EP4073587A1 - Précurseur de relief photopolymérisable ayant des propriétés de surface ajustables - Google Patents

Précurseur de relief photopolymérisable ayant des propriétés de surface ajustables

Info

Publication number
EP4073587A1
EP4073587A1 EP20821247.2A EP20821247A EP4073587A1 EP 4073587 A1 EP4073587 A1 EP 4073587A1 EP 20821247 A EP20821247 A EP 20821247A EP 4073587 A1 EP4073587 A1 EP 4073587A1
Authority
EP
European Patent Office
Prior art keywords
relief
exposure
photopolymerizable
uvc
uva
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.)
Pending
Application number
EP20821247.2A
Other languages
German (de)
English (en)
Inventor
Matthias Beyer
Armin Becker
Torben Wendland
Isabel Schlegel
Peter J FRONCZKIEWICZ
Anja WUNDLING
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.)
XSYS Germany GmbH
Original Assignee
XSYS Germany GmbH
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 XSYS Germany GmbH filed Critical XSYS Germany GmbH
Publication of EP4073587A1 publication Critical patent/EP4073587A1/fr
Pending legal-status Critical Current

Links

Classifications

    • 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
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/095—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer
    • 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
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • 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
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • 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
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • 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
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2022—Multi-step exposure, e.g. hybrid; backside exposure; blanket exposure, e.g. for image reversal; edge exposure, e.g. for edge bead removal; corrective exposure
    • G03F7/2024—Multi-step exposure, e.g. hybrid; backside exposure; blanket exposure, e.g. for image reversal; edge exposure, e.g. for edge bead removal; corrective exposure of the already developed image

Definitions

  • the invention relates to a photopolymerizable relief precursor with surface properties that can be adjusted by the exposure conditions, a method for producing relief structures from the relief precursors, the relief structures themselves and their use.
  • Printing with solvent inks requires an ink-repellent surface of the printing plate in order to prevent the gaps between halftone dots with ink from running into. This is usually achieved through the presence of a migratable, surface-active additive (MOA) in the relief layer, which lowers the surface tension of the printing surface.
  • MOA surface-active additive
  • the presence of this additive can be problematic when printing with UV or water-based inks, since, for example, poor ink transfer results in the solid surface. Therefore, various printing plates are used for printing with solvent ink, UV ink, or water-based ink.
  • An example of such a printing plate is given in EP1014194A1, but such a printing plate is only suitable for a certain type of solvent ink.
  • the object of the present invention is to provide a printing plate that is “switchable” in such a way that its surface properties can be adjusted by exposure parameters, so that the same printing plate can be used universally for different areas of application.
  • the object is achieved comprehensively by a photopolymerizable relief precursor
  • the MOA tends to diffuse to the surface of the relief layer and thus to it To make the surface more hydrophobic.
  • Exposure to UVA light with a higher penetration depth ensures stronger cross-linking in the entire relief layer and stabilizes the relief as a whole.
  • Exposure to UVC light shows a small depth of penetration into the photoactive layer and ensures that the monomers and polymers that are still present are crosslinked.
  • the migration of the MOA to the surface of the relief is reduced or prevented, which leads to a more hydrophilic surface, which favors wetting of the printing areas with a hydrophilic printing ink.
  • the UVC exposure can cause the oxidation of formulation components, which leads to the formation of polar and hydrophilic groups.
  • the surface properties can be adjusted in such a way that the gaps between the halftone dots are prevented or reduced when printing with solvent-based ink. This allows longer printing times before the plates need to be cleaned.
  • the surface tack and thus the tendency to accumulate dust and dirt on the surface can be reduced.
  • the same printing plate can be used for printing with different types of printing inks by adjusting the surface properties by selecting the post-exposure conditions so that the printing plate is suitable for printing with solvent-based inks, aqueous inks or UV-curable inks.
  • Dimensionally stable support materials which can optionally have further layers can be used as dimensionally stable supports (A).
  • suitable dimensionally stable supports are plates, foils and conical and cylindrical tubes (sleeves) made of metals such as steel, aluminum, copper or nickel or of plastics such as polyethylene terephthalate, polybutylene terephthalate, polyamide and polycarbonate, fabrics and fleeces such as fiberglass fabrics, and composite materials made of glass fibers and Plastics.
  • Dimensionally stable carrier films or metal sheets for example polyethylene or polyester films, steel or aluminum sheets, are particularly suitable as dimensionally stable carriers. These carrier foils or sheets are generally 50 to 1100 ⁇ m, preferably 75 to 400 ⁇ m, for example about 250 ⁇ m thick.
  • a plastic film is used, its thickness is in the range from 100 to 200 ⁇ m, preferably from 125 to 175 ⁇ m.
  • steel sheets are with a thickness of 0.05 to 0.3 mm is preferred. Tinned steel sheets are preferred for protection against corrosion.
  • These carrier films or carrier sheets can be coated with a thin, adhesion-promoting layer, for example a 0.05 to 5 ⁇ m thick layer, on the side of the carrier film facing the substrate layer.
  • This adhesive layer can consist, for example, of a mixture of a polycarbonate, a phenoxy resin and a multifunctional isocyanate.
  • carrier foils or carrier sheets can already be equipped with a thin adhesion-promoting layer (AH) or be provided with this.
  • AH adhesion-promoting layer
  • polyurethane adhesive lacquers e.g. according to DE3045516
  • polyisocyanate-crosslinked polyether or polyester lacquers in layer thicknesses between 0.1 and 50 ⁇ m, in particular between 2 and 30 ⁇ m, can serve as adhesive lacquer layers.
  • Additional adhesion-improving intermediate layers can be located on the side of the adhesive layer facing away from the carrier layer, have layer thicknesses between 0.1 and 50, in particular 1 and 10 ⁇ m, and can, for example, from dilute aqueous-alcoholic solution of (for example 80 mol %) partially saponified polyvinyl ester,
  • Phenyl glycerol ether monoacrylate and glyoxal drying and baking.
  • Adhesion improvement layers or intermediate layers are intended to increase the adhesion between individual layers and stabilize the layer structure.
  • materials are to be selected that can interact with both layers.
  • Preferred examples are surfactants, amphiphilic molecules with hydrophobic and hydrophilic areas and
  • Block copolymers and oligomers that contain blocks that are compatible with the two layers or compatible with the polymers in the layers.
  • the adhesion between the dimensionally stable carrier (A) and the relief-forming layer (B) should be greater than 0.5 N / cm when measured in a peel test at a peel angle of 90 ° and a peel speed of 30 mm / min.
  • the relief precursor comprises at least one photopolymerizable, relief-forming layer (B).
  • the photopolymerizable relief-forming layer can be applied directly to the carrier. However, there can also be other layers between the carrier and the relief-forming layer, such as, for example, adhesive layers or elastic or compressible sub-layers.
  • the relief-forming layer (B) can also consist of more than one layer, it generally comprising 2 to 20 layers, preferably 2 to 5 layers, particularly preferably 2 to 3 layers, very particularly preferably 2 layers.
  • the layers can contain the same components or different components and this in the same or different proportions. These layers preferably contain the same components.
  • the relief-forming layers which are closest to the carrier layer are preferably already fixed, crosslinked and / or reacted. At least one relief-forming layer, which can still be fixed, crosslinked or reacted, is arranged on these fixed, crosslinked, reacted layers.
  • Elastomeric binders for producing relief-forming layers of flexographic printing elements are known to the person skilled in the art. Examples are styrene-diene block copolymers, natural rubber, polybutadiene, polyisoprene, styrene-butadiene rubber, nitrile-butadiene rubber, butyl rubber, styrene-isoprene rubber, styrene-butadiene-isoprene rubber, polynorbornene rubber or ethylene - called propylene diene rubber (EPDM). Hydrophobic binders are preferably used. Such binders are soluble in organic solvents or mixtures thereof.
  • the elastomer is preferably a thermoplastic elastomeric block copolymer composed of alkenyl aromatics and 1,3-dienes.
  • the block copolymers can be either linear, branched or radial block copolymers. Usually they are three-block copolymers of the ABA type, but they can also be two-block polymers of the AB type, or those with several alternating elastomeric and thermoplastic blocks, for example ABABA. Mixtures of two or more different block copolymers can also be used. Commercially available three-block copolymers often contain certain proportions of two-block copolymers.
  • the diene units can be 1,2- or 1,4-linked.
  • Both block copolymers of the styrene-butadiene or of the styrene-isoprene type and of the styrene-butadiene-isoprene type can be used. They are commercially available, for example, under the name Kraton ⁇ . It is also possible to use thermoplastic elastomeric block copolymers with end blocks made of styrene and a random styrene-butadiene middle block. The block copolymers can also be fully or partially hydrogenated, for example in SEBS rubbers.
  • Preferred elastomeric binders are triblock copolymers of the ABA type or radial block copolymers of the (AB) n type, in which A is styrene and B is a diene, as well as random copolymers and random copolymers of styrene and a diene.
  • the thermoplastic elastomeric binders are at least one styrene-isoprene block copolymer, in particular styrene-isoprene-styrene block copolymers, the polymers also being able to contain proportions of diblock copolymers styrene-isoprene.
  • Preferred binders of the styrene-isoprene type generally contain 10 to 30% by weight, preferably 12 to 28% by weight and particularly preferably 13 to 25% by weight of styrene.
  • the binders are styrene-butadiene-styrene (SBS) block copolymers.
  • SBS polymers generally contain 20 to 35% by weight, preferably 22 to 33% by weight and particularly preferably 24 to 31% by weight styrene.
  • These block copolymers usually have an average molecular weight Mw (weight average) of 100,000 to 300,000 g / mol. It is of course also possible to use mixtures of different styrene-isoprene block copolymers or around styrene-butadiene block copolymers.
  • radial isoprene-styrene block copolymers can preferably be used.
  • the isoprene and / or butadiene units in the polyisoprene blocks can be 1,4-linked, i.e. the remaining double bond is arranged in the chain or 3,4-linked, i.e. the remaining double bond is arranged laterally.
  • block copolymers which essentially have 1,4-linkages and binders which have certain proportions of 3,4-linkages.
  • the pendant vinyl groups in binders with 3,4-linked units can react preferentially in the course of the crosslinking of the photopolymerizable layer and accordingly result in a plate with a high degree of crosslinking.
  • block copolymers can be used which have a vinyl group content of 20 to 70%.
  • a radial styrene-isoprene copolymer can be used which has a vinyl group content of less than 10%.
  • a mixture of two different styrene-isoprene block copolymers is used. One of them preferably has a vinyl group content of at least 20%, in particular 20 to 70%, preferably 25 to 45%. The other may have a low vinyl group content, e.g. less than 10%.
  • a mixture of two styrene-isoprene copolymers can also preferably be used, one of which has a high diblock content of more than 40% by weight and the second a lower diblock content of less than 30% by weight.
  • the photopolymerizable layer can also include further ones of the Block copolymers include various elastomeric binders.
  • additional binders also called secondary binders
  • the properties of the photopolymerizable layer can be modified.
  • An example of a secondary binder is vinyl toluene-alpha-methylstyrene copolymers.
  • the amount of such secondary binders should not exceed 25% by weight with respect to the total amount of all binders used.
  • the amount of such secondary binders preferably does not exceed 15% by weight, particularly preferably not 10% by weight.
  • the total amount of binders is usually 30 to 90% by weight based on the sum of all constituents of the relief-forming layer, preferably 40 to 85% by weight and particularly preferably 60 to 85% by weight.
  • water-soluble, swellable, dispersible or emulsifiable polymers are used.
  • polyvinyl acetates polyvinyl alcohols, polyvinyl acetals, polystyrene sulfonates, polyurethanes, polyamides (as described, for example, in EP 0085 472 or in DE 1522444) and any combinations thereof can be used.
  • polyamides as described, for example, in EP 0085 472 or in DE 1522444
  • Examples of such polymers can be found in EP 0 079 514, EP 0224 164, or EP 0059 988.
  • These polymers can be linear, branched, star-shaped or dendritic and be present as homopolymers, random copolymers, block copolymers or alternating copolymers.
  • the polymers mentioned are very often provided with functional groups which either increase the solubility and / or can take part in crosslinking reactions. These groups include, for example, carboxy, SO, OH, thiol, ethylenically unsaturated, (meth) acrylate, epoxy groups and any combinations thereof.
  • the total amount of elastomeric binders in the case of the relief-forming layer (B) is usually 30 to 90% by weight based on the sum of all components of the relief-forming layer, preferably 40 to 85% by weight and particularly preferably 45 to 85% by weight.
  • the relief-forming layer (B) can contain further constituents selected from the group consisting of plasticizers, solvents, further binders, colorants, stabilizers, regulators, UV absorbers, dispersants, crosslinkers, viscosity modifiers, surface-active substances and any combinations thereof.
  • additives or auxiliaries and additives are in the radiation-sensitive mixture in a total concentration in the range from 0.001 to 60% by weight, based on the entire formulation, preferably in the range from 0.01 to 50% by weight, especially in the range from 0 , 1 to 50% by weight, very particularly in the range from 1 to 50% by weight.
  • the individual additives are in concentrations of 0.001 to 40% by weight, based on the entire formulation, preferably in the range from 0.01 to 40% by weight, particularly in the range from 0.1 to 40% by weight, very particularly in the range from 0.1 to 35% by weight.
  • the photopolymerizable relief-forming layer (B) furthermore comprises, in a known manner, at least one ethylenically unsaturated monomer which is compatible with the binder or binders.
  • the ethylenically unsaturated monomer can also be mixtures of two or more different monomers. Suitable compounds have at least one olefinic double bond and are polymerizable. These are therefore referred to below as monomers.
  • Esters or amides of acrylic acid or methacrylic acid with monofunctional or polyfunctional alcohols, amines, amino alcohols or hydroxy ethers and esters, esters of fumaric or maleic acid, vinyl ethers, vinyl esters and allyl compounds have proven particularly advantageous.
  • the ethylenically unsaturated monomer preferably contains at least 2 ethylenically unsaturated groups, particularly preferably 2 to 10 ethylenically unsaturated groups, very particularly preferably 2 to 6 ethylenically unsaturated groups.
  • Compounds with C-C triple bonds can also be used in the radiation-sensitive mixture.
  • the ethylenically unsaturated group is preferably at least one acrylate and / or methacrylate group, but styrene derivatives, acrylamides, vinyl esters and vinyl ethers can also be used.
  • the ethylenically unsaturated monomer has a molecular weight of generally less than 600 g / mol, preferably less than 450 g / mol, particularly preferably less than 400 g / mol, very particularly preferably less than 350 g / mol and in particular less than 300 g / mol mole up.
  • derivatives of acrylic and / or methacrylic acid such as their esters with monohydric or polyhydric alcohols, for example acrylic or methacrylic acid esters of alkanols with 1 to 20 carbon atoms, such as methyl methacrylate, ethyl acrylate, propyl (meth) acrylate, isopropyl (meth ) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, (meth) acrylic esters of polyhydric alcohols with 2 to 20 carbon atoms, e.g.
  • acrylamide and methacrylamide such as ethers of their N-methylol derivatives with monohydric and polyhydric alcohols, e.g. ethylene glycol, glycerol, 1,1,1-trimethylolpropane, oligomeric or polymeric ethylene oxide derivatives, are also suitable. These are particularly suitable when polyamides or polyvinyl alcohol are used as binders.
  • epoxy and urethane (meth) acrylates such as can be obtained, for example, by reacting bisphenol A diglycidyl ether with (meth) acrylic acid or by reacting diisocyanates with hydroxyalkyl (meth) acrylates or with polyesters or polyethers containing hydroxyl groups.
  • Olefinically unsaturated compounds that can also be used are esters of acrylic or methacrylic acid, especially those with a low vapor pressure and those that have been modified with compatibilizers, e.g. with hydroxyl, amido, sulfoester or sulfonamide groups. Mixtures of the abovementioned copolymerizable ethylenically unsaturated organic compounds can also be used.
  • Preferred ethylenically unsaturated monomers are butanediol 1,4-di (meth) acrylate, neopentyl glycol di (meth) acrylate, 3-methylpentanediol di (meth) acrylate, 1,1,1-trimethylol propane tri (meth) acrylate, 1,4-butanediol diacrylate , 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, di-, tri- and tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate and pentaerythritol tetra (meth) acrylate.
  • the ethylenically unsaturated monomer is in a concentration in the range from 0.5 to 60% by weight, based on the entire formulation, preferably in the range from 1 to 50% by weight, particularly preferably in the range from 1 to 40% by weight. -%, very particularly preferably in the range from 2 to 40% by weight.
  • the photopolymerizable, relief-forming layer also contains a migratable, surface-active additive.
  • Preferred migratable, surface-active additives are selected from the group consisting of ionic or nonionic surfactants, long-chain hydrocarbons, Waxes, especially paraffin waxes, organosilicon compounds, especially silicone oils, silanes and siloxanes, or mixtures thereof.
  • organosilicon compounds the following are particularly suitable: polysiloxane (meth) acrylates, polysiloxane amines, vinyl-terminated polysilanes and polysiloxanes, polyether-polysiloxanes and mixtures thereof.
  • Examples of compounds from the aforementioned classes are available under the following trade names: Polyvest ST-E 100, Silico Glide T-41, Silico Glide T-57, AFCONA-3700, Silicon F. 1000, Silicon F. 60000, Rad 2010, Rad 2200N, Rad2300, Rad 2500, Rad2700, Rad 2800, Miramer SIU 2400, X- 22-2445, X-22-174BX, KBM-5103, X-22-161B, KF-8010, Silmer OH ACR C50, Silmer OH ACR Di- 400, Silmer ACR Di-10, Silmer OH ACR D4, AFCONA-3835 and Sartomer CN9800.
  • the surface-active additive capable of migration is a paraffin wax.
  • a paraffin wax Preferred are branched and / or unbranched paraffin waxes with a chain length of more than 15 carbon atoms, particularly preferred of more than 20 carbon atoms and very particularly preferred of more than 30 carbon atoms, further preferred are chain lengths in the range from 20 to 40 Carbon atoms.
  • the photopolymerizable, relief-forming layer furthermore contains a photoinitiator which can be activated with UVA light and a photoinitiator which can be activated with UVC light.
  • Preferred photoinitiators which can be activated with UVA light are selected from the group consisting of benzil ketals, acylphosphine oxides, bisacylphosphine oxides, aminophenyl ketones, phenyloxime esters and mixtures thereof.
  • Preferred photoinitiators which can be activated with UVC light are selected from the group consisting of hydroxyphenyl ketones, benzoyl formates, benzophenones, aryl alkyl ketones, aryl benzyl ketones and mixtures thereof.
  • the photoinitiator which can be activated with UVA light is selected from the group consisting of diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, benzil dimethyl ketal and benzil diethyl ketal and the photoinitiator which can be activated with UVC light is selected from the group consisting of oxyphenylacetic acid 2- [2-oxo-2-phenylacetoxyethoxyethyl ester, oxyphenylacetic acid 2- [2-hydroxyethoxy] ethyl ester, methylbenzoyl formate, p-tolylundecyl ketone, 1-hydroxycyclohexylphenyl ketone and 2-hydroxy-2-methyl-1-phenylpropan-1-one and theirs Mix.
  • the migratable, surface-active additive is generally in an amount of 0.1 to 10% by weight, preferably 0.2 to 5% by weight, particularly preferably 0.5 to 1.5% by weight, based on the Weight of the photopolymerizable, relief-forming layer contained in the photopolymerizable, relief-forming layer.
  • the photoinitiator which can be activated with UVA light is generally whole in an amount of from 0.5 to 20% by weight, preferably from 0.5 to 15% by weight, particularly preferably from 0.5 to 10% by weight particularly preferably from 0.5 to 6% by weight, based on the total amount of the photopolymerizable, relief-forming layer, contained in the photopolymerizable, relief-forming layer.
  • the photoinitiator which can be activated with UVC light is generally whole in a concentration of 0.1 to 20% by weight, preferably 0.1 to 10% by weight, particularly preferably 0.5 to 5% by weight particularly preferably from 0.25 to 3% by weight, based on the total amount of the photopolymerizable, relief-forming layer, contained in the photopolymerizable, relief-forming layer.
  • the mass ratio of photoinitiator that can be activated with UVA light to photoinitiator that can be activated with UVC light is from 0.1 to 50, preferably from 0.5 to 40, particularly preferably from 0.5 to 30, very particularly preferably from 0, 5 to 15.
  • the ratio of the amount of photoinitiator activatable with UVA light to migratable, surface-active additive is from 0.01 to 10, preferably from 0.1 to 5, particularly preferably from 0.1 to 3.
  • the photopolymerizable relief precursor according to the invention can have one or more further layers selected from the group consisting of an adhesive layer and / or a compressible layer between the carrier layer and the relief-forming layer, a functional layer arranged above the relief-forming layer, for example a structuring layer, a barrier layer , a cover layer and a digitally imageable mask layer, and combinations of two or more of these layers.
  • the photopolymerizable relief precursor between the carrier layer and the photopolymerizable relief-forming layer can have at least one intermediate layer, preferably an adhesive layer and / or a compressible layer.
  • the photopolymerizable relief precursor can have a further layer selected from the side of the photopolymerizable relief-forming layer facing away from the carrier layer the group consisting of a mask layer, a barrier layer, a cover layer and combinations of two or more of these layers.
  • the photopolymerizable relief precursor comprises
  • (AH) optionally an adhesion-promoting layer
  • the relief precursor according to the invention preferably contains a laser-ablatable mask layer (C) which is arranged over the relief-forming layer (B) and which can also be removed with solvents or by heating and adsorbing / absorbing.
  • This layer is heated and volatilized by selective irradiation by means of high-energy electromagnetic radiation, as a result of which an image-like structured mask is generated, which is used to transfer the structure to the relief precursor. To do this, it must be impermeable in the UV range and absorb radiation in the VIS-IR range, which leads to the heating of the layer and its ablation.
  • the optical density of the mask layer in the UV range from 330 to 420 nm is in the range from 1 to 5, preferably in the range from 1.5 to 4, particularly preferably in the range from 2 to 4.
  • the optical density is determined by using an X-rite 361TX densitometer in the "Density" setting with a UV filter.
  • the layer thickness M of the laser-ablatable mask layer (C) is generally 0.1 mih to 5 mih. With layer thicknesses below 0.1 mpi it is difficult to achieve a sufficient optical density. With layer thicknesses of more than 5 mih, the laser sensitivity of the element is too low, so that long laser times are necessary for imaging.
  • the layer thickness is preferably 0.3 mih to 4 mih, particularly preferably 1 mih to 3 mih.
  • the laser sensitivity of the mask layer (measured as the energy necessary to ablate 1 cm 2 of the layer) should be between 0.1 and 10 J / cm 2 , preferably between 0.3 and 5 J / cm 2 , particularly preferably between 0 , 5 and 5 J / cm 2 .
  • the mask layer (C) comprises at least one non-radically crosslinkable elastic polymer which is capable of uniformly distributing the components which absorb the electromagnetic radiation and which is ablated as efficiently as possible when heated.
  • the elastic polymer can be a linear, branched, star-shaped, comb-shaped, dendritic homo- or copolymer. Copolymers can be present as random and / or block copolymers.
  • the elastic polymer can also be a mixture of different polymers which differ, for example, in terms of structure, monomer composition, block lengths, molecular weights, functional groups, their number and / or distribution. Mixtures of polymers can also be used.
  • Suitable, non-radically crosslinkable, elastic polymers for the mask layer (C) are, for example, ethylene vinyl acetates, soft elastic polyamides, soft elastic polyurethanes, nitrocellulose, polyvinyl acetals such as poly (vinyl butyral vinyl alcohol) copolymers (or poly (vinyl butyral vinyl ethyral vinyl alcohol) copolymers can of course also be used Soft elastic materials are used as binders, such as partially saponified polyvinyl acetates, The preferred binder for the mask layer (C) is a soft elastic polyamide, a polyvinyl alcohol, a partially saponified polyvinyl acetate or a partially saponified polyvinyl acetal.
  • the mask layer (C) can be permeable or impermeable to oxygen.
  • the relief-forming layer (B) and the ablatable mask layer (C) are soluble in the customary, commercially available wash-out agents, which as a rule consist of solvent mixtures or aqueous solutions.
  • washout agents consist of one or more non-polar hydrocarbon solvents as the main component and a moderately polar alcohol, for example benzyl alcohol, n-pentanol, cyclohexanol, ethylhexanol or heptyl alcohol, as a minor component.
  • Aqueous solutions usually contain surfactants and / or flocculants and generally have a pH value> 7.
  • the relief-forming layer (B) can be processed in these wash-out agents in the usual times.
  • the relief-forming layer (B) and the ablatable mask layer (C) can also be developed or removed thermally (see, for example, EP 1 239 329 or EP 1 170 121).
  • the relief structures are heated to the softening or melting temperature after the imagewise exposure.
  • the unexposed and non-crosslinked areas of the relief structure become partially liquid and sticky and are then continuously removed by suction (absorption) with a fleece or a fabric.
  • a further layer (E) which is impermeable to oxygen is present in the relief precursor according to the invention between layers (B) and (C). If an oxygen-impermeable layer (E) is present, the layers (B) and / or (C) are preferably permeable to oxygen.
  • the layer thickness of layer (E) is in the range from 3 to 5 ⁇ m.
  • the layer mainly contains one or more elastic polymers which have a low oxygen permeability, these having an oxygen permeability of less than or equal to 1.5 * 10 5 cm 3 * pm / (m 2 * d * bar).
  • the polymers in layer (E) are also preferably not radically crosslinkable.
  • Suitable elastic polymers that are soluble in organic solvents and / or can be thermally developed and have a sufficient barrier effect against oxygen are, for example, partially saponified polyvinyl acetates with a degree of saponification between 30 and a maximum of 80 mol%, ethylene-vinyl acetate copolymers and ethylene-vinyl alcohol Copolymers and ethylene-vinyl acetate-vinyl alcohol copolymers.
  • Cyclic acetals of polyvinyl alcohol such as polyvinyl butyral, polyvinyl ethyl, polyvinyl formal, polyvinyl propyral, and copolymers which contain two or more different vinyl acetal units selected from vinyl formal, vinyl ethyral, vinyl propyral and vinyl butyral units, are also very suitable.
  • the polyvinyl acetals are always copolymers with vinyl alcohol units, since the conversion of polyvinyl alcohol to full acetal is incomplete for statistical and steric reasons.
  • poly (vinyl butyral) is actually a poly (vinyl butyral vinyl alcohol).
  • the residual OH content of the polyvinyl acetals mentioned is usually between 10 and 30% by weight.
  • V inylethyralvinylbutyral vinyl alcohol copolymers (poly (vinylethyral vinyl butyral)), for example, are very suitable.
  • the invention also relates to a method for producing a relief structure with the following steps:
  • step (v) Removal of the mask or the mask layer, any further layers present and the unexposed, non-photopolymerized areas of the relief-forming layer in step (iv), a relief being produced,
  • the invention also relates to a method for producing a relief structure with the following steps:
  • step (v) Removal of any further layers present and the unexposed, non-photopolymerized areas of the relief-forming layer in step (iv), a relief being produced
  • post-exposure is carried out in step (vii) with UVA light and UVC light.
  • the post-exposure with UVA light and UVC light can take place simultaneously (simultaneously), one after the other or alternately (alternating).
  • post-exposure is generally carried out with a dose of 100 to 30,000 mT / cm 2 of UVA light. 100 to 20,000 mJ / cm 2 are preferred, 100 to 7000 ml / cm 2 UVA light are particularly preferred, 500 to 7000 ml / cm 2 UVA light are very particularly preferred.
  • post-exposure is generally carried out with a dose of 100 to 20,000 mJ / cm 2 UVC light.
  • 100 to 20,000 mJ / cm 2 particularly preferably 100 to 8000 mJ / cm 2 UVC light, very particularly preferably 500 to 8000 mJ / cm 2 UVC light are preferred.
  • the ratio of the doses of UVA to UVC light (D UVA / D UVC ) generally being greater than 0.2, preferably greater than 0, 4, particularly preferably greater than 0.6, very particularly preferably greater than 0.8. While exposure to UVC light preferably seals the surface of the layer due to the lower penetration depth, exposure to UVA light ensures stronger crosslinking in the entire layer, so that mechanically stable reliefs are obtained.
  • the previously described relief precursor is provided. This can optionally be cleaned, whereby all methods familiar to Lachmann can be used, such as brushing, blowing, wiping (with and without solvent), rinsing and any combination thereof.
  • the wavelength of the radiated electromagnetic radiation is in the range from 200 to 2000 nm, preferably in the UV range, particularly preferably in the range from 200 to 550 nm, very particularly preferably in the range from 300 to 450 nm It may be advantageous to use narrow-band or monochromatic wavelength ranges, such as those that can be generated using the appropriate filters, lasers or light emitting diodes (LEDs). In these areas, wavelengths in the ranges 350, 365, 385, 395, 400, 405, 532, 830, 1064 nm are preferred individually (and about 5-10 nm above and / or below) or as combinations.
  • step (ii) the mask layer is imaged either by removing the layer and / or a spatially resolved change in the absorption and / or reflection properties so that the mask layer becomes at least partially transparent in the wavelength range used for imaging.
  • the mask layer is preferably ablated by means of a high-energy laser, laser beams being guided over the mask layer under computer control.
  • Mainly IR lasers with wavelengths in the range from 500 to 20,000 nm, preferably in the range from 800 to 10,000 nm, particularly preferably in the range from 1000 to 2000 nm, are used. In particular, wavelengths around 830 nm, 980 nm, 1064 nm and 10.6 pm or combinations thereof are preferred.
  • the relief precursor can be irradiated with electromagnetic radiation over a large area from at least one side.
  • This irradiation is preferably carried out from the side of the relief precursor which is opposite the mask layer, in order to achieve a base of the relief structure to be produced (rear side exposure).
  • This rear side exposure is preferably carried out through transparent, dimensionally stable materials such as, for example, polymer films and, in particular, polyester films as carrier material. In the case of non-transparent carrier materials, step (iii) is omitted.
  • a Triggered a reaction which leads to the crosslinking of the components present in the layer. This networking stabilizes these areas and cannot be removed in the later development step.
  • the irradiation is generally carried out over a large area, but can also be carried out over a small area (approximately punctiform) by means of guided laser beams or spatially resolved projection of electromagnetic radiation.
  • the electromagnetic radiation used for exposure generally has wavelengths in the range from 200 to 2000 nm, preferably in the range from 315 to 380 nm.
  • the irradiation can take place continuously, pulsed or in several short periods with continuous radiation.
  • the intensity of the radiation can be varied over a wide range, it being necessary to ensure that a dose is used which is sufficient to crosslink the layer (B) sufficiently for the later development process.
  • the intensity is generally in the range from 10 to 1000 mW / cm 2 .
  • the radiation dose is generally in the range from 3 to 100 J / cm 2 , preferably in the range from 6 to 20 J / cm 2 .
  • the energy source can also act in an inert atmosphere, for example in noble gases, C0 2 and / or nitrogen or under a liquid that does not damage the multilayer element.
  • the direct imagewise exposure can be achieved in that the areas to be crosslinked are exposed selectively. This can be achieved, for example, with one or more laser beams, which are controlled accordingly, through the use of screens in which certain pixels are activated that emit radiation, through the use of movable LED strips, through LED arrays in which individual LEDs can be switched on and off in a targeted manner, through the use of electronically controllable masks in which image points are switched to be transparent, which allow the radiation of a radiation source to pass, through the use of projection systems in which image points are exposed to radiation from a radiation source through the appropriate orientation of mirrors , or combinations thereof.
  • the direct exposure is preferably carried out by means of controlled laser beams or projection systems with mirrors.
  • the absorption spectra of the initiators or initiator systems and the emission spectra of the radiation sources must at least partially overlap.
  • step (v) the layers (C) and, if present, the layer (E) and non-crosslinked areas of the layer (B) are removed and the relief is produced in this way.
  • the unexposed, unphotopolymerized areas of the relief-forming layer can be removed in step (v) by treatment with a washout agent or by thermal treatment.
  • the layers can be removed individually or in groups or all together and at the same time. Preferably, all layers and the uncrosslinked areas of (B) are removed in a single step. Depending on the nature of the layers, this can be done by treatment with solvent-based or water-based washing agents, such as, for example, organic solvents, their mixtures, water, aqueous solutions or aqueous-organic solvent mixtures which are able to remove non-crosslinked areas in layer (B) to dissolve, emulsify and / or disperse.
  • solvent-based or water-based washing agents such as, for example, organic solvents, their mixtures, water, aqueous solutions or aqueous-organic solvent mixtures which are able to remove non-crosslinked areas in layer (B) to dissolve, emulsify and / or disperse.
  • the layers (C) and, if present, the layer (E) and the non-crosslinked areas of the layer (B) are removed in step (v) thermally, i.e. by introducing heat and removing the softened or partially liquefied material of the layers.
  • the exposed relief precursor can be heated using any of the methods known to those skilled in the art, such as, for example, irradiation with IR light, Exposure to hot gases (e.g. air), by means of hot rollers or any combination thereof.
  • the liquid material is taken up (absorbed and / or adsorbed) by a development medium which is continuously brought into contact with the heated surface of the relief precursor. The process is repeated until the desired relief height is reached.
  • Papers, fabrics, fleeces and films which can absorb the liquefied material and can consist of natural and / or synthetic fibers, can be used as development media.
  • nonwovens or nonwoven fibrous webs made from polymers such as celluloses, cotton, polyesters, polyamides, polyurethanes and any combination thereof which are stable at the temperatures used in development are used.
  • the invention also relates to a method for producing an optimized relief structure, in which the method with steps (i) to (viii) is carried out several times, with post-exposure with UVA light and / or UVC light in step (vii) the dose and / or the time sequence of the UVA and UVC post-exposure steps is varied in order to optimize the surface quality of the relief.
  • the invention also relates to the relief structures obtainable by the processes described above and to their use.
  • the relief structures can be used as pad printing plates, flexographic printing plates, letterpress printing plates, gravure printing plates, microfluidic components, microreactors, phoretic cells, photonic crystals or optical components.
  • microfluidic components or microreactors it can be advantageous to make the surface properties hydrophobic for the use of aqueous or strongly polar fluids in order to reduce the interactions with the walls or to produce a hydrophilic surface when using non-polar fluids.
  • phoretic cells, photonic crystals or optical components it can be advantageous in terms of soiling and cleaning to make the surface hydrophobic or hydrophilic.
  • the plates were assessed after printing about 1000 linear meters by assessing the tone value fields from 10% to 50%.
  • a strong taper (a lot of color in the spaces) was with marked, slight closing with "0” and little or no closing (no color in the spaces) with "+".
  • gloss measurements were carried out.
  • the gloss was measured using a micro-TRI-gloss m gloss meter (BYK -Gardner GmbH) at a gloss angle of 60 °.
  • the gloss meter was calibrated with the help of the integrated calibration standard before the measurements. The result is the mean of three measurements at different points on the plate surface. Removing the MOA by cleaning the surface with solvent increases the gloss to 40-50 GU.
  • FIGS. 1 to 3 show the development of the gloss in gloss units GU as a function of the time in days for various post-exposure times.
  • FT-IR measurements were carried out to detect the MOA on the plate surface.
  • a Tensor 27 FT-IR (Bruker) equipped with a PIKE MIRacle Diamant / ZnSe ATR-IR unit (PIKE Technologies) was used for the FT-IR measurements on the plate surface.
  • the data were recorded and evaluated using the software Opus Version 7.5 (Bruker). There was an automatic background correction of the spectra.
  • the integrals of the IR bands at 719 and 729 cm 1 were used as a measure of the presence of the MOA. For this purpose, these were normalized to the integral of the IR band at 1730 cm 1 and the zero value (result without MOA) subtracted.
  • FIGS. 4 to 6 show the integrals of the IR bands at 719 and 729 cm 1 after 7 days for the specified post-exposure times.
  • the effect of the MOA on the wetting of the surface with water was investigated by means of contact angle measurements.
  • a drop of 10 pL deionized water was dropped onto the cliché surface of a printing plate.
  • the profile of the water drop was recorded with the Keyence VHX-500F light microscope using the VH-Z20R objective and the VH-S30 tripod.
  • the associated software was used to measure the radius r and the height h of the drop from these recordings.
  • the contact angle Q was calculated using trigonometry (equation 1).
  • An SBS-based relief precursor (total thickness 1.14 mm) was made with 1% by weight of a paraffin wax (> C20) with a melting point of 50-57 ° C. as MOA and 2% by weight of benzil- ⁇ , ⁇ -dimethylacetal (IGM Resins BV) made on a polyester carrier.
  • the relief precursor was exposed from the back using the fluorescent tubes (Philips TL 80W / 10-R) in a nyloflex® Combi FIII exposure (Flint Group) for 25 seconds with an intensity of 16 mW / cm 2.
  • the precursor was imaged in a ThermoFlexX 20 (Xeikon) and then in a nyloflex® Combi FIII-B denser (Flint Group) using fluorescent tubes (Philips TL 80W / 10-R) for 15 minutes with an intensity of 16 mW / cm 2 exposed through the mask layer at 40 ° C.
  • the exposed precursor was washed out in a nyloflex® Digital Washer FIII (Flint Group) using nylosolv A and at a speed of 220 mm / min. Drying took place at 60 ° C. for 120 minutes.
  • Figures 1, 2 and 3 show the time course of the gloss on the surfaces of the printing plates under different post-exposure conditions. If the MOA diffuses to the surface, the gloss value decreases. In comparison with FIGS. 4, 5 and 6, it can be established that a decrease in the gloss value is associated with an increase in the IR signal.
  • FIGS. 4, 5 and 6 it can be established that a decrease in the gloss value is associated with an increase in the IR signal.
  • Table 1 shows the IR integrals and gloss on the printing surface after 2 days as a function of the post-exposure conditions.
  • the larger the value of the IR integral the more MOA there is on the plate surface.
  • the IR integral correlates with the reciprocal of the gloss.
  • a low gloss indicates the presence of the MOA on the surface. Without a MOA there is no MOA detectable by means of IR spectroscopy. If post-exposure is carried out for 10 min with UVA and 10 min with UVC, significantly less MOA reaches the printing surface than is the case without post-exposure or for 10 min UVA post-exposure time without UVC exposure. The properties of the printing surface can thus be controlled.
  • Table 2 shows the influence of UVA and UVC exposure on the presence of the MOA on the cliché surface. The duration of 7 days was chosen to prove that the MOA does not actually come to the surface. Reference 1 shows the values that result without MOA. The less UVA or UVC light was used on printing plates with MOA, the more more MOA is present on the cliché surface after 7 days. The influence of UVC light is stronger than that of UVA light. The values obtained for the combination of UVA and UVC post-exposure correspond to the values of a printing plate without MOA.
  • Example 2 An SIS-based relief precursor (thickness: 1.14 mm) with 1% by weight of a paraffin wax (> C35) with a melting point of 58 ° C. as MOA and 5% by weight of benzil- ⁇ , ⁇ -dimethylacetal (IGM Resins BV) and 0.5% by weight 1-Hydroxycyclohexylphenylketon (IGM Resins BV) is produced on a polyester carrier.
  • Both plate types were measured using fluorescent tubes (Philips TL 80W / 10-R) in a nyloflex® Combi FIII-B (Flint Group) for 15 seconds (a)) or for 10 seconds (b)) with an intensity of 16 mW / cm 2 exposed from the back.
  • the precursors were imaged in a ThermoFlexX 20 (Xeikon) and then in a nyloflex® Combi FIII-B denser (Flint Group) using fluorescent tubes (Philips TL 80W / 10-R) for 15 minutes with an intensity of 16 mW / cm 2 exposed through the mask layer at 40 ° C.
  • the precursors were washed out in a nyloflex® Digital Washer FIII (Flint Group) using nylosolv A and at a speed of 200 mm / min. Drying took place at 60 ° C. for 120 minutes. Subsequently, different post-exposures were carried out at 40 ° C in a nyloflex® Combi FIII exposure unit (Flint Group), with UVA and UVC exposures being used in parallel and started at the same time.
  • Table 3 shows the gloss on the surface of the clichés after 3 days and the flow of the printing plates after printing with solvent ink (LM).
  • Example 3 An SBS-based relief precursor (thickness 1.14 mm) with 1% by weight of a paraffin wax (> C35) with a melting point of 58 ° C. as MOA and 2% by weight of benzil- ⁇ , ⁇ -dimethylacetal (IGM Resins BV) was used made on a polyester carrier. This was exposed from the rear using a Next FV exposure unit (Flint Group) using fluorescent tubes (Light Emission Tech F100T12 / 10-R 100W) for 26 seconds with an intensity of 19 mW / cm 2.
  • a An SBS-based relief precursor (thickness 1.14 mm) with 1% by weight of a paraffin wax (> C35) with a melting point of 58 ° C. as MOA and 2% by weight of benzil- ⁇ , ⁇ -dimethylacetal (IGM Resins BV) was used made on a polyester carrier. This was exposed from the rear using a Next FV exposure unit (Flint Group) using
  • the precursor was imaged in a CDI 2530 (Esko) and then in a Next FV exposure unit (Flint Group) using fluorescent tubes (Light Emission Tech F100T12 / 10-R 100W) for 10 minutes with an intensity of 19 mW / cm 2 exposed through the mask layer.
  • the precursor was developed in a nyloflex Flowline Washer FV (Flint Group) using nylosolv A (Flint Group) and at a speed of 255 mm / min. Drying took place at 60 ° C. for 120 minutes.
  • UVA Philips TL 80W / 10-R SLV G13, intensity 12 mW / cm 2
  • UVC exposure Philips TUV TL-D 95W HO SLV / 25, intensity 11 mW / cm 2
  • the UVA exposure time was 10 minutes
  • the UVC exposure time was increased from 0 to 10 minutes in 2 minute intervals.
  • An SBS-based relief precursor (thickness 1.14 mm) with 1% by weight of a paraffin wax (> C35) with a melting point of 58 ° C.
  • the precursor was developed in a nyloflex Flowline Washer FV (Flint Group) using nylosolv A (Flint Group) and at a speed of 285 mm / min. Drying took place at 60 ° C. for 120 minutes. Post-exposure was then carried out at room temperature, the UVA (Philips TF 80W / 10-R SFV G13, intensity 12 mW / cm 2 ) and UVC exposure (Philips TUV TF-D 95W HO SFV / 25, intensity 11 mW / cm 2 ) were started and carried out in parallel at the same time. The UVA exposure time was 8 minutes, the UVC exposure time was increased from 0 to 10 minutes in 2 minute intervals. c.
  • An SBS-based relief precursor (thickness 1.14 mm) with 1% by weight of a paraffin wax (> C35) with a melting point of 58 ° C. as MOA and 5% by weight of benzil- ⁇ , ⁇ -dimethylacetal (IGM Resins BV) was used made on a polyester carrier. This was exposed from the rear using a Next FV exposure unit (Flint Group) using fluorescent tubes (Fight Emission Tech F100T12 / 10-R 100W) for 26 seconds with an intensity of 19 mW / cm 2.
  • the precursor was imaged in a CDI 2530 (Esko) and then in a Next FV exposure unit (Flint Group) using the UV FED Feiste with 3 x 250 mm / min and an intensity of 800 mW / cm 2 the mask layer is exposed.
  • the precursor was developed in a nyloflex Flowline Washer FV (Flint Group) using nylosolv A (Flint Group) and at a speed of 255 mm / min. Drying took place at 60 ° C. for 120 minutes.
  • UVA Philips TF 80W / 10-R SFV G13, intensity 12 mW / cm 2
  • UVC exposure Philips TUV TF-D 95 W HO SFV / 25, intensity 11 mW / cm 2
  • the UVA exposure time was 8 minutes
  • the UVC exposure time was increased from 0 to 10 minutes at 2 minute intervals.
  • a solvent ink Flexistar MV Process Cyan (Flint Group) was printed by means of an F&K Flexpress 6S / 8 printing machine (Fischer & Krecke) on an LD-PE film (Delo) pretreated on one side with corona with a width of 400 mm and a thickness of 55 ⁇ m.
  • a Lohmann 5.3 foam adhesive tape (Lohmann) was used to attach the printing plates.
  • the anilox roller used had a screen fineness of 420 lines / cm and a volume of 3.5 cm 3 / m 2 .
  • the printing speed was 200 m / min with a provision of 70 pm for the printing unit and 60 pm for the anilox roller. It was dried in 2 stages at 40 ° C and 60 ° C.
  • Table 4 Infeed of the printing plate with different ratios of simultaneous UVA and
  • UV CN post exposures UV CN post exposures.
  • Table 4 shows the evaluation of the feed of the printing plate after printing with solvent inks at different ratios of simultaneous UVA to UVC post-exposure.
  • the interspaces are largely prevented from running through the migration of the MOA.
  • An SIS-based relief precursor (thickness 1.14 mm) with 1% by weight of a paraffin wax (> C35) with a melting point of 58 ° C. as MOA and 5% by weight of benzil- ⁇ , ⁇ -dimethylacetal (IGM Resins BV) was used made on a polyester carrier. This was exposed from the rear using a Combi FIII exposure unit (Flint Group) using fluorescent tubes (Philips TL 60 W / 10-R) with an intensity of 28 mW / cm 2 for 14 seconds.
  • the precursor was imaged in a CDI 2530 (Esko) and then in a Next FV exposure unit (Flint Group) using fluorescent tubes (Light Emission Tech F100T12 / 10-R 100W) with an intensity of 19 mW / cm 2 for Exposed through the mask layer for 8 minutes.
  • the precursor was developed in a nyloflex Flowline Washer FV (Flint Group) using nylosolv A (Flint Group) and at a speed of 290 mm / min. Drying took place at 60 ° C. for 120 minutes.
  • UVA Philips TL 80 W / 10-R SLV G13
  • UVC exposure Philips TUV TL-D 95 W HO SLV / 25
  • the UVA exposure time was 8 minutes
  • a Nilpeter M04 printing machine with FA4 Flexo units was used for printing with the UV ink Flexocure Force (Flint Group).
  • the printing material was Self-adhesive label material based on PE (Raflatac) with 330 mm width and 130 mpi thickness or paper-based (Raflacoat, UPM) with 330 mm width and 120 mm thickness used.
  • Tesa Blue foam adhesive tape with medium hardness (Tesa) was used to attach the printing plates.
  • the anilox roller used was provided with a screen fineness of 500 lines / cm and a volume of 2.5 cm 3 / m 2 .
  • the printing speed was 100 m / min.
  • Table 5 Effects of the MOA in printing with UV inks on PE film or paper.
  • Table 5 shows the effects of the MOA when printing with UV inks on PE film or paper.
  • UVC post-exposure less MOA diffuses to the surface of the printing plate.
  • the absence of the MOA resulted in a reduced full-tone color density; when printing on paper, the occurrence of bleeding edges was observed.
  • the MOA diffuses to the surface of the printing plate and promotes the transfer of ink to the respective printing material.
  • the presence of the MOA resulted in an increase in the full-tone color density; when printing on paper, the leading edges were observed to disappear.
  • An SBS-based relief precursor (thickness 1.14 mm) with 0.1 or 2.5% by weight of a paraffin wax (> C35) with a melting point of 58 ° C as MOA, 5% by weight benzil-a, a-dimethylacetal (IGM Resins BV) was made on a polyester carrier. This was exposed from the rear using a Combi FIII exposure unit (Flint Group) using fluorescent tubes (Philips TU 60 W / 10-R) for 17 seconds with an intensity of 28 mW / cm 2.
  • the precursor was imaged in a CDI 2530 (Esko) and then in a Combi FIII exposure (Flint Group) using the fluorescent tubes (Philips TU 60 W / 10-R) for 8 minutes exposed through the mask layer at an intensity of 28 mW / cm 2.
  • the precursor was developed in a nyloflex Flowline Washer FV (Flint Group) using Cyrel® Flexosol-i (DuPont) as a washout agent at a speed of 250 mm / min. Drying took place at 60 ° C. for 120 minutes.
  • UVA Philips TL 80W / 10-R SLV G13, intensity 12 mW / cm 2
  • UVC exposure Philips TUV TL-D 95 W HO SLV / 25, intensity 11 mW / cm 2
  • the UVA exposure time was 8 minutes, the UVC exposure time 2 minutes.
  • a solvent ink Flexistar MV Process Cyan (Flint Group) was printed using an F&K Flexpress 6S / 8 printing machine (Fischer & Krecke) on an LD-PE film (Delo) pretreated on one side with corona with a width of 400 mm and a thickness of 55 ⁇ m.
  • a Lohmann 5.3 foam adhesive tape (Lohmann) was used to attach the printing plates.
  • the anilox roller used had a screen fineness of 420 lines / cm and a volume of 3.5 cm 3 / m 2 .
  • the printing speed was 200 m / min.
  • An SBS-based relief precursor (thickness 1.14 mm) with 1% by weight of a paraffin wax (> C35) with a melting point of 58 ° C as MOA, 5% by weight benzil-a, a-dimethylacetal (IGM Resins BV) and 0%; 0.25% or 0.5% of a 1-hydroxycyclohexylphenyl ketone (CI) or 0.5% of a mixture of oxyphenylacetic acid 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester and oxyphenylacetic acid 2- [2-hydroxyethoxy] ethyl ester (C2) (both IGM Resins BV) was produced on a polyester carrier.
  • the precursor was developed in a nyloflex Flowline Washer FV (Flint Group) using Cyrel® Flexosol-i (DuPont) as a washout agent at a speed of 250 mm / min. Drying took place at 60 ° C. for 120 minutes. Post-exposure was then carried out at room temperature, the UVA (Philips TF 80W / 10-R SFV G13, intensity 12 mW / cm 2 ) and UVC exposure (Philips TUV TF-D 95W HO SFV / 25, intensity 11 mW / cm 2 ) were started and carried out in parallel at the same time. The UVA exposure time was 8 minutes, the UVC exposure time 2 minutes.
  • a solvent ink Flexistar MV Process Cyan (Flint Group) was printed using an F&K Flexpress 6S / 8 printing machine (Fischer & Krecke) on an FD-PE film (Delo) pretreated on one side with corona, 400 mm wide and 55 ⁇ m thick.
  • Foam adhesive tape Fohmann 5.3 (Fohmann) was used to attach the printing plates.
  • the anilox roller used was provided with a screen fineness of 420 fins / cm and a volume of 3.5 cm 3 / m 2 .
  • the printing speed was 200 m / min. Table 7:
  • An SIS-based relief precursor (thickness 1.14 mm) with 1% by weight of a paraffin wax (> C35) with a melting point of 58 ° C as MOA, 5% by weight benzil-a, a-dimethylacetal (IGM Resins BV) and 0%; 0.25% or 0.5% of a 1-hydroxycyclohexylphenyl ketone (CI) (IGM Resins BV) was made on a polyester support. This was exposed from the rear using a Combi FIII exposure unit (Flint Group) using the fluorescent tubes (Philips TF 60 W / 10-R) for 14 seconds with an intensity of 28 mW / cm 2.
  • CI 1-hydroxycyclohexylphenyl ketone
  • the precursor was imaged in a CDI 2530 (Esko) and then in a Combi FIII-B denser (Flint Group) using fluorescent tubes (Philips TF 60 W / 10-R) for 8 minutes with an intensity of 28 mW / cm 2 exposed through the mask layer.
  • the precursor was developed in a nyloflex Flowline Washer FV (Flint Group) using Cyrel® Flexosol-i (DuPont) as a washout agent at a speed of 150 mm / min. Drying took place at 60 ° C. for 120 minutes.
  • UVA Philips TF 80W / 10-R SFV G13, intensity 12 mW / cm 2
  • UVC exposure Philips TUV TL-D 95 W HO SLV / 25, intensity 11 mW / cm 2
  • the UVA exposure time was 8 minutes, the UVC exposure time 2 minutes.
  • a solvent ink Flexistar MV Process Cyan (Flint Group) was printed by means of a F&K Flexpress 6S / 8 printing machine (Fischer & Krecke) on a single-sided corona-pretreated LD-PE film (Delo) with a width of 400 mm and a thickness of 55 ⁇ m.
  • a Lohmann 5.3 foam adhesive tape (Lohmann) was used to attach the printing plates.
  • the anilox roller used had a screen fineness of 420 lines / cm and a volume of 3.5 cm 3 / m 2 .
  • the printing speed was 200 m / min.
  • An SIS-based relief precursor (thickness 1.70 mm) with 1% by weight of a paraffin wax (> C35) with a melting point of 58 ° C, 5% by weight benzil-a, a-dimethylacetal (IGM Resins BV) and 0% ; 0.25% or 0.5% of a 1-hydroxycyclohexylphenyl ketone (CI) (IGM Resins BV) was made on a polyester support. This was denser using a Combi FIII-B (Flint Group) using the fluorescent tubes (Philips TL 60 W / 10-R) for 40 seconds with an intensity of 28 mW / cm 2 exposed from the back.
  • CI 1-hydroxycyclohexylphenyl ketone
  • the precursor was imaged in a CDI 2530 (Esko) and then in a Combi FIII exposure (Flint Group) using fluorescent tubes (Philips TF 60 W / 10-R) for 8 minutes with an intensity of 28 mW / cm 2 exposed through the mask layer.
  • the precursor was developed in a nyloflex Flowline Washer FV (Flint Group) using Nylosolv A (Flint Group) as a washout agent at a speed of 230 mm / min. Drying took place at 60 ° C. for 120 minutes.
  • UVA Philips TF 80W / 10-R SFV G13, intensity 12 mW / cm 2
  • UVC exposure Philips TUV TF-D 95W HO SFV / 25, intensity 11 mW / cm 2
  • the UVA exposure time was 8 minutes and the UVC exposure time 4 minutes.
  • a solvent ink Flexistar MV Process Cyan (Flint Group) was printed using an F&K Flexpress 6S / 8 printing machine (Fischer & Krecke) on an FD-PE film (Delo) pretreated on one side with corona, 400 mm wide and 55 ⁇ m thick.
  • Foam adhesive tape Fohmann 5.3 (Fohmann) was used to attach the printing plates.
  • the anilox roller used was provided with a screen fineness of 420 fins / cm and a volume of 3.5 cm 3 / m 2 .
  • the printing speed was 200 m / min.
  • An SBS-based relief precursor (thickness 1.70 mm) with 1% by weight of a paraffin wax (> C35) with a melting point of 58 ° C, 1% by weight benzil-a, a-dimethylacetal (IGM Resins BV) and 0% ; 0.5%; 1.0%; 1.5% or 2.0% 1- (4-methyllphenyl) -l-dodecanone (C3) (BASF) was produced on a polyester carrier. This was exposed to an intensity of 28 mW / cm 2 from the back for 40 seconds using a Combi FIII-B denser (Flint Group) using the fluorescent tubes (Philips TF 60 W / 10-R).
  • the precursor was imaged in a CDI 2530 (Esko) and then in a Combi FIII exposure unit (Flint Group) using fluorescent tubes (Philips TF 60 W / 10-R) for 9 minutes with an intensity of 28 mW / cm 2 exposed through a mask layer placed on top and fixed by vacuum.
  • the precursor was developed after removing the mask layer in a nyloflex Flowline Washer FV (Flint Group) using Cyrel® Flexosol-i (DuPont) as a washout agent at a speed of 250 mm / min. Drying took place at 60 ° C. for 120 minutes.
  • UVA Philips TF 80W / 10-R SFV G13, intensity 12 mW / cm 2
  • UVC exposure Philips TUV TF-D 95W HO SFV / 25, intensity 11 mW / cm 2
  • the UVA exposure time was 10 minutes
  • a solvent ink Flexistar MV Process Cyan (Flint Group) was printed using an F&K Flexpress 6S / 8 printing machine (Fischer & Krecke) on an FD-PE film (Delo) pretreated on one side with corona, 400 mm wide and 55 ⁇ m thick.
  • Foam adhesive tape Fohmann 5.3 (Fohmann) was used to attach the printing plates.
  • the anilox roller used was provided with a screen fineness of 420 fins / cm and a volume of 3.5 cm 3 / m 2 .
  • the printing speed was 200 m / min. Table 10:
  • An SIS-based relief precursor (total thickness 1.14 mm) was made with 1% by weight of a paraffin wax (> C20) with a melting point of 50-57 ° C. as MOA and 2% by weight of benzil- ⁇ , ⁇ -dimethyl acetal (IGM Resins BV) and 0% or 0.5% 1-Hydroxycyclohexylphenylketon (IGM Resins BV) on a polyester carrier.
  • the relief precursor was exposed from the back using the fluorescent tubes (Philips TL 80W / 10-R) in a nyloflex® Combi FIII exposure unit (Flint Group) for 10 seconds with an intensity of 16 mW / cm 2.
  • the precursor was imaged in a ThermoFlexX 20 (Xeikon) and then in a nyloflex® Combi FIII exposure unit (Flint Group) using fluorescent tubes (Philips TL 80W / 10-R) for 15 minutes with an intensity of 16 mW / cm 2 exposed through the mask layer at 40 ° C.
  • the exposed precursor was washed out in a nyloflex® Digital Washer FIII (Flint Group) using nylosolv A and at a speed of 200 mm / min. Drying took place at 60 ° C. for 120 minutes.
  • the contact angle is a measure of the wetting of the surface.
  • the uniform wetting of the surface with liquid (printing ink) is a basic requirement for a successful printing process. If there is no complete wetting, complete transfer of the printing form to the printing material is also not possible.
  • the difference between the surface tension of the printing ink and the surface energy of the printing plate is decisive for wetting.
  • a drop of liquid on a surface shows a large contact angle with a large difference between the surface tension of the liquid and the surface energy of the printing plate. If there is only a slight difference, the result is uniform wetting of the surface by the liquid and consequently a small contact angle.
  • MOA creates a hydrophobic surface. With polar liquids, such as water, a large contact angle is expected.
  • Table 11 shows the contact angle of a water droplet on printing plates with or without MOA on the cliché surface.
  • the presence of the MOA was controlled via the post-exposure.
  • the pure MOA served as a reference.
  • Table 11 The presence of the MOA on the surface affects the wetting of the surface with water. If the MOA is present on the printing plate surface, the contact angle of the water droplet is significantly larger than with a surface without MOA. If the MOA is present on the cliché surface (Examples 10b, 10d and 10f), the assumed contact angle of the water drop approaches that of the pure MOA (reference 10a). The photoinitiator concentration has a particular effect on the contact angle in the absence of the MOA. With 1% UVC PI (example 10e) a lower contact angle was obtained than without (example 10c). When printing with water-based inks, the presence of the MOA can consequently lead to wetting problems. The migration of the MOA can be controlled by post-exposure.
  • An SBS-based relief precursor (total thickness 1.14 mm) was made with 1% by weight of a paraffin wax (> C20) with a melting point of 50-57 ° C. as MOA and 5% by weight of benzil- ⁇ , ⁇ -dimethylacetal (IGM Resins BV) made on a polyester carrier.
  • the relief precursor was exposed from the back using the fluorescent tubes (Philips TL 80W / 10-R) in a nyloflex® Combi FIII exposure unit (Flint Group) for 18 seconds at an intensity of 16 mW / cm 2.
  • the precursor was imaged in a ThermoFlexX 20 (Xeikon) and then in a nyloflex® Combi FIII-B denser (Flint Group) using fluorescent tubes (Philips TL 80W / 10-R) for 15 minutes with an intensity of 16 mW / cm 2 exposed through the mask layer at 40 ° C.
  • the exposed precursor was washed out in a nyloflex® Digital Washer FIII (Flint Group) using nylosolv A and at a speed of 220 mm / min. Drying took place at 60 ° C. for 120 minutes.
  • the printing plate was then exposed to UVA light for 10 min (Philips TL 60W / 10-R, intensity 11 mW / cm 2 ) and for 5 min with UVC light (Philips TUV 75W HO G75 T8, intensity 13 mW / cm 2 ) post-exposed more densely in a nyloflex® Combi FIII-B. Both exposures (UVA and UVC) were started at the same time and carried out at 40 ° C each. After at least one week of storage after development of the printing plates, contact angle measurements were carried out on the printing surfaces formed. A surface made of pure MOA, which was obtained by melting and cooling it, served as a reference. Table 12:
  • Example 11b If the MOA is present on the printing plate surface (Example 11b), the contact angle approaches that on pure MOA (Reference 11a). Without MOA on the plate surface (example 11c), under otherwise identical processing conditions, a significantly lower contact angle is obtained.
  • An SBS-based relief precursor (thickness 1.14 mm) with 1% by weight of a paraffin wax (> C35) with a melting point of 58 ° C. as MOA and 2% by weight of benzil- ⁇ , ⁇ -dimethylacetal (IGM Resins BV) was used made on a polyester carrier.
  • the plates either contained no MOA, or 1% by weight of a paraffin wax (> C35) with a melting point of 58 ° C., or 0.5% by weight of a polysiloxane-polyester-acrylate (PPA) as MOA.
  • PPA polysiloxane-polyester-acrylate
  • the relief precursor was exposed from the rear using a Combi FIII (Flint Group) using the fluorescent tubes (Philips TF 60 W / 10-R) for 20 seconds with an intensity of 26 mW / cm 2.
  • the precursor was imaged in a CDI 2530 (Esko) and then in a Combi FIII (Flint Group) using fluorescent tubes (Philips TF 60 W / 10-R) for 10 minutes at an intensity of 26 mW / cm 2 exposed through the mask layer.
  • the precursor was developed in a nyloflex Flowline Washer FV (Flint Group) using nylosolv A (Flint Group) and at a speed of 255 mm / min.
  • UVA Philips TF 80W / 10-R SFV G13, intensity 12 mW / cm 2
  • UVC exposure Philips TUV TF-D 95W HO SFV / 25, intensity 11 mW / cm 2
  • a Nilpeter M04 printing machine with FA4 Flexo units was used for printing with the Flexocure Ancora Process Cyan UV ink (Flint Group).
  • Self-adhesive label material based on PE (Raflatac) with one-sided corona treatment or paper (Raflacoat, UPM) with a thickness of 120 mih was used as the printing material.
  • To attach the A medium hardness Tesa Blue foam adhesive tape (Tesa) was used for the printing plates.
  • the anilox roller used was provided with a screen fineness of 500 lines / cm and a volume of 2.5 cm 3 / m 2 .
  • the printing speed was 100 m / min.
  • the running-in was assessed after approx. 500 running meters.
  • Table 13 shows the effect of the MOAs on the blooming of the clichés when printing with UV ink. In the absence of MOA, strong tapering is observed. By adding a paraffin wax as MOA, the cliché can be significantly reduced. A further improvement in the feed is observed through the use of a polysiloxane-polyester-acrylate as MOA.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Inorganic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Architecture (AREA)
  • Engineering & Computer Science (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Materials For Photolithography (AREA)
  • Polymerisation Methods In General (AREA)
  • Shaping Of Tube Ends By Bending Or Straightening (AREA)
  • Manufacture Or Reproduction Of Printing Formes (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

L'invention concerne un précurseur de relief photopolymérisable, comprenant (A) un support dimensionnellement stable, (B) une couche de formation de relief photopolymérisable, contenant au moins un liant élastomère réticulable, un monomère éthyléniquement insaturé, un additif tensioactif pouvant migrer, un photo-initiateur qui peut être activé avec de la lumière UVA et un photo-initiateur qui peut être activé avec de la lumière UVC. L'invention concerne en outre un procédé de fabrication d'une structure en relief.
EP20821247.2A 2019-12-12 2020-12-14 Précurseur de relief photopolymérisable ayant des propriétés de surface ajustables Pending EP4073587A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP19215470.6A EP3835869A1 (fr) 2019-12-12 2019-12-12 Précurseur de relief photopolymérisable aux propriétés superficielles réglables
PCT/EP2020/086029 WO2021116496A1 (fr) 2019-12-12 2020-12-14 Précurseur de relief photopolymérisable ayant des propriétés de surface ajustables

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EP4073587A1 true EP4073587A1 (fr) 2022-10-19

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EP20821247.2A Pending EP4073587A1 (fr) 2019-12-12 2020-12-14 Précurseur de relief photopolymérisable ayant des propriétés de surface ajustables

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EP (2) EP3835869A1 (fr)
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CN (1) CN115210644A (fr)
BR (1) BR112022011485A2 (fr)
CA (1) CA3160941C (fr)
MX (1) MX2022007159A (fr)
WO (1) WO2021116496A1 (fr)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1014194B1 (fr) * 1998-12-23 2002-07-24 BASF Drucksysteme GmbH Plaques d'impression photopolymérisables avec couche supérieure pour la production de plaques d'impression en relief

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DE1522444B2 (de) 1967-03-10 1977-07-07 Basf Ag, 6700 Ludwigshafen Polymerisationsinhibitor enthaltendes lichtvernetzbares gemisch
DE2909992A1 (de) 1979-03-14 1980-10-02 Basf Ag Photopolymerisierbare aufzeichnungsmassen, insbesondere zur herstellung von druckplatten und reliefformen
DE3045516A1 (de) 1980-12-03 1982-07-08 Basf Ag, 6700 Ludwigshafen Lichtempfindliches mehrschichtenmaterial und verfahren zur herstellung von haftschichten dafuer
DE3144905A1 (de) 1981-11-12 1983-05-19 Basf Ag, 6700 Ludwigshafen Zur herstellung von druck- und reliefformen geeignetes lichtempfindliches auszeichnungsmaterial und verfahren zur herstellung von druck- und reliefformen mittels dieses aufzeichnungsmaterials
JPS58117537A (ja) 1982-01-06 1983-07-13 Toray Ind Inc 感光性樹脂組成物
DE3541162A1 (de) 1985-11-21 1987-05-27 Basf Ag Photoempfindliche aufzeichnungsmaterialien mit elastomeren pfropfcopolymerisat-bindemitteln sowie reliefformen daraus
DE60000237T2 (de) 2000-06-13 2003-03-06 Agfa-Gevaert, Mortsel Direktbeschreibbarer flexographischer Druckplattenprecursor
US6773859B2 (en) 2001-03-06 2004-08-10 E. I. Du Pont De Nemours And Company Process for making a flexographic printing plate and a photosensitive element for use in the process
EP1710093B1 (fr) 2004-01-27 2013-11-20 Asahi Kasei Chemicals Corporation Composition de resine photosensible pour substrat d'impression gravable par laser
JP4782580B2 (ja) 2005-11-01 2011-09-28 旭化成イーマテリアルズ株式会社 フレキソ印刷用感光性樹脂組成物
JP4673197B2 (ja) * 2005-11-24 2011-04-20 日立Ｇｅニュークリア・エナジー株式会社 液体試料のモニタリング方法及び液体試料分析装置
CN101416110A (zh) * 2006-04-07 2009-04-22 旭化成化学株式会社 柔性印刷用感光性树脂组合物
JP2010055021A (ja) * 2008-08-29 2010-03-11 Fujifilm Corp 平版印刷版の作製方法
EP3159740B1 (fr) * 2015-10-22 2018-08-01 Flint Group Germany GmbH Procede de fabrication generative de formes d'impression en relief
US11325368B2 (en) * 2017-03-27 2022-05-10 Flint Group Germany Gmbh Method for producing pictorial relief structures
CN111512231B (zh) * 2017-10-10 2024-03-15 恩熙思德国有限公司 具有低程度的杯形挤压和槽纹的凸纹前体
JP7012526B2 (ja) 2017-12-20 2022-01-28 旭化成株式会社 フレキソ印刷原版、及びフレキソ印刷版

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Publication number Priority date Publication date Assignee Title
EP1014194B1 (fr) * 1998-12-23 2002-07-24 BASF Drucksysteme GmbH Plaques d'impression photopolymérisables avec couche supérieure pour la production de plaques d'impression en relief

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CN115210644A (zh) 2022-10-18
CA3160941A1 (fr) 2021-06-17
US20230031598A1 (en) 2023-02-02
CA3160941C (fr) 2024-04-16
JP2023505912A (ja) 2023-02-13
EP3835869A1 (fr) 2021-06-16
WO2021116496A1 (fr) 2021-06-17
MX2022007159A (es) 2022-08-19

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