EP4228902A1 - Process for printing particles - Google Patents
Process for printing particlesInfo
- 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
Links
- 239000002245 particle Substances 0.000 title claims abstract description 45
- 238000007639 printing Methods 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000000758 substrate Substances 0.000 claims abstract description 25
- 238000000576 coating method Methods 0.000 claims abstract description 17
- 239000011248 coating agent Substances 0.000 claims abstract description 13
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 12
- 239000008199 coating composition Substances 0.000 claims abstract description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 10
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 8
- 125000001033 ether group Chemical group 0.000 claims abstract description 7
- 230000005670 electromagnetic radiation Effects 0.000 claims abstract description 5
- 239000000049 pigment Substances 0.000 claims description 15
- 150000002148 esters Chemical group 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- -1 benzoin ethers Chemical class 0.000 claims description 9
- 229920000642 polymer Chemical class 0.000 claims description 5
- 239000012965 benzophenone Substances 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 3
- 230000005855 radiation Effects 0.000 claims description 3
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical class C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 claims description 2
- ZWVHTXAYIKBMEE-UHFFFAOYSA-N 2-hydroxyacetophenone Chemical class OCC(=O)C1=CC=CC=C1 ZWVHTXAYIKBMEE-UHFFFAOYSA-N 0.000 claims description 2
- 244000028419 Styrax benzoin Species 0.000 claims description 2
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 2
- 150000004056 anthraquinones Chemical class 0.000 claims description 2
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 claims description 2
- 229960002130 benzoin Drugs 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 150000008366 benzophenones Chemical class 0.000 claims description 2
- 229930006711 bornane-2,3-dione Chemical class 0.000 claims description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 2
- 238000010017 direct printing Methods 0.000 claims description 2
- 238000000892 gravimetry Methods 0.000 claims description 2
- 238000007646 gravure printing Methods 0.000 claims description 2
- 235000019382 gum benzoic Nutrition 0.000 claims description 2
- 238000007645 offset printing Methods 0.000 claims description 2
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 claims description 2
- FAQJJMHZNSSFSM-UHFFFAOYSA-N phenylglyoxylic acid Chemical class OC(=O)C(=O)C1=CC=CC=C1 FAQJJMHZNSSFSM-UHFFFAOYSA-N 0.000 claims description 2
- 239000003505 polymerization initiator Substances 0.000 claims description 2
- 238000007650 screen-printing Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 28
- 239000011888 foil Substances 0.000 description 25
- 238000001465 metallisation Methods 0.000 description 11
- 238000005259 measurement Methods 0.000 description 10
- 230000003287 optical effect Effects 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000010030 laminating Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 101150009575 RH10 gene Proteins 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 125000004386 diacrylate group Chemical group 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000003384 imaging method Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 239000004971 Cross linker Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- FHLPGTXWCFQMIU-UHFFFAOYSA-N [4-[2-(4-prop-2-enoyloxyphenyl)propan-2-yl]phenyl] prop-2-enoate Chemical compound C=1C=C(OC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OC(=O)C=C)C=C1 FHLPGTXWCFQMIU-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000007774 anilox coating Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007723 die pressing method Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012939 laminating adhesive Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000011101 paper laminate Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000010022 rotary screen printing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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)
Abstract
:The invention relates to 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: (i) providing a receptive layer, at least partially covering said image-receiving surface, (ii) treating the receptive layer by electromagnetic radiation in order to enhance its affinity to the particles greater than the affinity of the particles to the donor surface, (iii) contacting the receptive layer with the donor surface to cause particles to transfer from the donor surface to the treated receptive layer, thereby exposing regions of the donor surface from which particles are transferred to the receptive layer and thereby generating a plurality of individual particles adhered to the receptive layer; and (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 comprising10 - 95 wt.-% of 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.
Description
Title Process for printing particles
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. There are two different types of foil imaging, foil stamping on the one hand and foil laminating on the other hand. In a foil stamping process a metallic foil is transferred onto a surface through the transfer of heat and pressure. During the stamping process, 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. In the printing step a UV-curable laminating adhesive is printed onto the substrate in the areas which are to be foiled. In a second step a foil is brought into contact with the substrate as well as the uncured adhesive by a laminating roller. Subsequently the adhesive is cured through the foil using a conventional UV-lamp which bonds the foil to the substrate via the adhesive. By removing the foil reel from the substrate path the now bonded foil areas are removed from the carrier material and non-bonded foil is wound up on a reel.
However, the production of this foil waste is considered as a serious disadvantage of foil stamping and laminating: in practice a large amount of foil that is wasted during each stamp/laminating process, as any foil area that is not transferred to form the desired image on the substrate cannot be recovered for successive prints.
WO 2016/189515 proposes a printing process in which the waste and the costs for the foil is
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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.
However, there still is a need to further improve the efficiency of the printing process and the quality of the received printing products.
Thus, it is an object of the present invention to provide an economical printing process which might be used as a metallization method. The corresponding print product should be of high quality.
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:
(i) providing a receptive layer, at least partially covering said image-receiving surface,
(ii) treating the receptive layer by electromagnetic radiation in order to enhance its affinity to the particles greater than the affinity of the particles to the donor surface,
(iii) contacting the receptive layer with the donor surface to cause particles to transfer from the donor surface to the treated receptive layer, thereby exposing regions of the donor surface from which particles are transferred to the receptive layer and thereby generating a plurality of individual particles adhered to the receptive layer; and
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(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
10 - 95 wt.-% of 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 acryloyl groups (sometimes “only” defined as H2C=CH-C(=O)-) in the relevant (invention) definition of the multifunctional acrylate MA are defined as to be (“the ester-type”): H2C=CH-C(=O)-O- (“acrylic acid ester function”). The ester segment contained in said acyryloyl group does not belong to the defined ..further moieties".
Additional explanation concerning the claim definition: “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 - 30 moiety-heteroatoms are provided”.
Said „Moiety-heteroatoms“ (generally O. possibly N) 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. For example an O atom of a
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possible additional hydroxyl group is not considered as to a „moiety-heteroatom”. With ..sufficient number" it is meant that there are enough of these (cited) “further moieties” in order to obtain (in addition) the requested number of moiety-heteroatoms.
The donor surface is typically made from a polymer that can be tailored in regard to its surface polarity and mechanical properties. Typically, the donor surface is made from an elastomer, for example a silicone-based material. One example 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.%. To the mixture were added: a platinum catalyst (Catalyst 512, Evonik) in an amount of about 0.05 wt.%, a inhibitor (Inhibitor 600, Evonik) in an amount of 2.0 wt.%, and finally 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). In other words: 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). Additionally, the cured layer provides universal and efficient acceptor properties (adoption from the donor surface) for the particles. According to the present invention a sufficient (particle) covering of the receptive layer is achieved: By "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. Generally, the received print product is optically
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attractive and has a good quality. The gloss of a metallized substrate might be deemed as to be a corresponding quality feature.
Due to a preferred embodiment of the printing process according to the present invention, in step (ii) the electromagnetic radiation is performed by UV radiation and the coating composition RC comprises a sufficient amount of suitable UV polymerisation initiator.
For the 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.
One possibility of applying the receptive layer is according to an analogues technology element: in 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.
Alternatively 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).
Normally, the receptive layer provided in step (i) has a thickness between 0.5 pm and 500 pm, where the thickness is determined via gravimetry.
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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.
Typically, the printed particles contain or consist of metal.
Due to a special embodiment the particles contain or consist of flaky metallic pigments (often formed like platelets). Such 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).
However, (even if not preferred) also non-metallic particles might be used. Examples of such „non-metallic“ particles: glass and ceramic (metal oxides), respectively including polymeric or inorganic coating of the particles.
If the effect to be achieved is similar to foil imaging, such as used for instance for metal printing, then 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.
In an embodiment of the present invention the coating composition RC comprises 20 - 90 wt.-% of the multifunctional acrylate MA.
Typically at least a partial quantity of 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).
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In one embodiment of the invention 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.-%.
Due to a special embodiment at least 80 wt.-% of 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.
Normally, 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. Preferably 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.
Furthermore, 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.
Below the invention is described in more detail by providing examples.
The adoption of pigments by the receptive layer in the print process should be experimentally shown. Relevant “indicators” are especially the metallic gloss and the optical density (microscopical view) of the received (intermediate) print product.
Gloss measurement:
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
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measurements in different areas were performed and the values were arithmetically averaged.
measurement:
The optical density provides an indication of the amount of transferred metallic pigments. To determine the optical density 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.
Coverage measurement:
To determine the area covered by aluminum platelets after the metallization process, 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 pm2 to the entire image are in pm2 resulting in a percentage value of an area covered by metallic pigments.
Print trials:
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). For the application an anilox roller from Sandon with 200 lines per inch (manufactured by Sandon Global, Cheshire WA7 1 SR, United Kingdom) and a flexographic printing plate nyloflex® Seal F (manufactured by Flint Group, D-70469 Stuttgart, Germany) were used. After application the trigger image was immediately cured inline using a conventional mercury-based UV-lamp
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(GEW E2C, 120 W/cm manufactured by GEW Ltd., Crawley RH10 9QR, United Kingdom) at 100% power setting. Following the curing of the receptive coating 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).
After application of the pigments 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). For the application a RotaMesh® 75 rotary screen with an open area of 32% and mesh opening of 192 p (manufactured by SPGPrints B.V., 5831 Boxmeer, The Netherlands) was used. After application 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 100% power setting. Following the curing of the receptive coating 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).
After application of the pigments 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.
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Metallized samples were prepared by jetting the receptive coating Example 3 using a MH5421 F piezoelectric inkjet print-head (manufactured by Ricoh Company, Ltd., Tokyo 143-8555, Japan) mounted on an Omet XFlex X6 (manufactured by Omet srl, 23900 Lecco, Italy) at 50 m/min on a gloss white polyethylene laminate substrate (RI-837/85 PE GLOSS WHITE manufactured by Ritrama S.p.A., 20867 Caponago, Italy). For the application the receptive coating was jetted with a triple pulse resulting in a drop volume of around 21 pL. After application 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. Following the curing of the receptive coating 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).
After application of the pigments 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. In these examples 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).
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Table 1: Examples of receptive coatings
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Table 2: Results of metallization with receptive coatings
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Claims
1 . 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:
(i) providing a receptive layer, at least partially covering said image-receiving surface,
(ii) treating the receptive layer by electromagnetic radiation in order to enhance its affinity to the particles greater than the affinity of the particles to the donor surface,
(iii) contacting the receptive layer with the donor surface to cause particles to transfer from the donor surface to the treated receptive layer, thereby exposing regions of the donor surface from which particles are transferred to the receptive layer and thereby generating a plurality of individual particles adhered to the receptive layer; and
(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
10 - 95 wt.-% of a multifunctional acrylate MA with 2 - 16 acryloyl groups and additionally at least a sufficient number of
SUBSTITUTE SHEET (RULE 26)
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. Printing process according to claim 1 , wherein in step (ii) the electromagnetic radiation is performed by UV radiation and the coating composition RC comprises a sufficient amount of suitable UV polymerisation initiator. Printing process according to claim 1 or 2, wherein step (i) comprises applying a receptive layer to selected regions by indirect printing which is performed by offset printing, screen printing, flexographic printing and/or gravure printing. Printing process according to claim 1 or 2, wherein in step (i) the receptive layer is applied to the substrate surface by direct printing, including by direct jetting. Printing process according to one of the preceding claims, wherein the receptive layer provided in step (i) has a thickness between 0.5 pm and 500 pm, where the thickness is determined via gravimetry. Printing process according to one of the preceding claims, wherein the particles contain or consist of metal. Printing process according to one of the preceding claims, wherein the particles contain or consist of flaky metallic pigments. Printing process according to claim 7, where the flaky metallic pigments have an average thickness (h50) value in the range of 20 - 200 nm which is
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15 determined with a scanning electron microscope. Printing process according to one of the preceding claims, wherein the coating composition RC comprises 20 - 90 wt.-% of the multifunctional acrylate MA. Printing process according to one of the preceding claims, wherein at least a partial quantity of 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.-%. Printing process according to one of the preceding claims, wherein 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.-%. Printing process according to one of the preceding claims, wherein at least 80 wt.-% of 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. Printing process according to one of claims 2 - 12, wherein the UV polymerization initiator is 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.
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16 Printing process according to one of the preceding claims, wherein the coating composition RC contains at least 60 wt.-% radical polymerizable components and preferably maximal 10 wt.-% non-radical-polymerizable solvents. An intermediate print product manufactured by a printing process according to of one of the claims 1 - 14. A print product on the basis of an intermediate print product according to claim 15 further comprising an overcoat layer covering the printed particles.
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Applications Claiming Priority (2)
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EP20202642 | 2020-10-19 | ||
PCT/EP2021/077440 WO2022084027A1 (en) | 2020-10-19 | 2021-10-05 | Process for printing particles |
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DE10315775A1 (en) | 2003-04-04 | 2004-10-14 | Eckart Gmbh & Co. Kg | Thin opaque aluminum pigments, process for producing the same and use of the aluminum pigments |
CA2520442A1 (en) * | 2005-09-15 | 2007-03-15 | Hamish Somerville | Vacuum metalized pigment patterns and method of making same |
WO2016013644A1 (en) * | 2014-07-25 | 2016-01-28 | コニカミノルタ株式会社 | Foil image formation method |
GB201509080D0 (en) * | 2015-05-27 | 2015-07-08 | Landa Labs 2012 Ltd | Coating apparatus |
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