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EP2188133A1 - Nanorevêtement opto- et thermo-inscriptible - Google Patents

Nanorevêtement opto- et thermo-inscriptible

Info

Publication number
EP2188133A1
EP2188133A1 EP08801644A EP08801644A EP2188133A1 EP 2188133 A1 EP2188133 A1 EP 2188133A1 EP 08801644 A EP08801644 A EP 08801644A EP 08801644 A EP08801644 A EP 08801644A EP 2188133 A1 EP2188133 A1 EP 2188133A1
Authority
EP
European Patent Office
Prior art keywords
layer
laser
particles
metallic
layers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP08801644A
Other languages
German (de)
English (en)
Inventor
Andreas Kornherr
Thomas Schalkhammer
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.)
Mondi Business Paper Services AG
Original Assignee
Mondi Business Paper Services AG
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 Mondi Business Paper Services AG filed Critical Mondi Business Paper Services AG
Priority to EP08801644A priority Critical patent/EP2188133A1/fr
Publication of EP2188133A1 publication Critical patent/EP2188133A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/28—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using thermochromic compounds or layers containing liquid crystals, microcapsules, bleachable dyes or heat- decomposable compounds, e.g. gas- liberating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C09D11/50—Sympathetic, colour changing or similar inks
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/02—Metal coatings
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/66—Coatings characterised by a special visual effect, e.g. patterned, textured
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/80—Paper comprising more than one coating
    • D21H19/82—Paper comprising more than one coating superposed
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31971—Of carbohydrate
    • Y10T428/31993—Of paper

Definitions

  • the invention relates to a novel process for the color coding of the surfaces of paper, films, plastic, metal, ceramic surfaces, artificial and natural stone, lacquer layers or anticorrosion layers.
  • Coloring labels of materials such as paper, films, plastics or other surfaces are usually made by printing, for example by known ink jet printers, laser printers and the like.
  • the printer is equipped with ink cartridges or toner cartridges, the pigment compositions contained therein are deposited during printing on the material to be printed.
  • an optochemical sensor for measuring substance concentrations with a reactive sensor layer is known, which is characterized in that a mirror layer (2), a reactive, in particular swellable matrix (4) and a layer (3) of a plurality of islands (5) of electrically conductive material, in particular metal, is provided, wherein the diameter of the islands (5) is smaller than the wavelength of the light used for the observation or evaluation.
  • metal parts and metallized surfaces are known, on their surface by an anodizing process, a thin layer of less than 1000 nm is applied, which carries on the surface of a layer of metallic or chromophore particles with a size of less than 200 nm that generate visible color effects through surface-enhanced cluster absorption.
  • JP 59-126468 z. B platelet-shaped pigments based on mica substrates, which are coated with a layer of titanium dioxide and titanium suboxides and / or titanium nitrides.
  • JP 60-60163 describes platelet-shaped pigments based on mica substrates which are coated with a first layer of titanium suboxides or titanium nitrides and coated with a second layer of titanium dioxide.
  • JP 3052945, JP 3052943, JP 3052944, JP 3059065, JP 3059062 and JP 3059064 disclose epoxy resin compositions which are laser printable.
  • WO 93/19131 a process for the preparation of platelet-shaped color pigments is described, in which titanium dioxide-coated platelet-shaped substrates are reduced with a selected reducing agent in solid form in a non-oxidizing gas atmosphere at elevated temperature.
  • the body color achievable here ranges from gray to yellowish black and bluish black to black, whereby the interference color can be varied by varying the titanium oxide layer thicknesses.
  • Pigments which use a high refractive layer as a base are e.g. known as Iriodin®. These are multilayered interference pigments consisting of layers of different refractive indices.
  • the object of the invention was to provide a material that can be provided with information such as characters, strings, lines, symbols, images and the like without the use of toner pigment-containing printing agents.
  • Another object of the invention was to provide a method for producing such materials.
  • the invention therefore paper, cardboard, corrugated cardboard, pigment particles, films, injection or pressure-cast plastic parts, metal, ceramic surfaces, paint layers or corrosion protection layers coated with a plurality of thin films, wherein the material itself or a first layer is a mirror layer itself or at the layer boundary electromagnetic waves (3) at least partially reflected, a second transparent layer (4) above and / or below this mirror layer is applied and on this transparent layer at least a third layer of metallic or strongly chromophoric particles or nanoparticles (5) or their chemical precursors or a metallic thin film is applied, and the entire structure can be spatially defined by the action of light or by direct contact or strong approach to hot objects spatially defined and structured for the human eye recognizable color.
  • Another object of the invention is a process for the color coding of materials, characterized in that on or in the material (1, 2) a plurality of thin films are applied, wherein the material or a first layer is a mirror layer, which itself or at the layer boundary Electromagnetic waves (3) at least partially reflected, a transparent layer (4) above and / or below this mirror layer is applied and on this transparent layer at least one layer of metallic or strongly chromophoric particles (5) or their chemical precursors or a metallic thin film is applied and the entire structure is spatially defined by the action of light or by direct contact or strong approach to hot objects and structurally changed in color to the human eye recognizable.
  • the invention further provides a process for producing optically thermally writable materials, such as paper, cardboard, corrugated cardboard, pigment particles, films, injection-molded or pressure-cast plastic parts, metal, ceramic surfaces, paint layers or anticorrosive coatings, characterized in that a plurality of thin layers are applied to or in the material (1, 2), the material or a layer representing a mirror layer which, at least partially, itself or at the layer boundary reflects electromagnetic waves (3), a transparent layer (4) is applied above and / or below this mirror layer and on this transparent layer at least one layer of metallic or strongly chromophoric particles or nanoparticles (5) or their chemical precursors or a metallic thin film is applied.
  • optically thermally writable materials such as paper, cardboard, corrugated cardboard, pigment particles, films, injection-molded or pressure-cast plastic parts, metal, ceramic surfaces, paint layers or anticorrosive coatings, characterized in that a plurality of thin layers are applied to or in the material (1, 2), the material or a layer representing a
  • a plurality of thin layers of preferably less than 800 nm, more preferably less than 500 nm in thickness are applied, wherein a layer or layer boundary can at least partially reflect electromagnetic waves (mirror layer).
  • a nanometer-thin spacer layer having a thickness of preferably less than 800 nanometers is mounted above and / or below this mirror layer.
  • Another layer is formed by metallic or at least strongly chromophoric particles or their chemical precursors or by a metallic thin film of less than 50 nm thickness.
  • the multilayer structure is applied either directly to the surface of the carrier material or else to mostly platelet-type pigments which in turn can be bound to the carrier material on a surface.
  • This structure may optionally be coated with a known protective film and / or with a layer of light-scattering properties.
  • This light-scattering layer contains, for example, light-scattering particles, for example latex particles which have a backscattered light color from white to whitish and become transparent by melting the particles to form a layer.
  • Suitable carrier material are paper, cardboard, corrugated cardboard, pigment particles, films, injection- or pressure-cast plastic parts, metals, ceramic surfaces, lacquer layers or corrosion protection layers.
  • the mirror layer is preferably a metallic layer or a layer of highly chromophoric particles selected from the group silver, gold, palladium, platinum, copper, indium, aluminum, nickel, chromium, vanadium, molybdenum, tungsten, titanium, niobium, tantalum, zirconium , Tin, germanium, bismuth, antimony or silicon or another conductive material, their compounds, alloys or precursors.
  • the transparent nanometrically thin spacer layer preferably consists of a layer of calcium, magnesium, barium fluoride or quartz or of polymeric layers.
  • the pores of a porous or foamy polymeric interlayer may be filled with a gas, preferably air.
  • the third layer of metallic or strongly chromophoric particles preferably consists of elements or compounds selected from the group silver, gold, palladium, platinum, copper, indium, aluminum, nickel, chromium, vanadium, molybdenum, tungsten, titanium, niobium, tantalum, zirconium , Tin, germanium, bismuth, antimony or silicon or another conductive material, their compounds, alloys or their precursors.
  • compounds are understood to mean predominantly metal salts, such as oxalates, carbonates, formates, acetates, hydroxides, phosphates or hypophosphites.
  • the metal salts may further be added with reducing or oxidizing agents.
  • Suitable reducing agents are salts of formic acid, oxalic acid, reducing hydrogen-hydrogen compounds such as hydrazines, or inorganic reducing agents such as tin (II) salts, hypophosphites, dithionites or hydrogen borohydrides.
  • Suitable oxidizing agents are peroxides, percarbonates, perborates, nitrates, chlorates, perchlorates, or analogous bromine compounds. Preferably, these additives are therefore laser activated.
  • nanoparticles or low oxides of the metal compounds are then produced under the action of heat or light (preferably laser light).
  • the entire structure is spatially defined and structured in color by the action of light, primarily laser light or another source of sufficient strength, or by direct contact or strong approximation to hot objects, any characters, letters, strings of patterns, lines of images, symbols, Designs or graphic information by a change in the structure of the nanolayers or the order or rearrangement of the nanoparticles or a part of the particles are visible.
  • the number of metallic or strongly chromophoric particles can be achieved by thermal modification or dissolution of the metallic particles, preferably by means of high-energy laser light to colorless products, preferably by solid and laser-liquefiable acids or alkalis or laser-activated oxidizing agents in the layer.
  • the layers may also comprise laser light absorbing additives, the additives preferably being molecules containing carboxyl groups.
  • the order or rearrangement of the coated particles or a part of the particles can also be carried out in particular by thermal or mechanical modification of the layers, such as embossing.
  • the multilayer structure (which preferably consists of at least 3 layers) causes by an optical resonance enhancement of the nanoparticle absorption with the electromagnetic wave reflective phase boundary or mirror or a layer of material (2/3) with a sufficiently high Refractive index a strong coloration of the object, the optical 2-dimensional coloring / structuring of the material is achieved with laser light or other local heat source.
  • the resulting color is dependent on the distance of the metal particles from the phase boundary and on the refractive index of the materials and not on the intrinsic color of the particles.
  • the invention is based on a novel printing system which makes materials directly describable with the heat and or light (preferably laser light).
  • Printing process here is the color or its precursor integrated as a nano-layer already in the material and is only selectively changed by the laser light locally.
  • the background material itself generates the optical effect by the local change of the multi-layer structure (also called resonant layer) by the action of laser light or local heat and this no pigments (as in a laser, inkjet or thermal transfer printer) are applied and this leads to colors with optical 2D / 3D microstructures.
  • the binding, the separation or the generation of mostly metallic particles in the special nanoparticles can be used for coloring.
  • a change in the thickness of the spacer layer is due to the resonance enhancement of the nanoparticles with the structured ones Refractive index layers converted into an easily visible optical signal.
  • FIGs 1 to 4 the embodiments of the invention are shown. 1 is the material, 2 the surface of the material, 3 the thin film (s), 4 the spacer layer, 5 the metallic or strongly chromophoric particles or their chemical precursors, 6, the optical information, (characters, strings, symbols, figures, lines , Images).
  • the structure consists at least of the at least partially light-reflecting surface of a carrier material, a spacer layer, a particle layer and optionally a cover layer.
  • the diameter of the nanoparticles is preferably chosen to be smaller than 50 nm, more preferably smaller than 40 nm.
  • a thin substantially more or less continuous metal film of less than 40 nm thickness may be used instead of the particle layer.
  • Nanoparticles on the material leads to the characteristic changes of the optical appearance of the surface.
  • Metallic or metal-like particle films having an average nanoparticle diameter of less than 500 nm (preferably less than 100 nm, particularly preferably less than 40 nm) have strong narrow-band reflection minima whose spectral positions are extremely sensitive to the spatial arrangement, in particular the distance to phase boundaries. (Very large particles scatter more than they absorb).
  • the design can convert even the smallest changes in the surface coverage of nanoparticles, the structure of the phase boundary material / thin film, or the refractive indices into clearly visible color changes, ie either in an absorbance change at a certain wavelength, or in a spectral shift of the absorption maximum.
  • an article coated according to the invention changes color depending on the viewing angle. This can be desired depending on the structure or kept almost invisible by the adequate choice of components.
  • nanoparticles or extremely thin nanosheets are produced, modified or destroyed.
  • a mirror layer or only a reflective surface a spacer layer of a few tens (maximum of a few hundred nanometers) nanometers and metal or chromophore layers of preferably a few nanometers with a mass thickness of 1-20 nm are used.
  • the laser be chemically continuously and permanently modified in the available time (typically ⁇ s or less) so that the resonance color is changed visually.
  • "Massive" layers in the range of 50 nm or more led to a strong self-heating of the materials, which leads eg in paper to a "fire inscription" with appropriate amount of exhaust gas and toxicologically questionable products.
  • the use of highly chromophoric resonator structures avoids this problem and, by means of chemical transformation of parts of the structure without significant release of gaseous products, enables the writing process in the office environment.
  • the dissolution of particles and the change of the mirror preference is given to the generation of nanoparticles from colorless precursors.
  • the generation of the nanoparticles then only generates a resonance color in situ after reaction of a colorless or slightly colored layer of precursor compounds.
  • the conversion of silver acetate into dark oxidic pigments the conversion of bismuth salts such as e.g. Bismuth oxalate, basic bismuth carbonate or basic bismuth nitrate in black, yellow, orange or brown pigments, the conversion of nickel oxalate or cobalt oxalate into black or dark colored oxides, called the transformation of labile copper compounds into copper oxides or metallic copper.
  • bismuth salts such as e.g. Bismuth oxalate, basic bismuth carbonate or basic bismuth nitrate in black, yellow, orange or brown pigments
  • nickel oxalate or cobalt oxalate into black or dark colored oxides
  • the transparent layer in particular its thickness, can be adjusted by thermal modification, foaming, crosslinking or thermal collapse, preferably by means of a laser or thermally.
  • the resonance layer can be applied directly, paper and large, in particular 3-dimensional objects are coated here with small particles with the structure described above.
  • These particles, to which the multilayer structure is applied preferably have a size of at most 3 mm, particularly preferably 0.5 to 60 ⁇ m, and are preferably flat metallic particles or inorganic platelets such as mica, kaolin, talc or glass.
  • paper can also be directly provided with the color effect and the cellulose fiber - calcium carbonate mixture with mirror, spacer and nanoparticle layer are coated - the observed colors are quite intense and strong in color.
  • the carrier material it is advantageous to bind the particles to the surface of the coated material with an adhesive, for example with a starch-based adhesive or based on biocompatible and / or degradable polymers.
  • an adhesive for example with a starch-based adhesive or based on biocompatible and / or degradable polymers.
  • Such adhesives are known to those skilled in the art.
  • the surface is subsequently coated with a material which is capable of absorbing the laser energy, forwarding the heat to the nanoparticle layer or its precursor and protecting the entire structure.
  • a material which is capable of absorbing the laser energy forwarding the heat to the nanoparticle layer or its precursor and protecting the entire structure.
  • this layer should be a few microns thick so that the laser energy can be absorbed with maximum intensity.
  • Many polymers are suitable for this purpose, for example PVP, PVAc, PVP-co-PVAc, cellulose and derivatives thereof such as ethers or esters, starch and derivatives thereof, up to epoxy resins and alkyd resins for long-term inscriptions on metal and plastic surfaces.
  • polystyrene polystyrene, polyvinyl acetate, cellulose esters or ethers, other vinyl polymers, acrylates, methacrylates, polyalkyd resins, or their copolymers or mixtures, particularly preferably polysiloxane latex.
  • the particle layers are formed by chemical processes, vapor deposition, sputtering, adsorptive attachment from solution, covalent coupling from solution, surface catalyzed processes, spraying or printing by known printing techniques such as flexographic, screen, offset digital printing techniques. Roller application method with direct or reverse running, curtain coating and the like either applied directly to the material or first formed on pigment particles.
  • the pigment particles are then transferred in the industry-specific order processes on the surface of the objects to be printed and bound there.
  • the material of these particles are mostly corrosion-resistant metals such as gold, silver, palladium, copper, nickel, chromium, tin, titanium, tantalum, niobium, tungsten, molybdenum, bismuth, antimony, germanium or silicon.
  • metals may be used for cost reasons or stability reasons (e.g., aluminum)
  • Lower-grade metals can be used with an inert protective film of, for example, aluminum oxide, titanium oxide, zirconium oxide, tin oxide, quartz, firmly adhering oxidation films or also polymers, layers of (poly) carboxylates, (poly) phosphates, (poly) phosphonates against corrosion.
  • these protective layers by their thickness, influence the color or refractive index of the protective material film.
  • any other metals and also alloys of all kinds or even color particles of suitable size and suitable (preferably mostly stable) optical behavior for example precipitates of porphyrins, phthalocyanines or the like.
  • the metals or metal salts used in the multi-layer structure are recoverable in a sewage treatment plant in the recycling process, preferably up to 80%.
  • all the materials of the structure can be thermally optically modified, and thus either the mirror, the mirror nanoparticle distance or the number of nanoparticles above or below the spacer layer can be changed in order to achieve the desired printing color effects.
  • the light sources required for the thermal inscription preferably have low beam divergence, small line / bandwidth: (a narrow linewidth is the frequency purity of the generated radiation), high energy density (due to the strong focusing and self-amplification of the laser beams in the resonator) and large temporal and spatial Coherence.
  • Other sources of light are
  • LEDS, high-energy lamps with Hg, or metal vapor or the like usually have too low energy density.
  • Thermal activation of the effect by hot surfaces is also possible and can be carried out analogously to the thermal printer at low speed.
  • Possible laser types are solid-state lasers, semiconductor lasers ,. Liquid laser ,. Gas lasers and chemical lasers.
  • the most important solid-state lasers are the ruby, the neodymium-YAG (Nd: YAG) and the Nd: glass laser
  • Semiconductor lasers, LEDs, krypton arc lamps and halogen lamps for cw operation and xenon flash lamps are particularly suitable for pulse operation.
  • the copper vapor laser is the best known representative of a number of metal vapor lasers that have similar operating data (lead vapor laser, calcium vapor laser, gold vapor laser, manganese vapor laser, thallium vapor laser, indium vapor laser). All these systems have in common that they have quite high operating temperatures, can only be operated pulsed but have very large amplification factors and sometimes also high efficiencies.
  • laser diodes are very small, very long life (up to millions of operating hours) and.
  • Laser diodes are suitable for continuous, partial duration and pulse operation.
  • the laser group of gas lasers is very large - various gases are suitable for laser emission. These gases are filled in gas discharge tubes with lengths between 10 to 200 cm. These lasers are pumped mainly by an electric high-voltage discharge of the electrodes.
  • the discharge currents can range from a few mA to 100 A.
  • One example is the helium-neon laser.
  • the ion laser uses as active medium a single gas, e.g. Argon or krypton.
  • the laser emission does not come from neutral, but from ionized atoms.
  • the laser operating with the triple ionized oxygen is also interested.
  • the excimer laser derives its name derives from the English term "excited dimer", which means "excited diatomic molecule”. However, these molecules decay as soon as there is no longer any excitation and release their energy in the form of laser radiation.
  • Excimer lasers are high-power pulsed lasers with wavelengths in the UV or blue range of the Spekrums. With their help, cold cuts of the human tissue can be achieved, ie cutting the tissue without heating it.
  • Another laser is, for example, the CO laser.
  • the carbon dioxide laser (CO 2 laser), is an electrically excited gas laser. In addition to solid-state lasers, it is one of the most widely used and most powerful industrially used lasers.
  • the N 2 molecules are excited in the resonator by a gas discharge. In this excited state, the N 2 molecules can remain for a very long time ( ⁇ 1 ms) and thus are highly likely to collide with CO 2 molecules and these stimulate.
  • Typical output powers are between 10 W and 15 kW. It is primarily used for material processing.
  • the radiation of such CO 2 laser is linearly polarized. With comparatively simple technology, very high output and high efficiency are achieved. and by their high refractive index and a high reflection so that they can be used as Auskoppelapt.
  • the HeNx TEA Laser is a transversely excited high pressure CO2 laser.
  • the wavelength of the CO 2 laser is in the infrared and can therefore - unlike neodymium-YAG lasers or diode lasers - not be led into glass fibers.
  • the primary form of the nanowriter lasers are diffusion-cooled (XV lasers), which use a high-frequency plasma discharge between two closely spaced plates, which at the same time cause cooling by diffusion, the beam path runs back and forth between the mirrors several times, the decoupling takes place at the shortened one They are often referred to as "slab lasers.”
  • XV lasers diffusion-cooled
  • the beam runs along two elongate electrodes, with these lasers no gas exchange takes place.With pulsed operation with short pulse times (0.01. At low power levels, cooling and helium addition can be dispensed with.
  • Such TEA-CO 2 lasers eg transversely excited atmospheric pressure
  • Marx generators eg transversely excited atmospheric pressure
  • the longitudinally-swept CO2 laser used in the power range of 500 W - 15 kW is the most widely used.
  • “slow-flow” lasers only gas is exchanged, cooling takes place by diffusion on the pipe walls.
  • ⁇ br /> ⁇ br/> The gas mixture introduced in the tube system "fast longitudinally flowing" laser is circulated with another pump (Roots pump or turbine) for gas exchange and cooling.
  • discharges and gas flow are transverse to the beam direction (cross-flow co 2 laser), so that a particularly fast gas exchange is possible.
  • streamed lasers are not useful as nanowriter lasers.
  • the Nanowriter laser system preferably contains a sealed carbon dioxide (CO 2 ) laser that produces intense and invisible laser radiation at a wavelength of 10.6 microns in the infrared spectrum
  • the whole system is completely enclosed in a protective housing. This completely covers the laser beam under normal use.
  • the system has a safety lock system. Opening the housing switches the (CO2) -
  • the laser beam can cause ignition of flammable materials and cause a fire.
  • the laser system will never be stable
  • a correctly configured, installed, maintained and operational filter is the prerequisite for the use of the laser system. Vapors and smoke in the writing process are minimal, since this is not an engraving process with process gases, however, the slight removal of material should be bound by an activated carbon filter if necessary.
  • Safety stickers are installed in the system. It is only visible when the case is opened using force. He is also on the laser tube next to the laser exit opening, as well as on top of the tube. These labels are only visible when the laser tube is exposed or removed and are not visible under normal operating conditions.
  • the room temperature should stay between 17 and 27 degrees Celsius.
  • the humidity should be less than 70%.
  • the laser system is a single output unit - laser printer, (a raster based output unit as well as inkjet, bubblejet and dot matrix printers (or a plotter ("vector" based output unit) .
  • a raster based output unit as well as inkjet, bubblejet and dot matrix printers (or a plotter ("vector" based output unit) .
  • the difference is how characters and other graphics are shaped While a vector plotter follows the outline of the character, a laser system can handle both raster and vector motion.
  • the laser system printer driver works directly with Windows, Unix (Linux, ..), or similar application programs to send the correct image to the laser system.
  • the laser system is an output unit just like a printer or plotter. After the graphing is done on the computer system, print the graph in the same way as if you were printing on a laser printer or a plotter. This information is sent to the laser system via a cable (typically USB) and is then stored in the laser system RAM. Once the user has loaded the file into (fully or partially) the memory, processing may begin.
  • a cable typically USB
  • the only important difference between a typical laser printer and the nanowriter is that the laser system printer driver can additionally control how high the laser's energy is.
  • the laser intensity can be controlled purely black white or is controlled by the fact that everyone in the graphic drawing the color used assign a percentage of intensity from 0 - 100%. Since the laser is proportionally pulsed or otherwise controlled in intensity, this percentage represents how long the laser pulses last or how high the intensity of the laser light is. Basically, the intensity setting is directly related to how deep the color effect is.
  • a speed adjustment via galvanomirror, rotating mirror and feed of the medium controls how fast the movement system works relative to the maximum speed of the system. For example, 100% speed is 100 centimeters, 10% speed is 10 centimeters. When writing, this is the rate at which the laser beam moves across the medium. High intensity settings and high speeds produce similar effects as low intensity and slow speed - with lower system speed. In raster mode, PPI (laser pulses / inch) often corresponds to the typical dpi values of a printer.
  • either rotating mirrors, Q-switches or various types of galvanometers are usually used.
  • Open loop, closed loop galvanometer From the computer, the galvanometer gets a voltage - it creates a short voltage spike and it is accelerated very fast. The position delivered by the sensor to the computer is now continuously compared. If the axis is now at the desired point, the polarity is turned on the galvnometer within a few nanoseconds, ie a short braking pulse is given which stops the axis abruptly. Overshoots are excluded and the speed of rotation is much higher.
  • Blanking of the laser beam can be done with mirrors, Q-switches or galvanometers - otherwise rotating mirrors or galvanometers would only produce closed lines or graphics.
  • the laser beam has to be faded out and faded in very quickly by a blanking galvo.
  • laser-assisted machining of various materials is an indispensable feature today: these tools have many advantages: laser beams can process fine, sharply defined areas, laser devices have good, precise programmability, laser systems have a very good reproducibility, i. H. Only the smallest tolerances on, laser beams have no wear, so they are very profitable, welding and soldering, in particular, the property of using only very small areas heated, cutting and drilling (with pulsed lasers) for drilling diameter ⁇ 0 , 5 mm and laser marking - very fast, with relatively little effort and with very good quality
  • Plastics can be processed with much lower performance than metals.
  • One reason for this is the surface quality of the metals, which can have reflection values of 90 to 100 percent in the bright state.
  • thermal conductivity and melting temperature of the metal play a major role. The higher the melting temperature, the more difficult the laser processing.
  • He-Ne lasers can be focused to about 1 ⁇ m
  • CO 2 lasers which are also the most commonly used laser group for material processing
  • the pulse duration must also be considered when choosing the laser, because drilling and cutting in particular would not be possible without pulsed lasers (usually Nd: YAG lasers).
  • the total energy consumption of the system results primarily only from the laser power plus waste heat, the energy consumption of the feed is insignificant, an additional fixing process of the toner with heat is not primarily intended but can be combined secondarily with the process. Therefore, the device only consumes energy primarily in direct printing mode.
  • Typical laser printers currently have "standby" power of between about 5 and 30 watts and draw up to 1000 watts of power when printing, and the Nanowriter can also stand out significantly from existing printing methods through lower energy consumption and the absence of any heat-up time to the first sheet.
  • CO 2 laser radiation allows flexible, fast and accurate perforation and cutting of various materials without residue on the workpiece, such as thin plastic and composite films, laminates, textiles and paper. This mode can be integrated as an additional option in the Nanaowriter.
  • a CO 2 laser can be tuned to a wavelength of 10.6 ⁇ m (default) or close to 9.6 ⁇ m. This wavelength is recorded by silicates and similar structures much better (difference more than a power of ten).
  • An Nd: YAG laser (1.06 ⁇ m) can also be used but requires the use of an additional chromophore for the directed introduction of the laser energy.
  • the transformation of a porous SiO 2 gel layer into a solid silicate layer with a significant reduction of the layer thickness (color effect) can therefore be done eg with hot air, hot surfaces (stamp, pin) or with laser energy of a CO2 or ErYAG or Ho: YAG (yttrium aluminum garnet) lasers are generated.
  • a dye preferably an inorganic salt of 0.1 to 5 weight percent, can be added to the material - in this case copper salts, chromium salts or rare earths are possible chromophores.
  • lasers with a power of up to 300 W are used for normal office supplies.
  • Higher laser powers are used for industrial applications, for example for labeling in production lines, for example for packaging or in large print shops.
  • a silver film of 45 nm thickness is sputtered on. Then, a quartz, magnesium fluoride, calcium fluoride or similar transparent layer is applied by high vacuum evaporation.
  • the paper is freed from adhering water in a high vacuum (water content up to 5% requires long pre-pumping times). Preheating the paper can greatly shorten the pumping process.
  • the desired material for layer (3) usually likewise silver, is evaporated thermally in a tungsten, molybdenum or tantalum boat or by means of electron beam (if appropriate also with AC plasma).
  • the surface temperature of the paper should not exceed 200 ° C. in order to avoid thermal decomposition of the paper matrix.
  • the bulk thickness of the vapor-deposited or sputter-coated silver layer is typically between 3 and 10 nanometers, the color pressure shifting with increasing layer thickness from a broadband spectrum across one (or more) sharp spectral bands in the direction of the impression of metallic surfaces.
  • gold or silver can be coated, for example, with 5 nm (mass thickness) within 10 seconds at a current intensity of about 10 mA / inch 2 and an argon pressure of 0.1 mbar. Often a bonding agent for the gold layer is necessary. Gold can also be replaced by other corrosion-resistant metals.
  • any thermally stable film can be used instead of paper.
  • PET, PEN, PP or PE films have been widely used industrially. In principle, however, any carrier material can be used.
  • adhesion problems on some surfaces eg PE or PP
  • pretreatment of the FONs by corona discharge, flaming, etching or plasma processes.
  • Example 3 Color effect on material with intermediate layer with higher refractive index
  • Example 1 On paper, foil, sheet, pigment (e.g., mica) or plastic surface, a layer of alumina, zirconia, tin oxide, titania, niobium oxide or other materials such as nitrides or oxynitrides is applied by reactive high vacuum evaporation or reactive sputtering. Most oxides have efficient reflection of light at the phase boundary. Thereafter, the procedure is as in Example 1 and a layer of low-refractive materials, e.g. Magnesium fluoride, calcium fluoride, barium fluoride applied. The further procedure is analogous as already described in Example 1.
  • a layer of low-refractive materials e.g. Magnesium fluoride, calcium fluoride, barium fluoride applied.
  • the further procedure is analogous as already described in Example 1.
  • Reactive vapor deposition and sputtering (usually oxides, nitrides or oxynitrides) requires precise process gas control to ensure the necessary stoichiometry of the materials.
  • sputtering of pure non-conductors is only possible with special sputtering systems, mostly AC or DC pulse systems, and with relatively high sputtering power.
  • Nitrides or oxides usually sputter up to about 10 times more slowly than the corresponding metals.
  • a non-dense particle layer or a very thin transparent layer of a metal of suitable adhesion and corrosion stability is first applied by chemical, high vacuum evaporation or sputtering.
  • Suitable metals are, for example, gold (usually only with an adhesive layer), silver (moderately stable and poorly adhering), palladium (stable but poorly adhering), better titanium, niobium, chromium, nickel, tin, or the like. This is done by sputtering or thermal or electron beam evaporation. The further construction is carried out as described in Example 1.
  • Example 5 Other application techniques
  • the coating or printing of nanoparticles according to the invention is possible both as nanoparticles (4) and for changing the phase-boundary properties of the material surface (2).
  • the procedure is then as described in Example 1.
  • a commercially available stainless steel, brass or aluminum foil is structured analogously to Example 1.
  • the material is usually first coated adhesive manure.
  • the silane is sprayed mostly on the oxide layer and baked between 80 0 C and 160 0 C.
  • the silane layers are crosslinked.
  • Nanoparticles can also be applied as metal colloids from a concentrated (»100 mg metal / l) and bound chemically or adsorptively. Colloidal solutions of lower concentration are usually unsuitable for technical processes (due to the long process time). Colloids are mostly used protected by polymers or coated with a 1 - 100 nm thick glass or polymer-like layer. Particle protection polymers can be loaded to bind with high affinity to the oppositely charged surface of the film. Hydrophobic attractive forces can also be used to advantage here (thin layer (3) of plastic lacquer + gold / silver / copper nanoparticles coated with hydrophobic monolayer thiol).
  • Objects prepared according to Examples 1 to 6 are coated with spray, doctor blade or dip paint from starch solution, polyacrylates, polymethacrylates, polyurethanes or epoxy resin.
  • the paint is dried and added if necessary cured at elevated temperature. The exact curing conditions are to be selected according to the paint manufacturer.
  • An object can also be coated with polymer solution by spraying, spinning or dipping, then the solvent is removed and the film is UV cured (eg acrylates), electron beam or thermally crosslinked.
  • Example 8 Surface protection in the sol / gel process
  • the objects are also coated with sol / gel coatings and these are usually baked at temperatures between 200 and 800 0 C.
  • Typical raw materials here are metallates of titanium (eg titanium ethoxylates), tetraethoxysilane, zirconium metallates or similar compounds which usually react with water under hydrolysis first to give hydroxides and after thermal treatment to crosslinked, chemically-mechanically stable oxides with good surface adhesion.
  • metallates of titanium eg titanium ethoxylates
  • tetraethoxysilane tetraethoxysilane
  • zirconium metallates or similar compounds which usually react with water under hydrolysis first to give hydroxides and after thermal treatment to crosslinked, chemically-mechanically stable oxides with good surface adhesion.
  • the layer thickness of the coatings is, depending on the application, between about 100 nm and many micrometers.
  • Objects produced according to Examples 1 to 6 are produced using a thermally or photochemically crosslinkable paint.
  • a surface film (2) is applied to the object or one of the thin layers (3) is replaced by the reactive lacquer.
  • laser-changeable lacquers and nanoparticle precursor lacquers which are transformed by laser light into dark metallic nanoparticles, are suitable.
  • the object is then described using IR radiation by an optical writing systems (eg laser writer) spatially definitely colored. This process causes either a local change in the refractive index and / or the layer thickness of the thin layers (3) and / or the number of nanoparticles on the surface (2) of the material.
  • Analog can also thermally, electrochemically, with microwaves or electron beams, the material optically to be changed.
  • the processes mentioned lead to a colored inscription of the surfaces.
  • This technology is suitable both for in-situ lettering, as a replacement for thermal paper but also for printing on films and especially as novel electronic paper ("e-paper").
  • Objects made according to Examples 1-7 are prepared using a thermally or photochemically crosslinkable paint having reactive properties (e.g., water swellable, temperature-reactive, ).
  • a surface film (2) is applied to the object or one of the thin layers (3) is replaced by the reactive lacquer.
  • UV-crosslinkable hydrogels polyvinylpyrrolidones crosslinked with bisazides
  • ionic polymers polyacrylic acid copolymers, ..
  • thermo-reactive polymers e.g., poly-N-isopropylacrylamide
  • the exact reaction conditions are highly material dependent.
  • the object coated with the necessary layers is then spatially definitely networked using the radiation of a laser writer. This process leads to a colored inscription of the films with reactive elements which specifically respond to temperature, humidity, pH or other environmental variables with spatial resolution.
  • the coated mica having a particle size of about 10 ⁇ m and 0.75 g of carbon black (mean particle size: 15 nm, or other black color pigment) are mixed and stirred.
  • the coated mica is suspended in 500 ml of water and adds, for example, teraethoxysilane, aluminum tri-propoxide, tetraethoxy titanate, tin chloride solution, titanium tetrachloride solution or other film-forming agents.
  • the pH of the solution must be constant by the addition of bases being held.
  • Nanoparticles or their chemical, laser-convertible precursors are coated on the pigments.
  • the mica can be replaced with glass slides, talc, kaolin, or other carriers. Also fibrous pigments such as cellulose or polymer fibers can be used,
  • Example 12 Coating of reactive layers for nanoparticle production
  • Pigments with a spacer layer (for setting the desired hue) is coated with a soluble metal salt or a suspension of very fine, preferably less than 100 nm, particles from the group of the metals V, Cr, Mn 1 Fe. Co, Ni, Cu, Ag, Sn, Pb, C, Si, Ge and Bi.
  • the process can be assisted by precipitation by pH change, solvent modification or addition of an anion having precipitating properties.
  • These particles are either themselves chromophoric or are preferably converted as a precursor with the laser into oxides or other oxidized compounds, for example phosphates with a chromophoric character.
  • the average mass thickness should be about 5 nm for metallic particles, and for chromophore particles, it should be proportional to their extinction coefficient.
  • Particles according to Example 12 are mixed with a coating agent, preferably a polymer, and applied to the surface of an object. Thereafter, usually a cover layer of a further preferably organic polymer (in outdoor use, however, also an inorganic eg SoI-GeI coating) is applied.
  • the layer thickness of the coating is between 0.1 and 100 ⁇ m, preferably between 1 and 20 ⁇ m.
  • the cover layer not only serves to protect the colored layers but also actively absorbs laser energy and passes as heat and or chemical energy to the nanoparticles or precursor layer on.
  • a structure analogous to Example 13 is coated with a cover layer of a scattering material (usually white), that after exposure to the laser beam transparent - because is briefly melted.
  • a cover layer of a scattering material usually white
  • nanoparticles e.g. made of polystyrene or similar polymer in use, which absorb the laser energy, forward and then form a protective cover film.
  • the scattering cover layer has a thickness of 1-100 .mu.m, preferably 3-20 .mu.m.
  • Figure 1 Structure of the thin-film structure according to claim 1
  • Figure 2 Labeling of the thin-film structure by changing the optical density of the cover layer (5) by means of laser or heat
  • Figure 3 Labeling of the thin-layer structure by changing the optical thickness of the layer (4) by means of laser or heat
  • Figure 4 Labeling of the thin-film structure by changing the optical density of the reflective layer (3) by laser or heat.
  • Figure 5 Structure of the thin-film structure with pigment subcarrier - The color effect is achieved on the pigment with the same nanometric structure as in Figure 1 and the same effects as in Figure 2 to 4 explained.

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Abstract

L'invention concerne un nouveau procédé et le système d'écriture utilisé pour l'encrage de surfaces. L'invention se caractérise en ce que plusieurs couches minces, présentant chacune une épaisseur inférieure à 800 nm, sont appliquées sur ou dans un matériau (1, 2), une couche ou une limite de couche réfléchissant au moins partiellement des ondes électromagnétiques (3), une couche transparente (4), qui présente une épaisseur inférieure à 700 nm, étant placée au-dessus et/ou au-dessous de cette couche réfléchissante, couche transparente sur laquelle est placée au moins une couche de particules (5) métalliques ou au moins à fortes propriétés chromophores, qui possède une épaisseur massique inférieure à 50 nm, ou, en variante, des précurseurs chimiques de ladite couche ou, en variante, une couche mince métallique présentant une épaisseur inférieure à 50 nm, et la structure globale variant d'une manière définie dans l'espace et changeant de couleur d'une manière structurée sous l'effet de la lumière ou par contact direct avec des objets chauds ou bien au voisinage très proche d'objets chauds. Selon l'invention, un texte quelconque, un dessin ou des informations graphiques (6) sont visibles par une modification de la structure des nanocouches et au moins certaines couleurs sont engendrées par une couleur résonante dépendant de l'épaisseur et de l'indice de réfraction de la couche.
EP08801644A 2007-08-25 2008-08-21 Nanorevêtement opto- et thermo-inscriptible Withdrawn EP2188133A1 (fr)

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EP2030797A1 (fr) 2009-03-04
RU2471634C2 (ru) 2013-01-10
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CA2707404A1 (fr) 2009-03-05

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