Classifications

• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
  • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
  • C03C8/16—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions with vehicle or suspending agents, e.g. slip
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M1/00—Inking and printing with a printer's forme
  • B41M1/26—Printing on other surfaces than ordinary paper
  • B41M1/34—Printing on other surfaces than ordinary paper on glass or ceramic surfaces
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
  • B41M7/0045—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using protective coatings or film forming compositions cured by mechanical wave energy, e.g. ultrasonics, cured by electromagnetic radiation or waves, e.g. ultraviolet radiation, electron beams, or cured by magnetic or electric fields, e.g. electric discharge, plasma
• • 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
  • C09D11/02—Printing inks
  • C09D11/10—Printing inks based on artificial resins
  • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
• • 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
  • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2214/00—Nature of the non-vitreous component
  • C03C2214/12—Polymers

Definitions

• the present specification relates to UV-curable enamel ink compositions for screen printing applications on glass.
• a primary function is to shield the glue that holds the glass components in place from ultraviolet radiation which would otherwise decompose the glue.
• a secondary function is to cover up electrical circuits, wires, and connectors that ensure functionality of electrical or electronic components attached to, or embedded into, the glass component and ensure a clean aesthetic appearance .
• Enamels are applied as a paste or ink in a screen printing or ink jet process to a flat glass substrate and are subsequently fired at high temperatures, during which the organic carrier medium of the paste or ink burns off and the enamel fuses together and establishes a bond to the substrate.
• the firing process softens the substrate which can be formed into the final shape by a bending process.
• the curable vehicle includes: (a) at least one polymerizable liquid oligomer containing a backbone including at least two acrylate or methacrylate functional end groups; (b) at least one photopolymerizable liquid monomer containing acrylate or methacrylate functional groups, the functionality of said monomer component (b) being in the range of from 1 to 6; and (c) a photoinitiator.
• the vehicle includes: (a) at least two polymerizable liquid oligomers containing acrylate or methacrylate functional end groups and selected from difunctional- or trifunct ional-polyester acrylates or methacrylates and difunctional or trifunctional polyurethane acrylates or methacrylates; (b) at least one monofunctional polyether acrylate or methacrylate; (c) at least one pentafunctional aliphatic penta-acrylate or penta-methacrylate; and (d) a photoinitiator.
• W02017009184A1 Jain et al discloses a curable composition comprising: (a) at least one (meth) acrylate monomer or oligomer; and (b) at least one mono-functional (meth) acrylate monomer comprising a polycyclic moiety having at least three rings that are fused or condensed.
• this document does not relate to the field of enamel compositions or to screen printing on a glass substrate .
• CA2807541A1 discloses a heat-curable acrylate- based printing medium.
• this document discloses a method of forming a decorated glass structure comprising applying to a first glass substrate an enamel paste composition which includes (i) a glass component and (ii) a low VOC, heat-curable medium.
• the heat curable medium comprises a functional acrylate monomer having at least one functionality.
• the medium is not UV-curable.
• a problem with certain compositions of the prior art is their tendency to shown high increase in ink viscosity upon application under certain application conditions, which is undesirable.
• Such conditions include screen printing conditions, whereby an ink is applied to the back of a printing screen, and a blade is then used to push the ink through holes or openings (defining the printing pattern) in the screen.
• a squeegee or rubber blade is used to cause the screen to contact the substrate thereby causing the ink to be transferred onto the substrate.
• This process involves several steps that may affect the rheology of the ink, including for example the application of a thin layer of ink using a blade and the removal of excess ink using a vacuum or suction device.
• ink compositions may not exhibit a satisfactory level of hardness or structural integrity after being applied, e.g. screen printed. This may be problematic when the enamel ink is subjected to further processing before the firing process, e.g. when it is overprinted with a conductive metallic (e.g. silver) layer that may, for example, form bus bars and/or wiring connections of a backlight defrosting system.
• a cured enamel ink layer may typically be over printed with a silver paste that forms a conductive metallic ink in the subsequent firing process.
• the silver paste is typically a solvent-based ink formulation and thus certain components of the paste, especially solvents, may penetrate the UV cured enamel layer after overprint and before drying of the silver overprint.
• an insufficient degree of hardness, structural integrity and/or chemical resistance of the enamel ink layer may cause damage to the enamel ink layer and/or may cause substances, e.g. solvents, of the overprinted layer to penetrate the enamel layer and cause chemical disruption to the ink layer, both of which may result in a decrease in the quality of the enamel layer, for example by negatively affecting its adhesion on a substrate, e . g . glass .
• the present inventors have found that, during screen printing, certain enamel ink compositions are susceptible to exhibiting an increase in viscosity.
• the present inventors have found a solution which advantageously provides a UV- curable composition as a vehicle for enamel inks and which exhibits a minimal or reduced change in viscosity in screen printing applications.
• an enamel composition comprising: glass frit; a pigment; and an organic carrier medium, wherein the organic carrier medium comprises a UV-curable composition, wherein the UV- curable composition comprises at least one mono-functional acrylate monomer, and wherein the at least one monofunctional acrylate monomer comprises a compound according to Formula (I) or Formula (II) : ) where n is 0 or 1.
• the at least one mono-functional acrylate monomer may comprise a compound according to Formula (la) : Formula (la)
• the compound of Formula (la) may commonly be named tricyclodecane methanol mono-acrylate.
• the at least one mono-functional acrylate monomer may comprise a compound according to Formula (Ila) : Formula (Ha)
• the compound of Formula (Ha) may commonly be named hexahydro- 4 , 7-methano-lH-indenyl acrylate .
• the enamel composition may exhibit a minimal change in viscosity, e.g. after about 30 mins, e.g. after about 1 hour, e.g. after about 2 hours.
• the enamel composition may exhibit a minimal change in viscosity before, during or after being applied, typically by screen printing.
• the change in the viscosity of the enamel composition may be less than 50%, e.g. less than 25%, e.g. less than 10%, e.g. less than 5%, typically less than 2%. It will be understood that the change of viscosity observed may depend on other parameters, such as the thickness of the enamel composition layer being applied by screen printing.
• the inventors have found that, advantageously, using one of the claimed compounds (such as tricyclodecane methanol mono-acrylate) as a mono-functional acrylate monomer in the UV-curable composition may help reduce the change of viscosity during a screen printing process compared to other compositions, such as compositions using isobornyl acrylate.
• a compound of Formula I or II such as tricyclodecane methanol mono-acrylate
• tricyclodecane methanol mono-acrylate may exhibit a lower evaporation rate than, for example, isobornyl acrylate. Additionally, it is thought that provision of the claimed compounds (e.g. tricyclodecane methanol mono-acrylate) as a mono-functional acrylate monomer in the UV-curable composition, may provide the resulting coating with superior hardness, structural integrity, and/or chemical resistance.
• an enamel composition comprising : glass frit; a pigment; and an organic carrier medium, wherein the organic carrier medium comprises a UV-curable composition, wherein a change in the viscosity of the enamel composition after being applied by screen printing is less than 50%, e.g. less than 25%, e.g. less than 10%, e.g. less than 5%, typically less than 2% .
• the change in viscosity of the enamel composition may be measured after about 30 mins, e.g. about 1 hour, e.g. about 2 hours, e.g. after being applied by screen printing.
• the UV-curable composition may comprise at least one mono-functional acrylate monomer, wherein the monofunctional acrylate monomer may comprise a compound according to Formula (I) , (la) , (II) , or (Ila) .
• a method of forming an enamel coating comprising : depositing an enamel composition as described herein on a substrate; curing the enamel composition; and firing the cured enamel composition.
• the enamel composition is deposited by screen printing.
• the curing step may comprise curing the UV-curable composition of the enamel composition.
• the method may comprise curing the enamel composition by exposing the composition to a source of radiation, e.g. by irradiating the composition with UV light.
• the method may comprise coating, e.g. printing, at least a portion of the enamel composition, with an outer coating.
• the outer coating may comprise or may be a conductive metallic (e.g. silver) layer that may, for example, form buss bars and/or wiring connections of a backlight defrosting system.
• the present enamel composition may have a superior hardness and/or chemical resistance making it particularly suitable to undergo such overprinting process.
• Figures 1 shows a graph illustrating the change in viscosity of a composition as described herein;
• Figures 2 and 3 show graphs illustrating the change in viscosity of alternative compositions.
• Figure 4 shows a graph plotting the viscosity increase for the composition of Figures 1 to 3.
• the present specification provides a enamel composition which comprises glass frit, a pigment, and an organic carrier, and which advantageously displays good viscosity stability after being applied by screen printing, and which also exhibit good adhesion on glass and high hardness, structural integrity and/or chemical resistance, compared to existing enamel compositions .
• the organic carrier medium comprises a UV-curable composition which includes a mono-functional acrylate monomer, wherein the mono-functional acrylate monomer comprises a compound according to Formula (I) or Formula (II) , such as tricyclodecane methanol mono-acrylate or hexahydro- 4 , 7-methano-lH-indenyl acrylate .
• a mono-functional acrylate monomer comprises a compound according to Formula (I) or Formula (II) , such as tricyclodecane methanol mono-acrylate or hexahydro- 4 , 7-methano-lH-indenyl acrylate .
• tricyclodecane methanol mono-acrylate as a mono-functional acrylate monomer in the UV-curable composition, may stabilise the viscosity of the UV-curable composition by exhibiting a low evaporation rate.
• tricyclodecane methanol mono-acrylate may exhibit a lower evaporation rate than, for example, isobornyl acrylate.
• provision of tricyclodecane methanol mono-acrylate as a mono-functional acrylate monomer in the UV-curable composition may provide the resulting coating with superior hardness, structural integrity, and/or chemical resistance.
• the organic carrier medium may consist of the UV-curable composition.
• the organic carrier medium e.g. UV-curable composition, may comprise one or more binders.
• the binder (s) may comprise or may be a polymer.
• the binder (s) may comprise an acrylic resin, a cellulosic resin, or the like.
• the binder (s) may comprise one or more resins selected from the list consisting of cellulose acetate butyrate resin, acrylic resin, or the like.
• the binder or combination of binders may be selected to provide the composition with a desired viscosity or rheology and/or with a desired level of harness.
• the organic carrier medium e.g.
• UV-curable composition may comprise the binder (s) in amount of about 0.1-20 wt%, e.g. about 1-10 wt %, e.g. about 2-6 wt % .
• the organic carrier medium, e.g. UV-curable composition may comprise one or more curable polymers.
• the curable polymer (s) may comprise an unsaturated polymer or oligomer, for example an acrylated polymer or oligomer.
• the curable polymer (s) may include an aliphatic polyurethane acrylate.
• the organic carrier medium, e.g. UV-curable composition may comprise the one or more curable polymers in amount of about 5-60 wt%, e.g. about 10-50 wt %, e.g. about 20-40 wt% .
• the organic carrier medium e.g. UV-curable composition
• the organic carrier medium may comprise one or more acrylic monomers.
• the one or more acrylic monomers may comprise at least one mono-functional acrylate monomer.
• the organic carrier medium, e.g. UV- curable composition may comprise the one or more acrylic monomers in amount of about 20-70 wt%, e.g. about 30-60 wt %, e.g. about 40-50 wt%.
• the organic carrier medium e.g. UV-curable composition
• the organic carrier medium, e.g. UV-curable composition may comprise the one or more difunctional acrylic monomers in amount of about 5-30 wt%, e.g. about 10-20 wt %.
• the UV-curable composition may comprise a compound according to Formula (I) or Formula (II) , e.g. tricyclodecane methanol mono-acrylate (TCDA) or hexahydro-4 , 7-methano-lH-indenyl acrylate.
• the organic carrier medium e.g. UV-curable composition
• the organic carrier medium, e.g. UV-curable composition may further comprise one or more surfactants or dispersants (e.g. Soja Lecithin) .
• the organic carrier medium e.g. UV-curable composition
• the organic carrier medium e.g. UV-curable composition
• the enamel composition e.g. organic carrier medium thereof, may further comprise one or more diluents, e.g. a solvent.
• the enamel composition, e.g. organic carrier medium thereof may not comprise a diluent, e.g. solvent.
• a solvent may not be required, for example when one of the components of the composition, e.g. one or more acrylic monomers, acts as a reactive diluent for the composition.
• the viscosity of the enamel composition may be in the range of about 5-25 Pa.s, e.g. about 10-20 Pa.s, e.g. about 15-18 Pa.s, e.g about 16-17 Pa.s.
• viscosity may be measured in a continuous shear rate measurement program (0.10-50 s -1 ) using cone plate geometry (CP 40mm 1°) at 21°C, recording the viscosity as paste viscosity at shear rate 10 s -1 .
• An enamel composition according to the present invention can be deposited, preferably using a screen printing on a substrate.
• the composition is then cured, for example by irradiating the composition with UV light.
• a portion of the enamel composition may be coated, e.g. printed, with an outer coating, such as a conductive metallic (e.g. silver) layer that may, for example, form bus bars and/or wiring connections of a backlight defrosting system.
• an outer coating such as a conductive metallic (e.g. silver) layer that may, for example, form bus bars and/or wiring connections of a backlight defrosting system.
• the present enamel composition may have a superior hardness and/or chemical resistance making it particularly suitable to undergo such overprinting process.
• Table 2 shows a formulation recipe to prepare the composition of Table 1 :
• Table 2 This recipe is based on the preparation of 100g of an enamel ink composition.
• the composition is prepared using the intermediate components labelled as # 1 -7. Some of these components, namely # 1, 3, 4, and 5, are provided as intermediate components identified respectively as A, B, C and D.
• the formulation of each of intermediate components is based on the preparation of 100g of an enamel ink composition.
• A, B, C and D is provided below in Table 2a, 2b, 2c and 2d.
• Components #1-7 were weighed into a plastic container and speed-mixed to yield a homogeneous solution.
• An enamel powder (component #8) and Thixatrol Max (Component #9) were added, and the mixture was speed-mixed for 20 seconds at 3000 rpm.
• the paste mixture was homogenized by triple roll milling twice.
• the paste was diluted with a medium based on mixture #1-7 to a viscosity of around 15 Pa.s.
• the visco-stability of paste was assessed by applying a thin paste film (200 pm) on glass plate and measuring viscosity and weight loss of thin film after exposure to 30°C and 65%RH in a climate chamber at interval times of 0.5, 1.0, 1.5 and 2.0 hrs .
• Measurement of viscosity was made in a continuous shear rate measurement program (0.10-50 s -1 ) using cone plate geometry (CP 40 mm 1°) at 21°C, recording the viscosity as paste viscosity at shear rate 10s -1 .
• composition 1 corresponds to the composition of Table 1.
• Compositions 2 to 4 are similar UV-curable compositions but based on different acrylate monomers .
• the organic carrier medium includes three acrylic monomeric components, namely a difunctional acrylic monomer in the form of tripropylene glycol diacrylate (TPGDA) and two monofunctional acrylic monomers in the form of tricyclodecane methanol mono-acrylate (TCDA) and a monofunctional urethane acrylate.
• TPGDA tripropylene glycol diacrylate
• TCDA tricyclodecane methanol mono-acrylate
• composition 2 contains TPGDA and a monofunctional urethane acrylate as the acrylic monomeric components. That is, composition 2 does not include tricyclodecane methanol mono-acrylate (TCDA) .
• TPGDA tricyclodecane methanol mono-acrylate
• the organic carrier medium includes a mixture of TPGDA, isobornyl acrylate (IBOA) and a monofunctional urethane acrylate. That is, it is similar to Composition 1 but uses IBOA instead of TCDA.
• IBOA isobornyl acrylate
• Composition 4 is similar to Composition 3 (both using isobornyl acrylate as a monofunctional acrylic monomer) , and only differs in the photo-initiator used, which does not affect qualitatively either viscosity behaviour or hardness.
• the viscosity of the UV-curable Composition 1, which uses tricyclodecane methanol mono acrylate (TCDA) as monofunctional acrylic monomer remained substantially stable over 2 hours.
• composition 2 contains TPGDA and a monofunctional urethane acrylate as the acrylic monomeric components, the solvent resistance of the resulting coating was found to be of lesser quality (see Table 5 later) , and was therefore not optimum for subsequent overprinting with, for example, a metallic bus bar.
• the viscosity of the UV-curable Composition 3 which uses only tripropylene glycol diacrylate (TPGDA) as the acrylic monomer component, exhibited a significant increase in viscosity over the same period of time. Without wishing to be bound by theory, this is believed to be due at least in part to the relatively high evaporation rate of isobornyl acrylate in comparison with tricyclodecane methanol mono-acrylate.
• TPGDA tripropylene glycol diacrylate
• Figure 4 shows a graph plotting the viscosity increase for each of Compositions 1, 2 and 3, further illustrating the above observations in respect of Figures 1, 2 and 3.
• the viscosity of the UV- curable Composition 1, which uses tricyclodecane methanol mono-acrylate (TCDA) as monofunctional acrylic monomer remained substantially stable over 2 hours.
• the viscosity of the UV-curable Composition 4 which uses only tripropylene glycol diacrylate (TPGDA) as the acrylic monomer component exhibited a significant increase in viscosity over the same period of time.
• Composition 4 is similar to Composition 3 (both using isobornyl acrylate as the monofunctional acrylic monomer) , and only differs in the photo-initiator used, which was not expected to affect either viscosity behaviour or hardness .
• compositions #1 including TCDA as a monofunctional monomer
• #2 no TCDA
• BDGA butyl diglycol acrylate
• UV-curable Composition 1 which uses tricyclodecane methanol monoacrylate (TCDA) as monofunctional acrylic monomer, exhibited improved solvent resistance to BDGA, compared to Composition 2 which was free of TCDA.
• TCDA tricyclodecane methanol monoacrylate
• the UV-curable paste (Composition 1) was screen printed on a glass sheet using screen mesh size (77T, 90T) . It will be understood that in practice the glass substrate may be any glass suitable for use in the automotive industry, such as clear, green or dark coloured (i.e. privacy glass) float glass.
• the screen-printed film (wet film thickness about 20-22 micron) was exposed to UV curing using an industrial UV curer.
• the cured film was over printed with silver paste (AG330L- 80) in the form of a bus bar (wet film thickness: 25-30 micron) and was dried in an industrial IR belt drier.
• the cured black enamel with silver overprint was in a roller kiln according to a firing cycle suitable for toughening enamel for backlight.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Life Sciences & Earth Sciences (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Wood Science & Technology (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Geochemistry & Mineralogy (AREA)
• Plasma & Fusion (AREA)
• Mechanical Engineering (AREA)
• Electromagnetism (AREA)
• Physics & Mathematics (AREA)
• Ceramic Engineering (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Paints Or Removers (AREA)
• Glass Compositions (AREA)
• Polymerization Catalysts (AREA)
• Graft Or Block Polymers (AREA)
• Macromonomer-Based Addition Polymer (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Polymerisation Methods In General (AREA)

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• 2021
  • 2021-10-18 GB GB2114865.5A patent/GB2611825A/en not_active Withdrawn
• 2022
  • 2022-10-07 CN CN202280074882.9A patent/CN118541453A/zh active Pending
  • 2022-10-07 MX MX2024004713A patent/MX2024004713A/es unknown
  • 2022-10-07 EP EP22790085.9A patent/EP4419607B1/en active Active
  • 2022-10-07 KR KR1020247016290A patent/KR20240093701A/ko active Pending
  • 2022-10-07 JP JP2024523155A patent/JP2024539062A/ja active Pending
  • 2022-10-07 WO PCT/NL2022/050568 patent/WO2023068923A1/en not_active Ceased
  • 2022-10-07 US US18/702,718 patent/US20240417313A1/en active Pending

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