EP3735352A1

EP3735352A1 - Printing process for transferring a printing substance

Info

Publication number: EP3735352A1
Application number: EP19706512.1A
Authority: EP
Inventors: Dietrich Speer; Alexander Zeig
Original assignee: Ferro GmbH
Current assignee: Vibrantz GmbH
Priority date: 2018-02-22
Filing date: 2019-02-15
Publication date: 2020-11-11
Also published as: US11458755B2; DE102018104059A1; WO2019162212A1; US20210086541A1

Abstract

The present invention relates to a printing process for transferring a printing substance from an ink carrier onto a print material, according to which the printing substance undergoes a change in volume and/or position due to the effect of an energy-emitting device which emits energy in the form of electromagnetic waves during a process time, the printing substance comprising a high-molecular binder. The present invention furthermore relates to a printing substance for carrying out the process and to the use thereof.

Description

Printing process for the transfer of printing substance

The present invention relates to printing methods for the transmission of

Printing substance from a color carrier on a substrate and a

Printing substance for carrying out the method.

Under a printing process is primarily a method for arbitrarily frequent duplication of text and / or image templates understood, formerly this duplication took place by means of a printing form, which was repainted after each reprinting. This method is also used today in the duplication of large numbers. In general, a distinction is made here between four fundamentally different printing methods. So that's one thing

High-pressure method known in which the printing elements of the printing form are raised, while the non-printing parts are recessed. These include, for example, the book printing and the so-called flexo or anil impression. Furthermore, planographic printing methods are known in which the printing elements and the non-printing parts of the printing form lie substantially in one plane. This includes, for example, the offset printing, in which, strictly speaking, the inked drawing on the printing plate is not printed directly on the substrate, but is first transferred to a blanket cylinder or a blanket and then printed by this only the substrate. If in the following of printing material is mentioned, but should both the actual substrate, that is, the material to be printed, as well as any transfer means, such as. As a blanket cylinder to be understood. A third method is the so-called gravure printing process, in which the printing elements of the printing form are recessed. An industrially applied gravure printing process is the so-called scoring gravure printing. Finally, a through-printing method is still known in which the ink is transferred through screen-like openings of the printing form to the printing material at the printing sites.

These printing methods are all characterized by the fact that they require a more or less elaborate printing form, so that these printing process only at very high volumes, usually well over 1000 pieces, work economically. Printers that are frequently connected to an electronic data processing system are already being used to print short runs. These generally use digitally controllable printing systems that are capable of printing individual printing dots as needed. Such printing systems use different methods with different printing substances

different substrates. Some examples of digitally controllable

Printing systems are: laser printers, thermal printers and inkjet printers. Digital printing processes are characterized by the fact that they do not require printing forms.

For example, from GB 20 07 162 an electrothermal

Ink printing method is known in which in a suitable ink jet, the water-based ink is briefly heated to boiling by electrical impulses, so that a gas bubble develops in a flash and an ink droplet is shot out of the nozzle. This method is well known by the term "bubble jet". These thermal ink printing processes, in turn, have the disadvantage that, on the one hand, they consume a great deal of energy for printing a single printing dot and, on the other hand, they are only suitable for printing processes based on water. Moreover, with the nozzle every single one has to

Pressure point to be controlled separately. On the other hand, piezoelectric ink printing processes suffer from the disadvantage that the nozzles required in this case clog easily, so that only very special and expensive paints can be used for this purpose.

Furthermore, from the publications US 2012/0164777 A1 and

US 2016/0167400 A1 printing inks which can be used in printing processes, in which, for example, by a laser beam, the ink applied to a carrier ink is transferred to a substrate. However, these publications do not disclose compositions comprising high molecular weight binders; in particular, no molecular weight data are set forth with respect to the polymers disclosed in a long list. Furthermore, the

Printing method unspecified, in particular from the document EP 0 530 018 A1 printing method are known in which the inks are applied to a solid film and detached from it. Here are the Inks in a solid phase, so that the support on which the ink is applied, after a printing process must be completely replaced. Very high viscosities for the printing inks are set forth in US 2016/0167400 A1, so that this is only suitable for processes in which the support must be completely replaced after each use. Hints for a

Printing method in which continuous ink is applied to a flexible belt or a roller and transferred from this carrier to a substrate to be printed, can not be found in the documents US 2012/0164777 A1 and

US 2016/0167400 A1. In the document EP 0 530 018 A1 is a

Melt transfer process in which the printing inks are melted so that they have a very high viscosity at room temperature, wherein the ink-containing layer comprises as main component a binder which has a softening point in the range of 50 to 160 ° C and solid or semisolid is fixed (see EP 0 530 018 A1, page 4, lines 51 to 55).

It is known from DE 197 46 174 that a laser beam induces a process by means of very short pulses in a printing substance, which is located in the cells of a printing roller, so that the printing substance undergoes a change in volume and / or position. As a result, the printing substance grows over the surface of the printing form and the transfer of a pressure point to an approximated thereto

Printing material is possible. In this method, however, has the disadvantage that the filling of the wells is very difficult due to the small well diameter. Therefore, it is proposed in DE 100 51 850 to apply the printing substance essentially forming a continuous film on the ink carrier. The energy can either be transferred directly into the printing substance or initially in an applied on the ink carrier absorption layer, which in turn emits the energy to the printing substance. In the first case special pressure substances must be used, which are able to supply the energy

absorb. This greatly limits the variety of usable inks. In addition, the absorption of light in the ink occurs within a relatively large volume that passes through the laser beam. For some colors, the energy is not fully absorbed. The absorption is also strongly dependent on the printing substance used and the actual thickness of the printing substance on the ink carrier. Due to the relatively large volume, adding the energy is absorbed, a relatively large amount of energy must be introduced into the printing substance to the necessary for the setting of a pressure point volume and / or

To induce change in position of the printing substance. Moreover, bumping often occurs, so that the temperature at which gas bubbles form in the printing substance can not be predicted. This has the consequence that the absorption - and the associated local heating of the printing substance - largely uncontrolled, which u. a. a strong variation in the

Pressure point size has the consequence. To ensure that the desired pressure point is set in each case, therefore, significantly more energy must be introduced into the printing substance than is normally necessary for inducing the desired position and / or volume change of the printing substance.

Furthermore, a generic printing method is set forth in DE 102 10 146 A1. In this case, printing inks, as previously stated in DE 197 46 174 or DE 100 51 850, are heated by a laser beam and thereby transferred from a color carrier to a printing substrate. In the method described here absorption bodies are used to improve the process.

The methods previously described, for example, in DE 197 46 174, DE 100 51 850 or DE 102 10 146 solve the economy problems previously presented for various printing methods, which consists of a small number of copies to be reproduced or the difficulty that in the previously set forth

Ink printing process, only very special inks can be used, which must not have a high solids content, in particular no proportion of larger particles. However, the print quality is not sufficient for certain requirements, as a clear formation of smaller droplets in the vicinity of the intended pressure points is visible (satellite formation). This problem is not only visually undesirable, but limits the minimum distance of printed lines that are generated for example when printing silver-containing inks for the production of printed conductors, otherwise short circuits can occur. Further, this limits the minimum size of barcodes and other machine-readable characters. In view of the prior art, it is now the object of the present

Invention to provide a printing process resulting in a higher

Contour sharpness leads, however, is suitable also for small series. Here, in particular colorfast decors should be able to be processed, glass colors can be processed or inks can be used for electronic circuits. Furthermore, the process should be as simple and inexpensive

can be performed. In this case, the properties of the printed decors or tracks should not be adversely affected. So should the

Coating to show the highest possible adhesion to different materials. Further, the decor which can be obtained by the method should have high image sharpness.

These are solved as well as other tasks that are not explicitly mentioned, but which can be easily deduced or deduced from the contexts discussed in the introduction by a printing process with all the features of the present invention

Patent claim 1. Advantageous modifications of the invention

Printing method are provided in subclaims 2 to 6 under protection.

With regard to the printing substance, the subjects of claims 6 to 18 provide a solution to the underlying object.

The present invention is a printing method for transferring printing substance from a color carrier to a substrate, in which the pressure substance undergoes a change in volume and / or position with the aid of an energy-emitting device which emits energy during a process time in the form of electromagnetic waves characterized in that the printing substance comprises a high molecular weight binder.

With this configuration can be produced inexpensively in a very high quality even for smaller series in a simple and cost-effective manner, the substrate is not subject to any special restrictions.

Surprising advantages arise in particular in the fields of car glass, flat glass for interior and exterior decoration, barcodes and silver conductive tracks. In particular, small series can be obtained inexpensively, wherein As a result, in particular, spare parts can be provided efficiently, so that storage costs can be reduced.

Further, in comparison to the prior art set out above, in particular the screen printing technique, inorganic materials are used in their usual manner

Grain size distributions can be used, no Sieblager needed, so that further cost and organization benefits are provided, since no provision of a Sieblagers is necessary. Furthermore, the printing system can be operated with a very short setup time, the design can be completely transferred from a computer that can be remotely located in the printing system. Furthermore, the designs on the PC can be changed as desired, so that very individual designs are possible. Due to the relatively low additional costs, the market share of individual designs can be increased. Since the printing is digital, any patterns and a serialization or individualization of the individual printed substrates are possible.

Furthermore, inorganic materials can be used in their usual particle size distributions, without the need for a complex fine grinding process as in the conventional ink-jet process. There, the particles must be in the range <1 pm. Through the grinding process, the pigments are damaged and lose color strength, so that several times must be printed on each other in order to obtain sufficient color intensity. Despite the fine milling process, nozzle clogging and sedimentation problems are not uncommon in conventional ink-jet processes. These problems can not occur in the method according to the invention.

Surprisingly, the measures according to the invention make it possible to improve the print quality, so that in particular the satellite formation described above and below is reduced.

The present printing method is used to transfer printing substance from a color carrier to a substrate. The color carrier from which the

Pressure substance is replaced, this is subject to no particular restriction. For example, the ink carrier can be made transparent, wherein the Light beam preferably from the printing substance side facing away from the

Color carrier is focused through this into the printing substance. It then forms on the color carrier side facing the absorption body explosively a gas bubble, which ensures the acceleration of the absorption body in the direction of the printing material. In particular, when using transparent printing substances, a color carrier is preferably used, on its intended for receiving the printing substance surface

Absorbent body are present, which preferably form a solid layer.

Furthermore, it can be provided that a color carrier is used, on whose intended for the recording of the printing substance surface absorption bodies are present, which preferably form a solid layer.

In one embodiment, the ink carrier can be designed as a circulating belt. Preferably, the ink carrier is designed in the form of a flexible band, which comprises a layer with a printing substance.

Preferably, the layer is renewed with a printing substance, which is provided on the ink carrier, after the process time at 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.

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

By the method according to the invention is a printing substance on a

Transfer substrate. The printing material is not subject to any specific limitation. Therefore, it may be made of common materials such as glass, ceramic, metal, wood or plastic. In the present printing process, the printing substance undergoes a change in volume and / or position with the aid of an energy-emitting device which emits energy during a process time in the form of electromagnetic waves. Accordingly, the printing substance is preferably transferred directly or indirectly by the action of electromagnetic waves from the ink carrier to the printing substrate.

Advantageously, the energy-emitting device emits energy in the form of laser light. With the help of highly coherent monochromatic laser light, a relatively high amount of energy can be dissipated to a very small area with very short light pulses. As a result, the quality of the printed image, in particular the resolution is increased. A short pulse of light does not necessarily have to come from a pulsed laser. On the contrary, it is even advantageous to use a laser in CW mode instead. The pulse duration or better the exposure time then does not depend on the length of the laser pulses, but on the scanning speed of the focus. In addition, the data to be transmitted no longer need to be synchronized to the fixed pulse rate.

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 absorption body through the

be accelerated electromagnetic waves of the energy-emitting device in the direction of the printing material. This will cause the volume and / or

Position change of the printing substance supported in an advantageous manner. Namely, it comes only by the acceleration of the absorption body to a kind

Shock wave in the printing substance, so that in combination with the forming gas bubble a defined drop separation is favored. In a preferred embodiment, the ink carrier from the side with the electromagnetic waves is paid, which is arranged opposite the ink layer. In this case, preferably transparent color carrier can be used, as has been explained in more detail above. The wavelength of the electromagnetic wave, with the energy-emitting device couples the energy in the color carrier or the printing substance, is not subject to any particular limitation, but can be tuned to the absorption body contained in the color carrier or the printing substance.

Preferably, it can be provided that energy is transferred from the electromagnetic wave into the printing substance with the aid of absorption bodies.

Preferably absorption bodies are used, which is smaller than the wavelength of the electromagnetic waves, preferably less than 1/10, particularly preferably less than 1/50 of the wavelength of the electromagnetic waves.

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

Furthermore, it can be provided that brightness differences of the image to be printed are realized by varying the printing dot size.

In addition, it can be provided that the printing takes place line by line, wherein areas to be printed within a line are formed by line segments arbitrarily selectable length and arbitrary selectable position.

Furthermore, it can be provided that the distance between the ink carrier with the ink layer and the substrate to be printed is 50 pm to 1000 m.

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

The present printing method is characterized in that the

Printing substance comprises a high molecular weight binder. This printing substance is new and therefore also the subject of the present invention. Accordingly, the following statements apply both to the process according to the invention and to the printing substance as such.

Surprisingly, preferred printing substances have the following criteria, wherein these can be fulfilled individually or all:

The viscosity is preferably adjusted so that the printing substance is readily flowable, thus enabling transport from the ink tank to the coating station and backflow.

Preferably, the printing substance has a high content of inorganic material in order to leave sufficient material on the substrate after a printing operation, e.g. to create a covering color layer.

The printing substance couples with the laser beam energetically, so that the

pulse-like detachment of the ink droplet can be done.

A preferred printing substance wets the substrate e.g. Glass sufficiently good, so that a printed line as such remains on the substrate, so sticks well without, however, spread wide. Among other things, this property can be influenced by the viscosity.

The printing substance comprises a high molecular weight binder. Preferably, the high molecular weight binder has a weight average molecular weight in the range of 150,000 to 5,000,000 g / mol, more preferably 200,000 to 2,000,000 g / mol, and especially preferably 250,000 to 1,000,000 g / mol, as measured by GPC ,

In a particular embodiment it can be provided that the high molecular weight binder is an amino group-containing polymer, an ether group-containing polymer, an ester group-containing polymer, an amide group-containing polymer

acid group-containing polymer or a hydroxy group-containing polymer, preferably a polyvinyl alcohol, a (meth) acrylate, a hydroxy-containing (meth) acrylate, a poly (meth) acrylic acid and salts thereof, a polyacrylamide, a polyvinylpyrrolidone, a polyethylene glycol, a styrene-maleic anhydride copolymer and salts thereof, is a polysaccharide, particularly preferably a cellulose or a modified cellulose, particularly preferably methyl methacrylate, Methyl methacrylate copolymer, hydroxyethyl cellulose, carboxymethyl cellulose, hydroxypropylmethyl cellulose, hydroxypropyl cellulose, ethyl hydroxyethyl cellulose.

Particular preference is given to hydroxyethyl celluloses having a molar degree of substitution in the range from 1 to 8, preferably 1.5 to 6, more preferably 2.0 to 5 and especially preferably 2.2 to 4.

Particular preference is given to hydroxypropylmethylcelluloses having a molar degree of substitution in the range from 1 to 10, preferably 2 to 7, more preferably 2.5 to 5.5, and especially preferably 3 to 5.

Also preferred are (meth) acrylates which are at least 80% by weight, preferably at least 90% by weight and more preferably at least 95% by weight

Have units derived from methyl methacrylate. Particular preference is given in particular to (meth) acrylates which have up to 20% by weight, preferably up to 10% by weight, of units which are derived from comonomers. Preferred comonomers are particularly preferably selected from alkyl (meth) acrylates, such as butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate; and

Hydroxylalkyl (meth) acrylates such as 3-hydroxypropyl (meth) acrylate, 3,4-dihydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate.

Of the aforementioned high molecular weight binders are in particular

Ethylhydroxyethylcelluloses, hydroxypropylmethylcelluloses and (meth) acrylates are preferred, with hydroxypropylmethylcelluloses and (meth) acrylates being particularly preferred.

These polymers can be obtained commercially from a variety of suppliers. These include, but are not limited to, polymers available under the tradename Degalan® and Klucel®, preferably Degalan® LP 62/05, Klucel® H, Klucel® M, and Klucel® G.

It can further be provided that the high molecular weight binder has a solubility in a polar solvent, for example dipropylene glycol methyl ether of at least 0.5 g, preferably at least 1 g, more preferably at least 1.5 g per 100 g of solvent.

Furthermore, it can be provided that the printing substance is 0.01 to 5 wt .-%, preferably 0.05 to 3 wt .-%, particularly preferably 0.07 to 2 wt .-%, and particularly preferably 0.08 to 1, 5 wt .-% of high molecular weight binder.

In a further preferred embodiment it can be provided that the printing substance contains absorption bodies. The absorption bodies interact with the electromagnetic waves described above. Accordingly, in particular, a pigment, preferably an inorganic pigment or carbon black may be contained in the printing substance.

Depending on the design of the printing substance, this may comprise more or less high proportions of absorption bodies. A printing substance which comprises only carbon black as absorption body preferably has a carbon black content in the range from 0.5 to 3.0% by weight, particularly preferably 0.8 to 1.5% by weight. Printing substances which contain inorganic pigments as absorption bodies preferably have from 2 to 40% by weight, particularly preferably from 3 to 25% by weight, of absorbent bodies or inorganic pigments.

In a particular embodiment, the printing substance preferably comprises

at least one high molecular weight binder, at least one low molecular weight binder and at least one functional carrier.

The function carrier here denotes a substance which leads to a function on a substrate, which may be given, for example, in a coloring and / or the provision of a conductivity of the decoration produced by the printing substance. The preferred functional carriers include inorganic pigments, glass fluxes and / or metal particles, preferably silver particles. The functional carrier therefore remains on the substrate after a later-described curing, while other solid constituents remain on the substrate after drying, but by a high-temperature curing of the Substrate are removed. Depending on the curing conditions, these other solid constituents include, inter alia, the binders described above and carbon black.

The printing substance preferably has mineral pigments, which particularly preferably act as absorption bodies. In a further embodiment, the printing substance preferably comprises metal particles, preferably silver particles.

It can further be provided 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 especially preferably in the range from 2 μm to 15 pm.

The printing substance preferably has a high content of functional carriers, in particular of inorganic pigments, glass fluxes and / or metal particles, wherein the printing substance preferably comprises up to 85% by weight, particularly preferably up to 70% by weight of functional carrier. A glass flow is preferred in

Pressure substances used, which are cured at very high temperatures on the substrate. Printing substances that are cured or dried at a temperature below 400 ° C preferably do not include glass flow.

The low molecular weight binder has a lower molecular weight than the high molecular weight binder. Preferably, the weight average of the

Molecular weight (Mw) of the high molecular binder at least 20% greater than the weight average molecular weight (Mw) of the low molecular weight

Binder, preferably at least 50%, more preferably at least 100%, wherein the percentages are based on the weight average molecular weight (Mw) of the low molecular weight binder. It can preferably be provided 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. The low molecular weight binder preferably comprises an amino group-containing polymer, an ether group-containing polymer, an ester group-containing polymer

amide group-containing polymer, an acid group-containing polymer or a hydroxy group-containing polymer is, 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 salts thereof, is a polysaccharide, particularly preferably a cellulose or a modified cellulose, particularly preferably methyl methacrylate, methyl methacrylate copolymer, hydroxyethyl cellulose, carboxymethyl cellulose, hydroxypropylmethyl cellulose, hydroxypropyl cellulose, ethyl hydroxyethyl cellulose.

These polymers can be obtained commercially from a variety of suppliers. These include Klucel® E and Klucel® J, among others

(Hydroxypropylmethylcellulose) and Aqualon® N10 and Aqualon® N22

(Hydroxyethyl cellulose).

Furthermore, it can be provided that the low molecular weight binder a

Solubility in a polar solvent, for example

Dipropylene glycol methyl ether of at least 0.5 g, preferably at least 1 g, more preferably at least 1, 5g to 100g solvent.

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.

Furthermore, it can be provided 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.

Preferably, it can be provided that the printing substance comprises at least one blowing agent, which preferably has a boiling point in the range of 60 ° C to 250 ° C, preferably in the range of 80 ° C to 200 ° C, particularly preferably in the range of 1 10 ° C to 200 ° C, especially preferably in the range of 140 ° C to 190 ° C. Preferably, the propellant is a solvent, which preferably ether, especially diglycols, aliphatic hydrocarbons, aromatic

Hydrocarbons, hydroaromatic hydrocarbons, Texanol, alcohols, esters, ketones and / or water. These are organic solvents, in particular ethers, preferably diglycols, aliphatic hydrocarbons, aromatic hydrocarbons, hydroaromatic hydrocarbons, texanol, alcohols, esters and / or ketones are preferred.

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

The printing substance is preferably flowable, the printing substance particularly preferably having a viscosity in the range from 400 to 4500 mPas, particularly preferably a viscosity in the range from 500 to 3200 mPas, furthermore particularly preferably in the range from 800 to 2600 mPas, especially preferably in the range of 1000 up to 2200 mPas, measured at 20 ° C., at a shear rate of 2 s ¹ , measured with plate / cone (rotary viscometer CVO120 from Bohlin, plate-and-cone method (2 °), basis 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 printing substance is preferably flowable, the printing substance particularly preferably having a viscosity in the range from 200 to 4000 mPas, particularly preferably a viscosity in the range from 400 to 2800 mPas, furthermore particularly preferably in the range from 550 to 2000 mPas, especially preferably in the range from 700 up 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 °), basis DIN 53019; 1: 2008-09, DIN 53019- - 2: 2001 -02, DIN 53019-3: 2008-09, DIN 53019-4: 2016-10).

The printing substance is preferably flowable, the printing substance particularly preferably having a viscosity in the range from 100 to 3500 mPas, particularly preferably a viscosity in the range from 200 to 2400 mPas, furthermore particularly preferably in the range from 400 to 1600 mPas, especially preferably in the range from 600 to 1200 mPas, measured at 20 ° C, at a shear rate of 50 s ¹ , measured with plate / cone (rotary viscometer CVO120 the Fa.Bohlin, plate-cone method (2 °), basis 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 printing substance is preferably free-flowing, with the printing substance particularly preferably having a viscosity in the range from 50 to 3000 mPas, particularly preferably a viscosity in the range from 100 to 2000 mPas, furthermore particularly preferably in the range from 250 to 1400 mPas, particularly particularly preferably in the range from 400 to 1200 mPas, especially preferred in the range of 500 to 1000 mPas, measured at 20 ° C, at a shear rate of 200 s measured with plate / cone (rotary viscometer CVO120 the Fa.Bohlin, plate-cone method (2 °) .

Basis 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 printing substance is preferably free-flowing, the printing substance particularly preferably having a viscosity in the range from 25 to 2800 mPas, particularly preferably a viscosity in the range from 50 to 2000 mPas, in the range from 200 to 1200 mPas, especially preferably in the range from 400 to 800 mPas measured at 20 ° C, at a shear rate of 600 s measured with plate / cone

(Rotary viscometer CVO120 from Bohlin, plate-cone method (2 °),

The viscosity properties set forth above, which are maintained at different shear rates, preferably printing substances, can be realized individually or completely, with preferably at least two, more preferably three, more preferably four, and most preferably all

Viscosity properties are met. In this way, a particularly preferred printing substance can be provided, which exhibits a specific thixotropy and is still flowable under the shearing force conditions in the printing apparatus.

In a preferred embodiment it can be provided that the

Pressure substance shows a viscoelastic behavior. Viscoelastic materials are those between the extremes - the ideal viscous liquids with tan (delta) = G2 / G1> 100 and the ideal elastic solids with tan (delta) = G2 / G1 <0.01. G1 is the memory module, G2 is the loss module. These parameters are determined in the context of oscillation measurements (jump test measurements), measured with a "Anton Paar Rheo-Compass" of the company Anton Paar. Plate plate, gap width approx.

0.5 mm at 20 ° C. (Modular Compact Rheometer MCR302 from Anton Paar, plate-plate method, basis 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 w, in particular during the jump, is preferably 3.14 rad / s and the deflection t is preferably 0.1%.

In a preferred embodiment it can be provided that the

Storage modulus G1 is at least 8 Pa, preferably at least 10 Pa and especially preferably at least 12 Pa, measured by means of oscillation measurements with an "Anton Paar Rheo-Compass" from Anton Paar. Plate plate, gap width about 0.5mm at 20 ° C.

In a preferred embodiment it can be provided that the loss modulus G2 is at least 6 Pa, preferably at least 8 Pa and especially preferably at least 10 Pa, measured by means of oscillation measurements with an "Anton Paar Rheo-Compass" from Anton Paar. Plate plate, gap width about 0.5mm at 20 ° C.

Most preferably, the printing substance has a high elastic component, i. G1 near G2 and at the same time it is flowable under the shearing forces prevailing in the apparatus (i.e., tan (delta) in the range of preferably 0.05 to 3.0, more preferably 0.05 to 1.3). The angular velocity w, in particular during the jump, is preferably 3.14 rad / s and the deflection t is preferably 0.1%.

In preferred embodiments, tan (delta) = G2 / G1 is preferably in the range of 0.05 to 3.0, more preferably 0.1 to 2.8, more preferably 0.2 to 2.5, and even more preferably 0.3 to 2,3, measured by means of oscillation measurements with an "Anton Paar Rheo-Compass" from the company Anton Paar. Plate plate, gap width about 0.5mm at 20 ° C. The angular velocity w, in particular during the jump, is preferably 3.14 rad / s and the deflection Y is preferably 0.1%.

In preferred embodiments, tan (delta) = G2 / G1 is preferably in the range of 0.05 to 1.3, more preferably 0.1 to 1.1, more preferably 0.2 to 1.0, and even more preferably 0.3 to 0.9, measured by means of oscillation measurements with an "Anton Paar Rheo-Compass" of the company Anton Paar. Plate plate, gap width about 0.5mm at 20 ° C. The angular velocity w, in particular during the jump, is preferably 3.14 rad / s and the deflection Y is preferably 0.1%.

In a further embodiment it can be provided that tan (delta) = G2 / G1 preferably by the presence of the high molecular binder by at least 30%, preferably by at least 50% compared to a substantially same composition, in particular the same viscosity at 25 ° C. and a shear stress of 200 s ¹ , but no high molecular weight binder decreases, measured by means of oscillation measurements with an "Anton Paar Rheo Compass" from Anton Paar. Plate plate, gap width about 0.5mm at 20 ° C. The angular velocity w, in particular during the jump, is preferably 3.14 rad / s and the deflection r is preferably 0.1%.

Preferably, it can be provided that 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 a substantially same

Composition without high molecular weight binder, which in particular has the same viscosity at 25 ° C and a shear stress of 200 Hz s ¹ , preferably at most 0.9, preferably at most 0.7, more preferably at most 0.6.

The previously described values of the memory module G1, the loss modulus G2 and the tan (delta) are determined at a plateau, which generally sets after a time of about 5 to 9 minutes in an oscillation test. These values are preferably reached again after a short shearing stress (about 20 seconds) by a rotation of 100 s ^-1 after a time of about 5 minutes, so that in preferred embodiments there is no degradation of the polymers which lead to these values.

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" Fa.Krüss at 20 ° C ( DIN53914: 1997-07). Another object of the present invention is the use of a printing substance according to the invention, which is characterized in that the printing substance is applied to glass, ceramic, metal, wood or plastic.

Preferably, after application of the printing substance can be cured on a substrate, wherein the curing is preferably carried out at a temperature in the range of 150 * Ό to 1200 ° C, more preferably 150 ° C to 220 ° C or 500 ° C to 1000 ° C.

In a preferred embodiment, after printing, the layer may be dried at 100 ° C to 150 ° C to remove volatile media components,

in particular to remove propellant or solvent. The penetration is then preferably at 500 ° C to 1000 ° C in the case of printing substances containing inorganic, preferably mineral pigments and / or glass fluxes. Printed substances with glass fluxes may contain metal particles, in particular silver particles. Printing substances, which are preferably baked at 500 ° C to 1000 ° C, are preferably intended to be applied to inorganic substrates, such as glass plates or the like. Printing substances with metal particles, preferably silver particles, which do not contain any mineral pigments or glass fluxes, are preferably cured at a temperature in the range of 10 ° 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 the like.

Hereinafter, the present invention will be explained in more detail by way of examples, without thereby limiting the invention.

Exemplary embodiment 1

A coloring paste of the Ferro GmbH based on the glass color powder 14305 and the medium C7 (both Ferro GmbH) becomes with Dowanol DPM and a

Hydroxylpropylcellulose having a molecular weight of 850000g / mol adjusted to a viscosity of 960 mPas, measured at 20 ° C and a shear rate of 200 / sec, wherein the concentration of this active substance is about 0.09% by weight. The color paste is transferred by means of the printing process described above on glass plates (format 100x100x4mm) and baked at 690 ° C. The dargestellen in Figure 1 photos show a section with 100- or 30-fold magnification. The printed substrate shows only a very small satellite formation, as can be seen from Figures 1A (100X magnification) and 1B (30X magnification), which represent light micrographs of the decor.

Comparative Example 1

Embodiment 1 is substantially repeated except that no hydroxypropyl cellulose having a molecular weight of 850000 g / mol is used, the viscosity also being in the range of about 960 mPas.

The color paste is transferred by means of the printing process described above on glass plates (format 100x100x4mm) and baked at 690 ° C. The photos show a section with 100x or 30x magnification. The printed substrate now shows a very clear satellite formation, as can be seen from Figures 1 C (100 times magnification) and 1 D (30 times magnification).

Exemplary embodiment 2

An ink based on the inorganic constituents of the silver paste TSP2002 from Ferro GmbH is adjusted with Dowanol DPM and a hydroxylpropyl cellulose having a molecular weight of 850000 g / cm ³ to a viscosity of 487 mPas, measured at 20 ° C and a shear rate of 200 / sec, the concentration of this active substance is about 0.13% by weight.

The ink is transferred to glass plates (100x100x4mm format) by the printing method described above and baked at 690 ° C. The printed substrate shows very little satellite formation, as can be seen in Figures 2A (100X magnification) and 2B (30X magnification), which are photomicrographs of the decor. Comparative Example 2

Embodiment 2 is substantially repeated except that no hydroxypropyl cellulose having a molecular weight of 850000 g / mol is used, and the viscosity is also in the range of 480 mPas.

The color paste is transferred by means of the printing process described above on glass plates (format 100x100x4mm) and baked at 690 ° C. The photos show a section with 100x or 30x magnification. The printed substrate now shows a very clear satellite formation, as can be seen in Figures 2C (100X magnification) and 2D (30X magnification).

Exemplary embodiment 3

A coloring paste of the Ferro GmbH based on the glass color powder 14297 and the medium C7 (both Ferro GmbH) becomes with Dowanol DPM and a

Hydroxylpropylcellulose having a molecular weight of 850000g / cm ³ adjusted to a viscosity of about 660 mPas, measured at 20 ° C and a shear rate of 200 / sec, the concentration of this active substance is about 0.09% by weight.

The viscosity properties are determined by a jump test, which is first oscillated for about 9 minutes, the oscillation is interrupted for about 15 seconds by a shear rotation at 100 s ¹ and then again oscillated for about 5 minutes (20 ° C). The storage modulus G1 is about 25.0 Pa after 8 minutes (plateau phase), the loss modulus G2 is about 13.9 and tan (delta) G2 / G1 is about 0.56. After about 12.5 minutes, the storage modulus G1 is about 25.1 Pa, the loss modulus G2 about 14.5 Pa and tan (delta) G2 / G1 about 0.58.

The color paste is transferred to a substrate by means of the previously described printing process and cured. The printed substrate shows only a very small satellite formation.

Exemplary embodiment 4 A color paste of Ferro GmbH based on the glass color powder 144012 and the medium 801026 (both Ferro GmbH) is adjusted with Dowanol DPM and a hydroxylpropyl cellulose with a molecular weight of 370000g / cm ³ to a viscosity of about 860 mPas, measured at 20 ° C and a shear rate of 200 / sec, wherein the concentration of this active substance is about 0.24% by weight.

Exemplary embodiment 5

A color paste of Ferro GmbFI based on the glass powder powder 14510 and the medium C7 (both Ferro GmbH) with Dowanol DPM and a

Hydroxylpropylcellulose having a molecular weight of 850000g / cm ³ adjusted to a viscosity of 860 mPas, measured at 20 ° C and a shear rate of 200 / sec, wherein the concentration of this active substance is about 0.09% by weight.

Exemplary embodiment 6

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 having a molecular weight of 250000 g / cm ³ in glycol ether at 20 ° C and a shear rate of 200 / sec, wherein the concentration of this active substance is about 1, 25% by weight. The viscosity properties are determined by a jump test, in which case oscillating for about 9 minutes, the oscillation is interrupted for about 15 seconds by a shear rotation at 100 s ¹ and then oscillated again for about 5 minutes (20 O). The storage modulus G1 after 8 minutes (plateau phase) is about 57.0 Pa, the loss modulus G2 about 31, 7 and tan (delta) G2 / G1 about 0.56. After about 13 minutes, the storage modulus G1 is about 44.6 Pa, the loss modulus G2 about 29.7 Pa and tan (delta) G2 / G1 about 0.67.

The color paste is transferred to a substrate by means of the previously described printing process and cured. The printed substrate shows only a very small satellite formation, which can be seen from FIG. 3, which shows enlarged details from a picture of the decoration.

Exemplary embodiment 7

An ink based on the inorganic constituents of the silver paste TSP2042 from Ferro GmbH is adjusted to a viscosity of 400 mPas with Dowanol DPM and a hydroxylpropyl cellulose having a molecular weight of 850000 g / cm ³ , the concentration of this active substance being about 0.18% by weight.

The ink is transferred to a substrate by the printing method described above and cured. The printed substrate shows only a very small satellite formation.

Exemplary embodiment 8

A color paste of Ferro GmbH based on the glass color powder 14297 and a glycol ether-based medium containing about 2.25% low molecular weight binder with about 50000g / cm ³ (both Ferro GmbH) and a

Hydroxylpropylcellulose having a molecular weight of 850000 g / cm ³ is adjusted to a viscosity of about 750 mPas, measured at 20 ° C and a shear rate of 200 / sec, wherein the concentration of the high molecular weight active substance is about 0.09% by weight. The color paste is transferred to a substrate by means of the previously described printing process and cured. The printed substrate shows only a very small satellite formation as Embodiment 1.

Exemplary embodiment 9

Hydroxylpropylcellulose having a molecular weight of 370000g / mol adjusted to a viscosity of 800 mPas, measured at 20 ° C and a shear rate of 200 / sec, the concentration of this active substance is about 0.17% by weight.

The viscosity properties are determined by a jump test, which is first oscillated for about 9 minutes, the oscillation is interrupted for about 15 seconds by a shear rotation at 100 s ¹ and then again oscillated for about 5 minutes (20 ° C). The storage modulus G1 is about 21.6 Pa after 8 minutes (plateau phase), the loss modulus G2 about 12.5 and tan (delta) G2 / G1 about 0.58. After about 12 minutes, the storage modulus G1 is about 22.6 Pa, the loss modulus G2 about 13.6 Pa and tan (delta) G2 / G1 about 0.60.

Comparative Example 3

Embodiment 9 is substantially repeated except that no hydroxypropyl cellulose having a molecular weight of 370000 g / mol is used, the viscosity also being in the range of about 800 mPas.

The viscosity properties are determined by a jump test, wherein initially oscillated for about 9 minutes, the oscillation for about 15 seconds interrupted by a shear rotation at 100 s ¹ and then again for about 5 Is oscillated for a few minutes (20 ° C). The storage modulus G1 is about 3.8 Pa after 8 minutes (plateau phase), the loss modulus G2 is about 5.4 and tan (delta) G2 / G1 is about 1.42. After about 13 minutes, the storage modulus G1 is about 3.8 Pa, the loss modulus G2 about 5.7 Pa and tan (delta) G2 / G1 about 1.50.

The color paste is transferred to a substrate by means of the previously described printing process and cured. The printed substrate now shows a very clear satellite formation.

Exemplary embodiment 10

100 parts by weight of a color paste of Ferro GmbFI based on the

Glass Ink Powder 14315 and Medium C7 (both Ferro GmbFI) are mixed with Dowanol DPM (9.9 parts by weight) and 6.5 parts by weight of a solution of flydroxylpropylcellulose having a molecular weight of 370000 g / mol in DPM (7.2 parts by weight of polymer in 200 parts by weight DPM). adjusted to a viscosity of about 1000 mPas, measured at 20 ° C and a shear rate of 200 / sec, wherein the concentration of this active substance is about 0.20% by weight.

The viscosity properties are determined by a jump test, wherein initially oscillated for about 9 minutes, the oscillation for about 15 seconds interrupted by a shear rotation at 100 s ¹ and then again for about 4 minutes is oscillated (20 ° C). The tan (delta) G2 / G1 after about 4 minutes about 1, 8.

Exemplary embodiment 1 1

100 parts by weight of a color paste of Ferro GmbFI based on the

Glass powder 14315 and medium C7 (both Ferro GmbFI) are mixed with Dowanol DPM (12.2 parts by weight) and 6.5 parts by weight of a solution of flydroxylpropylcellulose having a molecular weight of 850000 g / mol in DPM (3.6 Parts by weight of polymer in 200 parts by weight DPM) to a viscosity of about 590 mPas, measured at 20 ° C. and a shear rate of 200 / sec, the concentration of this active substance being about 0.10% by weight.

The viscosity properties are determined by a jump test, wherein initially oscillated for about 9 minutes, the oscillation for about 15 seconds interrupted by a shear rotation at 100 s ¹ and then again for about 4 minutes is oscillated (20 ° C). The tan (delta) G2 / G1 after about 4 minutes is about 2.2.

Exemplary embodiment 12

100 parts by weight of a color paste of Ferro GmbH based on the

Glass Ink Powder 14315 and Medium C7 (both Ferro GmbH) are mixed with Dowanol DPM (9.4 parts by weight) and 6.5 parts by weight of a solution of a hydroxylpropyl cellulose having a molecular weight of 850000 g / mol in DPM (3.6 parts by weight polymer in 200 parts by weight DPM). adjusted to a viscosity of about 1020 mPas, measured at 20 ° C and a shear rate of 200 / sec, wherein the concentration of this active substance is about 0.10% by weight.

The viscosity properties are determined by a jump test, wherein initially oscillated for about 9 minutes, the oscillation for about 15 seconds interrupted by a shear rotation at 100 s ¹ and then again for about 4 minutes is oscillated (20 ° C). The tan (delta) G2 / G1 is about 2.0 after about 4 minutes.

Comparative Example 4 Embodiment 10 is essentially repeated except that no hydroxypropyl cellulose having a molecular weight of 370000 g / mol is used, but the viscosity is adjusted merely by adding DPM, the viscosity also being in the range of about 1090 mPas.

The viscosity properties are determined by a jump test, wherein initially oscillated for about 9 minutes, the oscillation for about 15 seconds interrupted by a shear rotation at 100 s ¹ and then again for about 4 minutes is oscillated (20 ° C). The tan (delta) G2 / G1 after about 4 minutes about 3.7.

Comparative Example 5

The Ausführungsbeipiel 1 1 is substantially repeated, but no hydroxypropyl cellulose having a molecular weight of 850000g / mol is used, but the viscosity is adjusted only by the addition of DPM, wherein the viscosity is also in the range of about 660 mPas.

The viscosity properties are determined by a jump test, wherein initially oscillated for about 9 minutes, the oscillation for about 15 seconds interrupted by a shear rotation at 100 s ¹ and then again for about 4 minutes is oscillated (20 ° C). The tan (delta) G2 / G1 after about 4 minutes about 4.5.

Exemplary embodiment 13

100 parts by weight of a color paste of Ferro GmbH based on the

Glass powder 14316 and the medium C7 (both Ferro GmbH) is with Dowanol DPM (8.1 parts by weight) and 8 parts by weight of a solution of a

Hydroxylpropylcellulose having a molecular weight of 370000 g / mol in DPM (7.2 parts by weight of polymer in 200 parts by weight DPM) adjusted to a viscosity of about 990 mPas, measured at 20 ° C and a shear rate of 200 / sec, the concentration of this active substance about 0.25% by weight.

The viscosity properties are determined by a jump test, wherein initially oscillated for about 9 minutes, the oscillation for about 15 seconds interrupted by a shear rotation at 100 s ¹ and then again for about 4 minutes is oscillated (20 ° C). The tan (delta) G2 / G1 after about 4 minutes about 1, 9.

Exemplary embodiment 14

100 parts by weight of a color paste of Ferro GmbH based on the

Glass ink powder 14316 and medium C7 (both Ferro GmbH) is mixed with Dowanol DPM (10.3 parts by weight) and 8 parts by weight of a solution of a hydroxylpropyl cellulose having a molecular weight of 850000 g / mol in DPM (3.6 parts by weight of polymer in 200 parts by weight DPM) Viscosity of about 600 mPas set, measured at 20 ° C and a shear rate of 200 / sec, the concentration of this active substance is about 0.12 wt%.

The viscosity properties are determined by a jump test, wherein initially oscillated for about 9 minutes, the oscillation for about 15 seconds interrupted by a shear rotation at 100 s ¹ and then again for about 4 minutes is oscillated (20 ° C). The tan (delta) G2 / G1 after about 4.3 minutes was about 2.2.

The color paste is transferred to a substrate by means of the previously described printing process and cured. The printed substrate shows only a very small satellite formation. Exemplary embodiment 15

100 parts by weight of a color paste of Ferro GmbH based on the

Glasfarbenpulver 14316 and the medium C7 (both Ferro GmbH) with Dowanol DPM (7.5 parts by weight) and 8 parts by weight of a solution of

Hydroxylpropylcellulose having a molecular weight of 850000 g / mol in DPM (3.6 parts by weight of polymer in 200 parts by weight DPM) adjusted to a viscosity of about 1080 mPas, measured at 20 ° C and a shear rate of 200 / sec, the concentration of this active substance about 0.12% by weight.

The viscosity properties are determined by a jump test, wherein initially oscillated for about 9 minutes, the oscillation for about 15 seconds interrupted by a shear rotation at 100 s ¹ and then again for about 4 minutes is oscillated (20 ° C). The tan (delta) G2 / G1 after about 4 minutes is about 2.1.

Comparative Example 6

Embodiment 13 is substantially repeated except that no hydroxylpropyl cellulose having a molecular weight of 370000 g / mol is used, but the viscosity is adjusted merely by adding DPM, the viscosity also being in the range of about 1100 mPas.

The viscosity properties are determined by a jump test, wherein initially oscillated for about 9 minutes, the oscillation for about 15 seconds interrupted by a shear rotation at 100 s ¹ and then again for about 4 minutes is oscillated (20 ° C). The tan (delta) G2 / G1 after about 4 minutes is about 4.0.

The color paste is transferred to a substrate by means of the previously described printing process and cured. The printed substrate now shows a very clear satellite formation. Comparative Example 7

Embodiment 14 is substantially repeated, but without using hydroxypropyl cellulose having a molecular weight of 850000 g / mol, but adjusting the viscosity merely by adding DPM, the viscosity also being in the range of about 500 mPas.

The viscosity properties are determined by a jump test, wherein initially oscillated for about 9 minutes, the oscillation for about 15 seconds interrupted by a shear rotation at 100 s ¹ and then again for about 4 minutes is oscillated (20 ° C). The tan (delta) G2 / G1 after about 4 minutes is about 5.1.

Exemplary embodiment 16

100 parts by weight of a color paste of Ferro GmbH based on the

Glass powder 14501 and the medium C7 (both Ferro GmbH) with Dowanol DPM (9.5 parts by weight) and 8 parts by weight of a solution

Hydroxylpropylcellulose having a molecular weight of 370000 g / mol in DPM (7.2 parts by weight of polymer in 200 parts by weight of DPM) adjusted to a viscosity of about 1010 mPas, measured at 20 ° C and a shear rate of 200 / sec, the concentration of this active substance about 0.24% by weight.

The viscosity properties are determined by a jump test, wherein initially oscillated for about 9 minutes, the oscillation for about 15 seconds interrupted by a shear rotation at 100 s ¹ and then again for about 4 minutes is oscillated (20 ° C). The tan (delta) G2 / G1 after about 4 minutes about 1, 9. The color paste is transferred to a substrate by means of the previously described printing process and cured. The printed substrate shows only a very small satellite formation.

Exemplary embodiment 17

100 parts by weight of a color paste of Ferro GmbH based on the

Glass powder 14501 and the medium C7 (both Ferro GmbH) with Dowanol DPM (12.1 parts by weight) and 8 parts by weight of a solution of a hydroxylpropyl cellulose having a molecular weight of 370000g / mol in DPM (7.2 parts by weight of polymer in 200 parts by weight of DPM) to a Viscosity of about 640 mPas set, measured at 20 ° C and a shear rate of 200 / sec, the concentration of this active substance is about 0.24% by weight.

The viscosity properties are determined by a jump test, wherein initially oscillated for about 9 minutes, the oscillation for about 15 seconds interrupted by a shear rotation at 100 s ¹ and then again for about 4 minutes is oscillated (20 ° C). The tan (delta) G2 / G1 after about 4 minutes about 1, 5.

Exemplary embodiment 18

100 parts by weight of a color paste of Ferro GmbH based on the

Glasfarbenpulver 14501 and the medium C7 (both Ferro GmbH) with Dowanol DPM (12.5 parts by weight) and 8 parts by weight of a solution of a hydroxylpropyl cellulose having a molecular weight of 850000g / mol in DPM (3.6 parts by weight of polymer in 200 parts by weight of DPM) to a Viscosity of about 540 mPas set, measured at 20 ° C and a shear rate of 200 / sec, the concentration of this active substance is about 0.12 wt%. The viscosity properties are determined by jumping attempt being initially oscillated for about 9 minutes, the oscillation for approximately 15 seconds by a shear rotation at 100 s is interrupted ^1, and then again oscillated for about 4 minutes (20 O). The tan (delta) G2 / G1 after about 4 minutes about 0.4.

Exemplary embodiment 19

100 parts by weight of a color paste of Ferro GmbFI based on the

Glass powder 14501 and the medium C7 (both Ferro GmbFI) with Dowanol DPM (9.4 parts by weight) and 8 parts by weight of a solution

Flydroxylpropylcellulose having a molecular weight of 850000 g / mol in DPM (3.6 parts by weight of polymer in 200 parts by weight of DPM) adjusted to a viscosity of about 1040 mPas, measured at 20 ° C and a shear rate of 200 / sec, the concentration of this active substance about 0.12% by weight.

The viscosity properties are determined by a jump test, in which case oscillation is first carried out for about 9 minutes, the oscillation is interrupted for about 15 seconds by a shear rotation at 100 s ¹ and then oscillated again for about 4 minutes (20 ^° C.). The tan (delta) G2 / G1 after about 4 minutes is about 2.2.

Comparative Example 8

Embodiment 18 is essentially repeated except that no flydroxylpropyl cellulose having a molecular weight of 850000 g / mol is used, but the viscosity is adjusted merely by adding DPM, the viscosity also being in the range of about 480 mPas. The viscosity properties are determined by a jump test, wherein initially oscillated for about 9 minutes, the oscillation for about 15 seconds interrupted by a shear rotation at 100 s ¹ and then again for about 4 minutes is oscillated (20 ° C). The tan (delta) G2 / G1 after about 4 minutes is about 5.9.

Comparative Example 9

Embodiment 19 is substantially repeated except that no hydroxypropyl cellulose having a molecular weight of 850000 g / mol is used, but the viscosity is adjusted merely by adding DPM, the viscosity also being in the range of about 1060 mPas.

The viscosity properties are determined by a jump test, wherein initially oscillated for about 9 minutes, the oscillation for about 15 seconds interrupted by a shear rotation at 100 s ¹ and then again for about 4 minutes is oscillated (20 ° C). The tan (delta) G2 / G1 after about 4 minutes about 5.6.

Exemplary embodiment 20

100 parts by weight of a color paste of Ferro GmbH based on the

Glasfarbenpulver 14510 and the medium C7 (both Ferro GmbH) with Dowanol DPM (10.0 parts by weight) and 5 parts by weight of a solution of a hydroxylpropyl cellulose having a molecular weight of 370000g / mol in DPM (7.2 parts by weight of polymer in 200 parts by weight DPM) to a Viscosity of about 1010 mPas set, measured at 20 ° C and a shear rate of 200 / sec, the concentration of this active substance is about 0.16% by weight.

The viscosity properties are determined by jumping attempt being initially oscillated for about 9 minutes, the oscillation for approximately 15 seconds by a shear rotation at 100 s is interrupted ^1, and then again oscillated for about 4 minutes (20 O). The tan (delta) G2 / G1 after about 4 minutes about 1, 9.

Exemplary embodiment 21

100 parts by weight of a color paste of Ferro GmbFI based on the

Glass powder powder 14510 and the medium C7 (both Ferro GmbH) with Dowanol DPM (12.8 parts by weight) and 5 parts by weight of a solution of a hydroxylpropylcellulose having a molecular weight of 370000g / mol in DPM (7.2 parts by weight of polymer in 200 parts by weight DPM) to a Viscosity of about 580 mPas set, measured at 20 ° C and a shear rate of 200 / sec, the concentration of this active substance is about 0.15% by weight.

Exemplary embodiment 22 100 parts by weight of a color paste of Ferro GmbH based on the

Glasfarbenpulver 14510 and the medium C7 (both Ferro GmbH) with Dowanol DPM (12.5 parts by weight) and 5 parts by weight of a solution of a hydroxylpropyl cellulose having a molecular weight of 850000g / mol in DPM (3.6 parts by weight of polymer in 200 parts by weight of DPM) to a Viscosity of about 600 mPas set, measured at 20 ° C and a shear rate of 200 / sec, the concentration of this active substance is about 0.08% by weight.

Exemplary embodiment 23

100 parts by weight of a color paste of Ferro GmbH based on the

Glasfarbenpulver 14510 and the medium C7 (both Ferro GmbH) with Dowanol DPM (10.0 parts by weight) and 5 parts by weight of a solution of a hydroxylpropyl cellulose having a molecular weight of 850000g / mol in DPM (3.6 parts by weight of polymer in 200 parts by weight DPM) to a Viscosity of about 970 mPas set, measured at 20 ° C and a shear rate of 200 / sec, the concentration of this active substance is about 0.08% by weight.

The viscosity properties are determined by a jump test, wherein initially oscillated for about 9 minutes, the oscillation for about 15 seconds interrupted by a shear rotation at 100 s ¹ and then again for about 4 minutes is oscillated (20 ° C). The tan (delta) G2 / G1 after about 4 minutes is about 2.1. The color paste is transferred to a substrate by means of the previously described printing process and cured. The printed substrate shows only a very small satellite formation.

Comparative Example 10

Embodiment 22 is substantially repeated, except that no hydroxypropyl cellulose having a molecular weight of 850000 g / mol is used, but the viscosity is adjusted merely by adding DPM, the viscosity also being in the range of about 530 mPas.

The viscosity properties are determined by a jump test, wherein initially oscillated for about 9 minutes, the oscillation for about 15 seconds interrupted by a shear rotation at 100 s ¹ and then again for about 4 minutes is oscillated (20 ° C). The tan (delta) G2 / G1 after about 4 minutes about 6.2.

Comparative Example 1 1

Embodiment 23 is essentially repeated, but without using hydroxypropyl cellulose having a molecular weight of 850000 g / mol, but adjusting the viscosity merely by adding DPM, the viscosity also being in the range of about 970 mPas.

The viscosity properties are determined by a jump test, wherein initially oscillated for about 9 minutes, the oscillation for about 15 seconds interrupted by a shear rotation at 100 s ¹ and then again for about 4 minutes is oscillated (20 ° C). The tan (delta) G2 / G1 after about 4 minutes is about 4.0. The color paste is transferred to a substrate by means of the previously described printing process and cured. The printed substrate now shows a very clear satellite formation. Exemplary embodiment 24

100 parts by weight of a color paste of Ferro GmbH based on the

Glasfarbenpulver 14510 and the medium C7 (both Ferro GmbH) with Dowanol DPM (10.0 parts by weight) and 5 parts by weight of a solution of a hydroxylethyl cellulose having a molecular weight of 420000g / mol in DPM (7

Parts by weight of polymer in 100 parts by weight of DPM) to a viscosity of about 1000 mPas, measured at 20 ° C. and a shear rate of 200 / sec.

The examples show that the above-described objects are achieved by the present invention, in particular the satellite formation can be surprisingly significantly reduced without adversely affecting other properties of the printing substance.

Claims

claims

1 . Printing process for the transfer of printing substance from a color carrier to a printing material, in which by means of an energy-emitting device which emits energy during a process time in the form of electromagnetic waves, the printing substance undergoes a change in volume and / or position, characterized in that the printing substance 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, as measured by GPC.

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

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

4. Printing process according to at least one of the preceding claims, characterized in that the printing substance 0.01 to 5 wt .-%, preferably 0.05 to 3 wt .-%, particularly preferably 0.07 to 2 wt .-%, and especially preferably comprises from 0.08 to 1, 5 wt .-% of 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 preferably 0.1 to 2.8, particularly preferably 0.2 to 2.5, especially preferably 0.3 to 2.3, in particular especially preferred 0.05 to 1.3, particularly especially preferred 0.1 to 1.1, in particular particularly prefers 0.2 to 1.0 and very particularly prefers 0.3 to 0.9.

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

7. printing substance for performing a printing method according to any one of the preceding claims, characterized in that the

Printing substance comprises at least one high molecular weight binder, at least one low molecular weight binder and at least one functional carrier.

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 having a viscosity in the range of 250 to 1400 mPas, measured at 20 ° C and a shear 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 blowing agent, 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, especially preferably in the range of O'C to 190 ° C.

1 1. printing substance according to one of the preceding claims 7 to 10,

characterized in that the low molecular weight binder a

Weight average molecular weight (Mw) in the range of 10000 to 150000 g / mol, preferably in the range of 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 1 1,

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 of 0.5 pm to 30 pm, more preferably in the range of 1 pm to 20 pm and especially preferably in the range from 2 pm to 15 pm.

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 wt .-%, preferably at least 50 wt .-% and particularly preferably at least 60 wt .-%.

15. Use of a printing substance according to one of the preceding

Claims 7 to 14, characterized in that the printing substance is applied to glass, ceramic, metal, wood or plastic.