EP3426735A1 - Method for producing an ink, ink, and use of same - Google Patents
Method for producing an ink, ink, and use of sameInfo
- Publication number
- EP3426735A1 EP3426735A1 EP17709899.3A EP17709899A EP3426735A1 EP 3426735 A1 EP3426735 A1 EP 3426735A1 EP 17709899 A EP17709899 A EP 17709899A EP 3426735 A1 EP3426735 A1 EP 3426735A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- nanoparticles
- ink
- stabilizer
- molecules
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/322—Pigment inks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/36—Inkjet printing inks based on non-aqueous solvents
Definitions
- the invention relates to a process for the preparation of an ink, an ink and the use thereof.
- nanoparticles in particular pigments for inks
- surface modification in order to prevent the aggregation and flocculation of the nanoparticles in the ink.
- stabilization is also used for functional inks based on metallic nanoparticles.
- Stabilized nanoparticles can, for. Synthesis of thiol-derivatised gold nanoparticles in a two-phase liquid-liquid system, for example, from gold chloride (AuCl 3 ) via the breast-Schifffrin synthesis in a two-phase system (Brust et al. CHEM.SOC, CHEM.Commun., 1994. p.801). The process yields stabilized gold particles of about 1-3 nm size. Dodecanethiol was used as the stabilizer molecule.
- DE 10 2012 021 222 A1 discloses an ink-jet printing method in which a nanoporous layer is produced by subsequent sintering of a plurality of nanoparticle types.
- Nanoparticles for inks are usually incorporated in chemically synthesized solvents and additives. These are usually very toxic and therefore incompatible with some production processes. For example, these are not suitable for food packaging.
- Another disadvantage is the high melting temperature of the nanoparticles or sintering temperature of the inks based thereon.
- the object of the invention is to provide a process for producing an electrically conductive or semiconductive ink, paste or paint with a sintering temperature which is as low as possible, which differs greatly from one material to another, but preferably less than 200 ° C.
- Another object of the invention is to provide a corresponding low sintering temperature ink, preferably having a sintering temperature lower than 200 ° C, which does not have the disadvantages of the prior art.
- Another object of the invention is to provide a use of this ink.
- the process for producing the ink is characterized by the steps: a) nanoparticles having a size of from 0.1 to a maximum of 20 nm, in particular from 0.5 to a maximum of 5 nm, are provided;
- the nanoparticles can be prepared either with a "bottom up” or “top down”method;
- b) short-chain, branched organic stabilizer molecules are covalently bound to the surface of the nanoparticles by a coupling reaction.
- stabilizer molecules one or more types of molecules may be used sequentially or simultaneously.
- the term “short chain” refers to stabilizer molecules having a backbone of 2 to 30 carbon atoms, c) the stabilized nanoparticles are taken up and dispersed in a solvent to make the ink.
- the provided nanoparticles preferably comprise cores of metals or transition metals such. From Au, Pt, Ag, Pd, Cu, Cr, Ni, Sc, Ti, V, Mn, Fe, Zn, Y, Zr, Nb, Tc, Ru, Mo, Rh, W, Co, Cd, Hf , Ta, Re, Os, Al, Sn, In, Ga, Ir and others, their oxides and salts, and alloys of two or more of the aforementioned materials as well as non-alloyed combinations, such as. As mixtures of two or more of these materials. In particular, pure metals can be used as material for nanoparticles.
- step a) it is proposed to couple the nanoparticles provided in step a) with branched, short-chain, organic molecules to stabilize the nanoparticles (step b)) and then to convert them into a conductive or semiconducting ink by dispersion in solution (step c)).
- step b) branched, short-chain, organic molecules
- step c) it is proposed to couple the nanoparticles provided in step a) with branched, short-chain, organic molecules to stabilize the nanoparticles (step b)) and then to convert them into a conductive or semiconducting ink by dispersion in solution (step c)).
- the method according to the invention can provide nanoparticles of metals and transition metals, their oxides or salts and alloys of two or more of the abovementioned materials, and non-alloyed combinations thereof (mixtures).
- the nanoparticles are provided by a1) House-Schiffrin synthesis and / or a2) by dry or wet grinding with a solvent.
- the solvent in step a2) may already comprise the stabilizer molecule and / or further solvents which are necessary for the construction of the stabilization shell. This has far-reaching benefits. Thus, it has been recognized within the scope of the invention that in the above-described "bottom up" method according to House-Schiffrin for the production of nanoparticles disadvantageously large amounts of solvents and waste are produced, which are caused by the chemical reaction of the reactants.
- step a2) at least one "top-down" process for the production of nanoparticles is advantageously proposed.
- metallic nanoparticles of pure bulk metals such as Au, Pt, Ag, Pd, Cu, Cr, Ni, Sc, Ti, V, Mn, Fe, Zn, Y, Zr, Nb, Tc , Ru, Mo, Rh, W, Co, Cd, Hf, Ta, Re, Os, Al, Sn, In, Ga, Ir and others, their oxides and salts, and Alloys of two or more previously mentioned materials and non-alloyed combinations, such as.
- Both the dry and the wet grinding processes, as well as the other processes mentioned here have the advantage that the resources are gentler and cheaper than the House-Schiffrin synthesis.
- the coupling reaction according to step b) may optionally be carried out by adding a dissolved stabilizer molecule, optionally in a further solvent, during a wet milling according to step a2).
- This further solvent is used in the construction of the stabilizing shell as a lubricant and / or at the same time as a coolant during milling.
- wet grinding as a top-down process advantageously saves time and costs and leads to cleaner products.
- stabilized nanoparticles of pure metal it is readily possible for stabilized nanoparticles of pure metal to be provided in a single step which simultaneously comprises steps a) and b) of the process.
- the nanoparticles can thus be synthesized in the context of the invention with a known "bottom-up” method, for.
- a known “bottom-up” method for.
- the breast-Schiffrin synthesis and / or with a “top down” method.
- a “top down” method can z.
- the known laser ablation can also be used in the liquid and / or wet or dry grinding.
- a mill As a ball mill (ball mill) or planetary mill (planetary mill) proposed in the bulk material, for. As gold, used and ground into particles in the nanometer range. In such a mill, the material with hard balls, the z. B. zirconium oxide, crushed.
- the grinding process in the mill achieves high speeds or energies, which allow the hard spheres to break down the material into nanoparticles.
- the grinding process may involve either one or more steps and, as mentioned, either dry and / or wet. For example, only large gold granules with larger spheres (mm size) can be ground into small microparticles by dry grinding. Subsequently, the microparticles are milled into nanoparticles by a wet milling process with smaller spheres (pm size). Other variants and sequences of milling processes are just as possible.
- suitable stabilizer molecules and solvents are used in the wet milling process advantageous, which also serve as a lubricant or coolant.
- Other additives can be used.
- stabilizer molecules either those described above or others may be used.
- At least one milling step it may be necessary to use stable and chemically inert molecules as stabilizer molecules, because the high energies during the milling process can cause less stable molecules to undergo chemical changes.
- a first stabilizing sheath according to step b1) can then be exchanged for a second stabilizing sheath in a further step b2).
- This can be done using SAM (English: Self-Assembled Monolayer) principles, eg. B. so-called exchange reactions ("Hgand exchange" reactions).
- SAM Simple: Self-Assembled Monolayer
- B. so-called exchange reactions
- the manufactured nanoparticles are converted into a solution which contains the desired and above-mentioned second stabilizer molecules from one or more types of stabilizer molecules. These replace after a certain time the original stabilizer molecules in the shell.
- These "new” stabilizer molecules preferably have a stronger bond, that is a higher binding energy to the nanoparticles than the "old, first", so that the exchange reaction is complete.
- This can be z. B. be achieved in that the "new, second" stabilizer molecules covalently bind to the particles according to the invention, while the "old, first" stabilizer molecules are not covalently bound.
- a milling process has further advantages in contrast to chemical synthesis ("bot tom up”, eg, breast-Schifffrin synthesis):
- the starting material / raw material can then be very pure (eg gold
- nanoparticles are synthesized in “bottom-up” syntheses.
- purer nanoparticles are synthesized.
- Nanoparticles according to the invention are therefore more favorable than those of metal salts.
- the stabilizer molecules can be added to build up the stabilization shell.
- step c This serves the further cost reduction and environmentally friendly nanoparticle production, in particular if such environmentally friendly solvents are used in step c).
- the choice of a branched organic molecule as a stabilizer molecule for step b) is of great importance for the process.
- the stabilizer molecule should have a C 2 to a maximum of C 30 content.
- a stabilizer molecule are in particular, but not exclusively, 2-methyl-1-butanethiol or 3-methyl-2-butanethiol in question.
- Suitable stabilizer molecules are in particular molecules having the following chemical groups: alkyl, aryl, benzyl, alicyclic, heterocyclic and so on. At least one stabilizer molecule for step b) is used to covalently bond it to the surface of the nanoparticles.
- a main point in the subsequent suspension of nanoparticles in the ink according to step c) is thus the type of stabilization in the suspension according to step b).
- This stabilization is achieved by the stabilizer molecules.
- organic molecules in particular self-assembled monolayers (SAMs), polymers, surfactants and other materials.
- the stabilizer molecules form the shell around the nanoparticle cores. It has been recognized that the stabilization shell essentially determines the properties of the small (1-20 nm) nanoparticles, including their solubility in different solvents and the sintering temperature. That is why the selection and design of the right stabilization cover is essential.
- a monolayer of the stabilizer molecules is arranged around the nanoparticles by covalent bonding as a stabilization shell.
- the thickness of the stabilization shell should correspond to a maximum of 0.1-10 times the radius of the nanoparticles and is limited by the length of the individual stabilizer molecules. When using several stabilizer molecules in step b), the thickness of the monolayer also corresponds to the length of the longest stabilizer molecule.
- the coupling reaction after step b) and the size of the nanoparticles during the Method according to steps a) and / or b) can be checked in a suitable manner, for. By imaging or light scattering techniques.
- the thickness of the stabilization shell should be 0.1 to 10 times the nanoparticle radius, that is about 0.1 to 10 nm, and particularly advantageously, 0.5 to 5 nm.
- the thickness of the monolayer stabilization shell is in any case by the length of the individual or of the longest stabilizer molecule.
- the shell is molded either in situ directly during the synthesis, e.g. It is formed after the nanoparticle production on the surface of already existing nanoparticles, for example, by the breast-shiffrin method ("bottom-up") or in a particularly advantageous embodiment of the invention during a "top-down” process Production of the nanoparticles at the same time during comminution in the wet grinding process are arranged on the nanoparticle core.
- sheath or stabilizer molecules only short-chain, that is up to 30 carbon atoms (C30) containing molecules should be used.
- Branched organic molecules can also be arranged in situ during the "top down” process or after the synthesis on the nanoparticles.
- short linear molecules or very long polymers are used as stabilizers in the state of the art because they form a very dense and gap-free shell around the nanoparticle.
- the use of branched molecules according to the invention as stabilizer molecule is more advantageous, especially if they are substrates for food technology.
- Inks according to the invention are therefore particularly suitable and usable for the production of repackings in food technology.
- branched stabilizer molecules form by mutual steric hindrance, a relatively leaky shell with many gaps around the small nanoparticle core.
- This advantageously has the effect that the total number of stabilizer molecules per area is lower due to the steric hindrance than with linear stabilizer molecules.
- This effect is used according to the invention to provide inks with low sintering temperature.
- the short chain length (up to C30) advantageously ensures that the sintering temperature remains low and that the stabilizer molecules sublime at the sintering temperature of the nanoparticles or below and transition into the gas phase. In fact, in the finished product, especially the printed circuit, the stabilizer molecules are undesirable.
- At least one sort of stabilizer molecule should covalently bind to the nanoparticle cores.
- the stabilizer molecules R can be composed, inter alia, of alkyl, aryl,
- Benzyl, alicyclic and / or heterocyclic residues exist. These can be saturated or unsaturated, that is, with carbon double bonds (sp 2 - hybridization) or only carbon monoitatien (sp 3 hybridization) are present. Particularly advantageous are the branched radicals R.
- the head groups, the so-called alpha position of the stabilizer molecule R, z. B. from thiol or amine groups are formed.
- the end group, the so-called omega position of the stabilizer molecule can be selected from e.g. For example, carboxyl, alkyl, ester, thioether, ether, amine, hydroxyamine, amide groups and so on formed to ensure solubility in a wide range of solvents.
- the shell of stabilizer molecules has a great influence on the sintering temperature of the nanoparticles, and only if the nanoparticles (without shell) are particularly small, ie a radius, in particular of at most 20 nm, preferably of at most 10 nm , particularly preferably not more than 9, 8, 7, 6, 5, 4, 3, 2, 1 nm.
- the nanoparticle diameter or intrinsic properties of the material have a greater influence on the sintering temperature. Therefore, the thickness of the stabilizing shell should be 0.1 to 10 times the nanoparticle radius, that is 0.1 to 10 nm, and most preferably 0.5 to 5 nm thick.
- the thickness of the monolayer stabilization shell is, as mentioned, limited by the length of the individual or the longest stabilizer molecule used.
- nanoparticles with a particularly low sintering temperature
- the stabilization shell plays a very important role in the melting temperature or at the sintering temperature.
- Such particles can also be synthesized either in a “bottom-up” synthesis and / or be obtained by a “top down” method. At least one of the types of nanoparticles used in the final ink may follow this condition.
- the stabilized nanoparticles produced by the process after steps a) -b) are finally taken up again, in particular after a washing step and optionally filtering step and optionally drying step in a solvent as the basis for the ink according to step c). Both steps a) -b), if appropriate with washing step and / or filtering step and / or drying step and in particular steps a) -c), thus already solve the object of the invention.
- the liquid phase has a mass fraction of 30-95% in the ink.
- step c) Addition of the nanoparticles after step b) with a mass fraction of 5 to 70% in the solvent or the solvent mixture. 4. Mixing and dispersing the nanoparticles in the solvent to prepare the suspension or ink according to step c).
- the suspension or ink may be filtered before or after step c), e.g. B. with a filter with z. B. 0.8 ⁇ pore size.
- the suspension or ink may be added before or after step c) further additives. Dispersants, binders, humectants, adhesives and so on may be added to the ink of the present invention.
- the mass fraction of nanoparticles is preferably from 5 to 70%, especially 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39 and 40% respectively. Paints and pastes for other printing or landfill methods can have either greater or lesser parts by weight.
- the ready-made ink has environmentally friendly and food-compatible constituents, such as solvents and additives, preferably components which are not subject to labeling.
- terpene-based solvents or additives can be used. It may be both such terpene-based solvents such as a-terpineol, limonene, carvacrol, linalool, P-Cymene and so on, as well as mixtures thereof, as well as based thereon additives such as adhesion additives of natural resins, eg. B. Detrophene from DRT, France.
- the solvents according to step c) and, where appropriate, the additives should, above all, be chemically compatible with the end groups (omega) of the stabilizer molecules, ie the omega groups and the solvents should be readily miscible, so that higher nanoparticle concentrations on the Nanoparticles in the ink can achieve. It is possible to use both individual solvents and additives, as well as combinations of several.
- the solvent or solvent mixture should also evaporate after printing for a maximum of 30 minutes at 200 ° C, so that the printed structures can be properly sintered.
- the inventive method and the selection of small nanoparticles is advantageously causes an ink with nanoparticles with low sintering temperature, less than 200 ° C, or less than 160 ° C and more preferably less than 120 ° C is provided. This is particularly suitable for use in printed electronics on inexpensive polymer and paper substrates.
- the ink of the invention can be printed, e.g. with an inkjet printer, such as. Eg Dimatix DMP 2700.
- the ink thus preferably has nanoparticles of metals and / or transition metals. It can also consist of their oxides or salts.
- the ink may comprise a combination of two or more of these materials. Several such materials may also be present in a single type of particle as so-called Janus particles (alloy) or in a heterogeneous mixture of several materials.
- nanoparticles having the properties mentioned, of different materials eg. As Au and Ag as well as two or more types of nanoparticles of different sizes and / or shapes can be used.
- two types of nanoparticles can be used. Some have, for example, a radius of 1 nm and the others, for example, a radius of 20 nm, which thus differ at least in the sintering temperature.
- Conditions in the ink may be different for. B. 10 to 1, that is 10 parts of the smaller, here the 1 nm nanoparticles, and 1 part of the larger, here the 20 nm large, nanoparticles.
- the sintering temperature of the layer will still be very close to the sintering temperature of the smaller, here the 1 nm, gold nanoparticles.
- an advantage of such a mixture is that the larger nanoparticles have a greater weight of material per particle.
- the same or a greater weight concentration (wt%) with the same or a smaller particle concentration (mol / L, M) can be achieved by the larger nanoparticles.
- the smaller surface-to-volume ratio of larger nanoparticles requires fewer solvent molecules per atom or nanoparticle.
- Lower concentration suspensions are usually more stable (longer shelf life) and less sensitive (wider range of solvents). This effect allows a high loading of active material in the ink.
- Particle types A and B may be used in particular of gold and / or platinum nanoparticles or one of the other materials mentioned.
- step c) at least two types of particles A and B may be used in the solvent, in which the difference in the melting point S mA and S m e is due to the different chemical composition of the materials of the particles A and B.
- the difference in the melting point S mA and S m e is due to the different chemical composition of the materials of the particles A and B.
- gold and platinum nanoparticles could be used.
- step c) at least two types of particles A and B in the solvent (mixture) can be used, in which the difference in the melting point S mA and S mB is due to the different size of the particles of A and B.
- two gold nanoparticles of appropriate size could be used.
- step c) at least two types of particles A and B in the solvent (mixture) can be used, in which the difference in the melting point S mA and S m is due to the different shape of the particles of A and B.
- gold or platinum nanoparticles could be used which have a spherical shape or a rod shape.
- At least two types of particles A and B may be used in the solvent (mixture), which are adjusted in a weight ratio of A: B of 1: 1 to 1,000,000: 1 wt / wt to each other in the solvent for the ink.
- A: B 1: 1 to 1,000,000: 1 wt / wt to each other in the solvent for the ink.
- 1 part of smaller A and 10 parts of a larger nanoparticle B could be used.
- step c) at least two types of particles A and B can be used or selected in the solvent (mixture) in which the difference in melting point S mA and S mB is at least 1 K.
- a mixture of two types of stabilized nanoparticles advantageously results in a higher proportion by weight of the ink being achieved by larger nanoparticles, while small nanoparticles have a lower sintering temperature.
- the manufacturing costs of nanomaterials and inks through the top-down process are advantageously low.
- all nanoparticles, both large and small, are made by the top-down process to further reduce costs.
- the ink can be placed and sintered on the substrate by various printing methods, particularly ink jet printing, aerosol jet, screen printing, gravure printing, offset printing, flexography and so on.
- stabilized nanoparticles according to the invention have the desired low thermal stability.
- the nanoparticles stabilized with branched thiols or amines have weak binding energies to the core of the nanoparticles.
- This advantageously has the effect that the stabilizer molecules transgress from the surface into the gas phase during the sintering and the core of the nanoparticles is sintered on the substrate.
- stabilizer molecules one or more types of molecules can be used simultaneously. The combination of several types of stabilizer molecules allows the different advantages of the individual molecules such. B. to combine their solubility and melting point with each other. This particularly advantageously allows the use of the ink for producing printed circuits.
- the following materials are used as substrate: a wide variety of natural and artificial, partially biodegradable polymers such. Polyethylene (PE, HDPE - high density PE, LDPE - low density PE), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide (e.g., Kapton), polyamide, polypropylene, polylactate and so on coated and coated paper, Glass, metal, ceramics, fabric, and so on. The thickness usually ranges from one micron to several hundred microns. It can also have a few millimeters or centimeters.
- the substrates can be completely flat, curved or curved.
- the method advantageously results in that the sintering temperature of the prepared ink or the melting temperatures of the solution-dispersed nanoparticles and the sublimation energies in the stabilizing sheaths are relatively low compared to larger particles with unbranched stabilizing sheaths according to the prior art.
- Such high temperatures do not allow the ink to be used on inexpensive polymer substrates as they are normally only suitable for temperatures of ⁇ 200 ° C.
- sintering temperature refers to a temperature at which the printed ink is heated to melt-bond the individual nanoparticles together to form a bonded homogeneous layer
- the sintering temperature should also preferably be below or at the glass transition temperature of the substrate in order not to deform it during sintering.
- the ink can thus be printed in particular on a substrate and sintered at a correspondingly low temperature, less than 200 ° C., optionally also less than 160 ° C. and particularly advantageously less than 120 ° C., depending on the ink composition.
- a polymer or paper substrate can be printed and sintered.
- temperatures of less than 200 ° C can be set.
- Printed with an ink according to the invention and sintered at less than 200 ° C structures relate in particular, but not exclusively, electronic device as a device.
- a use of ink according to the invention thus consists in the Production of printed electronics on favorable polymer or paper substrates with a working temperature of less than 200 ° C, especially for outer packaging in the food industry.
- the printed layer should show good conductivity, that is, a conductivity as close as possible to the bulk material (eg smaller by a factor of ten). If semiconductive, the layer printed from the ink for the semiconductor should have good specific properties, e.g. Carrier mobility, that is, a charge-carrier mobility that is as close as possible to the bulk material (eg smaller by a factor of ten).
- Carrier mobility that is, a charge-carrier mobility that is as close as possible to the bulk material (eg smaller by a factor of ten).
- Both types of particles are equipped with a stabilization shell of branched 2-methyl-1-butanethiol molecules.
- the mixture of two types of nanoparticles provides a higher gold weight fraction in the ink through the larger nanoparticles, while small nanoparticles have a lower sintering temperature.
- the shell of branched thiol molecules advantageously causes a particularly low sintering temperature, especially in the case of the small nanoparticles.
- Natural, terpene-based solvents in step c) are used for the ink.
- the ink can be used as a conductive ink for a variety of purposes, e.g. be used as a non-oxidizing conductor, as a temperature sensor and electrode for electrochemical sensors, etc.
- TOAB tetraoctylammonium bromide
- the organic phase is washed first with a 1 M saline solution and then with deionized water.
- the organic phase is completely removed in the rotary evaporator.
- 100 ml of ethanol are added.
- the stabilized nanoparticles aggregate and are washed three times with ethanol on a ceramic filter. Thereafter, they are dried in a vacuum oven and stored as a powder (steps a) and b)).
- the mixture is applied on a coarse filter (pores should be ner than the diameter of the grinding balls) with a solvent in which the nanoparticles dissolve well, such as carvacrol, washed.
- a solvent in which the nanoparticles dissolve well such as carvacrol
- the nanoparticles pass through the filter.
- the nanoparticles are washed over a ceramic filter with very high porosity (porosity P 1, 6 and P 16 according to ISO 4793) with a solvent in which they do not dissolve well, such as ethanol, so that they aggregate and remain on the filter surface , Thereafter, the nanoparticles are dried in a vacuum oven and stored as a powder (steps a) and b)).
- a solvent mixture of carvacrol (5 g) and limonene (5 g) is weighed and mixed together to prepare the solvent according to step c).
- the nanoparticles of 1a (0.5 g) and 1b (2 g) are weighed and mixed and transferred to the solvent for step c).
- the dispersion is mixed.
- vortex mixers for this you can use vortex mixers, ultrasonic devices, ball mills or a similar method with high shear forces.
- the dispersion is filtered with a 0.8 micron filter to remove as large as possible undissolved large particles and to avoid the blocking of the printhead nozzles.
- This dispersion / ink can then be used, e.g. For example, it can be printed with an inkjet printer (eg Dimatix DMP 2700).
- the sintering temperature after the pressure is about 120 ° C.
- nanoparticles having a size of from 0.1 to a maximum of 20 nm, in particular from 0.5 to a maximum of 5 nm, are provided;
- Short-chain, branched organic stabilizer molecules are covalently bound to the surface of the nanoparticles by a coupling reaction.
- stabilizer molecules one or more types of molecules can be used simultaneously.
- the term "short-chain” denotes stabilizing molecules with a skeleton of 2 to 30 carbon atoms, optionally washing step and / or drying of the stabilized nanoparticles.
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102016002890.4A DE102016002890A1 (en) | 2016-03-09 | 2016-03-09 | Process for the preparation of an ink, ink and their use |
PCT/DE2017/000038 WO2017152892A1 (en) | 2016-03-09 | 2017-02-17 | Method for producing an ink, ink, and use of same |
Publications (1)
Publication Number | Publication Date |
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EP3426735A1 true EP3426735A1 (en) | 2019-01-16 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP17709899.3A Withdrawn EP3426735A1 (en) | 2016-03-09 | 2017-02-17 | Method for producing an ink, ink, and use of same |
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EP (1) | EP3426735A1 (en) |
JP (1) | JP2019512558A (en) |
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CN (1) | CN108779354A (en) |
DE (1) | DE102016002890A1 (en) |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US10694872B2 (en) | 2018-09-19 | 2020-06-30 | Sensormatic Electronics, LLC | Point of sale artificial intelligence quality determination system |
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US11311941B2 (en) * | 2019-04-01 | 2022-04-26 | General Electric Company | Fabrication of palladium-chromium alloy microparticles |
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GB0006050D0 (en) | 2000-03-14 | 2000-05-03 | Johnson Matthey Plc | Liquid gold compositions |
AU5967101A (en) * | 2000-05-10 | 2001-11-20 | Rtp Pharma Inc | Media milling |
IL161622A0 (en) | 2001-11-01 | 2004-09-27 | Yissum Res Dev Co | Ink jet inks containing metal nanoparticles |
AU2002360517A1 (en) * | 2001-12-07 | 2003-06-23 | Ximed Group Plc | Respiratory infection prevention and treatment with terpene-containing compositions |
US6923923B2 (en) * | 2001-12-29 | 2005-08-02 | Samsung Electronics Co., Ltd. | Metallic nanoparticle cluster ink and method for forming metal pattern using the same |
JP4642779B2 (en) | 2004-12-03 | 2011-03-02 | 独立行政法人科学技術振興機構 | Stabilized inorganic nanoparticles, stabilized inorganic nanoparticles, method for producing stabilized inorganic nanoparticles, and method for using stabilized inorganic nanoparticles |
DE602006013100D1 (en) | 2005-01-10 | 2010-05-06 | Yissum Res Dev Co | WATER-BASED DISPERSIONS OF METAL NANOPARTICLES |
US20060254387A1 (en) * | 2005-05-10 | 2006-11-16 | Samsung Electro-Mechanics Co., Ltd. | Metal nano particle and method for manufacturing them and conductive ink |
JP4434094B2 (en) | 2005-07-06 | 2010-03-17 | ソニー株式会社 | Tag information generation apparatus, tag information generation method and program |
US20070144305A1 (en) * | 2005-12-20 | 2007-06-28 | Jablonski Gregory A | Synthesis of Metallic Nanoparticle Dispersions |
US7727901B2 (en) * | 2007-05-03 | 2010-06-01 | Innovalight, Inc. | Preparation of group IV semiconductor nanoparticle materials and dispersions thereof |
WO2009052120A1 (en) | 2007-10-15 | 2009-04-23 | Nanoink, Inc. | Lithography of nanoparticle based inks |
CN102131602A (en) * | 2008-06-23 | 2011-07-20 | 耶路撒冷希伯来大学伊森姆研究发展有限公司 | Core-shell metallic nanoparticles, methods of production thereof, and ink compositions containing same |
US8017044B2 (en) * | 2008-07-08 | 2011-09-13 | Xerox Corporation | Bimodal metal nanoparticle ink and applications therefor |
US9005484B2 (en) * | 2009-03-31 | 2015-04-14 | Xerox Corporation | Low polarity nano silver gels |
US8324294B2 (en) * | 2011-03-07 | 2012-12-04 | Xerox Corporation | Solvent-based inks comprising silver nanoparticles |
US8586134B2 (en) * | 2011-05-06 | 2013-11-19 | Xerox Corporation | Method of fabricating high-resolution features |
JP6360039B2 (en) * | 2012-05-03 | 2018-07-18 | カラ ファーマシューティカルズ インコーポレイテッド | Composition comprising a plurality of coated particles, pharmaceutical composition, pharmaceutical formulation and method of forming the particles |
DE102012021222B4 (en) | 2012-10-27 | 2015-02-05 | Forschungszentrum Jülich GmbH | Process for producing a nanoporous layer on a substrate |
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2017
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US10694872B2 (en) | 2018-09-19 | 2020-06-30 | Sensormatic Electronics, LLC | Point of sale artificial intelligence quality determination system |
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CN108779354A (en) | 2018-11-09 |
KR20180130489A (en) | 2018-12-07 |
US20190040273A1 (en) | 2019-02-07 |
WO2017152892A1 (en) | 2017-09-14 |
JP2019512558A (en) | 2019-05-16 |
US10557051B2 (en) | 2020-02-11 |
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