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
  • C09D11/30—Inkjet printing 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
  • C09D11/10—Printing inks based on artificial resins
  • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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  • 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
  • C09D11/10—Printing inks based on artificial resins
  • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C09D11/108—Hydrocarbon resins
• • 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
  • C09D11/32—Inkjet printing inks characterised by colouring agents
  • C09D11/324—Inkjet printing inks characterised by colouring agents containing carbon black
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  • 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
  • C09D11/324—Inkjet printing inks characterised by colouring agents containing carbon black
  • C09D11/326—Inkjet printing inks characterised by colouring agents containing carbon black characterised by the pigment dispersant
• • 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
  • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
  • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
  • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
  • C09D127/18—Homopolymers or copolymers of tetrafluoroethene
• • 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
  • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
  • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
  • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
  • C09D127/20—Homopolymers or copolymers of hexafluoropropene
• • 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
  • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
  • C09D161/02—Condensation polymers of aldehydes or ketones only
• • 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
  • C09D17/00—Pigment pastes, e.g. for mixing in paints
• • 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
  • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
  • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • 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
  • C09D181/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Coating compositions based on polysulfones; Coating compositions based on derivatives of such polymers
  • C09D181/04—Polysulfides
• • 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
  • C09D181/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Coating compositions based on polysulfones; Coating compositions based on derivatives of such polymers
  • C09D181/06—Polysulfones; Polyethersulfones

Definitions

• Thermostable particulate ink for ink jet application is the most important particulate ink for ink jet application.
• the present invention generally relates to the formulation of a composition or thermostable particulate ink for inkjet application, which can be used on any type of substrate, but in particular on substrates which are, during their manufacture or use , subjected to high temperatures (especially at temperatures greater than or equal to 250 ° C).
• the field in question is primarily that of cookware, but the present invention may also relate to any other type of articles to be shaped and / or subjected to high temperatures of use, such as the sole of an iron ironing, or the plates of a hair straightener, the bowl of a fryer or a bread machine, the bowl of a "blender".
• thermostable particulate ink for ink-jet application is meant in the sense of the present invention an aqueous composition capable of being ejected by an ink jet printing device, which comprises at least one fluorinated thermostable binder .
• the ink is transparent and is rather a varnish, this type of ink being used, for example, when it is desired to obtain a film-coating or a relief effect.
• thermostable fluorinated binder also at least one heat-stable pigment
• a heat-stable particulate composition is such that the result of the printing does not exhibit a significant, undesired or uncontrolled change in color or properties after exposure to at least a temperature of 110 ° C. C, and especially at temperatures of at least 250 ° C.
• binder in the sense of the present invention a chemical compound of high molecular mass (greater than 1000 Da) initially present in the ink, capable of forming a film by drying, by coalescence or by heat treatment.
• thermoostable binder means a binder which, once the film has been formed, is stable in temperature and shows no evolution (for example chain breaks) even at temperatures of at least 250.degree.
• thermostable pigment means an insoluble or particulate coloring substance which has a good thermal resistance or in other words which has stable physicochemical properties as a function of temperature.
• the heat-stable pigments also include thermochromic pigments, whose stable behavior as a function of temperature is expressed by their ability to present the same coloristic contrast as a function of the temperature, even after having been exposed before a temperature higher than that of their color change.
• sublimation is the transformation of a solid body into gas or vapor without passing through the liquid state.
• the pattern initially printed on a support paper or plastic film
• the assembly is briefly brought to a temperature of between 150 ° C. C and 210 ° C.
• Traditional dye sublimation printing is only used on flat articles because the pressure of the medium on a non-flat shaped article leads to its wrinkling and consequently to printing defects.
• improvements in the sublimation printing process that allow the decoration of all the faces of an article of any shape.
• improvements make the sublimation printing processes very complex to implement and unproductive.
• inkjet printing which consists in projecting ink droplets from a small opening to perfectly determined positions on a support, so as to create an image .
• Inkjet printing is the only non-contact printing technique.
• the CIJ inkjet printing technique is based on the controlled fragmentation of a liquid jet. Disturbances cause the jet to break into droplets of controlled size, at a determined speed. This is achieved by a synchronization between jet failure and speed.
• the ink droplets that reach the printing medium are electrostatically selected (drop charge, then deflection of these drops by an electric field).
• the DOD inkjet printing technique is based on a different physical process: the ink is held in the reservoir, forming a meniscus at the nozzle, until a pressure applied to the volume of liquid exceeds the surface tension, and allows the ejection of a droplet.
• This technical choice which is the majority today, is based on four ejection techniques: piezoelectric ⁇ , thermal (or bubble-jet), jet-valve (or jet valve) and thermofusion.
• the technique of piezoelectric é ejection is currently the most developed. Its operating principle is as follows:
• the electrical excitation induces a deformation of the tank wall, which leads to an overpressure
• inkjet printing makes it possible to limit the number of ink formulations to be managed (four for a four-color printing, and six for a hexachrome printing), which is an undeniable advantage in terms of formulation and storage.
• inkjet printing is a non-contact printing technology with the medium: the absence of printer form (screen, engraved imprint, or pre-printed substrate for sublimation) makes it possible to eliminate the work of printing. preparation necessary for the implementation of other printing techniques, in particular the preparation of screens, the engraving of fingerprints or, where appropriate, of supports (paper or plastic film).
• inkjet printing makes it possible to create decorations that can present a great variety of colors and complex patterns (photos, textures, imitation stone, wood, marble ...) with a high definition. Such technology also makes it possible to print relief media by coupling the head with a robot.
• applications in the sense of nature of the media used to apply the ink by inkjet printing
• the applications of printing There are many types of inkjet posters: large and very large posters, textile printing, ceramic decoration, marking, addressing, food printing, active ingredient deposition, biomaterials deposition, conductive ink printing, etc.
• an application relates to the decoration of articles whose manufacturing process requires a very high temperature cooking, such as, for example, ceramic tiles.
• manufacturing techniques for example sintering or powder melting, provide for the articles to be brought to temperatures of at least 300 ° C and up to 1300 ° C and beyond.
• inkjet technique of using conventional inks as used in paper or textile printing, because they are aqueous inks based on compounds organic dyes that do not withstand high temperatures.
• the high temperatures of the cooking or use cycles lead to oxidation of both the generally organic pigments, but also the binders that constitute them.
• the object of the present invention is therefore to enable the manufacture, by inkjet printing, of functional or decorative layers on an article (for example a culinary article) which, during its manufacture or use, is subjected to high temperatures. above 110 ° C.
• the present invention therefore relates to a particulate composition for thermostable ink jet application comprising:
• the characteristic particle size is understood to mean a size characterizing the particle size (in this case the diameter for spherical particles), but also its particle size distribution, for example by the characteristic dimensions "D50 Or "D99".
• D50 is intended to mean the maximum dimension that is present in 50% of the particles (median of the particle distribution).
• D99 is intended to mean the maximum dimension that 99% of the particles present.
• thermostable binder in the particulate composition according to the invention makes it possible to ensure the surface and durability properties of the aqueous ink layer, and in some cases to escape from a protective film-coating layer.
• the heat-stable particulate composition according to the invention may also comprise at least one heat-stable pigment present in an amount such that said thermostable fluoro binder and said heat-stable pigment represent from 90 to 5% by weight of the total weight of the composition, thermostable pigment also in the form of particles at least one of whose characteristic dimensions is less than 800 nm.
• a characteristic dimension of binder particles, and optionally pigment, which is less than 800 nm makes it possible to eliminate, if not limit, the risk of clogging and damage to the nozzles of the print head.
• thermostable binders that can be used in the thermostable particulate composition according to the invention, mention may be made especially of polytetrafluoroethylene (PTFE), the copolymer of tetrafluoroethylene and perfluoropropylvinylether (PFA), and the copolymer of tetrafluoroethylene and hexafluoropropene (FEP), polyvinylidene fluoride (PVDF), MVA (TFE / PMVE copolymer), terpolymer TFE / PMVE / FAVE, ETFE , polychlorotrifluoroethylene (PCTFE), their associated copolymers and mixtures thereof.
• PTFE polytetrafluoroethylene
• PFA perfluoropropylvinylether
• FEP tetrafluoroethylene and hexafluoropropene
• PVDF polyvinylidene fluoride
• MVA TFE / PMVE copolymer
• thermostable pigments for example CoAl 2 0 4 , iron oxide III, chromium titanate and antimony, and silico-aluminates.
• nickel-titanium yellows titanium dioxide
• inorganic pigments with crystalline structure in spinel based on different metal oxides. mica flakes coated with iron oxide or titanium oxide, the flakes of aluminum coated with iron oxide, perylene red
• thermochromic semiconductor pigments for example semiconducting metal oxides such as Fe 2 O 3 , Bi 2 O 3 , or BiV0 4 .
• These pigments have excellent heat resistance, whether carbon blacks and metal oxides or organic molecules such as perylene red which are particularly stable in temperature.
• nanometric inorganic particles of sizes of between 5 and 200 nm not necessarily colored as a formulation in ink because of their extremely small size but whose color is expressed after drying by their reagglomeration into larger assemblies typically larger than 350 nm and thus becoming visibly colored.
• This solution is particularly interesting because it ensures operation without clogging the nozzles and also less wear thereof.
• the particles of thermostable binder, and optionally heat-stable pigment, contained in the composition according to the invention may have a characteristic dimension of less than 400 nm.
• the advantage of using particles having such dimensions is to be able to use nozzles themselves having a small opening, ideally with a ratio diameter of the particles / diameter nozzle opening of the order of 1 per 100. It follows that this makes it possible to limit the volume of the drop. This results in prints with more accurate outlines and therefore better rendering. This is also an advantage even when one wants to achieve flat (uniform color) because it allows to limit the ink consumption.
• thermostable particulate composition (or aqueous ink) according to the invention is compatible with use in a DOD ink jet printing device, since it has, besides a particle size adapted to the nozzles of the printing device, the following physicochemical and rheological properties:
• the viscosity and the surface tension of the fluid being parameters making it possible to control the formation of droplets of uniform size and shape.
• the pH of the composition according to the invention must be closer to neutrality.
• composition according to the invention further comprising at least 1% by weight relative to the total weight of said composition of at least one delayed evaporation compound which has a vapor pressure lower than that of water for a temperature of between 5 ° C and 50 ° C and at atmospheric pressure, said compound being in a form at least partially miscible with water.
• delayed evaporation compound is meant, within the meaning of the present invention, a compound which decreases / delays Evaporating the composition according to the invention.
• the aqueous ink forming a meniscus at the nozzle must not dry between two jets.
• the aqueous composition according to the invention has a vapor pressure lower than that of water: this makes it possible to keep the nozzle wet, the composition evaporating more slowly than water.
• a compound having a boiling point greater than 135 ° C. generally makes it possible to obtain a delayed evaporation fluid that can be used in the heat-stable particulate composition according to the invention.
• surfactant means dispersing agents (for the stabilization of pigments in particular), wetting agents, emulsifying agents and foaming agents.
• the term "humectant” means a compound which is soluble or partially soluble (respectively miscible or respectively miscible) in water and which makes it possible to increase the water retention of the ink in the water. the print head.
• humectants which may be used in the heat-stable particulate composition according to the invention, mention may in particular be made of sugars, sodium, magnesium, zinc and calcium salts of carboxylic acids (preferably with a carbon chain comprising more of 12 carbon atoms), and urea.
• Some compounds may have a dual role of humectant and solvent such as glycols.
• the composition according to the invention may comprise at least two compounds with delayed evaporation.
• the combination of two compounds with delayed evaporation makes it possible to appreciably improve the quality of the ink or its rendering.
• one of the delayed evaporation compounds may be chosen to enhance the stability of the dispersion of the pigments or thermostable binder and the other to facilitate wetting or spreading on the substrate.
• these two compounds with delayed evaporation are distributed preferentially as follows:
• the sum of the weight proportions of the two compounds with delayed evaporation is greater than 5% by weight, and preferably greater than 10% by weight relative to to the total weight of the composition.
• the weight ratio of the amount of the first compound to the second is 0.001 and 1000, and preferably between 0.01 and 100.
• composition according to the invention may further comprise the following additives:
• biocidal and / or fungicidal agents especially to prevent the development of bacteria and / or fungi
• the ejection of the composition by the print head is possible, but not in time without requiring human intervention (for cleaning nozzles in particular).
• the particulate composition according to the invention based on a thermostable fluorinated binder may be free of pigment and comprise at least one solvent, which is as defined above).
• Such an embodiment makes it possible to obtain a continuous film.
• the particulate composition according to the invention may be free of pigment and comprise at least one humectant, which is as defined above. Such an embodiment allows the spreading on the support of the composition according to the invention.
• composition according to the invention may further comprise at least one second heat-stable non-fluorinated binder.
• thermostable binders that may be used in the thermostable particulate composition according to the invention, mention may especially be made of phenyl polysulfide (PPS), ethylene polysulfide (PES), polyetheretherketones (PEEK), polyetherketones (PEK) , and polyamide-imides (PAI), polyimides.
• PPS phenyl polysulfide
• PES ethylene polysulfide
• PEEK polyetheretherketones
• PEK polyetherketones
• PAI polyamide-imides
• DOD Inkjet-based decoration device
• a device of the DOD type comprising a print head marketed under the name ARDEJE HA5, comprising a nozzle, a chamber and an ink circuit, is used as printing device.
• humectant glycerol
• Chromium and antimony titanate yellow pigment from Shepherd (trade name Y193);
• Iron oxide red pigment sold by Bayferrox (trade name 110M); Perylene red red pigment marketed by BASF under the trademark Paliogen® Red K 3911;
• Dispersant type surfactants are Dispersant type surfactants:
• High molecular weight hyperdispersing polymer marketed under the trademark SOLSPERSE® by LUBRIZOL;
• Nonionic surfactant derived from fatty acid marketed under the tradename TEGO® by the company Evonik;
• nonionic surfactant isotridecyl polyethylene glycol marketed under the trademark
• thermostable binders
• thermostable binders fluorinated thermostable binders
• thermostable particulate compositions for inkjet application
• the physico-chemical quantities such as the pH of the ink composition, the viscosity and the surface tension are necessary but not sufficient conditions to guarantee homogeneous and stable-time ejection of the ink composition. Indeed, the stresses experienced by a fluid at the time of ejection (shear force and activation frequency) are not simulable with conventional analysis equipment.
• jettability means that the following criteria are fulfilled by the composition tested:
• the jettability of the compositions tested is evaluated using a printing device sold under the name HA 5 by the company ARDEJE at a frequency of 1.7 kHz and working at a controlled temperature of 25 ° C or 35 ° C. vs.
• An observation and a stroboscopic recording are made to visualize the shape of the drops, the regularity of the train of drops as a function of time. Evaluation of the rheological profile / measurement of the viscosity
• the viscosity is evaluated on a Gemini rheometer from the company Malvern. The measurement is carried out at the target temperature for the ejection of the ink, with a mobile cone / plane (slope of 2% for a diameter of 55 mm). The viscosity is calculated as the average of the instantaneous viscosities taken for speed gradients greater than 5 s -1 .
• EXAMPLE 1 aqueous ink according to the invention EA1, pigmented and containing a thermostable fluorinated binder and comprising a delayed evaporation compound.
• a pigmented initial CP1 composition containing a thermostable fluorinated binder is prepared, with stirring, the various constituents of which, with their respective amounts, are indicated below in% by weight relative to the total weight of the composition:
• Ethylene glycol 24.3% isotridecyl polyethylene glycol: 6.1%
• the blue pigment 10C595 placed in solution has the following granular distribution:
• D50 which represents the median of the particle distribution is as defined above, and the term “D99” is also as defined above and represents, within the meaning of the present invention, the maximum dimension that 99% of the particles present.
• the granular distribution of the pigment in the aqueous composition CP1 is therefore not suitable, as it is, to be applied by ink jet.
• the pigmented composition CP1 is milled in a horizontal mill with fingers, filled with ZrC> 2 beads.
• This secondary composition CP1 ' has a solids content of 9%.
• a PTFE dispersion is added to the nanoparticle dispersion CP6 'according to the proportions (in parts by weight) indicated below, to form the aqueous ink composition EA1:
• the addition of PTFE does not cause agglomeration of the pigments.
• the rheological profile of the EA1 aqueous ink composition is of Newtonian type. The viscosity measured at 25 ° C is 20 mPa.s.
• the speed of the drops is equal to 4.5 m / s
• the opening time of the nozzle is greater than 1 minute
• the impression of the drop on the support is regular and example of halo.
• the result of the printing does not show any appreciable, undesired or uncontrolled change in color or properties after exposure to at least a temperature of 110 ° C, and especially at temperatures of at least 250 ° C.
• EXAMPLE 2 aqueous ink according to the invention EA2, unpigmented and containing a thermostable fluorinated binder and comprising at least one delayed evaporation compound.
• An unpigmented aqueous ink composition EA2 comprising a thermostable fluorinated binder, the various constituents of which with their respective amounts are given below in part by weight:
• the EA2 aqueous composition is prepared as follows:
• the surfactant, then the glycerol are added to the diluted dispersion of PTFE; a stable dispersion is obtained which is filtered, for example by frontal filtration on cellulose acetate syringe filters with a porosity of 0.8 ⁇ m and then 0.45 ⁇ m.
• the addition of glycerol and surfactant does not change the size of the different species in dispersion.
• the viscosity of the EA2 aqueous ink is measured at 25 ° C: it is equal to 2.8 mPa.s and the surface tension of the fluid measured by tensiometry at the WILHELMY blade is equal to 28.3 mN / m and the Newtonian type profile
• the speed of the drops is equal to 4 m / s
• the opening time of the nozzle is 1 minute
• the result of the printing does not show any appreciable, undesired or uncontrolled change in color or properties after exposure to at least a temperature of 110 ° C, and especially at temperatures of at least 250 ° C.
• EXAMPLE 3 aqueous ink according to the invention EA3, unpigmented and containing a thermostable fluorinated binder and comprising a delayed evaporation compound.
• An unpigmented aqueous ink composition EA3 comprising a thermostable fluorinated binder, the various constituents of which with their respective amounts are given below in part by weight:
• Aqueous non-pigmented EA3 composition :
• the EA3 aqueous composition is prepared as follows:
• the surfactant and then propylene glycol are added to the diluted PTFE dispersion; a stable dispersion is obtained, which is filtered, for example by frontal filtration on cellulose acetate syringe filters with a porosity of 0.8 ⁇ m and then 0.45 ⁇ m.
• the addition of propylene glycol and surfactant does not change the size of the different species in dispersion.
• the viscosity of the aqueous ink EA3 is measured: it is equal to 3.6 mPa.s at 35 ° C. and the surface tension of the fluid measured by tensiometry at the blade of WILHELMY is equal to 30.3 mN / m.
• the speed of the drops is equal to 4.5 m / s
• the opening time of the nozzle is 2 minutes
• the result of the printing does not show any appreciable, undesired or uncontrolled change in color or properties after exposure to at least a temperature of 110 ° C, and especially at temperatures of at least 250 ° C.
• EXAMPLE 4 aqueous ink according to the invention EA4, not pigmented and containing a thermostable fluorinated binder.
• An unpigmented aqueous ink composition EA4 comprising a thermostable fluorinated binder, the various constituents of which with their respective amounts are given below in part by weight:
• Aqueous nonpigmented EA4 composition :
• EA4 aqueous composition is prepared as follows:
• the surfactant and then the glycerol are added to the diluted dispersion of FEP; a stable dispersion is obtained, which is filtered, for example by frontal filtration on cellulose acetate syringe filters with a porosity of 0.8 ⁇ m and then 0.45 ⁇ m.
• the addition of glycerol and surfactant does not change the size of the different species in dispersion.
• the viscosity of the EA4 aqueous ink is measured: it is equal to 20 mPa.s at 25 ° C.
• the speed of the drops is equal to 4.5 m / s
• the opening time of the nozzle is 2 minutes
• EXAMPLE 5 aqueous ink according to the invention EA5, pigmented and containing a thermostable fluorinated binder and a non-fluorinated thermostable binder, as well as a delayed evaporation compound
• thermostable fluorinated binder containing a thermostable fluorinated binder and a non-fluorinated thermostable binder is prepared, the various constituents of which, with their respective amounts, are indicated below in% by weight relative to the total weight of the composition:
• the black pigments in solution have the following granular distribution:
• the pigments are, as is, compatible with inkjet printing.
• the addition of PTFE and PAI does not cause agglomeration of the pigments.
• the rheological profile of the aqueous ink composition EA10 is of Newtonian type and the viscosity at 25 ° C is 21 mPa.s.
• the speed of the drops is equal to 4.5 m / s
• the opening time of the nozzle is 2 minutes, it is observed that the trains of drops are well separated and that the front progresses regularly;
• the impression of the drop on the support is regular and example of halo.
• An initial composition EP1 pigmented and free of thermostable fluorinated binder is prepared, in which ethanol, which is a solvent having a vapor pressure lower than that of water for a temperature of between 5 ° C. and 5 ° C., is used as the solvent. 50 ° C and at atmospheric pressure.
• the black pigments in solution have the following granular distribution:
• the pigments are, as is, compatible with inkjet printing.
• the rheological profile of the EC1 aqueous ink composition is of Newtonian type and the viscosity of 4.5 mPa.s.
• the speed of the drops is equal to 4.5 m / s
• the opening time of the nozzle is 5 seconds
• COMPARATIVE EXAMPLE 2 particulate ink having a non-thermostable acrylic binder.
• a non-pigmented aqueous ink composition comprising a non-thermostable binder of acrylic type (copolymer of benzyl acrylate and methacrylic acid), the various constituents with their respective amounts are indicated below in parts. in weight :
• Nonpigmented aqueous composition
• Demineralized water 80% glycerol: 5.0
• the aqueous composition is prepared as follows:
• the surfactant and then glycerol are added to a polymer dispersion of benzyl acrylate and methacrylic acid;
• a stable dispersion is obtained which is filtered, for example by frontal filtration on cellulose acetate syringe filters with a porosity of 0.8 ⁇ m and then 0.45 ⁇ m.
• the addition of glycerol and surfactant does not change the size of the different species in dispersion.
• the viscosity of the aqueous ink is measured: it is equal to 22 mPa.s at 25 ° C.
• the speed of the drops is equal to 4.6 m / s
• the opening time of the nozzle is 2 minutes, we observe that the trains of drops are well separated and that the front progresses in a regular way;
• the result of the printing shows a significant evolution of its properties after having been subjected to a temperature of 250 ° C.
• the printed layer has indeed a significant yellowing after exposure to the temperature due to the degradation of the acrylic copolymer.
• COMPARATIVE EXAMPLE 3 particulate ink having a non-thermostable polyurethane binder.
• An unpigmented aqueous ink composition comprising a non-thermostable binder of the polyurethane resin type, the various constituents of which, with their respective amounts, are given below in part by weight:
• Aqueous nonpigmented EA4 composition :
• the aqueous composition is prepared as follows:
• the surfactant and then the glycerol are added to a polyurethane resin dispersion;
• a stable dispersion is obtained which is filtered, for example by frontal filtration on cellulose acetate syringe filters with a porosity of 0.8 ⁇ m and then 0.45 ⁇ m.
• the addition of glycerol and surfactant does not change the size of the different species in dispersion.
• the viscosity of the aqueous ink is measured: it is equal to 23 mPa.s at 25 ° C.
• the speed of the drops is equal to 4.6 m / s
• the opening time of the nozzle is 2 minutes
• the result of the printing shows a significant evolution of its properties after having been subjected to a temperature of 250 ° C.
• the printed layer has indeed a significant yellowing after exposure to the temperature due to the degradation of the acrylic copolymer.
• COMPARATIVE EXAMPLE 4 pigmented aqueous ink containing a non-thermostable acrylic binder and comprising a delayed evaporation compound.
• the blue pigment 10C595 dissolved in solution has the following granular distribution:
• D50 which represents the median of the particle distribution is as defined above, and the term “D99” is also as defined above and represents, within the meaning of the present invention, the maximum dimension that 99% of the particles present.
• the granular distribution of the pigment in the aqueous CP6 composition is therefore not suitable, as it is, to be applied by ink jet.
• the pigmented composition CP1 is milled in a horizontal mill with fingers, filled with balls of Zr0 2
• This secondary composition has a solids content of 9%.
• a PTFE dispersion is added to the nanometer dispersion of pigments according to the proportions (in parts by weight) indicated below, to form the aqueous ink composition: Composition of aqueous ink Proportions (parts)
• the rheological profile of the aqueous ink composition is Newtonian type.
• the viscosity measured at 25 ° C. is 20 mPa. s.
• the speed of the drops is equal to 4.5 m / s
• the opening time of the nozzle is greater than 1 minute
• COMPARATIVE EXAMPLE 5 pigmented aqueous ink containing a non-thermostable acrylic binder and a dispersion of thermostable fluorinated particles and a delayed evaporation compound.
• PTFE particles bound by an acrylic polymer-type substrate is known to provide lubricating and abrasion-resistant properties to compositions containing them once printed.
• composition pigmented and containing an acrylic binder, is prepared, with stirring, and the various constituents with their respective amounts are indicated below in% by weight relative to the total weight of the composition:
• the blue pigment 10C595 dissolved in solution has the following granular distribution:
• D50 which represents the median of the particle distribution is as defined above, and the term “D99” is also as defined above and represents, within the meaning of the present invention, the maximum dimension that 99% of the particles present.
• the granular distribution of the pigment in the aqueous composition CP6 is therefore not suitable, as it is, to be applied by inkjet.
• the pigmented composition CP1 is milled in a horizontal mill with fingers, filled with balls of Zr0 2
• This secondary composition has a solids content of 9%.
• a dispersion of PTFE and acrylic copolymer particles according to the proportions (in parts by weight) indicated below, to form the aqueous ink composition is added to the nanometric dispersion of pigments:
• the rheological profile of the aqueous ink composition is Newtonian type.
• the viscosity measured at 25 ° C. is 20 mPa. s.
• the jettability of the ink it was validated at 25 ° C with the ARDEJE HA5 printing device at a frequency of 1.7 kHz. The following characteristics are obtained: the speed of the drops is equal to 4.5 m / s,
• the opening time of the nozzle is greater than 1 minute
• the printed layer shows significant yellowing due to degradation of the acrylic copolymer.
• the quality of the film is poor with a total lack of cohesion of the pigments and PTFE particles on the substrate.
• the film is of poor quality because the degradation of the acrylic polymer prevents the filming of fluorinated species. In any case, the rendering of the print is tarnished by the browning of the acrylic with the temperature.

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