EP2406084A1 - Laser-markable substrate, and associated manufacturing method - Google Patents

Laser-markable substrate, and associated manufacturing method

Info

Publication number
EP2406084A1
EP2406084A1 EP10712538A EP10712538A EP2406084A1 EP 2406084 A1 EP2406084 A1 EP 2406084A1 EP 10712538 A EP10712538 A EP 10712538A EP 10712538 A EP10712538 A EP 10712538A EP 2406084 A1 EP2406084 A1 EP 2406084A1
Authority
EP
European Patent Office
Prior art keywords
laser
substrate
substrate according
agent
mark
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP10712538A
Other languages
German (de)
French (fr)
Inventor
Sandrine Rancien
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ArjoWiggins Security SAS
Original Assignee
ArjoWiggins Security SAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ArjoWiggins Security SAS filed Critical ArjoWiggins Security SAS
Publication of EP2406084A1 publication Critical patent/EP2406084A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
    • B41M3/14—Security printing
    • B41M3/142—Security printing using chemical colour-formers or chemical reactions, e.g. leuco-dye/acid, photochromes
    • 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
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/40—Agents facilitating proof of genuineness or preventing fraudulent alteration, e.g. for security paper
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/40—Agents facilitating proof of genuineness or preventing fraudulent alteration, e.g. for security paper
    • D21H21/44—Latent security elements, i.e. detectable or becoming apparent only by use of special verification or tampering devices or methods
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/40—Agents facilitating proof of genuineness or preventing fraudulent alteration, e.g. for security paper
    • D21H21/44—Latent security elements, i.e. detectable or becoming apparent only by use of special verification or tampering devices or methods
    • D21H21/46—Elements suited for chemical verification or impeding chemical tampering, e.g. by use of eradicators
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/40—Agents facilitating proof of genuineness or preventing fraudulent alteration, e.g. for security paper
    • D21H21/44—Latent security elements, i.e. detectable or becoming apparent only by use of special verification or tampering devices or methods
    • D21H21/48—Elements suited for physical verification, e.g. by irradiation
    • 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
    • B41M5/267—Marking of plastic artifacts, e.g. with laser

Definitions

  • the present invention relates to the field of laser-markable substrates, in particular security documents, in particular security papers, and concerns inter alia a substrate giving a colored mark under laser irradiation and the associated manufacturing method.
  • paper means any sheet obtained by wet process using a suspension of natural cellulose fibers and / or mineral, vegetable or organic fibers other than cellulose, possibly synthetic fibers, which may contain various fillers and various additives commonly used in stationery.
  • laser irradiation marking for example using an infrared laser, in particular a CO 2 laser, a YAG (Yttrium Alumina Garnet) laser or an Nd YAG (Neodymium Yttrium Alumina Garnet) laser.
  • an infrared laser in particular a CO 2 laser, a YAG (Yttrium Alumina Garnet) laser or an Nd YAG (Neodymium Yttrium Alumina Garnet) laser.
  • the laser irradiation marking of a standard paper substrate leads to obtaining a low-contrast marking, generally yellow or brownish, related to the carbonization of the substrate during marking.
  • a low-contrast marking generally yellow or brownish
  • sensitive laser materials such as mineral fillers, inorganic pigments including conductive pigments and / or optical effect pigments such as pearlescent changing silicate marketed under the name of Lazerflair ® (LS range) by Merck.
  • the application US 2006/0090868 discloses a laser-marked fibrous substrate comprising from 1 to 5% of absorbent materials in the form of inorganic platelets based on pearlescent and conductive pigments.
  • these sensitive laser materials based on conductive pigments or effect pigments in particular optically variable or interferential, although substantially improving the contrast of the marking (increase in optical density), do not allow not to obtain a dark marking, in particular of black color, required for automatic optical recognition of marks, for example such as bar codes.
  • compositions comprising laser-sensitive materials of different nature have been developed by different companies.
  • These compositions are coated locally on a substrate, in particular a paper, and make it possible to obtain a gray or black marking on the coated substrate after laser irradiation of the coated zone.
  • These compositions comprise, for example, a binder and an oxyanion of a metal with multiple valence, as proposed in the application WO 02/074548.
  • These compositions may also be based on carbohydrate.
  • compositions are expensive to implement, in particular because they must be applied locally to the substrate to be marked by an offline process such as printing.
  • these compositions are not and can not be adapted to an implementation online, especially during the manufacture of paper, for example for the following reasons:
  • DE 102 32 786 discloses a laser markable material for obtaining a relief marking which provides a tactile effect.
  • One of the main advantages of the laser marking exhibited in the documents of the prior art is its resistance to falsification, both mechanical and chemical.
  • Applications WO 99/16625, WO 98/48398, EP 0 308 904 and FR 2 496 936 notably provide tamper-resistant substrates comprising materials suitable for laser marking.
  • the markings created on said substrates are presented as being unfalsifiable, especially indelible, mechanically and chemically.
  • the Applicant has observed that it is possible to chemically erase the markings obtained by laser irradiation on substrates comprising the laser sensitive materials, or locally coated with laser marking sensitive compositions, in particular as described above, in particular with using certain chemicals or solvents such as oxidants or strong bases for example.
  • the substrates comprising these laser-sensitive materials or coated with these laser sensitive compositions, and labeled by laser irradiation do not offer the properties necessary to guard against the attempts of chemical falsification of the laser marking carried out on these substrates. These properties are nevertheless essential for any security application and especially the field of security documents.
  • the invention thus has, according to one of its aspects, a laser-marked substrate comprising at least one material capable of forming, under laser irradiation, a colored mark, and at least one tampering agent producing a visible coloration, in particular an irreversible visible coloration, during an attempt to erase the mark chemically, in order to detect said erasure attempt.
  • the mark and / or the coloration may for example be visible, in particular with the naked eye or with the aid of an optical magnification device, under normal light (visible light), infrared (IR) and / or ultraviolet (UV light). ).
  • the mark and / or the coloring may for example form a stain, characters for example such as ideograms or alpha-numeric signs, a symbol, an image, an acronym, a word or a code.
  • the invention it is possible to know whether the attempt to erase the mark has taken place, thanks to the presence of a colored product obtained by chemical reaction between said at least one chemical tampering agent present in or on the substrate and the chemicals used by the fraudsters to try to erase the marks previously made by laser irradiation on the substrate.
  • Said colored product forms a spot on the substrate.
  • the tampering agent may for example be incorporated in or on the substrate during its manufacture.
  • the substrate in bulk in the substrate, for example by mixing it with the fibrous suspension in the case of a paper substrate or with the plastic material intended to be extruded or injected in the case of a plastic substrate,
  • surfacing for example by a "film press” process
  • coating according to processes such as air-laid coating, roll coating, curtain coating and bar coating, or
  • the tampering agent can be incorporated online or offline. Preferably, it is incorporated in line during the manufacture of the substrate.
  • the tampering agent may for example be incorporated over the entire surface of the substrate or locally, for example in a continuous strip or in a particular pattern.
  • the tampering agent may, for example, make it possible to prevent the chemical erasure of the mark produced by laser irradiation of the substrate, with at least one of the following compounds: an oxidant, a strong or weak base,
  • the tampering agent can prevent the chemical erasure of the mark made by laser irradiation of the substrate, with oxidants, for example such as sodium hypochlorite.
  • oxidants for example such as sodium hypochlorite.
  • the tampering agent may be chosen from the following compounds: - derivatives of manganese, nickel, cobalt or cerium, and in particular their salts, p-diaminodiphenyl, its sulphate derivatives or its derivatives; phosphate derivatives, vanadium derivatives,
  • the tampering agent may make it possible to prevent the chemical erasure of the mark produced by laser irradiation of the substrate, with strong bases, for example such as sodium hydroxide, and / or weak, for example, such as sodium carbonate.
  • the tampering agent may be chosen from the following compounds: derivatives of manganese, nickel, cobalt or cerium, and in particular their salts, colored indicators such as paranitrophenol, phenolphthalein, pyranine or a xanthene derivative.
  • the tampering agent may make it possible to prevent the chemical erasure of the mark produced by laser irradiation of the substrate, with strong acids, for example such as sulfuric acid, and / or weak, for example, such as oxalic acid.
  • the tampering agent may be chosen from the following compounds: a colored indicator such as a xanthene derivative,
  • ferric chloride supplemented with ferric chloride, or a derivative of thiazole, benzothiazole or aminonaphthothiazole.
  • the tampering agent may make it possible to prevent the chemical erasure of the mark produced by laser irradiation of the substrate, with polar solvents, for example such as ethanol, and / or apolar solvents, for example such as toluene.
  • polar solvents for example such as ethanol
  • apolar solvents for example such as toluene.
  • the tampering agent may be chosen from water-insoluble dyes which are soluble in oils and solvents. These dyes are used in particular for coloring petroleum derivatives.
  • the forgery agent may be compatible with adhesives used for labels, protective films or visas.
  • the tampering agent of said substrate is compatible with the adhesive of said adhesive-coated substrate.
  • the tamper agent is compatible with the adhesive of a label, a protective film, in particular for the data page of a passport, or a visa intended to be in contact with or applied to the substrate.
  • Some adhesives used can indeed react with some tamper agents.
  • Those skilled in the art may therefore be required to select the agent (s) of tampering used (s) so as to avoid unwanted reaction with said adhesive a label, a protective film or a visa intended to be in contact with or applied to said substrate, and in particular it may be necessary to avoid certain tampering agents to prevent chemical erasure with an apolar solvent.
  • the substrate may comprise, for example, a single tampering agent which makes it possible to prevent chemical erasure by several erasing products. It may for example comprise manganese sulfate, and preferably manganese chloride, to prevent the erasure of the mark with bases, for example such as soda but also with oxidants such as hypochlorite of sodium, by the appearance in both cases of a brown spot revealing the attempt of erasure.
  • bases for example such as soda but also with oxidants such as hypochlorite of sodium
  • the substrate may also include several tampering agents to respectively prevent the chemical erasure with several erasing products, including the appearance of revealing stains of each of the erasing products. It may, for example, comprise a thiazole derivative and a xanthene derivative in order to prevent chemical erasure with oxidants such as sodium hypochlorite, respectively, by the appearance in particular of an orange spot indicative of an attempt to erasure, but also the chemical erasure with bases such as soda, by the appearance in particular of a blue spot revealing an attempt to erase and finally the chemical erasure with acids such as sulfuric acid, by the appearance in particular of a pink spot revealing an attempt of erasure.
  • oxidants such as sodium hypochlorite
  • the invention may allow a user to easily observe any attempt by a chemical to erase the marks made by laser irradiation on the substrate, particularly because of the appearance of a color change on the substrate at the location where the chemical has been applied.
  • a marking-reactive material with a laser emitting light in a wavelength between 100 nm and 11.5 ⁇ m may be the commercial product MICABS from MERCK.
  • a material responsive to the labeling infrared laser, in particular CO 2, which emits light in a wavelength of 9 to 11.5 microns may be selected from the following commercial products: MARK IT ® from Engelhard PACKMARK ® from the company DATALASE, FAST MARK ® from POLYONE, CERMARK ® from DMC2 or LAZERFLAIR ® from MERCK.
  • the material capable of forming a colored mark under laser irradiation can also cause the formation of a relief, in particular by swelling under the effect of said laser irradiation.
  • the laser used to create a mark may be: a gas laser, in particular a neutral atomic laser, for example a helium-cadmium laser emitting in the UV-visible at a wavelength of 442 nm, an ionized atomic laser or a molecular laser, for example a nitrogen laser (N 2 ) emitting in the UV at a wavelength of 337 nm or a CO 2 laser emitting in a wavelength of between 9 and 11.5 ⁇ m, a solid state laser, for example a ruby laser, neodymium doped glass, alexandrite or YAG optionally doped with rare earths, a liquid (or dye) laser, for example emitting in the UV at a wavelength between 100 and 350 nm or for example a laser pumped laser YAG X 2 or laser pumped N 2 , or - a semiconductor laser, for example an arsenic-gallium laser.
  • a gas laser in particular a neutral atomic laser, for example a helium-
  • the material capable of forming a colored mark under laser irradiation will be chosen from mica derivatives, or else from transition metals which induce a change of color by change of oxidation state such as molybdates, tungstates and vanadates, and in particular octamolybdates, heptamolybdates and molybdate amines.
  • transition metals which induce a change of color by change of oxidation state
  • Such materials are described in particular in the international application WO 02/074548.
  • the material capable of forming a colored mark under laser irradiation may for example be incorporated in or on the substrate during its manufacture.
  • surfacing for example by a "film press” process, or by coating according to processes such as air-laid coating, roll coating, curtain coating and coating at the bar, or
  • the material can be incorporated online or offline. Preferably, it is incorporated in line during the manufacture of the substrate.
  • the material capable of forming the colored mark will be incorporated in the surfacer composition of the substrate, in particular paper.
  • the material may for example be incorporated over the entire surface of the substrate or locally, for example in a continuous strip or in a particular pattern. Where appropriate, said continuous strip or said particular pattern may in particular be superimposed on or covered by respectively said continuous strip or said particular pattern according to which the tampering agent has been incorporated in the substrate.
  • the material may be suitable for marking with a laser such as those described above, in particular a UV laser or an infrared laser, in particular a CO 2 laser and / or a YAG laser, among others. The material may still be suitable for marking by a femtosecond laser.
  • the material suitable for laser marking and the tampering agent may be mixed in the same composition, in particular an ink, a varnish, a coating composition, coating, surfacing or impregnation.
  • Said composition may be incorporated according to the processes described above, over the entire surface of the substrate or locally, for example in a continuous strip or in a particular pattern.
  • the substrate may also comprise paper mineral fillers such as, for example, kaolin, talc, titanium dioxide, aluminum silicate, alumina hydrate, calcined kaolin, among others. Paper-based mineral fillers can be introduced in bulk into the substrate to increase the opacity and improve the printability, especially offset, of the substrate.
  • paper mineral fillers such as, for example, kaolin, talc, titanium dioxide, aluminum silicate, alumina hydrate, calcined kaolin, among others. Paper-based mineral fillers can be introduced in bulk into the substrate to increase the opacity and improve the printability, especially offset, of the substrate.
  • the choice of paper mineral fillers used in the substrate can also influence the contrast of the marking obtained.
  • a mineral filler absorbing in the infrared to improve the contrast obtained during the laser marking.
  • the Applicant has highlighted the fact that, among the usual paper mineral fillers, alumina trihydrate and especially calcined kaolin make it possible to reinforce the contrast of the marking produced, in particular with the CO 2 laser. It is for example possible to use calcined kaolin marketed under the name of ANSILEX 93 ® by the company ENGELHARD.
  • the substrate may further comprise surface binders. The presence of certain surface binders may also make it possible to improve the contrast.
  • the surface binders may be chosen for example from polyvinyl alcohol (PVA), starch or a latex, alone or as a mixture. These surface binders may or may not be accompanied by insolubilizers and surface bonding products to provide better final printability, especially offset, to the substrate.
  • PVA polyvinyl alcohol
  • starch starch
  • latex latex
  • insolubilizers and surface bonding products to provide better final printability, especially offset, to the substrate.
  • the surface binders may be PVA, in particular highly hydrolyzed, for example more than 94%, this having a high contrast, for example with CO 2 laser marking.
  • the substrate may be a plastic substrate.
  • the substrate may be a paper.
  • the substrate may for example be based on cellulosic fibers (in particular cotton fibers) and / or natural organic fibers other than cellulosic and / or synthetic fibers, for example such as polyester or polyamide fibers and / or optionally mineral fibers, for example such as glass fibers.
  • cellulosic fibers in particular cotton fibers
  • natural organic fibers other than cellulosic and / or synthetic fibers
  • polyester or polyamide fibers for example such as polyester or polyamide fibers
  • optionally mineral fibers for example such as glass fibers.
  • the substrate may comprise one or more impressions, for example made by offset printing, intaglio, laser, inkjet, gravure printing, screen printing and / or flexography, among others.
  • the concentration of material capable of forming a colored mark may be between 0.1 and 10% by dry weight relative to the weight of the substrate, and preferably between 1 and 10%.
  • the concentration of tampering agent reacting during an attempt at chemical erasure of the mark may be, where appropriate for each tamper agent used, between 0.01% and 5% by dry weight relative to the weight of the substrate.
  • the substrate may comprise on each of its faces an amount of material sensitive to laser marking of between 0.1 and 3 g / m 2 by dry weight.
  • the substrate may have a basis weight of between 30 and 200 g / m 2 .
  • the substrate may comprise a conventional or security ink, especially fluorescent, phosphorescent, magnetic, photochromic, thermochromic, piezochrome, among others.
  • the substrate may comprise an authentication and / or identification security element.
  • Some of the security features are detectable to the naked eye, in visible light, without the use of a particular device. These security features include, for example, a watermark, colored fibers or boards, printed, metallized or holographic wires, holographic foils, or optically variable impressions. These security elements are called first level.
  • security elements are detectable only with a relatively simple device such as a lamp emitting in the ultraviolet or infrared.
  • These security elements comprise, for example, fibers, boards, strips, wires or particles. These security elements may be visible to the naked eye or not, being for example luminescent under a lighting of a Wood lamp emitting in a wavelength of 365 nm.
  • security elements still require for their detection a more sophisticated detection device.
  • These security elements are for example capable of generating a specific signal when they are subjected, simultaneously or not, to one or more external excitation sources. The automatic detection of the signal makes it possible to authenticate, if necessary, the document.
  • These security elements comprise for example tracers in the form of active material, particles or fibers, capable of generating a specific signal when these tracers are subjected to optronic, electrical, magnetic or electromagnetic excitation.
  • the substrate may comprise at least one first, second and / or third level security element.
  • the invention further relates, in another of its aspects, the use of a laser marker substrate, as defined above, in a security document and / or a security article.
  • the security document may for example be a means of payment, such as a bank note, a check, a voucher or a restaurant ticket, an identity document such as an identity card or a document such as a visa, a passport or driver's license, a lottery ticket, a ticket, or a ticket to cultural or sporting events.
  • the security article may for example be selected from a security tag, a package, including a packaging for drugs or for food, for cosmetics, perfumes, electronic parts, spare parts, a sheet used in the medical or hospital field, including a paper used to make sterilization packaging, or a paper art.
  • the invention further relates, in another of its aspects, to a method of manufacturing a laser marker substrate as defined above.
  • the process may comprise the step consisting in impregnating, in particular according to a "size press” method, or by surfacing, in particular according to a “press-film” process, during the production of the substrate on a paper machine, the material capable of to form a colored mark under subsequent laser irradiation.
  • a size press or by surfacing, in particular according to a “press-film” process, during the production of the substrate on a paper machine, the material capable of to form a colored mark under subsequent laser irradiation.
  • the substrates described in the following presented examples were labeled with a CO 2 laser having the following characteristics: laser of wavelength 10600 nm,
  • Beam expander x 2 focal length 125 nm, lens 127 nm, and speed 3500 mm / s.
  • a laser-markable substrate is made using a conventional paper machine and using the following formulation according to the prior art. Pulper (refining at 35 degrees Schopper-Riegler - 0 SR)
  • Retention agent 1.5% by mass relative to the paper production of the cationic starch paper machine, for example based on potato
  • - Gluing agent 3.5% by mass of the solution commercial versus paper production of the cationic emulsion paper machine based on rosin.
  • Size press (surfacing, for 2000 L)
  • Binder 200 kg of modified corn starch, - Binder: 20 kg of polyvinyl alcohol (PVA),
  • Antifoam 0.35 kg of an aqueous emulsion of an aliphatic mixture of hydroxyl compounds
  • Insolubilizing agent 3 kg of a commercial solution modified glyoxal, sensitive material for laser marking: 250 kg Lazerflair ® 800 marketed by MERCK.
  • a laser-markable substrate is made using a conventional paper machine using the following formulation:
  • Pulper 35 degree Schopper-Riegler refining - 0 SR
  • Long fibers 60%
  • - Short fibers 40%.
  • Retention agent 1.5% by weight relative to the paper production of the cationic starch paper machine, for example potato-based,
  • Bonding agent 3.5% by weight of the commercial solution compared to the paper production of the cationic emulsion paper machine based on rosin.
  • Binder 200 kg of modified corn starch
  • Binder 20 kg of polyvinyl alcohol (PVA),
  • Antifoam 0.35 kg of an aqueous emulsion of an aliphatic mixture of hydroxyl compounds
  • Insolubilization agent 3 kg of a commercial solution of modified glyoxal,
  • Formulation 5 aluminum hydroxide (formulation 6), talc (formulation 7) and calcined kaolin (formulation 8).
  • Retention agent 1.5% by mass with respect to the paper production of the cationic starch paper machine, for example based on potato
  • Bonding agent 3.5% by weight of the commercial solution compared to the paper production of the cationic emulsion paper machine based on rosin.
  • Antifoam 0.35 kg of an aqueous emulsion of an aliphatic mixture of hydroxyl compounds
  • Insoluble agent 3 kg of a modified glyoxal commercial solution, material sensitive to laser marking: 250 kg of ammonium octamolybdate.
  • Size press for 2000 L for the formulation 10
  • Binder 200 kg of modified corn starch,
  • Binder 20 kg of polyvinyl alcohol (PVA)
  • Antifoam 0.35 kg of an aqueous emulsion of an aliphatic mixture of hydroxyl compounds, - insolubilizing agent: 3 kg of a commercial solution of modified glyoxal,
  • Antifoam 0.35 kg of an aqueous emulsion of an aliphatic mixture of hydroxyl compounds
  • Insoluble agent 3 kg of a commercial solution of modified glyoxal, - Material sensitive to laser marking: 250 kg of ammonium octamolybdate. "Sizepress" (surfacing, for 2000 L) for formulation 12 Binder: 100 kg polyvinyl alcohol (PVA),
  • Antifoam 0.35 kg of an aqueous emulsion of an aliphatic mixture of hydroxyl compounds
  • - Surface bonding agent 50 kg of a modified acrylic styrene derivative
  • insolubilising agent 3 kg of a solution modified glyoxal
  • Material sensitive to laser marking 250 kg ammonium octamolybdate.
  • the paper manufactured according to the formulation 12 has a better offset, laser and inkjet printability than that manufactured according to the formulation 11.
  • a laser-markable paper substrate according to the invention is manufactured on a conventional paper machine with the following characteristics: Pulper (35 degree refining Schopper-Riegler - 0 SR)
  • Xanthene tampering agent (colored indicator): 0.3% by weight of the commercial solution compared to the papermaking machine paper production. Headbox
  • Retention agent 1.5% by weight relative to the paper production of the cationic starch paper machine, for example potato-based
  • Bonding agent 3.5% by weight of the commercial solution compared to the paper production of the cationic emulsion paper machine based on rosin.
  • Sizepress (surfacing, for 2000 L) - Binder: 100 kg polyvinyl alcohol (PVA),
  • Antifoam 0.35 kg of an aqueous emulsion of an aliphatic mixture of hydroxylated compounds
  • Insoluble agent 3 kg of a commercial solution of modified glyoxal, material sensitive to laser marking: 250 kg of ammonium octamolybdate, anti-tampering agent: 20 kg of manganese chloride.
  • a high contrast paper is obtained, in particular by CO 2 laser irradiation marking.
  • an attempt to erase the laser mark for example using sodium hypochlorite at 12 degrees of chlorine or 5% sodium hydroxide solution, results in the appearance of a Brown colored stain that reveals the attempt to falsify the mark on the paper.
  • An attempt to erase the laser mark with acid such as for example 5% sulfuric acid, causes the appearance of a pink colored stain which also reveals the attempt to falsify the marking. on the substrate.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Paper (AREA)
  • Laser Beam Processing (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)

Abstract

The present invention relates to a laser-markable substrate, comprising at least one material capable of forming a colored mark under laser irradiation and at least one tamper-proof agent producing an irreversible visible coloration when an attempt is made to chemically erase the mark.

Description

Substrat marquable au laser et procédé de fabrication associé La présente invention se rapporte au domaine des substrats marquables au laser, notamment des documents de sécurité, en particulier des papiers de sécurité, et concerne entre autres un substrat donnant une marque colorée sous irradiation laser et le procédé de fabrication associé. The present invention relates to the field of laser-markable substrates, in particular security documents, in particular security papers, and concerns inter alia a substrate giving a colored mark under laser irradiation and the associated manufacturing method.
Dans la description, « papier » signifie toute feuille obtenue par voie humide à l'aide d'une suspension de fibres de cellulose naturelles et/ou de fibres minérales, végétales ou organiques autres que la cellulose, éventuellement synthétiques, pouvant contenir diverses charges et divers additifs couramment utilisés en papeterie. Arrière planIn the description, "paper" means any sheet obtained by wet process using a suspension of natural cellulose fibers and / or mineral, vegetable or organic fibers other than cellulose, possibly synthetic fibers, which may contain various fillers and various additives commonly used in stationery. Background
Afin de faire figurer des marques (ou inscriptions) visibles sur un substrat, notamment des marques telles que des codes à barre linéaires ou matriciels (2D), il est connu d'utiliser le marquage par irradiation laser, par exemple à l'aide d'un laser infrarouge, notamment un laser CO2, un laser YAG (Yttrium Alumine Grenat) ou encore un laser Nd YAG (Néodyme Yttrium Alumine Grenat).In order to include visible marks (or inscriptions) on a substrate, especially marks such as linear or matrix (2D) bar codes, it is known to use laser irradiation marking, for example using an infrared laser, in particular a CO 2 laser, a YAG (Yttrium Alumina Garnet) laser or an Nd YAG (Neodymium Yttrium Alumina Garnet) laser.
Le marquage par irradiation laser d'un substrat papier standard, par exemple pour impression écriture ou de sécurité, conduit à l'obtention d'un marquage à faible contraste, généralement de couleur jaune ou brunâtre, lié à la carbonisation du substrat lors du marquage. Aussi, pour améliorer le contraste du marquage par irradiation laser, il est connu d'incorporer dans ou d'appliquer sur les substrats papier ou plastique, des matériaux sensibles laser tels que des charges minérales, des pigments inorganiques incluant des pigments conducteurs et /ou des pigments à effet optique changeant tels que des silicates perlés commercialisés notamment sous le nom de LAZERFLAIR® (gamme LS) par la société MERCK.The laser irradiation marking of a standard paper substrate, for example for writing or security printing, leads to obtaining a low-contrast marking, generally yellow or brownish, related to the carbonization of the substrate during marking. . Also, to improve the contrast of the marking by laser irradiation, it is known to incorporate in or apply to the paper or plastic substrates, sensitive laser materials such as mineral fillers, inorganic pigments including conductive pigments and / or optical effect pigments such as pearlescent changing silicate marketed under the name of Lazerflair ® (LS range) by Merck.
La demande US 2006/0090868 décrit un substrat fibreux marquable au laser comprenant de 1 à 5% de matériaux absorbeurs sous forme de plaquettes inorganiques à base de pigments perlés et conducteurs.The application US 2006/0090868 discloses a laser-marked fibrous substrate comprising from 1 to 5% of absorbent materials in the form of inorganic platelets based on pearlescent and conductive pigments.
Or, ces matériaux sensibles laser à base de pigments conducteurs ou de pigments à effet, notamment optiquement variable ou interférentiel, bien qu'améliorant sensiblement le contraste du marquage (augmentation de la densité optique), ne permettent pas d'obtenir un marquage sombre, notamment de couleur noire, requis pour la reconnaissance optique automatique de marques, par exemple telles que des codes à barres.However, these sensitive laser materials based on conductive pigments or effect pigments, in particular optically variable or interferential, although substantially improving the contrast of the marking (increase in optical density), do not allow not to obtain a dark marking, in particular of black color, required for automatic optical recognition of marks, for example such as bar codes.
Afin de fournir des substrats qui sous irradiation laser donnent des marques de couleur noire, des compositions de revêtement comportant des matériaux sensibles au marquage laser de nature différente ont été développées par différentes sociétés. On connait par exemple les compositions commercialisées sous la marque PACKMARK® par la société DATALASE, PERGAMARK® par la société CIBA ou encore CODESTRAM® par la société FUJIHUNT. Ces compositions sont enduites localement sur un substrat, notamment un papier, et permettent d'obtenir un marquage gris ou noir sur le substrat enduit après irradiation au laser de la zone enduite. Ces compositions comprennent par exemple un liant et un oxyanion d'un métal à valence multiple, comme proposé dans la demande WO 02/074548. Ces compositions peuvent également être à base de carbohydrate.In order to provide substrates which under laser irradiation give black-colored marks, coating compositions comprising laser-sensitive materials of different nature have been developed by different companies. We know for example the compositions marketed under the brand PACKMARK ® by DataLase company PERGAMARK ® by Ciba or CODESTRAM ® by FUJIHUNT society. These compositions are coated locally on a substrate, in particular a paper, and make it possible to obtain a gray or black marking on the coated substrate after laser irradiation of the coated zone. These compositions comprise, for example, a binder and an oxyanion of a metal with multiple valence, as proposed in the application WO 02/074548. These compositions may also be based on carbohydrate.
Cependant, ces compositions sont coûteuses à mettre en œuvre, notamment parce qu'elles doivent être appliquées localement sur le substrat à marquer par un procédé hors ligne tel qu'une impression. En outre, ces compositions ne sont pas et ne peuvent pas être adaptées à une mise en œuvre en ligne, notamment lors de la fabrication du papier, par exemple pour les raisons suivantes :However, these compositions are expensive to implement, in particular because they must be applied locally to the substrate to be marked by an offline process such as printing. In addition, these compositions are not and can not be adapted to an implementation online, especially during the manufacture of paper, for example for the following reasons:
- leur formulation présente des incompatibilités chimiques avec les liants usuellement utilisés pour la fabrication et la transformation du papier, notamment pour le surfaçage du papier, par exemple par des procédés « size press » ou « film press »,- Their formulation has chemical incompatibilities with the binders usually used for the manufacture and processing of paper, especially for the surfacing of paper, for example by "size press" or "film press" processes,
- leur résistance aux températures élevées, par exemple telles que les températures mises en œuvre lors de la fabrication de substrats plastiques ou par les dispositifs de séchage couramment utilisés dans le domaine de la papeterie, est faible (c'est le cas par exemple pour les compositions sensibles au marquage laser à base de carbohydrates comme le saccharose ou le sucrose, ou à base de leuco colorants encapsulés),their resistance to high temperatures, for example such as the temperatures used during the manufacture of plastic substrates or by the drying devices commonly used in the field of paper mills, is low (this is the case, for example, for compositions sensitive to laser marking based on carbohydrates such as sucrose or sucrose, or based on leuco encapsulated dyes),
- elles modifient les propriétés de surface du papier, notamment son imprimabilité, par exemple offset ; c'est le cas de compositions comprenant une forte proportion de charges. La demande DE 102 32 786 décrit un matériau marquable au Laser permettant d'obtenir un marquage en relief qui procure un effet tactile. Un des principaux avantages du marquage au laser exposé dans les documents de l'art antérieur est sa résistance aux falsifications, aussi bien mécaniques que chimiques. Les demandes WO 99/16625, WO 98/48398, EP 0 308 904 et FR 2 496 936 proposent notamment des substrats infalsifiables comprenant des matériaux aptes au marquage par un laser. En particulier, du fait de liaisons créées lors de l'irradiation (du marquage) entre le matériau marquable laser et le substrat et de l'ancrage du matériau marquable laser dans le substrat, les marquages crées sur lesdits substrats sont présentés comme étant infalsifiables, notamment indélébiles, mécaniquement et chimiquement.they modify the surface properties of the paper, in particular its printability, for example offset; this is the case of compositions comprising a high proportion of fillers. DE 102 32 786 discloses a laser markable material for obtaining a relief marking which provides a tactile effect. One of the main advantages of the laser marking exhibited in the documents of the prior art is its resistance to falsification, both mechanical and chemical. Applications WO 99/16625, WO 98/48398, EP 0 308 904 and FR 2 496 936 notably provide tamper-resistant substrates comprising materials suitable for laser marking. In particular, because of bonds created during the irradiation (marking) between the laser marking material and the substrate and the anchoring of the laser marking material in the substrate, the markings created on said substrates are presented as being unfalsifiable, especially indelible, mechanically and chemically.
La Demanderesse a cependant observé qu'il est possible d'effacer chimiquement les marquages obtenus par irradiation laser sur des substrats comprenant les matériaux sensibles laser, ou enduits localement de compositions sensibles au marquage laser, en particulier telles que décrites précédemment, notamment à l'aide de certains produits chimiques ou solvants tels que des oxydants ou des bases fortes par exemple. De la sorte, les substrats comprenant ces matériaux sensibles laser ou enduits de ces compositions sensibles laser, et marqués par irradiation Laser, n'offrent pas les propriétés nécessaires pour se prémunir des tentatives de falsification chimique du marquage laser réalisé sur ces substrats. Ces propriétés sont pourtant indispensables pour toute application sécuritaire et notamment le domaine des documents de sécurité.However, the Applicant has observed that it is possible to chemically erase the markings obtained by laser irradiation on substrates comprising the laser sensitive materials, or locally coated with laser marking sensitive compositions, in particular as described above, in particular with using certain chemicals or solvents such as oxidants or strong bases for example. In this way, the substrates comprising these laser-sensitive materials or coated with these laser sensitive compositions, and labeled by laser irradiation, do not offer the properties necessary to guard against the attempts of chemical falsification of the laser marking carried out on these substrates. These properties are nevertheless essential for any security application and especially the field of security documents.
En particulier, il est relativement facile d'effacer un marquage par irradiation laser avec des produits chimiques tels que l'hypochlorite de sodium (javel) ou l'hydroxyde de sodium (soude), entre autres. RésuméIn particular, it is relatively easy to erase a laser irradiation marking with chemicals such as sodium hypochlorite (bleach) or sodium hydroxide (sodium hydroxide), among others. summary
II existe par conséquent un besoin pour remédier au moins à certains des inconvénients mentionnés ci-dessus. II existe notamment un besoin pour proposer un substrat marquable au laser, c'est-à-dire donnant une marque colorée sous irradiation laser, et ayant une composition optimisée pour permettre une incorporation en ligne, en particulier sur machine à papier, de matériaux sensibles au laser.There is therefore a need to remedy at least some of the disadvantages mentioned above. In particular, there is a need to provide a laser-markable substrate, that is to say giving a colored mark under laser irradiation, and having an optimized composition to allow on-line incorporation, in particular on a paper machine, of sensitive materials. laser.
Il existe encore un besoin pour obtenir un substrat marquable au laser présentant des propriétés d'impression, notamment offset, sensiblement analogues à celles d'un substrat papier traditionnel. Suite à l'observation de la Demanderesse précédemment décrite et malgré l'enseignement de l'art antérieur, il existe également un besoin pour obtenir un substrat marquable au laser permettant de détecter toute tentative de falsification, en particulier chimique, lors d'une tentative d'effacement des marquages laser. L'invention vise à répondre à tout ou partie de ces besoins.There is still a need to obtain a laser-marked substrate having printing properties, especially offset, substantially similar to those of a conventional paper substrate. Following the observation of the Applicant previously described and despite the teaching of the prior art, there is also a need to obtain a laser marker substrate to detect any attempt to falsify, especially chemical, during an attempt erasing laser markings. The invention aims to meet all or part of these needs.
L'invention a ainsi pour objet, selon l'un de ses aspects, un substrat marquable au laser comportant au moins un matériau apte à former sous irradiation laser une marque colorée, et au moins un agent d' infalsification produisant une coloration visible, notamment une coloration visible irréversible, lors d'une tentative d'effacement chimique de la marque, afin de permettre de détecter ladite tentative d'effacement.The invention thus has, according to one of its aspects, a laser-marked substrate comprising at least one material capable of forming, under laser irradiation, a colored mark, and at least one tampering agent producing a visible coloration, in particular an irreversible visible coloration, during an attempt to erase the mark chemically, in order to detect said erasure attempt.
Par « irréversible », on entend « permanent », c'est-à-dire que ladite coloration ne peut pas être effacée et qu'elle ne disparaît pas avec le temps.By "irreversible" is meant "permanent", that is to say that said coloration can not be erased and it does not disappear over time.
La marque et/ou la coloration peuvent par exemple être visibles, notamment à l'œil nu ou à l'aide d'un dispositif à grossissement optique, sous éclairage normal (lumière visible), infrarouge (IR) et/ou ultraviolet (UV).The mark and / or the coloration may for example be visible, in particular with the naked eye or with the aid of an optical magnification device, under normal light (visible light), infrared (IR) and / or ultraviolet (UV light). ).
La marque et/ou la coloration peuvent par exemple former une tache, des caractères par exemple tels que des idéogrammes ou des signes alpha-numériques, un symbole, une image, un sigle, un mot ou un code.The mark and / or the coloring may for example form a stain, characters for example such as ideograms or alpha-numeric signs, a symbol, an image, an acronym, a word or a code.
Grâce à l'invention, il est possible de savoir si la tentative d'effacement de la marque a eu lieu, grâce à la présence d'un produit coloré obtenu par réaction chimique entre ledit au moins un agent d' infalsification chimique présent dans ou sur le substrat et les produits chimiques utilisés par les fraudeurs pour tenter d'effacer les marques préalablement réalisées par irradiation laser sur le substrat. Ledit produit coloré forme une tache sur le substrat. L'agent d' infalsification peut par exemple être incorporé dans ou sur le substrat lors de sa fabrication.Thanks to the invention, it is possible to know whether the attempt to erase the mark has taken place, thanks to the presence of a colored product obtained by chemical reaction between said at least one chemical tampering agent present in or on the substrate and the chemicals used by the fraudsters to try to erase the marks previously made by laser irradiation on the substrate. Said colored product forms a spot on the substrate. The tampering agent may for example be incorporated in or on the substrate during its manufacture.
Il peut par exemple être incorporé :It can for example be incorporated:
- en masse dans le substrat, par exemple en le mélangeant à la suspension fibreuse dans le cas d'un substrat papier ou à la matière plastique destinée à être extrudée ou injectée dans le cas d'un substrat plastique,in bulk in the substrate, for example by mixing it with the fibrous suspension in the case of a paper substrate or with the plastic material intended to be extruded or injected in the case of a plastic substrate,
- par imprégnation, par exemple selon un procédé « size press »,by impregnation, for example according to a "size press" process,
- par surfaçage, par exemple par un procédé « film press », - par couchage selon des procédés tels que le couchage à lame d'air, le couchage rouleau, le couchage rideau et le couchage à la barre, ou encore,by surfacing, for example by a "film press" process, by coating according to processes such as air-laid coating, roll coating, curtain coating and bar coating, or
- par pulvérisation.- by spraying.
L'agent d' infalsification peut être incorporé en ligne ou hors ligne. De préférence, il est incorporé en ligne lors de la fabrication du substrat.The tampering agent can be incorporated online or offline. Preferably, it is incorporated in line during the manufacture of the substrate.
L'agent d' infalsification peut par exemple être incorporé sur toute la surface du substrat ou localement, par exemple selon une bande continue ou selon un motif particulier.The tampering agent may for example be incorporated over the entire surface of the substrate or locally, for example in a continuous strip or in a particular pattern.
L'agent d' infalsification peut par exemple permettre de prévenir l'effacement chimique de la marque réalisée par irradiation laser du substrat, avec au moins un des composés suivants : un oxydant, une base forte ou faible,The tampering agent may, for example, make it possible to prevent the chemical erasure of the mark produced by laser irradiation of the substrate, with at least one of the following compounds: an oxidant, a strong or weak base,
- un acide fort ou faible, ou - un solvant polaire ou apolaire.a strong or weak acid, or a polar or apolar solvent.
L'agent d' infalsification peut permettre de prévenir l'effacement chimique de la marque réalisée par irradiation laser du substrat, avec des oxydants, par exemple tels que de l'hypochlorite de sodium. Dans ce cas, l'agent d' infalsification peut être choisi parmi les composés suivants : - les dérivés de manganèse, de nickel, de cobalt ou de cérium, et en particulier leurs sels, le pp diamino-diphényl, ses dérivés sulfates ou ses dérivés phosphates, les dérivés du vanadium,The tampering agent can prevent the chemical erasure of the mark made by laser irradiation of the substrate, with oxidants, for example such as sodium hypochlorite. In this case, the tampering agent may be chosen from the following compounds: - derivatives of manganese, nickel, cobalt or cerium, and in particular their salts, p-diaminodiphenyl, its sulphate derivatives or its derivatives; phosphate derivatives, vanadium derivatives,
- le 4,4' diaminodinaphtyl (1,1 '),4,4'-diaminodinaphthyl (1,1 '),
- le S, N orthophenylène isothiourée, - la primuline, les dérivés de guanidine tels que les diarylguanidine comme par exemple la diphenylguanidine, ou les dérivés du thiazole, du benzothiazole ou de l'aminonaphtothiazole.- S, N orthophenylene isothiourea, - primulin, guanidine derivatives such as diarylguanidine such as diphenylguanidine, or derivatives of thiazole, benzothiazole or aminonaphthothiazole.
L'agent d' infalsification peut permettre de prévenir l'effacement chimique de la marque réalisée par irradiation laser du substrat, avec des bases fortes par exemple telles que la soude, et/ou faibles par exemple telles que le carbonate de sodium. Dans ce cas, l'agent d' infalsification peut être choisi parmi les composés suivants : - les dérivés de manganèse, de nickel, de cobalt ou de cérium, et en particulier leurs sels, les indicateurs colorés tels que le paranitrophénol, la phénolphtaléine, la pyranine ou un dérivé de xanthène.The tampering agent may make it possible to prevent the chemical erasure of the mark produced by laser irradiation of the substrate, with strong bases, for example such as sodium hydroxide, and / or weak, for example, such as sodium carbonate. In this case, the tampering agent may be chosen from the following compounds: derivatives of manganese, nickel, cobalt or cerium, and in particular their salts, colored indicators such as paranitrophenol, phenolphthalein, pyranine or a xanthene derivative.
L'agent d' infalsification peut permettre de prévenir l'effacement chimique de la marque réalisée par irradiation laser du substrat, avec des acides forts par exemple tels que l'acide sulfurique, et/ou faibles par exemple tels que le l'acide oxalique. Dans ce cas, l'agent d' infalsification peut être choisi parmi les composés suivants : un indicateur coloré tel qu'un dérivé du xanthène,The tampering agent may make it possible to prevent the chemical erasure of the mark produced by laser irradiation of the substrate, with strong acids, for example such as sulfuric acid, and / or weak, for example, such as oxalic acid. . In this case, the tampering agent may be chosen from the following compounds: a colored indicator such as a xanthene derivative,
- le ferrocyanure de potassium additionné de chlorure ferrique, ou - un dérivé du thiazole, du benzothiazole ou de l'aminonaphtothiazole.ferric chloride supplemented with ferric chloride, or a derivative of thiazole, benzothiazole or aminonaphthothiazole.
L'agent d' infalsification peut permettre de prévenir l'effacement chimique de la marque réalisée par irradiation laser du substrat, avec des solvants polaires par exemple tels que l'éthanol, et/ou apolaires par exemple tels que le toluène. Dans ce cas, l'agent d' infalsification peut être choisi parmi les colorants insolubles dans l'eau mais solubles dans les huiles et solvants. Ces colorants sont notamment utilisés pour la coloration de dérivés pétroliers.The tampering agent may make it possible to prevent the chemical erasure of the mark produced by laser irradiation of the substrate, with polar solvents, for example such as ethanol, and / or apolar solvents, for example such as toluene. In this case, the tampering agent may be chosen from water-insoluble dyes which are soluble in oils and solvents. These dyes are used in particular for coloring petroleum derivatives.
L'agent d' infalsification peut être compatible avec les adhésifs utilisés pour des étiquettes, des films de protection ou des visas.The forgery agent may be compatible with adhesives used for labels, protective films or visas.
En particulier si le substrat est un substrat adhésivé, l'agent d'infalsifïcation dudit substrat est compatible avec l'adhésif dudit substrat adhésivé.In particular, if the substrate is an adhesive-coated substrate, the tampering agent of said substrate is compatible with the adhesive of said adhesive-coated substrate.
Selon un autre cas particulier, l'agent d'infalsifïcation est compatible avec l'adhésif d'une étiquette, d'un film de protection, notamment pour la page de données d'un passeport, ou d'un visa destiné à être en contact avec ou appliqué sur le substrat. Certains adhésifs utilisés peuvent en effet réagir avec certains agents d'infalsifïcation. Il s'agit en particulier de certains agents d'infalsifïcation permettant de prévenir l'effacement chimique avec un solvant apolaire. L'homme du métier peut donc être amené à sélectionner le ou les agent(s) d'infalsifïcation utilisé(s) de manière à éviter une réaction non souhaitée avec ledit adhésif d'une étiquette, d'un film de protection ou d'un visa destinée à être en contact avec ou appliquée sur ledit substrat, et en particulier il peut être amené à éviter certains agents d'infalsifïcation permettant de prévenir l'effacement chimique avec un solvant apolaire. Le substrat peut comporter par exemple un seul agent d'infalsification permettant de prévenir l'effacement chimique par plusieurs produits d'effacement. Il peut par exemple comporter du sulfate de manganèse, et de préférence du chlorure de manganèse, pour permettre de prévenir l'effacement de la marque avec des bases, par exemple telles que de la soude mais aussi avec des oxydants tels que de l'hypochlorite de sodium, par l'apparition dans les deux cas d'une tache brune révélatrice de la tentative d'effacement.In another particular case, the tamper agent is compatible with the adhesive of a label, a protective film, in particular for the data page of a passport, or a visa intended to be in contact with or applied to the substrate. Some adhesives used can indeed react with some tamper agents. In particular, it is a question of certain tampering agents which make it possible to prevent chemical erasure with an apolar solvent. Those skilled in the art may therefore be required to select the agent (s) of tampering used (s) so as to avoid unwanted reaction with said adhesive a label, a protective film or a visa intended to be in contact with or applied to said substrate, and in particular it may be necessary to avoid certain tampering agents to prevent chemical erasure with an apolar solvent. The substrate may comprise, for example, a single tampering agent which makes it possible to prevent chemical erasure by several erasing products. It may for example comprise manganese sulfate, and preferably manganese chloride, to prevent the erasure of the mark with bases, for example such as soda but also with oxidants such as hypochlorite of sodium, by the appearance in both cases of a brown spot revealing the attempt of erasure.
Le substrat peut aussi comporter plusieurs agents d'infalsification permettant de prévenir respectivement l'effacement chimique avec plusieurs produits d'effacement, notamment par l'apparition de colorations révélatrices de chacun des produits d'effacement. Il peut par exemple comporter un dérivé du thiazole et un dérivé du xanthène pour permettre de prévenir respectivement l'effacement chimique avec des oxydants tels que de l'hypochlorite de sodium par l'apparition notamment d'une tache orange révélatrice d'une tentative d'effacement, mais aussi l'effacement chimique avec des bases telles que de la soude, par l'apparition notamment d'une tache bleue révélatrice d'une tentative d'effacement et enfin l'effacement chimique avec des acides tels que de l'acide sulfurique, par l'apparition notamment d'une tache rosé révélatrice d'une tentative d'effacement.The substrate may also include several tampering agents to respectively prevent the chemical erasure with several erasing products, including the appearance of revealing stains of each of the erasing products. It may, for example, comprise a thiazole derivative and a xanthene derivative in order to prevent chemical erasure with oxidants such as sodium hypochlorite, respectively, by the appearance in particular of an orange spot indicative of an attempt to erasure, but also the chemical erasure with bases such as soda, by the appearance in particular of a blue spot revealing an attempt to erase and finally the chemical erasure with acids such as sulfuric acid, by the appearance in particular of a pink spot revealing an attempt of erasure.
L'invention peut permettre à un utilisateur de constater facilement toute tentative d'effacement par un produit chimique des marques réalisées par irradiation laser sur le substrat, notamment du fait de l'apparition d'un changement de couleur sur le substrat à l'endroit où le produit chimique a été appliqué.The invention may allow a user to easily observe any attempt by a chemical to erase the marks made by laser irradiation on the substrate, particularly because of the appearance of a color change on the substrate at the location where the chemical has been applied.
Le choix du matériau apte à former une marque colorée sous irradiation laser peut dépendre du contraste que l'on souhaite obtenir et de la longueur d'onde d'irradiation du laser utilisée. En particulier, un matériau réagissant au marquage par un laser émettant une lumière dans une longueur d'onde entre 100 nm et 11,5 μm peut être le produit commercial MICABS de la société MERCK. En particulier, un matériau réagissant au marquage par laser infrarouge, notamment CO2, qui émet une lumière dans une longueur d'onde entre 9 et 11,5 μm, peut être choisi parmi les produits commerciaux suivants : MARK IT ® de la société ENGELHARD, PACKMARK® de la société DATALASE, FAST MARK ® de la société POLYONE, CERMARK® de la société DMC2 ou LAZERFLAIR® de la société MERCK. Le matériau apte à former une marque colorée sous irradiation laser peut en outre provoquer la formation d'un relief, notamment par gonflement sous l'effet de ladite irradiation laser.The choice of material capable of forming a colored mark under laser irradiation may depend on the contrast that one wishes to obtain and on the irradiation wavelength of the laser used. In particular, a marking-reactive material with a laser emitting light in a wavelength between 100 nm and 11.5 μm may be the commercial product MICABS from MERCK. In particular, a material responsive to the labeling infrared laser, in particular CO 2, which emits light in a wavelength of 9 to 11.5 microns, may be selected from the following commercial products: MARK IT ® from Engelhard PACKMARK ® from the company DATALASE, FAST MARK ® from POLYONE, CERMARK ® from DMC2 or LAZERFLAIR ® from MERCK. The material capable of forming a colored mark under laser irradiation can also cause the formation of a relief, in particular by swelling under the effect of said laser irradiation.
Le laser permettant de créer une marque peut être : - un laser à gaz, notamment un laser atomique neutre, par exemple un laser hélium- cadmiun émettant dans l'UV-visible à une longueur d'onde de 442 nm, un laser atomique ionisé ou un laser moléculaire, par exemple un laser azote (N2) émettant dans l'UV à une longueur d'onde de 337 nm ou un laser CO2 émettant dans une longueur d'onde comprise entre 9 et 11,5 μm, - un laser à solide, par exemple un laser rubis, verre dopé au néodyme, alexandrite ou YAG éventuellement dopé aux terres rares, un laser à liquide (ou à colorants), par exemple émettant dans l'UV à une longueur d'onde comprise entre 100 et 350 nm ou par exemple un laser pompé par laser YAG X2 ou pompé par laser N2, ou - un laser à semi-conducteurs, par exemple un laser arsenic-gallium.The laser used to create a mark may be: a gas laser, in particular a neutral atomic laser, for example a helium-cadmium laser emitting in the UV-visible at a wavelength of 442 nm, an ionized atomic laser or a molecular laser, for example a nitrogen laser (N 2 ) emitting in the UV at a wavelength of 337 nm or a CO 2 laser emitting in a wavelength of between 9 and 11.5 μm, a solid state laser, for example a ruby laser, neodymium doped glass, alexandrite or YAG optionally doped with rare earths, a liquid (or dye) laser, for example emitting in the UV at a wavelength between 100 and 350 nm or for example a laser pumped laser YAG X 2 or laser pumped N 2 , or - a semiconductor laser, for example an arsenic-gallium laser.
De préférence, le matériau apte à former une marque colorée sous irradiation laser sera choisi parmi les dérivés du mica, ou encore parmi les métaux de transition qui induisent un changement de couleur par changement d'état d'oxydation tels que des molybdates, des tungstates et des vanadates, et en particulier des octamolybdates, des heptamolybdates et des aminés molybdates. De tels matériaux sont notamment décrits dans la demande internationale WO 02/074548.Preferably, the material capable of forming a colored mark under laser irradiation will be chosen from mica derivatives, or else from transition metals which induce a change of color by change of oxidation state such as molybdates, tungstates and vanadates, and in particular octamolybdates, heptamolybdates and molybdate amines. Such materials are described in particular in the international application WO 02/074548.
Le matériau apte à former une marque colorée sous irradiation laser peut par exemple être incorporé dans ou sur le substrat lors de sa fabrication.The material capable of forming a colored mark under laser irradiation may for example be incorporated in or on the substrate during its manufacture.
Il peut par exemple être incorporé : - en masse dans le substrat, par exemple en le mélangeant à la suspension fibreuse dans le cas d'un substrat papier ou à la matière plastique destinée à être extrudée ou injectée dans le cas d'un substrat plastique,It may for example be incorporated: - in bulk in the substrate, for example by mixing it with the fibrous suspension in the case of a paper substrate or the plastic material intended to be extruded or injected in the case of a plastic substrate ,
- par imprégnation, par exemple selon un procédé « size press »,by impregnation, for example according to a "size press" process,
- par surfaçage, par exemple par un procédé « film press », - par couchage selon des procédés tels que le couchage à lame d'air, le couchage rouleau, le couchage rideau et le couchage à la barre, ou encoreby surfacing, for example by a "film press" process, or by coating according to processes such as air-laid coating, roll coating, curtain coating and coating at the bar, or
- par pulvérisation. Le matériau peut être incorporé en ligne ou hors ligne. De préférence, il est incorporé en ligne lors de la fabrication du substrat.- by spraying. The material can be incorporated online or offline. Preferably, it is incorporated in line during the manufacture of the substrate.
De préférence, le matériau apte à former la marque colorée sera incorporé dans la composition de surfaçage du substrat, notamment papier. Le matériau peut par exemple être incorporé sur toute la surface du substrat ou localement, par exemple selon une bande continue ou selon un motif particulier. Le cas échéant, ladite bande continue ou ledit motif particulier peut notamment être superposé à ou recouvert par, respectivement ladite bande continue ou ledit motif particulier selon lequel l'agent d' infalsification a été incorporé au substrat. Le matériau peut être apte au marquage par un laser tel que ceux décrits précédemment, notamment un laser UV ou un laser infrarouge, en particulier un laser CO2 et/ou un laser YAG, entre autres. Le matériau peut encore être apte au marquage par un laser femtoseconde.Preferably, the material capable of forming the colored mark will be incorporated in the surfacer composition of the substrate, in particular paper. The material may for example be incorporated over the entire surface of the substrate or locally, for example in a continuous strip or in a particular pattern. Where appropriate, said continuous strip or said particular pattern may in particular be superimposed on or covered by respectively said continuous strip or said particular pattern according to which the tampering agent has been incorporated in the substrate. The material may be suitable for marking with a laser such as those described above, in particular a UV laser or an infrared laser, in particular a CO 2 laser and / or a YAG laser, among others. The material may still be suitable for marking by a femtosecond laser.
Le matériau apte au marquage laser et l'agent d' infalsification peuvent être mélangés dans une même composition, notamment une encre, un vernis, une composition d'enduction, de couchage, de surfaçage ou d'imprégnation. Ladite composition peut être incorporée selon les procédés décrits précédemment, sur toute la surface du substrat ou localement, par exemple selon une bande continue ou selon un motif particulier.The material suitable for laser marking and the tampering agent may be mixed in the same composition, in particular an ink, a varnish, a coating composition, coating, surfacing or impregnation. Said composition may be incorporated according to the processes described above, over the entire surface of the substrate or locally, for example in a continuous strip or in a particular pattern.
Le substrat peut encore comporter des charges minérales papetières telles que par exemple du kaolin, du talc, du dioxyde de titane, du silicate d'aluminium, de l'hydrate d'alumine, du kaolin calciné, entre autres. Les charges minérales papetières peuvent être introduites en masse dans le substrat pour augmenter l'opacité et améliorer l'imprimabilité, notamment offset, du substrat.The substrate may also comprise paper mineral fillers such as, for example, kaolin, talc, titanium dioxide, aluminum silicate, alumina hydrate, calcined kaolin, among others. Paper-based mineral fillers can be introduced in bulk into the substrate to increase the opacity and improve the printability, especially offset, of the substrate.
Le choix des charges minérales papetières utilisées dans le substrat peut également influencer sur le contraste du marquage obtenu.The choice of paper mineral fillers used in the substrate can also influence the contrast of the marking obtained.
En particulier, il est préférable d'utiliser une charge minérale absorbant dans l'infrarouge pour améliorer le contraste obtenu lors du marquage laser. La Demanderesse a mis en évidence le fait que, parmi les charges minérales papetières usuelles, le trihydrate d'alumine et surtout le kaolin calciné permettent de renforcer le contraste du marquage réalisé, en particulier au laser CO2. Il est par exemple possible d'utiliser du kaolin calciné commercialisé sous le nom d' ANSILEX 93 ® par la société ENGELHARD. Le substrat peut encore comporter des liants de surface. La présence de certains liants de surface peut également permettre d'améliorer le contraste.In particular, it is preferable to use a mineral filler absorbing in the infrared to improve the contrast obtained during the laser marking. The Applicant has highlighted the fact that, among the usual paper mineral fillers, alumina trihydrate and especially calcined kaolin make it possible to reinforce the contrast of the marking produced, in particular with the CO 2 laser. It is for example possible to use calcined kaolin marketed under the name of ANSILEX 93 ® by the company ENGELHARD. The substrate may further comprise surface binders. The presence of certain surface binders may also make it possible to improve the contrast.
Les liants de surface peuvent être choisis par exemple parmi de l'alcool polyvinylique (PVA), de l'amidon ou un latex, seul ou en mélange. Ces liants de surface peuvent être accompagnés ou non d'insolubilisants et de produits de collage de surface pour offrir une meilleure imprimabilité finale, notamment offset, au substrat.The surface binders may be chosen for example from polyvinyl alcohol (PVA), starch or a latex, alone or as a mixture. These surface binders may or may not be accompanied by insolubilizers and surface bonding products to provide better final printability, especially offset, to the substrate.
De préférence, les liants de surface peuvent être du PVA, notamment hautement hydrolyse, par exemple à plus de 94 %, celui-ci offrant un contraste élevé, par exemple au marquage par laser CO2. Le substrat peut être un substrat plastique.Preferably, the surface binders may be PVA, in particular highly hydrolyzed, for example more than 94%, this having a high contrast, for example with CO 2 laser marking. The substrate may be a plastic substrate.
Le substrat peut être un papier.The substrate may be a paper.
Le substrat peut par exemple être à base de fibres cellulosiques (en particulier de fibres de coton) et/ou de fibres organiques naturelles autres que cellulosiques et/ou de fibres synthétiques, par exemple telles que des fibres de polyester ou de polyamide et/ou éventuellement de fibres minérales, par exemples telles que des fibres de verre.The substrate may for example be based on cellulosic fibers (in particular cotton fibers) and / or natural organic fibers other than cellulosic and / or synthetic fibers, for example such as polyester or polyamide fibers and / or optionally mineral fibers, for example such as glass fibers.
Le substrat peut comporter une ou plusieurs impressions, par exemple réalisées par impression offset, taille-douce, laser, jet d'encre, par héliogravure, par sérigraphie et/ou par flexographie, entre autres.The substrate may comprise one or more impressions, for example made by offset printing, intaglio, laser, inkjet, gravure printing, screen printing and / or flexography, among others.
La concentration en matériau apte à former une marque colorée peut être comprise entre 0,1 et 10 % en poids sec par rapport au poids du substrat, et de préférence entre 1 et 10 %.The concentration of material capable of forming a colored mark may be between 0.1 and 10% by dry weight relative to the weight of the substrate, and preferably between 1 and 10%.
La concentration en agent d' infalsification réagissant lors d'une tentative d'effacement chimique de la marque peut être comprise, le cas échéant pour chaque agent d'infalsifïcation utilisé, entre 0,01 % et 5 % en poids sec par rapport au poids du substrat. Le substrat peut comporter sur chacune de ses faces une quantité de matériau sensible au marquage laser comprise entre 0,1 et 3 g/m2 en poids sec.The concentration of tampering agent reacting during an attempt at chemical erasure of the mark may be, where appropriate for each tamper agent used, between 0.01% and 5% by dry weight relative to the weight of the substrate. The substrate may comprise on each of its faces an amount of material sensitive to laser marking of between 0.1 and 3 g / m 2 by dry weight.
Le substrat peut présenter un grammage compris entre 30 et 200 g/m2.The substrate may have a basis weight of between 30 and 200 g / m 2 .
Le substrat peut comporter une encre classique ou de sécurité, notamment fluorescente, phosphorescente, magnétique, photochrome, thermochrome, piézochrome, entre autres.The substrate may comprise a conventional or security ink, especially fluorescent, phosphorescent, magnetic, photochromic, thermochromic, piezochrome, among others.
Le substrat peut comporter un élément de sécurité d'authentifîcation et/ou d'identification. Parmi les éléments de sécurité, certains sont détectables à l'œil nu, en lumière visible, sans utilisation d'un appareil particulier. Ces éléments de sécurité comportent par exemple un filigrane, des fibres ou planchettes colorées, des fils imprimés, métallisés ou holographiques, des foils holographiques ou des impressions à effet optique variable. Ces éléments de sécurité sont dits de premier niveau.The substrate may comprise an authentication and / or identification security element. Some of the security features are detectable to the naked eye, in visible light, without the use of a particular device. These security features include, for example, a watermark, colored fibers or boards, printed, metallized or holographic wires, holographic foils, or optically variable impressions. These security elements are called first level.
D'autres types d'éléments de sécurité sont détectables seulement à l'aide d'un appareil relativement simple tel qu'une lampe émettant dans l'ultraviolet ou l'infrarouge. Ces éléments de sécurité comportent par exemple des fibres, des planchettes, des bandes, des fils ou des particules. Ces éléments de sécurité peuvent être visibles à l'œil nu ou non, étant par exemple luminescents sous un éclairage d'une lampe de Wood émettant dans une longueur d'onde de 365 nm.Other types of security elements are detectable only with a relatively simple device such as a lamp emitting in the ultraviolet or infrared. These security elements comprise, for example, fibers, boards, strips, wires or particles. These security elements may be visible to the naked eye or not, being for example luminescent under a lighting of a Wood lamp emitting in a wavelength of 365 nm.
Ces éléments de sécurité sont dits de deuxième niveau.These security elements are said to be second level.
D'autres types d'éléments de sécurité encore nécessitent pour leur détection un appareil de détection plus sophistiqué. Ces éléments de sécurité sont par exemple capables de générer un signal spécifique lorsqu'ils sont soumis, de manière simultanée ou non, à une ou plusieurs sources d'excitation extérieures. La détection automatique du signal permet d'authentifier, le cas échéant, le document.Other types of security elements still require for their detection a more sophisticated detection device. These security elements are for example capable of generating a specific signal when they are subjected, simultaneously or not, to one or more external excitation sources. The automatic detection of the signal makes it possible to authenticate, if necessary, the document.
Ces éléments de sécurité comportent par exemple des traceurs se présentant sous la forme de matière active, de particules ou de fibres, capables de générer un signal spécifique lorsque ces traceurs sont soumis à une excitation optronique, électrique, magnétique ou électromagnétique.These security elements comprise for example tracers in the form of active material, particles or fibers, capable of generating a specific signal when these tracers are subjected to optronic, electrical, magnetic or electromagnetic excitation.
Ces éléments de sécurité sont dits de troisième niveau.These security elements are said to be third level.
Le substrat peut comporter au moins un élément de sécurité de premier, de deuxième et/ou de troisième niveau. L'invention a encore pour objet, selon un autre de ses aspects, l'utilisation d'un substrat marquable au laser, tel que défini précédemment, dans un document de sécurité et/ou un article de sécurité.The substrate may comprise at least one first, second and / or third level security element. The invention further relates, in another of its aspects, the use of a laser marker substrate, as defined above, in a security document and / or a security article.
Le document de sécurité peut par exemple être un moyen de paiement, tel qu'un billet de banque, un chèque, un bon d'achat ou un ticket restaurant, un document d'identité tel qu'une carte d'identité ou un document officiel tel qu'un visa, un passeport ou un permis de conduire, un ticket de loterie, un titre de transport, ou encore un ticket d'entrée à des manifestations culturelles ou sportives. L'article de sécurité peut par exemple être choisi parmi une étiquette de sécurité, un emballage, notamment un emballage pour des médicaments ou pour des aliments, pour des cosmétiques, des parfums, des pièces électroniques, des pièces détachées, une feuille utilisée dans le domaine médical ou hospitalier, notamment un papier utilisé pour faire des emballages de stérilisation, ou encore un papier d'art.The security document may for example be a means of payment, such as a bank note, a check, a voucher or a restaurant ticket, an identity document such as an identity card or a document such as a visa, a passport or driver's license, a lottery ticket, a ticket, or a ticket to cultural or sporting events. The security article may for example be selected from a security tag, a package, including a packaging for drugs or for food, for cosmetics, perfumes, electronic parts, spare parts, a sheet used in the medical or hospital field, including a paper used to make sterilization packaging, or a paper art.
L'invention a encore pour objet, selon un autre de ses aspects, un procédé de fabrication d'un substrat marquable au laser tel que défini précédemment.The invention further relates, in another of its aspects, to a method of manufacturing a laser marker substrate as defined above.
Le procédé peut comporter l'étape consistant à introduire par imprégnation, notamment selon un procédé « size press », ou par surfaçage, notamment selon un procédé « film press », lors de la fabrication du substrat sur une machine à papier, le matériau apte à former une marque colorée sous irradiation laser ultérieure. Exemples Remarque préliminaireThe process may comprise the step consisting in impregnating, in particular according to a "size press" method, or by surfacing, in particular according to a "press-film" process, during the production of the substrate on a paper machine, the material capable of to form a colored mark under subsequent laser irradiation. Examples Preliminary remark
Les substrats décrits dans les exemples présentés suivants ont été marqués avec un laser CO2 ayant les caractéristiques suivantes : - laser de longueur d'onde 10600 nm,The substrates described in the following presented examples were labeled with a CO 2 laser having the following characteristics: laser of wavelength 10600 nm,
« beam expander » (augmentation de la taille du faisceau) x 2, distance focale 125 nm, lentille de 127 nm, et - vitesse de 3500 mm/s.Beam expander x 2, focal length 125 nm, lens 127 nm, and speed 3500 mm / s.
Les papiers marqués ont ensuite été évalués en termes de contraste du marquage laser par une mesure de densité optique, ainsi qu'en termes de résistance du marquage à des tentatives d'effacement chimique à l'acide, la soude, l'hypochlorite de sodium, l'éthanol et le toluène. Formulation 1 (échantillon témoin)The labeled papers were then evaluated in terms of the contrast of the laser marking by an optical density measurement, as well as in terms of the resistance of the marking to attempts of chemical erasure with acid, sodium hydroxide, sodium hypochlorite , ethanol and toluene. Formulation 1 (control sample)
On fabrique un substrat marquable au laser à l'aide d'une machine à papier traditionnelle et en utilisant la formulation suivante conforme à l'art antérieur. Pulpeur (raffinage à 35 degrés Schopper-Riegler - 0SR)A laser-markable substrate is made using a conventional paper machine and using the following formulation according to the prior art. Pulper (refining at 35 degrees Schopper-Riegler - 0 SR)
Fibres longues : 60 %, - Fibres courtes : 40 %.Long fibers: 60%, - Short fibers: 40%.
Mélangeuse Charge minérale : 15 % en poids sec de kaolin calciné. Caisse de têteMixer Mineral charge: 15% by dry weight of calcined kaolin. Headbox
Agent de rétention : 1,5 % en masse par rapport à la production de papier de la machine à papier d'amidon cationique, par exemple à base de pomme de terre, - Agent de collage : 3,5 % en masse de la solution commerciale par rapport à la production de papier de la machine à papier d'émulsion cationique à base de colophane. « Size press » (surfaçage, pour 2000 L)Retention agent: 1.5% by mass relative to the paper production of the cationic starch paper machine, for example based on potato, - Gluing agent: 3.5% by mass of the solution commercial versus paper production of the cationic emulsion paper machine based on rosin. "Size press" (surfacing, for 2000 L)
Liant : 200 kg d'amidon de maïs modifié, - Liant : 20 kg d'alcool polyvinylique (PVA),Binder: 200 kg of modified corn starch, - Binder: 20 kg of polyvinyl alcohol (PVA),
Antimousse : 0,35 kg d'une émulsion aqueuse d'un mélange aliphatique de composés hydroxylés,Antifoam: 0.35 kg of an aqueous emulsion of an aliphatic mixture of hydroxyl compounds,
Agent d'insolubilisation : 3 kg d'une solution commerciale de glyoxal modifié, Matériau sensible au marquage laser : 250 kg de LAZERFLAIR® 800 commercialisé par la société MERCK.Insolubilizing agent: 3 kg of a commercial solution modified glyoxal, sensitive material for laser marking: 250 kg Lazerflair ® 800 marketed by MERCK.
Les résultats montrent que l'on obtient un contraste jaune brun et non pas noir lors du marquage au laser CO2 du papier fabriqué selon la formulation 1. On remarque qu'il est facile d'effacer ledit marquage laser avec de l'hypochlorite de sodium à 12 % de chlore ou avec une solution d'hydroxyde de sodium à 5 %. Formulation 2The results show that a yellow-brown contrast is obtained, not black, during the CO 2 laser marking of the paper manufactured according to the formulation 1. It is noted that it is easy to erase said laser marking with hypochlorite of sodium at 12% chlorine or with 5% sodium hydroxide solution. Formulation 2
On fabrique un substrat marquable au laser à l'aide d'une machine à papier traditionnelle avec la même formulation que précédemment mais en remplaçant le LAZERFLAIR® 800 par un octamolybdate d'ammonium.Manufacturing a laser markable substrate using a conventional paper machine with the same formulation as above but replacing the Lazerflair ® 800 by an ammonium octamolybdate.
Les résultats montrent que l'on obtient cette fois-ci un contraste gris noir lors du marquage au laser CO2 du papier fabriqué selon la formulation 2. On remarque qu'il est facile d'effacer ledit marquage laser avec de l'hypochlorite de sodium à 12 % de chlore ou avec une solution d'hydroxyde de sodium à 5 %. Formulations 3, 4, 5, 6, 7 et 8The results show that this time we obtain a gray-black contrast during CO 2 laser marking of the paper manufactured according to formulation 2. It is noted that it is easy to erase said laser marking with hypochlorite. sodium at 12% chlorine or with 5% sodium hydroxide solution. Formulations 3, 4, 5, 6, 7 and 8
On fabrique un substrat marquable au laser à l'aide d'une machine à papier traditionnelle en utilisant la formulation suivante :A laser-markable substrate is made using a conventional paper machine using the following formulation:
Pulpeur (raffinage à 35 degrés Schopper-Riegler - 0SR) - Fibres longues : 60 %, - Fibres courtes: 40 %.Pulper (35 degree Schopper-Riegler refining - 0 SR) - Long fibers: 60%, - Short fibers: 40%.
MélangeuseMixer
Charges minérales : 15 % en poids sec.Mineral fillers: 15% by dry weight.
Caisse de têteHeadbox
Agent de rétention : 1 ,5 % en masse par rapport à la production de papier de la machine à papier d'amidon cationique, par exemple à base de pomme de terre,Retention agent: 1.5% by weight relative to the paper production of the cationic starch paper machine, for example potato-based,
Agent de collage : 3,5 % en masse de la solution commerciale par rapport à la production de papier de la machine à papier d'émulsion cationique à base de colophane.Bonding agent: 3.5% by weight of the commercial solution compared to the paper production of the cationic emulsion paper machine based on rosin.
« Sizepress » (surfaçage, pour 2000 L)"Sizepress" (surfacing, for 2000 L)
Liant : 200 kg d'amidon de maïs modifié,Binder: 200 kg of modified corn starch,
Liant : 20 kg d'alcool polyvinylique (PVA),Binder: 20 kg of polyvinyl alcohol (PVA),
Antimousse : 0,35 kg d'une émulsion aqueuse d'un mélange aliphatique de composés hydroxylés,Antifoam: 0.35 kg of an aqueous emulsion of an aliphatic mixture of hydroxyl compounds,
Agent d'insolubilisation : 3 kg d'une solution commerciale de glyoxal modifié,Insolubilization agent: 3 kg of a commercial solution of modified glyoxal,
Matériau sensible au marquage laser : 250 kg d'octamolybdate d'ammonium.Material sensitive to laser marking: 250 kg of ammonium octamolybdate.
On réalise des essais avec différents types de charges minérales papetières autres que le kaolin (utilisé dans la formulation 2) : du dioxyde de titane rutile (formulationTests are carried out with different types of paper mineral charges other than kaolin (used in formulation 2): rutile titanium dioxide (formulation
3), du carbonate de calcium précipité (formulation 4), du silicoaluminate de sodium3), precipitated calcium carbonate (formulation 4), sodium silicoaluminate
(formulation 5), de l'hydroxyde d'aluminium (formulation 6), du talc (formulation 7) et du kaolin calciné (formulation 8).(Formulation 5), aluminum hydroxide (formulation 6), talc (formulation 7) and calcined kaolin (formulation 8).
Les résultats des tests de marquage (mesure de la densité optique) par irradiation laser CO2 sont les suivants :The results of the marking tests (measurement of optical density) by CO 2 laser irradiation are as follows:
Les résultats montrent que l'on obtient un contraste meilleur du marquage par irradiation laser lors de l'utilisation du kaolin calciné, du silicoaluminate de sodium ou de l'hydroxyde d'aluminium comme charge minérale papetière. Cependant il est ensuite facile d'effacer la marque laser avec de l'hypochlorite de sodium à 12 % de chlore ou une solution d'hydroxyde de sodium à 5 %. Formulations 9, 10, 11 et 12The results show that a better contrast of the laser irradiation marking is obtained when using calcined kaolin, sodium silicoaluminate or aluminum hydroxide as paper mineral filler. However, it is then easy to erase the laser mark with sodium hypochlorite 12% chlorine or 5% sodium hydroxide solution. Formulations 9, 10, 11 and 12
On fabrique quatre substrats marquables par irradiation laser sur une machine à papier traditionnelle selon la formulation de masse (avant surfaçage) commune suivante : Pulpeur (raffinage à 35 degrés Schopper-Riegler - 0SR)Four markable substrates are produced by laser irradiation on a conventional paper machine according to the following common mass formulation (before surfacing): Pulper (35 degree Schopper-Riegler refining - 0 SR)
- Fibre longue : 60 %,- Long fiber: 60%,
- Fibre courte : 40 %. Mélangeuse - Charge minérale : 15 % en poids sec de kaolin calciné. Caisse de tête- Short fiber: 40%. Mixer - Mineral feed: 15% by dry weight of calcined kaolin. Headbox
Agent de rétention : 1 ,5 % en masse par rapport à la production de papier de la machine à papier d'amidon cationique, par exemple à base de pomme de terre, Agent de collage : 3,5 % en masse de la solution commerciale par rapport à la production de papier de la machine à papier d'émulsion cationique à base de colophane.Retention agent: 1.5% by mass with respect to the paper production of the cationic starch paper machine, for example based on potato, Bonding agent: 3.5% by weight of the commercial solution compared to the paper production of the cationic emulsion paper machine based on rosin.
On applique ensuite en ligne sur le matelas fibreux précédent respectivement les quatre formulations de « size press » suivantes : « Size press » (surfaçage, pour 2000 L) pour la formulation 9 - Liant : 200 kg d'amidon de maïs modifié,The following four size press formulations are then applied in line on the previous fibrous mat: "Size press" (for 2000 L) for formulation 9 - Binder: 200 kg of modified corn starch
Antimousse : 0,35 kg d'une émulsion aqueuse d'un mélange aliphatique de composés hydroxylés,Antifoam: 0.35 kg of an aqueous emulsion of an aliphatic mixture of hydroxyl compounds,
Agent d'insolubilisation : 3 kg d'une solution commerciale de glyoxal modifié, Matériau sensible au marquage laser : 250 kg d'octamolybdate d'ammonium. « Size press » (surfaçage, pour 2000 L) pour la formulation 10 Liant : 200 kg d'amidon de maïs modifié, Liant : 20 kg d'alcool polyvinylique (PVA),Insoluble agent: 3 kg of a modified glyoxal commercial solution, material sensitive to laser marking: 250 kg of ammonium octamolybdate. "Size press" (for 2000 L) for the formulation 10 Binder: 200 kg of modified corn starch, Binder: 20 kg of polyvinyl alcohol (PVA),
Antimousse : 0,35 kg d'une émulsion aqueuse d'un mélange aliphatique de composés hydroxylés, - Agent d'insolubilisation : 3 kg d'une solution commerciale de glyoxal modifié,Antifoam: 0.35 kg of an aqueous emulsion of an aliphatic mixture of hydroxyl compounds, - insolubilizing agent: 3 kg of a commercial solution of modified glyoxal,
Matériau sensible au marquage laser : 250 kg d'octamolybdate d'ammonium. « Size press » (surfaçage, pour 2000 L) pour la formulation 11 Liant : 100 kg d'alcool polyvinylique (PVA),Material sensitive to laser marking: 250 kg of ammonium octamolybdate. "Size press" (for 2000 L) for formulation 11 Binder: 100 kg of polyvinyl alcohol (PVA),
Antimousse : 0,35 kg d'une émulsion aqueuse d'un mélange aliphatique de composés hydroxylés,Antifoam: 0.35 kg of an aqueous emulsion of an aliphatic mixture of hydroxyl compounds,
Agent d'insolubilisation : 3 kg d'une solution commerciale de glyoxal modifié, - Matériau sensible au marquage laser : 250 kg d'octamolybdate d'ammonium. « Sizepress » (surfaçage, pour 2000 L) pour la formulation 12 Liant : 100 kg d'alcool polyvinylique (PVA),Insoluble agent: 3 kg of a commercial solution of modified glyoxal, - Material sensitive to laser marking: 250 kg of ammonium octamolybdate. "Sizepress" (surfacing, for 2000 L) for formulation 12 Binder: 100 kg polyvinyl alcohol (PVA),
- Antimousse : 0,35 kg d'une émulsion aqueuse d'un mélange aliphatique de composés hydroxylés, - Agent de collage de surface : 50 kg d'un dérivé de styrène acrylique modifié, Agent d'insolubilisation : 3 kg d'une solution commerciale de glyoxal modifié, Matériau sensible au marquage laser : 250 kg d'octamolybdate d'ammonium.- Antifoam: 0.35 kg of an aqueous emulsion of an aliphatic mixture of hydroxyl compounds, - Surface bonding agent: 50 kg of a modified acrylic styrene derivative, insolubilising agent: 3 kg of a solution modified glyoxal, Material sensitive to laser marking: 250 kg ammonium octamolybdate.
On remarque que de meilleurs résultats en terme de contraste du marquage par irradiation laser CO2 sont obtenus sur le papier fabriqué selon les formulations 11 et 12 lorsque l'on utilise un liant de surface sous la forme de polyvinylalcool (PVA).It is noted that better results in terms of CO 2 laser irradiation marking contrast are obtained on the paper manufactured according to the formulations 11 and 12 when a surface binder in the form of polyvinyl alcohol (PVA) is used.
Cependant il est ensuite facile d'effacer la marque laser avec de la javel à 12 % de chlore ou une solution d'hydroxyde de sodium à 5 %.However it is then easy to erase the laser mark with bleach at 12% chlorine or 5% sodium hydroxide solution.
Par ailleurs, le papier fabriqué selon la formulation 12 présente une meilleure imprimabilité offset, laser et jet d'encre que celui fabriqué selon la formulation 11. Formulation 13Moreover, the paper manufactured according to the formulation 12 has a better offset, laser and inkjet printability than that manufactured according to the formulation 11. Formulation 13
On fabrique un substrat papier marquable par irradiation laser selon l'invention sur une machine à papier traditionnelle avec les caractéristiques suivantes : Pulpeur (raffinage à 35 degrés Schopper-Riegler - 0SR)A laser-markable paper substrate according to the invention is manufactured on a conventional paper machine with the following characteristics: Pulper (35 degree refining Schopper-Riegler - 0 SR)
- Fibre longue : 60 %, - Fibre courte : 40 %.- Long fiber: 60%, - Short fiber: 40%.
MélangeuseMixer
Charge minérale : 15 % en poids sec de kaolin calciné,Mineral charge: 15% by dry weight of calcined kaolin,
Agent d' infalsification à base de xanthène (indicateur coloré) : 0,3 % en masse de la solution commerciale par rapport à la production de papier de la machine à papier. Caisse de têteXanthene tampering agent (colored indicator): 0.3% by weight of the commercial solution compared to the papermaking machine paper production. Headbox
Agent de rétention : 1 ,5 % en masse par rapport à la production de papier de la machine à papier d'amidon cationique, par exemple à base de pomme de terre, Agent de collage : 3,5 % en masse de la solution commerciale par rapport à la production de papier de la machine à papier d'émulsion cationique à base de colophane.Retention agent: 1.5% by weight relative to the paper production of the cationic starch paper machine, for example potato-based, Bonding agent: 3.5% by weight of the commercial solution compared to the paper production of the cationic emulsion paper machine based on rosin.
« Sizepress » (surfaçage, pour 2000 L) - Liant : 100 kg d'alcool polyvinylique (PVA),"Sizepress" (surfacing, for 2000 L) - Binder: 100 kg polyvinyl alcohol (PVA),
- Antimousse : 0,35 kg d'une émulsion aqueuse d'un mélange aliphatique de composés hydroxylés,Antifoam: 0.35 kg of an aqueous emulsion of an aliphatic mixture of hydroxylated compounds,
Agent d'insolubilisation : 3 kg d'une solution commerciale de glyoxal modifié, Matériau sensible au marquage laser : 250 kg d'octamolybdate d'ammonium, - Agent d'infalsifîcation : 20 kg de chlorure de manganèse.Insoluble agent: 3 kg of a commercial solution of modified glyoxal, material sensitive to laser marking: 250 kg of ammonium octamolybdate, anti-tampering agent: 20 kg of manganese chloride.
On obtient un papier qui présente un contraste élevé, notamment par marquage par irradiation laser CO2. De plus, une tentative d'effacement de la marque laser, par exemple à l'aide d'hypochlorite de sodium à 12 degrés de chlore ou d'une solution d'hydroxyde de sodium à 5 %, entraîne l'apparition d'une tâche colorée brune qui permet de révéler la tentative de falsification du marquage sur le papier. Une tentative d'effacement de la marque laser à l'aide d'acide, comme par exemple de l'acide sulfurique à 5%, entraîne l'apparition d'une tâche colorée rosé qui permet aussi de révéler la tentative de falsification du marquage sur le substrat.A high contrast paper is obtained, in particular by CO 2 laser irradiation marking. In addition, an attempt to erase the laser mark, for example using sodium hypochlorite at 12 degrees of chlorine or 5% sodium hydroxide solution, results in the appearance of a Brown colored stain that reveals the attempt to falsify the mark on the paper. An attempt to erase the laser mark with acid, such as for example 5% sulfuric acid, causes the appearance of a pink colored stain which also reveals the attempt to falsify the marking. on the substrate.
L'expression « comportant un » est synonyme de « comportant au moins un ». The phrase "having one" is synonymous with "having at least one".

Claims

REVENDICATIONS
1. Substrat marquable au laser, comportant au moins un matériau apte à former une marque colorée sous irradiation laser, et au moins un agent d'infalsifïcation produisant une coloration visible irréversible lors d'une tentative d'effacement chimique de la marque.1. Laser-marked substrate, comprising at least one material capable of forming a colored mark under laser irradiation, and at least one tampering agent producing an irreversible visible coloring during an attempt to chemically erase the mark.
2. Substrat selon la revendication 1, l'agent d'infalsifïcation étant incorporé en masse, par imprégnation, par surfaçage, par couchage ou par pulvérisation.2. Substrate according to claim 1, the tamper agent being incorporated by mass, impregnation, surfacing, coating or spraying.
3. Substrat selon l'une des revendications précédentes, l'agent d'infalsifïcation permettant de prévenir l'effacement chimique de la marque avec au moins un des composés suivants : un oxydant, une base forte ou faible,3. Substrate according to one of the preceding claims, the tampering agent for preventing the chemical erasure of the mark with at least one of the following compounds: an oxidant, a strong base or weak,
- un acide fort ou faible, - un solvant polaire ou apolaire.a strong or weak acid, a polar or apolar solvent.
4. Substrat selon l'une des revendications précédentes, l'agent d'infalsifïcation permettant de prévenir l'effacement chimique de la marque avec des oxydants et étant choisi parmi : les dérivés de manganèse, de nickel, de cobalt ou de cérium, et notamment leurs sels, - le pp diamino-diphényl, ses dérivés sulfates ou ses dérivés phosphates, les dérivés du vanadium,4. Substrate according to one of the preceding claims, the tampering agent for preventing the chemical erasure of the mark with oxidants and being chosen from: derivatives of manganese, nickel, cobalt or cerium, and in particular their salts, - diphenyl-diphenyl, its sulphate derivatives or its phosphate derivatives, the vanadium derivatives,
- le 4,4' diaminodinaphtyl (1,1 '),4,4'-diaminodinaphthyl (1,1 '),
- le S, N orthophenylène isothiourée, la primuline, - les dérivés de guanidine tels que les diarylguanidine comme par exemple la diphenylguanidine, ou les dérivés du thiazole, du benzothiazole ou de l'aminonaphtothiazole.- S, N orthophenylene isothiourea, primulin, - guanidine derivatives such as diarylguanidine such as diphenylguanidine, or thiazole derivatives, benzothiazole or aminonaphthothiazole.
5. Substrat selon l'une des revendications précédentes, l'agent d'infalsifïcation permettant de prévenir l'effacement chimique avec des bases fortes et/ou faibles et étant choisi parmi : les dérivés de manganèse, de nickel, de cobalt ou de cérium, et notamment leurs sels, les indicateurs colorés tels que le paranitrophénol, la phénolphtaléine, la pyranine ou un dérivé de xanthène.5. Substrate according to one of the preceding claims, the tamper-preventing agent for preventing chemical erasure with strong and / or weak bases and being chosen from: derivatives of manganese, nickel, cobalt or cerium , and in particular their salts, colored indicators such as paranitrophenol, phenolphthalein, pyranine or a xanthene derivative.
6. Substrat selon l'une quelconque des revendications précédentes, l'agent d'infalsifïcation permettant de prévenir l'effacement chimique de la marque avec des acides faibles et/ou forts et étant choisi parmi : un indicateur coloré tel qu'un dérivé du xanthène, - le ferrocyanure de potassium additionné de chlorure ferrique, ou un dérivé du thiazole, du benzothiazole ou de l'aminonaphtothiazole.6. Substrate according to any one of the preceding claims, the tampering agent for preventing the chemical erasure of the mark with weak and / or strong acids and being chosen from: a colored indicator such as a derivative of xanthene, - ferric ferrocyanide supplemented with ferric chloride, or a thiazole derivative, benzothiazole or aminonaphthothiazole.
7. Substrat selon l'une quelconque des revendications précédentes, l'agent d'infalsifïcation permettant de prévenir l'effacement chimique avec des solvants polaires et/ou apolaires et étant choisi parmi les colorants insolubles dans l'eau mais so lubies dans les huiles et solvants, notamment dans de l'éthanol et/ou du toluène.7. Substrate according to any one of the preceding claims, the tamper inhibiting agent for preventing chemical erasure with polar solvents and / or apolar and being selected from water-insoluble dyes but sucked in oils and solvents, especially in ethanol and / or toluene.
8. Substrat selon l'une quelconque des revendications précédentes, l'agent d'infalsifïcation étant un dérivé de manganèse, notamment un sel de manganèse et de préférence du chlorure de manganèse.8. Substrate according to any one of the preceding claims, the tampering agent being a manganese derivative, especially a manganese salt and preferably manganese chloride.
9. Substrat selon l'une quelconque des revendications précédentes, le matériau apte à former une marque colorée sous irradiation laser étant incorporé en masse, par imprégnation, par surfaçage, par couchage ou par pulvérisation.9. Substrate according to any one of the preceding claims, the material capable of forming a colored mark under laser irradiation being incorporated by mass, impregnation, surfacing, coating or spraying.
10. Substrat selon l'une quelconque des revendications précédentes, le matériau étant apte au marquage par un laser UV ou par un laser infrarouge, en particulier un laser CO2 et/ou un laser YAG.10. Substrate according to any one of the preceding claims, the material being suitable for marking by a UV laser or an infrared laser, in particular a CO 2 laser and / or a YAG laser.
11. Substrat selon l'une quelconque des revendications précédentes, ladite marque colorée présentant un relief.11. Substrate according to any one of the preceding claims, said colored mark having a relief.
12. Substrat selon l'une quelconque des revendications précédentes, le matériau apte à former une marque étant choisi parmi les dérivés du mica, les molybdates, les tungstates et les vanadates, et notamment les octamolybdates, les heptamolybdates et les aminés molybdates.12. Substrate according to any one of the preceding claims, the material capable of forming a mark being chosen from mica derivatives, molybdates, tungstates and vanadates, and in particular octamolybdates, heptamolybdates and amine molybdates.
13. Substrat selon l'une quelconque des revendications précédentes, comportant une charge minérale absorbant dans l'infrarouge, notamment du kaolin calciné ou du trihydrate d'alumine. Substrate according to any one of the preceding claims, comprising a mineral filler absorbing in the infrared, in particular calcined kaolin or alumina trihydrate.
14. Substrat selon l'une quelconque des revendications précédentes, comportant de l'alcool polyvinylique (PVA), notamment hautement hydrolyse, notamment à plus de 94 %.14. Substrate according to any one of the preceding claims, comprising polyvinyl alcohol (PVA), especially highly hydrolyzed, in particular more than 94%.
15. Substrat selon l'une quelconque des revendications précédentes, étant à base de fibres cellulosiques, notamment un papier.15. Substrate according to any one of the preceding claims, being based on cellulosic fibers, in particular paper.
16. Substrat selon l'une quelconque des revendications 1 à 14, étant un substrat plastique.The substrate of any one of claims 1 to 14, being a plastic substrate.
17. Substrat selon l'une quelconque des revendications précédentes, comprenant au moins un élément de sécurité d'authentifîcation et/ou d'identification. 17. Substrate according to any one of the preceding claims, comprising at least one authentication and / or identification security element.
18. Substrat selon l'une quelconque des revendications précédentes, la concentration en matériau apte à former une marque colorée étant comprise entre 0,1 et 10 % en poids sec par rapport au poids du substrat, de préférence entre 1 et 10 %.18. Substrate according to any one of the preceding claims, the concentration of material capable of forming a colored mark being between 0.1 and 10% by dry weight relative to the weight of the substrate, preferably between 1 and 10%.
19. Substrat selon l'une quelconque des revendications précédentes, la concentration en agent d'infalsifîcation étant comprise entre 0,01 et 5 % en poids sec par rapport au poids du substrat.19. Substrate according to any one of the preceding claims, the concentration of tamper agent being between 0.01 and 5% by dry weight relative to the weight of the substrate.
20. Utilisation d'un substrat marquable au laser selon l'une quelconque des revendications précédentes, dans un document de sécurité et/ou un article de sécurité.20. Use of a laser marker substrate according to any one of the preceding claims, in a security document and / or security article.
21. Procédé de fabrication d'un substrat marquable au laser selon l'une quelconque des revendications 1 à 19, comportant l'étape consistant à introduire en masse, par imprégnation, notamment selon un procédé « size press », ou par surfaçage, notamment selon un procédé « film press », lors de la fabrication du substrat sur une machine à papier, le matériau apte à former une marque colorée sous irradiation laser. 21. A method of manufacturing a laser marker substrate according to any one of claims 1 to 19, comprising the step of introducing by mass, impregnation, in particular according to a "size press" method, or by surfacing, in particular according to a "film press" method, during the production of the substrate on a paper machine, the material capable of forming a colored mark under laser irradiation.
EP10712538A 2009-03-13 2010-03-15 Laser-markable substrate, and associated manufacturing method Withdrawn EP2406084A1 (en)

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FR0951612A FR2943074B1 (en) 2009-03-13 2009-03-13 LASER MARKABLE SUBSTRATE AND METHOD FOR MANUFACTURING THE SAME
PCT/IB2010/051110 WO2010103499A1 (en) 2009-03-13 2010-03-15 Laser-markable substrate, and associated manufacturing method

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