WO2019152671A1

WO2019152671A1 - Laser-markable transparent varnish composition, laminate comprising said composition and device comprising this laminate

Info

Publication number: WO2019152671A1
Application number: PCT/US2019/016087
Authority: WO
Inventors: Laurence Bes; Anthony Gallo; Frédéric BOUSSELLIER
Original assignee: Itw Covid Security Group Inc.
Priority date: 2018-02-01
Filing date: 2019-01-31
Publication date: 2019-08-08
Also published as: FR3077298A1; FR3077298B1

Abstract

The invention relates to a laser-markable transparent varnish composition, a laminate comprising a layer of laser-markable transparent varnish composition, marked or unmarked, and a device comprising this laminate. The composition of the laser-markable is characterized in that it comprises: a) between 50% inclusive and 100% exclusive, by weight, with respect to the total weight of the composition, of at least one thermosetting and/or photocurable polymer, b) between 2% inclusive and 20% inclusive, and preferably between 2% and 15% inclusive, by weight, with respect to the total weight of the composition, of particles of at least one reactant sensitive to laser radiation chosen from the group consisting of titanium dioxide (TiO) particles, bismuth oxide (Bi₂O₃) particles and titanium oxide (TiO₂) particles covered with an antimony-doped tin oxide complex (Sn/Sb)O₂, and of their mixtures, and in that, when polymerized and dried, this laser-markable varnish composition has a transparency of greater than 80%, determined according to the ASTM D1003-00 method at the visible wavelengths. In particular, the invention finds application in the field of securing and authenticating documents.

Description

LASER-MARKABLE TRANSPARENT VARNISH COMPOSITION, LAMINATE COMPRISING SAID COMPOSITION AND DEVICE COMPRISING THIS

LAMINATE

[0001] The invention relates to a laser-markable transparent varnish composition, a laminate comprising a layer of laser-markable transparent varnish composition, marked or unmarked, and a device comprising this laminate.

[0002] Due to their nature and/or the rights they may confer, certain documents such as passports, ID cards or driver’s licenses must be protected against falsification and/or forgery attempts and/or to guarantee authentication and/or to guarantee their integrity, i.e. the fact that they have not been modified or altered.

[0003] Other documents require the same protection, especially bank cards, customer loyalty cards, bank checks, diplomas, certificates, travel tickets, access cards, badges, labels, legal documents, contracts, legal registers, cadastral plans, fiduciary documents, banknotes, etc.

[0004] The data contained in these documents may be personal data such as name, address, marital status, photographs, or common entries such as security details, matrixes, frames, field names, seals, holograms, signatures, etc.

[0005] In the following text, “personal data” or “sensitive data” shall refer to information that must be authenticated, in particular last name, first and middle name(s), photos etc., and“security data” shall refer to data authenticating personal data. Security data may be seals, holograms, signatures, marks printed with security ink, monochromatic or polychromatic photo luminescent ink, ink only visible under ultraviolet or infrared light, etc. [0006] In the attached figures, personal data are labeled 3 and security data are labeled 4.

[0007] In the figures:

[0008] FIG. 1 is a schematic representation of a prior art passport page containing personal data and security data,

[0009] FIG. 2 is a schematic representation of a prior art authentication card or passport with multiple layers containing personal data and security data,

[0010] FIG. 3 is a schematic representation of a laminate according to the invention,

[0011] FIG. 4 is a schematic representation of a first embodiment of a device according to the invention,

[0012] FIG. 5 is a schematic representation of a second embodiment of a device according to the invention,

[0013] FIG. 6 is a schematic representation of a third embodiment of a device according to the invention,

[0014] FIG. 7 is a schematic representation of a fourth embodiment of a device according to the invention, and

[0015] FIG. 8 is a photo of a device according to the invention.

[0016] Presently, in case of passports for example, as shown schematically in FIG. 1, the sensitive data labeled 3 in FIG. 1 is first printed on the surface of the paper, labeled 5 in FIG.1, of the passport, by inkjet or by xerography and thereafter, using an adhesive not shown, a film labeled 6 in FIG. 1 is affixed, transparent and comprising security data, labeled 4 in FIG. 1, on the printed personal data 3.

[0017] However, the printed personal data 3 may easily be modified. [0018] In fact, the film 2 containing the security data 4 may be removed by solubilizing the adhesive or softening of the latter on a hotplate. It then becomes easy to modify the original personal data 3 by solubilizing, when they have been printed by inkjet printing or by abrasion if they were printed by xerography, and to replace them with new personal data.

[0019] In recent years, ID cards and passport pages have emerged on the market that are made of multilayer thermoplastic materials of polycarbonate type, in particular such personalized with laser type DPSS (“diode pulsed solid state”) to Nd:YV0₄, 1064 nm- power 12 W, such as model XP24 of the company IXLA.

[0020] A schematic representation of these ID cards or passport pages is shown in FIG. 2

[0021] They comprise at least one white layer, labeled 11 in FIG. 2, to improve the legibility of the personal data 3.

[0022] One layer, labeled 10 in FIG. 2, containing security data 4 is superimposed on layer 11.

[0023] One layer, labeled 9 in FIG. 2, generally made of polycarbonate (PC) containing a reactant sensitive to laser radiation, is superimposed on layer 10.

[0024] Personal data are etched into layer 9 using laser radiation.

[0025] A protective layer, labeled 8 in FIG. 2, is deposited on layer 9.

[0026] In a symmetrical manner, according to the symmetry axis labeled X-X in FIG. 2, the same superposition of white layer- layer possibly containing security data 4 - layer generally made of polycarbonate (PC), containing a reactant sensitive to laser radiation - protective layer is achieved. [0027] The laser radiation causes a carbonization of the sensitive reactant and of the polycarbonate, creating a black coloration by carbonization of the plastic material.

[0028] The advantage of this type of cards or passport pages is, on the one hand, that the personal data 3 are etched inside layer 9, which makes them practically non-modifiable, and, on the other hand, that these personal data 3 can be engraved on the card or the finished page.

[0029] The terms“laser-markable” or“laser-etchable” mean, in the present text, that the object that is said to be laser-markable or laser-etchable contains a reactant sensitive to laser radiation, said reactant and a part of the area around this reactant taking on a black color under the effect of laser radiation.

[0030] However, for a passport application, this type of multilayer laminates, made of laser-markable polycarbonate sheets, have the disadvantage of being thick and of requiring the use of high temperatures (typically a temperature in the range of 150 °C to 200 °C) and high pressures (typically in the range of 10⁶ Pa to 2.10⁶ Pa) during their manufacture, which is performed by gluing/lamination at high temperature and high pressure.

[0031] Furthermore, they do not allow integrating a large number of security data to authenticate the document, since such data may interfere with the laser radiation.

[0032] French Patent Application 3,022, 183 Al describes such a data support comprising a plurality of superimposed layers including a layer comprising a marking agent sensitive to laser radiation, in particular infrared laser radiation.

[0033] This so-called laser marking layer may be formed of a varnish printed with an ink composition incorporating the marking agent sensitive to laser radiation, for example carbon black with a particle size of 95 nm, or mica particles covered with antimony-doped tin oxide, calcined powders of co-precipitated mixed oxides of tin and antimony, mixed oxides of copper or tin containing phosphorus. [0034] The laser-marking layer is deposited on a sheet, or between two sheets of a plastic material, usually polycarbonate.

[0035] For a passport application, this type of laminate with polycarbonate sheets must not only be laminated at high temperature and at high pressure, as stated above, but must also have a thickness greater than 100 pm for a sufficiently visible black marking, since this thickness provides stiffness and bulk for the final passport.

[0036] The invention aims to solve the problems of thickness, lack of flexibility, bulk and transparency of security data supports of prior art laminates, in particular security laminates, comprising a layer of laser-markable varnish covering the data to be authenticated in full or in part of the prior art.

[0037] Reducing the thickness of these laminates of the prior art to increase their flexibility and transparency may seem at first sight simple.

[0038] However, when the thickness of the laminate, and more specifically of the laser- markable varnish layer, is reduced, it becomes very difficult to have a contrasting marking because the amount of laser-markable pigments contained in this varnish composition must be reduced to maintain transparency to the etched layer of varnish, since this layer of varnish must also allow to maintain a good resolution of the image (personal data, photographs, security data) to allow the reading of the data printed on the support on which the security laminate of the invention is to be placed.

[0039] “Transparent” or “transparence” is understood in the invention as a transparence of 80% in the visible wavelength range, determined according to ASTM D1003-00, using a 310 Sheen reference reflectometer manufactured by the manufacturer Labomat Essor.

[0040] The transparency of the laser-markable varnish is an important concept because the varnish must not interfere with the view of the security data present in the security laminate, above or below the laser-markable varnish layer as well as the security data present on supports such as paper passport such as watermarks, iridescent background printing, microtext printing, etc.

[0041] Contrast” is understood in the invention as a black density greater than 1.3. Optical density refers to the decimal logarithm of opacity, i.e. the inverse of transparency.

[0042] The black density is measured with a reflection densitometer measuring absorbed light according to ISO 13655 using a densitometer of the manufacturer Mettler Toledo called Densito 30PX.

[0043] The laser marking in the varnish of the invention should have a black density greater than 1.3, preferably greater than 1.5.

[0044] Good resolution” is understood in the invention as a resolution greater than 500 dpi. The resolution of an image is the dot density per unit length expressed in dpi (dot per inch).

[0045] The laser marking in the varnish makes it possible to mark photos with a resolution greater than 500 dpi.

[0046] The term“laser-markable” varnish or“laser-engravable varnish” is understood as a transparent varnish (with a transparency greater than 80% measured according to ASTM D1003-00) which, once dried, is capable of being colored black after exposure to laser radiation either by blackening of the reactants sensitive to laser radiation present in the composition of the varnish or by carbonization of the surrounding plastic material to reactants sensitive to laser radiation present in the composition of the varnish.

[0047] Lasers that can be used for marking are UV or IR lasers.

[0048] As 355 nm UV laser, it is possible to use for example a Trumpf laser, the Trumark 6330 model (UV, Marking laser DPSS-diode pulsed solid state - Nd: YV04 - 355nm - Power <10 watt), which is available either in a compact version for static marking or integrated in the laser head on a production machine for continuous marking. [0049] The marking parameters may be for example:

• Bitmap photo: power: 5%, speed: 800 mm/s, frequency: 20 KHz

• Text: power: 55%, speed: 500 mm/s, frequency: 20 KHz

• Duration of photo-marking: l40s.

[0050] As 1064 nm IR laser, it is possible to use for example an IXLA laser, model XP24 (IR - Marking laser: DPSS-pulsed diode solid state -Nd: YVO4-l064nm-power: 12 Watts).

[0051] The marking parameters may be for example:

• Bitmap photo: power: 0 watt, speed: 600 mm/s, frequency: 10 KHz

• Small text: power: 25 watt, speed: 475 mm/s, frequency: 15 KHz

• Standard text: power: 28 watt, speed: 550 mm/s, frequency: 10 KHz

• Duration of the photo-marking: 30 s

[0052] Visible wavelengths refer to wavelengths between 400 and 800 nm.

[0053] UV wavelengths refer to wavelengths between 100 and 400 nm.

[0054] IR wavelengths refer to wavelengths between 800 and 1000 nm.

[0055] The inventors have now discovered that, surprisingly, to obtain security laminates of small thickness with a good marking definition, transparent in the visible wavelength range as to not mask or deform the secured data, it is necessary to use a laser marking varnish composition comprising specifically at least one thermosetting and/or photocurable polymer, in which particles of a reactant sensitive to laser radiation, i.e. that change color during irradiation by a UV and/or IR laser, must be uniformly dispersed, while said laser- sensitive reactant must be very precisely selected from titanium dioxide particles, bismuth oxide particles, and antimony-doped tin-covered T1O2 particles and their mixtures. [0056] Indeed, when carbon black is used, as in the prior art, to obtain a sufficient contrast, it is necessary to put a large amount of carbon black in the polymerizable polymer, which affects the transparency of the varnish layer.

[0057] This problem is solved in the invention by using titanium dioxide (T1O2) particles with a particle size of about 10 nm.

[0058] Particles of bismuth oxide (B12O3) with a particle size of about 10 pm may also be used successfully.

[0059] Titanium oxide (T1O2) particles covered with an antimony-doped tin oxide (SnCkiSb) (antimony-doped tin oxide complex (Sn/Sb)02) may also be advantageously used as reactant sensitive to laser radiation.

[0060] Such T1O2 particles covered with antimony-doped SnCk are described in patent application WO 2017/07645.

[0061] The particles of T1O2 measure between 15 nm and 20 nm determined by electron diffraction according to the Scherrer formula, the B12O3 particles measure 10 pm for 80% by number of particles determined by analysis of their laser diffraction scattering, the titanium oxide particles (T1O2) of an antimony-doped tin oxide complex (Sn/Sb)02 measure 1 pm for 80% by number of particles determined by analysis of their distribution by laser diffraction scattering.

[0062] The amount of reactant sensitive to laser radiation may vary between 2% inclusive, in order to have sufficient coloration, and 20% excluded, preferably between 2% inclusive and 15% exclusive, by weight relative to the total weight of the engravable varnish composition of the invention.

[0063] These laser-sensitive reactant particles are dispersed in a thermosetting and/or photocurable polymer that is also transparent to visible wavelengths when polymerized. [0064] Thermosetting polymer is understood as a polymer that hardens by polymerization of the monomers and/or oligomers forming a cross-linked network under heat.

[0065] Thermosetting polymer is understood as a polymer that hardens by polymerization of the monomers and/or oligomers forming a cross-linked network under UV radiation.

[0066] In fact, the inventors have discovered that when a thermoplastic polymer is used, the laser-irradiated reactant particles sensitive to laser radiation to form the desired security marking scatter beyond the irradiation zone of the laser, which harms the definition of the engraving.

[0067] Without wishing to be bound by this theory, the inventors believe that this “scattering” effect of the laser irradiation zone in the pigment is due to the fact that a thermoplastic polymer softens and even melts during laser irradiation.

[0068] Thus, the inventors have developed a laser-markable varnish composition comprising: a) between 50% inclusive and 100% exclusive, by weight, with respect to the total weight of the composition, of at least one thermosetting and/or photocurable polymer, b) between 2% inclusive and 20% inclusive, and preferably between 2% and 15% inclusive, by weight, with respect to the total weight of the composition, of particles of at least one reactant sensitive to laser radiation chosen from the group consisting of titanium dioxide (TiOS) particles, bismuth oxide (BriCb) particles and titanium oxide (T1O2) particles covered with an antimony-doped tin oxide complex (Sn/Sb)02, and of their mixtures, and in that, when polymerized and dried, this laser-markable varnish composition has a transparency of greater than 80%, determined according to the ASTM D 1003 -00 method at the visible wavelengths. [0069] Other reactants sensitive to laser radiation, such as carbon black, may be used in combination of the reactants sensitive to laser radiation defined above.

[0070] Preferably, said at least one thermosetting and/or photocurable polymer comprises at least 7% by weight, with respect to the total weight of the final composition, of monomers having a number of reactive functional groups of greater than or equal to 3.

[0071] Reactive functions are understood to mean in the invention the functions present on the monomer that are useful for the formation of a cross-linked network by polymerization of this monomer with other monomers under heat or UV radiation.

[0072] These reactive functional groups are in the invention preferably isocyanate or (meth)acrylate groups.

[0073] Monomers with isocyanate groups that can be used in the varnish composition of the invention include the following monomers: isocyanate, polyisocyanate, toluene diisocyanate (TDI), toluene diisocyanate trimethylolpropane, toluene diisocyanate isocyanurate, 4,4’-diphenylmethane diisocyanate, hexamethylene diisocyanate (HDI), hexamethylene diisocyanate biuret, hexamethylene isocyanurate, isophorone diisocyanate (IPDI), isophorone diisocyanate isocyanurate (IPDI), and their mixtures.

[0074] Examples for such monomers are those sold under the names DesmodurN 100, N75, N3200, N3300, N3390, N3600, N3790, N3800, XP2675, E XP 2747, XP2599, E3265, E3370, Z4470, XP2489, XP2838, XP2763 by the company Covestro, Lervekusen, Germany.

[0075] Monomers with acrylate groups that can be used in the varnish composition of the invention include the following monomers: tri(meth)acrylate, tetraacrylate, pentacrylate, hexaacrylate, pentaerythritol triacrylate (PETA), trimethylolpropane triacrylate (TMPTA), ethoxylated trimethylolpropane triacrylate (EO-TMPTA), trimethylolpropane trimethacrylate (TMPTMA), glycerol triacrylate (GPTA), glycerol trimethacrylate (GTMA), pentaerythritol tetraacrylate (PETTA), dipentaerythritol pentacrylate (DiPEPA), ditrimethylolpropane tetraacrylate (DiTMPTTA), dipentaerythritol hexaacrylate (DPHA), hexafunctional urethane acrylate, their ethoxylated versions and their mixtures.

[0076] Examples for such monomers with acrylate functions are the monomers sold under the name SARTOMER CN975 by the company Arkema, and the monomers sold under the names OMERATE of the company KPX green chemical and PHOTOMER of the company IGM.

[0077] Preferable for use in the invention is a polymer comprising at least 7% by weight, with respect to the total weight of the final composition, of ethoxylated trimethylolpropane triacrylate monomers (EO-TMPTA).

[0078] The laser-markable varnish composition of the invention may further comprise:

- a solvent for the polymer a), preferably in an amount of between 10% inclusive and 25% exclusive, by weight, relative to the total weight of the composition,

- a diluent of the polymer a), preferably in an amount between 10% inclusive and 25% exclusive, by weight, relative to the total weight of the composition,

- a ETV absorber, preferably in an amount between 2.5% inclusive and 10% exclusive, by weight, relative to the total weight of the composition,

- a polymerization initiator of the polymer a), preferably in an amount between 2.5% inclusive and 10% exclusive, by weight, relative to the total weight of the composition.

[0079] The invention also proposes a laminate, in particular a security laminate.

[0080] A schematic representation of an embodiment of a laminate according to the invention is shown in FIG. 3. [0081] This laminate, labeled 6 in FIG. 3, comprises a substrate, labeled G in FIG. 3, covered by a laser-markable layer, labeled 2 in FIG. 3, according to the invention.

[0082] The use of an adhesive layer, labeled 20 in FIG. 3, may be necessary to join layer 2 to the surface of the substrate 1’ .

[0083] Even though in FIG. 3 the layer 2 only covers a sole area of the surface of the substrate G, it will be readily understood by a person skilled in the art that the layer 2 may cover the entire surface of the substrate 1’ or several areas of the surface of the substrate l\

[0084] The substrate G may contain personal data 3 and/or security data 4 as shown in FIG. 3, or may not contain such.

[0085] The substrate G is transparent just like layer 2, because the laminate of the invention is intended to be affixed on a document to be authenticated.

[0086] The substrate G may be, for example, polyethylene terephthalate (PET), polyvinyl chloride (PVC), polyethylene terephthalate glycol (PETG), polycarbonate (PC) or polyester co-extruded polycarbonate (PEC) or any desired material.

[0087] The substrate V may also be a varnish protection layer with a different composition than the laser-markable varnish, such as holographic varnishes sold by the company ITW Covid called Transfilm^® or the varnish sold by the company Tiflex called 3Y0530 varnish S3HN1^®.

[0088] In this case, the varnish protection layer is deposited on a detachable film that will be removed.

[0089] This detachable film is different from the detachable substrate V detachable described below, even though it may be made from the same materials. [0090] Since the detachable film is meant to be removed, it does not have to be transparent, but it may be.

[0091] The laminate of the invention may be a laminate in which layer 2 is engraved by an end user with the desired personal data 3 and optionally with the security data 4, or a laminate as presented in FIG. 3 with the desired security data 4 engraved and optionally the personal data 3.

[0092] The substrate G may be detachable.

[0093] As an example for a detachable substrate G, mention may be made of the PS film sold by the company Vitasheet Group (Italy) called Robbex 515PH, a layer of a detachment aid agent, such as a PET layer, on which a polyethylene wax or a l20g/m² paper based layer coated on both sides with a high density polyethylene film sold under the name Captive 600/105 by Loparex BV (Apeldoom, The Netherlands) is deposited, making it possible to detach it from layer 2 to deposit layer 2 only on the document (device) to be secured.

[0094] The substrate G of the laminate 6 according to the invention is preferably a flexible material, with low thickness, i.e. a thickness between 10 and 250 pm, preferably between 10 and 100 pm, and the thickness of layer 2 of markable varnish according to the invention is between 5 and 30 pm, preferably 25 pm.

[0095] The laminate 6 in accordance with the invention has a maximum thickness of 300 pm and a minimum thickness of 15 pm if no adhesive or detachment aid agent is used.

[0096] Preferably, laminate 6 according to the invention has a maximum thickness of 150 pm and a minimum thickness of 25 pm.

[0097] Laminate 6 may be applied to the desired data support (passport, ID card, bank card, etc.) by any known technique.

[0098] However, preferably it will be applied by adhesion to the data support. [0099] For this purpose, preferably, the laminate of the invention further comprises, on the surface of the substrate not covered with the varnish layer according to the invention, an adhesive layer.

[00100] This adhesive layer is a layer of self-adhesive or heat sealable or pressure sensitive adhesive.

[00101] The invention also provides a device, labeled 7 in FIG. 4 and 7 'in FIG. 5, comprising a support, labeled 5 in FIGS. 4 and 5, coated with the laminate according to the invention or directly with the laser-marking varnish composition according to the invention.

[00102] This support 5 may already contain personal data 3 and/or security data 4 printed or engraved or stamped.

[00103] It can be made of paper, polyvinyl chloride (PVC), polycarbonate, etc.

[00104] Such a device is in particular a passport, an ID card, a bank card, a bank note.

[00105] A first embodiment of a device according to the invention is shown schematically in FIG. 4.

[00106] It comprises a support 5 containing personal data 3, covered with a layer 2 of a laser-marking varnish composition according to the invention.

[00107] In the device 7 shown in FIG. 4, the layer 2 does not contain data, which must then be introduced by the end user.

[00108] A second embodiment of a device according to the invention is shown schematically in FIG. 5, where it is labeled 7’.

[00109] It comprises a support 5 covered with a layer of adhesive, labeled 20 in FIG. 5, containing security data 4. [00110] The layer 20 is covered by a layer 2 of a laser-markable varnish composition according to the invention.

[00111] In device 7’ shown in FIG. 5, layer 2 does not contain data, which must then be introduced by the end user.

[00112] The device 7’ shown in FIG. 5 further comprises the substrate 1’ of the laminate 6 used.

[00113] This substrate G may be detachable.

[00114] It may also be a varnish protection layer.

[00115] The support 5 has preferably a thickness between 100 pm and 1000 pm.

[00116] The support 5 may be paper, passport paper, security paper, synthetic paper, paper made from polyvinyl chloride (PVC), polyethylene terephtalate glycol (PETG), polycarbonate (PC), PET, etc.

[00117] The laser-markable varnish layer may be deposited on the substrate G using any technique known to the person skilled in the art such as silk-screen, flexographic, offset or photoetched printing, etc.

[00118] In order to better facilitate an understanding of the invention, we will now describe several examples of implementations purely for illustration purposes and not to limit the disclosure.

[00119] Example 1: Varnish composition according to the invention, which can be marked with a UV laser at 355 nm.

[00120] This varnish is composed of 54% by weight, relative to the total weight of the composition, of an acrylate resin called photomer 5435 sold by the company IGM Resins (Fontainebleau, France), 15% by weight, relative to the total weight of the composition of oxybis (methyl-26 l-ethanediyl) diacrylate called photomer 4226TF sold by the company IGM Resins (Fontainebleau, France), 7% by weight, relative to the total weight of the ethoxylated trimethylolpropane triacrylate composition (EO-TMPTA) called photomer 4149TF sold by the company IGM Resins (Fontainebleau, France), 10% by weight, relative to the total weight of the composition of l,6-hexanediol diacrylate called photomer 4017 sold by the company IGM Resins, 2% by weight, relative to the total weight of the composition of ethyl, phenyl (2,4,6-trimethyl benzoyl) phosphinate called Omnirad 819 sold by IGM Resins, 2% by weight, relative to the total weight of the composition of 2- hydroxy-2-methylpropiophenone called Omnirad 1000 sold by the company IGM Resins, 10% by weight, relative to the total weight of the composition, of T1O2 powder with a particle size of 10 nm called RM300 of the Hombitec range produced by Sachtleben (Poli, Finand).

[00121] Example 2: Varnish composition according to the invention, which can be marked with an IR laser at 1064 nm.

[00122] This varnish is composed of 55% by weight, relative to the total weight of the composition, of an acrylate resin called photomer 5435 sold by the company IGM Resins (Fontainebleau, France), 15% by weight, relative to the total weight of the composition of oxybis (methyl-26 l-ethanediyl) diacrylate called photomer 4226TF sold by IGM Resins (Fontainebleau, France), 9% by weight, relative to the total weight of the ethoxylated trimethylolpropane triacrylate composition (EO- TMPTA) called photomer 4149TF sold by the company IGM Resins (Fontainebleau, France), 10% by weight, relative to the total weight of the composition, of l,6-hexanediol diacrylate called photomer 4017 sold by the company IGM Resins, 2% by weight, relative to the total weight of the composition of ethyl, phenyl (2,4,6-trimethyl benzoyl) phosphinate called Omnirad 819 sold by IGM Resins, 2% by weight, relative to the total weight of the composition of 2-hydroxy-2- methylpropiophenone called Omnirad 1000 sold by the company IGM Resins, 7% by weight, relative to the total weight of the composition, B12O3 powder with a particle size of 10 pm called Iriotec 8826 produced by Merck (Darmstadt, Germany). [00123] Example 3: Varnish composition according to the invention, which can be marked with an IR laser at 1064 nm.

[00124] This varnish is composed of 54% by weight, relative to the total weight of the composition, of an acrylate resin called photomer 5435 sold by the company IGM Resins (Fontainebleau, France), 15% by weight, relative to the weight total of the composition of oxybis (methyl-26 l-ethanediyl) diacrylate called photomer 4226TF sold by the company IGM Resins (Fontainebleau, France), 14% by weight, relative to the total weight of the ethoxylated trimethylolpropane triacrylate composition (EO-TMPTA) called photomer 4149TF sold by the company IGM Resins (Fontainebleau, France), 10% by weight, relative to the total weight of the composition, l,6-hexanediol diacrylate called photomer 4017 sold by the IGM Resins company, 2% by weight, relative to the total weight of the composition of ethyl, phenyl (2,4,6-trimethylbenzoyl) phosphinate called Omnirad 819 sold by the company IGM Resins, 2% by weight, relative to the total weight of the composition, of 2- hydroxy-2-methylpropiophenone called Omnirad 1000 sold by IGM Resins, 2% by weight, relative to the total weight of the composition, of titanium oxide powder covered with d an antimony-doped tin oxide complex with a particle size of 1 pm called Iriotec 8850 produced by the company Merck (Darmstadt, Germany).

[00125] Comparative Example 1: Varnish composition comprising the same reactant sensitive to laser radiation as the composition of Example 3 but not comprising a thermosetting and/or photocurable polymer.

[00126] In this example, a copolymer of methyl methacrylate was used as a transparent polymer: a thermoplastic polymer sold by the company Dow Chemical (Midland, USA) under the name Paraloid B^®. 50% by weight, based on the total weight of the composition, of this copolymer were used. As solvent, 30% by weight, relative to the total weight of the composition, Dowanol™ DPM monomethyl dipropylene glycol ether sold by Dow Chemical (Midland, USA) was used. This composition additionally contains 10% by weight, relative to the total weight of the composition, of ethyl 3-ethoxypropanoate called Ucar™ ester EEP sold by Dow Chemical (Midland, USA) and 2% by weight, by relative to the total weight of the composition, titanium oxide fine powder covered with an antimony-doped tin oxide complex with a particle size of 1 pm called Iriotec 8850 produced by Merck (Darmstadt, Germany).

[00127] Comparative Example 2: Varnish composition comprising the same sensitive photocurable polymer composition of Example 3 but comprising a reactant sensitive to laser radiation other than those of the invention.

[00128] This varnish is composed of 55% by weight, relative to the total weight of the composition, of an acrylate resin called photomer 5435 sold by the company IGM Resins (Fontainebleau, France), 15% by weight, relative to the total weight of the composition of oxybis (methyl-26 l-ethanediyl) diacrylate called photomer 4226TF sold by IGM Resins (Fontainebleau, France), 14% by weight, relative to the total weight of the ethoxylated trimethylolpropane triacrylate composition (EO- TMPTA) called photomer 4149TF sold by the company IGM Resins (Fontainebleau, France), 10% by weight, relative to the total weight of the composition of l,6-hexanediol diacrylate called photomer 4017 sold by the company IGM Resins, 2% by weight, relative to the total weight of the composition of ethyl, phenyl (2,4,6-trimethyl benzoyl) phosphinate called Omnirad 819 sold by IGM Resins, 2% by weight, relative to the total weight of the composition of 2-hydroxy-2- methylpropiophenone called Omnirad 1000 sold by IGM Resins, 2% by weight, relative to the total weight of the composition, of fine mica powder covered with an oxide complex antimony-doped tin with a particle size of 15 pm called Iriotec 8825 produced by Merck (Darmstadt, Germany).

[00129] Comparative Example 3: Varnish composition comprising the same sensitive photocurable polymer composition of Example 3 but comprising a reactant sensitive to laser radiation other than those of the invention.

[00130] This varnish is composed of 47% by weight, relative to the total weight of the composition, of an acrylate resin called photomer 5435 sold by the company IGM Resins (Fontainebleau, France), 15% by weight, relative to the total weight of the composition of oxybis (methyl-26 l-ethanediyl) diacrylate called photomer 4226TF sold by IGM Resins (Fontainebleau, France), 14% by weight, relative to the total weight of the ethoxylated trimethylolpropane triacrylate composition (EO- TMPTA) called photomer 4149TF sold by the company IGM Resins (Fontainebleau, France), 10% by weight, relative to the total weight of the composition of l,6-hexanediol diacrylate called photomer 4017 sold by the company IGM Resins, 2% by weight, relative to the total weight of the composition of ethyl, phenyl (2,4,6-trimethyl benzoyl) phosphinate called Omnirad 819 sold by IGM Resins, 2% by weight, relative to the total weight of the composition of 2-hydroxy-2- methylpropiophenone called Omnirad 1000 sold by the company IGM Resins, 10% by weight, relative to the total weight of the composition of fine mica powder covered with an oxide complex of antimony-doped tin with a particle size of 15 pm called Iriotec 8825 produced by Merck (Darmstadt, Germany).

[00131] Example 4: Making of a device according to the invention.

[00132] A protective varnish based on polyurethane comprising a varnish base called 3Y0530 varnish S3HN1^® (screen printing product) sold by the company Tiflex (France) and a catalyst called 3X9096^® sold by the company Tiflex is printed on a polystyrene transfer support sold by the company Vitasheet Group (Italy) called Robbex 515PH^®. The added amount of this reference catalyst is 53 parts by volume per 100 parts by volume of protective varnish.

[00133] A print is performed in solid silk screen, mesh count 77 threads/cm, so that the layer of protective varnish deposited has a thickness between 8 pm and 12 pm.

[00134] The laser-markable varnish composition obtained in Example 1 is deposited on the protective varnish.

[00135] This varnish composition according to the invention is deposited by way of solid printing on the entire surface of the protective varnish, mesh count 77 threads/cm or 120 threads/cm and in at least two layers. [00136] The varnish of the varnish composition of the invention can be printed on the entire surface of the protective lacquer or only on a part thereof.

[00137] It is possible to print on the layer of the varnish composition of Example 1 notices with security inks of different types, invisible fluorescent, optically variable or dichroic, thermochromic, photochromic, etc. as known in the art.

[00138] Each layer of the laminate is dried prior to printing the next layer.

[00139] The laminate of the invention is finalized by adding a heat sealable adhesive layer called 3YI836NF^® (screen printing product) sold by the company Tiflex.

[00140] This laminate is integrated, stitched, into a passport opposite of page 2 which must receive the personal data.

[00141] Page 2 can be customized, or partially customized by conventional customization processes, inkjet, xenography, etc.

[00142] The laminate of the invention is then laminated on page 2 in a passport type laminator.

[00143] Model 6061P from Thermal Laminating Corporation, Evanston, Israel was used here. After removal of the polystyrene transfer support, a thin laminate, 10 to 20 pm thick is obtained on page 2 of the passport.

[00144] The customization of the laminate of the invention is then carried out by UV laser marking at 355 nm of the markable varnish layer of the invention directly on page 2.

[00145] The marking is performed inside the film in the varnish layer, which increases security: it is not possible to take off or detach this laminate without completely destroying the marking.

[00146] Example 5: Making of a laminate according to the invention. [00147] A protective varnish is printed using UV curable screen printing called UV 3x4708 from Tiflex (Poncin, France) on 120 g/m² paper, coated on both sides with a high density polyethylene film called Captive 600/105 from Loparex BV (Apeldoorn, The Netherlands). This is a solid print with a mesh of 150 threads/cm, so as to form a film with a thickness in the range of 5 pm.

[00148] The varnish composition obtained in Example 3 is printed on this protective varnish. The printing is carried out as a solid print on the entire surface of the varnish, mesh count 77 threads/cm or 120 threads/cm and in at least two layers.

[00149] The composition of the varnish of Example 2 could of course, and as will be apparent to the person skilled in the art, be applied only on a portion of the protective varnish.

[00150] On the varnish composition of Example 3, printed patterns may be deposited using security inks of different types, invisible fluorescent, optically variable or dichroic, thermochromic, photochromic, etc.

[00151] Each layer is allowed to dry between each print.

[00152] The laminate of the invention is finalized by addition of a heat sealable adhesive layer per silk screen printing with a mash count of 77 threads/cm of the heat sealable adhesive sold by the company Tiflex called 3YI836NF^®.

[00153] Example 6: Making of a device according to the invention.

[00154] This device is shown in FIG. 6.

[00155] Security inks and the varnish composition obtained in Example 3 are deposited on a PET film with a thickness of 50 to 150 pm comprising a 250 pm thick fusible polyethylene film sold by the company Plastic System Industrie (Orgeval, France). The laminate labeled 12 in FIG. 6 is obtained. [00156] The printing this varnish composition obtained in Example 3 is performed as solid screen print on the entire surface of the protective varnish, mesh count 77 threads/cm or 120 threads/cm and in at least two layers.

[00157] The laminate 12 is then formed into a pouch, in which a paper coupon labeled 13 in FIG. 6 is added, customized or partly customized or blank. The complex is laminated to provide a card. The card is customized or partially customized by marking using the IR laser at 1064 nm. The marking is done inside the film in the varnish layer.

[00158] Example 7: Making of a laminate according to the invention.

[00159] The varnish composition obtained in Example 1 is printed onto a holographic laminate composed of a releasable polyethylene terephthalate substrate containing a release layer based on polyethylene wax and a holographic stamped varnish produced by the company ITW Covid (Cranbury, ETSA). The printing is performed as solid screen print on the entire surface of the protective varnish with a mesh count of 77 threads/cm or 120 threads/cm and in at least two layers.

[00160] It is possible to deposit on the laser-marking varnish composition obtained in Example 1 security inks of different types, invisible fluorescent, optically variable or dichroic, thermochromic, photochromic, etc.

[00161] Each layer is allowed to dry between each print.

[00162] Next, a heat sealable adhesive layer is added sold by the company Tiflex under the name 3YI836NF^®.

[00163] The film in form of a coil is laminated continuously on page 2 containing personal data in full or in part, for instance by a laminator of the model ID- 6 from the manufacturer Miihlbauer, Roding, Germany. [00164] Once page 2 is covered with its security film, the customization in the film can be carried out by laser marking. The marking is performed inside the film in the layer of the laser varnish.

[00165] Example 8: Other examples of markable laser devices.

[00166] These devices are shown schematically in FIGS. 7 and 8.

[00167] In these embodiments, the varnish composition of the invention is deposited directly on the second page paper, labeled 28 in FIG. 7, of the passport, labeled 27 in FIG. 7 or on the document, labeled 29 in FIG. 8, to be covered with a security layer.

[00168] A layer of the varnish composition obtained in example 2 is printed directly on the second page 28 of a passport 27 or the document 29, containing the photograph and the personal data of the holder of this passport.

[00169] The printing is performed as solid silk screen print across the entire surface of page 28 of passport 27 or document 29, or only on a part of the latter in series with mash count of 77 threads/cm and in at least two layers.

[00170] Once page 28 of passport 27 or document 29 covers its security film, the customization in this film is carried out by activation with a 1064 nm IR laser, labeled 26 in FIGS. 7 and 8. The marking is performed in side the film in the laser varnish layer.

[00171] Comparative example 4:

[00172] The varnish composition obtained in the comparative example 1 is printed as in the laminate of example 5.

[00173] Comparative example 5:

[00174] The varnish composition obtained in the comparative example 2 is printed as in the laminate of example 5. [00175] Example 9: Laser marking test

[00176] The laminates obtained pursuant to example 5 and comparative examples 3 and 4 are laminated on a support paper.

[00177] Photo and text type markings are carried out by a 1064 nm IR laser in laser marking settings.

[00178] The table below summarizes the results obtained:

[00179] By way of example, a photograph of a laser marking obtained on a device according to the invention, which is a national ID card, comprising a support that comprises personal data (photograph) coated with a laminate according to the invention including security data (hologram of a person from Arles) is shown in FIG. 9.

Claims

WHAT IS CLAIMED IS:

1. Laser-markable varnish composition, characterized in that it comprises: a) between 50% inclusive and 100% exclusive, by weight, with respect to the total weight of the composition, of at least one thermosetting and/or photocurable polymer, b) between 2% inclusive and 20% inclusive, and preferably between 2% and 15% inclusive, by weight, with respect to the total weight of the composition, of particles of at least one reactant sensitive to laser radiation chosen from the group consisting of titanium dioxide (Ti02) particles, bismuth oxide (Bi203) particles and titanium oxide (Ti02) particles covered with an antimony-doped tin oxide complex (Sn/Sb)02, and of their mixtures, and in that, when polymerized and dried, this laser-markable varnish composition has a transparency of greater than 80%, determined according to the ASTM D 1003 -00 method at the visible wavelengths.

2. Laser-markable varnish composition according to Claim 1, characterized in that said at least one thermosetting and/or photocurable polymer comprises at least 7% by weight, with respect to the total weight of the final composition, of monomers having a number of reactive functional groups of greater than or equal to 3.

3. Laser-markable varnish composition according to Claim 2, characterized in that the reactive functional groups are isocyanate or (meth)acrylate groups.

4. Laser-markable varnish composition according to any one of the preceding claims, characterized in that said at least one thermosetting and/or photocurable polymer comprises at least one of the following monomers: monomers having isocyanate group: isocyanate, polyisocyanate, toluene diisocyanate (TDI), toluene diisocyanate trimethylolpropane, toluene diisocyanate isocyanurate, 4,4’-diphenylmethane diisocyanate, hexamethylene diisocyanate (HDI), hexamethylene diisocyanate biuret, hexamethylene isocyanurate, isophorone diisocyanate (IPDI), isophorone diisocyanate isocyanurate (IPDI), and their mixtures, monomers having acrylate group: tri(meth)acrylate, tetraacrylate, pentacrylate, hexaacrylate, pentaerythritol triacrylate (PETA), trimethylolpropane triacrylate (TMPTA), ethoxylated trimethylolpropane triacrylate (EO-TMPTA), trimethylolpropane trimethacrylate (TMPTMA), glycerol triacrylate (GPTA), glycerol trimethacrylate (GTMA), pentaerythritol tetraacrylate (PETTA), dipentaerythritol pentacrylate (DiPEPA), ditrimethylolpropane tetraacrylate (DiTMPTTA), dipentaerythritol hexaacrylate (DPHA), hexafunctional urethane acrylate, their ethoxylated versions and their mixtures.

5. Laser-markable varnish composition according to any one of the preceding claims, characterized in that the Ti02 particles have a size of between 15 nm and 20 nm, determined by electron diffraction following the Scherrer formula, the Bi203 particles have a size of 10 pm for 80% by number of the particles, determined by analysis of their distribution by laser diffraction/scattering, and the titanium oxide (Ti02) particles covered with an antimony-doped tin oxide complex ((Sn/Sb)02) have a size of 1 pm for 80% by number of the particles, determined by analysis of their distribution by laser diffraction/ scattering.

6. Laminate (6) comprising a transparent substrate (L) on which is placed a layer (2) of laser-markable varnish composition according to any one of the preceding claims.

7. Laminate (6) according to Claim 6, characterized in that said layer (2) of laser-markable varnish composition is not laser-marked.

8. Laminate (6) according to Claim 6, characterized in that said layer (2) of laser-markable varnish composition is laser-marked and optionally additionally contains security data (4).

9. Laminate (6) according to any one of Claims 6 to 8, characterized in that the transparent substrate (G) has a thickness of between 10 pm and 250 pm, preferably between 10 pm and 100 pm.

10. Laminate (6) according to any one of Claims 6 to 9, characterized in that it has a total thickness of between 15 pm and 300 pm, preferably of between 25 pm and 150 pm.

11. Device (7, 7’) comprising a laminate (6) according to any one of Claims 6 to 10 or a layer (2) of laser-markable varnish composition according to any one of Claims 1 to 5.

12. Device (7, 7’) according to Claim 1 1, comprising a support (5) coated with the laminate (6) according to any one of Claims 6 to 11 or with a layer (2) of laser-markable varnish composition according to any one of Claims 1 to 5.

13. Device (7, 7’) according to Claim 12, characterized in that said support (5) has a thickness of between 100 pm and 1000 pm, inclusive, and optionally contains security information (4).

14. Device (7) according to any one of Claims 11 to 13, characterized in that it is formed of a support (5) covered with a layer (2) of laser-markable varnish composition according to any one of Claims 1 to 5, the layer (2) being marked or unmarked.