforementioned single-pass inkjet printing method.
    The concept and construction of a single-pass inkjet printer is widely known to the person skilled in the art. An example of this single-pass inkjet printer is: Dotrix Modular by Agfa Graphics. The single-pass inkjet printer for printing ink capable of UV curing on an ink receiver typically contains one or more inkjet printheads, means for transporting the ink receiver below the s ) printhead (s), some curing media (UV or electron beam) and electronic components to control the printing procedure.
    The single-pass inkjet printer is preferably at least capable of printing cyan (C), magenta (M), yellow (Y) and black (K) inkjet inks. According to a preferred embodiment, the CMYK inkjet ink set used in the single-pass inkjet printer can also be extended with extra inks, such as red, green, blue, orange and / or violet to further enlarge plus the color gamut of the image. The CMYK ink set can also be extended by combining full density and light density inks for colored and / or black inks
    10/50 to improve - image quality through reduced grain.
    Inkjet Printheads
    Radiation-curable inks can be blasted using one or more printheads that eject small ink droplets in a controlled manner through nozzles on an ink-receiving surface, which is moved in relation to the printhead (s) (s).
    A preferred printhead for the inkjet printing system is comprised of a piezoelectric printhead. Piezoelectric inkjet printing is based on the movement of a piezoelectric ceramic transducer when a voltage is applied to it. The application of -a voltage changes the shape of the piezoelectric ceramic transducer on the printhead creating a void, which is then filled with ink. When the voltage is removed again, the ceramic expands to its original shape, ejecting a drop of ink from the printhead. However, the inkjet printing method according to the present invention is not restricted to piezoelectric inkjet printing. Other inkjet printheads can be used and include several types, such as a continuous type and a thermal, electrostatic and acoustic drop type on demand.
    At high printing speeds, the inks must be ejected promptly from the printheads, which implies a number of restrictions on the physical properties of the ink, for example, a low viscosity under the blasting temperature, which can vary from 25 ° C to 110 ° C, a surface energy such that the printhead nozzle can form the
    11/50 small droplets required, homogeneous ink capable of rapid conversion to a dry printed area, etc.
    In so-called multi-pass inkjet printers, the inkjet printhead scans back and forth in a transverse direction over the moving ink receiving surface, but in a “single pass printing process , printing is performed using the page width inkjet printheads or multiple staggered inkjet printheads that cover the entire width of the ink receiving surface. In a single pass printing process, the inkjet printheads preferably remain stationary while the ink receiving surface is transported under the inkjet printhead (s). All curable inks must then be cured downstream of the printing area by means of radiation curing.
    By avoiding cross-printhead scanning, high print speeds can be achieved. In the single-pass inkjet printing method according to the present invention, the printing speed is at least 35 m / min, more preferably at least 50 m / min. The resolution of the single-pass inkjet printing method according to the present invention should preferably be at least 180 dpi, more preferably at least 300 dpi. The ink receiver used in the single-pass inkjet printing method according to the present invention preferably has a width of at least 240 mm, more preferably the width of the ink receiver is at least 300 mm, and with particularity preferably at least 500 mm.
    12/50
    Means of cure
    A suitable single-pass inkjet printer according to the present invention contains the curing means necessary to provide partial and final curing treatment. Radiation-curable inks can be cured by exposure to actinic radiation. Preferably, these radiation-curable inks comprise a photoinitiator that allows radiation curing, preferably ultraviolet radiation.
    In the preferred embodiment, a static static radiation source is used. The radiation source provided is preferably an elongated radiation source that extends transversely over the ink receiver surface to be cured and positioned downstream of the inkjet printhead.
    There are many sources of light in UV radiation, which include a high or low pressure mercury lamp, a cold cathode tube, a black light, an ultraviolet LED, an ultraviolet laser and a sparkling light. Of these, the preferred source is one that exhibits a relatively long wavelength UV contribution, having a predominant wavelength of 300 to 400 nm. Specifically, a UV-A light source is preferred due to the reduced light diffusion in it, resulting in more efficient interior curing.
    In general, UV radiation is
    classified as GRAPE, UV-B and UV-C as follows: - GRAPE: 400 nm The 320 nm - UV-B: 320 nm The 290 nm - UV-C: 290 nm The 100 nm.
    In addition, it is possible to cure the image using two light sources of different wavelengths or luminances. For example, the first source of UV
    13/50 for partial curing can be selected to be rich in UV-A, for example, a lead-induced lamp and the UV source for final curing can then be rich in UV-C, for example, a lamp not induced.
    According to a preferred embodiment of the apparatus configured to carry out the single-pass inkjet printing method according to the present invention, radiation-curable inkjet inks receive a final cure treatment by electron beam or by through a mercury lamp.
    According to a preferred embodiment of the apparatus configured to carry out the single-pass inkjet printing method according to the present invention, partial curing is carried out by means of UV LEDs.
    In the present invention, partial curing is used to increase the image quality of an inkjet image printed by a single pass inkjet printer using inkjet inks that are endowed with a dynamic surface tension of no more than 30 mN / m measured by maximum bubble pressure tensiometry under a surface age of 50 ms and under 25 ° C.
    The terms partial cure and full cure refer to the degree of cure, that is, the percentage of converted functional groups, and can be determined, for example, using RT-FTIR (Real-Time Fourier Transformation Infrared Spectroscopy) ) a method widely known to those skilled in the art of formulations capable of being cured. A partial cure is defined as a degree of cure in which at least 5%, preferably 10%, of the functional groups in the coated formulation are converted. A full cure is defined as
    14/50 a degree of cure in which the increase in the percentage of converted functional groups, with increased exposure to radiation (time and / or dose), is insignificant. A full cure corresponds to a percentage of conversion that is within 10%, preferably 5%, from the maximum conversion percentage defined by means of the horizontal asymptote in the RT-FTIR graph (percentage of conversion versus curing energy or time of cure).
    To facilitate curing, the inkjet printer preferably includes one or more oxygen depleting units. A preferred oxygen depletion unit places a blanket of nitrogen or other relatively inert gas (eg CO2), with adjustable position and adjustable inert gas concentration, in order to reduce the oxygen concentration in the curing environment. Residual oxygen levels are usually kept as low as 200 ppm, but are generally in the range of 200 ppm to 1200 ppm.
    Inkjet inks
    The radiation-curable inks used in the single-pass inkjet printing method according to the present invention are preferably UV-curable inkjet inks. Preferably, the radiation curable inkjet inks contain at least one photoinitiator.
    In a radiation-curable inkjet ink set for a single-pass inkjet printing method, preferably all inks are provided with a dynamic surface tension of no more than 30 mN / m measured by tensiometry of maximum bubble pressure under a surface age of 50 ms and under 25 ° C.
    Inkjet inks that are radiation curable preferably contain one or more dyes, with
    15/50 most preferably one or more color pigments. The set of curable inkjet inks preferably comprises at least one yellow curable inkjet ink (Y), at least one cyan curable inkjet ink (C) and at least one magenta curable inkjet ink (M) and preferably also at least one black curable ink jet ink (K). The CMYK curable inkjet ink set can also be extended with extra inks, such as red, green, blue, orange and / or violet to further expand the color range of the image. The CMYK ink set can also be extended by combining full density and light density inks for both color and / or black inks to improve image quality by reduced grain.
    Preferably, the radiation-curable inkjet ink also contains at least one surfactant, so that the inkjet ink has a dynamic surface tension of no more than 30 mN / m as measured by bubble pressure tensiometry maximum under a surface age of 50 ms and under 25 ° C.
    Radiation-curable inkjet ink is comprised of a non-aqueous inkjet ink. The term non-aqueous refers to a liquid carrier that should not contain water. However, sometimes a small amount may be present, generally less than 5% by weight of water based on the total weight of the paint. This water was not added intentionally, but came into the formulation through other components such as contamination, such as, for example, polar organic solvents. Higher amounts of water greater than 5% by weight tend to make non-aqueous inkjet ink unstable; in
    Preferably the water content is less than 1% by weight based on the total weight of the dispersion medium and even more preferably no water will be present.
    The radiation-curable inkjet ink preferably does not contain a component that can be evaporated, such as an organic solvent. But, sometimes, it may be advantageous to incorporate a small amount of an organic solvent in order to improve the adhesion to the surface of a substrate after UV curing. In this case, the added solvent may be in any amount in the range that does not cause solvent and VOC resistance problems, and preferably 0.1 to 10.0% by weight and particularly preferably 0.1 to 5.0% by weight, each based on the total weight of the curable ink.
    The pigmented radiation curable inkjet ink preferably contains a dispersing agent, more preferably a polymeric dispersing agent, to promote pigment dispersion. The pigmented curable ink may contain a dispersing synergist to improve the dispersion quality of the ink. Preferably, at least the magenta ink contains a dispersing synergist. A mixture of dispersing synergists can be used to further improve the dispersion stability.
    Most preferably, the viscosity of radiation-curable inkjet inks is less than 100 mPa.s under 30 ° C and under a shear rate of 100 s 1 . The viscosity of the inkjet ink under the blasting temperature is preferably less than 30 mPa.s, more preferably lower than 15 mPa.s, and and even more preferably is located
    17/50 between 2 and 10 mPa.s at a shear rate of 100 s -1 and a blasting temperature between 10 and 70 ° C.
    The radiation-curable inkjet ink may also additionally contain at least one inhibitor.
    Surfactants
    It is known to use surfactants in inkjet inks to reduce the surface tension of the ink and to reduce the angle of contact in the substrate, that is, to moisten the substrate through the ink. On the other hand, inkjet ink must meet strict performance criteria in order to be adequately blastable with high precision, safety and over an extended period of time. To achieve both the wetting of the substrate by means of the paint and the high blasting performance, typically, the surface tension of the paint is reduced by the addition of one or more surfactants. However, in the case of curable inkjet inks, the surface tension of inkjet ink is determined not only by the amount and type of surfactant, but also by the polymerizable compounds, polymeric dispersing agents and other additives in the ink composition.
    The radiation-curable inks used in the single-pass inkjet printing method according to the present invention are preferably provided with a dynamic surface tension of not more than 30 mN / m, and preferably also a static surface tension of not more than 24 mN / m, more preferably a static surface tension of not more than 22 mN / m.
    The radiation-curable inks used in the single-pass inkjet printing method according to
    18/50 with the present invention preferably contain silicone surfactants because low dynamic surface stresses can be more easily and better controlled with silicone surfactants than with fluorinated surfactants.
    The surfactant (s) may be anionic, cationic, nonionic (s) or zwitterionic (s) and are usually added in a total amount of less than 10% by weight based on the total weight of the radiation curable inks and in particular a total of less than 5% by weight based on the total weight of the radiation curable ink.
    In a preferred embodiment, the radiation curable inks used in the single pass inkjet printing method according to the present invention contain at least 0.6% by weight of silicone surfactant based on the total weight of the ink, more preferably at least 1.0% by weight of silicone surfactant based on the total weight of the paint.
    Silicone surfactants are typically siloxanes and can be alkoxylated, modified by polyether, functional hydroxyl modified by polyether, modified by amine, modified by epoxy and other modifications or combinations thereof. Preferred siloxanes are polymeric, for example, polydimethylsiloxane.
    The radiation curable inks used in the single-pass inkjet printing method according to the present invention preferably contain a polyether modified polydimethylsiloxane surfactant.
    In the radiation-curable inks used in the single-pass inkjet printing method according to the present invention, a fluorinated or
    19/50 silicone can be used as a surfactant, however, a surfactant capable of crosslinking is preferred, especially for food packaging applications. For this reason, it is preferred to use a surfactant capable of being polymerized, that is, a monomer capable of being copolymerized with active surface effects, for example, silicone modified acrylates, silicone modified methacrylates, acrylated siloxanes, siloxanes modified by acrylic modified by polyether, fluorinated acrylates and fluorinated methacrylates; these acrylates can be mono-, di-, tri- or higher (meth) acrylates.
    The radiation-curable inks used in the single-pass inkjet printing method according to the present invention preferably contain a polymerizable silicone surfactant.
    According to a preferred embodiment of the single-pass inkjet printing method according to the present invention, the polymerizable silicone surfactant is comprised of a silicone modified (meth) acrylate or an (meth) acrylated siloxane.
    Examples of commercial silicone surfactants that are suitable are those supplied by BYK CHEMIE GMBH (which include Byk (TM) -302, 307, 310, 331, 333, 341, 345, 346, 347, 348, UV3500, UV3510 and UV3530 ), those supplied by TEGO CHEMIE SERVICE (which include Tego Rad (TM) 2100, 2200N, 2250, 2300, 2500, 2600 and 2700), Ebecryl (TM) 1360 a polysiloxane hexaacrylate from CYTEC INDUSTRIES BV and the Efka (TM series) ) -3000 (including Efka (TM) 3232 and Efka (TM) -3883) from EFKA CHEMICALS BV
    20/50
    Monomers and Oligomers
    The monomers and oligomers used in radiation-curable compositions and paints, especially for food packaging applications, are preferably purified compounds that have no or virtually no impurities, more particularly no toxic or carcinogenic impurities. Impurities are usually derived compounds obtained during the synthesis of the polymerizable compound. Sometimes, however, some compounds can be deliberately added to pure polymerizable compounds in harmless amounts, for example, polymerization inhibitors or stabilizers.
    Any monomer or oligomer capable of free radical polymerization can be used as a polymerizable compound. A combination of monomers, oligomers and / or prepolymers can also be used. Monomers, oligomers and / or prepolymers can have different degrees of functionality, and a mixture that includes combinations of monomers, oligomers and / or prepolymers of mono-, di-, tri- and higher functionality can be used. The viscosity of radiation-curable compositions and inks can be adjusted by varying the relationship between monomers and oligomers.
    Particularly preferred monomers and oligomers are those listed in [0106] to [0115] in EP 1911814 A (AGFA GRAPHICS) incorporated in this context as a specific reference.
    A class of preferred monomers and oligomers comprises vinyl ether acrylates, such as those described in US 6310115 (AGFA), incorporated herein by reference. Particularly preferred compounds are 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, with
    21/50 most preferably the compound is 2- (2-vinyloxyethoxy) ethyl acrylate.
    Dyes
    The dyes used in radiation-curable inks can be dyes, pigments or a combination thereof. Organic and / or inorganic pigments can be used. The dye is preferably a pigment or polymeric dye, and most preferably a pigment.
    Pigments can be black, white, cyan, magenta, yellow, red, orange, violet, blue, green, brown, mixtures thereof, and the like. This colored pigment can be chosen from those exposed by HERBST, Willy, et al. Industrial Organic Pigments, Production, Properties, Applications. 3rd edition. Wiley VCH, 2004. ISBN 3527305769.
    Pigments that are suitable are set out in paragraphs [0128] to [0138] of WO 2008/074548 (AGFA GRAPHICS).
    Mixed crystals can also be used. Mixed crystals are also referred to as solid solutions. For example, under certain conditions, different quinacridones mix with each other to form solid solutions, which are totally different from both the physical mixtures of the compounds and the compounds themselves. In a solid solution, the components' molecules enter the same crystal lattice, usually, but not always, that of one of the components. The X-ray diffraction pattern of the resulting crystalline solid is characteristic of that solid and can be clearly differentiated from the pattern of a physical mixture of the same components in the same proportion. In these physical mixtures, the X-ray pattern of each component can be
    22/50 differentiated, and the disappearance of many of these lines is one of the criteria for the formation of solid solutions. A commercially available example is Cinquasi ™ Magenta RT355-D from Ciba Specialty Chemicals.
    Pigment mixtures can also be used in pigment dispersions. For some inkjet applications, a neutral black inkjet ink is preferred and can be obtained, for example, by mixing a black pigment and a cyan pigment in the ink. The inkjet application may also require one or more colors, for example, for packaging inkjet printing or textile product inkjet printing. Silver and gold colors are often desired colors for inkjet printing of posters and point of sale displays.
    Non-organic pigments can be used in pigment dispersions. Preferred particular pigments are CI Pigment Metal 1, 2 and 3. Illustrative examples of inorganic pigments include iron (III) oxide red, cadmium red, ultramarine blue, Prussian blue, chromium oxide green, cobalt green, amber , titanium black and synthetic iron black.
    The pigment particles in inkjet inks should be small enough to allow free flow of ink through the inkjet printing device, especially at the nozzles. It is also desirable to use small particles for maximum color intensity and to delay sedimentation.
    The numerical average pigment particle size is preferably between 0.050 and 1 pm, more preferably between 0.070 and 0.300 pm and particularly preferably between 0.080 and 0.200 pm. Most preferably, the average pigment particle size
    Numerical 23/50 is not greater than 0.150 μιη. An average particle size less than 0.050 pm is less desirable due to the decreased light resistance, but mainly also because very small pigment particles or their individual pigment molecules can still be extracted in food packaging applications. The average particle size of the pigment particles is determined with a Brookhaven Instruments BI90plus particle sizer based on the principle of dynamic light scattering. The ink is diluted with ethyl acetate to a pigment concentration of 0.002% by weight. The measurement settings of the Bl90plus are: 5 runs under 23 ° C, 90 ° angle, 635 nm wavelength and graphs = correction function.
    However, for a white radiation-curable ink, the numerical mean particle diameter of the white pigment is preferably 50 to 500 nm, more preferably 150 to 400 nm, and most preferably 200 to 350 nm. Sufficient hiding power may not be obtained when the average diameter is less than 50 nm, and the storage capacity and blasting suitability of the paint tend to be degraded when the average diameter exceeds 500 nm. The determination of the numerical mean particle diameter is best performed by photon correlation spectroscopy under a wavelength of 633 nm with a 4mW HeNe laser in a diluted sample of the pigment inkjet ink. A suitable particle size analyzer used was a Malvern ™ nano-S available from Goffin-Meyvis. A sample can, for example, be prepared by adding a drop of paint to a vat containing 1.5 ml of ethyl acetate and mixed until a homogeneous sample is obtained. The measured particle size is the average value of 3 measurements
    24/50 consecutive runs consisting of 6 runs of 20 seconds.
    Suitable white pigments are given in Table 2 in [0116] of WO 2008/074548 (AGFA GRAPHICS). The white pigment is preferably a pigment with a refractive index greater than 1.60. White pigments can be used simply or in combination. Preferably, titanium dioxide is used as a pigment with a refractive index greater than 1.60. Suitable titanium dioxide pigments are those set out in [0117] and [0118] of WO 2008/074548 (AGFA GRAPHICS).
    The pigments are present in the range of 0.01 to 10% by weight, preferably in the range of 0.1 to 5% by weight, each based on the total weight of the pigment dispersion. For white inks, the white pigment is preferably present in an amount of 3% to 30% by weight of the pigment dispersion, and more preferably 5% to 25%. An amount less than 3% by weight cannot achieve sufficient covering power and usually exhibits very poor storage stability and ejection property.
    Polymeric dispersants
    Typical polymeric dispersants are comprised of two monomer copolymers, but can contain three, four, five or even more monomers. The properties of polymeric dispersants depend both on the nature of the monomers and on their distribution in the polymer. Suitable copolymeric dispersants have the following polymer compositions:
    - statistically polymerized monomers (for example, A and B monomers polymerized in ABBAABAB);
    - alternatively polymerized monomers (for example, A and B monomers polymerized in ABABABAB);
    25/50 gradient polymerized monomers (gradually decreased) (for example, A and B monomers polymerized in AAABAABBABBB);
    - block copolymers (for example, monomers A and B polymerized in AAAAABBBBBB) where the block length of each block (2, 3, 4, 5 or even more) is important for the dispersion capacity of the polymeric dispersant;
    - graft copolymers (graft copolymers consist of a polymeric structure with polymeric side chains linked to the structure); and
    - mixed forms of these polymers, for example, massive gradient copolymers.
    Suitable polymeric dispersants are listed in the section Dispersants, more specifically [0064] to [0070] and [0074] to [0077], in EP 1911814 A (AGFA GRAPHICS), incorporated in this context as a specific reference.
    The polymeric dispersant preferably has a number of Mn average molecular weight between 500 and 30000, more preferably between 1500 and 10,000.
    The polymeric dispersant preferably has an average molecular weight Mw less than 100,000, more preferably less than 50,000 and more preferably less than 30,000.
    polymeric dispersant preferably has a polymeric dispersivity PD less than 2, more preferably less than 1.75 and more preferably less than 1.5.
    Commercial examples of polymeric dispersants are as follows:
    DISPERBYK ™ dispersants available from BYK CHEMIE GMBH;
    26/50
    - SOLSPERSE ™ dispersants available from NOVEON;
    - TEGO ™ DISPERS ™ dispersants from DEGUSSA;
    - EDAPLAN ™ dispersants from MÜNZING CHEMIE;
    - ETHACRYL ™ dispersants from LYONDELL;
    - ISP GANEX ™ dispersants;
    - DISPEX ™ and EFKA ™ dispersants from CIBA SPECIALTY CHEMICALS INC;
    - DEUCHEM DISPONER ™ dispersants; and
    - JONCRYL ™ dispersants from JOHNSON POLYMER.
    Polymeric dispersants that are particularly preferred include Solsperse ™ dispersants from NOVEON, Efka ™ dispersants from CIBA SPECIALTY CHEMICALS INC and Disperbyk ™ dispersants from BYK CHEMIE GMBH. Dispersants that are particularly preferred include Solsperse ™ 32000, 35000 and 39000, available from NOVEON.
    The polymeric dispersant is preferably used in an amount of 2 to 600% by weight, more preferably from 5 to 200% by weight based on the weight of the pigment.
    Synergistic Dispersion Agent
    A dispersion synergist usually consists of an anionic part and a cationic part. The anionic part of the dispersion synergist that exhibits a certain molecular similarity with the colored pigment and the cationic part of the dispersion synergist consists of one or more protons and / or cations to compensate the load of the anionic part of the dispersion synergist.
    The synergist is preferably added in a lesser amount than the polymeric dispersant (s). The ratio of the polymeric dispersant / dispersion synergist depends on the pigment and should be
    27/50 determined experimentally. Typically, the ratio,% by weight of polymeric dispersant /% by weight of dispersing synergist, is selected between 2: 1 to 100: 1, preferably between 2: 1 and 20: 1.
    Suitable dispersing synergists that are found commercially available include Solsperse ™ 5000 and Solsperse ™ 22000 from NOVEON.
    Particular preferred pigments for the magenta ink used are a diketopyrrole-pyrrole pigment or a quinacridone pigment. Suitable dispersing synergists include those exposed in EP 1790698 A (AGFA GRAPHICS), EP 1790696 A (AGFA GRAPHICS), WO 2007/060255 (AGFA GRAPHICS) and EP 1790695 A (AGFA GRAPHICS).
    In the dispersion of the C.I. Pigment Blue 15: 3, it is preferred to use a sulfonated Cuftalocyanina dispersion synergist, for example, Solsperse ™ 5000 from NOVEON. Suitable dispersing agents for yellow inkjet inks include those exposed in EP 1790697 A (AGFA GRAPHICS).
    Photoinitiators Photoinitiator is preferably a free radical initiator. A free radical photoinitiator is a chemical compound that initiates a polymerization of monomers and oligomers when exposed to actinic radiation through the formation of a free radical.
    Two types of free radical photoinitiators can be differentiated and used in the pigment or ink dispersion of the present invention. A Norrish Type I initiator is an initiator that will bond after excitation, producing the initiation radical immediately. A Norrish Type II initiator is a photoinitiator that is activated by means of actinic radiation and forms free radicals by
    28/50 means of abstraction of hydrogen from a second compound that becomes the free radical of current initiation. This second compound is called a polymerizing or synergizing agent. Photoinitiators of both type I and type II can be used in the present invention, alone or in combination.
    Suitable photoinitiators are disclosed by CRIVELLO, J.V., et al. VOLUME III: Photoinitiators for Free Radical Cationic, 2nd edition, Edited by BRADLEY, G., London, UK; John Wiley and Sons Ltd, 1998, page 287 - 294.
    Specific examples of photoinitiators may include, but are not limited to, the following compounds or combinations thereof: benzophenone and substituted benzophenones, 1-hydroxycyclohexyl phenyl ketone, thioxanthones, such as isopropyloxanthone, 2-hydroxy-2methyl-l-phenylpropan-l-one, 2-benzyl-2-dimethylamino- (4morpholinophenyl) butan-l-one, benzyl dimethyl ketal, bis (2,6-dimethylbenzoyl) -2,4,4-trimethyl pentylphosphine oxide, 2,4, β-trimethylbenzyldiphenyl phosphine oxide , 2-methyl-l- [4 (methylthio) phenyl] -morpholinopropan-l-one, 2,2-dimethoxy-1,2,2diphenylethan-l-one or 5,7-diiodine-3-butoxy-6-fluorone , diphenyliodonium fluoride and triphenylsulfonium hexafluophosphate.
    Commercial photoinitiators that are suitable include Irgacure ™ 184, IrgacureTM 500, Irgacure ™ 907, Irgacure ™ 369, Irgacure ™ 379, Irgacure ™ 1700, Irgacure ™ 651, Irgacure ™ 819, Irgacure ™ 907, Irgacure ™ 1000, Irgacure ™ 1300, Irgacure ™ 1870, Darocur ™ 1173, Darocur ™ 2959, Darocur ™ 4265 and Darocur ™ ITX available from CIBA SPECIALTY CHEMICALS, Lucirin ™ TPO, Lucirin ™ TPO-L available from BASF AG, Esacure ™ KT046, Esacure ™ KIP150, Esacure ™ KT37 and EsacureTM EDB available from LAMBERTI, H-Nu ™ 470 and Η-Nu ™ 470X available from SPECTRA GROUP Ltd ..
    29/50
    Suitable cationic photoinitiators include compounds, which form aprotic acids or Bronstead acids upon exposure to ultraviolet and / or visible light sufficient to initiate polymerization. The photoinitiator that is used can be a single compound, a mixture of two or more active compounds, or a combination of two or more different compounds, i.e., co-initiators. Non-limiting examples of suitable cationic photoinitiators are aryl diazonium salts, diaryliodonium salts, triarylsulfonium salts, triarylselenonium salts and the like.
    However, for safety reasons, in particular for food packaging applications, the photoinitiator is preferably a photoinitiator called diffusion prevented. A diffusion impeded photoinitiator is a photoinitiator that exhibits much lower mobility in a cured layer of curable liquid or ink than a monofunctional photoinitiator, such as benzophenone. Several methods can be used to decrease the mobility of the photoinitiator. One way is to increase the molecular weight of the photoinitiator so that the rate of diffusion is reduced, for example, bifunctional photoinitiators or polymeric photoinitiators. Another way is to increase its reactivity so that it is built within the polymerization network, for example, multifunctional photoinitiators and polymerizable photoinitiators. Preferably, the diffusion impeded photoinitiator is selected from the group consisting of di- or multifunctional non-polymeric photoinitiators, oligomeric or polymeric photoinitiators and polymerizable photoinitiators. Di- or multifunctional nonpolymeric photoinitiators are considered to be
    30/50 having a molecular weight between 300 and 900 Dalton. Non-polymerizable monofunctional photoinitiators with a molecular weight in this range are not diffusion impeded photoinitiators. Most preferably, the diffusion impeded photoinitiator is a polymerizable initiator.
    A suitable diffusion prevented photoinitiator may contain one or more functional photoinitiation groups derived from a Norrish type I photoinitiator selected from the group consisting of benzoin ethers, benzyl ketals, a, α-dialcoxyacetophenones, a-hydroxyalkyl phenones, a- aminoalkylphenones, acylphosphine oxides, acylphosphine sulfides, α-halocetones, α-halosulfones and phenylglyoxalates.
    A suitable diffusion prevented photoinitiator may contain one or more functional photoinitiation groups derived from a Norrish type II primer selected from the group consisting of benzophenones, thioxanthones, 1,2-diketones and anthraquinones.
    The diffusion prevented photoinitiators that are suitable are also those exposed in EP 2053101 A (AGFA GRAPHICS) in paragraphs [0074] and [0075] for bifunctional and multifunctional photoinitiators, in paragraphs [0077] to [0080] for polymeric photoinitiators and in paragraphs [0081] to [0083] for polymerizable photoinitiators.
    A preferred amount of photoinitiator is situated at 0 to 50% by weight, more preferably 0.1 to 20% by weight, and even more preferably 0.3 to 15% by weight of the total weight of the curable pigment or ink dispersion. .
    In order to further increase photosensitivity, radiation curable ink may contain
    31/50 additionally co-offenders. Examples of suitable co-offenders can be categorized into 4 groups:
    (1) tertiary aliphatic amines, such as methyldiethanolamine, dimethylethanolamine, triethanolamine, triethylamine and N-methylmorpholine;
    (2) aromatic amines, such as amylparadimethylaminobenzoate, 2-n-butoxyethyl-4 (dimethylamino) benzoate, 2- (dimethylamino) ethylbenzoate, ethyl4 - (dimethylamino) benzoate and 2-ethylexyl-4 (dimethylamino) benzoate; and (3) methacrylated amines, such as dialkylamino alkylmethacrylates (for example, diethylaminoethylacrylate) or N-morpholinoalkyl-methacrylates (for example, Nmorfolinoethylacrylate).
    Preferred co-offenders are aminobenzoates.
    When one or more co-offenders are included in the radiation-curable ink, preferably these co-offenders are prevented from diffusion for safety reasons, in particular for food packaging applications.
    A diffusion impeded coinicidator is preferably selected from the group consisting of non-polymeric di- or multifunctional coiniciators, oligomeric or polymeric coiniciators and polymerizable coiniciators. Most preferably, the diffusion impeded co-initiator is selected from the group consisting of polymeric co-initiators and polymerizable co-initiators. More preferably, the diffusion impeded coiniciator is comprised of a polymerizable coiniciator with at least one methacrylate group, more preferably with at least one acrylate group.
    32/50
    The preferred diffusion prevented coiniciators are the polymerizable coiniciators set out in EP 2053101 A (AGFA GRAPHICS) in paragraphs [0088] and [0097].
    Preferred diffusion-prevented coiniciators include a polymeric coiniciator that is endowed with a dendritic polymeric architecture, more preferably a hyper-branched polymeric architecture. Preferred hyperbranched polymeric coinitiators are those set out in US 2006014848 (AGFA) incorporated in this context in the form of specific reference.
    The ink capable of being cured by radiation preferably comprises the diffusion inhibitor in an amount of 0.1 to 50% by weight, more preferably in an amount of 0.5 to 25% by weight, and even more preferably in an amount of 1 to 10% by weight of the total weight of the paint.
    Polymerization inhibitors
    The radiation-curable inkjet ink may contain a polymerization inhibitor. Suitable polymerization inhibitors include phenol-type antioxidants, hindered amine light stabilizers, phosphorus-type antioxidants, hydroquinone monomethyl ether commonly used in methacrylate monomers, and hydroquinone, t-butylcatechol, pyrogallol can also be used.
    Suitable commercial inhibitors are, for example, Sumilizer ™ GA-80, Sumilizer ™ GM and Sumilizer ™ GS produced by Sumitomo Chemical Co. Ltd .; Genorad ™ 16, Genorad ™ 18 and Genorad ™ 20 from Rahn AG; Irgastab ™ UV10 and Irgastab ™ UV22, Tinuvin ™ 460 and CGS20 from Ciba Specialty Chemicals; Floorstab ™ UV series (UV-1, UV-2, UV-5 and UV-8) from Kromachem Ltd, Additol ™ S series (S100, S110, S120 and S130) from Cytec Surface Specialties.
    33/50
    Since the excessive addition of these polymerization inhibitors will decrease the ink's sensitivity to curing, it is preferred that the amount capable of preventing polymerization is determined before mixing. The amount of a polymerization inhibitor is preferably less than 2% by weight of the total inkjet ink.
    Preparation of Pigment and Paints Dispersions
    Pigment dispersions can be prepared by precipitation or grinding the pigment in the dispersion medium in the presence of the dispersing agent.
    Mixing apparatus may include a pressure kneader, an open kneader, a planetary mixer, a solvent and a Dalton Universal Mixer. Suitable grinding and dispersing apparatus comprise a ball mill, a pearl mill, a colloid mill, a high speed disperser, double rollers, a bead mill, an ink conditioner and triple rollers. Dispersions can also be prepared using ultrasonic energy.
    Many different types of materials can be used as grinding media, such as glass, ceramics, metals and plastics. In a preferred embodiment, the grinding media can include particles, preferably substantially spherical, for example beads consisting essentially of a polymeric resin or yttrium-stabilized zirconium oxide beads.
    In the mixing, grinding and dispersing process, each process is performed with cooling to prevent the formation of heat, and as much as possible under light conditions in which the actinic radiation has been
    34/50 substantially excluded.
    The pigment dispersion can contain more than one pigment, the pigment or ink dispersion can be prepared using separate dispersions for each pigment, or alternatively, several pigments can be mixed and can be ground together in preparing the dispersion.
    The dispersion process can be carried out in a continuous mode, in batch or semi-batch.
    The preferred quantities and proportions of the grinding ingredients will vary widely, depending on the specific materials and the intended applications. The content of the grinding mixture comprises the material to be ground and the grinding medium. The material to be molded comprises pigment, polymeric dispersant and a liquid carrier. For inkjet inks, the pigment is normally present in the material to be ground by 1 to 50%, excluding the grinding medium. The weight ratio of pigment to the polymeric dispersant is 20: 1 to 1: 2.
    grinding time can vary widely and can depend on the pigment, selected mechanical means and conditions of permanence, the desired initial and final particular dimension, etc. Pigment dispersions with an average particle size of less than 100 nm can be prepared in the present invention.
    After grinding is completed, the grinding medium is separated from the ground particulate product (either in a dry or liquid dispersion form) using conventional separation techniques, such as through filtration, sieving through a mesh screen, and similar. The sieve is often built in the mill, for example, for a bead mill. The concentrate of
    35/50 milled pigment is preferably separated from the grinding medium by means of filtration.
    In general, it is desirable to prepare the inks in the form of a concentrated molten material, which is subsequently diluted to the appropriate concentration for use in the printing system. This technique allows the preparation of a larger amount of pigmented ink from the equipment. By means of dilution, the inkjet ink is adjusted to the desired viscosity, surface tension, color, hue, saturation density and printed area coverage for the particular application.
    EXAMPLES
    Measurement Methods
    1. Drainage
    Dripping between paint colors occurs when two colors overlap and create an undesirable color mix. Drainage was assessed by printing 100 pm lines of one color in a wide printed area of another color, for example, a black line in a wide yellow area. The evaluation was carried out according to a criterion as described in Table 1.
    Table 1
    Criterion Note ++ no dripping + almost no dripping visible through microscope - runny visible through microscope - some oozing to be seen with the naked eye - - - oozing to be seen with the naked eye
    . Coalescence
    The inkjet ink receiver must be easily moistened using inkjet inks in a way that no puddling occurs, that is,
    36/50 coalescence of adjacent ink droplets to form large droplets on the inkjet ink receiver surface. A visual assessment was carried out according to a criterion described in Table 2.
    Table 2
    Criterion Note ++ no coalescence + almost no coalescence - coalescence - almost full coalescence - - - full coalescence
    3. Brightness
    A 10 x 10 cm square patch of red, green and blue was printed. Differences in dissemination
    and healing of paints j act in ink led to inhomogeneities in the glow what are visible with the naked eye. 10 There was a evaluation visual in a deal with a criterion
    described in Table 3.
    Table 3
    Criterion Note ++ no inhomogeneity visible in brightness + almost no inhomogeneity visible in the brightness - small inhomogeneities visible in the brightness - wide inhomogeneities visible in brightness - Very large inhomogeneities visible in brightness
    4. Dynamic Surface Tension
    The dynamic surface tension (DST) was measured using a Bubble Pressure Tensiometer (Bubble
    Pressure Tensiometer) BP2 available from KRUSS. The inkjet ink was placed in a thermostatic vessel on the tensiometer under a temperature of 25 ° C. A capillarity of silane glass with a capillarity radius of 0.221 mm 20 was dipped to a depth of 10 mm in the paint. THE
    37/50 surface tension was measured as a function of surface age using Labdesk software and using air as the gas to create the bubbles.
    5. Static Surface Tension
    The static surface tension of liquids and curable inks was measured with a KRÜSS K9 tensiometer from KRÜSS GmbH, Germany under 25 ° C after 60 sequences.
    6. Surface energy
    The surface energy of a substrate was measured using a set of test pens, containing fluids of a defined surface tension from 30 to 44 mN / m, available from ARCOTEST, Germany.
    A result of the measurement of surface energy from 36 to 38 mJ / m 2 (= mN / m) means that the red ink of a test pen with a surface tension of 36 mN / m results in the spread of red ink, while that the red ink of a test pen with a surface tension of 38 mN / m did not result in the spread of the red ink.
    Materials
    All materials used in the following examples were found to be readily available from ALDRICH Chemical Co. (Belgium) or ACROS (Belgium), unless otherwise specified. The water used in the examples was demineralized water.
    VEEA is 2- (vinylethoxy) ethyl acrylate, a bifunctional monomer that is available from NIPPON SHOKUBAI, Japan:
    THE
    DPGDA is a dipropylene glycoldiacrylate from
    SARTOMER.
    38/50
    M600 is dipenta erythritol hexa-acrylate and an abbreviation for Miramer ™ M600 available from RAHN AG ..
    ITX is Darocur ™ ITX is an isomeric mixture of
    2- and 4-isopropylthioxanthone from CIBA SPECIALTY CHEMICALS.
    Irgacure ™ 819 is a photoinitiator available from
    CIBA SPECIALTY having as chemical structure:
    Irgacure ™ 379 is a photoinitiator that is available from CIBA SPECIALTY having
    O as chemical structure:
    Irgacure ™ 907 is 2-methyl-l- [4- (methylthio) phenyl] 2-morpholino-propan-l-one, a photoinitiator available from CIBA SPECIALTY CHEMICALS.
    PB15: 4 is an abbreviation used for Hostaperm ™
    Blue P-BFS, a C.I. Pigment Blue 15: 4 pigment from
    CLARIANT.
    PY150 an abbreviation used for
    Chromophtal ™ Yellow LA2, a C.I. Pigment Yellow pigment
    150 of CIBA SPECIALTY CHEMICALS.
    PV19 / PR202 is Cromophtal ™ Jet Magenta 2BC which is a mixed crystal of C.I. Pigment Violet 19 and C.I. Pigment Red 122 available from CIBA-GEIGY.
    PB7 is an abbreviation used for Special Black ™ 550, which is a carbon black available from EVONIK DEGUSSA.
    39/50
    SOLSPERSE ™ 35000 is a polyethylene imine-polyester dispersant available from NOVEON.
    S35000 is a 35% solution of SOLSPERSE ™ 35000 in DPGDA.
    SYN is a dispersing synergistic agent according to Formula (A):
    Formula (A), and was synthesized in the same manner as described in Example 1 of WO 2007/060254 (AGFA GRAPHICS) for the synergist QAD-3.
    BYK ™ UV3510 is a polyether modified polydimethyl siloxane wetting agent available from BYK CHEMIE GMBH.
    INHIB is a mixture that forms a polymerization inhibitor that has a composition according to the
    Table 4.
    Table 4
    Component % by weight DPGDA 82.4 p-methoxyphenol 4.0 2,6-di-tert-butyl-4-methylphenol 10.0 Cupferron ™ AL 3, 6
    Cupferron ™ AL is aluminum N-nitrous phenyl hydroxylamine from WAKO CHEMICALS LTD.
    HIFI is a substantially non-absorbent polyester film available in the form of HiFi ™ PMX749 from HiFi
    40/50
    Industrial Film (UK), which has a surface energy of 37 mJ / m 2 .
    IG is bleached cardboard available as Invercote ™ G (180 g / m 2 ) from Iggesund Paperboard AB (Sweden), which has a surface energy of 45 mJ / m 2 . Inkjet Printer
    A custom-designed single-pass inkjet printer was used, which was equipped with a lower carriage on which a linear motor is mounted. The linear motor sled was fixed to a substrate table. Paint receivers are held in position on the substrate table by means of a vacuum suction system. A bridge was built on the lower carriage, perpendicular to the direction of the linear motor. Connected to the bridge, a cage was mounted for four inkjet printheads (Kyocera type KJ4A). This cage was provided with the necessary mechanical adjustment means for aligning the printheads in such a way that they could one by one print the same surface on the substrate table that moved under them in a single pass.
    The linear motor and the inkjet printheads were controlled using a specific program and separate electronic circuits. The synchronization between the linear motor and the inkjet printheads was possible because the encoder pulses of the linear motor were also fed to the electronic circuits that controlled the inkjet printheads. The pulses of the inkjet printheads were supplied synchronously with the encoder pulses of the linear motor and thus, in this way, the movement of the substrate table was synchronized with the inkjet printhead. The drive software for the heads
    41/50 printing could translate any image encoded in CMYK into control signals for the printheads.
    The UV curing media covered five mercury vapor lamps. These lamps were movably connected to two fixed rails. Four lead-induced mercury vapor lamps were placed each immediately after one of the four inkjet printheads for pin cure. The fifth uninduced mercury vapor lamp was positioned at the end of the two rails attached after the substrate table passed the four printheads and their lead-induced mercury vapor lamps, in order to provide a final cure. All of these lamps were individually adjustable in terms of orientation and power of UV light emitted as an output. By positioning the lead-induced mercury vapor lamps closer or further from the printhead, the curing time after blasting could be reduced, respectively, increased.
    Each printhead had its own ink supply. The main circuit was a closed circuit, in which circulation was provided by means of a pump. This circuit started from a feed tank, mounted in the immediate vicinity of the inkjet printhead, to a degassing membrane and then through a filter and the pump back to the feed tank. The membrane was impermeable to paint, but permeable to air. By applying strong pressure to one side of the membrane, air was extracted from the paint located on the other side of the membrane.
    The function of the feeder tank is threefold. The feed tank is contains an amount of ink
    42/50 permanently degassed which can be distributed to the inkjet printhead. Second, a small under pressure was exerted on the feed tank to prevent ink leakage from the printhead and to form a meniscus on the ink jet nozzle. The third function was that by means of a float in the feed tank, the ink level in the circuit could be monitored.
    In addition, two short channels were connected to the closed circuit: an input channel and an output channel. With a signal from the float in the feed tank, an amount of ink from an ink storage container was taken through the inlet channel into the closed circuit just before the degassing membrane. The short outlet channel was extended from the feeder tank to the inkjet printhead, where the ink was consumed, that is, blasted onto the ink receiver. Inkjet inks
    The preparation of the concentrated pigment dispersions for the CMYK inkjet ink sets were all prepared in a similar manner. Preparation of DIS-C Concentrated Cyan Pigment Dispersion
    A concentrated cyan pigment dispersion DIS-C was prepared by mixing the components according to Table 5 for 30 minutes in a 20-liter vessel. The vessel was then connected to a Bachofen DYNOMILL ECM Pilot mill with an internal volume from 1.5 1 filled to 63% with zirconite beads stabilized with 0.4 mm yttrium. The mixture was circulated over the mill for 2 hours at a flow rate of about 21 per minute and a rotational speed in the mill of around
    43/50 m / s. After grinding, the dispersion was separated from the beads using a filter cloth. The dispersion was then discharged into a 10 1 vessel.
    Table 5
    Component Quantity (in g) PB15: 4 1400 S35000 4000 INHIB 70 DPGDA 1530
    Preparation of DIS-M Concentrated Magenta Pigment Dispersion
    A concentrated dispersion of magenta DIS-M pigments was prepared by mixing the components according to Table 6 for 30 minutes in a 20 L pot. The pot was then connected to a Bachofen DYNOMILL ECM Pilot mill with an internal volume of
    1.5 L filled to 53% with stabilized zirconite globules with 0.4 mm diameter. The mixture was circulated over the mill for 2 hours at a flow rate of about 2 L per minute and a rotation speed in the mill of around 13 m / s. After grinding, the dispersion was separated from the globules using a filter cloth. The dispersion was then discharged into a 10 L vessel.
    Table 6
    Component Quantity (in g) PV19 / PR202 1050 SYN 15 S35000 3000 INHIB 70 DPGDA 2865
    Preparation of DIS-Y Yellow Pigment Concentrated Dispersion
    A concentrated dispersion of yellow pigment DIS-Y was prepared by mixing the components according to Table 7 for 30 minutes in a 20 L pot. The pot was then connected to a Bachofen DYNOMILL ECM Pilot mill with an internal volume of
    44/50
    1.5 L filled to 63% with stabilized zirconite globules with 0.4 mm diameter. The mixture was circulated over the mill for 2 hours at a flow rate of about 2 L per minute and a rotation speed in the mill of around 13 m / s. After grinding, the dispersion was separated from the globules using a filter cloth. The dispersion was then discharged into a 10 L vessel.
    Table 7
    Component Quantity (in g) PY150 1050 S35000 3000 INHIB 70 DPGDA 2880
    Preparation of DIS-K Black Pigment Concentrated Dispersion
    A concentrated dispersion of black pigment DIS-K was prepared by mixing for 30 minutes the components according to Table 8 in a 20 L pot. The pot was then connected to a Bachofen DYNOMILL ECM Pilot mill with an internal volume of
    1.5 L filled to 63% with stabilized zirconite globules with 0.4 mm diameter. The mixture was circulated over the mill for 2 hours at a flow rate of about 2 L per minute and a rotation speed in the mill of around 13 m / s. After grinding, the dispersion was separated from the globules using a filter cloth. The dispersion was then discharged into a 10 L vessel.
    Table 8
    Component Quantity (in g) PB7 1050 S35000 3000 INHIB 70 DPGDA 2880
    45/50
    Preparation of Inkjet Ink Sets Set-1 to Set-4
    All inkjet inks were prepared in the same way. For example, the cyan inkjet ink Cl was prepared by combining the concentrated dispersion of cyan pigments DIS-C with monomers, photoinitiators, surfactant, ... to obtain the composition given for the inkjet ink Cl ink in Table 9.
    In the Inkjet Ink Set-1 in Table 9, all inkjet inks have a static surface tension of 22 mN / m and a dynamic surface tension of 40 mN / m.
    Table 9
    % by weight of C-l M-l Y-l K-l VEEA 62.34 63.45 63.59 62.34 DPGDA 12.56 14.60 11.31 12.56 M600 6.00 1.80 6.60 6.00 ITX 2.00 2.00 2.00 2.00 Irgacure ™ 819 3.00 3.00 3.00 3.00 Irgacure ™ 907 5.00 5.00 5.00 5.00 Irgacure ™ 379 2.00 2.00 2.00 2.00 PB15: 4 3.00 - - 0.80 PV19 / PR202 - 3.50 - - PY150 - - 2.70 - PB7 - - - 2.20 SYN - 0.05 ---- - S35000 3.00 3.50 2.70 3.00 INHIB 1.00 1.00 1.00 1.00 BYK ™ UV3510 0.10 0.10 0.10 0.10
    In the Inkjet Ink Set-2 of Table 10, all inkjet inks have a static surface tension of 22 mN / m and a dynamic surface tension of 31 mN / m.
    46/50
    Table 10
    % by weight of C-2 M-2 Y-2 K-2 VEEA 62.14 63.25 63.39 62.14 DPGDA 12.56 14.60 11.31 12.56 M600 6.00 1.80 6.60 6.00 ITX 2.00 2.00 2.00 2.00 Irgacure ™ 819 3.00 3.00 3.00 3.00 Irgacure ™ 907 5.00 5.00 5.00 5.00 Irgacure ™ 379 2.00 2.00 2.00 2.00 PB15: 4 3.00 - - 0.80 PV19 / PR202 - 3.50 - - PY150 - - 2.70 - PB7 - - - 2.20 SYN - - 0.05 - - S35000 3.00 3.50 2.70 3.00 INHIB 1.00 1.00 1, 00 1.00 BYK ™ UV3510 0.30 0.30 0.30 0.30
    In the inkjet ink set-3 of Table 11, all inkjet inks have a static surface tension of 22 mN / m and a dynamic surface tension of 30 mN / m.
    Table 11
    % by weight of C-3 M-3 Y-3 K-3 VEEA 61.84 62.95 63.09 61.84 DPGDA 12.56 14.60 11.31 12.56 M600 6.00 1.80 6.60 6.00 ITX 2.00 2.00 2.00 2.00 Irgacure ™ 819 3.00 3.00 3.00 3.00 Irgacure ™ 907 5.00 5.00 5.00 5.00 Irgacure ™ 379 2.00 2.00 2.00 2.00 PB15: 4 3.00 - - 0.80 PV19 / PR202 - 3.50 - - PY150 - - 2.70 - PB7 - - - 2.20
    47/50
    SYN - 0.05 - - S35000 3.00 3.50 2.70 3.00 INHIB 1.00 1.00 1.00 1.00 BYK ™ UV3510 0.60 0.60 0.60 0.60
    In Set-4 of inkjet inks from
    Table 12, all inkjet inks have a static surface tension of 22 mN / m and a dynamic surface tension of 28 mN / m.
    Table 12
    % by weight of C-4 M-4 Y-4 K-4 VEEA 61.44 62.55 62.69 61.44 DPGDA 12.56 14.60 11.31 12.56 M600 6.00 1.80 6.60 6.00 ITX 2.00 2.00 2.00 2.00 Irgacure ™ 819 3.00 3.00 3.00 3.00 Irgacure ™ 907 5.00 5.00 5.00 5.00 Irgacure ™ 379 2.00 2.00 2.00 2.00 PB15: 4 3.00 - - 0.80 PV19 / PR202 - 3.50 - - PY150 - - 2.70 - PB7 - - - 2.20 SYN - 0.05 - - S35000 3.00 3.50 2.70 3.00 INHIB 1.00 1.00 1.00 1.00 BYK ™ UV3510 1.00 1.00 1.00 1.00
    Results and evaluation
    Sets of ink jet inks Set-1 to Set-4 were printed, in a black-cyan-magenta-yellow print order, with the custom-designed 10-pass single inkjet printer under print speeds 35 m / min and 50 m / min in a substantially non-absorbent HIFI inkjet ink receiver. If the inkjet ink has been partially cured by means of UV after it has reached the
    48/50 ink receiver, the delay that occurred before partial curing is shown in Table 13. All inkjet inks received a final curing, which was 1728 ms and 2469 ms respectively after blasting 5 of the first inkjet ink for a print speed of 50 m / min and 35 m / min respectively. Runoff, coalescence and gloss were evaluated in all printed samples and the results are shown in Table 13.
    Table 13
    Printed Sample Ink set Print speed (m / min) Partial UV curing (ms) Drainage Coalescence Brightness COMP-1 Set- 50 none ---. - - COMP-2 1138- ++ COMP-3 414- ++ COMP-4 690 - COMP-5 966 - - - COMP-635 none - - - COMP-7 197- ++ COMP-8 591 - - ++ COMP-9 986- - COMP-10 1380 - - - COMP-11 Set- 50 none- - COMP-12 2138- ++ COMP-13 414+ + COMP-14 690- - COMP-15 966- - COMP-1635 none- - COMP-17 197 + - ++ COMP-18 591 - - ++ COMP-19 986 - - + COMP-20 1380- - COMP-21 Set- 50 none - - - INV-1 3138 + + ++ INV-2 414 + + ++ COMP-22 690 - - + COMP-23 966 + - - COMP-2435 none - - - INV-3 197 + + ++ COMP-25 591 ++ + ++ COMP-26 986 ++ - + COMP-2 7 1380 -
    49/50
    COMP-28 Set- 50 none - - - INV-4 4138 ++ + ++ INV-5 414 + + ++ COMP-29 690 ++ + ++ COMP-30 966 +- COMP-3135 none - - - INV-6 197 ++ + ++ COMP-32 591 + - ++ COMP-33 986- + COMP-34 1380 + - -
    Da from Table 13, it is evident that only the Set-3 and Set-4 ink sets, where all radiation-curable inkjet inks had a dynamic surface tension of no more than 30 mN / m, were able to produce printed samples that exhibited superior image quality within the specific time frame for partial UV curing from 50 to 500 ms.
    The same printing experiment was repeated, with the exception that the HIFI substantially non-absorbent inkjet ink receiver was replaced by an IG absorbent inkjet ink receiver. Runoff, coalescence and gloss were again evaluated in all printed samples and the results 15 are shown in Table 14.
    Table 14
    Printed Sample Ink set SpeedPrinting (m / min.) Partial UV curing (ms) Drainage Coalescence Brightness COMP-35 Set- 50 none--- - COMP-36 1138 ++ COMP-37 414 ++ COMP-38 690- - COMP-39 966 - COMP-4035 none- - COMP-41 197 ++ COMP-42 591 ++ COMP-43 986 - COMP-44 1380 - COMP-45 Set- 50 none- - COMP-46 2138 ++ + ++
    50/50
    COMP-47 414 - - + COMP-48 690 - - - COMP-49 966 -- COMP-5035 none - - - COMP-51 197 ++ + ++ COMP-52 591 - - ++ COMP-53 986 - - + COMP-54 1380 - - - COMP-55 Set- 50 none - - - INV-7 3138 ++ + ++ INV-8 414 ++ + ++ COMP-56 690 ++ + + COMP-57 966 - - - COMP-5835 none - - - INV-9 197 ++ + ++ COMP-59 591 ++ + ++ COMP-60 986 + + + COMP-61 1380 - - - COMP-62 Set- 50 none - ++ - INV-10 4138 ++ ++ ++ INV-11 414 ++ + + COM2-63 690 - - ++ COMP-64 966 - - - COMP-6535 none - + - INV-12 197 ++ ++ ++ COM2-6 6 591 + ++ ++ COM2-67 986 ++ - + COM2-68 1380 - - -
    It is evident from Table 14 that again only the ink sets Conjunto-3 and Conjunto-4 were able to produce printed samples that exhibited superior image quality. Although the use of an IG absorbent inkjet ink receiver 5 is more tolerant, even some good results have been obtained outside the specific time frame for partial UV curing of 50 to 500 ms or with inks with a voltage of dynamic surface higher than 30 mN / m.
    权利要求:
    Claims (11)
    [1]
    1. Single-pass inkjet printing method characterized by including the steps of:
    a) provide a radiation-curable inkjet ink set containing at least one first and a second radiation-curable inkjet ink that has a dynamic surface tension equal to or less than 30 mN / m measured by tensiometry maximum bubble pressure under a surface age of 50 ms and at 25 ° C;
    b) blasting a first radiation-curable inkjet ink into an inkjet ink receiver that moves at a printing speed of at least 35 m / min;
    c) at least partially cure the first inkjet ink in the ink receiver within the range of 40 to 500 ms after the first inkjet ink has been discharged into the ink receiver;
    d) blasting a second radiation curable inkjet ink onto the first inkjet ink at least partially cured; and
    e) at least partially cure the second inkjet ink within the range of 40 to 500 ms after the second inkjet ink has been discharged into the first inkjet ink.
    [2]
    2. Single-pass inkjet printing method according to claim 1, characterized in that the inkjet ink receiver is a substantially non-absorbent inkjet ink receiver.
    [3]
    A single-pass inkjet printing method according to either of claims 1 and 2, characterized in that the ink receiver moves at a printing speed of at least 50 m / min.
    [4]
    4. Single-pass inkjet printing method according to any one of claims 1
    Petition 870200024968, of 02/20/2020, p. 5/13
    2/3 to 3, characterized by the first and / or second inkjet ink being at least partially cured within 200 ms.
    [5]
    5. Single-pass inkjet printing method according to any one of claims 1 to 4, characterized in that the at least partial curing treatment of the first and / or second inkjet ink begins after at least 100 ms.
    [6]
    6. Single-pass inkjet printing method according to any one of claims 1 to 4, characterized in that the first and / or second inkjet ink contains at least 0.6% by weight of silicone surfactant based on the total weight of the ink.
    [7]
    7. Single-pass inkjet printing method according to claim 6, characterized in that the silicone surfactant is a polyether modified polydimethylsiloxane surfactant.
    [8]
    8. Single-pass inkjet printing method according to any of claims 6 and 7, characterized in that the silicone surfactant is a polymerizable silicone surfactant.
    [9]
    9. Single-pass inkjet printing method according to claim 8, characterized in that the polymerizable silicone surfactant is a silicone modified (meth) acrylate or an (meth) acrylated siloxane.
    [10]
    A single-pass inkjet printing method according to any one of claims 1 to 9, characterized in that the first and second inkjet ink have a static surface tension equal to or less than 24 mN / m.
    [11]
    11. Single-pass inkjet printing method according to any one of claims 1 to 10, characterized by the first and second inkjet ink.
    Petition 870200024968, of 02/20/2020, p. 6/13
    3/3 partially cured paint receives a final curing treatment within 2.5 s.
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    同族专利:
    公开号 | 公开日
    CA2780072C|2014-09-02|
    AU2010335211B2|2013-10-24|
    CN102656018B|2015-12-02|
    BR112012013314A2|2016-03-01|
    EP2335940A1|2011-06-22|
    JP2013514904A|2013-05-02|
    CA2780072A1|2011-06-30|
    CN102656018A|2012-09-05|
    JP5697686B2|2015-04-08|
    PL2335940T3|2012-12-31|
    US20120281034A1|2012-11-08|
    EP2335940B1|2012-07-11|
    ES2387341T3|2012-09-20|
    WO2011076703A1|2011-06-30|
    AU2010335211A1|2012-05-03|
    US8646901B2|2014-02-11|
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    法律状态:
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-04-24| B25D| Requested change of name of applicant approved|Owner name: AGFA NV (BE) |
    2018-12-11| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2019-11-26| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2020-03-31| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-06-09| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 20/12/2010, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP09180074A|EP2335940B1|2009-12-21|2009-12-21|Single pass inkjet printing method|
    US29218410P| true| 2010-01-05|2010-01-05|
    PCT/EP2010/070180|WO2011076703A1|2009-12-21|2010-12-20|Single pass inkjet printing method|
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