Classifications

• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
  • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
  • B22F1/107—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing organic material comprising solvents, e.g. for slip casting
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F9/00—Making metallic powder or suspensions thereof
  • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
  • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
  • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
• • 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
• • 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
  • C09D11/322—Pigment 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
  • C09D11/30—Inkjet printing inks
  • C09D11/36—Inkjet printing inks based on non-aqueous solvents
• • 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
  • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
  • H05K1/092—Dispersed materials, e.g. conductive pastes or inks
  • H05K1/097—Inks comprising nanoparticles and specially adapted for being sintered at low temperature
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
  • B22F1/05—Metallic powder characterised by the size or surface area of the particles
  • B22F1/052—Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
  • B22F1/05—Metallic powder characterised by the size or surface area of the particles
  • B22F1/054—Nanosized particles
  • B22F1/0545—Dispersions or suspensions of nanosized particles
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/08—Metals
  • C08K2003/0806—Silver
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
  • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
  • H05K2201/0203—Fillers and particles
  • H05K2201/0242—Shape of an individual particle
  • H05K2201/0257—Nanoparticles
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
  • H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
  • H05K3/1241—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by ink-jet printing or drawing by dispensing
  • H05K3/125—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by ink-jet printing or drawing by dispensing by ink-jet printing

Definitions

• the present invention relates to ink formulations based on silver nanoparticles and more particularly to ink formulations based on dispersions of silver nanoparticles.
• the present invention relates to stable inks and high concentration of silver nanoparticles.
• the present invention relates to ink formulations based on silver nanoparticles, said inks being characterized by a set of improved properties, among which we will mention by way of illustration:
• the present invention relates to the field of conductive nanoparticle-based inks suitable for many printing methods.
• printing methods inkjet, spray, screen printing, gravure printing, flexography, doctor blade, spin coating, and slot die coating; the inkjet application being particularly suitable for the type of ink claimed.
• the inks based on conductive nanoparticles according to the present invention can be printed on all types of supports. Examples include the following: polymers and polymer derivatives, composite materials, organic materials, inorganic materials. Inks based on conductive nanoparticles according to the present invention have numerous advantages, among which we will mention as non-limiting examples:
• the present invention also relates to a method of improved preparation of said inks; Finally, the present invention also relates to the use of said inks in the fields of printed electronics (for example RFID (Radio Frequency Identification) supports), photovoltaics, OLEDs (organic light-emitting diode), sensors (eg gas sensors), touch panels, biosensors, and contactless technologies.
• printed electronics for example RFID (Radio Frequency Identification) supports
• OLEDs organic light-emitting diode
• sensors eg gas sensors
• touch panels eg gas sensors
• biosensors e.g., biosensors, and contactless technologies.
• nanoparticles have a very important surface / volume ratio and the substitution of their surface by surfactants leads to the change of certain properties, in particular optical properties, and the possibility of dispersing them.
• Nanoparticles are compounds of which at least one of their dimension is less than 100 nm. They can have different shapes:
• rods L ⁇ 200 to 300 nm
• wires a few hundred nanometers even a few microns
• discs stars, pyramids, tetrapods, cubes or crystals when they have no predefined shape.
• Vapor Deposition - CVD when a substrate is exposed to volatilized chemical precursors that react or decompose on its surface. This process generally leads to the formation of nanoparticles whose morphology depends on the conditions used;
• the laser pulse in solution when a solution containing a precursor is irradiated with laser beam.
• the nanoparticles form in the solution along the light beam;
• Physical syntheses consume more raw materials with significant losses. They generally require time and high temperatures which make them unattractive for the transition to production on an industrial scale. This makes them unsuitable for certain substrates, for example flexible substrates. Moreover, the syntheses are carried out directly on the substrates in frames with reduced dimensions. These production methods are relatively rigid and do not produce on large substrates.
• ligands prevent risks of aggregation and sedimentation. They offer a second advantage by also impacting the properties of the ink formulated based on these conductive nanoparticles. It is thus possible to adjust the nature of the ligands according to the intended application. In the context of biomedical application, it is thus preferred ligands such as peptides that increase the biocompatibility of nanoparticles in the biological medium. In the case of the printed electronics industry, this paves the way for the use of substrates of different sizes and types. Finally, these synthetic methods make it possible to produce stable quantities of nanoparticles in a relatively short time. All these points emphasize the strengths and flexibility of chemical synthesis routes to consider nanoparticle production on an industrial scale.
• the present invention aims to overcome one or more disadvantages of the prior art by providing a dispersion-based ink of stable and high concentration of silver nanoparticles, said inks having significant improvements in the field of their disposability and / or their homogeneity and / or conductivity as well as reduced volatility. According to an embodiment of the present invention, this objective is achieved thanks to an ink based on silver nanoparticles whose composition comprises
• the compound "X" is a cyclooctane solvent
• terpene alcohol and aliphatic monohydric alcohol or a mixture of terpene alcohol and glycol and / or glycol ether, or a mixture of terpene alcohol and aliphatic monohydric alcohol and glycol and / or glycol ether.
• the Applicant has unexpectedly discovered that the specific combination of the ink components according to the present invention made it possible to obtain inks based on dispersions of silver nanoparticles in high concentrations and with improved stability.
• the viscosity of the ink according to the present invention is preferably between 1 and 10,000 mPa.s, more preferably between 1 and 1000 mPa.s, for example between 2 and 20 mPa.s.
• the compound "a” according to the present invention therefore consists of silver nanoparticles.
• the objectives of the present invention are particularly well achieved when the compound "a" consists of silver nanoparticles whose dimensions are between 1 and 50 nm, preferably between 2 and 20 ⁇ m. nm.
• the size of the nanoparticles is defined as the average diameter of the silver-containing particles, excluding stabilizers, as determined for example by transmission electron microscopy.
• the silver nanoparticles are of spheroidal and / or spherical shape.
• spheroidal means that the shape resembles that of a sphere but is not perfectly round (“quasi-spherical"), for example an ellipsoidal shape.
• the shape of the nanoparticles is usually identified by means of microscopic photographs.
• the nanoparticles have diameters of between 1 and 50 nm, preferably between 2 and 20 nm.
• the silver nanoparticles were previously synthesized by chemical synthesis. Any chemical synthesis may be preferentially used in the context of the present invention.
• the silver nanoparticles are obtained by a chemical synthesis which uses as silver precursor an organic or inorganic silver salt.
• an organic or inorganic silver salt By way of non-limiting example, mention may be made of silver acetate, silver nitrate, silver carbonate, silver phosphate, silver trifluorate, silver chloride, sodium perchlorate and the like. money, alone or in combination.
• the precursor is silver acetate.
• the silver nanoparticles are thus synthesized by chemical synthesis, by reducing the silver precursor by means of a reducing agent in the presence of the dispersing agent referred to as the "c" compound.
• this reduction can be carried out in the absence or in the presence of a solvent (hereinafter also referred to as the "synthesis solvent").
• the dispersing agent generally acts both as a dispersing agent and as a solvent for the silver precursor; a particular example of synthesis of nanoparticles in a medium without solvent and preparation of the dispersion according to the present invention is described by way of illustration below.
• the synthetic dispersing agent compound “c", for example dodecylamine
• compound “c" for example dodecylamine
• the hydrazine reducing agent is then rapidly added to the mixture and the mixture is left stirring for about 60 minutes.
• the mixture is treated by the addition of methanol (or any other suitable solvent, for example another monohydric alcohol having 2 to 3 carbon atoms, for example ethanol) and the supernatant is removed during several washes successive (silver nanoparticles thus formed remain in the state of dispersion and in contact with liquid).
• the cyclooctane solvent (compound “b") is added and the residual methanol is evaporated.
• the compound “d” (a dispersing agent different from the compound “b” used, for example an octylamine) is then added and the mixture is stirred for 15 minutes at room temperature.
• the silver nanoparticle dispersions thus obtained are used directly for the formulation of conductive inks.
• the silver precursor is dissolved in said synthetic solvent; preferably, this synthetic solvent is different from the compound "b" (hereinafter also referred to as the "dispersion solvent”).
• the synthesis solvent is preferably an organic solvent selected from the following list of hydrocarbons:
• alkanes having from 5 to 20 carbon atoms which may be exemplified by Pentane (C5H12), Hexane (C6H14), Heptane (C7H16), Octane (C8H18), Nonane (C9H20), Decane (C10H22), Undecane ( C11H24), Dodecane (C12H26), Tridecane (C13H28), Tetradecane (C14H30), Pentadecane (C15H32), Cetane (C16H34), Heptadecane (C17H36), Octadecane (C18H38), Nonadecane (C19H40), Eicosane (C20H42), Cyclopentane ( C5H10) cyclohexane (C6H12), methylcyclohexane (C7H14); cycloheptane (C7H14), cyclononane (C9H18), cyclodecane
• aromatic hydrocarbons having 7 to 18 carbon atoms for example toluene, xylene, ethylbenzene or ethyltoluene;
• At least one dispersing agent (the compound "c") is also present in addition to the silver precursor (and the synthesis solvent when the latter is used).
• This dispersing agent which we will call the synthetic dispersing agent corresponding to the above-mentioned compound "c", is preferably chosen from the list of dispersing agents described hereinafter in the present description.
• the silver nanoparticles are therefore synthesized by chemical synthesis, by reducing the silver precursor by means of a reducing agent in the presence of the synthetic dispersing agent (the compound "C"), all preferably taking place in the synthesis solvent.
• This synthesis is preferably carried out under non-binding pressure and temperature conditions as defined hereinafter in the present description.
• the reducing agent may be selected from a wide range of compounds for reducing the silver precursor.
• compounds for reducing the silver precursor By way of illustration, mention may be made of the following compounds: hydrogen; hydrides, among which we will mention by way of example NaBH4, LiBH4, KBH4, and tetrabutylammonium borohydride; hydrazines, among which we will mention by way of example hydrazine (H2N-NH2), substituted hydrazine (methylhydrazine, phenylhydrazine, para-methoxyphenylhydrazine, dimethylhydrazine, diphenylhydrazine, etc.), hydrazine salt (substituted), and the like. ; amines, among which we will mention by way of example trimethylamine, triethylamine, etc ...; and their mixtures.
• the nanoparticles are then subjected to a washing / purification step that eliminates anything that is not chemically or physically related to the nanoparticles.
• a liquid phase is always present, both during the reduction step of the silver precursor and during all the steps (for example the washing and purification steps). above) that precede the addition of compound "b" (cyclooctane).
• a liquid phase for example a solvent
• this characteristic makes it possible to considerably improve certain properties (monodispersion, homogeneity, stability and annealing at lower temperature) of the silver nanoparticles. This approach eliminates the nanoparticle isolation step, which has a positive impact in terms of production costs and personal health and safety.
• the compound "b" according to the present invention therefore consists of a cyclooctane solvent.
• the compounds "c” (synthetic dispersing agent) and “d” (dispersing agent) according to the present invention therefore consist of dispersing agents characterized in that the dispersing agent "d” is different from the agent "c” used .
• This difference is displayed by a different chemistry; for example, a different carbon chain length (e.g., a difference of at least two carbon atoms in the chain), and / or a linear carbon chain compound and the other not, and / or a cyclic carbon chain and the other not and / or an aromatic carbon chain compound and the other not.
• the compound “c” has a molecular weight and / or a carbon chain length at least 20% greater than that of the compound "d", for example at least 40%> greater .
• These dispersing agents may advantageously be selected from the families of organic dispersing agents which comprise at least one carbon atom. These organic dispersing agents may also comprise one or more nonmetallic heteroatoms such as a halogenated compound, nitrogen, oxygen, sulfur, silicon.
• thiols and their derivatives for example amino alcohols and amino alcohol ethers
• carboxylic acids and their carboxylate derivatives for example polyethylene glycols, and / or their mixtures.
• the organic dispersing agents "c” and “d” will be selected from the group consisting of amines such as, for example, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, hexadecylamine, diaminopentane, diaminohexane, diaminoheptane, diaminooctane, diaminononane, diaminodecane, dipropylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, methylpropylamine, ethylpropylamine, propylbutylamine, octy
• the compounds "b” (cyclooctane) and “d” are added to the silver nanoparticles already synthesized in the presence of the compound "c".
• the synthetic dispersing agent (compound “c", for example dodec) is added and the mixture is stirred.
• the hydrazine reducing agent is then rapidly added to the mixture and the mixture is left stirring for about 60 minutes.
• the mixture is treated by the addition of methanol (or any other suitable solvent, for example another monohydric alcohol having 2 to 3 carbon atoms, for example ethanol) and the supernatant is removed during three washes successive (silver nanoparticles thus formed remain in the state of dispersion and in contact with liquid, in this case in contact with methanol).
• the cyclooctane solvent (compound "b") is added and the residual methanol is evaporated.
• the compound “d” (a dispersing agent different from the compound “b” used, for example an octylamine) is then added and the mixture is stirred for 15 minutes at room temperature.
• the silver nanoparticle dispersions thus obtained are used directly for the formulation of conductive inks.
• the nanoparticles that are used are characterized by D50 values (which can be measured for example by means of the method described below) which are preferably between 2 and 12 nm; they are also preferably characterized by a monodisperse (homogeneous) distribution without aggregate.
• D50 will be between 2 and 8 nm; for the nanoparticles synthesized in the absence of a solvent, the preferred range of D50 will be between 5 and 12 nm.
• the dispersion thus obtained can be used directly or diluted to obtain the desired properties before being incorporated, for example, in an ink.
• dispersions according to the present invention are characterized by superior stability (before dilution) as demonstrated in the examples.
• the dispersion of silver nanoparticles comprises
• a compound "a” (silver nanoparticles) in a content greater than 30% by weight, preferably greater than 35% by weight, for example greater than 40% by weight,
• a compound "b” (cyclooctane) in a content of between 20 and 65% by weight, preferably between 40 and 60% by weight,
• a compound "c” (dispersing agent) in a content of between 3 and 15% by weight, preferably between 3 and 10% by weight, and
• the dispersion of silver nanoparticles may also include in its composition additional compounds among which we will mention by way of example solvents (for example ethers, alcohols, esters). and / or additives (for example polymers) whose objective may be for example the improvement of the dispersion of the nanoparticles.
• the compounds "a", “b", “c”, and “d” (within the ranges of proportions indicated above) will preferably comprise at least 55% by weight of the final dispersion, preferably at least 75% by weight of the final dispersion. % by weight, for example at least 90% by weight, at least 95% by weight, at least 99% by weight, or even 100% by weight of the final dispersion.
• the dispersion of silver nanoparticles does not include water in its composition.
• the dispersion can tolerate traces of water depending on their degree of purity, it is obvious that the sum of these corresponding traces of water will be acceptable in the dispersions of silver nanoparticles according to the present invention.
• the water content in the final dispersion generally depends essentially on the water content of the solvents used for its preparation; the monohydric alcohol (the dispersion washing methanol in our example embodiment above) will have this citrate the most important impact - in comparison with the other solvents used in the preparation of the dispersion - on the content final water dispersion.
• the dispersions of silver nanoparticles comprise water concentrations of less than 2% by weight, preferably less than 1% by weight, for example less than 0.5% by weight. or even less than 0.2% by weight.
• water is not added during the formulation of dispersions of silver nanoparticles.
• the compound “e” present in the ink according to the present invention therefore consists of a solvent which is different from the “b” compound (cyclooctane) used and its content in the ink is greater than 10% by weight and less than 80% by weight. weight; the said compound "e” is
• a mixture of terpene alcohol and aliphatic monohydric alcohol and glycol and / or glycol ether A mixture of terpene alcohol and aliphatic monohydric alcohol and glycol and / or glycol ether.
• this solvent compound "e” is a terpene alcohol selected from the family of menthol, nerol, cineol, lavandulol, myrcenol, terpineol (alpha-, beta-, gamma-terpineol, and / or or terpinen-4-ol, preferably alpha-terpineol), isoborneol, citronellol, linalool, terminalol, geraniol, and / or a mixture of two or more of said alcohols.
• this solvent compound "e” is a mixture of terpene alcohol as defined above and aliphatic monohydric alcohol which is divided among the group consisting of ethanol, propanol, butanol, pentanol and hexanol and their isomers (eg isopropanol, tert-butanol), and / or a mixture of two or more of said aliphatic monohydric alcohols.
• this solvent compound "e” is a mixture of terpene alcohol as defined above and glycol and / or glycol ether which will preferably be selected - for glycols examples of which are ethylene glycol, propylene glycol, diethylene glycol, hexylene glycol, trimethylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 2,3-butylene glycol, pentamethylene glycol - for example glycol ethers among the mono- or di-ethers of glycols among which we will mention by way of example ethylene glycol propyl ether, ethylene glycol butyl ether, ethylene glycol phenyl ether, propylene glycol phenyl ether, diethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol propyl ether, diethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol butyl ether, propylene glycol methyl ether, prop
• this solvent compound "e” is a mixture of terpene alcohol as defined above and aliphatic monohydric alcohol as defined above and glycol and / or glycol ether as defined above.
• the ink is characterized in that the compound "e” is a mixture of terpene alcohol and aliphatic monohydric alcohol whose weight ratio [terpene alcohol] / [aliphatic monohydric alcohol ] is between 1/6 and 11/1, for example between 1/1 and 11/1.
• the ink is characterized in that the compound "e” is a mixture of terpene alcohol and glycol and / or glycol ether whose weight ratio [terpene alcohol] the glycol and / or glycol ether is between 1/6 and 11/1, for example between 1/1 and 11/1.
• the ink is characterized in that the content of terpene alcohol (compound “e”) is greater than or equal to 30% by weight.
• the optional compound "f” according to the present invention therefore consists of a rheology modifier.
• cellulosic agents for example alkyl-cellulose, preferably ethylcellulose, nitro-celluloses, and / or mixtures thereof.
• the optional compound "g” according to the present invention therefore consists of an antioxidant.
• an antioxidant for example,
• ascorbic acid or vitamin C E300
• sodium ascorbates E301
• calcium E302
• diacetyl 5-6-1 -ascorbic acid E303
• palmityl 6-1 -ascorbic acid E304
• citric acid E330
• sodium citrate E331
• potassium E332
• calcium citrate E333
• the ink compositions also comprise an additional solvent, which we will call "X" solvent which is cyclooctane.
• the inks formulated according to the present invention contain a content of less than 60% by weight of nanoparticles (compound "a”), preferably between 5 and 45%, and more particularly between 10% by weight. and 40% by weight.
• compound "a" nanoparticles
• the silver ink comprises
• a dispersion according to the present invention (with compounds “a”, “b”, “c” and “d"), in a content of less than or equal to 60% by weight, and preferably greater than 5% by weight preferably greater than 10% by weight, for example greater than 20% by weight and even greater than 40% by weight,
• An optional compound "f” (rheology modifying agent) in a content of less than 20% by weight, preferably between 0.1 and 2% by weight,
• An optional compound "g” consisting of an antioxidant agent in a content of less than 10% by weight, preferably less than 3% by weight, and
• the silver ink comprises the compound "g” consisting of an antioxidant in a content greater than 0.01% by weight.
• the ink may also include in its composition other compounds among which we will mention by way of example additives (for example, an additive of the family of silanes) whose objective may for example be to improve the resistance to different types of mechanical stress, for example adhesion to many substrates; the following substrates may be mentioned as examples: polyimide, polycarbonate, PET polyethertetphthalate), polyethylene naphthalate (PEN), polyaryletherketone, polyester, thermostabilized polyester, glass, ITO glass, AZO glass, SiN glass.
• additives for example, an additive of the family of silanes
• substrates may be mentioned as examples: polyimide, polycarbonate, PET polyethertetphthalate), polyethylene naphthalate (PEN), polyaryletherketone, polyester, thermostabilized polyester, glass, ITO glass, AZO glass, SiN glass.
• the compounds "a”, “b”, “c”, “d”, “e”, “f”, “g” and “X” (in the ranges of proportions indicated above) will preferably be less than 50% by weight of the final ink, preferably at least 75% by weight, for example at least 90% by weight, at least 95% by weight, at least 99% by weight, or even 100% by weight of the final ink.
• the ink does not include water in its composition.
• the ink components can tolerate traces of water depending on their degree of purity, it goes without saying that the sum of these corresponding traces of water will be acceptable in the inks according to the present invention.
• the water content in the final ink generally depends essentially on the water content of the solvents used for its preparation; the monohydric alcohol (the dispersion washing methanol in our example embodiment above) will have the citrate the greatest impact - compared with the other solvents used in the preparation of the ink - on the final water content of the ink.
• the inks comprise water concentrations of less than 2% by weight, preferably less than 1% by weight, for example less than 0.5% by weight, or even less than 1% by weight. 0.2% by weight.
• water is not added during the formulation of the inks .
• the preparation of the nanoparticle dispersion according to the present invention is characterized by the following steps:
• a liquid phase is always present during all these preparation steps.
• a preferred characteristic according to the present invention is that the silver nanoparticles are never isolated and dried; they therefore preferably remain in contact with a liquid phase (for example a solvent) in which they are dispersed.
• step "a" the addition of the reducing agent is carried out in any suitable container (for example a reactor) with the characteristic that it is carried out sub-level, for example using a plunger directly introduced into the reaction medium.
• a suitable container for example a reactor
• An additional advantage of the dispersion according to the present invention lies in the fact that its preparation can be carried out under non-binding pressure and / or temperature conditions, for example at pressure and / or temperature conditions close to normal conditions or ambient. It is preferable to remain within 40% of the normal or ambient pressure conditions and, with respect to temperature, the latter is generally less than 80 ° C, preferably less than 70 ° C.
• the Applicant has found that it is preferable to maintain the pressure conditions during the preparation of the dispersion at values oscillating at most 30%, preferably 15% around the values of the normal or ambient pressure conditions. preferably near atmospheric pressure.
• a control of these pressure and / or temperature conditions can therefore advantageously be included in the device for preparing the dispersion so as to fulfill these conditions.
• the preparation of the nanoparticle-based ink according to the present invention is characterized by the following consecutive steps:
• the ink thus obtained can be used directly or diluted to obtain the desired properties.
• a rheology modifying agent compound "f”
• the preparation of the nanoparticle-based ink according to the present invention is characterized by the following consecutive steps:
• An additional advantage of the ink according to the present invention lies in the fact that its preparation can be carried out under non-constraining pressure and / or temperature conditions, for example at pressure and / or temperature conditions close to or identical to the normal or ambient conditions. It is preferable to stay within 40% of normal or ambient pressure and / or temperature conditions. For example, the Applicant has found that it is preferable to maintain the pressure and / or temperature conditions during the preparation of the ink at values oscillating at most 30%, preferably 15% around the values of the conditions. normal or ambient. A control of these pressure and / or temperature conditions can therefore be advantageously included in the ink preparation device so as to fulfill these conditions.
• This advantage related to an ink preparation under non-binding conditions obviously also results in a facilitated use of said inks.
• the ink may advantageously be used in any printing method, in particular inkjet, spray, screen printing, gravure printing, flexography, doctor blade, spin coating, and slot die coating. ; the inkjet application being particularly suitable for the type of ink claimed.
• the square resistance of the ink as mentioned in the present invention may be measured by any suitable method.
• it can advantageously be measured according to the following method:
• An ink deposited by spincoating on a substrate (600 rpm / 3 min - for example glass) is annealed using a hot plate or an oven.
• An analysis of the square resistance is carried out under the following conditions:
• the Applicant has found that the square resistance values (measured as described above) of the inks obtained according to the present invention were preferably less than 100 mohms / sq for higher thicknesses or equal to 1 ⁇ (annealing temperature of
• the silver nanoparticles content as mentioned in the present invention may be measured to any appropriate extent.
• it can advantageously be measured according to the following method:
• the size distribution of the silver nanoparticles (in the D50 dispersion) as mentioned in the present invention may be measured by any suitable method.
• it can be advantageously measured according to the following method: use of a device of the Nanosizer S type of Malvern with the following characteristics:
• FIGS. 1 and 2 are representative of a general example of DLS (Dynamic light scattering) spectrum obtained during the synthesis of the nanoparticles according to the present invention, respectively with synthetic solvent (FIG. 1) and when the dispersing agent is used as a solvent for synthesis ( Figure 2).
• FIGS. 1 and 2 We can see the particle size spectra in the size (in nm) of the silver nanoparticles.
• D 50 is the diameter for which 50% of the silver nanoparticles in number are smaller. This value is considered representative of the average grain size.
• the viscosity of the ink as mentioned in the present invention may be measured by any suitable method. By way of example, it can be advantageously measured according to the following method:
• the surface tension of the ink as mentioned in the present invention may be measured by any suitable method.
• it can be advantageously measured according to the following method:
• Needle diameter 1.65 mm
• the square resistance was measured according to the protocol described above (600 rpm 3 min, annealed 150 ° C 30 min). The values are shown in the table below.

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• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
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• Microelectronics & Electronic Packaging (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)

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• 2015
  • 2015-05-20 FR FR1501041A patent/FR3036401B1/fr not_active Expired - Fee Related
• 2016
  • 2016-05-19 EP EP16726815.0A patent/EP3298088A1/fr not_active Withdrawn
  • 2016-05-19 WO PCT/EP2016/061306 patent/WO2016184975A1/fr unknown
  • 2016-05-20 TW TW105115743A patent/TWI714585B/zh not_active IP Right Cessation

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