EP2574458A1 - Procédé pour la préparation d'un support d'impression flexographique - Google Patents

Procédé pour la préparation d'un support d'impression flexographique Download PDF

Info

Publication number
EP2574458A1
EP2574458A1 EP11183419A EP11183419A EP2574458A1 EP 2574458 A1 EP2574458 A1 EP 2574458A1 EP 11183419 A EP11183419 A EP 11183419A EP 11183419 A EP11183419 A EP 11183419A EP 2574458 A1 EP2574458 A1 EP 2574458A1
Authority
EP
European Patent Office
Prior art keywords
printing
fluid
curable fluid
curing
curable
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP11183419A
Other languages
German (de)
English (en)
Inventor
Luc Vanmaele
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agfa NV
Original Assignee
Agfa Graphics NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Agfa Graphics NV filed Critical Agfa Graphics NV
Priority to EP11183419A priority Critical patent/EP2574458A1/fr
Priority to PCT/EP2012/068595 priority patent/WO2013045349A1/fr
Publication of EP2574458A1 publication Critical patent/EP2574458A1/fr
Withdrawn legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/003—Forme preparation the relief or intaglio pattern being obtained by imagewise deposition of a liquid, e.g. by an ink jet

Definitions

  • the present invention relates to a method for making a flexographic printing master comprising an aerosol jet printing step.
  • Flexography is a form of printing process which utilizes a flexible relief plate, the flexographic printing master. It is basically an updated version of letterpress that can be used for printing on almost any type of substrate including plastic, metallic films, cellophane, and paper. Flexography is widely used for printing on packaging material, for example food packaging. Also, with flexography continuous patterns, such as for gift wrap and wall paper, can be printed.
  • flexographic printing masters are prepared by both analogue and digital imaging techniques.
  • Analogue imaging typically uses a film mask through which a flexographic printing precursor is exposed.
  • Digital imaging techniques include:
  • the major advantage of an inkjet method for preparing a flexographic printing master is an improved sustainability due to the absence of any processing step and the consumption of no more material as necessary to form a suitable relief image (i.e. removal of material in the non printing areas is no longer required).
  • EP-A 641648 discloses a method of making a photopolymer relief-type printing plate wherein a positive or negative image is formed on a substrate by inkjet printing with a photopolymeric ink and subjecting the resulting printed substrate to UV radiation, thereby curing the ink composition forming the image.
  • US6520084 discloses a method of preparing flexographic printing masters by inkjet wherein a removable filler material is used to support the relief image being printed and wherein the relief image is grown in inverted orientation on a substrate. Disadvantages of this method are the removal of the filler material and the release of the relief image from the substrate.
  • EP-A 1428666 discloses a method of making a flexographic printing master by means of jetting subsequent layers of a curable fluid on a flexographic support. Before jetting the following layer, the previous layer is immobilized by a curing step.
  • a flexographic printing master is prepared by inkjet wherein each layer of ink is first jetted and partially cured on a blanket whereupon each such layer is then transferred to a substrate having an elastomeric floor, thereby building up the relief image layer by layer.
  • a similar method is disclosed in EP-A 1449648 wherein a lithographic printing plate is used to transfer such layers of ink to a substrate.
  • US2008/0053326 discloses a method of making a flexographic printing master by inkjet wherein successive layers of a polymer are applied to a specific optimized substrate.
  • curing means are provided to additionally cure, for example, the side surfaces of the image relief being formed.
  • EP-A 2223803 a UV curable hot melt ink is used. Each of the deposited layers of ink is gelled before a subsequent layer is deposited. After a printing master with sufficient thickness is formed, a curing step is carried out.
  • EP-As 1637926 and 1637322 disclose a specific curable jettable fluid for making flexographic printing masters comprising a photo-initiator, a monofunctional monomer, a polyfunctional monomer or oligomer and at least 5 wt. of a plasticizer. The presence of the plasticizer is necessary to obtain a flexographic printing master having the necessary flexibility. Also in EP-A 2033778 , the curable jettable fluid for making a relief image by inkjet on a sleeve body contains a plasticizer.
  • a flexographic printing master formed on a support by an inkjet method typically comprises an elastomeric floor, an optional mesa relief and an image relief as disclosed in EP-A 2199082 .
  • a print head with small nozzle diameters for example producing 3 pl fluid droplets.
  • Print heads with such small nozzle diameters however require low viscosity fluids.
  • the requirement for such a low viscosity however imposes constraints on the choice of the ingredients of the fluid. For example it limits the amount of monomers having a high viscosity or the amount of plasticizers, while often a high amount of such ingredients is preferred to prepare flexographic printing masters with optimal physical properties.
  • the object of the present invention is realised with by the method for preparing a flexographic printing master as defined in claim 1.
  • the present invention relates to a method for preparing a flexographic printing master comprising an aerosol jet printing step.
  • Aerosol Jet Printing which has been developed by Optomec, preserves most of the advantages of inkjet printing, while reducing many of its limitations.
  • the technique is developed for use in the field of printed electronics. The technique is disclosed in for example US2003/0048314 , US2003/0020768 , US2003/0228124 and WO2009/049072 .
  • An Aerosol Jet Print Engine is commercially available from Optomec, for example the Aerosol Jet Printer OPTOMEC AJ 300 CE. More details on the Aerosol Jet Printing technique and engine are found on the Optomec website www.optomec.com.
  • Aerosol Jet Printing a collimated beam of material is dispensed on a substrate. This allows the resolution to be maintained over a wide range of standoff (head to substrate) distances. This enables larger standoff distances to be used than are possible with inkjet printing.
  • the differences between inkjet and Aerosol Jet Printing are schematically shown in Figure 2 .
  • the drops are typically of low density.
  • the standoff (500) between the nozzle and the substrate is usually about 1 mm.
  • the droplets spread out upon leaving the nozzle, and the system is normally optimized to achieve optimum results at the fixed standoff distance.
  • Aerosol Jet Printing a collimated beam of material is formed which is then deposited on the substrate.
  • standoff distances from 1 to 5 mm can be used without loss of resolution.
  • This feature is very important for printing features over an existing topology as found in many electrical devices and circuits, and enables conformal printing, which is the application for which the Aerosol Jet Printing technology was originally developed.
  • the thickness of the total relief image (floor - mesa relief and image relief) of a flexographic printing master may be up to several mm.
  • the standoff distance between the print head and the lower layers of the printing master may be several mm resulting in a different resolution of the lower an upper layers making up the printing master.
  • the resolution of the lower and the upper layers will almost not vary when using Aerosol Jet Printing.
  • Aerosol Jet Printing system rather than producing individual droplets of ink, an aerosol is produced, focused and directed toward the substrate.
  • the basic system consists of two key components: a first module (200) for forming an aerosol (210) from a fluid (220) and a second module (300) focussing the aerosol (210) and depositing the aerosol droplets on a substrate (400). Similar to continuous inkjet, this aerosol stream can be shuttered to interrupt the stream.
  • Aerosols can be formed from fluids as viscous as 5000 mPa.s.
  • An ultrasonic transducer can be used for nebulizing low viscosity fluids (0.7 to 10 mPa.s).
  • a piezoelectric transducer produces high frequency pressure waves, which are transmitted through a coupling fluid (typically water) into the deposition fluid.
  • This atomization technique works best for suspended particles of less than 50 nm.
  • For higher viscosity fluids (10 to 5000 mPa.s) or larger suspended particles ( ⁇ 0.5 ⁇ m) pneumatic atomization is used.
  • a high velocity gas stream is used to shear the liquid stream into droplets.
  • the aerosol stream can be focused to a fine, collimated (the cross sectional diameter does not vary as a function of the distance from the nozzle) beam.
  • the focusing gas (300) surrounds the aerosol completely so that droplets do not touch the inner walls of the nozzle, eliminating clogging and other problems.
  • This aerosol jet focusing gives rise to a jet diameter which is much smaller than that of the nozzle orifice.
  • a variety of line widths can be produced, from about 10 to 150 ⁇ m.
  • a preferred flexographic printing master according to the present invention is disclosed in EP-A 2199082 . It typically comprises on a substrate (1000), preferably a sleeve body, in this order, a floor (600), a mesa relief (700) and an image relief (800).
  • EP-A 2199082 disclosed a method for preparing such a flexographic printing master with inkjet.
  • the above mentioned methods of preparing a flexographic printing master are modified in that all layers are now deposited by the aerosol jet printing technique instead of the inkjet printing technique.
  • inkjet printing may be used to optimize the throughput of the method, for example by using large fluid droplets.
  • image relief where resolution must be as high as possible, may then be deposited using the aerosol jet printing technique.
  • only the upper most layer (the top layer of the image relief) is deposited using aerosol jet printing, while all other layers are deposited using inkjet printing.
  • High viscous fluids may then be used to deposit the top layer to optimize the properties of the printing areas of the flexographic printing master.
  • more then one top layer for example two, three or more, may be applied using aerosol jet printing.
  • the upper most layer(s) of the floor and the mesa relief may be applied using aerosol jet printing while the other layers are applied using inkjet.
  • the floor may be precoated on a sleeve body by conventional coating techniques.
  • the mesa relief and the image relief are then applied on the precoated floor by aersol jet printing, or the combination aerosol jet printing - inkjet printing.
  • the image relief may be directly applied on the floor.
  • the method according to the present invention may use aerosol jet printing only, or a combination of aerosol jet printing and inkjet printing.
  • the same fluid may be used in both the aerosol jet printing step and the inkjet printing step but preferably different fluids are used, optimized towards the printing technique, hereinafter referred to as the curable aerosol jet fluid and the curable inkjet fluid.
  • the curable aerosol jet fluid and the curable inkjet fluid are preferably used for the aerosol jet printing step.
  • high viscous fluids are preferably used to optimize the properties of the obtained flexographic printing master.
  • Typical ingredients for both types of fluids are preferably selected from the group consisting of a monofunctional (meth)acrylate monomer, a difunctional (meth)acrylate monomer, a multifunctional (meth)acrylate monomer or oligomer, a low viscous monofunctional urethane acrylate oligomer (especially for curable inkjet fluid), a higher viscous mono-or multifunctional urethane acrylate (especially for the curable aerosol jet fluid), an initiator, a plasticizer, an inhibitor, an elastomeric binder, a surfactant, a colorant, a solvent, an humectants, a biocide.
  • the curable fluid may comprises a monofunctional (meth)acrylate monomer. Any monofunctional (meth)acrylate monomer, such as disclosed for example in EP-A 1637322 , paragraph [0055], may be used.
  • the curable fluid preferably comprises a cyclic monofuntional (meth)acrylate monomer.
  • cyclic monofunctional (meth)acrylates are isobornyl acrylate (SR506D from Sartomer), tetrahydrofurfuryl methacrylate (SR203 from Sartomer), 4-t.butylcyclohexyl arylate (Laromer TBCH from BASF), dicyclopentadienyl acrylate (Laromer DCPA from BASF), dioxalane functional acrylates (CHDOL10 and MEDOL10 from San Esters Corporation), cyclic trimethylolpropane formal acrylate (SR531 from Sartomer), 2-phenoxyethyl acrylate (SR339C from Sartomer), 2-phenoxyethyl methacrylate (SR340 from Sartomer), tetrahydrofurfuryl acrylate (SR285 from Sartomer), 3,3,5-trimethyl cyclohexyl acrylate
  • Particularly preferred cyclic monofunctional (meth)acrylates monomers are isobornyl acrylate (IBOA) and 4-t.butylcyclohexyl arylate (Laromer TBCH from BASF).
  • the amount of the cyclic monofunctional (meth)acrylate monomer is preferably at least 25 wt.%, more preferably at least 30 wt.%, relative to the total weight of the curable fluid.
  • a preferred difunctional (meth)acrylate monomer is a polyalkylene glycol di(meth)acrylate.
  • Such compounds have two acrylate or methacrylate groups attached by an ester linkage at the opposite ends of a hydrophilic polyalkylene glycol.
  • the longer the length of the polyalkylene chain the softer and more flexible the obtained layer after curing.
  • polyalkylene glycol di(meth)acrylates examples include: 1,3-butylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, dipropylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol (200) diacrylate, polyethylene glycol (400) diacrylate, polyethylene glycol (400) dimethacrylate, polyethylene glycol (600) diacrylate, polyethylene glycol (600) dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol (400) dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tripropylene glycol diacrylate, tripropylene glycol diacrylate, tripropylene glycol diacrylate, tripropylene glycol diacrylate, and combinations thereof.
  • polyethylene glycol diacrylates are polyethylene glycol diacrylates.
  • Specific examples of commercially available polyethylene glycol diacrylate monomers include SR259 [polyethylene glycol (200) diacrylate], SR344 [polyethylene glycol (400) diacrylate], SR603 [polyethylene glycol (400) dimethacrylate], SR610 [polyethylene glycol (600) diacrylate], SR252 [polyethylene glycol (600) dimethacrylate], all Sartomer products; EBECRYL 11 [poly ethylene glycol diacrylate from Cytec; Genomer 1251 [polyethylene glycol 400 diacrylate] from Rahn. Polyethylene glycol (600) diacrylate, available as SR610 from Sartomer, is particularly preferred.
  • difunctional acrylate or methacrylate monomers are e.g. butane diol diacrylate, alkoxylated hexanediol diacrylate, alkoxylated neopentyl glycol diacrylate and alkoxylated hexanediol dimethacrylate.
  • the amount of the difunctional (meth)acrylate monomer is preferably at least 10 wt.% of the total monomer content.
  • Particularly preferred difunctional (meth)acrylate monomers are those according to Formula I or II, wherein k and m in Formula I is an integer ranging from O to 5, 1 in Formula I is an integer ranging from 1 to 20 n in Formula II is 1, 2, 3 or 4, R is H or CH 3 , and R' is H or an alkyl group.
  • Difunctional (meth)acrylate monomers according to Formula I are typically derived from diols containing an -(CH 2 )- backbone.
  • Preferred compounds according to Formula I are polyoxytetramethylene diacrylate (Blemmer ADT250); 1,9 nonanediol diacrylate; 1,6 hexanediol diacrylate (SR238); 1,6 hexanediol dimethacrylate (SR239); 1,4 butanediol diacrylate (SR213); 1,2 ethanediol dimethacrylate (SR206); 1,4 butanediol dimethacrylate (SR214); ethoxylated 1,6 hexanediol diacrylate (Miramer M202)
  • Difunctional (meth)acrylate monomers according to Formula II are typically derived from diols containing a glycol ether backbone.
  • the R' group in Formula II is preferably H or methyl.
  • Preferred compounds according to Formula II are dipropyleneglycol diacrylate (DPGDA, SR508), diethylene glycol diacrylate (SR230), triethyleneglycol diacrylate (SR272), 1,3-butylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, dipropylene glycol diacrylate, ethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tripropylene glycol diacrylate, tripropylene glycol diacrylate, tripropylene glycol diacrylate, tripropylene glycol diacrylate, and combinations thereof
  • the amount of the difunctional acrylate monomer according to Formula I or II is at least 1 wt.%, preferably at least 5 wt.%, more preferably at least 7.5 wt.%, relative to the total weight of the curable fluid.
  • the curable fluid further comprises a tri-, tetra- or penta-functional (meth)acrylate monomer. It has been observed that the hardness of the cured layer obtained from the curable fluid becomes too high when too much tri-, tetra- or penta-functional (meth)acrylate monomer is present in the fluid.
  • the Shore A hardness of the cured layer must be kept below 80, to ensure good physical properties of the flexographic printing master. It has been observed that the maximum concentration of the tri-, tetra- or penta-functional (meth)acrylate monomer to ensure a proper hardness depends on their functionality. Typically, the higher their functionality, the lower their maximum allowable concentration to ensure a Shore A hardness below 80.
  • the functionality of the tri-, tetra- or penta-functional (meth)acrylate monomers also influences their viscosity, and thus also the viscosity of the curable fluid.
  • the higher their functionality the higher their viscosity.
  • the viscosity of the curable inkjet fluid measured at jetting temperature, is preferably below 15 mPa.s, this also limits the maximum concentration of the tri- tetra- or penta-functional (meth)acrylate monomer in the jettable fluid.
  • the maximum concentration of the tri-, tetra- or penta-functional (meth)acrylate monomer, dependent on their viscosity, is as depicted in the following table.
  • visco (mPa.s) ⁇ 100 100 - 250 250 - 5000 > 5000 functionality 3 20 wt.% 17.5 wt.% 15 wt.% 10 wt.% 4 15 wt.% 12.5 wt.% 10 wt.% 7.5 wt.% 5 10 wt.% 8 wt.% 6 wt.% 4 wt.%
  • the minimum concentration is preferably 0.5 wt.%, more preferably 1 wt.%).
  • the higher viscosities are allowable as described above. Therefore, higher concentrations of multifunctional (meth)acrylate monomers may be used.
  • Preferred examples are ditrimethylol propane tetraacrylate (DTMPTA), glycerol triacrylate and their alkoxylated, i.e. ethoxylated or propoxylated, derivatives.
  • DTMPTA ditrimethylol propane tetraacrylate
  • glycerol triacrylate and their alkoxylated, i.e. ethoxylated or propoxylated, derivatives.
  • TMPTA trimethylol propane tetraacrylate
  • SR492 propoxylated TMPTA
  • ethoxylated TMPTA commercially available as Miramer M3130
  • DTMPTA commercially available as SR355
  • propoxylated glyceryl triacrylate commercially available as SR9021 and SR9020.
  • DIPEPA dipentaerythritol pentaacrylate
  • SR399LV tri-acrylate esters of pentaerythritol, such as pentaerythritol triacrylate (PETIA); tetraacrylate esters of pentaerythritol, such as PETRA, commercially available as SR295; ethoxylated PETRA, commercially available as SR494; alkoxylated PETRA, commercially available as Ebecryl 40.
  • the curable fluid especially the curable inkjet fluid, may further contain monofunctional urethane acrylate oligomers.
  • Urethane acrylates oligomers are well known and are prepared by reacting polyisocyanates with hydroxyl alkyl acrylates, usually in the presence of a polyol compound. Their functionality (i.e. number of acrylate groups) varies from 1 to 6. A lower functionality results in lower reactivity, better flexibility and a lower viscosity.
  • the polyol compound forms the backbone of the urethane acrylate.
  • the polyol compounds are polyether or polyester compounds with a functionality (hydroxyl groups) ranging from two to four.
  • Polyether urethane acrylates are generally more flexible, provide lower cost, and have a slightly lower viscosity and are therefore preferred.
  • urethane (meth)acrylates are e.g. CN9170, CN910A70, CN966H90, CN962, CN965, CN9290 and CN981 from SARTOMER; BR-3741B, BR-403, BR-7432, BR-7432G, BR-3042, BR-3071 from BOMAR SPECIALTIES CO.; NK Oligo U-15HA from SHIN-NAKAMURA CHEMICAL CO.
  • the curable inkjet fluid preferably comprises monofunctional urethane acrylate oligomers, more preferably monofunctional aliphatic urethane acrylates, having a very low viscosity of 100 mPa.s or lower at 25°C, like for example Genomer 1122 (2-acrylic acid 2- ⁇ [(butylamino) carbonyl]oxy ⁇ ethyl ester, available from Rahn AG) and Ebecryl 1039 (available from Cytec Industries Inc.).
  • the total amount of the monofunctional urethane acrylate oligomer is preferably at least 5 wt.%, more preferably at least 7.5 wt.%, relative to the total weight of the curable fluid.
  • the aerosol jet fluid may contain both mono- and multifunctional urethane acrylates
  • Additional mono- or multifunctional monomers or oligomers may be used to further optimize the properties of the curable fluid.
  • the curable fluid comprises an initiator which, upon exposure to radiation or heat, initiates the curing, i.e. polymerization, of the jetted droplets.
  • a photo-initiator which upon absorption of actinic radiation, preferably UV-radiation, forms high-energy species (for example radicals) inducing polymerization and crosslinking of the monomers and oligomers of the jetted droplets.
  • actinic radiation preferably UV-radiation
  • high-energy species for example radicals
  • a combination of two or more photo-initiators may be used.
  • a photo-initiator system comprising a photo-initiator and a co-initiator, may also be used.
  • a suitable photo-initiator system comprises a photo-initiator, which upon absorption of actinic radiation forms free radicals by hydrogen abstraction or electron extraction from a second compound, the co-initiator. The co-initiator becomes the actual initiating free radical.
  • Irradiation with actinic radiation may be realized in two steps, each step using actinic radiation having a different wavelength and/or intensity. In such cases it is preferred to use 2 types of photo-initiators, chosen in function of the different actinic radiation used.
  • copolymerizable photo-initiators such as disclosed in the unpublished EP-A 10195896.5 (filed on 2010-12-20 ) may be used.
  • a preferred total amount of initiator is 1 to 10 wt.%, more preferably 2.5 to 7.5 wt.%, of the total curable fluid weight.
  • a plasticizer as disclosed in for example EP-A 1637926 ([0085] - [0091]) may be added to the curable fluid.
  • a plasticizer is typically a substance which, when added to a flexographic printing master, increases the softness and flexibility of that printing master.
  • plasticizers may migrate to the surface of the relief image or may be extracted out of the relief image by the flexo printing ink during printing. For that reason, it is preferred to use a copolymerizable plasticizing monomer such as a low Tg monomer of which the corresponding homopolymer has a glass transition temperature below -15°C or diallylphthalate, as disclosed in the unpublished EP-A 10195895.7 (filed on 2010-12-20 ).
  • Suitable polymerization inhibitors include phenol type antioxidants, hindered amine light stabilizers, phosphor type antioxidants, hydroquinone monomethyl ether commonly used in (meth)acrylate monomers, and hydroquinone, methylhydroquinone, t-butylcatechol, pyrogallol may also be used.
  • a phenol compound having a double bond in molecules derived from acrylic acid is particularly preferred due to its having a polymerization-restraining effect even when heated in a closed, oxygen-free environment.
  • Suitable inhibitors are, for example, Sumilizer ® GA-80, Sumilizer GM and Sumilizer ® GS produced by Sumitomo Chemical Co., Ltd.
  • the amount capable of preventing polymerization be determined prior to blending.
  • the amount of a polymerization inhibitor is generally between 200 and 20 000 ppm of the total curable fluid weight.
  • Suitable combinations of compounds which decrease oxygen polymerization inhibition with radical polymerization inhibitors are: 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane-1 and 1-hydroxy-cyclohexyl-phenyl-ketone; 1-hydroxy-cyclohexyl-phenyl-ketone and benzophenone; 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropane-1-on and diethylthioxanthone or isopropylthioxanthone; and benzophenone and acrylate derivatives having a tertiary amino group, and addition of tertiary amines.
  • An amine compound is commonly employed to decrease an oxygen polymerization inhibition or to increase sensitivity.
  • an amine compound is used in combination with a high acid value compound, the storage stability at high temperature tends to be decreased. Therefore, specifically, the use of an amine compound with a high acid value compound in inkjet printing should be avoided.
  • Synergist additives may be used to improve the curing quality and to diminish the influence of the oxygen inhibition.
  • Such additives include, but are not limited to ACTILANE ® 800 and ACTILANE ® 725 available from AKZO NOBEL, Ebecryl ® P115 and Ebecryl ® 350 available from UCB CHEMICALS and CD 1012, Craynor CN 386 (amine modified acrylate) and Craynor CN 501 (amine modified ethoxylated trimethylolpropane triacrylate) available from CRAY VALLEY.
  • the content of the synergist additive is in the range of 0 to 20 wt.%, preferably in the range of 5 to 15 wt.%, based on the total weight of the curable fluid.
  • the elastomeric binder may be a single binder or a mixture of various binders.
  • the elastomeric binder is an elastomeric copolymer of a conjugated diene-type monomer and a polyene monomer having at least two non-conjugated double bonds, or an elastomeric copolymer of a conjugated diene-type monomer, a polyene monomer having at least two non-conjugated double bonds and a vinyl monomer copolymerizable with these monomers.
  • Preferred elastomeric binders are disclosed in EP-A 1637926 paragraph [0092] and [0093].
  • the amount of elastomeric binder is preferably less than 5 wt.% for the curable inkjet fluid. In a particular preferred embodiment, no elastomeric binder is added to the curable inkjet fluid. As viscosity is not an issue, more elastomeric binder, preferably more than 5 wt.%, more preferably more than 10 wt.%, may be used for the curable aerosol jet fluid.
  • the surfactant(s) may be anionic, cationic, non-ionic, or zwitterionic and are usually added in a total amount below 20 wt.%, more preferably in a total amount below 10 wt.%, each based on the total curable fluid weight.
  • Fluorinated or silicone compounds are preferably used as a surfactant, however, a potential drawback is bleed-out after image formation because the surfactant does not cross-link. It is therefore preferred to use a copolymerizable monomer having surface-active effects, for example, silicone-modified acrylates, silicone modified methacrylates, fluorinated acrylates, and fluorinated methacrylates.
  • Colorants may be dyes or pigments or a combination thereof.
  • Organic and/or inorganic pigments may be used.
  • Suitable dyes include direct dyes, acidic dyes, basic dyes and reactive dyes.
  • Suitable pigments are disclosed in EP-A 1637926 paragraphs [0098] to [0100].
  • the pigment is present in the range of 0.01 to 10 wt.%, preferably in the range of 0.1 to 5 wt.%, each based on the total weight of curable fluid.
  • the curable fluid preferably does not contain an evaporable component, but sometimes, it can be advantageous to incorporate an extremely small amount of a solvent to improve adhesion to the ink-receiver surface after UV curing.
  • the added solvent may be any amount in the range of 0.1 to 10.0 wt.%, preferably in the range of 0.1 to 5.0 wt.%, each based on the total weight of curable fluid.
  • a humectant may be added to prevent the clogging of the nozzle, due to its ability to slow down the evaporation rate of curable fluid.
  • Suitable humectants are disclosed in EP-A 1637926 paragraph [0105].
  • a humectant is preferably added to the curable jettable liquid formulation in an amount of 0.01 to 20 wt.% of the formulation, more preferably in an amount of 0.1 to 10 wt.% of the formulation.
  • Suitable biocides include sodium dihydroacetate, 2-phenoxyethanol, sodium benzoate, sodium pyridinethion-1-oxide, ethyl p-hydroxybenzoate and 1,2-benzisothiazolin-3-one and salts thereof.
  • a preferred biocide is Proxel ® GXL available from ZENECA COLOURS.
  • a biocide is preferably added in an amount of 0.001 to 3 wt.%, more preferably in an amount of 0.01 to 1.00 wt.%, each based on the total weight of the curable fluid.
  • the curable fluids may be prepared as known in the art by mixing or dispersing the ingredients together, optionally followed by milling, as described for example in EP-A 1637322 paragraph [0108]and [0109].
  • the method according to the present invention may use the aerosol jet printing only, or a combination of aerosol jet printing and inkjet printing.
  • the curable fluids to be used for inkjet printing have a viscosity at jetting temperature of less than 15 mPa.s, preferably of less than 12 mPa.s and more preferably of less than 10 mPa.s.
  • the curable fluids to be used for aerosol jet printing have a viscosity of less than 5000 mPa.s at jetting temperature, preferably of less than 2500 mPa.s and more preferably of less than 1000 mPa.s.
  • a plate form Two forms of flexographic printing supports may be used: a plate form and a cylindrical form, the latter commonly referred to as a sleeve.
  • the print master is created as a plate form
  • the mounting of the plate form on a printing cylinder may introduce mechanical distortions resulting in so-called anamorphic distortion in the printed image.
  • Such a distortion may be compensated by an anamorphic pre-compensation in an image processing step prior to halftoning.
  • sleeves may be well-suited for mounting on an inkjet printer having a rotating drum, as shown in Figure 1 . This also makes it possible to create seamless flexographic printing sleeves, which have applications in printing continuous designs such as in wallpaper, decoration, gift wrapping paper and packaging.
  • flexographic printing support often encompasses two types of support:
  • the flexographic printing support referred to is a support, preferably a sleeve, without one or more elastomeric layers forming an elastomeric floor.
  • a sleeve is also referred to as a basic sleeve or a sleeve base.
  • Basic sleeves typically consist of composites, such as epoxy or polyester resins reinforced with glass fibre or carbon fibre mesh.
  • Metals, such as steel, aluminium, copper and nickel, and hard polyurethane surfaces (e.g. durometer 75 Shore D) can also be used.
  • the basic sleeve may be formed from a single layer or multiple layers of flexible material, as for example disclosed by US2002466668 .
  • Flexible basic sleeves made of polymeric films can be transparent to ultraviolet radiation and thereby accommodate backflash exposure for building a floor in the cylindrical printing element.
  • Multiple layered basic sleeves may include an adhesive layer or tape between the layers of flexible material.
  • Preferred is a multiple layered basic sleeve as disclosed in US5301610 .
  • the basic sleeve may also be made of non-transparent, actinic radiation blocking materials, such as nickel or glass epoxy.
  • the basic sleeve typically has a thickness from 0.1 to 1.5 mm for thin sleeves and from 2 mm to as high as 100 mm for other sleeves.
  • sleeve bases may be conical or cylindrical. Cylindrical sleeve bases are used primarily in flexographic printing.
  • the basic sleeve or flexographic printing sleeve is stabilized by fitting it over a steel roll core known as an air mandrel or air cylinder.
  • Air mandrels are hollow steel cores which can be pressurized with compressed air through a threaded inlet in the end plate wall. Small holes drilled in the cylindrical wall serve as air outlets. The introduction of air under high pressure permits to float the sleeve into position over an air cushion.
  • Certain thin sleeves are also expanded slightly by the compressed air application, thereby facilitating the gliding movement of the sleeve over the roll core.
  • Foamed adapter or bridge sleeves are used to "bridge" the difference in diameter between the air-cylinder and a flexographic printing sleeve containing the printing relief. The diameter of a sleeve depends upon the required repeat length of the printing job.
  • FIG. 1 A particularly preferred drum based printing device (100) using a sleeve body as flexographic support is shown in Figure 3 .
  • the sleeve body 130 is mounted on a drum 140.
  • the drum 140 rotates in at a certain speed in the X-direction around axis 110.
  • a printing device 160 moves in the Y-direction.
  • the printing device 160 may be an aerosol jet printing device (module 200 in Figure 1 ) when only aerosol jet printing is used to prepare the flexographic printing master or a both such an aerosol jet printing device and a conventional inkjet print head when both aerosol jet printing and inkjet printing are used to prepare the flexographic printing master.
  • a curing means may be arranged in combination with the printing device, travelling therewith so that the curable fluid is exposed to curing radiation very shortly after been jetted (see Figure 3 , curing means 150, printing device 160). It may be difficult to provide a small enough radiation source connected to and travelling with the printing device. Therefore, a static fixed radiation source may be employed, e.g. a source of UV-light, which is then connected to the printing device by means of flexible radiation conductive means such as a fibre optic bundle or an internally reflective flexible tube.
  • a source of radiation arranged not to move with the printing device may be an elongated radiation source extending transversely across the flexographic printing support surface to be cured and parallel with the slow scan direction of the print head (see Figure 3 , curing means 170).
  • each applied fluid droplet is cured when it passes beneath the curing means 170.
  • the time between jetting and curing depends on the distance between the printhead and the curing means 170 and the rotational speed of the rotating drum 140.
  • a combination of both curing means 150 and 170 can also be used as depicted in Figure 3 .
  • the printing device for aerosol jet printing has already been described.
  • the means for inkjet printing includes any device capable of coating a surface by breaking up a radiation curable fluid into small droplets which are then directed onto the surface.
  • the radiation curable fluids are jetted by one or more printing heads ejecting small droplets in a controlled manner through nozzles onto a flexographic printing support, which is moving relative to the printing head(s).
  • a preferred printing 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 inkjet printing method is not restricted to piezoelectric inkjet printing.
  • Other inkjet printing heads can be used and include various types, such as a continuous type and thermal, electrostatic and acoustic drop on demand types.
  • the radiation curable fluids must be ejected readily from the printing heads, which puts a number of constraints on the physical properties of the fluid, e.g. a low viscosity at the jetting temperature, which may vary from 25°C to 110°C and a surface energy such that the printing head nozzle can form the necessary small droplets.
  • An example of a printhead according to the current invention is capable to eject droplets having a volume between 0.1 and 100 picoliter (pl) and preferably between 1 and 30 pl. Even more preferably the droplet volume is in a range between 1 pl and 8 pl. Even more preferably the droplet volume is only 2 or 3 pl.
  • Curing can be "partial” or “full”.
  • the terms “partial curing” and “full curing” refer to the degree of curing, i.e. the percentage of converted functional groups, and may be determined by, for example, RT-FTIR (Real-Time Fourier Transform Infra-Red Spectroscopy) which is a method well known to the one skilled in the art of curable formulations.
  • Partial curing is defined as a degree of curing wherein at least 5 %, preferably 10 %, of the functional groups in the coated formulation or the fluid droplet is converted.
  • Full curing is defined as a degree of curing wherein the increase in the percentage of converted functional groups with increased exposure to radiation (time and/or dose) is negligible.
  • Full curing corresponds with a conversion percentage that is within 10 %, preferably 5 %, from the maximum conversion percentage.
  • the maximum conversion percentage is typically determined by the horizontal asymptote in a graph representing the percentage conversion versus curing energy or curing time.
  • no curing this means that less than 5 %, preferably less than 2.5 %, most preferably less than 1 %, of the functional groups in the coated formulation or the fluid droplet are converted.
  • applied fluid droplets which are not cured are allowed to spread or coalesce with adjacent applied fluid droplets.
  • Curing may be performed by heating (thermal curing), by exposing to actinic radiation (e.g. UV curing) or by electron beam curing.
  • actinic radiation e.g. UV curing
  • electron beam curing e.g. UV curing
  • the curing process is performed by UV radiation.
  • the curing means may be arranged in combination with the printing device, travelling therewith so that the curable fluid is exposed to curing radiation very shortly after been jetted (see Figure 3 , curing means 150, printing device 160). It may be difficult to provide a small enough radiation source connected to and travelling with the printing device. Therefore, a static fixed radiation source may be employed, e.g. a source of UV-light, which is then connected to the printing device by means of flexible radiation conductive means such as a fibre optic bundle or an internally reflective flexible tube.
  • a source of radiation arranged not to move with the printing device may be an elongated radiation source extending transversely across the flexographic printing support surface to be cured and parallel with the slow scan direction of the print head (see Figure 3 , curing means 170).
  • each applied fluid droplet is cured when it passes beneath the curing means 170.
  • the time between jetting and curing depends on the distance between the printing device and the curing means 170 and the rotational speed of the rotating drum 140.
  • a combination of both curing means 150 and 170 can also be used as depicted in Figure 3 .
  • any UV light source as long as part of the emitted light can be absorbed by the photo-initiator or photo-initiator system of the fluid droplets, may be employed as 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 imaging apparatus preferably has a plurality of UV light emitting diodes. The advantage of using UV LEDs is that it allows a more compact design of the imaging apparatus.
  • UV radiation is generally classified as UV-A, UV-B, and UV-C as follows:
  • UV-C radiation has poor penetration capabilities and enables to cure droplets primarily on the outside.
  • a typical UV-C light source is low pressure mercury vapour electrical discharge bulb. Such a source has a small spectral distribution of energy, with only a strong peak in the short wavelength region of the UV spectrum.
  • UV-A radiation Long wavelength UV radiation, such as UV-A radiation, has better penetration properties.
  • a typical UV-A source is a medium or high pressure mercury vapour electrical discharge bulb.
  • UV-LEDs have become commercially available which also emit in the UV-A spectrum and that have the potential to replace gas discharge bulb UV sources. By doping the mercury gas in the discharge bulb with iron or gallium, an emission can be obtained that covers both the UV-A and UV-C spectrum.
  • the intensity of a curing source has a direct effect on curing speed. A high intensity results in higher curing speeds.
  • the curing speed should be sufficiently high to avoid oxygen inhibition of free radicals that propagate during curing. Such inhibition not only decreases curing speed, but also negatively affects the conversion ratio of monomer into polymer.
  • the imaging apparatus preferably includes one or more oxygen depletion units.
  • the oxygen depletion units place a blanket of nitrogen or other relatively inert gas (e.g. CO 2 ), 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.
  • Another way to prevent oxygen inhibition is the performance of a low intensity pre-exposure before the actual curing.
  • a partially cured fluid droplet is solidified but still contains residual monomer.
  • This approach improves the adhesion properties between the layers that are subsequently printed on top of each other.
  • Partial intermediate curing is possible with UV-C radiation, UV-A radiation or with broad spectrum UV radiation.
  • UV-C radiation cures the outer skin of a fluid droplet and therefore a UV-C partially cured fluid droplet will have a reduced availability of monomer in the outer skin and this negatively affects the adhesion between neighbouring layers of the relief image. It is therefore preferred to perform the partial curing with UV-A radiation.
  • a final post curing however is often realized with UV-C light or with broad spectrum UV light.
  • Final curing with UV-C light has the property that the outside skin of the print master is fully hardened.

Landscapes

  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Ink Jet (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
EP11183419A 2011-09-30 2011-09-30 Procédé pour la préparation d'un support d'impression flexographique Withdrawn EP2574458A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP11183419A EP2574458A1 (fr) 2011-09-30 2011-09-30 Procédé pour la préparation d'un support d'impression flexographique
PCT/EP2012/068595 WO2013045349A1 (fr) 2011-09-30 2012-09-21 Procédé de préparation d'une matrice d'impression flexographique

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP11183419A EP2574458A1 (fr) 2011-09-30 2011-09-30 Procédé pour la préparation d'un support d'impression flexographique

Publications (1)

Publication Number Publication Date
EP2574458A1 true EP2574458A1 (fr) 2013-04-03

Family

ID=44719609

Family Applications (1)

Application Number Title Priority Date Filing Date
EP11183419A Withdrawn EP2574458A1 (fr) 2011-09-30 2011-09-30 Procédé pour la préparation d'un support d'impression flexographique

Country Status (2)

Country Link
EP (1) EP2574458A1 (fr)
WO (1) WO2013045349A1 (fr)

Citations (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5301610A (en) 1993-04-30 1994-04-12 E. I. Du Pont De Nemours And Company Method and apparatus for making spiral wound sleeves for printing cylinders and product thereof
EP0641648A1 (fr) 1993-09-03 1995-03-08 Uri Adler Procédé et appareil pour la fabrication de plaques d'impression photopolymères
EP1170121A1 (fr) 2000-06-13 2002-01-09 Agfa-Gevaert naamloze vennootschap Précurseur de plaque d'impression flexographique à impression directe
US20020046668A1 (en) 2000-06-16 2002-04-25 Rossini North America, Inc. And Erminio Rossini S.P.A. Multi-layered printing sleeve
US20030020768A1 (en) 1998-09-30 2003-01-30 Renn Michael J. Direct write TM system
US6520084B1 (en) 2000-11-13 2003-02-18 Creo Inc. Method for making printing plate using inkjet
US20030048314A1 (en) 1998-09-30 2003-03-13 Optomec Design Company Direct write TM system
US20030228124A1 (en) 1998-09-30 2003-12-11 Renn Michael J. Apparatuses and method for maskless mesoscale material deposition
EP1428666A1 (fr) 2002-12-11 2004-06-16 Agfa-Gevaert Préparation des plaques d'impression flexographiques utilisant l'enregistrement à jet d'encre
EP1449648A2 (fr) 2003-02-18 2004-08-25 Kodak Polychrome Graphics LLC Procédé de fabrication d'une palque flexografique par transfert lithographique d'une composition polymérisable
US6806018B2 (en) 2002-03-25 2004-10-19 Macdermid Graphic Arts, Inc. Processless digitally imaged printing plate using microspheres
EP1637926A2 (fr) 2004-09-16 2006-03-22 Agfa-Gevaert Composition durcissable et jettable pour la pour la fabrication d'une plaque flexographique
EP1637322A2 (fr) 2004-09-16 2006-03-22 Agfa-Gevaert Procédé de fabrication d'une une plaque d'impression flexographique
US7036430B2 (en) 2002-12-26 2006-05-02 Creo Il Ltd. Method for producing a flexographic printing plate formed by inkjetted fluid
EP1710093A1 (fr) 2004-01-27 2006-10-11 Asahi Kasei Chemicals Corporation Composition de resine photosensible pour substrat d'impression permettant la sculpture laser
US20080053326A1 (en) 2006-08-29 2008-03-06 Anderson Vreeland Inkjet composite stereographic printing plate and method for producing such printing plate
EP1936438A1 (fr) 2006-12-20 2008-06-25 Agfa Graphics N.V. Précurseur de forme d'impression flexographique pour la gravure au laser
WO2008077850A2 (fr) 2006-12-21 2008-07-03 Agfa Graphics Nv Procédés d'impression à jet d'encre en 3d
EP2033778A1 (fr) 2007-09-10 2009-03-11 Agfa Graphics N.V. Procédé pour la fabrication d'une forme de manchon d'impression flexographique
WO2009049072A2 (fr) 2007-10-09 2009-04-16 Optomec, Inc. Jet d'aérosol à capillaires multiples et à gainages multiples
US20090197013A1 (en) 2008-02-04 2009-08-06 Ffei Limited Producing a flexographic printing plate
EP2199081A1 (fr) 2008-12-19 2010-06-23 Agfa Graphics N.V. Appareil d'impression à jet d'encre et procédé pour la fabrication de supports d'impression flexographique
EP2199082A1 (fr) 2008-12-19 2010-06-23 Agfa Graphics N.V. Appareil d'imagerie et procédé pour la fabrication de supports d'impression flexographique
EP2223803A1 (fr) 2009-02-26 2010-09-01 Xerox Corporation Préparation de supports d'impression flexographiques utilisant un procédé additif

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6924308B1 (en) 1997-07-30 2005-08-02 Howard L. Elford Therapeutic process for inhibiting NF-κB
DE19741175A1 (de) 1997-09-18 1999-03-25 Siemens Ag Automatisches Verbindungs-Handover zwischen DECT-ISDN Basisstationen
GB9815533D0 (en) 1998-07-17 1998-09-16 Hatorex Ag Setting of time delays in a sequence of explosive detonations
DE19834379C2 (de) 1998-07-30 2001-03-08 Dieter Braun Wandelement

Patent Citations (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5301610A (en) 1993-04-30 1994-04-12 E. I. Du Pont De Nemours And Company Method and apparatus for making spiral wound sleeves for printing cylinders and product thereof
EP0641648A1 (fr) 1993-09-03 1995-03-08 Uri Adler Procédé et appareil pour la fabrication de plaques d'impression photopolymères
US20030048314A1 (en) 1998-09-30 2003-03-13 Optomec Design Company Direct write TM system
US20030020768A1 (en) 1998-09-30 2003-01-30 Renn Michael J. Direct write TM system
US20030228124A1 (en) 1998-09-30 2003-12-11 Renn Michael J. Apparatuses and method for maskless mesoscale material deposition
EP1170121A1 (fr) 2000-06-13 2002-01-09 Agfa-Gevaert naamloze vennootschap Précurseur de plaque d'impression flexographique à impression directe
US20020046668A1 (en) 2000-06-16 2002-04-25 Rossini North America, Inc. And Erminio Rossini S.P.A. Multi-layered printing sleeve
US6520084B1 (en) 2000-11-13 2003-02-18 Creo Inc. Method for making printing plate using inkjet
US6806018B2 (en) 2002-03-25 2004-10-19 Macdermid Graphic Arts, Inc. Processless digitally imaged printing plate using microspheres
EP1428666A1 (fr) 2002-12-11 2004-06-16 Agfa-Gevaert Préparation des plaques d'impression flexographiques utilisant l'enregistrement à jet d'encre
US7036430B2 (en) 2002-12-26 2006-05-02 Creo Il Ltd. Method for producing a flexographic printing plate formed by inkjetted fluid
EP1449648A2 (fr) 2003-02-18 2004-08-25 Kodak Polychrome Graphics LLC Procédé de fabrication d'une palque flexografique par transfert lithographique d'une composition polymérisable
EP1710093A1 (fr) 2004-01-27 2006-10-11 Asahi Kasei Chemicals Corporation Composition de resine photosensible pour substrat d'impression permettant la sculpture laser
EP1637322A2 (fr) 2004-09-16 2006-03-22 Agfa-Gevaert Procédé de fabrication d'une une plaque d'impression flexographique
EP1637926A2 (fr) 2004-09-16 2006-03-22 Agfa-Gevaert Composition durcissable et jettable pour la pour la fabrication d'une plaque flexographique
US20080053326A1 (en) 2006-08-29 2008-03-06 Anderson Vreeland Inkjet composite stereographic printing plate and method for producing such printing plate
EP1936438A1 (fr) 2006-12-20 2008-06-25 Agfa Graphics N.V. Précurseur de forme d'impression flexographique pour la gravure au laser
WO2008077850A2 (fr) 2006-12-21 2008-07-03 Agfa Graphics Nv Procédés d'impression à jet d'encre en 3d
EP2033778A1 (fr) 2007-09-10 2009-03-11 Agfa Graphics N.V. Procédé pour la fabrication d'une forme de manchon d'impression flexographique
WO2009049072A2 (fr) 2007-10-09 2009-04-16 Optomec, Inc. Jet d'aérosol à capillaires multiples et à gainages multiples
US20090197013A1 (en) 2008-02-04 2009-08-06 Ffei Limited Producing a flexographic printing plate
EP2199081A1 (fr) 2008-12-19 2010-06-23 Agfa Graphics N.V. Appareil d'impression à jet d'encre et procédé pour la fabrication de supports d'impression flexographique
EP2199082A1 (fr) 2008-12-19 2010-06-23 Agfa Graphics N.V. Appareil d'imagerie et procédé pour la fabrication de supports d'impression flexographique
EP2223803A1 (fr) 2009-02-26 2010-09-01 Xerox Corporation Préparation de supports d'impression flexographiques utilisant un procédé additif

Also Published As

Publication number Publication date
WO2013045349A1 (fr) 2013-04-04

Similar Documents

Publication Publication Date Title
EP2537675B1 (fr) Fluide durcissable jetable pour fabriquer un support d'impression flexographique
EP2466380B1 (fr) Procédé de fabrication d'une plaque d'impression flexographique
EP2746058B1 (fr) Procédé pour la préparation d'un support d'impression flexographique
EP2153991B1 (fr) Appareil d'imagerie et procédé pour la fabrication de supports d'impression flexographique
US9126394B2 (en) Method of preparing a flexographic printing master
US7401552B2 (en) Method for manufacturing a flexographic printing master
EP1637322B1 (fr) Procédé de fabrication d'une une plaque d'impression flexographique
EP1637926B1 (fr) Composition durcissable et jettable pour la pour la fabrication d'une plaque flexographique
US20060054040A1 (en) Curable jettable liquid for flexography
EP2033779B1 (fr) Procédé pour la préparation d'une forme d'impression flexographique
WO2010079017A2 (fr) Procédé de traitement d'image pour impression tridimensionnelle
EP2656144B1 (fr) Fluide approprié au jet et durcissable pour la fabrication d'une matrice d'impression flexographique
EP2656145B1 (fr) Fluide approprié au jet durcissable pour la fabrication d'une matrice d'impression flexographique
WO2012175525A1 (fr) Fluide pulvérisable durcissable pour fabrication d'une matrice d'impression flexographique
EP2574458A1 (fr) Procédé pour la préparation d'un support d'impression flexographique
JP7233876B2 (ja) 印刷方法およびインク組成物

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20131005