PRINTING METHOD FOR TRANSFERRING PRINTING SUBSTANCE

Description

[0001] The present invention relates to printing methods for transferring printing substance from a color carrier to a substrate and to a printing substance for carrying out the method.

[0002] A printing process is primarily understood as a method for the unlimited reproduction of text and / or image originals. In the past, this reproduction was achieved using a printing plate that was re-inked after each print. This method is still used today for the reproduction of large quantities. Generally, a distinction is made between four fundamentally different printing processes. One is relief printing, in which the printing elements of the printing plate are raised, while the non-printing areas are recessed. Examples include letterpress printing and flexographic or aniline printing. Another type is planographic printing, in which the printing elements and the non-printing areas of the printing plate essentially lie in the same plane.This includes, for example, offset printing, in which, strictly speaking, the inked image on the printing plate is not printed directly onto the substrate, but is first transferred to a rubber cylinder or blanket, and only then is the substrate printed from this. However, when the term "substrate" is used below, it refers both to the actual substrate, i.e., the material to be printed, and to any transfer medium, such as a rubber cylinder. A third method is the so-called gravure printing process, in which the printing elements of the printing form are recessed. An industrially used gravure printing process is the so-called doctor blade gravure. Finally, there is also a stencil printing process, in which the ink is transferred to the substrate through screen-like openings in the printing form at the printing areas.

[0003] These printing processes are all characterized by the fact that they require a more or less elaborately created printing form, so that these printing processes only work economically with very high print runs, usually well over 1000 pieces.

[0004] For printing small print runs, printers are already in use, often connected to an electronic data processing system. These generally employ digitally controlled printing systems capable of printing individual dots on demand. Such systems utilize various methods with different printing media on different substrates. Some examples of digitally controlled printing systems include laser printers, thermal printers, and inkjet printers. Digital printing processes are characterized by the fact that they do not require printing plates.

[0005] For example, GB 20 07 162 discloses an electrothermal inkjet printing process in which water-based ink is briefly heated to boiling in a suitable ink nozzle by electrical impulses, causing a gas bubble to form instantly and an ink droplet to be ejected from the nozzle. This process is commonly known as "bubblejet." These thermal inkjet printing processes have the disadvantage that they consume a great deal of energy to print a single dot and are only suitable for water-based printing processes. Furthermore, each individual dot must be controlled separately via the nozzle. Piezoelectric inkjet printing processes, on the other hand, suffer from the disadvantage that the nozzles required for them clog easily, meaning that only very special and expensive inks can be used.

[0006] Furthermore, printing inks are known from US patents 2012 / 0164777 A1 and US patent 2016 / 0167400 A1, which can be used in printing processes in which, for example, a laser beam transfers the printing ink applied to a carrier onto a substrate. However, these patents do not disclose compositions comprising high-molecular-weight binders; in particular, no molecular weight data are provided for the polymers disclosed in a long list. Moreover, the printing processes are not described in detail, although printing processes are known, in particular, from patent EP 0 530 018 A1, in which the printing inks are applied to and removed from a solid film. In this case, the printing inks are in a solid phase, so that the carrier onto which the printing ink is applied must be completely replaced after a printing process.US 2016 / 0167400 A1 describes very high viscosities for the printing inks, making it suitable only for processes where the carrier must be completely replaced after each use. Information on a printing process in which ink is continuously applied to a flexible belt or roller and transferred from this carrier to a substrate to be printed is not found in US 2012 / 0164777 A1 or US 2016 / 0167400 A1. EP 0 530 018 A1 describes a melt transfer process in which the printing inks are melted, resulting in very high viscosity at room temperature. The ink-containing layer comprises as its main component a binder with a softening point in the range of 50 to 160°C, which is solid or semi-solid (see EP 0 530 018 A1, page 4, lines 51 to 55).

[0007] From DE 197 46 174, it is known that a laser beam, through very short pulses, induces a process in a printing substance located in the cells of a printing roller, causing the printing substance to undergo a change in volume and / or position. This allows the printing substance to grow across the surface of the printing form, enabling the transfer of a printed dot to a substrate that is close to it. However, a disadvantage of this method is that filling the cells is very difficult due to their small diameter. Therefore, DE 100 51 850 proposes applying the printing substance essentially as a continuous film to the ink carrier. The energy can either be transferred directly into the printing substance or first into an absorption layer applied to the ink carrier, which then transfers the energy to the printing substance.In the first case, special printing substances capable of absorbing the energy must be used. This severely limits the variety of usable printing inks. Furthermore, the light is absorbed within the printing ink over a relatively large volume that the laser beam passes through. With some inks, the energy is not completely absorbed. Absorption is also highly dependent on the printing substance used and its thickness on the substrate. Due to the relatively large volume in which the energy is absorbed, a considerable amount of energy must be introduced into the printing substance to induce the necessary volume and / or positional change required to create a print dot. Moreover, boiling delay often occurs, making it impossible to predict the temperature at which gas bubbles form within the printing substance.This results in absorption—and the associated local heating of the pressurized substance—occurring largely uncontrolled, leading, among other things, to significant variation in the pressure point size. To ensure that the desired pressure point is achieved in every case, considerably more energy must therefore be introduced into the pressurized substance than is normally required to induce the desired change in position and / or volume of the substance.

[0008] Furthermore, a generic printing process is described in DE 102 10 146 A1. In this process, printing inks, as previously described in DE 197 46 174 or DE 100 51 850, are heated by a laser beam and thereby transferred from an ink carrier to a substrate. In the described process, absorption elements are used to improve the process.

[0009] The methods previously described, for example, in DE 197 46 174, DE 100 51 850, or DE 102 10 146, solve the economic problems previously outlined for various printing processes. These problems arise when the number of copies to be reproduced is small, or when addressing the difficulty that, with the previously described inkjet printing processes, only very specific inks can be used, which must not have a high solids content, especially no proportion of larger particles. However, the print quality is insufficient for certain requirements because a distinct formation of smaller droplets is visible in the vicinity of the intended print dots (satellite formation). This problem is not only visually undesirable but also limits the minimum distance between printed lines, which are produced, for example, when printing with silver-containing inks for the production of conductive traces, as otherwise short circuits can occur.Furthermore, this limits the minimum size of barcodes and other machine-readable characters.

[0010] In light of the prior art, the object of the present invention is to provide a printing process that results in higher contour sharpness but is also suitable for small production runs. In particular, it should be possible to obtain colorfast decorations, process glass colors, or use inks for electronic circuits. Furthermore, the process should be as simple and cost-effective as possible. The properties of the printed decorations or conductive traces should not be adversely affected. For example, the coating should exhibit the highest possible adhesion to various materials. Finally, the decoration obtained by the process should have a high degree of image sharpness.

[0011] These and other problems not explicitly mentioned, which can nevertheless be readily derived or inferred from the contexts discussed in the introduction herein, are solved by a printing process with all the features of claim 1. Advantageous modifications of the printing process according to the invention are protected by dependent claims 2 to 6. With regard to the printing substance, the subject matter of claims 7 to 15 provides a solution to the underlying problem.

[0012] The present invention relates to a printing method for transferring printing substance from a color carrier to a substrate, in which, with the aid of an energy-emitting device that emits energy in the form of electromagnetic waves during a process time, the printing substance undergoes a change in volume and / or position, characterized in that the printing substance comprises at least one functional carrier and a high molecular weight binder, wherein the high molecular weight binder has a weight average molecular weight in the range of 150,000 to 5,000,000 g / mol, measured by GPC.

[0013] This design allows for the simple and cost-effective production of high-quality decor even for smaller series, without any special restrictions on the substrate.

[0014] Surprising advantages arise particularly in the areas of automotive glass, flat glass for interior and exterior decoration, barcodes, and silver conductive tracks. Small production runs can be obtained cost-effectively, which also allows for the efficient provision of spare parts, thus reducing warehousing costs.

[0015] Furthermore, compared to the previously described state of the art, particularly screen printing, where inorganic materials with their usual particle size distributions can be used, no screen storage is required. This results in further cost and organizational advantages, as maintaining a screen storage facility is unnecessary. The printing system can also be operated with very short setup times, as the design can be transferred entirely from a remotely located computer to the printing system. Designs can also be modified as desired on the PC, enabling highly customized designs. The relatively low additional costs allow for an increase in the market share of customized designs. Since printing is digital, any pattern and serialization or individualization of the printed substrates are possible.

[0016] Furthermore, inorganic materials with their usual particle size distributions can be used without the need for a complex fine grinding process as required in conventional inkjet printing. In conventional inkjet printing, the particles must be in the <1 µm range. The grinding process damages the pigments and reduces their color intensity, necessitating multiple layers of printing to achieve sufficient color vibrancy. Despite the fine grinding process, nozzle clogging and sedimentation problems are not uncommon in conventional inkjet printing. These problems cannot occur with the inventive method.

[0017] Surprisingly, the measures according to the invention result in an improvement in print quality, so that in particular the satellite formation described above and below is reduced.

[0018] The present printing process serves to transfer printing substance from a substrate to a substrate. The substrate from which the printing substance is transferred is not subject to any particular restrictions. For example, the substrate can be transparent, with the light beam preferably focused from the side of the substrate facing away from the printing substance, through the substrate, and into the printing substance. A gas bubble then forms explosively on the side of the absorption layer facing the substrate, accelerating the absorption layer towards the substrate. Particularly when using transparent printing substances, a substrate is preferably used on whose surface intended for receiving the printing substance there are absorption layers, which preferably form a solid layer.

[0019] Furthermore, it may be provided that a color carrier is used on whose surface intended for receiving the printing substance there are absorption bodies which preferably form a solid layer.

[0020] In one embodiment, the ink carrier can be designed as a circumferential band. Preferably, the ink carrier is designed in the form of a flexible band which comprises a layer containing a printing substance.

[0021] Preferably, the layer of printing substance provided on the ink carrier is renewed after the process time during which at least part of the printing substance undergoes a change in volume and / or position. In a further embodiment, the layer thickness of the printing substance on the ink carrier is preferably constant, so that the ink carrier preferably has no depressions.

[0022] Furthermore, it may be provided that the layer with a printing substance which is provided on the ink carrier is first at least partially removed, preferably scraped off, after the process time in which at least part of the printing substance undergoes a change in volume and / or position, before it is preferably renewed.

[0023] The inventive method transfers a printing substance onto a substrate. The substrate is not subject to any specific limitations. Therefore, it can be made of conventional materials such as glass, ceramic, metal, wood, or plastic.

[0024] In the present printing process, the printing substance undergoes a change in volume and / or position with the aid of an energy-emitting device that emits energy in the form of electromagnetic waves during a process period. Accordingly, the printing substance is preferably transferred directly or indirectly from the ink carrier to the substrate by the action of electromagnetic waves.

[0025] The energy-emitting device advantageously emits energy in the form of laser light. Using highly coherent monochromatic laser light, a relatively high amount of energy can be delivered to a very small area with very short light pulses. This increases the quality of the printed image, especially the resolution. A short light pulse does not necessarily have to originate from a pulsed laser. In fact, it is even advantageous to use a laser operating in continuous wave (CW) mode. The pulse duration, or rather the exposure time, then depends not on the length of the laser pulse, but on the scanning speed of the focus. Furthermore, the data to be transmitted no longer needs to be synchronized to a fixed pulse frequency.

[0026] In a particularly preferred embodiment of the present invention, the energy-emitting device or the beam path of the electromagnetic waves is arranged such that the absorbers are accelerated by the electromagnetic waves of the energy-emitting device in the direction of the substrate. This advantageously supports the change in volume and / or position of the printing substance. The acceleration of the absorbers alone creates a kind of shock wave in the printing substance, which, in combination with the gas bubble that forms, promotes a defined droplet detachment. In a preferred embodiment, the ink carrier is irradiated with the electromagnetic waves from the side opposite the ink layer. A transparent ink carrier can preferably be used here, as explained in more detail above.

[0027] The wavelength of the electromagnetic wave, with which the energy-emitting device couples the energy into the ink carrier or printing substance, is not subject to any particular limitation, but can be matched to the absorbers contained in the ink carrier or printing substance. Preferably, it can be provided that energy is transferred from the electromagnetic wave into the printing substance with the aid of absorbers. Preferably, absorbers are used that are smaller than the wavelength of the electromagnetic waves, preferably less than 1 / 10, and particularly preferably less than 1 / 50 of the wavelength of the electromagnetic waves.

[0028] Furthermore, it may be provided that the pressure point size is controlled by the amount of energy released by the energy-emitting device.

[0029] Furthermore, it may be possible to achieve differences in brightness of the image to be printed by varying the print dot size.

[0030] Furthermore, it can be provided that printing takes place line by line, whereby areas to be printed within a line are formed by line segments of arbitrarily selectable length and arbitrarily selectable position.

[0031] Furthermore, it may be provided that the distance between the ink carrier with the ink layer and the substrate to be printed is 50µm to 1000µ.

[0032] Further information on the implementation of the present procedure, in particular with regard to the technical design of the printing plant, can be found in documents DE 197 46 174 A1, DE 100 51 850 A1 and DE 102 10 146 A1, which are incorporated in full into the present application for the purposes of disclosure.

[0033] The present printing process is characterized by the fact that the printing substance comprises a high molecular weight binder.

[0034] This printing substance is novel and therefore also the subject of the present invention. The following explanations accordingly apply to both the method according to the invention and the printing substance itself.

[0035] Surprisingly, preferred printing substances exhibit the following criteria, which may be met individually or all at once: The viscosity is preferably adjusted so that the printing substance is highly fluid and thus enables transport from the ink tank to the coating station and backflow.

[0036] Preferably, the printing substance has a high content of inorganic material in order to leave enough material on the substrate after a printing process, e.g. to create an opaque layer of color.

[0037] The printing substance couples energetically with the laser beam, allowing the ink droplets to detach in a pulse-like manner.

[0038] A preferred printing substance wets the substrate, e.g., glass, sufficiently well so that a printed line remains as such on the substrate, adhering well without spreading out. This property can be influenced, among other things, by the viscosity.

[0039] The printing substance comprises a high-molecular-weight binder. According to the invention, the high-molecular-weight binder has a weight-average molecular weight in the range of 150,000 to 5,000,000 g / mol, particularly preferably 200,000 to 2,000,000 g / mol and especially preferably 250,000 to 1,000,000 g / mol, as measured by GPC.

[0040] In a particular embodiment, the high molecular weight binder may be an amino group-containing polymer, an ether group-containing polymer, an ester group-containing polymer, an amide group-containing polymer, an acid group-containing polymer or a hydroxy group-containing polymer, preferably a polyvinyl alcohol, a (meth)acrylate, a hydroxy group-containing (meth)acrylate, a poly(meth)acrylic acid and its salts, a polyacrylamide, a polyvinylpyrrolidone, a polyethylene glycol, a styrene-maleic anhydride copolymer and its salts, a polysaccharide, particularly preferably a cellulose or a modified cellulose, particularly preferably methyl methacrylate, methyl methacrylate copolymer, hydroxyethylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose, hydroxypropylcellulose, ethylhydroxyethylcellulose.

[0041] Particularly suitable are hydroxyethyl celluloses with a molar degree of substitution in the range of 1 to 8, preferably 1.5 to 6, particularly preferably 2.0 to 5 and especially preferably 2.2 to 4.

[0042] Particularly preferred are hydroxypropylmethylcelluloses with a molar degree of substitution in the range of 1 to 10, preferably 2 to 7, particularly preferably 2.5 to 5.5 and especially preferably 3 to 5.

[0043] Furthermore, (meth)acrylates are preferred that contain at least 80 wt.%, preferably at least 90 wt.%, and particularly preferably at least 95 wt.% units derived from methyl methacrylate. Particularly preferred are (meth)acrylates that contain up to 20 wt.%, preferably up to 10 wt.%, units derived from comonomers. Preferred comonomers are particularly preferably selected from alkyl (meth)acrylates, such as butyl (meth)acrylate, cyclohexyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; and hydroxylalkyl (meth)acrylates, such as 3-hydroxypropyl (meth)acrylate, 3,4-dihydroxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate.

[0044] Of the aforementioned high molecular weight binders, ethylhydroxyethylcelluloses, hydroxypropylmethylcelluloses and (meth)acrylates are particularly preferred, with hydroxypropylmethylcelluloses and (meth)acrylates being especially preferred.

[0045] These polymers can be obtained commercially from a variety of suppliers. These include, among others, polymers available under the trade names Degalan® and Klucel®, preferably Degalan® LP 62 / 05, Klucel® H, Klucel® M and Klucel® G.

[0046] Furthermore, it can be provided that the high molecular weight binder has a solubility in a polar solvent, for example dipropylene glycol methyl ether, of at least 0.5g, preferably at least 1g, particularly preferably at least 1.5g per 100g of solvent.

[0047] Furthermore, it can be provided that the printing substance comprises 0.01 to 5 wt.%, preferably 0.05 to 3 wt.%, particularly preferably 0.07 to 2 wt.%, and especially preferably 0.08 to 1.5 wt.% of high molecular weight binder.

[0048] In a further preferred embodiment, the printing substance may contain absorbers. These absorbers interact with the electromagnetic waves described above. Accordingly, the printing substance may contain a pigment, preferably an inorganic pigment or carbon black.

[0049] Depending on its specific formulation, the printing substance can contain varying proportions of absorbent materials. A printing substance comprising only carbon black as an absorbent material preferably has a carbon black content in the range of 0.5 to 3.0 wt.%, and particularly preferably 0.8 to 1.5 wt.%. Printing substances containing inorganic pigments as absorbent materials preferably contain 2 to 40 wt.%, and particularly preferably 3 to 25 wt.%, of absorbent materials or inorganic pigments.

[0050] In a particular embodiment, the printing substance comprises at least one high molecular weight binder, at least one low molecular weight binder and at least one functional carrier.

[0051] In this context, the functional agent refers to a substance that, when applied to a substrate, performs a function, such as providing color and / or conductivity to the decoration created by the printing substance. Preferred functional agents include, among others, inorganic pigments, glass fluxes, and / or metal particles, preferably silver particles. The functional agent therefore remains on the substrate after curing, as described later, while other solid components, although remaining on the substrate after drying, are removed by curing at high temperature. Depending on the curing conditions, these other solid components include, among others, the previously described binders and carbon black.

[0052] Preferably, the printing substance comprises mineral pigments, which particularly preferably act as absorbents. In a further embodiment, the printing substance preferably comprises metal particles, preferably silver particles.

[0053] Furthermore, it can be provided that the functional carrier is particle-shaped, wherein the particles preferably have a d50 value in the range of 0.5 µm to 30 µm, particularly preferably in the range of 1 µm to 20 µm and especially preferably in the range of 2 µm to 15 µm.

[0054] Preferably, the printing substance has a high content of functional carriers, in particular inorganic pigments, glass fluxes, and / or metal particles, wherein the printing substance preferably comprises up to 85 wt.%, and particularly preferably up to 70 wt.%, of functional carriers. A glass flux is preferably used in printing substances that are cured on the substrate at very high temperatures. Printing substances that are cured or dried at a temperature below 400 °C preferably do not contain a glass flux.

[0055] The low-molecular-weight binder has a lower molecular weight than the high-molecular-weight binder. Preferably, the weight-average molecular weight (Mw) of the high-molecular-weight binder is at least 20% greater than the weight-average molecular weight (Mw) of the low-molecular-weight binder, preferably at least 50%, and particularly preferably at least 100%, where the percentages are based on the weight-average molecular weight (Mw) of the low-molecular-weight binder. Preferably, the low-molecular-weight binder may have a weight-average molecular weight (Mw) in the range of 10,000 to 150,000 g / mol, preferably in the range of 50,000 to 100,000 g / mol, as measured according to GPC.The low-molecular-weight binder preferably comprises an amino group-containing polymer, an ether group-containing polymer, an ester group-containing polymer, an amide group-containing polymer, an acid group-containing polymer or a hydroxy group-containing polymer, preferably a polyvinyl alcohol, a (meth)acrylate, a hydroxy group-containing (meth)acrylate, a poly(meth)acrylic acid and their salts, a polyacrylamide, a polyvinylpyrrolidone, a polyethylene glycol, a styrene-maleic anhydride copolymer and their salts, a polysaccharide, particularly preferably a cellulose or a modified cellulose, particularly preferably methyl methacrylate, methyl methacrylate copolymer, hydroxyethylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose, hydroxypropylcellulose, ethylhydroxyethylcellulose.

[0056] These polymers are commercially available from a variety of suppliers. These include, among others, Klucel®< E and Klucel®< J (hydroxypropylmethylcellulose) as well as Aqualon®< N10 and Aqualon®< N22 (hydroxyethylcellulose).

[0057] Furthermore, it can be provided that the low molecular weight binder has a solubility in a polar solvent, for example dipropylene glycol methyl ether, of at least 0.5 g, preferably at least 1 g, particularly preferably at least 1.5 g per 100 g of solvent.

[0058] Preferably, the printing substance comprises 0.1 to 10 wt.%, preferably 0.2 to 7 wt.% and particularly preferably 0.3 to 5 wt.% of low molecular weight binder.

[0059] Furthermore, it can be provided that the printing substance has a solids content of at least 30 wt.%, preferably at least 50 wt.% and particularly preferably at least 60 wt.%.

[0060] Preferably, the printing substance may comprise at least one propellant, which preferably has a boiling point in the range of 60 °C to 250 °C, more preferably in the range of 80 °C to 200 °C, particularly preferably in the range of 110 °C to 200 °C, and especially preferably in the range of 140 °C to 190 °C. The propellant is preferably a solvent, which preferably comprises ethers, in particular diglycols, aliphatic hydrocarbons, aromatic hydrocarbons, hydroaromatic hydrocarbons, Texanol, alcohols, esters, ketones, and / or water. Organic solvents, in particular ethers, are preferably diglycols, aliphatic hydrocarbons, aromatic hydrocarbons, hydroaromatic hydrocarbons, Texanol, alcohols, esters, and / or ketones.

[0061] Preferably, the printing substance comprises 15 to 80 wt.%, preferably 20 to 70 wt.% and particularly preferably 25 to 50 wt.% propellant.

[0062] Preferably, the printing substance is free-flowing, wherein the printing substance particularly preferably has a viscosity in the range of 400 to 4500 mPas, particularly preferably a viscosity in the range of 500 to 3200 mPas, further particularly preferably in the range of 800 to 2600 mPas, especially preferably in the range of 1000 to 2200 mPas, measured at 20 °C, at a shear rate of 2 s⁻¹, measured with plate / cone (rotational viscometer CVO120 from Bohlin, plate-cone method (2°), based on DIN 53019; in particular DIN 53019-1:2008-09, DIN 53019-2:2001-02, DIN 53019-3:2008-09, DIN 53019-4:2016-10).

[0063] Preferably, the printing substance is free-flowing, wherein the printing substance particularly preferably has a viscosity in the range of 200 to 4000 mPas, particularly preferably a viscosity in the range of 400 to 2800 mPas, further particularly preferably in the range of 550 to 2000 mPas, especially preferably in the range of 700 to 1600 mPas, measured at 20 °C, at a shear rate of 10 s⁻¹, measured with plate / cone (rotational viscometer CVO120 from Bohlin, plate-cone method (2°), based on DIN 53019; in particular DIN 53019-1:2008-09, DIN 53019-2:2001-02, DIN 53019-3:2008-09, DIN 53019-4:2016-10).

[0064] Preferably, the printing substance is free-flowing, wherein the printing substance particularly preferably has a viscosity in the range of 100 to 3500 mPas, particularly preferably a viscosity in the range of 200 to 2400 mPas, further particularly preferably in the range of 400 to 1600 mPas, especially preferably in the range of 600 to 1200 mPas, measured at 20 °C, at a shear rate of 50 s⁻¹, measured with plate / cone (rotational viscometer CVO120 from Bohlin, plate-cone method (2°), based on DIN 53019; in particular DIN 53019-1:2008-09, DIN 53019-2:2001-02, DIN 53019-3:2008-09, DIN 53019-4:2016-10).

[0065] Preferably, the printing substance is free-flowing, wherein the printing substance particularly preferably has a viscosity in the range of 50 to 3000 mPas, particularly preferably a viscosity in the range of 100 to 2000 mPas, further preferably in the range of 250 to 1400 mPas, particularly preferably in the range of 400 to 1200 mPas, and especially preferably in the range of 500 to 1000 mPas, measured at 20 °C, at a shear rate of 200 s⁻¹, measured with a plate / cone (rotational viscometer CVO120 from Bohlin, plate-cone method (2°), based on DIN 53019; in particular DIN 53019-1:2008-09, DIN 53019-2:2001-02, DIN 53019-3:2008-09, DIN 53019-4:2016-10).

[0066] Preferably, the printing substance is free-flowing, wherein the printing substance particularly preferably has a viscosity in the range of 25 to 2800 mPas, particularly preferably a viscosity in the range of 50 to 2000 mPas, in the range of 200 to 1200 mPas, especially preferably in the range of 400 to 800 mPas, measured at 20 °C, at a shear rate of 600 s⁻¹, measured with plate / cone (rotational viscometer CVO120 from Bohlin, plate-cone method (2°), based on DIN 53019; in particular DIN 53019-1:2008-09, DIN 53019-2:2001-02, DIN 53019-3:2008-09, DIN 53019-4:2016-10).

[0067] The viscosity properties of preferred printing substances, as previously described and maintained at various shear rates, can be achieved individually or completely, with preferably at least two, more preferably three, more preferably four, and most preferably all viscosity properties being maintained. This allows for the provision of a particularly preferred printing substance that exhibits specific thixotropy and yet remains fluid under the shear force conditions in the printing apparatus.

[0068] In a preferred embodiment, the printing substance may exhibit viscoelastic behavior. Viscoelastic substances are those that lie between the extremes of ideally viscous liquids with tan(delta) = G2 / G1 > 100 and ideally elastic solids with tan(delta) = G2 / G1 < 0.01. G1 is the storage modulus, and G2 is the loss modulus. These parameters are determined through oscillation measurements (jump tests) using an Anton Paar Rheo-Compass from Anton Paar. Plate-to-plate, gap width approx. 0.5 mm at 20 °C (Modular Compact Rheometer MCR302 from Anton Paar, plate-to-plate method, based on DIN 53019; in particular DIN 53019-1:2008-09, DIN 53019-2:2001-02, DIN 53019-3:2008-09, DIN 53019-4:2016-10). The angular velocity ω, especially during the jump, is preferably 3.14 rad / s and the displacement γ is preferably 0.1%.

[0069] In a preferred embodiment, the storage module G1 can be provided to have a pressure of at least 8 Pa, preferably at least 10 Pa, and particularly preferably at least 12 Pa, as measured by oscillation measurements with an "Anton Paar Rheo-Compass" from Anton Paar. Plate-to-plate, gap width approx. 0.5 mm at 20 °C.

[0070] In a preferred embodiment, the loss modulus G2 can be at least 6 Pa, preferably at least 8 Pa, and particularly preferably at least 10 Pa, measured by oscillation measurements with an "Anton Paar Rheo-Compass" from Anton Paar. Plate-to-plate, gap width approx. 0.5 mm at 20 °C.

[0071] The printing substance preferably has a high elastic component, i.e., G1 close to G2, and is simultaneously fluid under the shear forces prevailing in the apparatus (i.e., tan(delta) in the range of preferably 0.05 to 3.0, particularly preferably 0.05 to 1.3). The angular velocity ω, especially during the jump, is preferably 3.14 rad / s and the displacement γ is preferably 0.1%.

[0072] In preferred embodiments, tan (delta) = G2 / G1 is preferably in the range of 0.05 to 3.0, particularly preferably 0.1 to 2.8, especially preferably 0.2 to 2.5, and particularly preferably 0.3 to 2.3, measured by oscillation measurements with an "Anton Paar Rheo-Compass" from Anton Paar. Plate-to-plate, gap width approximately 0.5 mm at 20 °C. The angular velocity ω, particularly during the jump, is preferably 3.14 rad / s, and the displacement γ is preferably 0.1%.

[0073] In preferred embodiments, tan (delta) = G2 / G1 is preferably in the range of 0.05 to 1.3, particularly preferably 0.1 to 1.1, especially preferably 0.2 to 1.0, and particularly preferably 0.3 to 0.9, measured by oscillation measurements with an "Anton Paar Rheo-Compass" from Anton Paar. Plate-to-plate, gap width approximately 0.5 mm at 20 °C. The angular velocity ω, particularly during the jump, is preferably 3.14 rad / s, and the displacement γ is preferably 0.1%.

[0074] In a further embodiment, it can be provided that tan (delta) = G2 / G1 is preferably reduced by at least 30%, preferably by at least 50%, by the presence of the high-molecular-weight binder compared to a substantially identical composition, which in particular has the same viscosity at 25 °C and a shear stress of 200 s⁻¹, but does not contain any high-molecular-weight binder, as measured by oscillation measurements with an "Anton Paar Rheo-Compass" from Anton Paar. Plate-plate, gap width approx. 0.5 mm at 20 °C. The angular velocity ω, particularly during the jump, is preferably 3.14 rad / s and the displacement γ preferably 0.1%.

[0075] Preferably, the ratio of tan (delta) = G2 / G1 of a composition according to the invention with a high molecular weight binder to the tan (delta) = G2 / G1 of an essentially identical composition without a high molecular weight binder, which in particular has the same viscosity at 25 °C and a shear stress of 200 Hz s -1<, is preferably at most 0.9, preferably at most 0.7, particularly preferably at most 0.6.

[0076] The previously stated values ​​for the storage modulus G1, the loss modulus G2, and the tan (delta) are determined at a plateau, which generally occurs after approximately 5 to 9 minutes in an oscillation test. These values ​​are preferably reached again after a short shear stress (approximately 20 seconds) by a rotation of 100 s⁻¹ after approximately 5 minutes, so that in preferred embodiments no degradation of the polymers that lead to these values ​​occurs.

[0077] Furthermore, it can be provided that the surface tension of the printing substance is in the range of 26 to 34 mN / m, preferably 28 to 32 mN / m, measured according to the Wilhelmy plate method with a "Force Tensiometer" from Krüss at 20 °C (DIN53914:1997-07).

[0078] Another object of the present invention is the use of a printing substance according to the invention, characterized in that the printing substance is applied to glass, ceramic, metal, wood or plastic.

[0079] Preferably, the printing substance can be hardened after application to a substrate, with the hardening preferably taking place at a temperature in the range of 150 °C to 1200 °C, particularly preferably 150 °C to 220 °C or 500 °C to 1000 °C.

[0080] In a preferred embodiment, the layer can be dried at 100 °C to 150 °C after printing to remove volatile components of the medium, particularly propellants and solvents. The subsequent firing is preferably carried out at 500 °C to 1000 °C in the case of printing substances containing inorganic, preferably mineral, pigments and / or glass fluxes. Printing substances containing glass fluxes may contain metal particles, particularly silver particles. Printing substances that are preferably fired at 500 °C to 1000 °C are preferably intended for application to inorganic substrates, for example, glass plates or similar materials. Printing substances containing metal particles, preferably silver particles, that do not contain mineral pigments or glass fluxes are preferably cured at a temperature in the range of 150 °C to 250 °C.Such printing substances, which are preferably cured at 150 °C to 250 °C, are preferably intended to be applied to plastic substrates or similar materials.

[0081] The present invention will now be explained in more detail by means of examples, without this being intended to limit the invention. Example of implementation 1

[0082] A color paste from Ferro GmbH based on the glass color powder 14305 and the medium C7 (both Ferro GmbH) is adjusted to a viscosity of 960 mPas with Dowanol DPM and a hydroxylpropylcellulose with a molecular weight of 850000g / mol, measured at 20 °C and a shear rate of 200 / sec, whereby the concentration of this active substance is approximately 0.09 wt%.

[0083] The color paste is transferred to glass plates (100x100x4mm format) using the printing process described above and fired at 690 °C. The in Figure 1The photos shown depict a section magnified 100x and 30x, respectively. The printed substrate exhibits very little satellite distortion, as can be seen from... Figures 1A (100x magnification) and 1B (30x magnification) are visible, which are light microscopic images of the decoration. Comparative example 1

[0084] Example 1 is essentially repeated, except that hydroxypropylcellulose with a molecular weight of 850000g / mol is not used, and the viscosity is also in the range of approximately 960 mPas.

[0085] The color paste is transferred to glass plates (100x100x4mm) using the previously described printing process and fired at 690°C. The photos show a section magnified 100x and 30x, respectively. The printed substrate now exhibits a very distinct satellite pattern, as can be seen from Figures 1C(100x magnification) and 1D (30x magnification) are visible. Example of Implementation 2

[0086] An ink based on the inorganic components of the silver paste TSP2002 from Ferro GmbH is adjusted to a viscosity of 487 mPas with Dowanol DPM and a hydroxylpropylcellulose with a molecular weight of 850000g / cm 3<, measured at 20 °C and a shear rate of 200 / sec, whereby the concentration of this active substance is approximately 0.13 wt%.

[0087] The ink is transferred to glass plates (100x100x4mm format) using the printing process described above and fired at 690 °C. The printed substrate exhibits only very slight satellite formation, which is due to Figures 2A (100x magnification) and 2B (30x magnification) are visible, which are light microscopic images of the decoration. Comparative example 2

[0088] Example 2 is essentially repeated, except that hydroxypropylcellulose with a molecular weight of 850000g / mol is not used, and the viscosity is also in the range of 480 mPas.

[0089] The color paste is transferred to glass plates (100x100x4mm) using the previously described printing process and fired at 690°C. The photos show a section magnified 100x and 30x, respectively. The printed substrate now exhibits a very distinct satellite pattern, as can be seen from Figures 2C (100x magnification) and 2D (30x magnification) are visible. Example of implementation 3

[0090] A color paste from Ferro GmbH based on the glass color powder 14297 and the medium C7 (both Ferro GmbH) is adjusted to a viscosity of approximately 660 mPas with Dowanol DPM and a hydroxylpropylcellulose with a molecular weight of 850000g / cm 3<, measured at 20 °C and a shear rate of 200 / sec, whereby the concentration of this active substance is approximately 0.09 wt%.

[0091] The viscosity properties are determined by a jump test, in which the system oscillates for approximately 9 minutes, interrupts the oscillation for approximately 15 seconds with a shear rotation at 100 s⁻¹, and then oscillates again for approximately 5 minutes (20 °C). After 8 minutes (plateau phase), the storage modulus G1 is approximately 25.0 Pa, the loss modulus G2 is approximately 13.9 Pa, and tan(delta) G2 / G1 is approximately 0.56. After approximately 12.5 minutes, the storage modulus G1 is approximately 25.1 Pa, the loss modulus G2 is approximately 14.5 Pa, and tan(delta) G2 / G1 is approximately 0.58.

[0092] The color paste is transferred to a substrate and hardened using the printing process described above. The printed substrate exhibits very little satellite formation. Example of implementation 4

[0093] A color paste from Ferro GmbH based on the glass color powder 144012 and the medium 801026 (both Ferro GmbH) is adjusted to a viscosity of approximately 860 mPas with Dowanol DPM and a hydroxylpropylcellulose with a molecular weight of 370000g / cm 3<, measured at 20 °C and a shear rate of 200 / sec, whereby the concentration of this active substance is approximately 0.24 wt%.

[0094] The color paste is transferred to a substrate and hardened using the printing process described above. The printed substrate exhibits very little satellite formation. Example of implementation 5

[0095] A color paste from Ferro GmbH based on the glass color powder 14510 and the medium C7 (both Ferro GmbH) is adjusted to a viscosity of 860 mPas with Dowanol DPM and a hydroxylpropylcellulose with a molecular weight of 850000g / cm 3<, measured at 20 °C and a shear rate of 200 / sec, whereby the concentration of this active substance is approximately 0.09 wt%.

[0096] The color paste is transferred to a substrate and hardened using the printing process described above. The printed substrate exhibits very little satellite formation. Example of implementation 6

[0097] A color paste from Ferro GmbH based on the glass color powder 14297 and the medium C7 (both Ferro GmbH) is adjusted to a viscosity of 625 mPas with a solution of an n-BUMA / MMA copolymer with a molecular weight of 250000g / cm 3< in glycol ether, measured at 20 °C and a shear rate of 200 / sec, where the concentration of this active substance is approximately 1.25 wt%.

[0098] The viscosity properties are determined by a jump test, in which the system oscillates for approximately 9 minutes, interrupts the oscillation for approximately 15 seconds with a shear rotation at 100 s⁻¹, and then oscillates again for approximately 5 minutes (20 °C). After 8 minutes (plateau phase), the storage modulus G1 is approximately 57.0 Pa, the loss modulus G2 is approximately 31.7 Pa, and tan(delta) G2 / G1 is approximately 0.56. After approximately 13 minutes, the storage modulus G1 is approximately 44.6 Pa, the loss modulus G2 is approximately 29.7 Pa, and tan(delta) G2 / G1 is approximately 0.67.

[0099] The color paste is transferred to a substrate using the printing process described above and then hardened. The printed substrate exhibits very little satellite formation, which is due to Figure 3 As can be seen, the image shows enlarged sections from a photograph of the decor. Example of implementation 7

[0100] An ink based on the inorganic components of the silver paste TSP2042 from Ferro GmbH is adjusted to a viscosity of 400 mPas with Dowanol DPM and a hydroxylpropylcellulose with a molecular weight of 850000g / cm 3<, where the concentration of this active substance is approximately 0.18 wt%.

[0101] The ink is transferred to a substrate and cured using the printing process described above. The printed substrate exhibits very little satellite distortion. Example of implementation 8

[0102] A color paste from Ferro GmbH, based on glass color powder 14297 and a glycol ether-based medium containing approximately 2.25% low-molecular-weight binder with approximately 50,000 g / cm³ (both from Ferro GmbH) and hydroxypropyl cellulose with a molecular weight of 850,000 g / cm³, is adjusted to a viscosity of approximately 750 mPas, measured at 20 °C and a shear rate of 200 / sec, with the concentration of the high-molecular-weight active ingredient being approximately 0.09 wt%.

[0103] The color paste is transferred to a substrate and cured using the printing process described above. The printed substrate exhibits only very slight satellite formation, as in embodiment 1. Example of implementation 9

[0104] A color paste from Ferro GmbH based on the glass color powder 14297 and the medium C7 (both Ferro GmbH) is adjusted to a viscosity of 800 mPas with Dowanol DPM and a hydroxylpropylcellulose with a molecular weight of 370000g / mol, measured at 20 °C and a shear rate of 200 / sec, whereby the concentration of this active substance is approximately 0.17 wt%.

[0105] The viscosity properties are determined by a jump test, in which the system oscillates for approximately 9 minutes, interrupts the oscillation for approximately 15 seconds with a shear rotation at 100 s⁻¹, and then oscillates again for approximately 5 minutes (20 °C). After 8 minutes (plateau phase), the storage modulus G1 is approximately 21.6 Pa, the loss modulus G2 is approximately 12.5 Pa, and the tan(delta) G2 / G1 is approximately 0.58. After approximately 12 minutes, the storage modulus G1 is approximately 22.6 Pa, the loss modulus G2 is approximately 13.6 Pa, and the tan(delta) G2 / G1 is approximately 0.60.

[0106] The color paste is transferred to a substrate and hardened using the printing process described above. The printed substrate exhibits very little satellite formation. Comparative example 3

[0107] Example 9 is essentially repeated, except that hydroxypropylcellulose with a molecular weight of 370000g / mol is not used, and the viscosity is also in the range of about 800 mPas.

[0108] The viscosity properties are determined by a jump test, in which the system oscillates for approximately 9 minutes, interrupts the oscillation for approximately 15 seconds with a shear rotation at 100 s⁻¹, and then oscillates again for approximately 5 minutes (20 °C). After 8 minutes (plateau phase), the storage modulus G1 is approximately 3.8 Pa, the loss modulus G2 is approximately 5.4 Pa, and the tan(delta) G2 / G1 is approximately 1.42. After approximately 13 minutes, the storage modulus G1 is approximately 3.8 Pa, the loss modulus G2 is approximately 5.7 Pa, and the tan(delta) G2 / G1 is approximately 1.50.

[0109] The color paste is transferred to a substrate using the printing process described above and then hardened. The printed substrate now exhibits a very distinct satellite pattern. Example of implementation 10

[0110] 100 parts by weight of a color paste from Ferro GmbH based on the glass color powder 14315 and the medium C7 (both Ferro GmbH) is adjusted to a viscosity of approximately 1000 mPas with Dowanol DPM (9.9 parts by weight) and 6.5 parts by weight of a solution of hydroxypropylcellulose with a molecular weight of 370000g / mol in DPM (7.2 parts by weight polymer in 200 parts by weight DPM), measured at 20 °C and a shear rate of 200 / sec, whereby the concentration of this active substance is approximately 0.20 wt%.

[0111] The viscosity properties are determined by a jump test, in which the system oscillates for approximately 9 minutes, interrupts the oscillation for approximately 15 seconds by a shear rotation at 100 s⁻¹, and then oscillates again for approximately 4 minutes (20 °C). The tan(delta) G2 / G1 after approximately 4 minutes is approximately 1.8.

[0112] The color paste is transferred to a substrate and hardened using the printing process described above. The printed substrate exhibits very little satellite formation. Example of implementation 11

[0113] 100 parts by weight of a color paste from Ferro GmbH based on the glass color powder 14315 and the medium C7 (both Ferro GmbH) is adjusted to a viscosity of approximately 590 mPas with Dowanol DPM (12.2 parts by weight) and 6.5 parts by weight of a solution of hydroxypropylcellulose with a molecular weight of 850000g / mol in DPM (3.6 parts by weight polymer in 200 parts by weight DPM), measured at 20 °C and a shear rate of 200 / sec, whereby the concentration of this active substance is approximately 0.10 wt%.

[0114] The viscosity properties are determined by a jump test, in which the system oscillates for approximately 9 minutes, interrupts the oscillation for approximately 15 seconds by a shear rotation at 100 s⁻¹, and then oscillates again for approximately 4 minutes (20 °C). The tan(delta) G2 / G1 after approximately 4 minutes is approximately 2.2.

[0115] The color paste is transferred to a substrate and hardened using the printing process described above. The printed substrate exhibits very little satellite formation. Example of implementation 12

[0116] 100 parts by weight of a color paste from Ferro GmbH based on the glass color powder 14315 and the medium C7 (both Ferro GmbH) is adjusted to a viscosity of approximately 1020 mPas with Dowanol DPM (9.4 parts by weight) and 6.5 parts by weight of a solution of hydroxypropylcellulose with a molecular weight of 850000g / mol in DPM (3.6 parts by weight polymer in 200 parts by weight DPM), measured at 20 °C and a shear rate of 200 / sec, whereby the concentration of this active substance is approximately 0.10 wt%.

[0117] The viscosity properties are determined by a jump test, in which the system oscillates for approximately 9 minutes, interrupts the oscillation for approximately 15 seconds by a shear rotation at 100 s⁻¹, and then oscillates again for approximately 4 minutes (20 °C). The tan(delta) G2 / G1 after approximately 4 minutes is approximately 2.0.

[0118] The color paste is transferred to a substrate and hardened using the printing process described above. The printed substrate exhibits very little satellite formation. Comparative example 4

[0119] Example 10 is essentially repeated, except that instead of using hydroxypropylcellulose with a molecular weight of 370000g / mol, the viscosity is adjusted by adding DPM, with the viscosity also being in the range of approximately 1090 mPas.

[0120] The viscosity properties are determined by a jump test, in which the system oscillates for approximately 9 minutes, interrupts the oscillation for approximately 15 seconds by a shear rotation at 100 s⁻¹, and then oscillates again for approximately 4 minutes (20 °C). The tan(delta) G2 / G1 after approximately 4 minutes is approximately 3.7.

[0121] The color paste is transferred to a substrate using the printing process described above and then hardened. The printed substrate now exhibits a very distinct satellite pattern. Comparative example 5

[0122] Example 11 is essentially repeated, except that hydroxypropylcellulose with a molecular weight of 850000g / mol is not used, but the viscosity is adjusted by adding DPM, with the viscosity also being in the range of about 660 mPas.

[0123] The viscosity properties are determined by a jump test, in which the system oscillates for approximately 9 minutes, interrupts the oscillation for approximately 15 seconds by a shear rotation at 100 s⁻¹, and then oscillates again for approximately 4 minutes (20 °C). The tan(delta) G2 / G1 after about 4 minutes is approximately 4.5.

[0124] The color paste is transferred to a substrate using the printing process described above and then hardened. The printed substrate now exhibits a very distinct satellite pattern. Example of implementation 13

[0125] 100 parts by weight of a color paste from Ferro GmbH based on the glass color powder 14316 and the medium C7 (both Ferro GmbH) is adjusted to a viscosity of approximately 990 mPas with Dowanol DPM (8.1 parts by weight) and 8 parts by weight of a solution of hydroxypropylcellulose with a molecular weight of 370000g / mol in DPM (7.2 parts by weight polymer in 200 parts by weight DPM), measured at 20 °C and a shear rate of 200 / sec, whereby the concentration of this active substance is approximately 0.25 wt%.

[0126] The viscosity properties are determined by a jump test, in which the system oscillates for approximately 9 minutes, interrupts the oscillation for approximately 15 seconds by a shear rotation at 100 s⁻¹, and then oscillates again for approximately 4 minutes (20 °C). The tan(delta) G2 / G1 after approximately 4 minutes is approximately 1.9.

[0127] The color paste is transferred to a substrate and hardened using the printing process described above. The printed substrate exhibits very little satellite formation. Example of implementation 14

[0128] 100 parts by weight of a color paste from Ferro GmbH based on the glass color powder 14316 and the medium C7 (both Ferro GmbH) is adjusted to a viscosity of approximately 600 mPas with Dowanol DPM (10.3 parts by weight) and 8 parts by weight of a solution of hydroxypropylcellulose with a molecular weight of 850000g / mol in DPM (3.6 parts by weight polymer in 200 parts by weight DPM), measured at 20 °C and a shear rate of 200 / sec, whereby the concentration of this active substance is approximately 0.12 wt%.

[0129] The viscosity properties are determined by a jump test, in which the system oscillates for approximately 9 minutes, interrupts the oscillation for approximately 15 seconds by a shear rotation at 100 s⁻¹, and then oscillates again for approximately 4 minutes (20 °C). The tan(delta) G2 / G1 after approximately 4.3 minutes is approximately 2.2.

[0130] The color paste is transferred to a substrate and hardened using the printing process described above. The printed substrate exhibits very little satellite formation. Example of implementation 15

[0131] 100 parts by weight of a color paste from Ferro GmbH based on the glass color powder 14316 and the medium C7 (both Ferro GmbH) is adjusted to a viscosity of approximately 1080 mPas with Dowanol DPM (7.5 parts by weight) and 8 parts by weight of a solution of hydroxypropylcellulose with a molecular weight of 850000g / mol in DPM (3.6 parts by weight polymer in 200 parts by weight DPM), measured at 20 °C and a shear rate of 200 / sec, whereby the concentration of this active substance is approximately 0.12 wt%.

[0132] The viscosity properties are determined by a jump test, in which the system oscillates for approximately 9 minutes, interrupts the oscillation for approximately 15 seconds by a shear rotation at 100 s⁻¹, and then oscillates again for approximately 4 minutes (20 °C). The tan(delta) G2 / G1 after approximately 4 minutes is approximately 2.1.

[0133] The color paste is transferred to a substrate and hardened using the printing process described above. The printed substrate exhibits very little satellite formation. Comparative example 6

[0134] Example 13 is essentially repeated, except that instead of using hydroxylpropylcellulose with a molecular weight of 370000g / mol, the viscosity is adjusted by adding DPM, with the viscosity also being in the range of approximately 1100 mPas.

[0135] The viscosity properties are determined by a jump test, in which the system oscillates for approximately 9 minutes, interrupts the oscillation for approximately 15 seconds by a shear rotation at 100 s⁻¹, and then oscillates again for approximately 4 minutes (20 °C). The tan(delta) G2 / G1 after approximately 4 minutes is approximately 4.0.

[0136] The color paste is transferred to a substrate using the printing process described above and then hardened. The printed substrate now exhibits a very distinct satellite pattern. Comparative example 7

[0137] Example 14 is essentially repeated, except that instead of using hydroxypropylcellulose with a molecular weight of 850000g / mol, the viscosity is adjusted by adding DPM, with the viscosity also being in the range of about 500 mPas.

[0138] The viscosity properties are determined by a jump test, in which the system oscillates for approximately 9 minutes, interrupts the oscillation for approximately 15 seconds by a shear rotation at 100 s⁻¹, and then oscillates again for approximately 4 minutes (20 °C). The tan(delta) G2 / G1 after approximately 4 minutes is approximately 5.1.

[0139] The color paste is transferred to a substrate using the printing process described above and then hardened. The printed substrate now exhibits a very distinct satellite pattern. Example of implementation 16

[0140] 100 parts by weight of a color paste from Ferro GmbH based on the glass color powder 14501 and the medium C7 (both Ferro GmbH) is adjusted to a viscosity of approximately 1010 mPas with Dowanol DPM (9.5 parts by weight) and 8 parts by weight of a solution of hydroxypropylcellulose with a molecular weight of 370000g / mol in DPM (7.2 parts by weight polymer in 200 parts by weight DPM), measured at 20 °C and a shear rate of 200 / sec, whereby the concentration of this active substance is approximately 0.24 wt%.

[0141] The viscosity properties are determined by a jump test, in which the system oscillates for approximately 9 minutes, interrupts the oscillation for approximately 15 seconds by a shear rotation at 100 s⁻¹, and then oscillates again for approximately 4 minutes (20 °C). The tan(delta) G2 / G1 after approximately 4 minutes is approximately 1.9.

[0142] The color paste is transferred to a substrate and hardened using the printing process described above. The printed substrate exhibits very little satellite formation. Example of implementation 17

[0143] 100 parts by weight of a color paste from Ferro GmbH based on the glass color powder 14501 and the medium C7 (both Ferro GmbH) is adjusted to a viscosity of approximately 640 mPas with Dowanol DPM (12.1 parts by weight) and 8 parts by weight of a solution of hydroxypropylcellulose with a molecular weight of 370000g / mol in DPM (7.2 parts by weight polymer in 200 parts by weight DPM), measured at 20 °C and a shear rate of 200 / sec, whereby the concentration of this active substance is approximately 0.24 wt%.

[0144] The viscosity properties are determined by a jump test, in which the system oscillates for approximately 9 minutes, interrupts the oscillation for approximately 15 seconds by a shear rotation at 100 s⁻¹, and then oscillates again for approximately 4 minutes (20 °C). The tan(delta) G2 / G1 after approximately 4 minutes is approximately 1.5.

[0145] The color paste is transferred to a substrate and hardened using the printing process described above. The printed substrate exhibits very little satellite formation. Example of implementation 18

[0146] 100 parts by weight of a color paste from Ferro GmbH based on the glass color powder 14501 and the medium C7 (both Ferro GmbH) is adjusted to a viscosity of approximately 540 mPas with Dowanol DPM (12.5 parts by weight) and 8 parts by weight of a solution of hydroxypropylcellulose with a molecular weight of 850000g / mol in DPM (3.6 parts by weight polymer in 200 parts by weight DPM), measured at 20 °C and a shear rate of 200 / sec, whereby the concentration of this active substance is approximately 0.12 wt%.

[0147] The viscosity properties are determined by a jump test, in which the system oscillates for approximately 9 minutes, interrupts the oscillation for approximately 15 seconds by a shear rotation at 100 s⁻¹, and then oscillates again for approximately 4 minutes (20 °C). The tan(delta) G2 / G1 after approximately 4 minutes is approximately 0.4.

[0148] The color paste is transferred to a substrate and hardened using the printing process described above. The printed substrate exhibits very little satellite formation. Example of implementation 19

[0149] 100 parts by weight of a color paste from Ferro GmbH based on the glass color powder 14501 and the medium C7 (both Ferro GmbH) is adjusted to a viscosity of approximately 1040 mPas with Dowanol DPM (9.4 parts by weight) and 8 parts by weight of a solution of hydroxypropylcellulose with a molecular weight of 850000g / mol in DPM (3.6 parts by weight polymer in 200 parts by weight DPM), measured at 20 °C and a shear rate of 200 / sec, whereby the concentration of this active substance is approximately 0.12 wt%.

[0150] The viscosity properties are determined by a jump test, in which the system oscillates for approximately 9 minutes, interrupts the oscillation for approximately 15 seconds by a shear rotation at 100 s⁻¹, and then oscillates again for approximately 4 minutes (20 °C). The tan(delta) G2 / G1 after approximately 4 minutes is approximately 2.2.

[0151] The color paste is transferred to a substrate and hardened using the printing process described above. The printed substrate exhibits very little satellite formation. Comparative example 8

[0152] Example 18 is essentially repeated, except that instead of using hydroxypropylcellulose with a molecular weight of 850000g / mol, the viscosity is adjusted by adding DPM, with the viscosity also being in the range of approximately 480 mPas.

[0153] The viscosity properties are determined by a jump test, in which the system oscillates for approximately 9 minutes, interrupts the oscillation for approximately 15 seconds by a shear rotation at 100 s⁻¹, and then oscillates again for approximately 4 minutes (20 °C). The tan(delta) G2 / G1 after approximately 4 minutes is approximately 5.9.

[0154] The color paste is transferred to a substrate using the printing process described above and then hardened. The printed substrate now exhibits a very distinct satellite pattern. Comparative example 9

[0155] Example 19 is essentially repeated, except that instead of using hydroxypropylcellulose with a molecular weight of 850000g / mol, the viscosity is adjusted by adding DPM, with the viscosity also being in the range of approximately 1060 mPas.

[0156] The viscosity properties are determined by a jump test, in which the system oscillates for approximately 9 minutes, interrupts the oscillation for approximately 15 seconds by a shear rotation at 100 s⁻¹, and then oscillates again for approximately 4 minutes (20 °C). The tan(delta) G2 / G1 after approximately 4 minutes is approximately 5.6.

[0157] The color paste is transferred to a substrate using the printing process described above and then hardened. The printed substrate now exhibits a very distinct satellite pattern. Example of implementation 20

[0158] 100 parts by weight of a color paste from Ferro GmbH based on the glass color powder 14510 and the medium C7 (both Ferro GmbH) is adjusted to a viscosity of approximately 1010 mPas with Dowanol DPM (10.0 parts by weight) and 5 parts by weight of a solution of hydroxypropylcellulose with a molecular weight of 370000g / mol in DPM (7.2 parts by weight polymer in 200 parts by weight DPM), measured at 20 °C and a shear rate of 200 / sec, whereby the concentration of this active substance is approximately 0.16 wt%.

[0159] The viscosity properties are determined by a jump test, in which the system oscillates for approximately 9 minutes, interrupts the oscillation for approximately 15 seconds by a shear rotation at 100 s⁻¹, and then oscillates again for approximately 4 minutes (20 °C). The tan(delta) G2 / G1 after approximately 4 minutes is approximately 1.9.

[0160] The color paste is transferred to a substrate and hardened using the printing process described above. The printed substrate exhibits very little satellite formation. Example of implementation 21

[0161] 100 parts by weight of a color paste from Ferro GmbH based on the glass color powder 14510 and the medium C7 (both Ferro GmbH) is adjusted to a viscosity of approximately 580 mPas with Dowanol DPM (12.8 parts by weight) and 5 parts by weight of a solution of hydroxypropylcellulose with a molecular weight of 370000g / mol in DPM (7.2 parts by weight polymer in 200 parts by weight DPM), measured at 20 °C and a shear rate of 200 / sec, whereby the concentration of this active substance is approximately 0.15 wt%.

[0162] The viscosity properties are determined by a jump test, in which the system oscillates for approximately 9 minutes, interrupts the oscillation for approximately 15 seconds by a shear rotation at 100 s⁻¹, and then oscillates again for approximately 4 minutes (20 °C). The tan(delta) G2 / G1 after approximately 4 minutes is approximately 2.0.

[0163] The color paste is transferred to a substrate and hardened using the printing process described above. The printed substrate exhibits very little satellite formation. Example of implementation 22

[0164] 100 parts by weight of a color paste from Ferro GmbH based on the glass color powder 14510 and the medium C7 (both Ferro GmbH) is adjusted to a viscosity of approximately 600 mPas with Dowanol DPM (12.5 parts by weight) and 5 parts by weight of a solution of hydroxypropylcellulose with a molecular weight of 850000g / mol in DPM (3.6 parts by weight polymer in 200 parts by weight DPM), measured at 20 °C and a shear rate of 200 / sec, whereby the concentration of this active substance is approximately 0.08 wt%.

[0165] The viscosity properties are determined by a jump test, in which the system oscillates for approximately 9 minutes, interrupts the oscillation for approximately 15 seconds by a shear rotation at 100 s⁻¹, and then oscillates again for approximately 4 minutes (20 °C). The tan(delta) G2 / G1 after approximately 4 minutes is approximately 1.5.

[0166] The color paste is transferred to a substrate and hardened using the printing process described above. The printed substrate exhibits very little satellite formation. Example of implementation 23

[0167] 100 parts by weight of a color paste from Ferro GmbH based on the glass color powder 14510 and the medium C7 (both Ferro GmbH) is adjusted to a viscosity of approximately 970 mPas with Dowanol DPM (10.0 parts by weight) and 5 parts by weight of a solution of hydroxypropyl cellulose with a molecular weight of 850000g / mol in DPM (3.6 parts by weight polymer in 200 parts by weight DPM), measured at 20 °C and a shear rate of 200 / sec, whereby the concentration of this active substance is approximately 0.08 wt%.

[0168] The viscosity properties are determined by a jump test, in which the system oscillates for approximately 9 minutes, interrupts the oscillation for approximately 15 seconds by a shear rotation at 100 s⁻¹, and then oscillates again for approximately 4 minutes (20 °C). The tan(delta) G2 / G1 after approximately 4 minutes is approximately 2.1.

[0169] The color paste is transferred to a substrate and hardened using the printing process described above. The printed substrate exhibits very little satellite formation. Comparative example 10

[0170] Example 22 is essentially repeated, except that hydroxypropylcellulose with a molecular weight of 850000g / mol is not used, but the viscosity is adjusted by adding DPM, with the viscosity also being in the range of about 530 mPas.

[0171] The viscosity properties are determined by a jump test, in which the system oscillates for approximately 9 minutes, interrupts the oscillation for approximately 15 seconds by a shear rotation at 100 s⁻¹, and then oscillates again for approximately 4 minutes (20 °C). The tan(delta) G2 / G1 after approximately 4 minutes is approximately 6.2.

[0172] The color paste is transferred to a substrate using the printing process described above and then hardened. The printed substrate now exhibits a very distinct satellite pattern. Comparative example 11

[0173] Example 23 is essentially repeated, except that hydroxypropylcellulose with a molecular weight of 850000g / mol is not used, but the viscosity is adjusted by adding DPM, with the viscosity also being in the range of about 970 mPas.

[0174] The viscosity properties are determined by a jump test, in which the system oscillates for approximately 9 minutes, interrupts the oscillation for approximately 15 seconds by a shear rotation at 100 s⁻¹, and then oscillates again for approximately 4 minutes (20 °C). The tan(delta) G2 / G1 after approximately 4 minutes is approximately 4.0.

[0175] The color paste is transferred to a substrate using the printing process described above and then hardened. The printed substrate now exhibits a very distinct satellite pattern. Example of implementation 24

[0176] 100 parts by weight of a color paste from Ferro GmbH based on the glass color powder 14510 and the medium C7 (both Ferro GmbH) is adjusted to a viscosity of approximately 1000 mPas with Dowanol DPM (10.0 parts by weight) and 5 parts by weight of a solution of hydroxyethylcellulose with a molecular weight of 420000g / mol in DPM (7 parts by weight polymer in 100 parts by weight DPM), measured at 20 °C and a shear rate of 200 / sec.

[0177] The examples show that the present invention solves the problems set out above, in particular that satellite formation can be reduced surprisingly significantly without adversely affecting other properties of the printing substance.

Claims

1. Printing method for transferring printing ink from an ink carrier to a printing substrate, in which, with the aid of an energy-emitting device, which emits energy in the form of electromagnetic waves during a process time, the printing substance undergoes a change in volume and / or position, wherein the printing substance comprises at least one functional carrier and comprises a high-molecular-weight binder, wherein the high-molecular-weight binder has a weight-average molecular weight in the range of 150,000 to 5,000,000 g / mol, measured by GPC.

2. Printing method according to claim 1, characterized in that energy from the electromagnetic wave is transferred to the printing substance with the aid of absorption bodies.

3. Printing method according to claim 1 or 2, characterized in that the high-molecular-weight binder has a weight-average molecular weight in the range of 200,000 to 2,000,000 g / mol, and preferably 250,000 to 1,000,000 g / mol, measured by GPC.

4. Printing method according to at least one of the preceding claims, characterized in that the printing substance comprises 0.01 to 5 wt.%, preferably 0.05 to 3 wt.%, particularly preferably 0.07 to 2 wt.%, and especially preferably 0.08 to 1.5 wt.% of a high molecular weight binder.

5. Printing method according to at least one of the preceding claims, characterized in that the printing substance has a ratio of loss modulus (G2) to storage modulus (G1) [tan (Delta) = G2 / G1] in the range from 0.05 to 3.0, particularly preferred 0.1 to 2.8, especially preferred 0.2 to 2.5, specially preferred 0.3 to 2.3, particularly specially preferred 0.05 to 1.3, particularly specially preferred 0.1 to 1.1, especially particularly preferred 0.2 to 1.0 and very specially preferred 0.3 to 0.9.

6. Printing method according to at least one of the preceding claims, characterized in that the printing substance comprises an absorbent, preferably carbon black or at least one inorganic pigment.

7. Printing substance for carrying out a printing process according to one of the preceding claims, wherein the printing substance comprises at least one high-molecular-weight binder, at least one low-molecular-weight binder, and at least one functional carrier, wherein the high-molecular-weight binder has a weight-average molecular weight in the range of 150,000 to 5,000,000 g / mol, measured by GPC, and the low molecular weight binder has a lower molecular weight than the high molecular weight binder.

8. Printing substance according to claim 7, characterized in that the functional carrier comprises an inorganic pigment and / or metal particles, preferably silver particles.

9. Printing substance according to claim 7 or 8, characterized in that the printing substance is flowable, preferably has a viscosity in the range of 250 to 1400 mPas, measured at 20 °C and a shear rate of 200 s-1 with plate / cone.

10. Printing substance according to at least one of the preceding claims 7 to 9, characterized in that the printing substance comprises at least one propellant, which preferably has a boiling point in the range from 60°C to 250°C, more preferably in the range from 80 °C to 200 °C, and most preferably in the range from 140 °C to 190 °C.

11. Printing substance according to one of the preceding claims 7 to 10, characterized in that the low molecular weight binder has a weight average molecular weight (Mw) in the range from 10,000 to 150,000 g / mol, preferably in the range from 50,000 to 100,000 g / mol, measured according to GPC, standard media.

12. Printing substance according to one of the preceding claims 7 to 11, characterized in that the surface tension of the printing substance is 26 to 34 mN / m, preferably 28 to 32 mN / m.

13. Printing substance according to one of the preceding claims 7 to 12, characterized in that the functional carrier is particulate, wherein the particles preferably have a d50 value in the range from 0.5 µm to 30 µm, more preferably in the range from 1 µm to 20 µm, and most preferably in the range from 2 µm to 15 µm.

14. Printing substance according to one of the preceding claims 7 to 13, characterized in that the printing substance has a solids content of at least 30% by weight, preferably at least 50% by weight, and particularly preferably at least 60% by weight.

15. Use of a printing substance according to one of the preceding claims 7 to 14, wherein the printing substance is applied to glass, ceramics, metal, wood, or plastic.