EP3598870A1 - Procédé servant à fabriquer des structures en relief sous forme d'images - Google Patents

Procédé servant à fabriquer des structures en relief sous forme d'images

Info

Publication number
EP3598870A1
EP3598870A1 EP17715072.9A EP17715072A EP3598870A1 EP 3598870 A1 EP3598870 A1 EP 3598870A1 EP 17715072 A EP17715072 A EP 17715072A EP 3598870 A1 EP3598870 A1 EP 3598870A1
Authority
EP
European Patent Office
Prior art keywords
relief
substrate layer
liquid
layer
reactive component
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
EP17715072.9A
Other languages
German (de)
English (en)
Inventor
Thomas Telser
Matthias Beyer
Daniel Fleischer
Claudia MAY
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
Flint Group 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 Flint Group Germany GmbH filed Critical Flint Group Germany GmbH
Publication of EP3598870A1 publication Critical patent/EP3598870A1/fr
Pending legal-status Critical Current

Links

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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/02—Engraving; Heads therefor
    • B41C1/04—Engraving; Heads therefor using heads controlled by an electric information signal
    • B41C1/05—Heat-generating engraving heads, e.g. laser beam, electron beam
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • 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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • G03F7/2032—Simultaneous exposure of the front side and the backside
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/36—Imagewise removal not covered by groups G03F7/30 - G03F7/34, e.g. using gas streams, using plasma
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
    • B41M3/16—Braille printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B41M7/0081—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using electromagnetic radiation or waves, e.g. ultraviolet radiation, electron beams
    • 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
    • G03F7/0037—Production of three-dimensional images

Definitions

  • the invention relates to a method for producing information-containing relief structures, for example with pictorial structures, which are produced in a targeted and structured manner, wherein a layer structure with a substrate layer is provided, a liquid containing a reactive component is applied imagewise to the polymeric substrate layer and optionally subsequently Excess liquid is removed from the surface and the resulting relief is fixed by polymerization and / or crosslinking.
  • Relief structures such as printing plates, are used, for example, for printing a wide variety of substrates (paper, films, cardboard, etc.) with low-viscosity printing inks.
  • printing inks are usually used polar inks based on water or alcohol.
  • the printing process requires printing forms that are soft, elastic and resistant to polar inks.
  • the relief depth is typically in the range of 50 ⁇ to 4 mm.
  • Conventional precursors for relief structures therefore contain an elastic nonpolar binder, usually block copolymers based on styrene-isoprene or styrene-butadiene, in combination with monomers, plasticizers and one or more photoinitiators (see, for example, US Pat. No. 4,323,636).
  • This radiation-sensitive layer is generally a few millimeters thick and is located on a dimensionally stable support, usually a PET film.
  • the relief is produced by exposure to electromagnetic waves through a masking film. During exposure, the exposed areas crosslink, but the unexposed areas of the precursor remain soluble or liquefiable and are removed by suitable methods.
  • relief structures can also be exposed by means of a laser-generated mask.
  • the thin ablatable mask layer is located directly on the radiation-sensitive layer (see, for example, US Pat. No. 5,262,275). By imagewise ablation, a mask is generated, is then exposed by the electromagnetic waves. Regardless of whether exposure of the radiation-sensitive layer is through a film or laser-formed integral mask, the relief must then be created by washing in suitable organic solvents (see, for example, EP332070).
  • relief structures that can be developed faster.
  • printing plates can also be thermally developed (see, for example, EP1239329 or EP1 170121).
  • the relief structures are heated to the melting temperature after the imagewise exposure.
  • the unexposed areas of the relief structure thereby become partially liquid and sticky and are then continuously removed by contact by means of a nonwoven or a fabric, because the liquid material adheres thereto.
  • the method is complicated in terms of apparatus since several layers have to be removed one after the other in order to produce a sufficient relief.
  • the possible resolution of the relief structures produced in this way is lower than the resolution of relief structures washed out in solvents.
  • free-standing elements up to a fineness of 100 ⁇ m (freestanding relief point) or 30 ⁇ m (free-standing line) can be imaged on a relief printing plate. Finer elements could only be imaged on a relief printing form if a lower relief depth is chosen.
  • DE 10 2012 013532 describes a method which works with relief depths of less than 250 ⁇ m. The advantage of this method is that the web to be printed is better guided and there is no motivational mechanical vibrations in the printing press. Important in the process is that the relief background must not be colored with printing ink, otherwise it prints with. This is still difficult to achieve under production conditions today. Another difficulty of the method is the exact setting of a low relief depth.
  • US2008 / 0053326 describes a process with which elastic prepolymers or polymers are applied by means of an ink-jet printing process and crosslinked, and a relief material is built up in layers.
  • the materials must be heated to produce low-viscosity melts that can be applied by the inkjet process.
  • the still relatively high viscosity causes relatively large nozzle openings, which brings the achievable structure size in areas that are not suitable for high-resolution prints.
  • EP1552922 avoids the viscosity problem by dispersing solid particles in a carrier liquid and then coating this dispersion in an ink jet printing process.
  • the carrier liquid must be removed in this process but again, which makes the process consuming and inaccurate.
  • the particles must be very small in order to avoid clogging of the nozzles and the stability of the dispersions used is low due to the sedimentation of the particles.
  • No. 6,641,772 describes a stereolithography method with which relief structures can be constructed.
  • a temperature-sensitive resin solution or melt is selectively heated with an IR laser and thermally cured to form three-dimensional structures.
  • the process is complex in terms of apparatus and the resolution is severely limited both by the diameter of the laser beam and the fuzzy temperature profile which is produced in the melt.
  • the problem to be solved is to produce an elastic relief structure by means of an additive process which does not have the abovementioned disadvantages and gives detailed relief structures.
  • the viscosity and stability problems in inkjet processes are to be solved.
  • a method for the production of pictorial relief structures on a layer structure comprises the steps:
  • a layer structure comprising at least one substrate layer is provided.
  • the layer structure can only consist of the substrate layer or have additional layers.
  • carrier, compression, adhesion promoter, barrier and protective layers and any desired combinations thereof can be located on one side of the substrate layer.
  • mask, adhesion, release, intermediate, barrier, mask and protective layers and any combinations thereof may be arranged in any order.
  • Dimensionally stable carrier materials which optionally can carry further layers can be used as carrier layers.
  • suitable dimensionally stable carriers are plates, films and conical and cylindrical tubes (SIeeves) made of metals such as Steel, aluminum, copper or nickel, or of plastics such as polyethylene terephthalate, polybutylene terephthalate, polyamide and polycarbonate, woven and nonwoven fabrics such as glass fiber fabrics, and composites of glass fibers and plastics.
  • Dimensionally stable substrates are, in particular, dimensionally stable carrier films or metal sheets, for example polyethylene or polyester films or steel or aluminum sheets. These carrier foils or sheets are generally between 50 ⁇ m and 1100 ⁇ m, preferably 75 ⁇ m to 400 ⁇ m, for example about 250 ⁇ m thick.
  • steel sheets with a thickness of 0.05 ⁇ m to 0.3 mm are preferred.
  • These carrier films or carrier plates can be coated with a thin adhesion-promoting layer, for example a 1 to 5 ⁇ m thick layer on the side of the carrier film facing the substrate layer.
  • This adhesive layer may consist, for example, of a mixture of a polycarbonate, a phenoxy resin and a multifunctional isocyanate.
  • carrier films or carrier plates can already be pre-equipped with a thin adhesion-promoting layer (primer) or be provided with this subsequently.
  • Adhesive layers may be present between the carrier layer and the substrate layer.
  • Polyurethane adhesive paints eg according to DE3045516
  • polyisocyanate-crosslinked polyether or polyester paints in layer thicknesses between 0.1 ⁇ m and 50 ⁇ m, in particular between 2 ⁇ m and 30 ⁇ m, can be used as the adhesive lacquer layers, for example.
  • Intermediate layers can be located on the side of the adhesive layer facing away from the carrier layer, have layer thicknesses between 0.1 ⁇ m and 50 ⁇ m, in particular 1 ⁇ m and 10 ⁇ m, and can be prepared, for example, from dilute aqueous-alcoholic solution of (for example: 80 mol%). ) partially saponified polyvinyl esters, phenylglycerol ether monoacrylate and glyoxal, are obtained by means of application, drying and baking.
  • the adhesion between the dimensionally stable substrates and the substrate layer should be greater than 0.5 N / cm when measured in a peel test at a peel angle of 90 ° and a peel rate of 30 mm / min.
  • the substrate layer may also consist of more than one layer, wherein it generally comprises 2 to 20 layers, preferably 2 to 5 layers, more preferably 2 to 3 layers, and most preferably 2 layers.
  • the layers may contain the same constituents or different constituents and this in equal and / or different proportions. Preferably, these layers contain the same constituents.
  • the substrate layer or the substrate layers closest to the carrier layer is preferably already fixed, crosslinked and / or reacted. At least one substrate layer is arranged on these fixed, crosslinked, reacted layers, which can still be fixed and / or crosslinked and / or reacted.
  • Barrier or protective layers can be used to protect the substrate layer from negative environmental influences such as light, moisture, oxygen, or ozone, or combinations thereof. However, it is also possible to combine different barrier properties in one layer and this layer can also be the carrier layer. Barrier layers against light can be made of plastics which themselves absorb appropriate wavelengths (eg, polyethylene naphthalate which absorbs in the UV region) or of plastics containing materials which absorb or reflect the respective wavelengths (as for example in EP0504824A1 DuPont or EP0767406A1 BASF described).
  • Moisture barrier layers can be made of polymers that have a low water diffusion coefficient. Examples are polyethylenes, polypropylenes, polyesters, polyvinyl alcohol and any combination thereof. Oxygen barrier layers can play a major role in the subsequent exposure to electromagnetic waves, since radical reactions are strongly influenced and slowed down by oxygen. As materials for non-photopolymerizable barrier layers, both water-soluble and organic-solvent-soluble binders are proposed, namely, polyamides, polyvinyl alcohols, hydroxyalkylcelluloses, ethylene-vinyl acetate copolymers, amphoteric interpolymers, cellulose acetate butyrate, alkylcelluloses, butyral, cyclic rubbers, and combinations thereof.
  • the thickness of the barrier layer is generally 0.25 ⁇ to 76 ⁇ , preferably 0.38 ⁇ to 64 ⁇ .
  • a protective layer will usually represent the outermost view from the carrier layer and has the primary task of protecting the substrate layer from mechanical damage (eg scratches) and dirt or dust and is usually removed before further processing steps in step a).
  • the protective layer is usually a thin and preferably likewise dimensionally stable plastic film of polyesters (for example polyethylene terephthalate, polybutylene terephthalate), polyamides, polyurethanes or polyethylene.
  • the protective layer may also contain light-absorbing materials to prevent premature undesired reaction in the layers and degradation of the materials therein.
  • Adhesion improving layers or intermediate layers are said to increase the adhesion between individual layers and to stabilize the layer structure.
  • materials to choose that can build an interaction to both layers Preferred examples thereof are surfactants, amphiphilic molecules having hydrophobic and hydrophilic regions, and block copolymers. and oligomers containing blocks compatible with the two layers or compatible with the polymers in the layers.
  • Release layers are intended to lower the adhesion between individual layers and, for example, facilitate the removal of at least one other layer. These layers can be located at various positions in the layer structure and used for easy removal of one or more layers.
  • a mask layer should preferably be ablatable by means of a laser and be blocked against the reactive components or the monomer used in the liquid, i. diffusion of the monomer through the mask should not take place.
  • the laser-ablatable mask layer consists of at least one polymeric binder and at least one light-absorbing component, wherein the second polymeric binder may also be the light-absorbing component at the same time.
  • the choice of polymeric binder of the mask layer depends on the particular application of the printing form. Will you with the inventive method produce soft elastic, non-polar flexographic printing plates, one will select as a binder for the mask layer, a polar binder, so as to ensure the blocking effect against the non-polar monomer. If the carrier is mounted on a drum laser in the ablation procedure of the invention, then the mask layer must be sufficiently flexible. In this case, the mask layer is considered to be sufficiently flexible if it shows no cracks in the curvature of the support on the drum and the mask layer shows no waves, wrinkles or other surface structures during disassembly of the polymeric support.
  • the mask layer should be well ablatable.
  • the ablation process should produce sharp-edged structures. In particular, around the ablated structures no melt edges or deposits from the Ablationsabluft should be found.
  • Highly suitable polar binders for the mask layer are, for example, polyvinyl alcohols, low, medium or highly hydrolyzed polyvinyl acetates, polyvinyl acetals such as polyvinyl butyral, water- or alcohol-soluble polyamides, alcohol-soluble polyurethanes or polyesters, polyacrylic acid, cellulose or cellulose derivatives such as hydroxypropyl cellulose or hydroxy ethyl cellulose or nitrocellulose, ethylene-vinyl alcohol copolymers, polycyanoacrylates, polyethylene oxide or polyethylene oxide copolymers.
  • Binders for the mask layer are, for example, ethylene-vinyl acetates, flexible elastomers, soft-elastic polyurethanes, nitrocellulose, polyvinyl acetals such as, for example, poly (vinyl butyral-vinyl alcohol) copolymers (Butvar®, Mowital®) or poly (vinyl butyral-vinylethyral-vinyl alcohol) copolymers (Pioloform®).
  • other soft elastic materials can be used as a binder, such as partially hydrolyzed polyvinyl acetates.
  • the preferred binder for the mask layer is the soft-elastic polyamide Makromelt® 6900. Examples of the imaging of flexographic printing elements with IR-ablative masks are disclosed, for example, in US Pat. Nos. 5,262,275, WO1994 / 00383, EP0741330 or EP1069475.
  • polyvinyl acetates having an average degree of saponification between 50 mol% and 90 mol%.
  • These binders are strictly copolymers of vinyl acetate and vinyl alcohol units. These binders are sufficiently polar, lock to nonpolar monomers, have good flexibility, and are also readily ablatable. Of course, mixtures of said binders can be used.
  • the laser-ablatable mask layer contains the binder or binders in a proportion of 35% by weight to 99% by weight, based on all constituents of the mask layer. Furthermore, the mask layer contains a light-absorbing component.
  • the mask layer contains UV absorbers or UV-absorbing dyes or pigments (UV lasers), VIS dyes or NIR dyes or NIR pigments or IR pigments in addition to the second polymeric binder (VIS, IR laser).
  • UV absorbers or UV-absorbing dyes or pigments UV lasers
  • VIS dyes or NIR dyes or NIR pigments or IR pigments in addition to the second polymeric binder (VIS, IR laser).
  • Carbon black, graphite, nanotube particles or carbon nanotubes are preferably used as the light-absorbing component. Carbon black as a light-absorbing component has the advantage that migration from the mask layer into the underlying polymeric substrate layer does not take place.
  • the weight-wise proportion of the light-absorbing component can be from 1% by weight to 65% by weight.
  • the amount depends on the layer thickness of the mask layer, which has a thickness of 0.5 ⁇ m to a maximum of 10 ⁇ m, preferably from 0.5 ⁇ m to 5 ⁇ m. At layer thicknesses below 0.5 ⁇ m it is difficult to produce a homogeneous, dense and blocking layer. At layer thicknesses above 10 ⁇ too high ablation energies are needed and the ablation times are too long.
  • the light absorption of the mask layer in the region of the wavelength of the laser used should be> 10%.
  • the mask layer may optionally contain further components such as plasticizers, crosslinking components, dispersing aids, leveling agents, adhesive components or surface-active substances.
  • the mask layer contains other ingredients such as binders and additives that provide good processability, filming and development.
  • binders and additives that provide good processability, filming and development.
  • laser ablation has been found.
  • the mask layer is removed by the high energy input by the laser radiation and only where the laser beam strikes the mask layer. This creates a negative image of the relief structure to be created in the mask layer.
  • the use of IR lasers to ablate the mask layer and exposure to UV electromagnetic radiation has proven to be robust and efficient.
  • Such layers are described, for example, in WO94 / 03839, US Pat. No. 5,262,275, US Pat. WO94 / 03838 and EP0767406.
  • a mask layer can simultaneously serve as a barrier layer and prevent or slow down the diffusion of oxygen or other interfering substances.
  • the layer structure provided in step a) comprises a protective layer
  • this is removed before the execution of the following steps b) to g), which is possible both mechanically and chemically by treatment with solvents, water or aqueous solutions.
  • the protective layer is peeled off.
  • step b) if a mask layer is present, it is at least partially removed and the underlying substrate layer is exposed in a pictorial manner. The imaging of the mask layer is done by removing the layer.
  • a mask layer is used which can be ablated by means of high-energy radiation. In the case of ablation with high-energy radiation, steels are guided in computer-assisted fashion over the radiation-sensitive layer and material is removed in the irradiated area.
  • the wavelength of the irradiated electromagnetic waves is in the range from 200 nm to 100 ⁇ m, preferably in the IR range, particularly preferably in the range from 500 nm to 50 ⁇ m, very particularly preferably in the range from 800 nm to 20 ⁇ m. It may be advantageous to use narrowband or monochromatic wavelength ranges, as they can be generated using lasers or light emitting diodes (LEDs). In these cases, wavelengths in the ranges 355 nm, 405 nm, 415 nm, 490 nm, 532 nm, 830 nm, 980 nm, 1064 nm and 10.6 ⁇ m are preferred individually or as combinations.
  • a pictorial exposure of the substrate layer is understood here to mean that the regions of the substrate layer exposed by the partial removal of the mask layer essentially correspond to the shape of the pictorial relief structures to be produced.
  • the openings in the mask layer may be larger or smaller than the relief structures to be formed to compensate for shrinkage or enlargement of the structures.
  • a pictorial application of at least one liquid containing at least one first reactive component to the surface of the substrate layer takes place.
  • This can be done by any methods that allow a liquid to be applied selectively in the form of droplets at specific positions of the surface, such as applying drops by an ink-jet method, applying by a movable nozzle, and any combinations thereof.
  • the pictorial application of the Liquid may be assisted by the presence of an optional mask layer which has been partially removed in optional step b).
  • the openings in the mask layer can provide additional confinement of the applied liquid and increase the resolution of the structures produced.
  • the at least one liquid is applied, but it may also be advantageous to apply two or more different liquids to influence locally in different areas, for example, the relief height, a physical and / or a chemical property of the relief.
  • the pictorial application of the at least one liquid is understood to mean that the quantity and arrangement of the droplets follows the shape of the relief structure to be produced.
  • the at least one liquid is applied by means of an inkjet process, in which jets or droplets are applied selectively and in a pictorial manner to the substrate layer either continuously and / or by "drop on demand.”
  • inkjet processes are suitable for application
  • the ink jet exits the print head via a nozzle, which is passed through a piezoelectric transducer located behind the nozzle.
  • the droplets thus formed are more or less electrostatically charged via a charging electrode, and the droplets fly through a larger deflecting electrode where, depending on their specific characteristics, the droplets are then deflected to a more uniform degree (Rayleigh drip decay) elektrisc charge - to be deflected sideways.
  • the charged or uncharged drops reach the substrate. Unnecessary drops are collected again at the print head and returned to the ink circuit.
  • binary-deflecting and multi-deflecting methods In the former, the drop either comes onto the substrate or it is deflected into a drip. With the multi-deflecting method, the drops can be deflected differently by different charge states.
  • BubbleJet printheads produce tiny drops of liquid by means of a heating element that heats the liquid in the ink. In the process, a tiny vapor bubble explosively forms, which presses an ink drop out of the nozzle due to its pressure.
  • a bubble-jet technique is used, with the nozzles at right angles to the heating elements (edgeshooter).
  • the method is very similar to the piezo method, except that the extrusion pressure is generated not by a piezoelectric element but by a vapor bubble.
  • the single heating element works with a frequency up to 24 kHz.
  • flat nozzle elements are used, which consist essentially of two plates. The substrate facing plate contains a tiny nozzle bore and the vapor bubble forms opposite this bore (Sideshooter).
  • Printheads that use this process are very easy to manufacture and are therefore inexpensive. But these printheads have the disadvantage of a limited life. The procedure is used with all alternating pressure heads. With pressure valve printers, individual valves are attached to the nozzles, which open when a drop is to leave the nozzle.
  • the preferred piezo printheads use the piezoelectric effect for pressing the liquid through a fine nozzle, whereby ceramic elements deform under electrical tension.
  • the ink forms drops whose volume can be controlled by the magnitude of the applied electrical pulse.
  • the operating frequency of a piezocrystal reaches up to 23 kHz.
  • the application of the drops takes place in a flat arrangement in which the surface of the substrate layer is aligned horizontally, so that the drops do not flow away.
  • the total area of the area to be structured is subdivided into smaller areas in such a way that an inkjet head with at least one nozzle can image the area within the shortest possible reaction time. You may need more than one print head.
  • the size of the droplets can vary over wide ranges and is in the range of 0.1 pl (picoliter) to 2 ⁇ , preferably in the range of 0.5 pl to 0.5 ⁇ , particularly preferably in the range of 1 pl to 300 nl (nanoliter) and more preferably in the range of 1 pl to 100 nl. In special cases, the drop size may also be less than 100 pl.
  • building a relief is preferably at the beginning with relatively large Start droplets to reach a broader and higher base and reduce the droplet size in subsequent layers to achieve the required resolution.
  • the application of the liquid can take place at room temperature or at other temperatures adapted to the corresponding conditions. In addition to higher temperatures, lower temperatures may be required, especially when very reactive systems with very reactive components are used.
  • the temperature may be in the range from -20 ° C to 200 ° C, preferably in the range of 0 ° C to 200 ° C, more preferably in the range of 20 ° C to 180 ° C, most preferably in the range of 20 ° C to 150 ° C.
  • cooler liquid can be applied to warmer substrate, warmer liquid to cooler substrate or warm liquid to warm substrate.
  • the substrate and liquid preferably have the same temperature when applied, but the temperatures may also differ.
  • step d) at least some of the applied liquid at least partially diffuses or migrates into the substrate layer and / or diffusible constituents of the substrate layer, in particular at least one second reactive component, into the droplets.
  • This process can take place over a wide period of time.
  • the exposure time can vary between 1 second to 30 minutes, preferably 1 second to 10 minutes, more preferably from 10 seconds to 10 minutes, most preferably from 1 minute to 5 minutes.
  • the diffusion can also take several hours.
  • the diffusion can be influenced by the adjustment of the temperature, wherein the temperatures are limited by the solidification point of the liquid to be applied down and their boiling point upwards.
  • the temperature may be in the range from -20 to 200 ° C, preferably in the range of 0 ° C to 200 ° C, more preferably in the range of 20 ° C to 180 ° C, most preferably in the range of 20 ° C. up to 150 ° C.
  • the diffusion conditions can be adapted to the specific circumstances and, for example, be longer with the use of large droplets than with small droplets. In order to allow larger drops to diffuse faster, the process can be carried out at higher temperatures than if smaller droplets are to be used to produce more detailed structures.
  • the exposure time depends on how fast this diffusion is vonstattenxx and a state is reached, which leads to stable structures in the subsequent fixation.
  • the diffusion time at each step may be the same length or adjusted to the circumstances of different lengths.
  • the extent in the plane of the substrate layer surface is influenced by the size of the droplets or amount of material used for the application and / or the size of an opening of the mask layer and the spreading behavior of the liquid on the surface. As a rule, the extent is equal to or greater than an applied drop or opening of the mask layer.
  • the expansion is in the range of 10 ⁇ 2 to 50 mm 2 , preferably in the range of 10 ⁇ 2 to 20 mm 2 , more preferably in the range 20 ⁇ 2 to 10 mm 2 , most preferably in the range 50 ⁇ 2 to 10 mm2.
  • the height of the relief structure which can be achieved after a single application of a liquid, is in the range of 0.01 ⁇ to 50 ⁇ , preferably in the range of 0.1 ⁇ to 20 ⁇ , more preferably in the range 1 ⁇ to 10 ⁇ , completely particularly preferably in the range 5 ⁇ to 10 ⁇ .
  • the relief height is in the range from 0.05 ⁇ m to 1000 ⁇ m, preferably in the range from 1 ⁇ m to 500 ⁇ m, particularly preferably in the range from 1 ⁇ m to 200 ⁇ m, very particularly preferably in the range from 1 ⁇ m to 10 ⁇ m.
  • the individual droplets can be placed in such a way that they overlap and flow into each other, thus forming a closed surface or separating them so that individual hillocks are created.
  • the droplets can be placed in the resulting recesses and a compact structure can be created.
  • hillocks these can be applied directly on top of each other, so that the substrate surface vertical or inclined depressions or networks arise whose cavities contribute to the elasticity and / or can absorb other materials. Any combinations of the aforementioned applications are also possible.
  • one will choose the exposure time so that the liquid is largely diffused and preferably completely absorbed by the substrate layer has been. Subsequently, further drops can be applied or further steps, such as fixation of the resulting relief done.
  • the height and the shape of the resulting relief for example, a line relief, then depend substantially on the selected duration of action or the diffusion rate of the selected liquid and its components in the selected substrate.
  • the optimum exposure time can be determined experimentally by determining the amount of liquid remaining on the surface or the height of the reliefs obtained after exposure to energy and plotted against the exposure time.
  • the pattern width (eg the width of a line) at the surface of the relief will always be slightly less than the width of the applied drop or the opening in the mask layer).
  • this then has a line profile which corresponds approximately to a Gaussian distribution curve.
  • the droplet size is selected to be larger by the distance of the lateral diffusion. If, for example, one wishes to build up a relief height of 5 ⁇ m, the lateral diffusion is likewise of the order of magnitude of 5 ⁇ m.
  • the line width of the line produced by droplets is preferably wider by 10 ⁇ m (twice the lateral diffusion), ie a 60 ⁇ m line applied. It is thus preferred, when applying the drops whose shape and dimensions substantially correspond to the picture elements to be produced, to select their dimensions larger than the dimensions of the picture elements to be produced.
  • the dimensions of the drops are increased by an amount corresponding to twice the lateral diffusion of the liquid. As dimensions, the diameter of points as well as the length and width of lines are understood here in particular. Since the lateral diffusion corresponds in first approximation to the relief height, it is preferred to increase the dimensions by twice the amount of the relief height.
  • the diffusion flux per unit area can be set to a desired value and, for example, a desired relief base can be constructed around the relief element or a flank of a relief element can be made steeper or flatter.
  • the speed of the relief structure expressed as a formed relief in ⁇ per exposure time, can be set in a targeted manner by the number of drops (or openings in the mask layer) per unit area at each point of the substrate surface.
  • step e) it may be advantageous in optional step e) to remove excess liquid.
  • Excess liquid is that part of the applied liquid which has not been transferred by diffusion into the substrate.
  • the removal of excess liquid may be accomplished by a method selected from the group consisting of suction, blow-off, stripping, shaking, spin-off, wash-off, pick-up, blotting, picking with a medium, and any combinations thereof.
  • At least one barrier layer can be applied, which can ensure the subsequent action of heat and / or radiation, the components from the environment, which negatively influence the reactions occurring during the action, are excluded.
  • the constituents mentioned may be substances or molecules which inhibit the reactions or slow them down or lead to side reactions which bring about disadvantageous effects or produce undesired by-products. These include, in particular, oxygen, which slows down and influences reactions which can proceed via radical intermediates and lead to the formation of undesired peroxides, or which act, for example, to moisture which, for example, inhibits cationic polymerizations.
  • barrier layers the abovementioned layers and materials are also suitable in this case. Preferably, 02 barriers are used.
  • the barrier layer all common application methods for solid and / or liquid layers can be used, such as, for example, laying on, lamination, Rolling, spraying, pouring, rolling, brushing, dipping, extruding, forming a barrier by migrating constituents of the substrate layer to the surface and any combinations thereof.
  • further treatment steps may be necessary, such as drying, rolling, cooling and any combinations.
  • these layers can also be removed again with simple methods, which is possible both physically, for example by stripping, rubbing, rubbing, milling and / or ablation, and chemically, for example by treatment with solvents, water or aqueous solutions and any combinations thereof.
  • the protective layer is peeled off or rinsed off.
  • the fixing of the relief according to step f) can also be carried out in an inert atmosphere, for example in noble gases, C0 2 and / or nitrogen or under a liquid, for example water.
  • step f) the relief is exposed to heat and / or radiation by the action of an energy source and at least one reaction is triggered which fixes the resulting relief structure.
  • reactions polymerizations and / or crosslinking reactions may be used, such as a radical, an ionic, a condensation, an addition reaction and any combinations thereof. Preference is given to free-radical polymerizations and / or crosslinking.
  • heat sources and / or sources of electromagnetic radiation can be used.
  • heat sources all sources known to those skilled in the art are usable, such as ovens, IR lamps or lamps, microwave generators, and any combinations thereof.
  • Plasmas can also be used as the energy source, which may be high-pressure, normal-pressure and / or low-pressure plasmas, cold and / or hot plasmas, non-ideal plasmas and / or dense plasmas.
  • excitation all known to the expert methods can be used, such as thermal excitation, chemical excitation, electrostatic excitation, radiation excitation, electromagnetic application, inductive excitation and / or microwave excitation.
  • the temperature may range from 20 ° C to 200 ° C, preferably in the range of 30 ° C to 200 ° C, more preferably in the range of 40 ° C to 180 ° C, most preferably in the range of 50 ° C up to 150 ° C.
  • sources of Electromagnetic radiation lamps flashlamps, fluorescent lamps, spotlights, lasers, light emitting diodes (LED) can be used.
  • the irradiation can take place over a large area or over a small area (approximately punctiform) by means of guided laser beams or spatially resolved projection of electromagnetic radiation.
  • the wavelength of the irradiated electromagnetic waves is in the range of 200 nm to 20,000 nm, preferably in the range of 250 nm to 1100 nm, particularly preferably in the UV range, very particularly preferably in the range of 300 nm to 450 nm.
  • narrowband or monochromatic wavelength ranges such as can be generated using appropriate filters, lasers or light emitting diodes (LEDs).
  • wavelengths in the ranges 350 nm, 365 nm, 385 nm, 395 nm, 400 nm, 405 nm, 532 nm, 830 nm, 1064 nm (and approximately 5 nm to 10 nm above and / or below) are individual or preferred as combinations.
  • the irradiation can be continuous or pulsed or carried out in several short periods of continuous radiation.
  • the intensity of the radiation can be varied over a wide range, it being ensured that a dose is used which is sufficient to sufficiently stabilize the swollen substrate layer for later use.
  • the radiation-induced reaction may also be advanced after further thermal treatments such that the swollen regions of the substrate layer become at least partially insoluble and / or non-meltable / liquefiable.
  • Intensity and dose of radiation depend on the reactivity of the formulation and the aggressiveness of the development.
  • the intensity of the radiation is in the range from 1 mW / cm 2 to 15000 mW / cm 2 , preferably in the range from 5 mW / cm 2 to 5000 mW / cm 2 , particularly preferably in the range from 10 mW / cm 2 to 1000 mW / cm 2 .
  • the dose of radiation is in the range of 0.3 J / cm 2 to 6000 J / cm 2 , preferably in the range of 3 J / cm 2 to 100 J / cm 2 , more preferably in the range of 6 J / cm 2 to 20 J / cm 2 .
  • the action of the energy source can also be carried out in an inert atmosphere, for example in noble gases, C0 2 and / or nitrogen or under a liquid, for example water.
  • flatbed imagesetters can be used with curved or cylindrical geometry.
  • the relief structures may be on or on rotating drums at one or more light sources be passed several times, the rotational speed and frequency can be varied.
  • flatbed platesetters either several sources are arranged so that they uniformly irradiate the surface, or one or more sources are passed over the relief structure in such a way that all regions are exposed with the same dose.
  • an elongated light source eg an LED strip
  • the relief are moved relative to each other at a constant speed.
  • a further preferred possibility is to move a light source in combination with the nozzle and to expose the application of the last layer directly after the settling of the drops.
  • step g further treatment steps for aftertreatment can then be carried out following the preceding steps (step g).
  • steps g include, for example, mechanical treatment, thermal treatment, drying, treatment with electromagnetic radiation, attachment of identification features, trimming, coating, and any combination thereof.
  • a thermal treatment can be used, for example, to start and / or complete reactions, to increase the mechanical and / or thermal stability of the relief structure and to remove volatile constituents.
  • the known methods can be used, such as heating by heated gases or liquids, IR radiation and any combinations thereof. This can be ovens, blowers, lamps, spotlights and any combination thereof and used.
  • treatment with electromagnetic radiation may be used to render the surfaces of the relief structure tack-free, initiate and / or complete the polymerization and / or crosslinking reactions.
  • the wavelength of the irradiated electromagnetic waves is in the range of 200 nm to 2000 nm, preferably in the UV range, more preferably in the range of 250 nm to 550 nm, most preferably in the range of 300 nm to 450 nm.
  • broadband irradiation of the electromagnetic Waves may be advantageous to use narrowband or monochromatic wavelength ranges, such as may be generated using appropriate filters, lasers or light emitting diodes (LEDs).
  • wavelengths in the ranges 350 nm, 365 nm, 385 nm, 395 nm, 400 nm, 405 nm, 532 nm, 830 nm, 1064 nm (and approximately 5 nm to 10 nm above and / or below) are individual or preferred as combinations.
  • a detackification is preferably achieved by irradiation with UV-C light, wherein preferably fluorescent lamps are used.
  • UV-C light has a wavelength in the range of 100 nm to 280 nm.
  • High-energy laser radiation can be used to remove parts of the relief structures, for example to increase the heights of the relief structures or to structure the surface of the raised areas.
  • Treatment with liquids such as solvents and / or aqueous solutions (alkalis or acids) or abrasive media, such as particle or liquid jets, can be used to further increase the relative height of the relief structures, as the untreated areas of the substrate layer are more sensitive are less stable and are eroded and / or dissolved faster and more.
  • liquids such as solvents and / or aqueous solutions (alkalis or acids) or abrasive media, such as particle or liquid jets
  • a further aftertreatment may be to treat the side of the substrate layer or the layer structure, which is the relief structure opposite, over the entire surface with a liquid containing a first reactive component to allow them to act at least partially and then exposed to an energy source.
  • a thermal treatment may lead to at least partial liquefaction of the areas which have not been treated with the at least one liquid. These unfixed areas can then be removed and the relief height thus additionally increased.
  • any methods and methods known to those skilled in the art may be employed, such as blowing, aspirating, blotting, blasting (with particles and / or droplets), wiping, wiping, transfer to a developing medium, and any combinations thereof.
  • the liquid material is taken up (absorbed and / or adsorbed) by a developing medium, which is continuously brought into contact with the surface of the layered structure.
  • development media papers, fabrics, flows, films can be used, which can accommodate the liquefied material and can consist of fibers of natural and / or plastics.
  • flow or nonwoven fibrous webs of polymers such as celluloses, cotton, polyesters, polyamides, polyurethanes and any combinations thereof are used that are stable at the temperatures used in the development.
  • a mechanical treatment can serve to level the surfaces of the relief structures, to structure the surface of the relief structures and / or to influence the height of the relief structures.
  • leveling are all surface abrading mechanical methods can be used, such as milling, grinding, planing, embossing and any combination thereof. Structuring of the surfaces can be achieved, for example, by embossing, grinding and any combinations thereof.
  • Mechanical changes in the relief height are preferably achieved by abrasive methods that remove the less stable areas of the relief.
  • rays with abrasive particles or liquid jets in particular should be mentioned. By means of these methods, a uniform height and flat surface of the raised relief areas is achieved. It can also be used to roughen the surface, which can increase ink transfer in printing applications.
  • steps c) and d) are preferably run through only once.
  • steps c) to f) or c) to g) can be repeated one or more times.
  • the number of repetitions of the individual steps as well as the combination of steps depends on the relief height to be achieved and is in the range of 1 to 100, preferably in the range of 1 to 50, particularly preferably in the range of 1 to 10 and very particularly preferably in the range from 1 to 5. If, for example, before the fixing according to step f), a barrier layer has been used, it must be removed before the new application of liquid according to step c).
  • steps c) and d) at least once or more than before step e) and subsequent steps f) and g) are performed.
  • the number of repetitions of the individual steps as well as the combination of steps depends on the relief height to be achieved and is preferably in the range from 1 to 100, particularly preferably in the range from 1 to 50, very particularly preferably in the range from 1 to 10 and on most preferably in the range of 1 to 5. These repeats allow for larger amounts of liquid to be applied and incorporated into the substrate layer to achieve higher relief heights.
  • step f) and c) to e) at least once or several times before step f) and the optional subsequent step g) are carried out.
  • the number of repetitions of the individual steps as well as the combination of steps depends on the relief height to be achieved and is preferably in the range from 1 to 100, particularly preferably in the range from 1 to 50, most preferably in the range of 1 to 10 and most preferably in the range of 1 to 5.
  • the amount of liquid introduced can also be increased, the resolution in a likewise repeated rinsing of the excess of the liquid according to step e) the resolution less is impaired.
  • steps c) and d) or c) to e) at least once or more than once before step f) and optional step g) are performed.
  • the number of repetitions of the individual steps as well as the combination of steps depends on the relief height to be achieved and is preferably in the range from 1 to 100, particularly preferably in the range from 1 to 50, very particularly preferably in the range from 1 to 10 and on Most preferred is in the range of 1 to 5.
  • an excessive energy input is avoided by the fixation according to step f), which could otherwise lead to an excessive increase in the rigidity of the relief and / or the substrate layer.
  • the substrate layer comprises a binder, optionally at least one second reactive component and optionally further constituents.
  • the at least one first reactive component and / or the second reactive component is preferably selected from the group consisting of a polymer, an oligomer, a monomer, a low molecular weight compound, a catalyst, an initiator and combinations of at least two of these components.
  • the first and second reactive components are each independently selected from this group.
  • the liquid preferably comprises further constituents, such as solvents and additives.
  • the substrate layer includes at least one second reactive component, which may be selected from an initiator, a catalyst, a polymer, an oligomer, a monomer, and any combinations thereof.
  • the at least one second component is capable of a reaction: The ability to react may be present through the component per se or corresponding chemical groups or functions.
  • reactions polymerizations and / or crosslinking reactions can be used, such as a radical, an ionic, a condensation, an addition reaction and any combinations from that.
  • condensation reactions are in particular the reactions of acids, preferably polyfunctional acids such as dicarboxylic acids with alcohols, preferably polyfunctional alcohols, eg diols, polyols, amines, preferably polyfunctional amines, polyamines, phenols, preferably polyfunctional phenols such as dihydroxyphenol, bisphenol A.
  • acids preferably polyfunctional acids such as dicarboxylic acids with alcohols, preferably polyfunctional alcohols, eg diols, polyols, amines, preferably polyfunctional amines, polyamines, phenols, preferably polyfunctional phenols such as dihydroxyphenol, bisphenol A.
  • Polyphenols with aldehydes, preferably polyfunctional aldehydes, which may also be metal-catalyzed.
  • cycloaddition reactions such as Diels-Alder additions, the so-called "click chemistry" or azide-alkyne cycloadditions can be used.
  • homo and hetero coupling reactions can be used which are catalyzable by metals, in particular transition metals, such as CC cross-coupling reactions using organometallic compounds or activated C-H bonds (eg Kumada, Negishi, Suzuki, Heck, Sonogashira coupling), oxidative homo and heterocoupling reactions (eg Glaser reactions), NC (Buchwald-Hartwig amination), OH, SH, Si-C coupling or olefin metathesis reactions (eg ring-opening metathesis polymerization ROMP).
  • transition metals such as CC cross-coupling reactions using organometallic compounds or activated C-H bonds (eg Kumada, Negishi, Suzuki, Heck, Sonogashira coupling), oxidative homo and heterocoupling reactions (eg Glaser reactions), NC (Buchwald-Hartwig amination), OH, SH, Si-C coupling or olefin metathesis reactions (eg ring-opening metathesis polymerization ROMP).
  • the separation of the components into the liquid and the substrate layer increases the storage stability of the overall system, since a reaction only occurs when the two reactants come together.
  • the isocyanate may be present in the substrate layer and the alcohol in the liquid or vice versa.
  • the catalyst may be applied with the liquid and the reaction initiated by energy input in the form of heat.
  • the reaction is preferably a free-radical polymerization and / or crosslinking.
  • RAFT polymerization reversible addition-fragmentation chain transfer or reversible addition-fragmentation chain transfer reaction
  • ATRP atom transfer radical polymerization
  • NMP nitroxide-mediated polymerization
  • the second reactive component may be a low molecular weight, oligomeric or high molecular weight compound or any combination thereof.
  • oligomeric or polymeric compounds may be linear, branched, star-shaped and / or dendritic structures, which may be constructed from one or more basic building blocks, which in turn may be arranged in block form, alternating or random.
  • Particularly preferred are CC double bonds, CC triple bonds, acrylic groups, methacrylic groups, vinyl ether groups, very particularly preferably acrylic groups and methacrylic groups.
  • the second reactive component should carry at least one of the abovementioned reactive groups, but may also have two or more of the reactive groups, which is advantageous in particular in crosslinking and is preferably used there.
  • low molecular weight second reactive components are polybutadiene oils, acrylated or methacrylated polybutadienes, liquid isoprene polymers and / or styrene-diene copolymers.
  • the substrate layer preferably contains a second reactive component in the form of an ethylenically unsaturated compound which contains at least one ethylenically unsaturated group.
  • Suitable ethylenically unsaturated compounds are those which are compatible with the respectively selected polymeric binders. In general, these are non-gaseous compounds at room temperature.
  • the ethylenically unsaturated compound preferably contains at least 2 ethylenically unsaturated groups, particularly preferably 2 to 6 ethylenically unsaturated groups, very particularly preferably 2 ethylenically unsaturated groups. In special cases, very many ethylenically unsaturated groups may also be present, for example in polybutadienes.
  • the ethylenically unsaturated group is at least one acrylate and / or one methacrylate group, but acrylamides and vinyl ethers are also used.
  • the ethylenically unsaturated compound can be in the form of monomer, oligomer or polymer and in linear, branched, star-shaped or dendritic form and has a molecular weight in the range of less than 50,000 g / mol.
  • the molecular weight is less than 30,000 g / mol, more preferably less than 10,000 g / mol, most preferably less than 5,000 g / mol and may also be less than 300 g / mol.
  • derivatives of acrylic and / or methacrylic acid such as their esters with mono- or polyhydric alcohols, for example acrylic or methacrylic esters of alkanals having 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 having 2 to 20 carbon atoms, eg 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, ethylene glycol di (meth) acryl
  • Pentaerythritol tetra (meth) acrylate further poly (ethylene oxide) di (meth) acrylate, m-methylpoly (ethylene oxide) -yl (meth) acrylate, ⁇ , ⁇ -diethylaminoethyl acrylate, a reaction product of 1 mole of glycerol, 1 mole of epichlorohydrin and 3 Mole of acrylic acid and glycidyl methacrylate and bisphenol A diglycidyl ether.
  • derivatives of acrylamide and methacrylamide such as ethers of their N-methylol derivatives with monohydric and polyhydric alcohols, for example ethylene glycol, glycerol, 1,1,1-trimethylolpropane, oligomeric or polymeric ethylene oxide derivatives. These are particularly suitable when polyamides or polyvinyl alcohol are used as binders.
  • so-called epoxide and urethane (meth) acrylates 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 hydroxyl-containing polyesters or polyethers.
  • esters of acrylic or methacrylic acid especially those with low vapor pressure and those which are modified with compatibilizers, for example with hydroxy, amido, sulfoester or sulfonamide.
  • compatibilizers for example with hydroxy, amido, sulfoester or sulfonamide.
  • Mixtures of the abovementioned copolymerizable ethylenically unsaturated organic compounds can also be used.
  • the ethylenically unsaturated compound used as the second reactive component is present in a concentration in the range from 0.5% by weight to 60% by weight, based on the total mass of the substrate layer, preferably in the range from 1 to 50% by weight. -%, more preferably in the range of 1 wt .-% to 40 wt .-%, most preferably in the range of 5 wt .-% to 40 wt .-%.
  • the first and second reactive components are not identical.
  • the first reactive component is usually chosen so that a high diffusion rate and thus a low exposure time result.
  • the second reactive component does not have to have a high diffusion rate since it is homogeneously distributed in the substrate layer.
  • the first reactive component should therefore be rather low molecular weight.
  • the first reactive component and the second reactive component may also be identical. In this case, by adjusting the concentration of the second reactive component in the substrate layer, the diffusion rate can be partially controlled.
  • the second reactive component is preferably an initiator and / or catalyst.
  • the liquid is fixed on the substrate surface.
  • the at least one substrate layer contains as second reactive component at least one catalyst or initiator which is capable of initiating and / or catalyzing a reaction by taking up the introduced energy.
  • catalysts and initiators can be used which are obtained by thermal treatment or irradiation with electromagnetic waves form active species.
  • reactive species radicals, ions, complexes and coordination compounds can serve.
  • catalysts are cobalt and zinc salts, which catalyze condensation reactions, platinum complexes that catalyze a hydrosilylation, amines that catalyze the crosslinking of epoxides
  • initiators that can initiate ionic reactions are, for example, ferrocenes (eg (5-cyclopentadienyl) (6 - isopropylbenzene) iron hexafluorophosphate) and onium salts, such as iononium and sulfonium salts, which generate ions upon thermal stress and / or irradiation and can initiate cationic polymerization and / or crosslinking.
  • ferrocenes eg (5-cyclopentadienyl) (6 - isopropylbenzene) iron hexafluorophosphate
  • onium salts such as iononium and sulfonium salts, which generate ions upon thermal stress and / or irradiation and can
  • onium salts can also be used to generate radicals when the formation of the ions occurs via a radical intermediate.
  • initiators or initiator systems composed of two or more components which generate radicals thermally or photochemically, which in turn can effect free-radical polymerization and / or crosslinking.
  • diazo compounds eg AIBN,
  • peroxides benzoyl peroxide
  • initiator systems comprising more than one component, it may be advantageous to use one component, preferably the slower-diffusing, than a second reactive component in the substrate layer, and another component, preferably the faster-diffusing component, as further constituent in the at least one liquid.
  • the substrate layer preferably contains, as second reactive component, initiators or initiator systems comprising at least two components which, upon irradiation with electromagnetic waves, generate radicals which cause polymerization and / or crosslinking.
  • initiators of this kind are known to the person skilled in the art and described, for example, in the following literature: Bruce M. Monroe et al., Chemical Review, 93, 435 (1993), RS Davidson, Journal of Photochemistry and Biology A: Chemistry, 73, 81 (1993), JP Faussier, Photoinitiated Polymerization Theory and Applications: Rapra Review, Vol.
  • initiators are described in JP45-37377, JP44-86516, US3567453, US4343891, EP109772, EP109773, JP63138345, JP63142345, JP63142346 and RS Davidson, Exploring the Science , JP63143537, JP4642363, JP59152396, JP61,151,197, JP6341484, JP2249 and JP24705, JP626223, JPB6314340, JP1559174831, JP1304453 and JP1 152109.
  • Norrish type I initiators include benzoyl radical initiators, ⁇ -hydroxy ketones, o-aminoketones, acylphosphine oxides, bisacylphosphine oxides, triazines, and hexaarylbisimidazoles, which may be further combined with dyes or sensitizers to increase sensitivity.
  • Combinations of ketones or aldehydes with H-carriers, such as, for example, amines or thiols, may be mentioned in particular in the case of the Norrish type II initiators.
  • the initiators are selected from the group consisting of benzil dimethyl ketal, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxides, 2, 4, 6-trimethylbenzoylphenyl phosphinates; Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxides, bis (2,6-dimethoxybenzoyl) -2, -1,4-trimethylpentylphosphine oxides, Michler's ketone, benzophenone alone and / or combined with sensitizers, amines or thiols and any combinations thereof.
  • initiators which can be used are onium salts, organic peroxides, thio compounds, ketoximes, borates, azinium and azo compounds, metallocenes and compounds having a carbon-halogen group which can also be combined or used together with sensitizers, amines or thiols.
  • sensitizers for example, xanthones, thioxanthones, anthracenes, perylenes, phenothiazines, benzophenones, acetophenones and dyes are used.
  • the substrate layer contains the initiator or the initiator system in a concentration in the range of 0th , 1 wt .-% to 20 wt .-% based on the total mass of the substrate layer.
  • concentrations are in the range of 1 to 10 Wt .-%, particularly preferably in the range of 1 wt .-% to 8 wt .-%, most preferably in the range of 2 wt .-% to 6 wt .-%.
  • the substrate layer may optionally contain further components which may be selected from the group consisting of a solvent, a stabilizer, a dye, a pigment, an additive, a surfactant, a UV absorber, a regulator, a plasticizer, a binder, a and any combinations thereof.
  • the substrate layer may in further embodiments contain further constituents selected from the group consisting of a plasticizer, a solvent, a binder, a colorant, a stabilizer, a regulator, a UV absorber, a dispersing aid, a crosslinker, a viscosity modifier, a surface-active substance and any combinations thereof.
  • additives or auxiliaries and additives are contained in the substrate layer in a total concentration in the range of 0.001 wt .-% to 60 wt .-% based on the total mass of the substrate layer, preferably in the range of 0.01 wt .-% to 50 Wt .-%, especially in the range of 0.1 to 50 wt .-%, especially in the range of 1 wt .-% to 50 wt .-%.
  • the individual additives are present in concentrations of 0.001 wt .-% to 40 wt .-% based on the total mass of the substrate layer, preferably in the range of 0.01 wt .-% to 40 wt .-%, especially in the range of From 0.1% to 40% by weight, most preferably from 0.1% to 35% by weight.
  • plasticizers include modified and unmodified natural oils and resins, such as high boiling paraffinic, naphthenic or aromatic mineral oils, synthetic oligomers or resins such as oligostyrene, high boiling esters, styrene-butadiene oligomeric copolymers, [alpha] -methylstyrene / p-methylstyrene oligomeric copolymers, liquid oligobutadienes, in particular those having a molecular weight between 500 g / mol and 5000 g / mol, or liquid oligomeric acrylonitrile-butadiene copolymers or oligomeric ethylene-propylene-diene copolymers.
  • suitable plasticizers include modified and unmodified natural oils and resins, such as high boiling paraffinic, naphthenic or aromatic mineral oils, synthetic oligomers or resins such as oligostyrene, high boiling esters, styrene-butadiene oli
  • polybutadiene oils liquid oligobutadienes
  • high-boiling aliphatic esters such as, in particular, alkyl mono- and dicarboxylic acid esters, for example stearates or adipates
  • mineral oils particularly preferred are high-boiling, substantially paraffinic and / or naphthenic mineral oils.
  • paraffin-based solvates and Spezialole are below the names Shell Catenex S and Shell Catenex PH are commercially available.
  • the expert distinguishes mineral oils from technical white oils, which may still have a very low aromatics content, as well as medicinal white oils, which are essentially free of aromatics. They are commercially available and equally well suited.
  • Particularly common plasticizers are white oils or oligomeric plasticizers, in particular polybutadienols, carboxylic esters, phthalates. Reference may be made to EP992849 and EP2279454 for this purpose.
  • the amount of optional plasticizer will be determined by the skilled person depending on the desired properties of the substrate layer. It will generally not exceed 50% by weight of the sum of all constituents of the substrate layer, in general it is 0.1% by weight to 50% by weight, preferably 0.05% by weight to 40% by weight. ,
  • Elastomeric binders suitable for the substrate layer are known to the person skilled in the art. Both hydrophilic and hydrophobic binders can be used. Examples are ethylene-acrylic acid copolymers, polyethylene oxide, polyvinyl alcohol graft copolymers, natural rubber, polybutadiene, polyisoprene, styrene-butadiene rubber, nitrile-butadiene rubber, butyl rubber, styrene-isoprene rubber, styrene-butadiene-isoprene rubber , Polynorbornene rubber or ethylene-propylene-diene rubber (EPDM). Preference is given to using hydrophobic binders. Such binders are soluble or at least swellable in organic solvents, while they are substantially insoluble in water and also are not or at least not substantially swellable in water.
  • the elastomer is preferably a thermoplastic elastomeric block copolymer of alkenylaromatics and 1,3-dienes.
  • the block copolymers may be linear, branched or radial block copolymers. These are usually ABA-type triblock copolymers, but they can also be AB-type diblock polymers, or those having multiple alternating elastomeric and thermoplastic blocks, eg, ABABA. It is also possible to use mixtures of two or more different block copolymers. Commercially available triblock copolymers often contain certain proportions of diblock copolymers.
  • the diene units can be 1, 2 or 1, 4 linked.
  • Both styrene-butadiene or styrene-isoprene type block copolymers and styrene-butadiene-isoprene type block copolymers can be used. They are commercially available, for example, under the name Kraton. Also usable are thermoplastic elastomeric block copolymers with end blocks of styrene and a random styrene Butadiene midblock, available under the name Styroflex. The block copolymers may also be fully or partially hydrogenated, as in SEBS rubbers.
  • 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 Very particular preference is given to triblock copolymers of the ABA type, radial block copolymers of the type (AB) n, in which A is styrene and B is a diene, and also random copolymers and random copolymers of styrene and a diene.
  • thermoplastic elastomeric binders are particularly preferably at least one styrene-isoprene block copolymer, in particular a styrene-isoprene-styrene block copolymer, wherein the polymers may also contain portions of diblock copolymers styrene-isoprene.
  • Preferred styrene-isoprene-type binders generally contain from 10% by weight to 30% by weight, preferably from 12% by weight to 28% by weight and particularly preferably from 14% by weight to 25% by weight. % Styrene.
  • These block copolymers usually have an average molecular weight Mw (weight average) of 100,000 to 300,000 g / mol. Of course, mixtures of different styrene-isoprene block copolymers can be used.
  • radial isoprene-styrene block copolymers can preferably be used.
  • the isoprene units in the polyisoprene blocks can be 1,4-linked, i. the remaining double bond is located in the chain or 3,4-linked, i. the remaining double bond is arranged on the side.
  • Block copolymers can be used which have essentially 1,4-linkages and binders which have certain proportions of 3,4-linkages.
  • the pendant vinyl groups in binders with 3,4-linked isoprene units can also react in the course of crosslinking of the substrate layer and accordingly give a plate with high crosslinking.
  • styrene-isoprene block copolymers can be used which have a vinyl group content of 20% to 70%.
  • the binder used may preferably be a radial styrene-isoprene copolymer which has a vinyl group content of less than 10 mol%. Particular preference is given to using a mixture of two different styrene-isoprene block copolymers. One of these preferably has a vinyl group content of at least 20 mol%, in particular from 20 mol% to 70 mol%, preferably from 25 mol% to 45 mol%. The other may have a low vinyl group content, for example one of less than 10 mol%.
  • the photopolymerizable layer may also comprise further elastomeric binders other than the block copolymers. With such additional binders, also called secondary binders, the properties of the substrate layer can be modified.
  • a secondary binder is vinyltoluene-a-methylstyrene copolymers.
  • the amount of such secondary binder should not exceed 25% by weight with respect to the total amount of all the binders used.
  • the amount of such secondary binder does not exceed 15% by weight, more preferably not 10% by weight.
  • the total amount of binders is usually 40 wt .-% to 90 wt .-% with respect to the sum of all components of the substrate layer, preferably 50 wt .-% to 90 wt .-% and particularly preferably 60 wt .-% to 85 wt. %.
  • Thermal polymerization inhibitors having no appreciable inherent absorption in the actinic region in which the photoinitiator absorbs may be added to the substrate layer, such as, for example, 2,6-di-tert-butyl-p-cresol, hydroquinone, p-butadiene.
  • Thiazine dyes such as Tionin Blue G (Cl 52025), Methylene Blue B (Cl 52015) or Toluidine Blue (Cl 52040)
  • N-nitrosamines such as N-nitrosodiphenylamine, or the salts, for example the potassium, calcium or aluminum salts of N-nitrosocyclohexylhydroxylamine.
  • other inhibitors or stabilizers as described, for example, in
  • Suitable colorants may also be added to dyes, pigments or photochromic additives of the substrate layer in an amount of 0.0001 wt .-% to 2 wt .-%, based on the total mass of the substrate layer. They are used to control the exposure properties, as a slider, the identification, the direct control of the exposure result or aesthetic purposes.
  • the prerequisite for the selection and the amount of such additives is that, just as the inhibitors of the thermally initiated polymerization, they do not disturb the photopolymerization of the mixtures.
  • soluble phenazinium, phenoxazinium, acridinium and phenothiazinium dyes such as neutral red (Cl 50040), safranine T (Cl 50240), rhodanil blue, the salt or amide of rhodamine D (Basic Violet 10, Cl 45170), methylene blue B ( Cl 52015), thionin blue G (Cl 52025), or acridine orange (Cl 46005); as well as Solvent Black 3 (Cl 26150).
  • These dyes can also be used in conjunction with a sufficient amount of a reducing agent which does not reduce the dye in the absence of actinic light, but which can reduce the excited state dye upon exposure.
  • mild reducing agents are ascorbic acid, anethole, thiourea, for example diethylallylthiourea, in particular N-allylthiourea, and also hydroxylamine derivatives, in particular salts of N-nitrosocyclohexylhydroxylamine, preferably the potassium, calcium and aluminum salts.
  • the latter can, as mentioned, also serve as inhibitors of the thermally initiated polymerization.
  • the reducing agents may generally be added in amounts of 0.005 wt .-% to 5 wt .-%, based on the total mass of the substrate layer, wherein in many cases the addition of a 3 to 10 times the amount of co-used dye proven Has.
  • UV absorber compounds are used, as described for example in A. Valet, Lichtschuzusch for paints, 20ff, Vincentz Verlag Hannover 1996, such as hydroxyphenyl-benzotriazoles, hydroxybenzophenones, hydroxyphenyl-s-triazines, oxalanilides, hydroxyphenylpyrimidines, salicylic acid derivatives and cyanoacrylates and any Combinations of it.
  • Surfactants include compounds that, in a particular composition, tend to accumulate on the surface of the material of the substrate layer.
  • Waxes are preferably used, such as paraffin waxes, polyethylene waxes, polypropylene waxes, and belmige mixtures thereof.
  • the substrate layer contains at least one wax in a concentration in the range of 0.1 wt .-% to 10 wt .-% based on the total mass the substrate layer.
  • the wax concentration is in the range of 0.2 to 5 wt .-%, more preferably in the range of 0.5 wt .-% to 5 wt .-%, most preferably in the range of 0.5 wt .-% to 4% by weight.
  • These surface-active substances and in particular the waxes can develop an effect as a mobile barrier layer for oxygen and / or prevent excessive spreading of the applied liquid droplets. As a result, oxygen-inhibited fixation reactions become faster and the level of detail becomes higher.
  • waxes and surfactants are used.
  • elastomeric binders such as styrene-butadiene rubbers, nitrile-butadiene rubbers, butyl rubbers, styrene-isoprene rubbers, styrene-butadiene-isoprene rubbers
  • waxes such as paraffin waxes, polyethylene waxes, polypropylene waxes are used.
  • the viscosity of the at least one liquid is preferably in the range from 0.1 mPas to 10 Pas, preferably in the range from 0.1 mPas to 1 Pas, more preferably in the range from 0.1 to 500 mPas, very particularly preferably in the range from 0 , 1 mPas to 200 mPas.
  • the viscosity is in the range of 0.1 mPas to 10 mPas.
  • the information on the viscosity refers to a temperature of 20 ° C.
  • the surface tensions of the substrate surface and of the liquid are selected so that the highest possible contact angle between the surface of the substrate layer and the liquid is formed and a large-area spreading of the liquid is avoided.
  • the contact angle is preferably in a range of 5 ° to 1 10 °, preferably in the range of 5 ° to 90 °, particularly preferably in the range of 5 ° to 50 °.
  • This is possible by lowering the surface tension of the substrate layer, for example by using binders with low surface tension and / or surface-active substances such as waxes.
  • the surface tension of the substrate layer can be changed by applying a low surface tension material, such as by applying wax or fluorinated compounds.
  • the surface tension of the liquid can be increased by, for example, polar substances are used and / or polar additives such as polar solvents and additives are used. These mixtures may be solutions, emulsions and / or suspensions.
  • the selection of suitable combinations of liquid and substrate layer can be optimized via simple contact angle measurements.
  • the main components of and / or the substrate layer can be provided in film form with drops of the individual components and / or the liquid and the contact angle can be measured.
  • the at least one liquid includes at least one first reactive component, which may be selected from a polymer, an oligomer, a monomer, and any combinations thereof.
  • the at least one first reactive component is capable of a reaction. The ability to react may be present through the component per se or corresponding chemical groups or functions. As reactions polymerizations and / or crosslinking reactions may be used, such as a radical, an ionic, a condensation, an addition reaction and any combinations thereof. The reaction is preferably a free-radical polymerization and / or crosslinking.
  • the first reactive component may be a low molecular weight or low viscosity oligomeric compound or any combination thereof.
  • oligomeric compounds may be linear, branched, star-shaped and / or dendritic structures, which may be composed of one or more basic building blocks, which in turn may be arranged in block form, alternating or random.
  • the first reactive component generally has a molecular weight in the range of less than 1000 g / mol.
  • the molecular weight is preferably less than 800 g / mol, particularly preferably less than 600 g / mol, very particularly preferably less than 500 g / mol and may also be less than 300 g / mol.
  • molecular weights are not limited to the top.
  • the first reactive component is the rate of diffusion in the substrate layer. On the one hand, it should be high in order to achieve a short exposure time, but not so high that the swollen relief structure is not leveled by diffusion too fast, before fixation by the action of heat or radiation can take place.
  • the selection of the first reactive component is also dependent on its compatibility or solubility in the substrate layer. The highest possible compatibility and solubility is advantageous.
  • the first reactive component should carry at least one of the abovementioned reactive groups, but may also have 2 or more of the reactive groups, which is advantageous in particular in crosslinking and is preferably used there.
  • the first reactive component is preferably present in a concentration in the range from 5 to 100% by weight, based on the total liquid, preferably in the range from 10 to 100% by weight, particularly preferably in the range from 20 to 99% by weight. , most preferably in the range of 50 to 99 wt .-%.
  • the first reactive component is at least one ethylenically unsaturated compound containing at least one ethylenically unsaturated group.
  • Suitable ethylenically unsaturated compounds are those which are compatible with the respectively selected polymeric binders. In general, these are non-gaseous compounds at room temperature.
  • the ethylenically unsaturated compound contains at least 2 ethylenically unsaturated groups, more preferably 2 to 6 ethylenically unsaturated groups, most preferably 2 ethylenically unsaturated groups.
  • compounds with CC triple bonds can be used in the radiation-sensitive mixture.
  • the ethylenically unsaturated group is at least one acrylate and / or one methacrylate group, but it is also possible to use acrylamides and vinyl ethers.
  • the ethylenically unsaturated compound can be in the form of monomer, oligomer or polymer and in linear, branched, star-shaped or dendritic form.
  • esters of acrylic and / or methacrylic acid such as their esters with mono- or polyhydric alcohols, for example acrylic or methacrylic esters of alkanals having 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-ethyl-hexyl (meth) acrylate, lauryl (meth ) acrylate, (meth) acrylic esters of polyhydric alcohols having 2 to 20 carbon atoms, for example 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, ethylene glycol di
  • Trimethylolpropane tri (meth) acrylate 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate, 1, 9-nonanediol diacrylate, di-, tri- and
  • Pentaerythritol tetra (meth) acrylate further poly (ethylene oxide) di (meth) acrylate, m-methylpoly (ethylene oxide) -yl (meth) acrylate, ⁇ , ⁇ -diethylaminoethyl acrylate, a reaction product of 1 mole of glycerol, 1 mole of epichlorohydrin and 3 Mole of acrylic acid and glycidyl methacrylate and bisphenol A diglycidyl ether.
  • derivatives of the acrylamide and the methacrylamide e.g. 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. These are particularly suitable when polyamides or polyvinyl alcohol are used as binders.
  • epoxide and urethane (meth) acrylates are so-called epoxide and urethane (meth) acrylates, 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 hydroxyl-containing polyesters or polyethers.
  • olefinically unsaturated compounds are esters of acrylic or methacrylic acid, especially those with low vapor pressure and those which are modified with compatibilizers, e.g. with hydroxy, amido, sulfoester or sulfonamide groups. Mixtures of the abovementioned copolymerizable ethylenically unsaturated organic compounds can also be used.
  • Examples of -SH group components are linear, branched, cyclic or dendritic thiols, aromatic thiols and any combinations thereof. Preferably, the less volatile thiols are used. Examples of such thiols are pentaerythritol tetra (3-mercaptopropionate), pentaerythritol tetramercaptoacetate, Ethoxylated trimethylolpropane tri (3-mercaptopropionate) which can also be used in any combination.
  • the at least one liquid preferably contains further constituents selected from the group consisting of at least one initiator, a catalyst, an initiator system, a stabilizer, a dye, a pigment, an additive, a UV absorber, a plasticizer and any desired combinations thereof.
  • the other ingredients in the liquid may be identical to the particular ingredients described in connection with the substrate layer unless they increase the viscosity of the liquid too much. Examples of this have already been described above.
  • the concentration of the other constituents of the liquid is in the range from 0 to 50 wt .-% based on the total liquid, preferably in the range of 0 to 50 wt .-%, particularly preferably in the range of 1 to 20 wt .-%, completely particularly preferably in the range of 1 to 5 wt .-%.
  • the concentration of a single further constituent may vary from 0 wt .-% to 10 wt .-%.
  • the liquid does not contain a combination of a polymerizable or crosslinkable first reactive component and an initiator or catalyst. Particular preference is given to liquids which are free from initiators.
  • the liquid preferably contains, as the first reactive component, catalysts, initiators or initiator systems of at least two components which, upon irradiation with electromagnetic waves, generate radicals which cause polymerization and / or crosslinking.
  • catalysts, initiators and initiator systems are known to the person skilled in the art (see above under the second reactive component).
  • the liquid preferably contains the catalyst, initiator or initiator system in a concentration in the range from 0.1% by weight to 99.9% by weight, based on the total mass of the liquid. Preferred concentrations are in the range of 1 to 99% by weight. %, more preferably in the range of 1 wt .-% to 80 wt .-%, most preferably in the range of 2 wt .-% to 60 wt .-%.
  • the liquid contains only catalysts, initiators and / or initiator systems as reactive components, then it is preferred that the substrate layer contains components that are crosslinked or modified in their solubility by the catalysts, initiators and / or initiator systems.
  • Another aspect of the invention relates to a relief structure obtained by one of the methods described.
  • An additional aspect of the invention relates to the use of such a relief structure as a printing plate.
  • the printing form can be used in various printing methods, such as high-pressure, intaglio, flexo, offset, pad printing, micro embossing and any combination thereof.
  • Other possible uses of the generated relief structure are: optical components (eg Fresnel lens), diffractive optical components (eg optical lattice), components with lotus leaf structure and / or lotus leaf effect, template for directed growth of biological structures (eg cells, tissues), membranes in separation processes , Separating materials, membranes for batteries and / or batteries or structured insulators for electronic components.
  • the further layer may be stiff or inflexible, so that it does not sink into the depressions, but flexible layers can also be used if suitable measures are taken to ensure that the further layer can not sink into the depressions. This can be achieved, for example, by filling the wells with liquids and / or gases. After application of the further layer, the liquids and / or gases can be removed again.
  • the channels and / or cavities thus produced can optionally be provided with other materials and / or liquids.
  • Such components can be used as a microfluidic component (eg for microanalysis and / or for high throughput screening), as a microreactor, as a phoretic cell (as shown, for example, in WO2004 / 015491), as a light-controlling element for color representation (as for example in WO2003 / 062900 described) or used as photonic crystals.
  • the further layer can be applied, for example, as part of the aftertreatment according to step g).
  • the abovementioned components and components can be designed to be both rigid and / or flexible. Flexible embodiments are particularly preferred if they are to be worn on and / or in the body and / or used in fabrics and / or garments.
  • a mixture (composition of the individual plates, see Table 1 a), containing a polymeric binder, a plasticizer oil and 5 parts of benzil dimethyl ketal as a photoinitiator was added at elevated temperatures (120 ° C.) C to 180 ° C) melted in the extruder and calendered over a slot die between two PET films having a thickness of 125 ⁇ , so that the substrate layer (photopolymer + carrier film) had a thickness of 1450 ⁇ .
  • the lower PET film serves as a carrier film and the upper PET film serves as a protective layer.
  • the viscosity measurement was carried out with a MC 120 rotational rheometer (from Physica) with a cone-and-plate geometry at 20 ° C, the cone having a diameter of 50 mm and an angle of 1 °. It was running at a speed of 120 rpm measured over a period of 2 minutes at a shear rate of 720 s -1 and the software UC 200/32 (V 2.50) was used.
  • a microscope Digital Microscope VHX 500F with objective VH-Z250R of Keyence
  • the contact angle is the angle between the substrate surface and the tangent to the drop surface at the point of contact.
  • EHA ethylhexyl acrylate
  • HDDA hexanediol diacrylate
  • HDMA hexanediol dimethacrylate
  • PETA pentaerythritol triacrylate
  • HOA 2-hydroxyethyl acrylate
  • a mixture of HDDA and HDMA was tested at a mixing ratio of 1: 1.
  • Binder 1 SIS rubber 14% styrene 42 ° Shore A
  • Binder 2 SBS rubber 25% Styrene 61 ° Shore A
  • Binder 4 SBS rubber 60% Styrene 84 ° Shore A
  • Binder 5 SIS rubber 15% Styrene 32 ° Shore A
  • Table 1 d Variation of the surface tension of the substrate layer Tables 1 c and 1 d illustrate that by choosing the liquid and / or the substrate layer, the contact angle can be varied over a wide range. It also becomes clear that fluids with quite different viscosities can be used.
  • Example 2
  • the supernatant liquid was removed by rinsing with a mixture of 1-propanol / water (4: 1) and the surface for 10 min UVA (Flint Group, FIII platesetter main exposure,) and then for 5 min UVC (Flint Group, FIII platesetter Drawer) exposed.
  • the resulting reliefs were measured with a perthometer and the height of the elevation H and the diameter at half height (0 R ) were determined. The tests were each carried out 5 times and the indicated measured values represent the arithmetic mean.
  • the perthometer measurements were carried out with a Marahr M 300 mobile roughness tester from Marahr with the software "MarWin XR20" (V 4.26) using a scanning speed of 0.5 mm / s and a measuring force of 0.00075 N.
  • Table 2 shows that relief structures are obtainable in this way and that the use of wax results in a higher contact angle, less liquid droplets spread and more detailed structures can be produced. Furthermore, it was found that the relief structures were stable when using wax after shorter exposure times.
  • Examples 3b and 3c were additionally 2 and 4 wt .-% of a paraffin wax (solidification point 58 ° C to 60 ° C, density 0.91 g / cm 3 ) were used. Following the same procedure as in Example 2, the surfaces were provided with liquid F1. After diffusion, the surfaces were exposed for a period of 20 minutes. The results
  • Table 3 shows that relief structures are obtainable in this way and that the use of wax results in a higher contact angle, less liquid droplets spread and therefore more detailed and higher structures can be produced.
  • Example 4 the plate-like materials of Examples 2a and 3a to 3c were used and treated as follows.
  • Table 4 shows that the height of the relief structures can be increased by applying further drops and that the use of wax causes the liquid droplets do not spread, so detailed and higher structures can be produced.
  • Example 2 was repeated except that the liquid F2 was used which consisted of 98% by weight of hexanediol diacrylate and 2% by weight of benzil dimethyl ketal. It was found that the similarly sized reliefs were already stable (at least halved) after significantly shorter exposure times.
  • Example 2 was repeated except that the liquid F3 was used which consisted of 95% by weight of hexanediol diacrylate and 2% by weight of triethanolamine. It was found that the similarly sized reliefs were already stable after about 20% shorter exposure times.
  • Example 7
  • Example 2 was repeated except that the liquid F4 was used which consisted of 99.5% by weight of hexanediol diacrylate and 0.5% by weight of butylhydroxytoluene. It was found that formulation F4 was significantly more stable and blocked the pipette tips less and about 5 to 10 times slower.
  • Example 1 was repeated except that the liquid F5 was used which consisted of 95% by weight of hexanediol diacrylate and 5% by weight of azoisobutyronitrile.
  • a 0.5 ⁇ thick PET film was laminated as a barrier layer on the surface before fixing in step f).
  • the sample was then treated for 1 hour at 150 ° C in an oven (FDL 1 15 from Binder GmbH).
  • Relief structures were obtained their heights by wiping with a cloth, in a mixture of 33 wt .-% cyclohexanol, 47 wt .-% of a hydrocarbon mixture (CAS: 64742-47-8 and 64742-48-9) with a low aromatic content and 20 wt.
  • Example 1 was repeated, but prior to exposure, a PET film was laminated to the surface. It was found that the similarly sized reliefs were already stable after significantly shorter exposure times.
  • SIS copolymer 240,000 g / mol, styrene content 14.3%, 25% diblock
  • Mn 300 g / mol
  • benzil dimethyl ketal melted at elevated temperatures (120-180 ° C) in the extruder and calendered over a slot die between two PET films with a thickness of 125 ⁇ , so that the layer structure had a thickness of 1450 ⁇ .
  • droplets of the liquid F1 consisting of hexanediol diacrylate (Laromer HDDA BASF) with a volume of 1 ⁇ were deposited on the plate surfaces with the aid of a pipette (VWR dispenser with pipette tips of corresponding volume).
  • the supernatant liquid was removed by rinsing with a mixture of 1-propanol / water (4: 1) and the surface for 10 min UVA (Flint Group, FIII platesetter main exposure,) and then for 5 min UVC (Flint Group, FIII platesetter Drawer) exposed.
  • Example 1 1 the surfaces were heated by means of an IR radiator, so that the non-swollen and crosslinked areas became viscous.
  • the heated surface was contacted with a polyester nonwoven one or more times and softened areas were removed on stripping the nonwoven. After cooling, up to 100% increased relief heights were measured.
  • Example 1 1 the surfaces were heated by means of an IR radiator, so that the non-swollen and crosslinked areas became viscous.
  • the heated surface was contacted with a polyester nonwoven one or more times and softened areas were removed on stripping the nonwoven. After cooling, up to 100% increased relief heights were measured.
  • Example 2a was repeated, but after the top PET film had been removed, an imageable mask layer was applied.
  • the coating solution was knife-coated onto a 100 ⁇ m thick Mylar film and dried.
  • the Mylar film coated with the laser-ablatable mask layer was laminated onto the substrate layer at a laminating temperature of 120 ° C. After cooling the composite, the Mylar film was stripped off leaving the laser-ablatable mask layer on the substrate layer.
  • the layer structure of carrier film, substrate layer and laser-ablatable mask layer was fixed on the drum of an IR laser (Thermoflex 20, Xeikon) and imaged with a power of 30 W at a resolution of 5080 dpi.
  • image information points with a diameter 20 ⁇ , 40 ⁇ , 60 ⁇ , 80 ⁇ , enrolled.
  • Individual drops of the liquid F2 were applied into the openings, after a waiting time of 10 minutes was rinsed with a water / n-propanol 3: 1 solution until the mask layer was completely washed off and the surface for 10 min UVA (Flint Group, FIII Exposer main exposure,) and then exposed for 5 min UVC (Flint Group, FIII platesetter drawer).
  • Relief structures were obtained whose relief height was slightly lower than without the mask layer.
  • the openings of the mask layer were provided with liquid F2, but first exposed and then the mask layer removed by rinsing with the water isopropanol mixture. It was then dried for 20 minutes at 50 ° C. Relief structures were obtained whose relief height was up to 50% higher than without the mask layer.
  • Example 12
  • Example 2b an additional 2% by weight of a paraffin wax (solidification point 58-60 ° C, density 0.91 g / cm 3 ) were used.
  • droplets of hexanediol diacrylate of a volume of 6-7 pl per drop were applied using an Omni Jet 100 (Unijet).
  • Omni Jet 100 Unijet
  • the exposure was carried out by means of a rapid 3000 lamp (Welisch Elektronik GmbH at a power of 3 mW / cm 2, at a distance of 75 mm and for 12 minutes.)
  • a rapid 3000 lamp Welisch Elektronik GmbH at a power of 3 mW / cm 2, at a distance of 75 mm and for 12 minutes.
  • 40 relief structures with an area of about 1 mm ⁇ 1 mm were obtained the height of which changed as a function of the time of exposure, for the purpose of illustration the heights of the first fields of a row measured by means of a perthometer are given.
  • Droplets were applied to a plate as described with reference to Example 13, but first a series of 30 fields of 50 x 50 drops were printed and after a waiting time of 730 seconds, a second layer of fields was applied centrically to the generated fields 25 x 25 drops passed. This structure was then exposed as in Example 13 for 3 minutes.
  • the first layer after fixing had an edge length of about 1 mm and a height of 20 ⁇ to 24 ⁇ .
  • the second layer had an edge length of about 800 ⁇ and a height of 3 ⁇ to 7 ⁇ .
  • Example 14 The experiments of Example 14 were repeated, but after the application of the first layer and an exposure time of 3 minutes, exposure was carried out for 3 minutes (conditions as in Example 13). Subsequently, the second layer of 25 ⁇ 25 drops was applied to the existing fields and, after a further 3 minutes exposure time, exposed again for 3 minutes.
  • the first layer after the wide fixation had an edge length of about 1 mm and a height of 18 ⁇ to 25 ⁇ .
  • the second layer had an edge length of about 800 ⁇ and a height of 2 ⁇ to 8 ⁇ .

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Abstract

L'invention concerne un procédé servant à fabriquer des structures en relief sous forme d'images sur un ensemble de couches. Le procédé comprend la mise à disposition d'un ensemble de couches comprenant une couche de substrat. Au moins un liquide contenant au moins un premier composant réactif est appliqué immédiatement après, conformément à l'image sur le substrat, l'application conformément à l'image sous la forme d'une pluralité de gouttes étant effectuée avec un volume de gouttes inférieur à 2 µl et les gouttes étant placées conformément à l'image. S'ensuivent une diffusion au moins partielle du ou des premiers composants réactifs dans la couche de substrat pendant un temps de pose prédéfini et/ou une diffusion au moins partielle d'au moins un deuxième composant réactif dans les gouttes placées conformément à l'image du liquide pendant un temps de pose prédéfini, la couche de substrat comprenant le ou les deuxièmes composants réactifs. Le relief en résultant est fixé immédiatement après sous l'action de la chaleur et/ou d'un rayonnement par une réaction impliquant la participation du premier composant réactif et/ou du deuxième composant réactif. L'invention concerne selon d'autres aspects une structure en relief sous forme d'image fabriquée selon le procédé, ainsi que l'utilisation de la structure en relief sous forme d'image en tant que moule de pression, composant microfluidique, microréacteur, cellule phorétique, élément de contrôle de lumière d'affichage en couleurs, cristaux photoniques ou de parties flexibles de pièces de vêtement.
EP17715072.9A 2017-03-27 2017-03-27 Procédé servant à fabriquer des structures en relief sous forme d'images Pending EP3598870A1 (fr)

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JP2020515431A (ja) 2020-05-28
US20200055303A1 (en) 2020-02-20
US11325368B2 (en) 2022-05-10
CN110678332B (zh) 2021-11-26
WO2018177500A1 (fr) 2018-10-04
CN110678332A (zh) 2020-01-10

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