WO2021069406A1 - Articles marquables au laser - Google Patents

Articles marquables au laser Download PDF

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Publication number
WO2021069406A1
WO2021069406A1 PCT/EP2020/077926 EP2020077926W WO2021069406A1 WO 2021069406 A1 WO2021069406 A1 WO 2021069406A1 EP 2020077926 W EP2020077926 W EP 2020077926W WO 2021069406 A1 WO2021069406 A1 WO 2021069406A1
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WO
WIPO (PCT)
Prior art keywords
laser markable
laser
layer
agent
colour
Prior art date
Application number
PCT/EP2020/077926
Other languages
English (en)
Inventor
Fabienne Goethals
Marie LEHERICEY
Charles REEB
Original Assignee
Agfa Nv
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
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Publication of WO2021069406A1 publication Critical patent/WO2021069406A1/fr

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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
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/46—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography characterised by the light-to-heat converting means; characterised by the heat or radiation filtering or absorbing means or layers
    • B41M5/465—Infra-red radiation-absorbing materials, e.g. dyes, metals, silicates, C black
    • 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
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/323—Organic colour formers, e.g. leuco dyes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/04—Direct thermal recording [DTR]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/38—Intermediate layers; Layers between substrate and imaging layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/40—Cover layers; Layers separated from substrate by imaging layer; Protective layers; Layers applied before imaging
    • 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
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/333—Colour developing components therefor, e.g. acidic compounds
    • 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
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/333—Colour developing components therefor, e.g. acidic compounds
    • B41M5/3333—Non-macromolecular compounds

Definitions

  • the present invention relates to laser markable articles and to methods of preparing such laser markable articles.
  • Various substrates for example paper, paperboard or plastics, are very often marked with information such as logos, bar codes, expiry dates or batch numbers.
  • Laser marking is typically carried out by applying a laser markable composition on a substrate followed by an image-wise laser exposure.
  • the laser markable composition may be applied on the substrate by inkjet printing, flexographic printing, rotogravure printing, offset printing or any other printing technique. Also, the laser markable composition may be applied on the substrate by any coating or spraying technique.
  • a laser markable composition typically includes a so-called optothermal converting agent that converts radiation energy into heat and a colour forming agent.
  • W02005/068207 discloses copper salts, W02007/141522 (Datalase) other metal salts such as Indium Tin Oxide and WO2015/015200 (Datalase) Tungsten Bronze.
  • WO2014/057018 disclose cyanine compounds that may act as optothermal converting agents.
  • a laser markable composition includes a colour forming agent that forms a colour upon laser marking.
  • a colour forming agent that forms a colour upon laser marking.
  • Several colour forming agents are proposed.
  • a transition metal oxide, such as molybdenum trioxide, has been disclosed in W02008/075101 (Siltech).
  • These colour forming agents are capable of forming a black colour upon laser marking.
  • Diacetylene compounds such as disclosed in WO2013/014436 (Datalase) are capable of forming multiple colours.
  • Leuco dyes are disclosed in for example WO2015/165854 (Agfa Gevaert).
  • a disadvantage of leuco dyes may be a limited stability of the dyes formed upon laser marking. It has been observed that different colours may be obtained due to alteration, for example decomposition, of the formed dyes due to the heat generated during laser marking. This may result in a limited operational window of the laser marking parameters, for example laser power, that can be used in the laser marking process.
  • Figure 1 illustrates an embodiment of a laser markable article according to the present invention.
  • a laser markable layer covers the whole surface of a support (10) while in Figure 1b the laser markable layer (20) covers part of the surface of the support (10).
  • alkyl means all variants possible for each number of carbon atoms in the alkyl group i.e. methyl, ethyl, for three carbon atoms: n-propyl and isopropyl; for four carbon atoms: n-butyl, isobutyl and tertiary-butyl; for five carbon atoms: n-pentyl, 1,1 -dimethyl-propyl, 2,2-dimethyl-propyl and 2-methyl- butyl, etc.
  • a substituted or unsubstituted alkyl group is preferably a Ci to C 6 -alkyl group.
  • a substituted or unsubstituted alkenyl group is preferably a C2 to C 6 -alkenyl group.
  • a substituted or unsubstituted alkynyl group is preferably a C2 to C 6 -alkynyl group.
  • a substituted or unsubstituted aralkyl group is preferably a phenyl or naphthyl group including one, two, three or more Ci to C 6 -alkyl groups.
  • a substituted or unsubstituted alkaryl group is preferably a C7 to C2o-alkyl group including a phenyl group or naphthyl group.
  • a substituted or unsubstituted aryl group is preferably a phenyl group or naphthyl group
  • a substituted or unsubstituted heteroaryl group is preferably a five- or six-membered ring substituted by one, two or three oxygen atoms, nitrogen atoms, sulphur atoms, selenium atoms or combinations thereof.
  • substituted in e.g. substituted alkyl group means that the alkyl group may be substituted by other atoms than the atoms normally present in such a group, i.e. carbon and hydrogen.
  • a substituted alkyl group may include a halogen atom or a thiol group.
  • An unsubstituted alkyl group contains only carbon and hydrogen atoms
  • a substituted alkyl group, a substituted alkenyl group, a substituted alkynyl group, a substituted aralkyl group, a substituted alkaryl group, a substituted aryl and a substituted heteroaryl group are preferably substituted by one or more constituents selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tertiary-butyl, ester, amide, ether, thioether, ketone, aldehyde, sulfoxide, sulfone, sulfonate ester, sulfonamide, -Cl, -Br, -I, -OH, -SH, -CN and -NO2.
  • the laser markable article is preferably substituted by one or more constituents selected from the group consisting of methyl, ethyl, n-propyl, iso
  • the laser markable article according to the present invention comprises a laser markable layer (20) including a colour forming agent and a layer adjacent to the laser markable layer including an optothermal converting agent (30).
  • Both layers referred to above are preferably contiguous to each other.
  • both layers are applied on a support (10).
  • the layer including the optothermal converting agent (30) is provided on top of the laser markable layer including the colour forming agent (20), as depicted in Figure 1.
  • a layer referred to herein may cover the whole surface of the support, as depicted in Figure 1. Flowever, the layer may also cover a part of the surface of the support as depicted in Figure 2.
  • the layers referred to are prepared by applying a laser markable composition including a colour forming agent and a composition including an optothermal converting agent on a support, as described below.
  • compositions may be aqueous compositions or solvent based compositions.
  • compositions may be radiation curable, preferably UV curable.
  • a preferred laser markable composition comprises a developing agent.
  • the laser markable composition including a colour forming agent and/or the composition including the optothermal converting agent are preferably radiation curable compositions, more preferably UV curable compositions.
  • compositions such as surfactants, wetting/levelling agents, colorants, rheology modifiers, adhesion promoting compounds, biocides or antioxidants.
  • the laser markable composition includes a colour forming agent.
  • a preferred laser markable composition includes a leuco dye and a developing agent.
  • the laser markable composition may be aqueous or non-aqueous, the latter also referred to herein as solvent based.
  • a preferred aqueous based composition includes encapsulated leuco dyes. Such aqueous compositions wherein the leuco dyes are encapsulated are disclosed in for example EP-A 3297837, EP-A 3470134 and EP-A 3470135, all from Agfa Gevaert.
  • the aqueous based composition may be radiation curable, preferably UV curable.
  • radiation curable aqueous composition are disclosed in EP-A 18196206.9 and EP-A 18196211.9 (both from Agfa Gevaert and filed on 24- 09-2018).
  • Non-aqueous laser markable compositions are disclosed in for example EP-A 3083261 (Agfa Gevaert).
  • the non-aqueous laser markable composition are preferably radiation curable, more preferably UV curable.
  • Such radiation curable compositions preferably comprise a polymerizable compound and optionally a photoinitiator and a polymerization inhibitor.
  • Composition including an optothermal converting agent
  • composition including an optothermal converting agent may be aqueous or non- aqueous, the latter also referred to herein as solvent based.
  • a preferred aqueous based composition includes an encapsulated optothermal converting agent. Especially the infrared radiation absorbing dyes described below are preferably encapsulated in an aqueous composition.
  • Such aqueous compositions wherein the optothermal converting agents are encapsulated are disclosed in for example EP-A 3297837 and EP-A 3470134.
  • the non-aqueous compositions including an optothermal converting agent are preferably radiation curable, more preferably UV curable.
  • Such radiation curable compositions preferably comprise a polymerizable compound and optionally a photoinitiator and a polymerization inhibitor.
  • both composition i.e. the laser markable composition and the composition including the optothermal converting agent are radiation curable, more preferably UV curable.
  • both solutions comprise the same polymerizable compounds and photoinitiators.
  • the laser markable composition comprises a colour forming agent, which is capable of forming a colour upon laser marking.
  • These colour forming agents are capable of forming a black colour upon laser marking.
  • Diacetylene compounds such as disclosed in WO2013/014436 (Datalase) are capable of forming multiple colours.
  • Preferred colour formers are leuco dyes, as described below.
  • a leuco dye is preferably used in combination with a developing agent.
  • a combination of different colour forming agents may be used, for example to produce different colours.
  • WO2013/068729 Datalase
  • a combination of a diacetylene compound and a leuco dye is used to produce a full colour image upon exposure to UV and IR radiation.
  • a leuco dye is a substantially colourless compound, which may form a coloured dye upon an inter- or intra-molecular reaction.
  • the inter- or intra-molecular reaction may be triggered by heat, preferably heat formed during exposure with an IR laser.
  • the laser markable layer may comprise more than one leuco dye. Using two, three or more leuco dyes may be necessary to realize a particular colour.
  • the amount of leuco dye in the laser markable layer is preferably in the range from 0.05 to 2 g/m 2 , more preferably in the range from 0.1 to 1 g/m 2 .
  • the laser markable composition preferably comprises a developing agent.
  • a developing agent is capable of reacting with a colourless leuco dye resulting in the formation of a coloured dye upon laser marking. Typically, upon laser marking a compound is released that may react with a leuco dye thereby forming a coloured dye.
  • Thermal acid generators are for example widely used in conventional photoresist material. For more information see for example “Encyclopaedia of polymer science”, 4 th edition, Wiley or “Industrial Photoinitiators, A Technical Guide”, CRC Press 2010.
  • Preferred classes of photo- and thermal acid generators are iodonium salts, sulfonium salts, ferrocenium salts, sulfonyl oximes, halomethyl triazines, halomethylarylsulfone, a-haloacetophenones, sulfonate esters, t-butyl esters, allyl substituted phenols, t-butyl carbonates, sulfate esters, phosphate esters and phosphonate esters.
  • Preferred developing agents for aqueous laser markable compositions are disclosed in EP-A 3470134, paragraph [0142] to [0149].
  • a particular preferred developing agent is a metal salt of salicylic acid, for example zinc salicylate.
  • a particularly preferred colour developing agent is zinc 3,5-bis(a-methylbenzyl) salicylate.
  • a preferred developing agents has a structure according to Formula (I)
  • R1 represent an optionally substituted alkyl group, an optionally substituted (hetero)cyclic alkyl group, an optionally substituted alkanyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted (hetero)aryl group, an optionally substituted aralkyl group, an optionally substituted alkoxy group, an optionally substituted (hetero)cyclic alkoxy group, or an optionally substituted (hetero)aryl group.
  • R2 represent an optionally substituted alkyl, an optionally substituted aliphatic (hetero)cyclic alkyl group or an optionally substituted aralkyl group;
  • R1 and Ft2 may represent the necessary atoms to form a ring.
  • the amount of developing agent in the laser markable layer is preferably in the range from 0.05 to 5 g/m 2 , more preferably in the range from 0.1 to 3 g/m 2 .
  • An optothermal converting agent generates heat upon absorption of radiation.
  • the optothermal converting agent preferably generates heat upon absorption of infrared (IR) radiation, more preferably near infrared (NIR) radiation.
  • IR infrared
  • NIR near infrared
  • Near infrared radiation has a wavelength between 750 and 2500 nm.
  • Optothermal converting agents may be an infrared radiation absorbing dye but is preferably an infrared radiation absorbing pigment, or a combination thereof.
  • a preferred inorganic infrared absorber is a copper salt as disclosed in W02005/068207 (Datalase).
  • Another preferred inorganic infrared absorber is a non-stoichiometric metal salt, such as reduced indium tin oxide as disclosed in WO2007/141522 (Datalase).
  • Particular preferred inorganic infrared absorbers are tungsten oxide or tungstate as disclosed in W02009/059900 (Datalase) and WO2015/015200 (Datalase).
  • a lower absorption in the visible region while having a sufficient absorption in the near infrared region is an advantage of these tungsten oxide or tungstate.
  • IR pigment is carbon black, such as acetylene black, channel black, furnace black, lamp black, and thermal black.
  • the amount of carbon black in the laser markable layer is preferably less than 0.1 g/m 2 , more preferably less than 0.01 g/m 2 , most preferably less than 0.005 g/m 2 .
  • IR dyes Infrared absorbing dyes
  • a narrow absorption band is also mandatory for multicolour laser marking using multiple laser each having a different emission wavelength, as disclosed in for example EP-A 3297838.
  • any IR dye may be used, for example the IR dyes disclosed in “Near-Infrared Dyes for High Technology Applications” (ISBN 978-0-7923-5101-6).
  • Preferred IR dyes are polymethine dyes due to their low absorption in the visible region and their selectivity, i.e. narrow absorption peak in the infrared region.
  • Particular preferred polymethine IR dyes are cyanine IR dyes.
  • Preferred IR dyes having an absorption maximum of more than 1100 nm are those disclosed in EP-A 2722367, paragraphs [0044] to [0083] and WO2015/165854, paragraphs [0040] to [0051].
  • IR dyes having an absorption maximum between 1000 nm and 1100 nm are preferably selected from the group consisting of quinoline dyes, indolenine dyes, especially a benzo[cd]indoline dye.
  • a particularly preferred IR dye is 5-[2,5-bis[2-[1 -(1 -methylbutyl)-benz[cd]indol-2(1 H)-ylidene]ethylidene]- cyclopentylidene]-1 -butyl-3-(2-methoxy-1 -methylethyl)- 2, 4, 6(1 H ,3H ,5H)- pyrimidinetrione (CASRN 223717-84-8) represented by the Formula IR-1 , or the IR dye represented by Formula IR-2:
  • Both IR dyes IR-1 and IR-2 have an absorption maximum Amax around 1052 nm making them very suitable for a Nd-YAG laser having an emission wavelength of 1064 nm.
  • NIR absorbing compounds are those disclosed in WO2019/007833, paragraph [0034] to [0046]. It has been observed that these NIR absorbing compounds have a better daylight stability compared to the IR dyes described above and are therefore more suitable to be used in UV curable compositions.
  • the amount of optothermal converting agent is preferably at least 10 -10 g/m 2 , more preferably between 0.0001 and 0.5 g/m 2 , most preferably between 0.0005 and 0.1 g/m 2 .
  • the laser markable composition including the color forming agent and/or the composition including the optothermal converting agent may be radiation curable compositions, preferably UV curable compositions.
  • Such radiation curable compositions comprise a polymerizable compound.
  • the polymerizable compounds may be monomers, oligomers or prepolymers.
  • the polymerizable compounds may be free radical polymerizable compounds or cationic polymerizable compounds.
  • Cationic polymerization is superior in effectiveness due to lack of inhibition of the polymerization by oxygen, however it is expensive and slow, especially under conditions of high relative humidity. If cationic polymerization is used, it is preferred to use an epoxy compound together with an oxetane compound to increase the rate of polymerization.
  • Preferred monomers and oligomers are those listed in paragraphs [0103] to [0126] of EP-A 1911814.
  • Radical polymerization is the preferred polymerization process.
  • Preferred free radical polymerizable compounds include at least one acrylate or methacrylate group as polymerizable group, referred to herein as (meth)acrylate monomers, oligomers or prepolymers. Due to their higher reactivity, particularly preferred polymerizable compounds are acrylate monomers, oligomers or prepolymers.
  • N-vinylamides such as N-vinylcaprolactam and acryloylmorpholine.
  • Particular preferred (meth)acrylate monomers, oligomers or prepolymers are selected from the group consisting of tricyclodecanedimethanol diacrylate (TCDDMDA), isobornyl acrylate (IBOA), dipropylene glycol diacrylate (DPGDA) , ethoxylated [4] bisphenol diacrylate and urethane acrylate.
  • TCDDMDA tricyclodecanedimethanol diacrylate
  • IBOA isobornyl acrylate
  • DPGDA dipropylene glycol diacrylate
  • ethoxylated [4] bisphenol diacrylate and urethane acrylate ethoxylated
  • the radiation curable laser markable composition preferably contains a photoinitiator.
  • the initiator typically initiates the polymerization reaction.
  • the photo initiator may be a Norrish type I initiator, a Norrish type II initiator or a photo-acid generator, but is preferably a Norrish type I initiator, a Norrish type II initiator or a combination thereof.
  • a preferred Norrish type l-initiator is selected from the group consisting of benzoinethers, benzil ketals, a, a -dialkoxyacetophenones, a-hydroxyalkylphenones, a-aminoalkylphenones, acylphosphine oxides, acylphosphine sulphides, a- haloketones, a-halosulfones and a-halophenylglyoxalates.
  • a preferred Norrish type ll-initiator is selected from the group consisting of benzophenones, thioxanthones, 1 ,2-diketones and anthraquinones.
  • a preferred amount of photoinitiator is 0.3 - 20 wt% of the total weight of the radiation curable composition, more preferably 1 - 15 wt% of the total weight of the radiation curable composition.
  • the radiation curable compositions may additionally contain co-initiators.
  • a preferred co-initiator is selected from the group consisting of an aliphatic amine, an aromatic amine and a thiol. Tertiary amines, heterocyclic thiols and 4- dialkylamino-benzoic acid are particularly preferred as co-initiator.
  • the most preferred co-initiators are aminobenzoates for reason of shelf-life stability of the radiation curable composition.
  • a preferred amount of photoinitiator is 0.3 - 20 wt% of the total weight of the radiation curable composition, more preferably 1 - 15 wt% of the total weight of the radiation curable composition.
  • the amount of co-initiator or co-initiators is preferably from 0.1 to 20.0 wt%, more preferably from 1.0 to 10.0 wt%, based in each case on the total weight of the radiation curable composition.
  • the radiation curable compositions may contain a polymerization inhibitor.
  • Suitable polymerization inhibitors include phenol type antioxidants, hindered amine light stabilizers, phosphor type antioxidants, hydroquinone monomethyl ether commonly used in (meth)acrylate monomers, and hydroquinone, t-butylcatechol, pyrogallol may also be used.
  • Suitable commercial inhibitors are, for example, SumilizerTM GA-80, SumilizerTM GM and SumilizerTM GS produced by Sumitomo Chemical Co.
  • the amount capable of preventing polymerization is determined prior to blending.
  • the amount of a polymerization inhibitor is preferably lower than 2 wt% of the total radiation curable laser markable composition.
  • the radiation curable laser markable compositions may contain at least one surfactant.
  • the surfactant(s) can be anionic, cationic, non-ionic, or zwitter-ionic and are usually added in a total quantity less than 5 wt%, more preferably less than 2 wt%, based on the total weight of the composition.
  • Preferred surfactants are selected from fluoro surfactants (such as fluorinated hydrocarbons) and/or silicone surfactants.
  • the silicone surfactants are preferably siloxanes and can be alkoxylated, polyester modified, polyether modified, polyether modified hydroxy functional, amine modified, epoxy modified and other modifications or combinations thereof.
  • Preferred siloxanes are polymeric, for example polydimethylsiloxanes.
  • Preferred commercial silicone surfactants include BYKTM 333 and BYKTM UV3510 from BYK Chemie.
  • Silicone surfactants are often preferred in radiation curable laser markable composition, especially the reactive silicone surfactants, which are able to be polymerized together with the polymerizable compounds during the curing step.
  • CHEMIE GMBH including BykTM-302, 307, 310, 331 , 333, 341 , 345, 346, 347, 348, UV3500, UV3510 and UV3530
  • TEGO CHEMIE SERVICE including Tego RadTM 2100, 2200N, 2250, 2300, 2500, 2600 and 2700
  • EbecrylTM 1360 a polysilixone hexaacrylate from CYTEC INDUSTRIES BV and EfkaTM-3000 series (including EfkaTM-3232 and EfkaTM-3883) from EFKA CHEMICALS B.V..
  • the laser markable composition preferably comprises at least 1 wt% of an inorganic filler, relative to the total weight of the composition.
  • inorganic fillers that may be used are selected from the group consisting of calciumcarbonate, clays, alumina trihydrate, talc, mica, and calcium sulphate.
  • an inorganic nanofiller is used to obtain optimal transparency of the laser markable composition.
  • a preferred nanofiller is nanosilica.
  • Nanosilica as referred to herein consist of amorphous silicon dioxide particles having a nano-particle size.
  • the particle size of the nanosilica is preferably in the range from 5 to 250 nm, more preferably in the range from 7.5 to 100 nm, most preferably in the range from 10 to 50 nm.
  • dispersions of nanosilica in acrylate monomers are used.
  • Such commercially available dispersions are for example the Nanocryl® nanosilica dispersions available from Evonik.
  • the amount of the inorganic filler is preferably in the range from 1 to 15 wt%, more preferably in the range from 2 to 10 wt%, most preferably in the range from 2.5 and 7.5 wt%, all relative to the total weight of the composition.
  • the amount of the inorganic filler is preferably in the range from 0.1 to 1.5 g/m 2 , more preferably in the range from 0.2 to 1 g/m 2 , most preferably in the range from 0.25 to 0.75 g/m 2 .
  • the method of preparing a laser markable article comprises the steps of applying the laser markable composition including a colour forming agent and the composition including an optothermal converting agent both as described above, on a support (10).
  • compositions may be applied in any order on the substrate.
  • the method comprises the steps of, in order:
  • compositions may be provided onto a support by co-extrusion or any conventional coating technique, such as dip coating, knife coating, extrusion coating, spin coating, spray coating, slide hopper coating and curtain coating.
  • the compositions may also be provided onto a support by any printing method such as intaglio printing, screen printing, flexographic printing, offset printing, inkjet printing, rotogravure printing, etc. Using a printing method is preferred when only a part or several parts of a support has to be provided with a laser markable layer.
  • compositions are preferably applied by flexographic printing or inkjet printing.
  • the thickness of the applied compositions is preferably 50 pm or less, more preferably 20 pm or less, most preferably 10 pm or less.
  • the method further comprises a curing step, preferably a UV curing step.
  • a curing step may be carried out after the application of each composition or may be carried out after the application of both compositions.
  • compositions may be applied on any type of surface, for example a metallic support, a glass support, a polymeric support, or a paper support.
  • the compositions may also be applied on a textile surface.
  • the support may be provided with a primer to improve the adhesion between the support and the applied layers.
  • a primer containing a dye or a pigment, for example a white primer, may also be provided on the support, for example to improve the contrast of the laser marked image.
  • the support may be a paper support, such as plain paper or resin coated paper, e.g. polyethylene or polypropylene coated paper.
  • paper boards such as white lined chipboard, corrugated (fiber) board and packaging board.
  • so-called synthetic papers such as the SynapsTM synthetic papers from Agfa Gevaert, which are opaque polyethylene terephthalate sheets, may be used as support.
  • Suitable polymeric supports include cellulose acetate propionate or cellulose acetate butyrate, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyamides, polycarbonates, polyimides, polyolefins, polyvinylchlorides, polyvinylacetals, polyethers, polysulfonamides, polylactide (PLA) and polyimide.
  • a preferred polymeric support is a biaxially stretched polyethylene terephthalate foil (PET-C foil) due to its very high durability and resistance to scratches and chemical substances.
  • PET-C foils and supports are well-known in the art of preparing suitable supports for silver halide photographic films.
  • suitable supports for silver halide photographic films for example,
  • GB 811066 (ICI) teaches a process to produce biaxially oriented polyethylene terephthalate foils and supports.
  • Another preferred polymeric support includes (co)polyesters based on cyclohexyldimethanol (CHDM).
  • CHDM cyclohexyldimethanol
  • Thermoplastic polyesters containing CHDM exhibit enhanced strength, clarity, and solvent resistance.
  • the exact properties of the polyesters vary from the high melting crystalline poly(1,4-cyclohexylenedimethylene terephthalate), PCT, to the non crystalline copolyesters with the combination of ethylene glycol and CHDM in the backbone.
  • the properties of these polyesters is also dependent on the cis/trans ratio of the CHDM monomer.
  • CHDM has low melting point and reduces the degree of crystallinity of PET homopolymer, improving its processability. With improved processability, the polymer tends to degrade less to acetaldehyde and other undesirable degradation products.
  • the copolymer with PET is known as glycol- modified polyethylene terephthalate, PETG. PETG is used in many fields, including electronics, automobiles, barrier, and medicals etc.
  • Another preferred polymeric support includes (co)polyesters based on 2,5- furandicarboxylic acid (FDCA).
  • FDCA 2,5- furandicarboxylic acid
  • Such PEF films have, compared to standard PET films, a 10x higher oxygen barrier, a 2 ⁇ 3 x higher water vapor barrier, an improved mechanical strength and are fully transparent.
  • polymeric supports include copolyesters based on isosorbide, e.g. copolymers of terephtalic acid and ethylene glycol and isosorbide.
  • the polymeric support may be a single component extrudate or co-extrudate.
  • suitable co-extrudates are PET/PETG and PET/PC.
  • the shape of the support can be a flat sheet, such as a paper sheet or a polymeric film or it can be a three dimensional object like e.g. a plastic coffee cup.
  • the three dimensional object can also be a container like a bottle or a jerry-can for including e.g. oil, shampoo, insecticides, pesticides, solvents, paint thinner or other type of liquids.
  • the laser markable composition may also be applied on a so-called shrink foil. Such a foil shrinks tightly over whatever it is covering when heat is applied.
  • shrink foils are polyolefin foils, i.e. polyethylene or polypropylene foils.
  • other shrink foils include PCV.
  • the laser markable article is prepared by the method described above.
  • the laser markable article is preferably selected from the group consisting of a packaging, a foil, a laminate, a security document, a label, a decorative object and an RFID tag.
  • the laser marking method according to the present invention is preferably used to laser mark a packaging.
  • Laser marking is typically used to add variable data, for example batch numbers, expiry dates, addressees, etc. on the packaging.
  • laser marking is carried out in-line in the packaging process.
  • the laser marked “image” on a packaging may comprises data, images, barcodes, QR codes, or a combination thereof.
  • An advantage of using laser marking in a packaging process is the ability to mark information through a wrapping foil, for example the flavour-protective foil used for cigarette packs. In such a way, variable data may be provided on the cigarette packs after the protective foil has already been provided.
  • Another preferred laser markable packaging is used for pharmaceutical packaging.
  • track and trace requirements become more and more demanding to comply with the ever evolving legislation.
  • the package may be provided with data or images in any colour.
  • a preferred packaging is folded cardboard or corrugated cardboard laminated with paper. Such packaging is preferably used for cosmetics, pharmaceuticals, food or electronics. [094] Multiple colour, even full colour, images may be obtained when the packaging is provided with multiple laser markable compositions, each containing a different leuco dye and optothermal converting agent, as disclosed in EP-A2719540 (Agfa Gevaert) and EP-A 2719541 (Agfa Gevaert).
  • the laser marking method may also be used to prepare security documents, such as for example ID cards.
  • laser markable security documents are prepared by laminating a laser markable foil or laminate, optionally together with other foils or laminates, onto one or both sides of a core support.
  • the laser markable laminate may be prepared by providing a laser markable composition according to the present invention on a support.
  • the support is described above and is preferably a transparent polymeric support.
  • the laser markable laminate may comprise more than one laser markable layers or may comprise additional layers such as an ink receiving layer, a UV absorbing layer, intermediate layers or adhesion promoting layers.
  • the laser markable laminate is typically laminated on one or both sides of a core support using elevated temperatures and pressures.
  • Preferred core supports are disclosed in WO2014/057018 (Agfa Gevaert), paragraphs [0112] to [0015].
  • the lamination temperature depends on the type of core support used.
  • lamination temperatures are preferably between 120 and 140°C, while they are preferably above 150°C - 160°C for a polycarbonate core.
  • any laser may be used in the laser marking step.
  • Preferred lasers are ultraviolet (UV) and infrared (IR) lasers, infrared laser being particularly preferred.
  • the infrared laser may be a continuous wave or a pulsed laser.
  • NIR near infrared
  • a particularly preferred NIR laser is an optically pumped semiconductor laser.
  • Optically pumped semiconductor lasers have the advantage of unique wavelength flexibility, different from any other solid-state based laser.
  • the output wavelength can be set anywhere between about 900 nm and about 1250 nm. This allows a perfect match between the laser emission wavelength and the absorption maximum of an optothermal converting agent present in the laser markable layer.
  • a preferred pulsed laser is a solid state Q-switched laser.
  • Q-switching is a technique by which a laser can be made to produce a pulsed output beam. The technique allows the production of light pulses with extremely high peak power, much higher than would be produced by the same laser if it were operating in a continuous wave (constant output) mode, Q-switching leads to much lower pulse repetition rates, much higher pulse energies, and much longer pulse durations.
  • Laser marking may also be carried out using a so-called Spatial Light Modulator (SLM) as disclosed in WO2012/044400 (Vardex Laser Solutions).
  • SLM Spatial Light Modulator
  • the radiation curable laser markable composition can be cured by exposing them to actinic radiation, such as electron beam or ultraviolet radiation.
  • the radiation curable laser markable composition is cured by exposing it to ultraviolet radiation, more preferably using UV LED curing.
  • WR is an abbreviation used for WinCon-Red, a magenta leuco dye from Connect Chemicals GmbH.
  • CpTs is an abbreviation for cyclohexyl p-toluenesulfonate with the CAS number 953- 91-3 from Chemgo.
  • Genocure DMHA is a photoinitiator from RAHN AG.
  • Omnirad 481 is a photoinitiator from IGM Resins b.v.
  • Speedcure TPO is a photoinitiator from Lambson Limited.
  • Photomer4012 is isobornyl acrylate (I BOA), a monofunctional acrylic monomer from IGM.
  • Sartomer508 is dipropylene glycol diacrylate, a difunctional acrylic monomer from Arkema.
  • Sartomer 601 E is ethoxylated [4] bisphenol diacrylate, a difunctional acrylic monomer from Arkema.
  • BYK-UV 3510 is a surface additive from BYK-Chemie GmbH.
  • CTO is an inorganic pigment of cesium tungsten oxide from Keeling & Walker Limited.
  • Cupferron AL is aluminum N-nitrosophenylhydroxylamine from WAKO CHEMICALS LTD.
  • INHIB is a mixture forming a polymerization inhibitor having a composition according to Table 1.
  • EFKA PX4733 is a high-molecular-weight dispersant from BASF SE.
  • DISP1 is a concentrated pigment dispersion prepared as follows: 100.0g of CTO pigment powder, 100.0g of dispersant EFKA PX4733 and 5.0g of INHIB stabilizer were mixed into 295. Og of Photomer4012 using a DISPERLUXTM dispenser. Stirring was continued for 30 minutes. The vessel was connected to a DynoMill-RL mill filled with 200 g of 0.4 mm yttrium stabilized zirconia beads ("high wear resistant zirconia grinding media" from TOSOH Co.). The mixture was circulated over the mill for 108 minutes with a rotation speed of 4500 t/min. During the complete milling procedure the content in the mill was cooled to keep the temperature below 60°C.
  • the resulting concentrated pigment dispersion exhibited an average particle size of 131.0nm as measured with a MalvernTM nano-S and a viscosity of 134.11mPa.s at 20°C and at a shear rate of 10 s-1.
  • OPV is a concentrated solution prepared as follow: 1 00g of DISP1 and 9.00g of
  • the solutions S1 to S3 were prepared by mixing the ingredients according to Table 2 expressed in grams. The solutions were mixed in 30ml_ brown glass flasks with a plastic screw cap and stirred at 350 rpm with a magnetic stirring bar at room temperature overnight.
  • Sample C1 was prepared by applying a single layer on the substrate, whereas samples 11 and I2 were prepared by applying two layers.
  • the first layer was cured before applying the second one.
  • the first layer is touching the substrate, whereas the second layer is above the first one and therefore in contact with air.
  • the coatings were subsequently exposed to an infrared laser.
  • the infrared laser was an optically pumped semiconductor laser emitting at 1064 nm (Genesis MX 1064-10000 MTM from COH ERENT) with a maximum power of 4.0 W, a spot size in X of 78.9 pm at 1/e 2 and a spot size in Y of 90.6 pm at 1/e 2 .
  • the used laser settings are depicted in Table 4.
  • the addressability is the distance between dots centre to centre and the energy density was calculated assuming no overlap according to the following formula:
  • X-RiteTM eXact spectrophotometer in the range from 400 up to 700 nm in steps of 10 nm.
  • the CIE L * a * b * coordinates were determined for a 2° observer and a D50 light source.
  • the densities were measured with the density standard ANSI A.
  • the densities Dc, Dm, Dy and Db correspond respectively to the densities in cyan, magenta, yellow and black according to the density filters of ANSI A.
  • the density Dm was of more interest because here the laser marks are magenta. Measurements were done for both the laser marks and the areas of the inks that were not exposed to the laser (background).
  • magenta colour formed during laser marking may alter (“burn”) due to the heat formed during the laser exposure.
  • the laser marked colour then changes and becomes more “yellow”.
  • the colour does not seem to sublimate (white smoke), possibly further increasing the colour density (Dm).

Abstract

L'invention concerne un article marquable au laser (1) qui comprend une couche marquable au laser comportant un agent de formation de couleur (20) et une couche adjacente à la couche marquable au laser comportant un agent de conversion optothermique (30).
PCT/EP2020/077926 2019-10-11 2020-10-06 Articles marquables au laser WO2021069406A1 (fr)

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WO2023053925A1 (fr) * 2021-09-30 2023-04-06 富士フイルム株式会社 Encre d'enregistrement par jet d'encre et procédé d'enregistrement par jet d'encre
WO2023170288A1 (fr) * 2022-03-11 2023-09-14 Datalase Ltd. Produit en plastique

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