[go: up one dir, main page]

EP3291995B1 - Document de valeur ou de sécurité, procédé de production d'une liaison adhésive entre un élément de sécurité et la surface du document de valeur ou de sécurité, ainsi qu'utilisation d'une substance adhésive à un composant - Google Patents

Document de valeur ou de sécurité, procédé de production d'une liaison adhésive entre un élément de sécurité et la surface du document de valeur ou de sécurité, ainsi qu'utilisation d'une substance adhésive à un composant Download PDF

Info

Publication number
EP3291995B1
EP3291995B1 EP16720419.7A EP16720419A EP3291995B1 EP 3291995 B1 EP3291995 B1 EP 3291995B1 EP 16720419 A EP16720419 A EP 16720419A EP 3291995 B1 EP3291995 B1 EP 3291995B1
Authority
EP
European Patent Office
Prior art keywords
meth
acrylate
adhesive
radiation
security
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.)
Active
Application number
EP16720419.7A
Other languages
German (de)
English (en)
Other versions
EP3291995A1 (fr
Inventor
Michael Stasiak
Jeffry Gahlbeck
Timm HAUG
Stefan Singer
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.)
Bundesdruckerei GmbH
Original Assignee
Bundesdruckerei GmbH
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 Bundesdruckerei GmbH filed Critical Bundesdruckerei GmbH
Publication of EP3291995A1 publication Critical patent/EP3291995A1/fr
Application granted granted Critical
Publication of EP3291995B1 publication Critical patent/EP3291995B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/20—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof characterised by a particular use or purpose
    • B42D25/23—Identity cards
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/20—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof characterised by a particular use or purpose
    • B42D25/29—Securities; Bank notes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • B42D25/328—Diffraction gratings; Holograms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/40—Manufacture
    • B42D25/45—Associating two or more layers
    • B42D25/465—Associating two or more layers using chemicals or adhesives
    • B42D25/47—Associating two or more layers using chemicals or adhesives using adhesives

Definitions

  • the present invention relates to a value or security document which has a security element connected thereto by means of a one-component adhesive, in particular a diffraction element, for example a holographic data carrier. Furthermore, the present invention also relates to a method for producing a primer bond between a support of a value or security document and a security element by means of a one-component adhesive. Finally, the present invention also relates to a use of the one-component adhesive.
  • Value or security products serve to verify the identity of a person or thing or a claim, for example, for payment of a sum of money or for the issue of a product or service.
  • the product therefore contains security features whose imitation is extremely difficult or even practically impossible.
  • the product such as banknotes, consists of a not readily available material.
  • security features may be formed by special colors, for example luminescent or optically variable colors, optical elements, such as holograms, tilt images, kinegraphic objects, lens or prism arrays, also guilloches, mottled fibers, security threads and others.
  • the value or security documents are easy to produce.
  • optical security elements may be manufactured separately and then adhered as patches, security threads, security strips or the like to an exterior surface on the security or security product or to an interior surface in the security or security product.
  • Such security elements may be optically variable elements such that visually perceivable phenomena produced therewith may either be discernible and / or take different shapes depending on the angle at which the asset or security document is viewed.
  • a multi-layered security document comprising a printable substrate, a photopolymer film bonded to the substrate on a first side, and a first cover film bonded to the photopolymer film or a first cover film composite bonded to the photopolymer film.
  • the photopolymer film is connected to the carrier material via a first adhesive film.
  • a volume hologram is imprinted.
  • a so-called transfer adhesive film is used. It is an acrylate-based adhesive material.
  • the carrier is formed, for example, from polyethylene or polyethylene terephthalate.
  • the adhesive film may be pressure and / or thermally activated.
  • Out DE 10 2010 033 049 A1 discloses a laminate composite having a first polymer layer, a second polymer layer and a security element laminated between the first polymer layer and the second polymer layer, wherein a layer of a reactive adhesive is disposed at least between the security element and the first polymer layer.
  • a layer of a reactive adhesive is disposed at least between the security element and the first polymer layer.
  • For lamination of the security element at least one side of the security element or the side of the first polymer layer facing the security element is coated with a reactive adhesive. Then, the first polymer layer and the security element are positioned to each other and connected to each other. Thereafter, the adhesive is crosslinked, and finally, the first and second polymer layers are laminated together with the inclusion of the security element under pressure and heating.
  • one-component systems are used as reactive adhesives, namely heat-crosslinkable systems comprising a base polymer and a heat-activated crosslinker, for example epoxides, urethanes, polyesters and polyimides, furthermore radiation-crosslinkable systems, which are usually based on acrylate, and systems which crosslink by moisture, for example cyanoacrylates and urethanes.
  • heat-crosslinkable systems comprising a base polymer and a heat-activated crosslinker, for example epoxides, urethanes, polyesters and polyimides
  • radiation-crosslinkable systems which are usually based on acrylate
  • systems which crosslink by moisture for example cyanoacrylates and urethanes.
  • two-component systems can also be used.
  • the term 'actinic radiation' means radiation which is capable of curing the one-part adhesive according to the present invention.
  • electromagnetic radiation for example radiation in the UV and / or visible (VIS) spectral range or higher-energy radiation, such as X-ray radiation, synchrotron radiation and the like
  • body radiation with a suitable wavelength for example electron beams.
  • alkyl groups include, but are not limited to, methyl (-CH 3 ), ethyl (-CH 2 CH 3 ), 1-propyl (-CH 2 CH 2 CH 3 ), 2-propyl (-CH (CH 3 ) 2 ), 1-butyl (-CH 2 CH 2 CH 2 CH 3 ), 2-methyl-1-propyl (-CH 2 CH (CH 3 ) 2 ), 2-butyl (-CH (CH 3 ) CH 2 CH 3 ), 2-methyl-2-propyl (-C (CH 3 ) 3 ), 1-pentyl (-CH 2 CH 2 CH 2 CH 3 ), 2-pentyl (-CH (CH 3 ) CH 2 CH 2 CH 3 ), 3-pentyl (-CH (CH 2 CH 3 ) 2 ), 2-methyl-2-butyl (-C (CH 3 ) 2 CH 2 CH 3 ) 3-methyl-2-butyl (-CH (CH 3 ) CH (CH 3 ) 2 ), 3-methyl-1-butyl (-CH 2 CH 2 CH (CH (CH
  • alkylene' is a saturated linear or branched chain divalent among them Hydrocarbon radical having one to twelve carbon atoms to understand, wherein the alkylene radical may optionally be independently substituted with one or more substituents.
  • alkylene groups include, but are not limited to, methylene (-CH 2 -), ethylene (-CH 2 CH 2 -), propylene (-CH 2 CH 2 CH 2 - or -CH (CH 3 ) CH 2 -) , and the same.
  • alkylene oxide' is to be understood as meaning a saturated linear or branched chain group having the general formula - (alkylene-O) q -, where q is an integer, the value thereof For example, it is determined that the number of carbon atoms of the alkylene groups is in a range of 12 to about 500, for example.
  • the term 'substituent' is taken to mean a monovalent chemical radical selected from a group comprising C 1 to C 12 alkyl, Hal (F, Cl, Br , I), -OR 1 , -NR 1 R 2 , -COOR 1 , -CONR 1 R 2 , wherein R 1 and R 2 are independently H and C 1 - to C 6 alkyl.
  • R 1 and R 2 are independently H and C 1 - to C 6 alkyl.
  • the adhesive is easy to process, ie has a sufficiently long pot life under normal daylight conditions, while ensuring that the Curing with actinic radiation also passes quickly through the security element.
  • the viscosity of the adhesive must be sufficiently low to ensure that it can be applied to the bonding partner or compounds without the formation of air bubbles and streaks. This also includes the fact that the adhesive sufficiently wets the connection partner or partners sufficiently to achieve a full-surface and seamless coating of the surface.
  • the adhesive must be used to ensure that the visually recognizable security element is not compromised by the Adhesive layer should be recognizable by, transparent and to be as colorless as possible transparent, which also presupposes that the adhesive does not nachgilbt during the curing process and / or aging, especially when exposed to UV light or otherwise changes the color.
  • the adhesive must also not attack the carrier and the security element and lead to a color shift, for example, in the material of the security element.
  • the adhesive must have high flexibility to prevent tearing or flaking of the security element.
  • the adhesive must have a very high peel strength of the security element on the support, i. a very high adhesion between the partners, ensure. This requires good chemical compatibility with the materials of the carrier and the security element and also includes the requirement that the adhesive strength and all other requirements must be maintained over a longer period of 10 to 15 years.
  • the requirements mentioned above are met.
  • an exceptionally stable composite strength of polycarbonate-containing or polycarbonate-formed materials is achieved with other polymers, for example polyethylene terephthalate, polyvinyl acetate or fluoropolymers.
  • the adhesive forms a curable composition that is liquid at room temperature and has a dynamic viscosity at room temperature (20 ° C) that is in the range of 500 to 3000 mPa ⁇ s (measured with a cylinder-cup geometry rotary viscometer).
  • the dynamic viscosity is 1000 mPa ⁇ s (20 ° C). This ensures that the adhesive mass can be applied without streaks and bubbles and that it wets the surfaces to be bonded well.
  • the adhesive has a high transparency and is optionally completely colorless, so that the security element itself is easily visually recognizable without being impaired by the adhesive.
  • the adhesive has excellent stability to moisture. Water does not alter the physical and chemical properties of the adhesive, such as its transparency, color and bond strength.
  • the one-component adhesive according to the present invention is also sufficiently storage-stable.
  • the adhesive is highly flexible.
  • the one-component adhesive is preferably solvent-free, resulting in advantageous properties with regard to the processability of the adhesive.
  • an additional radiation-curing compound crosslinker
  • the adhesive is irreversibly crosslinked under the action of actinic radiation.
  • the properties of the adhesive composition are optimized so that the durability of the adhesive bond is as great as possible.
  • the one-component adhesive also has sufficient flexibility, ie the adhesive or the adhesive layer ideally shows under the given conditions, no breaks and cracks.
  • the one-component adhesive contains, as at least one component A, an oligomeric urethane (meth) acrylate based on a polycarbonate diol, i. based on an oligomeric compound having a polycarbonate chain which forms the backbone for the urethane (meth) acrylate, wherein the polycarbonate chain is functionalized at least at the chain ends with radically polymerizable groups, in particular (meth) acrylic groups.
  • the at least one polycarbonate diol (compound (i)) can be synthesized in a known manner by polycondensation of polyols and dialkyl carbonates suitable for their preparation, for example dimethyl carbonate, diaryl carbonates, such as diphenyl carbonate, or phosgene.
  • a polyol may be reacted with, for example, a dialkyl carbonate, diaryl carbonate or phosgene, or a polyol may be reacted with a plurality of different compounds selected from dialkyl carbonates, diaryl carbonates and phosgene, or several different polyols with a dialkyl carbonate , Diaryl carbonate or phosgene, or several different polyols can be reacted with several various compounds selected from dialkyl carbonates, diaryl carbonates and phosgene.
  • Polyols used are polyhydric, preferably saturated or unsaturated, aliphatic, cycloaliphatic or araliphatic alcohols having at least two hydroxyl groups, it being possible for the hydroxyl groups to be bonded both primarily and secondarily.
  • Suitable polyols are, for example, polyols having two hydroxyl groups, for example ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butenediol, 1, 4-butynediol, 1,5-pentanediol and the isomeric pentanediols, including neopentyl glycol, also pentene diols or pentynediols or mixtures of two or more thereof, 1,6-hexanediol, and the isomeric hexanediols, hexenediols or hexynediols or mixtures of two or more thereof , 1,7-heptanediol and the isomeric heptane, heptene or
  • polyols having more than two hydroxyl groups such as glycerol, trimethylolethane, trimethylolpropane, di (trimethylolpropane) -dimethylolpropionic acid, trimethylolethane, ditrimethylolpropane, pentaerythritol, dipentaerythritol and anhydroeneneaheptitol.
  • glycerol trimethylolethane
  • trimethylolpropane di (trimethylolpropane) -dimethylolpropionic acid
  • trimethylolethane ditrimethylolpropane
  • pentaerythritol dipentaerythritol and anhydroeneneaheptitol
  • mixtures of two or more of said polyols can be used.
  • the polycarbonate diol has a molar mass of 500 to 10,000 g / mol, preferably from 1,000 to 5,000 g / mol, and most preferably from 1,500 to 2,500 g / mol. Most preferred is a molar mass of about 2,000 g / mol.
  • Polycarbonate diols are also commercially available, for example under the trade names Desmophen® C2200 from Bayer MaterialScience AG.
  • the polycarbonate diol is reacted in the first step of the synthesis with a polyfunctional, preferably difunctional, isocyanate compound (ii), i. a diisocyanate compound to yield an isocyanate-functionalized polycarbonate diol.
  • a polyfunctional, preferably difunctional, isocyanate compound (ii), i. a diisocyanate compound to yield an isocyanate-functionalized polycarbonate diol.
  • a polyfunctional isocyanate compound (ii) i. a diisocyanate compound to yield an isocyanate-functionalized polycarbonate diol.
  • a polyfunctional isocyanate compound (ii) i. a diisocyanate compound to yield an isocyanate-functionalized polycarbonate diol.
  • several different polycarbonate diols can be reacted with a polyfunctional isocyanate, or a polycarbonate diol can be reacted with several different polyfunctional isocyanates, or several
  • At least one compound is selected from a group comprising isophorone diisocyanate (IPDI: 1-isocyanatomethyl-3-isocyanato-1,5,5-trimethylcyclohexane), 1,5-naphthylene diisocyanate, diphenylmethane diisocyanate (MDI), namely 2,2 '.
  • IPDI isophorone diisocyanate
  • MDI diphenylmethane diisocyanate
  • the polycarbonate diol is reacted with the polyisocyanate preferably in a molar ratio (polycarbonate diol to polyisocyanate) in a range of 1: 1.8 to 1: 2.2, most preferably in a ratio of 1: 2.
  • the reaction can be carried out in the usual manner in an aprotic solvent, for example in a halogenated organic solvent.
  • aprotic solvent for example in a halogenated organic solvent.
  • solvents which are not halogen-containing for example acetone, methyl isobutyl ketone or ethyl acetate.
  • the reaction temperature may be at room temperature.
  • the temperature of the reaction mixture can usually be increased, for example to 40 to 80 ° C.
  • the catalysts known in polyurethane chemistry in particular organometallic compounds, for example at least one compound selected from a group comprising dibutyltin laurate (DBTL), dibutyltin acetate or dibutyltin versat, tin octoate, iron (II) chloride, zinc chloride and Lead octoate.
  • DBTL dibutyltin laurate
  • II iron
  • Tin salts are preferably used, for example Zinndioctoat, Zinndiethylhexoat and dibutyltin-bis-dodecyl-mercaptide.
  • lead salts for example lead phenyl ethyldithiocarbamate
  • bismuth salts for example triaryl bismuth compounds, oxides of these compounds and also bismuth phenates and carboxylates.
  • Other organometallic salts are derived from compounds of iron, titanium and zirconium.
  • the catalysts can be used in the reaction mixture in a concentration, for example, from 0.1 to 5 wt .-%.
  • reaction may be conducted to form the isocyanate-functionalized polycarbonate diol in the presence of stabilizers, for example in the presence of butylated hydroxytoluene (BHT) and hydroquinone monomethyl ether (HQMME).
  • BHT butylated hydroxytoluene
  • HQMME hydroquinone monomethyl ether
  • reaction of the at least one polycarbonate diol with the at least one polyfunctional isocyanate is carried out in a preferred development of the present invention in the presence of a diluent.
  • the diluent used is a (meth) acrylate which is selected from a group comprising 3,3,5-trimethylcyclohexyl (meth) acrylate, tert- butylcyclohexyl (meth) acrylate, 2- (2- Ethoxyethoxy) ethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, (5-ethyl-1,3-dioxane-5 yl) methyl (meth) acrylate, 1,6-hexanediol di (meth) acrylate, lauryl (meth) acrylate, isodecyl (meth) acrylate, isooctyl (meth) acrylate,
  • a second synthesis step in which the at least one oligomeric urethane (meth) acrylate (component A) is formed, all NCO groups present are subsequently reacted with at least one compound (iii) which carries a functional group which reacts with isocyanates can, and which has as a further functional group a crosslinkable by free-radical polymerization double bond.
  • These compounds usually have a molecular weight of at most 1000 g / mol (at least 100 g / mol).
  • These compounds can be selected from a group comprising esters and amides of ⁇ , ⁇ -unsaturated carboxylic acids with one or more low molecular weight, aliphatic alcohols or amines, which additionally have a further OH or SH group.
  • the isocyanate-functionalized polycarbonate obtained by reacting the at least one polycarbonate diol with the at least one polyfunctional isocyanate and the compound (iii) containing the radically polymerizable groups are preferably used in a molar ratio (isocyanate-functional polycarbonate to compound (iii)) in a range from 1: 1.8 to 1: 2.2, most preferably in a molar ratio of 1: 2 used.
  • reaction conditions for the reaction of the isocyanate-functionalized polycarbonate diol with the compound (iii) are basically the same as in the reaction of the compounds (i) and (ii) (see above).
  • the second component of the adhesive composition according to the present invention is formed by the at least one component B. It is a radiation curing compound, i. a compound which undergoes radical polymerization under the influence of actinic radiation.
  • the at least one radiation-curing compound is selected from a group comprising monomers, oligomers and polymers containing up to 20 radiation-reactive groups. It is very particularly preferred if the at least one component B carries 1 to 5 radiation-reactive groups. Optionally, a mixture of such monomers and / or oligomers and / or polymers may be used. In a most preferred embodiment of the present invention, at least one of the components B contains 3 to 5 radiation-reactive groups.
  • the at least one component B radiation-curing compounds are selected from a group comprising (meth) acrylic acid esters, (meth) acrylic acid amides, vinyl ethers and bismaleimides.
  • Further preferred free-radically polymerizable compounds are prepolymers based on polyols or polyurethanes which react with radiation-curing groups, such as (meth) acrylic esters, are substituted.
  • polyols the polyols specified above for the formation of the polycarbonate backbone of the at least one component A can be used (in this regard, reference is made to the disclosure therein).
  • reaction products of the diisocyanates mentioned above for the formation of the isocyanate-functionalized polycarbonate backbone (to which extent reference is made to the disclosure therein) and further higher-value polyisocyanates (tri-, tetraisocyanates) with the abovementioned polyols (in this respect, reference is again made to the disclosure there ) are used.
  • polyols of higher value or when using polyurethanes reacted for preparing the polyurethanes for example tri-, tetra- or penta-alcohols
  • dendrimers are formed which, likewise reacted with radiation-curing groups, can be used as component (s) B.
  • At least one, for example one, two, three or even more, preferably all, of the at least one radiation-curing compound (component B) has at least two, for example two, three, four, five, six or even more, functional groups for radiation curing, in particular at least two, for example two, three, four, five, six or even more, unsaturated bonds, in particular ethylenically unsaturated bonds.
  • component (s) B especially acid amides with radiation-reactive groups are / are suitable, for example (meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-ethyl (meth) acrylamide, N , N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N- tert- butyl (meth) acrylamide, N, N-dibutyl (meth) acrylamide, N-phenyl (meth ) acrylamide, N - ((meth) acryloyl) morpholine, N - ((meth) acryloyl) piperidine, N- (1,1-dimethyl-3-oxobutyl) (meth) acrylamide, N-1,1,3,3 Tetramethylbutyl (meth) acrylamide, dimethylene bis (meth
  • acids with radiation-reactive groups are also suitable, of which, for example, the abovementioned (meth) acrylamides are derived, namely, for example, (meth) acrylic acid and the like (in this respect, reference is made to the above list of acrylamides).
  • (meth) acrylates of polyols for example pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritolhexa (meth) acrylate, tripentaerythritol (meth ) acrylate, suitable.
  • polyols for example pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritolhexa (meth) acrylate, tripentaerythritol (meth ) acrylate,
  • the components B are selected from the group consisting of poly (meth) acrylates (di (meth) acrylates, tri (meth) acrylates, tetra (meth) acrylates, penta (meth) acrylates, etc.) of polyols, in particular pentaerythritol tri (meth) acrylate, poly (meth) acrylates having more than two acrylate groups being very particularly preferred.
  • polyfunctional acrylate compounds can also be used in combination with mono- and / or di-functional acrylate compounds, for example in order to specifically control the crosslinkability of the adhesive composition.
  • vinyl ethers and maleimides and bismaleimides are also suitable.
  • Typical examples of vinyl ether monomers are methyl vinyl ether, ethyl vinyl ether, hydroxybutyl vinyl ether, tert- butyl vinyl ether, isobutyl vinyl ether, triethylene glycol divinyl ether (available under the trade name RAPI-CURE® DVE-3 from International Specialty Products, U.S.A.), 1,4-cyclohexanedimethanol divinyl ether (available under the trade name RAPI-CURE® CHVE, International Specialty Products), trimethylolpropane trivinyl ether (available as TMPTVE from BASF Corp., US), divinyl ether resins (such as VECTOMER 2010, VECTOMER 2020, VECTOMER 4010, VECTOMER 4020), as well as similar materials and blends thereof.
  • the adhesive composition according to the present invention further contains at least one photoinitiator for radical polymerization.
  • at least one photoinitiator for radical polymerization it is possible to use the customary commercially available compounds which, upon the action of preferably UV radiation and / or radiation in the visible spectral region, decompose into reactive radicals, provided that the adhesive according to the invention is curable through the security element, i. the security element is transparent to the actinic radiation needed for curing.
  • the at least one photoinitiator it is also required that the adhesive has a sufficiently long processing time in daylight, for example, 1 hour (at least 30 minutes using artificial light).
  • photoinitiator ⁇ -hydroxyketones, benzophenone, ⁇ -aminoketones, benzophenone derivatives, such as 2,4,6-trimethylbenzophenone, 4-methylbenzophenone and 2-hydroxy-2-methylpropiophenone , benzyl dimethyl ketals, acyl phosphine oxides, for example diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (available as Lucirin® TPO-L from BASF), phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide, 2,4, 6-trimethylbenzoylethoxyphenylphosphine oxide, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone.
  • the Irgacure® types from BASF for example the types Irgacure® 184, Irgacure® 500, Irgacure® 1173, Irgacure® 651, Irgacure® 369, Irgacure® 127, Irgacure® 907, Irgacure® 1300, CGI 277, can be used .
  • These photoinitiators are UV photoinitiators, i. the radical polymerization takes place when irradiated in the UV spectral region.
  • the initiators Irgacure® 2022, Irgacure® 2100, Irgacure® TPO and Irgacure® TPO-L can only be used in small amounts of less than 1% by weight, based on the adhesive composition, since the processing time in daylight is otherwise too short , Particularly suitable is the initiator CGI 277, available from BASF SE. It is an ⁇ -amino ketone.
  • the adhesive composition in a most preferred embodiment of the present invention comprises an oligomeric urethane (meth) acrylate based on a polycarbonate as component A, pentaerythritol triacrylate as component B, and a mixture of diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide and 2-hydroxy 2-methylpropiophenone as components C.
  • the adhesive composition according to the present invention may contain at least one other modifier as component (s) D.
  • the modifiers are preferably selected from a group comprising fillers, dyes, pigments, luminescent agents, stabilizers, moisture scavengers, accelerators, adhesion promoters, crosslinkers, flexibilizers, polymeric thickeners, flame retardants, corrosion inhibitors, plasticizers and tackifiers.
  • dyes and pigments it is possible to use all commercially available compounds and compound mixtures which are soluble or at least miscible in the mixture of components A, B and C.
  • cationic, anionic or neutral colorants can be used.
  • Cartasol® Orange K3 GL, Cartasol® Yellow K4 GL, Cartasol® K GL, or Cartasol® Red K-3B where Bayscript® is a trademark of Lanxxess, DE, Cartasol® and Flexonyl® trademarks of Clariant, DE and Hostafine® are a trademark of Hoechst GmbH, DE.
  • anthraquinone, azo, quinophthalone, coumarin, methine, perinone, and / or pyrazole dyes can be used as soluble colorants.
  • the luminescent agent it is also possible to use all commercially available compounds and compound mixtures which are soluble in the mixture of components A, B and C.
  • the luminescent agents are in particular photoluminophores, electroluminophores, Antistokes luminophores, fluorophores and magnetizable, photoacoustically addressable and piezoelectric materials.
  • fluorescein, 2 ', 7'-dichlorofluorescein, xanthene dyes and rosamines and rhodamines, for example rhodamine B can be used.
  • silane compounds having the chemical structural formula (III) can be used: wherein: R 1 , R 2 , R 3 and R 4 are independently of one another: H, OH, Cl, F, C 4 to C 20 alkyl; C 1 to C 20 ether; C 1 to C 20 alkyl with an N, O or S-containing substituent; C 2 to C 20 alkenyl with an N, O or S-containing substituent; C 2 to C 20 alkynyl with an N, O or S-containing substituent; C 1 - to C 20 -ester, C 1 - to C 20 -hydroxyl, C 2 - to C 20 -alkenyl; or C 2 to C 20 alkynyl; on cyclic molecule containing 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or more rings optionally containing one or more side chains containing
  • Water-soluble starch in particular having an average molecular weight of 3,000 to 7,000 g / mol, polyvinylpyrolidone, in particular having an average molecular weight of 25,000 to 250,000 g / mol, polyvinyl alcohol, in particular having an average molecular weight of 10,000 to 20,000 g / mol, can be used as the polymeric thickener.
  • An example of the latter block copolymer is the product series Pluronic® from BASF, DE.
  • plasticizers phthalates, citric acid esters and other substances known for this purpose can be used.
  • the sum of the mass fractions of the components A, B and C gives a maximum of 100 mass fractions. If only components A, B and C are included in the adhesive composition, the sum of the mass fractions of these three components is exactly 100 parts by mass. If further additional components are included, the sum of the mass fractions of the three components A, B and C is less than 100 mass fractions, wherein the difference between 100 mass fractions and the sum of the mass fractions of the three components A, B and C is given by the mass fraction of the further component (s).
  • the sum of the mass fractions of the components A, B, C and D is 100 parts by mass, if not further constituents are contained in the adhesive composition, for example a solvent. If the sum of the mass fractions of the components A, B, C and D corresponds to less than 100 parts by mass of the adhesive composition, the difference between 100 parts by mass and the sum of the mass fractions of the four components A, B, C and D is given by the mass fraction of further constituents ,
  • the adhesive composition is applied to at least one bonding surface of the two bonding partners, namely the security element and / or the backing.
  • the one-component adhesive can be applied in a conventional manner to the at least one bonding surface, for example by means of printing, brushing, casting, rollercoating, curtain casting, spincoating, knife coating, dipping, dispensing or other coating techniques.
  • the layer thickness produced depends on the viscosity of the adhesive, on the wettability of the at least one bonding surface, the application method and on other parameters.
  • the layer thickness can preferably at least 1 ⁇ m, more preferably at least 2 ⁇ m, even more preferably at least 5 ⁇ m, and most preferably at least 7 ⁇ m.
  • the layer thickness may preferably be at most 1000 ⁇ m, more preferably at most 500 ⁇ m, even more preferably at most 50 ⁇ m and most preferably at most 30 ⁇ m.
  • the individual adhesive layers may be thinner, for example in the range of 1 to 20 microns.
  • the security element After placing the security element on the carrier at the connection point at which it is to be connected to the carrier on the surface thereof, the security element is brought into contact with the carrier surface at the connection point and connected thereto.
  • actinic radiation is used which causes activation of the at least one photoinitiator.
  • the actinic radiation is thus matched in terms of their spectral distribution and intensity to the at least one photoinitiator.
  • the at least one photoinitiator is adapted to the available actinic radiation.
  • the spectral distribution is to be determined so that the actinic radiation is absorbed by the at least one photoinitiator.
  • the intensity of the actinic radiation must be set so high that radical polymerization is promoted.
  • the actinic radiation is preferably in the UV spectral range, but may alternatively or additionally also be in another spectral range, for example in the visible (VIS) or IR spectral range.
  • UV radiation is advantageous because it allows for processability under normal daylight if the adhesive composition is not curable by irradiation of electromagnetic radiation in the VIS spectral range.
  • the curing step by means of the actinic radiation creates a very strong and irreversible connection between the security element and the carrier of the security document.
  • the curing time may be short or long, depending on the effect of actinic radiation on the one-part adhesive.
  • the curing time ranges from 0.5 seconds to 5 hours, preferably from 1 second to 30 minutes, more preferably from 2 seconds to 1 minute, and most preferably from 5 seconds to 20 seconds.
  • the irradiation of the adhesive layer is preferably carried out through the security element. Also possible is irradiation by the wearer of the value or security document. For this purpose, this is transparent form at least in the connection region for the actinic radiation.
  • the method according to the invention can be used in particular for applying a security element to a carrier of a security or security document, in particular a security or security document.
  • the security element may be in the form of a so-called optically variable element, i. an element that has a different appearance depending on the viewing direction.
  • the security element is preferably formed by a diffraction element, very particularly preferably by a holographic data carrier.
  • the security element can be formed for example by diffractive structures, such as zero-order diffraction gratings, rainbow-effect diffraction gratings and relief and volume holograms, as well as microlenses and lenticular grids.
  • the security element is typically manufactured separately and applied to the backing of the security or security document as a patch, security thread, security strip or the like.
  • the structure of a semifinished product which can be used for applying the security element to the carrier depends on its type.
  • the semi-finished product is multilayered. It can, for example, have a base on which there is a functional layer, and a protective layer can be located above the functional layer so that the functional layer is arranged between the base and the protective layer.
  • the functional position forms the actual security element, which is finally located on the carrier.
  • the pad and the protective layer serve to handle and protect the functional layer during the manufacturing process of the security element and to protect it when applied to the carrier.
  • auxiliary layers may for example consist of polyvinyl alcohol, a fluoropolymer, a polyester such as polyethylene terephthalate, or an acrylate polymer or contain one of these materials.
  • the auxiliary layers are typically removed from the functional layer so that only the functional layer remains on the carrier after application.
  • the dimensions of the security element can be arbitrary and are adapted to the application.
  • the security element can be as large as the value or security document to which it is applied, so that it covers the entire surface, or it is smaller, so that it is only a partial surface of the value or Security document covers, for example, 0.5 to 75%, preferably 1 to 50% and most preferably 2 to 25% of the surface of the security document.
  • One or more security elements may be applied to one side of the security or security document, or one or more security elements may be applied to either side of the security or value document.
  • the support of the security or security document is formed from a polycarbonate-containing material formed from polycarbonate at least on a surface on which the security element is connected to the carrier.
  • the one-part adhesive according to the present invention is particularly well-suited for producing a stable adherent bond between the security element and a polycarbonate-containing or polycarbonate surface of the support.
  • the value or security document may in particular be a passport, identity card, driving license, an access control card or other ID card, a vehicle registration document, vehicle registration document, visa, check, means of payment, in particular a banknote, a check, bank, credit or cash card, Customer card, health card, chip card, company card, credentials, membership card, gift or shopping voucher, bill of lading or other credentials, tax stamp, postage stamp, ticket, token, sticky label (for example for product security) or other document.
  • the document may be, for example, a smart card.
  • the value or security document may be in ID 1, ID 2, ID 3, or any other normalized or non-normalized format, such as a booklet form, such as a passport-like item.
  • a value or security document is generally a laminate of several document layers, which have been connected in register under the influence of heat and under increased pressure. These documents should meet the standardized requirements, for example ISO 10373, ISO / IEC 7810, ISO 14443.
  • the document layers are made of a material suitable for lamination.
  • the security or security document may be formed from a polymer selected from a group comprising polycarbonate (PC), especially bisphenol A polycarbonate, polyethylene terephthalate (PET), their derivatives such as glycol modified PET (PETG), polyethylene naphthalate (PCT).
  • PC polycarbonate
  • PET polyethylene terephthalate
  • PET glycol modified PET
  • PCT polyethylene naphthalate
  • PEN polyvinyl chloride
  • PVB polyvinyl butyral
  • PMMA polymethylmethacrylate
  • PI polyimide
  • PVA polyvinyl alcohol
  • PS polystyrene
  • PVP polyvinylphenol
  • PP polypropylene
  • PE polyethylene
  • TPE thermoplastic elastomers
  • TPU thermoplastic polyurethane
  • ABS acrylonitrile-butadiene-styrene copolymer
  • the document may also be made of several of these materials. It preferably consists of PC or PC / TPU / PC.
  • the polymers may be either unfilled or filled.
  • the documents are preferably transparent or translucent. If the polymers are filled, they are opaque.
  • the above information relates both to films to be bonded together and to liquid formulations applied to a precursor, such as a resist.
  • the document is made from 3 to 12, preferably 4 to 10, films (including the carrier of a data communication device contained therein).
  • a laminate formed in this way can finally be coated on one or both sides with a protective lacquer. Overlay layers formed in this way protect security features arranged underneath and / or give the document the required abrasion resistance.
  • the security element according to the present invention may also be arranged protected under an overlay position. Likewise, the security element can alternatively also be integrated into an inner laminate plane by lamination.
  • a stack of a plurality of polymer films can first be collected.
  • the films of the stack are then laminated under the action of a pressing pressure and at an elevated temperature.
  • the stack is laminated in a hot press typically at 190 to 200 ° C and a pressure of, for example, 350 N / cm 2 and in a cold press at a pressure of 600 N / cm 2 when the document layers are made of polycarbonate.
  • the security element for example a holographic data carrier, can then be glued onto the carrier produced in this way in accordance with the invention. So that the security element is protected, the laminate can then be provided with a protective varnish.
  • At least the outer polymer film on which the security element is attached is preferably a polycarbonate film.
  • the security element can also first be applied to a carrier film and fixed there with the method according to the invention.
  • This polymer film is preferably formed from polycarbonate.
  • This carrier film with the security element applied thereon can then be combined with other polymer films, for example likewise polycarbonate films or films of different materials, into a stack be collected. The films in the stack are then laminated together.
  • the security element may in this case be arranged inside in the laminate stack. So that the security element is visually recognizable from the outside, the film layers arranged between a viewer's point of view and the security element are transparent and preferably colorless.
  • the further document layers in the laminate may contain additional security features, such as a photograph of the document owner and / or security printing features and functional colors.
  • the stack can also contain a film layer with an RFID circuit with RFID chip and RFID antenna.
  • the stack may be completed by cover sheet layers (overlays) or coated with a protective varnish.
  • cover sheet layers or the protective lacquer are preferably transparent, thereby allowing the view of underlying document layers and security features.
  • the overlays protect the underlying document layers and / or offer the possibility of optical laser personalization and generation of text and image information.
  • the carrier film layer and the further document layers can have, for example, additional security features.
  • the document can be equipped with further security features.
  • the further security features can be either individualizing or not individualizing.
  • Other security features include guilloches, watermarks, embossing prints, a security thread, microfilm, tipping, füranderpasser and the like.
  • the document may also comprise electronic components, for example an RFID circuit with antenna and RFID microchip, electronic display elements, LEDs, touch-sensitive sensors and the like.
  • the electronic components may be hidden between two opaque layers of the document.
  • an identity card can be 100.
  • the identity card has an upper side 101 and a lower side (not shown).
  • the identity card is essentially formed from a carrier 110 which has been produced by lamination of one or more polymer layers 111, 112.
  • the upper polymer layer 111 can be made of polycarbonate, for example, and the lower polymer layer 112 of another polymer, such as polyethylene terephthalate, or also of polycarbonate.
  • a passport photo 120 is printed on the top side 101 of the identity card 100.
  • a security element 200 for example a hologram patch
  • the hologram patch may for example be formed from two layers, for example from a first carrier facing the first layer 210 and a second layer 220, which forms the actual functional position, in the present case, the hologram.
  • the hologram patch is applied to a contact side 211 facing the carrier 110 of the identity card.
  • the first layer may preferably consist of polycarbonate.
  • an adhesive layer 300 between the hologram patch and the carrier 110.
  • a prepolymer corresponding to component A according to the present invention
  • a plurality of radiation-curing compounds corresponding to components B according to the present invention
  • a plurality of photoinitiators corresponding to US Pat the components C according to the present invention.
  • other ingredients are included, namely a primer and UV light stabilizers.
  • a bifunctional aliphatic urethane acrylate based on polycarbonate and isophorone diisocyanate (SUO 1200, Polygon Chemie AG) is used for the inventive example.
  • prepolymers (component A) for the comparative examples 1 to 3 are bifunctional aliphatic urethane acrylates, but not based on polycarbonate, or polyester (meth) acrylates, namely on the basis of an aliphatic urethane acrylate based on a polyether (CN 9002 by Sartomer Arkema Group), a polyether-based aliphatic urethane acrylate (UV-3300B from Nippon Gohsei) or a mixed polyether obtained by ring-opening polymerization from two cyclic monomers (diol-6000-DMA (dimethacrylate)).
  • the radiation-curable compounds (components B) are mono- and polyfunctional acrylate monomers.
  • the photoinitiator (components C) used is CGI 277 from BASF.
  • compositions are given in Table 1.
  • the adhesives with these compositions were prepared by mixing the components with the photoinitiator added under yellow light conditions.
  • the amounts of the ingredients are given in wt .-%.
  • the adhesive compositions of Comparative Examples 1, 2 and 3 also contain a prepolymer based on an oligomeric urethane acrylate, but not on the basis of polycarbonate, but on the basis of polyethers or a prepolymer based on a polyester (meth) acrylate.
  • the Compositions of Comparative Examples 4 and 5 as well as the composition of the example according to the invention contain a urethane acrylate based on a polycarbonate as component A.
  • the product SUO-1200IB20 used in the composition of the example of the invention additionally contains isobornyl acrylate.
  • the total amount of the radiation-curing compounds constituting the components B in this composition is 64.1% by weight as in the case of Comparative Examples 1, 2 and 3.
  • the proportion of the urethane acrylate is 32.8% by weight in the composition of the present invention as well as in the compositions of Comparative Examples 1, 2 and 3 for the same reason.
  • the compositions of Comparative Examples 4 and 5 differ in the composition of the radiation-curing compounds (Components B).
  • the composition of Comparative Example 5 contains a total of 59.1% by weight of isobornyl acrylate (partially contained in SUO-1200IB20) while the composition of Comparative Example 4 Contains 50.9 wt .-% of the compound 3,3,5-trimethylcyclohexanol acrylate.
  • the former compound is much more hydrophobic than the latter.
  • the content of isobornyl acrylate in the compositions of the inventive example and comparative examples 1, 2, 3 and 4 is the same (8.2% by weight) and thus significantly lower than in the composition of comparative example 5 (50.9% by weight). %).
  • the inclusion of media (solvents) in a cured adhesive, the adhesive strength of the cured adhesive on a substrate, the compressive shear strength of the cured adhesive, the viscosity of the uncured adhesive composition, and the reactivity of the adhesive composition in the Light curing examined.
  • DIN circular disks (diameter 50 mm, height 5 mm) were produced from the adhesive compositions.
  • the compositions were each cured on both sides for 60 s at an intensity of 60 mW / cm 2 , then dried for 72 hours in a desiccator, weighed and then stored for 24 hours at 21 ° C in the media.
  • the media used were DELOTHEN® EP (acetone / isopropanol mixture, hydrohilic solvent) and DELOTHEN® NK1 (Hydrocarbon mixture, hydrophobic solvent) used by DELO Industrial Adhesives. After storage in these media, the surface of the respective round disc was dried with filter paper. The round disc was weighed after drying within one minute. The measurement resulted in a mass difference between the specimen mass after storage and the specimen mass before storage.
  • the respective media intake for the adhesive compositions according to the inventive example and the comparative examples as a quotient of this mass difference and the initial mass is given in Table 2.
  • the respective adhesive composition was applied to a substrate (polycarbonate) and cured as described above.
  • the adhesion was carried out with the cross-cut test according to DIN EN ISO 2409. The results of these measurements are also given in Table 2 for the adhesive compositions according to the example of the invention and the comparative examples.
  • a high adhesive strength is then represented by a test value Gt 0, while a test value Gt 2 indicates a lower adhesive strength.
  • the complex viscosity was determined using a Physica MCR301 rheometer from Anton Paar. The measurement was carried out with a standardized measuring cone PP20 and a 200 ⁇ m gap at 23.5 ° C. The viscosity was determined at a shear rate of 1 / s. The results of these measurements are also given in Table 2 for the adhesive compositions according to the example of the invention and the comparative examples.
  • the adhesive composition according to the invention has a substantially lower media uptake both in a relatively polar solvent (DELOTHEN® EP) and in a non-polar solvent (DELOTHEN® NK1). This indicates that a dissolution by these solvents is lower than in the case of the compositions according to the comparative examples. This applies not only to compositions in which the proportion of component A (prepolymer) is the same as in the case of the composition of the invention but also for cases in which this proportion is significantly higher (Comparative Examples 4, 5).
  • the adhesive strength of a non-solvent-impaired adhesive bond determined by the cross-cut test is very good in the case of the adhesive composition according to the invention and comparable to the compositions of the comparative examples.
  • the compressive shear strength of a specimen obtained with the adhesive composition of the invention is also still higher than in the case of the compositions compared therewith.
  • the viscosity of the adhesive composition according to the invention is somewhat higher than in the case of the comparative samples, it is within the usual range.
  • the adhesive composition according to the present invention which is shown in Table 1, is prepared and applied, for example, by means of a flexographic printing process over the entire surface of a substrate, preferably of polycarbonate.
  • a hologram / ldentigram (photopolymer) film is laminated to the substrate wetted with the adhesive composition with a laminating roller.
  • the adhesive composition is then cured / polymerized by UV radiation through the hologram / ldentigram sheet. There is obtained a very strong bond between the hologram / ldentigramm film and the substrate, which is not affected even after prolonged exposure to hydrocarbon solvents or polar solvents such as acetone and / or ethanol.

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Business, Economics & Management (AREA)
  • Accounting & Taxation (AREA)
  • Finance (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Claims (18)

  1. Document de valeur ou de sécurité (100), présentant un support (110) et un élément de sécurité (200) relié au support (110) au moyen d'une colle (300) à un composant, dans lequel
    la colle (300) à un composant a une composition de colle avec des constituants suivants :
    (A) au moins un (méth)acrylate d'uréthane oligomère à base d'un polycarbonate ;
    (B) au moins un composé durcissant par rayonnement ; et
    (C) au moins un photoinitiateur.
  2. Document de valeur ou de sécurité (100) selon la revendication 1, caractérisé en ce que l'élément de sécurité (200) est formé par un élément de diffraction.
  3. Document de valeur ou de sécurité (100) selon l'une quelconque des revendications précédentes, caractérisé en ce que l'élément de sécurité (200) est formé par un support de données holographique.
  4. Document de valeur ou de sécurité (100) selon l'une quelconque des revendications précédentes, caractérisé en ce que le support (110) est formé au moins au niveau d'une surface (101), au niveau de laquelle l'élément de sécurité (200) est relié au support (110), à partir d'un matériau contenant du polycarbonate et formé à partir de polycarbonate.
  5. Document de valeur ou de sécurité (100) selon l'une quelconque des revendications précédentes, caractérisé en ce que l'élément de sécurité (200) est formé au moins au niveau d'un côté (211) par lequel il est relié à une surface (101) du support (110), à partir d'un matériau qui contient un polymère ou est formé à partir d'un polymère qui est choisi parmi un groupe comprenant le polytéréphtalate d'éthylène, le polyacétate de vinyle et des polymères fluorés.
  6. Document de valeur ou de sécurité (100) selon l'une quelconque des revendications précédentes, caractérisé en ce qu'au moins un composé durcissant par rayonnement présente au moins deux groupes fonctionnels servant au durcissement par rayonnement.
  7. Procédé servant à fabriquer un composite d'agent d'adhérence entre un support (110) d'un document de valeur ou de sécurité (100) et un élément de sécurité (200) au moyen d'une colle (300) à un composant, qui est durcissable avec un rayonnement actinique, dans lequel l'élément de sécurité (200) est collé sur la surface (101) du support (110) au moyen de la colle (300) à un composant,
    dans lequel
    la colle (300) à un composant présente une composition de colle avec des constituants suivants :
    (A) au moins un (méth)acrylate d'uréthane oligomère à base d'un polycarbonate ;
    (B) au moins un composé durcissant par rayonnement ; et
    (C) au moins un photoinitiateur.
  8. Procédé servant à fabriquer un composite d'agent d'adhérence selon la revendication 7, caractérisé en ce qu'au moins un composé durcissant par rayonnement présente au moins deux groupes fonctionnels servant au durcissement par rayonnement.
  9. Procédé servant à fabriquer un composite d'agent d'adhérence selon l'une quelconque des revendications 7 et 8, caractérisé en ce qu'au moins un composant durcissant par rayonnement est choisi parmi un groupe comprenant des (méth)acrylates de polyols, de préférence des poly(méth)acrylates de polyols.
  10. Procédé servant à fabriquer un composite d'agent d'adhérence selon la revendication 9, caractérisé en ce que l'au moins un composé durcissant par rayonnement est choisi parmi un groupe comprenant des poly(méth)acrylates, dans lequel ledit composé présente plus de deux groupes acrylate, en particulier du tri(méth)acrylate de pentaérythrite.
  11. Procédé servant à fabriquer un composite d'agent d'adhérence selon l'une quelconque des revendications 7 à 10, caractérisé en ce qu'au moins un (méth)acrylate d'uréthane oligomère est obtenu
    (a) par transformation d'au moins un polycarbonate-diol et d'au moins un isocyanate polyfonctionnel en formant un polycarbonate-diol présentant une fonction isocyanate lors d'une première étape de synthèse ; et
    (b) par transformation du polycarbonate-diol présentant une fonction isocyanate obtenu lors de la première étape de synthèse avec au moins un ester ou un amide d'un acide carboxylique à insaturation α,β avec un ou plusieurs alcools aliphatiques à faible poids moléculaire, qui présentent en supplément un autre groupe OH ou SH, lors d'une deuxième étape de synthèse.
  12. Procédé servant à fabriquer un composite d'agent d'adhérence selon la revendication 11, caractérisé en ce que la transformation d'au moins un polycarbonate-diol est effectuée avec au moins un isocyanate polyfonctionnel en présence d'un diluant.
  13. Procédé servant à fabriquer un composite d'agent d'adhérence selon la revendication 12, caractérisé en ce que le diluant est un (méth)acrylate, qui est choisi parmi un groupe comprenant le 3,3,5-triméthyl-cyclohexyl(méth)acrylate, le tertbutylcyclohexyl(méth)-acrylate, le 2(2-éthoxyéthoxy)éthyl(méth)acrylate, le tétrahydrofurfuryl(méth)acrylate, le 2-phénoxyéthyl-(méth)acrylate, le 2-éthylhexyl(méth)acrylate, l'iso-bornyl(méth)acrylate, le (5-éthyl-1,3-dioxan-5-yl)méthyl-(méth)acrylate, le 1,6-hexandiol(méth)acrylate, le lauryl(méth)acrylate, l'isodécyl(méth)acrylate, l'iso-octyl(méth)acrylate, l'octyl(méth)acrylate, le 3-méthyl-1,5-pentandioldi(méth)acrylate et le cyclotriméthylol-propanformyl(méth)acrylate.
  14. Procédé servant à fabriquer un composite d'agent d'adhérence selon l'une quelconque des revendications 7 à 13, caractérisé en ce que les constituants de la colle (300) à un composant sont contenus dans la colle (300) en des quantités suivantes :
    (A) 5 à 70 parties en masse d'au moins un (méth)acrylate d'uréthane oligomère ;
    (B) 5 à 90 parties en masse d'au moins un composé durcissant par rayonnement ; et
    (c) 0,1 à 20 parties en masse d'au moins un photoinitiateur,
    par rapport à 100 parties en masse de la composition de colle,
    dans lequel la somme des parties en masse des composants A, B et C donne 100 parties en masse.
  15. Procédé servant à fabriquer un composite d'agent d'adhérence selon l'une quelconque des revendications 7 à 14, caractérisé en ce que la colle (300) à un composant contient en outre d'autres substances faisant office de modificateurs.
  16. Procédé servant à fabriquer un composite d'agent d'adhérence selon la revendication 15, caractérisé en ce que les constituants de la colle (300) à un composant sont contenus dans la colle (300) en des quantités suivantes :
    (A) 5 à 80 parties en masse d'au moins un (méth)acrylate d'uréthane oligomère ;
    (B) 5 à 90 parties en masse d'au moins un composé durcissant par rayonnement ;
    (C) 0,1 à 20 parties en masse d'au moins un photoinitiateur ; et
    (D) 0 à 10 parties en masse d'au moins un modificateur,
    par rapport à 100 parties en masse de la composition de colle,
    dans lequel la somme des parties en masse des composants A, B, C et D donne 100 parties en masse.
  17. Procédé servant à fabriquer un composite d'agent d'adhérence selon l'une quelconque des revendications 7 à 16, caractérisé en ce que la colle (300) à un composant est appliquée avec un procédé d'impression sur l'élément de sécurité (200) et/ou sur la surface (101) du support (110) et l'élément de sécurité (200) et le support (110) sont amenés en contact l'un avec l'autre.
  18. Utilisation d'une colle (300) à un composant servant à fabriquer un document de valeur ou de sécurité (100), dans laquelle la colle (300) a une composition de colle avec des constituants suivants :
    (A) au moins un (méth)acrylate d'uréthane oligomère à base d'un polycarbonate ;
    (B) au moins un composé durcissant par rayonnement ; et
    (C) au moins un photoinitiateur.
EP16720419.7A 2015-05-07 2016-05-03 Document de valeur ou de sécurité, procédé de production d'une liaison adhésive entre un élément de sécurité et la surface du document de valeur ou de sécurité, ainsi qu'utilisation d'une substance adhésive à un composant Active EP3291995B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102015208534.1A DE102015208534A1 (de) 2015-05-07 2015-05-07 Wert- oder Sicherheitsdokument, Verfahren zum Herstellen eines Haftvermittlerverbundes zwischen einem Sicherheitselement und der Oberfläche des Wert- oder Sicherheitsdokuments sowie Verwendung eines einkomponentigen Klebstoffes
PCT/EP2016/059925 WO2016177748A1 (fr) 2015-05-07 2016-05-03 Document de valeur ou de sécurité, procédé de production d'une liaison adhésive entre un élément de sécurité et la surface du document de valeur ou de sécurité, ainsi qu'utilisation d'une substance adhésive à un composant

Publications (2)

Publication Number Publication Date
EP3291995A1 EP3291995A1 (fr) 2018-03-14
EP3291995B1 true EP3291995B1 (fr) 2019-11-27

Family

ID=55910964

Family Applications (1)

Application Number Title Priority Date Filing Date
EP16720419.7A Active EP3291995B1 (fr) 2015-05-07 2016-05-03 Document de valeur ou de sécurité, procédé de production d'une liaison adhésive entre un élément de sécurité et la surface du document de valeur ou de sécurité, ainsi qu'utilisation d'une substance adhésive à un composant

Country Status (3)

Country Link
EP (1) EP3291995B1 (fr)
DE (1) DE102015208534A1 (fr)
WO (1) WO2016177748A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113366072A (zh) * 2019-01-30 2021-09-07 克瑞尼股份有限公司 用于安全文件的性能粘合剂
DE102020126574B4 (de) * 2020-10-09 2025-02-20 Bundesdruckerei Gmbh Verfahren und vorrichtung zum fügen eines sicherheitselements und eines rohlings eines ausweis-, wert-oder sicherheitsdokuments

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0394695B1 (fr) * 1989-03-30 1997-07-02 Toyo Boseki Kabushiki Kaisha Résine durcissable par rayonnement et composition contenant cette résine
DE59804415D1 (de) * 1997-03-07 2002-07-18 Henkel Kgaa Klebstoffsysteme für ein ein- oder mehrstufiges klebebindungsverfahren, verfahren zur klebebindung von druckschriften
DE19853813A1 (de) * 1997-12-10 1999-06-17 Henkel Kgaa Klebstoff mit mehrstufiger Aushärtung und dessen Verwendung bei der Herstellung von Verbundmaterialien
DE102008019871B3 (de) 2008-04-17 2009-11-05 Bundesdruckerei Gmbh Mehrschichtiges Sicherheitsdokument und Verfahren zu dessen Herstellung
DE102008049631A1 (de) * 2008-09-30 2010-04-01 Giesecke & Devrient Gmbh Karte mit eingebettetem Sicherheitsmerkmal
DE102009007552A1 (de) * 2009-02-04 2010-08-05 Bundesdruckerei Gmbh Verfahren zur Herstellung von mehrlagigen Sicherheitsprodukten
DE102010033049A1 (de) 2010-08-02 2012-02-02 Bundesdruckerei Gmbh Haftvermittlerschicht für die Verbindung eines holografischen Datenträgers mit einem Substrat

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
EP3291995A1 (fr) 2018-03-14
DE102015208534A1 (de) 2016-11-10
WO2016177748A1 (fr) 2016-11-10

Similar Documents

Publication Publication Date Title
EP1776240B1 (fr) Element de securite et procede pour le realiser
EP2460668B1 (fr) Document de sécurité et/ou de valeur doté d'une couche de revêtement équipée de manière à résister aux égratignures
EP2676803B1 (fr) Procédé de fabrication d'un composite en couches de polymère doté d'une personnalisation et/ou d'une individualisation à plusieurs couches
EP2214912B1 (fr) Composite de couches polymères pour un document de sécurité et/ou un document de valeur
EP2396359B1 (fr) Compositions photopolymères en tant que formules imprimables
EP2700510B1 (fr) Documents de valeur et/ou de sécurité à base de polycarbonate avec hologramme dans le corps de la carte
EP2557098B1 (fr) Feuille inscriptible au laser à température constante
EP2344342A2 (fr) Carte à élément de sécurité intégré
EP2205437B1 (fr) Procédé de fabrication d'un composite stratifié de polycarbonate
DE2952322A1 (de) Verfahren zur herstellung faelschungssicherer dokumente
KR20150047487A (ko) 홀로그램을 갖는 시각적으로 변화가능한 윈도우를 함유하는 보안 문서 및/또는 중요 문서
EP3291995B1 (fr) Document de valeur ou de sécurité, procédé de production d'une liaison adhésive entre un élément de sécurité et la surface du document de valeur ou de sécurité, ainsi qu'utilisation d'une substance adhésive à un composant
EP3684610B1 (fr) Feuille inscriptible au laser
EP3622353A1 (fr) Feuille plastique dotée d'une couche de colle durcissable aux uv et destinée à la protection d'un hologramme en composite de feuilles-photopolymère
EP2185355B1 (fr) Procédé de fabrication d'un document de sécurité et/ou de papier-valeur, et document ainsi obtenu
WO2008014529A1 (fr) Feuille infalsifiable et emballage thermoformé comprenant cette feuille
DE102021100143A1 (de) Transferfolie, Verwendung einer Transferfolie, Verfahren zur Herstellung einer Transferfolie, Verfahren zum Dekorieren eines Kunststoffartikels sowie Kunststoffartikel
WO2022136283A1 (fr) Film de transfert, utilisation d'un film de transfert, procédé de fabrication d'un film de transfert, procédé de décoration d'un article en matière plastique ainsi que article en matière plastique
EP2302005B1 (fr) Laque à faisceau de rayonnement pigmenté
EP3186328A1 (fr) Composition adhésive de contact résistante à l'eau permettant un collage sur des surfaces humide, en particulier dans des applications automobiles
DE102019127734A1 (de) Transferfolie, Bauteil sowie Verfahren zu deren Herstellung
EP3418052A1 (fr) Panneaux stratifies et leur procede de fabrication
DE102017223464A1 (de) Temperaturbeständige laserbeschriftbare Folie
DE102024103441A1 (de) Lichthärtender reaktiver Klebstofffilm auf Basis von (Meth)Acrylat-funktionalisiertem Polyurethan
DE202022000962U1 (de) Schichtaufbau zur Herstellung eines Scharniers, insbesondere für die Herstellung mehrschichtiger Buchdecken mit Sicherheitsmerkmalen

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20171206

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: BUNDESDRUCKEREI GMBH

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20190619

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1206231

Country of ref document: AT

Kind code of ref document: T

Effective date: 20191215

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502016007736

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20191127

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200228

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200227

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200227

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200327

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200419

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502016007736

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20200828

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200531

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200531

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20200531

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200503

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200503

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200531

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 1206231

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210503

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210503

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20250519

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20250522

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20250523

Year of fee payment: 10