WO2013113572A1 - Radiation curable etch resistant inkjet ink printing - Google Patents
Radiation curable etch resistant inkjet ink printing Download PDFInfo
- Publication number
- WO2013113572A1 WO2013113572A1 PCT/EP2013/050943 EP2013050943W WO2013113572A1 WO 2013113572 A1 WO2013113572 A1 WO 2013113572A1 EP 2013050943 W EP2013050943 W EP 2013050943W WO 2013113572 A1 WO2013113572 A1 WO 2013113572A1
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- WIPO (PCT)
- Prior art keywords
- radiation curable
- curable inkjet
- inkjet ink
- polymerizable
- polymerizable composition
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/02—Local etching
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J11/00—Devices or arrangements of selective printing mechanisms, e.g. ink-jet printers or thermal printers, for supporting or handling copy material in sheet or web form
- B41J11/0015—Devices or arrangements of selective printing mechanisms, e.g. ink-jet printers or thermal printers, for supporting or handling copy material in sheet or web form for treating before, during or after printing or for uniform coating or laminating the copy material before or after printing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/0023—Digital printing methods characterised by the inks used
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/22—Removing surface-material, e.g. by engraving, by etching
- B44C1/227—Removing surface-material, e.g. by engraving, by etching by etching
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—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
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
-
- 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
- C09D11/30—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
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/328—Inkjet printing inks characterised by colouring agents characterised by dyes
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- 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
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
- H05K3/061—Etching masks
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/50—Mask blanks not covered by G03F1/20 - G03F1/34; Preparation thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24479—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness
- Y10T428/24612—Composite web or sheet
Definitions
- the present invention relates to inkjet printing of radiation curable inkjet inks that are etch resistant.
- Etching is the process of using a chemical, usually a strong acid or
- a conductive pattern e.g. a printed circuit board, or a design for decorative purposes.
- Printed circuit boards are generally made by bonding a layer of copper over the entire substrate, applying a temporary mask and removing by etching unwanted copper leaving only the desired conductive copper pattern.
- the temporary mask can be made by screen printing etch resistant ink onto the copper foil.
- the screen printing method by nature has low resolution and requires a relatively high viscosity for avoiding adverse phenomena such as bleeding and smudges.
- Another method to provide a temporary mask is photoengraving.
- photomask is usually prepared by laser-printing an image onto a transparent film using computer-aided manufacturing software. After exposing the photoresist coating on the copper foil through the
- US5270368 discloses a UV curable, etch-resistant ink for inkjet printing circuit boards comprising a resin formulation having at least two acrylate components, one of which is an aromatic acrylate having a pendant carboxyl group and one of which is an acrylated epoxy monomer or dimer, a photoinitiator and an organic carrier.
- the preferred organic carrier of methanol and methyl ethyl ketone is employed in a range of 40% to 90% by weight of the ink composition.
- polymerizable acidic compounds are included in the radiation curable ink to promote adhesion to the metal surface.
- US2011024392 A (NISSHIN STEEL & TOKYO PRINTING INK MFG CO) discloses an etch resist inkjet ink having excellent adhesion to metallic plates by including a specific polymerizable phosphoric ester compound, a polyfunctional monomer having two or more ethylenic double-bond groups per molecule and having no phosphoric ester group and a monofunctional monomer having one ethylenic double-bond group per molecule and having neither phosphoric ester group nor carboxy group.
- WO2004106437 A1 discloses a process for etching a metal or alloy surface which comprises applying an etchresistant ink by ink jet printing to selected areas of the metal or alloy, exposing the etch-resistant ink to actinic radiation and/or particle beam radiation to effect
- etch-resistant inks include an acidic polymerizable compound.
- WO2004462260 A2 discloses a radiation-curable hot melt ink composition
- a colorant comprising: a colorant ; a polymerizable monomer; and a photoinitiating system comprising 0.5- .5% by weight of an aromatic ketone photoinitiator, 2-10% by weight of an amine synergist, 3-8% by 2013/050943
- radiation curable inkjet inks including at least 70 percent by weight of a polymerizable composition based on the total weight of radiation curable inkjet ink, wherein the polymerizable composition was controlled to have a minimum oxygen content and cross linking capability, and without the need of an acidic monomer for improving adhesion to the metal surface.
- UV curable ink means that the ink is curable by UV
- alkyl means all variants possible for each number of carbon atoms in the alkyl group i.e. methyl, ethyl, for three carbon atoms: n-propyl and isopropyl; for four carbon atoms: n-butyl, isobutyl and tertiary-butyl; for five carbon atoms: n-pentyl, 1,1-dimethyl-propyl, 2,2-dimethylpropyl and 2- methyl-butyl etc.
- monofunctional monomer means a monomer having only one polymerizable group, for example an acrylate group.
- polyfunctional monomer means a monomer having two, three or more polymerizable groups, e.g. two acrylate groups and one vinyl ether group.
- polyacrylate means a monomer having two, three or more
- a method of inkjet printing according to the present invention includes the steps of :
- the radiation curable inkjet ink includes at least 70 percent by weight of a polymerizable composition based on the total weight of radiation curable inkjet ink,
- the polymerizable composition has an oxygen fraction OFR > ty WPF > 0.0050,
- n the number of polymerizable compounds in the polymerizable composition having a different chemical structural formula
- No.i the number of oxygen atoms in polymerizable compound i
- %wt i the weight percentage of the polymerizable compound i based on the total weight of the radiation curable inkjet ink.
- %wt p the weight percentage of the polymerizable composition based on the total weight of the radiation curable inkjet ink
- the polymerizable composition contains no polymerizable compound with an ethylenic double bond and including a phosphoester group or a carboxylic acid group in the molecule thereof.
- WPF polymerizable functionality WPF is exemplified here below. If a radiation curable inkjet ink contains a single polymerizable compound in the polymerizable composition of radiation curable inkjet ink, then the value of i and n are both 1.
- the metal surface preferably consist of copper, aluminium, nickel, iron, tin, titanium or zinc, but may be also be alloys including these metals.
- the metal surface is made of copper. Copper has a high electrical conductivity and is a relatively cheap metal, making it very suitable for making printed circuit boards.
- the metal surface may be self-supporting or may be present on a support.
- the support can be a non-flexible support as conventionally used in the production of PCB's, but may also be a flexible substrates made of e.g. polyethylene terephthalate or polyimide.
- Self supporting metal surfaces are generally used when a decorative metal panel is made.
- a decorative metal panel may serve a purpose other than being purely decorative, such as providing information.
- an aluminium name plate wherein the etch resistant radiation curable inkjet ink was printed as information, such as a name of a person or a company, and then removed to result in a glossy shiny name on a mat etched background, is also considered a decorative metal panel including a decorative element.
- the metal surface is not self-supporting and when removed by etching exposes the color of or the information on the support.
- the metal surface is cleaned before printing the radiation curable inkjet ink. This is especially desirable when the metal surface is handled by hand and no gloves are worn.
- the cleaning removes dust particles and grease which can interfere in the adhesion of the radiation curable inkjet ink to the metal surface.
- Etching of a metal surface, as in step b) of the inkjet printing method is performed by using an etchant.
- the etchant is preferably an aqueous solution having a pH ⁇ 3 or wherein 8 ⁇ pH ⁇ 10.
- the etchant is an acid aqueous solution having a pH of less than 2.
- the acid etchant preferably includes at least one acid selected from the group consisting of nitric acid, picric acid, hydrochloric acid, hydrofluoric acid and sulfuric acid.
- Preferred etchants known in the art include Kalling's N°2, ASTM N° 30,
- the etchant is an alkaline aqueous
- the alkaline etchant preferably includes at least one base selected from the group consisting of ammonia or ammonium hydroxide, potassium hydroxide and sodium hydroxide.
- the etchant may also contain a metal salt such as copper dichloride, copper sulphate, potassium ferricyanide and iron trichloride.
- Etching is preferably performed in a time frame of seconds to a few
- Etching is preferably performed at room temperature (20°C). [0037] Etching is preferably followed by rinsing with water to remove any residual etchant.
- the cured radiation curable inkjet ink After etching, the cured radiation curable inkjet ink must at least partially be removed from the metal surface, so that e.g. electric or electronic devices can make contact with the remaining metal surface (conductive pattern) or that the decorative feature of an etched metal panel becomes fully visible.
- an electronic component such as a transistor must be able to make electrical contacts with the conductive (copper) pattern on the printed circuit board.
- the cured radiation curable inkjet ink is completely removed from the metal surface.
- the cured radiation curable inkjet ink is
- an alkaline stripping bath is usually an aqueous solution with a pH > 10.
- the cured radiation curable inkjet ink is removed from the protected area in step c) by dry delamination. This technique of "dry stripping" is currently unknown in the art of
- Dry stripping not only eliminates the need of a corrosive alkaline stripping bath and its inherent liquid waste, but also allows for a higher throughput. Dry stripping can be implemented, for example, by using an adhesive foil and a roll-to- roll laminator-delaminator.
- the adhesive foil is first laminated with its adhesive side onto the cured radiation curable inkjet ink present on the metal surface and subsequently delaminated thereby removing the cured radiation curable inkjet ink from the metal surface. Delamination by a roll- to-roll laminator-delaminator can be performed in seconds, while alkaline stripping takes minutes.
- the inkjet printing method of the present invention is used in a method for manufacturing a conductive pattern, such as a PCB.
- the conductive pattern corresponds to the cured radiation curable inkjet ink having an oxygen fraction OFR > 0.250 and a weighted polymerizable functionality WPF > 0.0050.
- inks including a polymerizable composition having an oxygen fraction OFR ⁇ 0.250 and a weighted polymerizable functionality WPF ⁇ 0.0055 exhibited good etch resistance but no strippability.
- a solder mask is a polymeric layer providing a permanent protective
- solder mask is traditionally green but is now available in many colors.
- the solder mask is preferably translucent or transparent, most preferably transparent. The advantage of using a transparent solder mask is that the letters and numbers of the legend are clearly readable and that the legend is also protected against scratching.
- the solder mask is preferably an epoxy liquid that is silk-screened onto the PCB.
- the inkjet printing method of the present invention is used in a method for manufacturing a decorative etched metal panel.
- the metal panel may consist of metal or can be some kind of support with a metallic surface. In the latter, all metal can be removed to reveal the color and texture of the support.
- Etching causes a change in optical properties of a metal surface, such as a change of gloss. After removal of the cured radiation curable inkjet ink from the metal surface an aesthetic effect is created between the etched and the non-etched metal surface.
- one or more differently colored radiation curable inkjet inks including a polymerizable composition having an oxygen fraction OFR ⁇ 0.250 and a weighted polymerizable functionality WPF ⁇ 0.0055 can be printed on the metal surface to produce permanent colored decorational features.
- a metal surface is combined with a radiation
- curable inkjet ink including at least 70 percent by weight of a polymerizable composition based on the total weight of radiation curable inkjet ink, wherein the polymerizable composition has an oxygen fraction OFR > ty WPF > 0.0050,
- n the number of polymerizable compounds in the polymerizable composition having a different chemical structural formula
- ⁇ , ⁇ the number of oxygen atoms in polymerizable compound i
- %wt i the weight percentage of the polymerizable compound i based on the total weight of the radiation curable inkjet ink.
- %wt p the weight percentage of the polymerizable composition based on the total weight of the radiation curable inkjet ink
- the polymerizable composition contains no polymerizable compound with an ethylenic double bond and including a phosphoester group or a carboxylic acid group in the molecule thereof.
- the polymerizable composition may be further combined with a radiation curable inkjet legend ink wherein the polymerizable composition has an oxygen fraction OFR ⁇ 0.250 and a weighted polymerizable functionality WPF ⁇ 0.0055.
- the radiation curable inkjet inks may be cationically curable inkjet inks but are preferably free radical curable inkjet inks.
- the radiation curable inkjet inks can be cured by e-beam, but are preferably cured by light, more preferably UV light.
- the radiation curable inkjet ink is a UV curable inkjet ink, more preferably a free radical UV curable inkjet ink.
- the radiation curable ink may contain a colorant.
- the advantage is that the printed ink pattern is clearly visible which allows orienting the metal surface during handling.
- the colorant may be a dye or a pigment. If the colorant is a pigment preferably a dispersant is present, more preferably a polymeric dispersant.
- the pigmented curable ink may contain a dispersion synergist to improve the dispersion quality and stability of the ink.
- the viscosity of the radiation curable inkjet inks is preferably smaller than 20 mPa.s at 45°C and at a shear rate of 1 ,000 s- , more preferably between 1 and 14 mPa.s at 45°C and a shear rate of 1 ,000 S " .
- the viscosity measured at 45°C is preferably smaller than 20 mPa.s, more preferably between 1 and 14 mPa.s at 45°C and at a shear rate of 90 s- Such measurement can be performed using a Brookfield DV-H+ viscometer at 45°C and at 12 rotations per minute.
- the surface tension of the curable inkjet inks is preferably in the range of about 20 mN/m to about 70 mN/m at 25°C, more preferably in the range of about 22 mN/m to about 40 mN/m at 25°C.
- the curable inkjet inks may further also contain at least one inhibitor for improving the thermal stability of the ink.
- the curable inkjet inks may further also contain at least one surfactant for obtaining desired spreading characteristics on a substrate.
- the n polymerizable compounds in the combination according to present invention all have a viscosity of less than
- polymerization may be used as polymerizable compound.
- a combination of monomers, oligomers and/or prepolymers may also be used.
- the monomers, oligomers and/or prepolymers may possess different degrees of functionality, and a mixture including combinations of mono-, di-, tri-and higher functionality monomers, oligomers and/or prepolymers may be used.
- the viscosity of the radiation curable inkjet inks can be adjusted by varying the ratio between the monomers and oligomers.
- Preferred monomers and oligomers are those listed in [0106] to [0115] in EP 1911814 A (AGFA GRAPHICS) incorporated herein as a specific reference.
- Particularly preferred polymerizable compounds are selected from the
- (2'-vinylethoxy)ethyl acrylate triethyleneglycol diacrylate, triethyleneglycol dimethacrylate, propoxylated neopentylglycol diacrylate, propoxylated glycerine triacrylate, trimethylolpropane trimethylacrylate, tripropylene glycol diacrylate, diethylene glycol diacrylate, dipropylene glycol diacrylate, ethoxylated trimethylolpropane triacrylate and propoxylated
- the photoinitiator is preferably a free radical initiator.
- a free radical is preferably a free radical initiator.
- photoinitiator is a chemical compound that initiates polymerization of monomers and oligomers when exposed to actinic radiation by the formation of a free radical.
- a Norrish Type I initiator is an initiator which cleaves after excitation, yielding the initiating radical immediately.
- a Norrish type ll-initiator is a photoinitiator which is activated by actinic radiation and forms free radicals by hydrogen abstraction from a second compound that becomes the actual initiating free radical. This second compound is called a polymerization synergist or co-initiator. Both type I and type II photoinitiators can be used in the present invention, alone or in combination.
- Suitable photo-initiators are disclosed in CRIVELLO, J.V., et al. VOLUME III: Photoinitiators for Free Radical Cationic . 2nd edition. Edited by BRADLEY, G. London.UK: John Wiley and Sons Ltd, 1998. p.287-294.
- photo-initiators may include, but are not limited to, the following compounds or combinations thereof: benzophenone and substituted benzophenones, 1-hydroxycyclohexyl phenyl ketone, thioxanthones such as isopropylthioxanthone, 2-hydroxy-2-methyl-1- phenylpropan-1 -one, 2-benzyl-2-dimethylamino- (4-morpholinophenyl) butan-1-one, benzil dimethylketal, bis (2,6- dimethylbenzoyl) -2,4, 4- trimethylpentylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,2-dimethoxy-1 , 2-diphenylethan-1-one or 5,7-diiodo-3- butoxy-6- fluorone.
- Suitable commercial photo-initiators include IrgacureTM 184, IrgacureTM 500, IrgacureTM 907, IrgacureTM 369, IrgacureTM 1700, IrgacureTM 651, IrgacureTM 819, IrgacureTM 1000, IrgacureTM 1300, IrgacureTM 1870, DarocurTM 1173, DarocurTM 2959, DarocurTM 4265 and DarocurTM ITX available from CIBA SPECIALTY CHEMICALS, LucerinTM TPO available from BASF AG, EsacureTM KT046, EsacureTM KIP150, EsacureTM KT37 and EsacureTM EDB available from LAMBERTI, H-NuTM 470 and H-NuTM 470X available from SPECTRA GROUP Ltd.
- the photoinitiator is preferably a so-called diffusion hindered photoinitiator.
- a diffusion hindered photoinitiator is a diffusion hindered photoinitiator.
- benzophenone Several methods can be used to lower the mobility of the photoinitiator. One way is to increase the molecular weight of the photoinitiator so that the diffusion speed is reduced, e.g. polymeric photoinitiators. Another way is to increase its reactivity so that it is built into the polymerizing network, e.g. multifunctional photoinitiators (having 2, 3 or more photoinitiating groups) and polymerizable photoinitiators.
- the diffusion hindered photoinitiator is preferably selected from the group consisting of non-polymeric multifunctional photoinitiators, oligomeric or polymeric photoinitiators and polymerizable photoinitiators.
- Non-polymeric di- or multifunctional photoinitiators are considered to have a molecular weight between 300 and 900 Dalton.
- Non-polymerizable monofunctional photoinitiators with a molecular weight in that range are not diffusion hindered photoinitiators. Most preferably the diffusion hindered
- photoinitiator is a polymerizable initiator.
- Suitable diffusion hindered photoinitiators are also those disclosed in EP 2053101 A (AGFA) in paragraphs [0074] and [0075] for difunctional and multifunctional photoinitiators, in paragraphs [0077] to [0080] for polymeric photoinitiators and in paragraphs [0081] to [0083] for polymerizable photoinitiators.
- a preferred amount of photoinitiator is 0 - 50 wt%, more preferably 0.1 - 20 wt%, and most preferably 0.3 - 15 wt% of the total weight of the curable inkjet ink.
- the radiation curable inkjet ink may additionally contain co-initiators.
- co-initiators can be categorized in three groups:
- tertiary aliphatic amines such as methyldiethanolamine
- aromatic amines such as amylparadimethylaminobenzoate, 2-n- butoxyethyl-4-(dimethylamino) benzoate, 2-(dimethylamino)ethylbenzoate, ethyl-4-(dimethylamino)benzoate, and 2-ethylhexyl-4- (dimethylamino)benzoate; and
- (meth)acrylated amines such as dialkylamino alkyl(meth)acrylates (e.g., diethylaminoethylacrylate) or N-morpholinoalkyl-(meth)acrylates (e.g., N-morpholinoethyl-acrylate).
- dialkylamino alkyl(meth)acrylates e.g., diethylaminoethylacrylate
- N-morpholinoalkyl-(meth)acrylates e.g., N-morpholinoethyl-acrylate
- the preferred co-initiators are aminobenzoates.
- the one or more co-initiators included into the radiation curable inkjet ink are preferably diffusion hindered co-initiators for safety reasons.
- a diffusion hindered co-initiator is preferably selected from the group consisting of non-polymeric di- or multifunctional co-initiators, oligomeric or polymeric co-initiators and polymerizable co-initiators. More preferably the diffusion hindered co-initiator is selected from the group consisting of polymeric co-initiators and polymerizable co-initiators.
- the radiation curable inkjet ink preferably comprises a co-initiator in an amount of 0.1 to 50 wt%, more preferably in an amount of 0.5 to 25 wt%, most preferably in an amount of 1 to 10 wt% of the total weight of the radiation curable inkjet ink.
- the radiation curable inkjet ink may further also contain at least one
- Suitable polymerization inhibitors include phenol type antioxidants,
- hindered amine light stabilizers phosphor type antioxidants
- Suitable commercial inhibitors are, for example, SumilizerTM GA-80,
- SumilizerTM GM and SumilizerTM GS produced by Sumitomo Chemical Co. Ltd.; GenoradTM 16, GenoradTM18 and GenoradTM 20 from Rahn AG;
- lrgastabTMUV10 and IrgastabTM UV22 TinuvinTM 460 and CGS20 from Ciba Specialty Chemicals
- FloorstabTM UV range UV-1 , UV-2, UV-5 and UV-8 from Kromachem Ltd
- AdditolTM s range S100, S110, S120 and S130 from Cytec Surface Specialties.
- the inhibitor is preferably a polymerizable inhibitor.
- the amount capable of preventing polymerization is determined prior to blending.
- the amount of a polymerization inhibitor is preferably lower than 5 wt%, more preferably lower than 3 wt% of the total radiation curable inkjet ink.
- Colorants used in the radiation curable inkjet inks may be dyes, pigments or a combination thereof.
- Organic and/or inorganic pigments may be used.
- the colorant is preferably a pigment or a polymeric dye, most preferably a pigment.
- the pigments may be black, white, cyan, magenta, yellow, red, orange, violet, blue, green, brown, mixtures thereof, and the like.
- a colour pigment may be chosen from those disclosed by HERBST, Willy, et al. Industrial Organic Pigments, Production, Properties, Applications. 3rd edition. Wiley - VCH , 2004. ISBN 3527305769.
- Pigment particles in inkjet inks should be sufficiently small to permit free flow of the ink through the inkjet-printing device, especially at the ejecting nozzles. It is also desirable to use small particles for maximum colour strength and to slow down sedimentation.
- the numeric average pigment particle size is preferably between 0.050 and 1 ⁇ , more preferably between 0.070 and 0.300 ⁇ and particularly preferably between 0.080 and 0.200 ⁇ . Most preferably, the numeric average pigment particle size is no larger than 0.150 ⁇ .
- the average particle size of pigment particles is determined with a Brookhaven
- Instruments Particle Sizer BI90plus based upon the principle of dynamic light scattering.
- the ink is diluted with ethyl acetate to a pigment concentration of 0.002 wt%.
- diameter of the white pigment is preferably from 50 to 500 nm, more preferably from 150 to 400 nm, and most preferably from 200 to 350 nm. Sufficient hiding power cannot be obtained when the average diameter is less than 50 nm, and the storage ability and the jet-out suitability of the ink tend to be degraded when the average diameter exceeds 500 nm.
- the determination of the numeric average particle diameter is best performed by photon correlation spectroscopy at a wavelength of 633 nm with a 4mW HeNe laser on a diluted sample of the pigmented inkjet ink.
- a suitable particle size analyzer used was a MalvernTM nano-S available from Goffin- Meyvis.
- a sample can, for example, be prepared by addition of one drop of ink to a cuvette containing .5 ml_ ethyl acetate and mixed until a homogenous sample was obtained.
- the measured particle size is the average value of 3 consecutive measurements consisting of 6 runs of 20 seconds.
- Suitable white pigments are given by Table 2 in [0116] of WO
- the white pigment is preferably a pigment with a refractive index greater than 1.60.
- the white pigments may be employed singly or in combination.
- titanium dioxide is used as pigment with a refractive index greater than 1.60.
- Suitable titanium dioxide pigments are those disclosed in [0117] and in [0118] of WO
- the pigments are preferably present in the range of 0.01 to 15 %, more preferably in the range of 0.05 to 10 % by weight and most preferably in the range of 0.1 to 5 % by weight, each based on the total weight of the inkjet ink.
- the white pigment is preferably present in an amount of 3% to 40% by weight of the inkjet ink, and more preferably 5% to 35%. An amount of less than 3% by weight cannot achieve sufficient covering power and usually exhibits very poor storage stability and ejection property.
- the colorant in the radiation curable inkjet ink is an anthraquinone dye, such as MacrolexTM Blue 3R (CASRN 325781-98-4) from LANXESS. Dispersants
- the dispersant is preferably a polymeric dispersant.
- Typical polymeric dispersants are copolymers of two monomers but may contain three, four, five or even more monomers.
- the properties of polymeric dispersants depend on both the nature of the monomers and their distribution in the polymer.
- Suitable copolymeric dispersants have the following polymer compositions:
- alternating polymerized monomers e.g. monomers A and B polymerized into ABABABAB
- block copolymers e.g. monomers A and B polymerized into
- AAAAABBBBBB wherein the block length of each of the blocks (2, 3, 4, 5 or even more) is important for the dispersion capability of the polymeric dispersant;
- graft copolymers consist of a polymeric backbone with polymeric side chains attached to the backbone; and mixed forms of these polymers, e.g. blocky gradient copolymers.
- Suitable polymeric dispersants are listed in the section on "Dispersants", more specifically [0064] to [0070] and [0074] to [0077], in EP 1911814 A
- the polymeric dispersant has preferably a number average molecular weight Mn between 500 and 30000, more preferably between 1500 and
- the polymeric dispersant has preferably a weight average molecular
- weight Mw smaller than 100000, more preferably smaller than 50000 and most preferably smaller than 30000.
- the polymeric dispersant has preferably a polydispersity PD smaller than 2, more preferably smaller than 1.75 and most preferably smaller than 1.5.
- polymeric dispersants are the following:
- Particularly preferred polymeric dispersants include SolsperseTM
- the polymeric dispersant is preferably used in an amount of 2 to 600 wt%, more preferably 5 to 200 wt% based on the weight of the pigment.
- a dispersion synergist usually consists of an anionic part and a cationic part.
- the anionic part of the dispersion synergist usually exhibits a certain molecular similarity with the colour pigment and the cationic part of the dispersion synergist consists of one or more protons and/or cations to compensate the charge of the anionic part of the dispersion synergist.
- the synergist is preferably added in a smaller amount than the polymeric dispersant(s).
- the ratio of polymeric dispersant/dispersion synergist depends upon the pigment and should be determined experimentally.
- the ratio wt% polymeric dispersant wt% dispersion synergist is selected between 2:1 to 100:1 , preferably between 2:1 and 20:1.
- Suitable dispersion synergists that are commercially available include
- Suitable dispersion synergists include those disclosed in EP 1790698 A (AGFA GRAPHICS) , EP 790696 A (AGFA GRAPHICS) , WO
- NOVEON is preferred.
- Suitable dispersion synergists for yellow inkjet inks include those disclosed in EP 790697 A (AGFA GRAPHICS) .
- the dispersion synergist includes one, two or more carboxylic acid groups and preferably no sulfonic acid groups.
- the radiation curable inkjet ink may further also contain a surfactant for obtaining good spreading characteristics on a substrate.
- the surfactant(s) can be anionic, cationic, non-ionic, or zwitterionic and are usually added in a total quantity less than 10 wt% based on the total weight of the radiation curable liquid or ink and particularly in a total less than 5 wt% based on the total weight of the radiation curable liquid or ink.
- Preferred surfactants include fluoro surfactants (such as fluorinated
- silicones are typically siloxanes and can be polyether modified, polyester modified, polyether modified hydroxy functional, amine modified, epoxy modified and other modifications or combinations thereof. Silicone surfactants, especially the reactive silicone surfactants, are preferred in radiation curable inkjet inks.
- the radiation curable inkjet ink contains no surfactant.
- radiation curable inkjet inks may be jetted by one or more print heads ejecting small droplets in a controlled manner through nozzles onto a substrate, which is moving relative to the print head(s).
- a preferred print head for the inkjet printing system is a piezoelectric head.
- Piezoelectric inkjet printing is based on the movement of a piezoelectric ceramic transducer when a voltage is applied thereto.
- the application of a voltage changes the shape of the piezoelectric ceramic transducer in the print head creating a void, which is then filled with ink.
- the ceramic expands to its original shape, ejecting a drop of ink from the print head.
- the inkjet printing method according to the present invention is not restricted to piezoelectric inkjet printing.
- Other inkjet print heads can be used and include various types, such as a continuous type.
- the inkjet print head normally scans back and forth in a transversal
- Another preferred printing method is by a "single pass printing process", which can be performed by using page wide inkjet print heads or multiple staggered inkjet print heads which cover the entire width of the ink-receiving metal surface. In a single pass printing process the inkjet print heads usually remain stationary and the metal surface is transported under the inkjet print heads.
- radiation curable inkjet inks are cured by exposing them to actinic radiation, preferably by ultraviolet radiation.
- the curing means may be arranged in combination with the print head of the inkjet printer, travelling therewith so that the curable inkjet ink is exposed to curing radiation very shortly after been jetted.
- the actinic radiation may be supplied from a fixed source to the radiation head by an arrangement of mirrors including a mirror upon the radiation head.
- the source of radiation arranged not to move with the print head may also be an elongated radiation source extending transversely across the ink- receiver surface to be cured and adjacent the transverse path of the print head so that the subsequent rows of images formed by the print head are passed, stepwise or continually, beneath that radiation source.
- a radiation source such as, a high or low pressure mercury lamp, a cold cathode tube, a black light, an ultraviolet LED, an ultraviolet laser, and a flash light.
- the preferred source is one exhibiting a relatively long wavelength UV-contribution having a dominant wavelength of 300-400 nm.
- a UV-A light source is preferred due to the reduced light scattering therewith resulting in more efficient interior curing.
- UV radiation is generally classed as UV-A, UV-B, and UV-C as follows:
- UV-A 400 nm to 320 nm
- UV-C 290 nm to 100 nm.
- the inkjet printing device contains one or more UV LEDs with a wavelength larger than 360 nm, preferably one or more UV LEDs with a wavelength larger than 380 nm, and most preferably UV LEDs with a wavelength of about 395 nm.
- the first UV-source can be selected to be rich in UV-C, in particular in the range of 260 nm-200 nm.
- the second UV-source can then be rich in UV-A, e.g. a gallium-doped lamp, or a different lamp high in both UV-A and UV-B.
- the use of two UV-sources has been found to have advantages e.g. a fast curing speed and a high curing degree.
- the inkjet printer may include one or more oxygen depletion units.
- the oxygen depletion units place a blanket of nitrogen or other relatively inert gas (e.g. CO2), with adjustable position and adjustable inert gas concentration, in order to reduce the oxygen concentration in the curing environment. Residual oxygen levels are usually maintained as low as 200 ppm, but are generally in the range of 200 ppm to 1200 ppm.
- ITX is DarocurTM ITX is an isomeric mixture of 2- and 4- isopropylthioxanthone from CIBA SPECIALTY CHEMICALS.
- IrgacureTM 907 is 2-methyI-1-[4-(methylthio)phenyl]-2-morpholino-propan-
- IrgacureTM 819 is bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, a photoinitiator available from CIBA SPECIALTY CHEMICALS.
- DarocurTMTPO is 2,4,6-trimethylbenzoyl-diphenyl-phosphineoxide, a photoinitiator available from CIBA SPECIALTY CHEMICALS.
- MBF is an aromatic photoinitiator (CAS 15206-55-0) available as
- lnhib-1 is a mixture forming a polymerization inhibitor having a
- CupferronTM AL is aluminum N-nitrosophenylhydroxylamine from WAKO CHEMICALS LTD.
- MacrolexTM Blue 3R is a blue anthraquinone dye from LANXESS.
- IsolaTM 400 is a Cu-plate available from CCI Eurolam having a metal surface consisting of a 18 ⁇ Cu-laminate.
- VEEA is available from NIPPON SHOKUBAI, Japan.
- CarduraTM ACE is available from HEXION SPECIALTY CHEMICALS.
- CD420 Sartomer I CD420 3,3,5-Trimethylcyclohexyl acrylate
- CD561 Sartomer ,M CD561 1 ,6-Hexanediol (5.6x ethoxylated) diacrylate
- the etch resistance was evaluated by the determining the percentage of the cured inkjet ink layer that remained on the copper plate after etching.
- An etch resistance of 100% means that the whole cured inkjet ink layer survived the etching bath.
- An etch resistance of 0% means that no cured inkjet ink could be found to be present on the copper plate after etching.
- An intermediate percentage, e.g. 80% means that about 80% of the cured inkjet ink could be found to be present on the copper plate after etching.
- a good etch resistance means a value of at least 80%.
- Excellent etch resistance means a value of at least 90% but preferably 100%.
- the strippability was evaluated by the determining the percentage of the cured inkjet ink layer that was removed from the copper plate after stripping.
- a strippability of 100% means that the whole cured inkjet ink layer was removed.
- a strippability of 0% means that no cured inkjet ink could be removed from the copper plate.
- An intermediate percentage, e.g. 30% means that only about 30% of the cured inkjet ink could be removed from the copper plate by stripping.
- a good strippability means a value of at least 80%.
- Excellent strippability means a value of at least 90% but preferably 100%.
- a value of 30% or less is a very poor strippability.
- the viscosity is preferably less than 20 mPa.s at 45°C. More preferably the viscosity is less than 15 mPa.s at 45°C.
- a radiation curable inkjet ink was coated on a PET100 substrate using a bar coater and a 10 m wired bar.
- the coated sample was cured using a Fusion DRSE-120 conveyer, equipped with a Fusion VPS/I600 lamp (D- bulb), which transported the samples under the UV-lamp on a conveyer belt at a speed of 20 m/min.
- the maximum output of the lamp was 1.05
- This example illustrates an inkjet printing method for an etching process using a radiation curable inkjet ink including a single polymerizable compound.
- the radiation curable inkjet inks COMP-1 to COMP-18 and INV-1 to INV- 24 were prepared by mixing the components according to the weight percentages based on the total weight of the ink listed in Table 1 and using the polymerizable compound of Table 2.
- IsolaTM 400 copper plates were cleaned for 5 seconds at 25 °C with a solution called MecbriteTM CA-95 from MEC Europe, which has pH ⁇ 1 and contained H2SO 4) H2O2 and Cu 2+ . During this operation a thin top layer of Cu (0.3 - 0.5 ⁇ ) was removed. The plates were then rinsed with a water jet for 90 seconds.
- a pattern of the radiation curable inkjet inks COMP-1 to COMP-18 and INV-1 to INV-24 was coated at a thickness of 10 ⁇ on the copper plate and cured by a Fusion DRSE-120 conveyer, equipped with a Fusion VPS/I600 lamp (D-bulb), which transported the samples under the UV- lamp on a conveyer belt at a speed of 20 m/min.
- the maximum output of the lamp was 1.05 J/cm 2 and a peak intensity of 5.6 W/cm 2 . All inkjet inks were fully cured.
- This example illustrates an inkjet printing method for an etching process using a radiation curable inkjet ink including a mixture of two polymerizable compounds.
- INV-54 were prepared by mixing the components according to Table 3 and using the polymerizable compounds P1 and P2 in the weight percentages based on the total weight of ink as indicated in Table 4.
- EXAMPLE 1 A pattern of the radiation curable inkjet inks COMP-19 to COMP-30 and INV-25 to INV-54 was coated at a thickness of 10 pm and cured on the cleaned copper plate in the same manner as in EXAMPLE 1. The plates were then etched and stripped in the same manner as in EXAMPLE 1. The results are shown in Table 4.
- INV-77 were prepared by mixing the components according to Table 5 and using the polymerizable compounds P1 (and P2 if present) in the weight percentages based on the total weight of ink as indicated in Table 6.
- IsolaTM 400 copper plates were cleaned in the same manner as in
- EXAMPLE 1 A pattern of the radiation curable inkjet inks COMP-31 to COMP-42 and INV-55 to INV-77 was coated at a thickness of 10 pm and cured on the cleaned copper plate in the same manner as in EXAMPLE 1.
- a second set of copper plates made with the radiation curable inkjet inks COMP-31 to COMP-42 and INV-55 to INV-77 was subjected for 60 seconds at 35°C to an alkaline etch bath Metal etch 50 from Centurion Speciality Chemicals Ltd which contained NH 4 OH, NH 4 CI, (NH 4 )2CO3 and Cu(NH 4 )Cl3 at pH 8.5.
- the plates were subsequently rinsed for 90 seconds with water and dried.
- the copper plates having their inkjet ink layer not removed during etching were subjected for 5 minutes at 50°C to an alkaline strip bath (containing 10 % Ristoff C-71 from Centurion
- a third set of copper plates made with the radiation curable inkjet inks COMP-31 to COMP-42 and INV-55 to INV-77 was etched in the same manner as in EXAMPLE 1.
- a TESAFILM 4014 Black tape (type PV-025- 066-B4 04 5) from Tesa AG was attached to the pattern of the radiation curable inkjet ink on the copperplate. The tape was then pulled from the copper plate, thereby peeling off the pattern in a number of cases.
- the strippability results are indicated Table 7 by Strippability "Dry Strip".
- COMP-41 0% 0% n.a. n.a. n.a.
- COMP-42 0% 0% n.a. n.a. n.a.
- Table 7 shows that only the radiation curable inkjet inks wherein the
- polymerizable composition has an oxygen fraction OFR > 0.250 and a weighted polymerizable functionality WPF > 0.0050 supported very different etching and stripping conditions .
- INV-81 were prepared by mixing the components according to Tables 8 to
- All the radiation curable inkjet inks COMP-43 to COMP-58 and INV-78 to INV-81 had a polymerizable composition having an oxygen fraction OFR > 0.250 and a weighted polymerizable functionality WPF > 0.0050.
- No homogeneous inkjet ink could be prepared for the compositions according to COMP-43 and COMP-45, some components could not be dissolved adequately and therefore no further tests were performed on these inks.
- All the radiation curable inkjet inks contained no surfactant, yet all had a surface tension between 20 and 40 mN/m measured with a KRLISS tensiometer K9 from KRLISS GmbH, Germany at 25°C after 60 seconds.
- EXAMPLE 1 A pattern of the radiation curable inkjet inks COMP-43 to COMP-58 and INV-78 to INV-81 was coated at a thickness of 10 pm and cured on the cleaned copper plate in the same manner as in EXAMPLE 1. The plates were then etched and stripped in the same manner as in EXAMPLE 1. Excellent etch resistance was observed for all inkjet inks. The results of strippability are shown in Table 12.
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Abstract
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Priority Applications (9)
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US14/370,253 US9556349B2 (en) | 2012-01-31 | 2013-01-18 | Radiation curable etch resistant inkjet ink printing |
KR1020167022178A KR102026992B1 (en) | 2012-01-31 | 2013-01-18 | Radiation curable etch resistant inkjet ink printing |
AU2013214473A AU2013214473B2 (en) | 2012-01-31 | 2013-01-18 | Radiation curable etch resistant inkjet ink printing |
EP13700736.5A EP2809735B1 (en) | 2012-01-31 | 2013-01-18 | Radiation curable etch resistant inkjet ink printing |
KR1020147016283A KR20140092917A (en) | 2012-01-31 | 2013-01-18 | Radiation curable etch resistant inkjet ink printing |
CN201380007454.5A CN104066590B (en) | 2012-01-31 | 2013-01-18 | The etch resistant jetted ink printing of radiation-hardenable |
JP2014542899A JP6012749B2 (en) | 2012-01-31 | 2013-01-18 | Radiation curable etching resistant ink jet ink printing |
BR112014016337A BR112014016337A8 (en) | 2012-01-31 | 2013-01-18 | radiation-curable, chemical-resistant inkjet inkjet printing |
US15/381,161 US20170096572A1 (en) | 2012-01-31 | 2016-12-16 | Radiation curable etch resistant inkjet ink printing |
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JP6012749B2 (en) | 2016-10-25 |
KR102026992B1 (en) | 2019-09-30 |
AU2013214473A1 (en) | 2014-05-29 |
CN104066590A (en) | 2014-09-24 |
US20170096572A1 (en) | 2017-04-06 |
EP2809735B1 (en) | 2018-05-30 |
BR112014016337A2 (en) | 2017-06-13 |
JP2015507079A (en) | 2015-03-05 |
CN104066590B (en) | 2015-11-25 |
US20140363632A1 (en) | 2014-12-11 |
EP2809735A1 (en) | 2014-12-10 |
BR112014016337A8 (en) | 2017-07-04 |
KR20160101207A (en) | 2016-08-24 |
US9556349B2 (en) | 2017-01-31 |
AU2013214473B2 (en) | 2016-03-17 |
KR20140092917A (en) | 2014-07-24 |
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