EP4228902A1 - Verfahren zum bedrucken von partikeln - Google Patents

Verfahren zum bedrucken von partikeln

Info

Publication number
EP4228902A1
EP4228902A1 EP21787395.9A EP21787395A EP4228902A1 EP 4228902 A1 EP4228902 A1 EP 4228902A1 EP 21787395 A EP21787395 A EP 21787395A EP 4228902 A1 EP4228902 A1 EP 4228902A1
Authority
EP
European Patent Office
Prior art keywords
receptive layer
particles
printing
process according
donor surface
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
EP21787395.9A
Other languages
English (en)
French (fr)
Inventor
Laura GILSBACH
Maike TROMPA
Matthias DREIER
Rahul AGNIHOTRI
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.)
Actega Metal Print
Original Assignee
Actega Metal Print
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 Actega Metal Print filed Critical Actega Metal Print
Publication of EP4228902A1 publication Critical patent/EP4228902A1/de
Pending 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
    • B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
    • B41M3/006—Patterns of chemical products used for a specific purpose, e.g. pesticides, perfumes, adhesive patterns; use of microencapsulated material; Printing on smoking articles
    • 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

Definitions

  • the present invention relates to a process for printing onto a substrate, an intermediate print product and a print product.
  • Foil imaging is deemed as to be one of the most practicable technologies for printing solid material on a substrate and might be used e.g. for metallization purposes.
  • foil stamping on the one hand
  • foil laminating on the other hand.
  • a metallic foil is transferred onto a surface through the transfer of heat and pressure.
  • a die is heated and applied to the foil and is then sandwiched between the die and the surface which should be stamped.
  • the heated die pressing against the surface activates an adhesive within the foil, which fuses the foil to the substrate. Pressure and heat cause the relevant sections of the foil to become detached from the carrier material and become bonded with the printing surface.
  • Foil laminating on the other hand differs from said foil stamping technology, as the latter requires a die to be heated.
  • a typical foil laminating process consists of two steps: printing on the substrate and foiling itself.
  • a UV-curable laminating adhesive is printed onto the substrate in the areas which are to be foiled.
  • a foil is brought into contact with the substrate as well as the uncured adhesive by a laminating roller.
  • the adhesive is cured through the foil using a conventional UV-lamp which bonds the foil to the substrate via the adhesive.
  • WO 2016/189515 proposes a printing process in which the waste and the costs for the foil is
  • SUBSTITUTE SHEET (RULE 26) reduced.
  • Said process is a continuous method for printing particles (e.g. metal pigment flakes) and uses a printed trigger image before passing into an application unit, where a donor roll carries the particles from a reservoir to a receptive layer of the substrate to be printed. Only those particles that are in contact with the trigger image are used, the remainder return to the reservoir for future rotations. After transferring the particles to the receptive layer the donor surface is returned to coat it again with particles in order to allow a continuous printing process. Said process is especially used as an economical metallization technology which provides attractive metallic effects.
  • particles e.g. metal pigment flakes
  • the solution is a process for printing onto a substrate having an image-receiving surface, which comprises providing a donor surface, passing the donor surface through a coating station from which the donor surface exits coated with individual particles, and repeatedly performing the steps of:
  • SUBSTITUTE SHEET (RULE 26) (iv) returning the donor surface to the coating station to coat it again with individual particles in order to permit printing of a subsequent image on the substrate, characterized in that the receptive layer provided in step (i) contains or consists of a coating composition RC comprising
  • a multifunctional acrylate MA with 2 - 16 acryloyl groups and additionally at least a sufficient number of further moieties selected from the group consisting of urethane functions, ester functions and ether functions, with the proviso that the sufficient number is such that in total at least 6 - 90 moiety-heteroatoms are provided, and with optionally a limited number of phenyl groups, where said number is limited by the proviso that there are at least 6 of the moiety-heteroatoms per one phenyl group.
  • the ester segment contained in said acyryloyl group does not belong to the defined ..further moieties”.
  • Said propositionMoiety-heteroatoms“ are only provided by the heteroatoms of the cited functions (urethane, ester and ether):
  • the individual contribution of a single urethane group is 3 heteroatoms, of a single ester group is 2 heteroatoms and of a single ether group is 1 heteroatom.
  • the donor surface is typically made from a polymer that can be tailored in regard to its surface polarity and mechanical properties.
  • the donor surface is made from an elastomer, for example a silicone-based material.
  • a silicone-based material is made by combining three silicone- based materials: a vinyl-terminated polydimethylsiloxane (Polymer VS 5000, Evonik) in an amount of about 58.45% by weight of the total composition (wt.%), a vinyl functional polydimethylsiloxane containing both terminal and pendant vinyl groups (Polymer RV 5000, Evonik), in an amount of about 11 wt.% and a branched structure vinyl functional polydimethylsiloxane (VQM 906, Evonik) in an amount of about 22.5 wt.%.
  • VQM 906, Evonik branched structure vinyl functional polydimethylsiloxane
  • a platinum catalyst Catalyst 512, Evonik
  • a inhibitor Inhibitor 600, Evonik
  • a reactive cross-linker such as a methyl-hydrosiloxane-dimethylsiloxane copolymer (Crosslinker 101 , Evonik) in an amount of 6.0 wt.%.
  • This composition can be thermally cured to produce a hydrophobic elastomeric donor surface.
  • the process according the present invention provides a sufficient transfer of the particles from the donor surface to the receptive layer.
  • the curing properties of the receptive layer (of the coating composition RC) are such (universal) that an efficient curing is even possible at different printing speeds and receptive layer thicknesses.
  • the hardening of the receptive layer is on the one hand fast enough in order to provide the appropriate acceptor properties (sufficient stickiness to the particles even in a fast printing process) but on the other hand not too intensive so that the flexibility of the hardened layer is remained (brittleness avoided).
  • the cohesion of the cured layer should be appropriate (sufficient mechanic solidity/ strength) so that the coating does not deposit on the printing pressure roller and does not show mechanical brittleness (to hard).
  • the cured layer provides universal and efficient acceptor properties (adoption from the donor surface) for the particles.
  • a sufficient (particle) covering of the receptive layer is achieved:
  • sufficient covering it is meant that the coat of particles on the relevant substrate regions will be especially devoid of defects perceptible to the naked eye so that the intended visual effect is achieved.
  • the received print product is optically
  • SUBSTITUTE SHEET (RULE 26) attractive and has a good quality.
  • the gloss of a metallized substrate might be deemed as to be a corresponding quality feature.
  • step (ii) the electromagnetic radiation is performed by UV radiation and the coating composition RC comprises a sufficient amount of suitable UV polymerisation initiator.
  • UV radiation corresponding lamps using wavelengths of e.g. 200 - 350 nm might be provided.
  • the UV polymerization initiator might be selected from the group consisting of so called Type I photoinitiators such as hydroxyacetophenones, alkylaminoacetophenones, benzil ketals, dialkoxyacetophenones, benzoin ethers, phosphine oxides, acyloximino esters, so called Type II photoinitiators such as benzophenone, substituted benzophenones, thioxanthones, anthraquinones, benzoylformate esters, camphorquinone, as well as polymers with before mentioned radical forming groups attached to them.
  • Type I photoinitiators such as hydroxyacetophenones, alkylaminoacetophenones, benzil ketals, dialkoxyacetophenones, benzoin ethers, phosphine oxides, acyloximino esters
  • Type II photoinitiators such as benzophenone, substituted benzophenones, thiox
  • step (i) the receptive layer is applied to selected regions by indirect printing which is performed by offset printing, screen printing, flexographic printing and/or gravure printing.
  • the receptive layer is applied according to a digital technology embodiment: in step (i) the receptive layer is applied to the substrate surface by direct printing, especially by direct jetting. In the latter case the coating composition RC should have an appropriate viscosity (low enough).
  • the receptive layer provided in step (i) has a thickness between 0.5 pm and 500 pm, where the thickness is determined via gravimetry.
  • SUBSTITUTE SHEET (RULE 26)
  • the particles are preferably selected to adhere to the donor surface more strongly than they do to one another. This results in the applied layer being substantially a thin layer (preferably being a monolayer) of individual particles.
  • the printed particles contain or consist of metal.
  • the particles contain or consist of flaky metallic pigments (often formed like platelets).
  • flaky metallic pigments typically have an average thickness (h50) value in the range of 20 - 200 nm (which is determined with a scanning electron microscope according to the corresponding method as described in WO 2004/087816).
  • non-metallic particles might be used.
  • examples of such choirnon-metallic“ particles glass and ceramic (metal oxides), respectively including polymeric or inorganic coating of the particles.
  • the particles may be grains or flakes of metals, such as aluminum, copper, iron, zinc, nickel, tin, titanium, gold or silver, or alloys, such as steel, bronze or brass, and like metallic compounds primarily including metals.
  • the coating composition RC comprises 20 - 90 wt.-% of the multifunctional acrylate MA.
  • the multifunctional acrylate MA contains no phenyl group, 2 - 10 acryloyl groups and additionally at least a sufficient number of further moieties selected from the group consisting of urethane functions, ester functions and ether functions, with the proviso that the sufficient number is such that in total at least 11 - 20 moiety-heteroatoms are provided, where said partial quantity is preferably at least 30 wt.-%.
  • the total absence (or sometimes also a “very” low number) of phenyl groups generally improves the quality (e.g. often by improving particle adoption properties and/or typically by avoiding mechanical brittleness).
  • At least a partial quantity of the multifunctional acrylate MA has a molecular weight of at least 500, where said partial quantity is at least 20 wt.-%.
  • the multifunctional acrylate MA contains maximal 6 acryloyl groups and additionally at least 4 moieties selected from the group consisting of urethane functions and ester functions.
  • the coating composition RC contains at least 60 wt.-% radical polymerizable components and preferably maximal 10 wt.-% non-radical-polymerizable solvents.
  • Components which are normally not contained in the coating composition are thermal radical initiators and mineral fillers. However, polymeric (organic) resins might be contained.
  • the receptive layer is selected so that it does not interfere with the desired printing effect (e.g., clear, transparent, and/or colorless).
  • the invention also concerns an intermediate print product manufactured by a printing process as described above.
  • the invention concerns a print product on the basis of said intermediate print product additionally comprising an overcoat layer covering the printed particles.
  • the overcoat layer improves the stability of the print product.
  • the gloss of the metallized surface of printed samples was measured using a glossmeter (device: micro-TRI-gloss manufactured by BYK-Gardner GmbH, D-82538 Geretsried, Germany). Since the measured surfaces are highly reflective, the measurement was performed using a 20° angle setting. For each sample five
  • the optical density provides an indication of the amount of transferred metallic pigments.
  • a black/white transmission densitometer (device: 341 C manufactured by X-Rite Inc., Grand Rapids Ml 49512, USA) was used. To calibrate the pure substrate was first measured and the value set to zero. For each sample three measurements in different areas were performed and the values were arithmetically averaged.
  • microscope images were made using a laser-scanning microscope VK-X 1100 (manufactured by Keyence Corporation, Osaka 533-8555, Japan). After generating a composite image at 150 x magnification, overlaying optical and laser images, it is possible to distinguish areas covered by pigment from free areas. Using the MultiFileAnalyzer Software (by Keyence Corporation, Osaka 533-8555, Japan) the free area can be calculated by relating the covered are in pm 2 to the entire image are in pm 2 resulting in a percentage value of an area covered by metallic pigments.
  • Metallized samples were prepared by applying the receptive coatings Example 1 and Wessco 3501 (comparative example - not according to the invention, manufactured by ACTEGA Schmid Rhyner AG, 8134 Adliswil, Switzerland) using a flexographic print station on a Digicon Series 3 finishing unit (manufactured by AB Graphics International Ltd., Bridlington YO15 3QY, United Kingdom) at different speeds on a gloss white polyethylene laminate substrate (RI-837/85 PE GLOSS WHITE manufactured by Ritrama S.p.A., 20867 Caponago, Italy).
  • SUBSTITUTE SHEET (RULE 26) (GEW E2C, 120 W/cm manufactured by GEW Ltd., Crawley RH10 9QR, United Kingdom) at 100% power setting.
  • the web was fed through an EcoLeaf metallization unit (manufactured by ACTEGA Metal Print GmbH, D-31275 Lehrte, Germany).
  • the pigments used in the metallization process were EcoLeaf P110 aluminum platelets with a median thickness of around 40 nm (distributed by ACTEGA Metal Print GmbH, D-31275 Lehrte, Germany).
  • the metallized samples were characterized by gloss (20° angle setting), optical density and measurement of covered area using a confocal laser scanning microscope.
  • Metallized samples were prepared by applying the receptive coatings Example 2 and Flint Tactile Varnish UV D0-1200-408 N (comparative example - not according to the present invention, manufactured by Flint Group, D-70469 Stuttgart, Germany) using a rotary screen printing station on an Omet XFlex X6 (manufactured by Omet srl, 23900 Lecco, Italy) at 20 m/min on a coated paper laminate substrate (ADESTOR High Gloss Ws 80 manufactured by Lecta, 08019 Barcelona, Spain).
  • the metallized samples were characterized by gloss (20° angle setting) and measurement of the covered area using a confocal laser scanning microscope. A measurement of the optical density was not feasible due to the low transparency of the substrate laminate.
  • the trigger image was immediately cured inline using a conventional mercury-based UV-lamp (GEW E2C, 120 W/cm manufactured by GEW Ltd., Crawley RH10 9QR, United Kingdom) at 80% power setting.
  • GEW E2C 120 W/cm manufactured by GEW Ltd., Crawley RH10 9QR, United Kingdom
  • the web was fed through an EcoLeaf metallization unit (manufactured by ACTEGA Metal Print GmbH, D-31275 Lehrte, Germany).
  • the pigments used in the metallization process were EcoLeaf P110 aluminum platelets with a median thickness of around 40 nm (distributed by ACTEGA Metal Print GmbH, D-31275 Lehrte, Germany).
  • the metallized samples were characterized by gloss (20° angle setting), optical density and measurement of covered area using a confocal laser scanning microscope.
  • Examples 1 , 2 and 3 were presented in order to provide an improved process.
  • the used multifunctional acrylates MA are Ebecryl 230 (difunctional which contains around 42 “moiety-heteroatoms” stemming from urethan and ether moieties), Ebecryl 5129 (hexafunctional which contains 6 “moiety-heteroatoms” stemming from urethan moieties), Ebecryl 8409 (difunctional which contains 14 “moiety-heteroatoms” stemming from urethane and ester moieties) and CN2505 (tetrafunctional which contains 10 “moiety-heteroatoms” stemming from ester and ether moieties).
  • Each of said mentioned multifunctional acrylates MA do not contain a phenyl group.
  • Further multifunctional acrylates MA which can be employed and have shown good results are e.g. SR344 (polyethyleneglycol (400) diacrylate), SR610 (polyethyleneglycol (600) diacrylate), SR499 (ethoxylated (6) trimethylolpropane triacrylate), SR502 (ethoxylated (9) trimethylolpropane triacrylate), SR9035 (ethoxylated (15) trimethylolpropane triacrylate), SR415 (ethoxylated (20) trimethylolpropane triacrylate), Miramer M2040 (polypropyleneglycol (400) diacrylate) and Miramer M2300 (ethoxylated (30) bisphenol A diacrylate).

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Printing Methods (AREA)
  • Laminated Bodies (AREA)
EP21787395.9A 2020-10-19 2021-10-05 Verfahren zum bedrucken von partikeln Pending EP4228902A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP20202642 2020-10-19
PCT/EP2021/077440 WO2022084027A1 (en) 2020-10-19 2021-10-05 Process for printing particles

Publications (1)

Publication Number Publication Date
EP4228902A1 true EP4228902A1 (de) 2023-08-23

Family

ID=72944015

Family Applications (1)

Application Number Title Priority Date Filing Date
EP21787395.9A Pending EP4228902A1 (de) 2020-10-19 2021-10-05 Verfahren zum bedrucken von partikeln

Country Status (2)

Country Link
EP (1) EP4228902A1 (de)
WO (1) WO2022084027A1 (de)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10315775A1 (de) 2003-04-04 2004-10-14 Eckart Gmbh & Co. Kg Dünne deckende Aluminiumpigmente, Verfahren zur Herstellung derselben und Verwendung der Aluminiumpigmente
CA2520442A1 (en) * 2005-09-15 2007-03-15 Hamish Somerville Vacuum metalized pigment patterns and method of making same
US10350910B2 (en) * 2014-07-25 2019-07-16 Konica Minolta, Inc. Foil image formation method
GB201509080D0 (en) * 2015-05-27 2015-07-08 Landa Labs 2012 Ltd Coating apparatus

Also Published As

Publication number Publication date
WO2022084027A1 (en) 2022-04-28

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