EP3046777A1 - Procédé de production d'un signe de sécurité d'un produit de valeur ou de sécurité et procédé de fabrication d'un tel produit - Google Patents

Procédé de production d'un signe de sécurité d'un produit de valeur ou de sécurité et procédé de fabrication d'un tel produit

Info

Publication number
EP3046777A1
EP3046777A1 EP14771544.5A EP14771544A EP3046777A1 EP 3046777 A1 EP3046777 A1 EP 3046777A1 EP 14771544 A EP14771544 A EP 14771544A EP 3046777 A1 EP3046777 A1 EP 3046777A1
Authority
EP
European Patent Office
Prior art keywords
colorant
layer
pattern
security
polymer
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.)
Granted
Application number
EP14771544.5A
Other languages
German (de)
English (en)
Other versions
EP3046777B1 (fr
Inventor
Franziska Peinze
Matthias Kromphardt
Olga Kulikovska
Manfred Paeschke
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 EP3046777A1 publication Critical patent/EP3046777A1/fr
Application granted granted Critical
Publication of EP3046777B1 publication Critical patent/EP3046777B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • B42D25/40—Manufacture
    • B42D25/405—Marking
    • B42D25/41—Marking using electromagnetic radiation

Definitions

  • the present invention relates to a method for producing a security feature of a value or security product and to a method for producing a value or security product.
  • Value or security products such as security documents and security elements, are used in a variety of ways to verify the identity of individuals and property or to secure a financial transfer. For this purpose, these products have security features that guarantee their authenticity and / or the identity of the person or thing. Value products, such as banknotes, stocks and the like, also have security features in order to verify their authenticity. In order to verify the identity of a person or thing associated with the product, the security features must individualize the product, e.g., personalize it, e.g. the security feature has individualizing features that indicate the particular person or thing and thus the affiliation of the product to the person or thing.
  • ID documents i. Documents associated with a person generally have a face image of the person as well as personal data in plain text or in coded form.
  • Important for the authenticity of this personalization information is that it can not be falsified or falsified. It is therefore advantageous for the production of an ID document if the personal data, including the facial image, are formed not on the surface of the document but in its interior, since in this case it would be necessary for the forgery or falsification to expose the personal data ,
  • an identity card which consists of two cover films, of which at least one is transparent, and a Receiveinlett made of an opaque material, in particular paper.
  • the card is provided with information that are visually recognizable through the transparent cover sheet. This information is applied to the tick by means of a laser beam.
  • the information is personalization data in the form of alphanumeric data and / or a photograph reproduced in grid technique.
  • the laser radiation generates local burns on the card inlay, which are visible.
  • DE 10 2010 062 046 A1 specifies a value and / or security document that comprises a first pattern arranged in one or more first planes and formed from first pattern elements and one formed in one or more planes and from second pattern elements comprises second pattern arranged in register with the first pattern elements of the first pattern.
  • the second pattern elements are located in front of the first pattern elements, as seen from one of the outer sides.
  • the first pattern elements are transparent and / or translucent and can be colored.
  • the first pattern may be in the form of a regular grid of pattern elements in primary colors.
  • the second pattern elements are formed by means of laser action.
  • the document layers in the desired areas may be blackened more or less, resulting in a gray or black tint of the material.
  • starting materials may also be contained in the document body, which are caused to undergo a synthesis reaction under the action of suitable reaction conditions, so that colored patterns are produced.
  • Polymer layer composite specified from several substrate layers, in which at least a first individualizing information is stored by printing technology.
  • the method comprises the steps of providing a plurality of polymer layers as the substrate layers, printing the first individualizing information on at least one substrate layer, assembling the substrate layers to a substrate layer stack, and laminating the substrate layers to the polymer layer composite.
  • the first individualizing information is decomposed into at least two print extracts, each of which includes partial information of this information.
  • the at least two print separations are printed matched to at least two different substrate layer surfaces, so that the printed print separations in the polymer layer composite lie one above the other in registration and together reproduce the information.
  • the surfaces printed with the indentations are inside.
  • the Polymer layers may be at least partially made of polycarbonate.
  • the printing extracts are produced, for example, by means of an ink-jet printing process, for example by means of a transfer printing process, with a customary ink which acts as a binder
  • a heat transfer medium in the form of a substrate which carries on at least part of a surface a coating of a thermally transferable ink comprising a binder and a plurality of discrete particles of the optically variable pigment dispersed in the binder.
  • the ink can be printed using a conventional thermal transfer printing apparatus.
  • the known methods for producing a value or security document have the disadvantage that they are relatively complicated and expensive. Furthermore, some of the documents produced by the above methods do not provide the necessary security against counterfeiting and falsification.
  • the security feature may be a component of a valuable or security product, namely a value or security document or a security element, ie an element which is connected, for example, to an article to be protected against counterfeiting, counterfeiting or falsification, for example as part of a sticker, label or similar.
  • this includes, for example, a passport, identity card, driver's license or another ID document (in particular ID card) or an access control 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, a company card, proof of entitlement, membership card, gift or purchase voucher, bill of lading or other proof of eligibility, Control characters, postage stamps, ticket, (game) token, adhesive label (for example, for product security) to understand.
  • the document may be, for example, a smart card.
  • a security or value product is generally a laminate of several layers, which have been connected in register under the influence of heat and under increased pressure.
  • the products should meet the standardized requirements, for example ISO 10373, ISO / IEC 7810, ISO 14443.
  • the product layers consist, for example, of a carrier material which is suitable for lamination.
  • PC polycarbonate'
  • the diol is preferably selected from a group comprising bis (hydroxyphenyl) methane derivatives, in particular bisphenol A.
  • bisphenol A it is also possible to use other bifunctional reagents having at least two hydroxyl groups, for example geminally disubstituted bis (hydroxyphenyl). cycloalkanes.
  • polyethylene terephthalate includes a condensation product of terephthalic acid or derivatives thereof with a bifunctional reagent containing at least two hydroxyl groups for the condensation reaction (diol), for example with ethylene glycol understand.
  • condensation reaction condensation reaction
  • diol condensation reaction
  • the term "security feature” is to be understood according to the present invention, the impression acting on a viewer, which is generated by a pattern.
  • the security feature can be manufactured as part of a value or security document or a separate product (security element). The latter can be glued to the document, for example.
  • the security feature will generally only occupy part of the surface of the document.
  • a security feature according to the present invention preferably also includes the facial image of the owner of the document and other individualizing, in particular personalizing, markings.
  • pattern is a somehow designed distribution of at least one optical impression for the human eye mediating element, preferably in a two-dimensional arrangement on one or more surfaces to understand which produces a self-contained representation, such as an image, picture element, character, in particular an alphanumeric character, a symbol, a crest, a line, formula or the like.
  • a self-contained representation such as an image, picture element, character, in particular an alphanumeric character, a symbol, a crest, a line, formula or the like.
  • the visual impression mediating elements are perceptible by contrasting surface areas, the contrast by different hues, brightness or different surface textures (gloss, roughness or the like) is generated.
  • pattern element As far as in the description and in the claims of the present application, the term, pattern element 'is called, it is to be understood as a constituent part of a pattern (pixels), wherein the pattern elements can be separated from each other or transition into each other seamlessly.
  • a pattern element serves as the smallest structural element for forming the pattern, with all pattern elements forming the pattern.
  • the patterning material may be either transparent, translucent or opaque. Furthermore, it may have a certain brightness (absorption, remission), ie it may, for example, have blackening, gray tinting or whitening, and / or it may have a (spectral) coloring and, in turn, a certain brightness.
  • the pattern elements may have a circular (punctiform), have rectangular, square, hexagonal or other shape and a size / diameter of, for example, 1 to 150 ⁇ .
  • Pattern elements can be the smallest elements of a perceptible representation to which one of the color values or color tones can be assigned in a multicolor color space (for example in the subtractive CMYK color space, additive RGB color space).
  • raster and "rasterized” are used in this description and in the claims, this is to be understood as a decomposition of an image into individual pattern elements, which typically occur regularly, for example in lines or in another regular arrangement, or irregularly arranged.
  • the pattern elements may be arranged, for example, in a honeycomb arrangement or in a row arrangement with pattern elements offset from one another or not offset from one another.
  • the security feature of a value or security product is formed by at least one pattern.
  • the first variant of the method comprises the following method steps, preferably in the order indicated, it being possible for further method steps to be carried out between individual of the following method steps, if appropriate:
  • an intermediate carrier provided with a colorant is provided.
  • the intermediary provided with the colorant can be prepared by the colorant is at least once, for example, rastered applied to the intermediate carrier.
  • the colorant contains particles, each containing at least one dye and / or at least one pigment, and a binder of a polymer, preferably from a PC-containing polymer.
  • the optionally screened colorant is transferred from the intermediate carrier to a surface of a polymer layer, wherein on the surface of the respective polymer layer, a colorant layer is formed.
  • a colorant layer is formed on the respective polymer layer.
  • optionally arranged in a grid pattern elements can be formed on the respective polymer layer.
  • color splitting For example, all or just a part the structures formed on the intermediate carrier are transferred to the polymer layer.
  • the polymer layer is made of at least one material selected from a group comprising PC and PET. This does not exclude that the polymer layer additionally contains further substances, such as fillers, for example pigments and dyes, and / or other additives, reinforcing materials, such as glass fiber mats, and the like,
  • the stated object according to the first variant of the method is also achieved by the method according to the invention for producing a value or security product having a pattern.
  • the process comprises the following process steps, preferably in the order given, it being possible for further process steps to be carried out between individual ones of the following process steps:
  • the intermediary carrier provided with the colorant can be prepared by applying the colorant to the intermediate carrier at least once, optionally screened.
  • the colorant contains particles, each containing at least one dye and / or at least one pigment, and a binder of a polymer, preferably from a PC-containing polymer.
  • the preferably screened colorant is transferred from the intermediate carrier to the surface of the polymer layer, wherein on the surface of the respective polymer layer, the colorant layer is formed.
  • the colorant layer is formed on the respective polymer layer.
  • optionally arranged in a grid pattern elements can be formed on the respective polymer layer.
  • the polymer layer is made of at least one material selected from a group comprising PC and PET.
  • Polymer layer and other polymer layers collected into a stack. Thereafter, all polymer layers are combined to form a laminate.
  • the above-mentioned object is achieved in a second variant of the method by the method according to the invention for producing a security feature of a value or security product, wherein the security feature is formed by at least one pattern.
  • the second process variant comprises the following process steps, preferably in the order given, it being possible for further process steps to be carried out between individual ones of the following process steps: (a) First, an intermediate carrier provided with a colorant is provided.
  • the intermediary carrier provided with the colorant can be prepared by applying the colorant to the intermediate carrier at least once, optionally screened.
  • the colorant contains at least one dye and / or at least one pigment and a binder of a polymer.
  • the colorant layer is transferred from the intermediate carrier to the surface of the polymer layer, wherein on the surface of the respective polymer layer, the colorant layer is formed.
  • the colorant layer is formed on the respective polymer layer.
  • the polymer layer is made of at least one material selected from a group comprising PC and PET.
  • the constituents of the polymer layer the same applies as for the production process for the security feature according to the first process variant.
  • Polymer layer and at least one cover layer gathered into a stack, so that the cover layer conceals the colorant layer to a viewer.
  • the at least one polymer layer and the at least one cover layer are joined to form a laminate.
  • a method for producing a value or security product having a pattern.
  • the method comprises the above method steps.
  • a visually perceptible contrast arises between first places of the value or security product into which energy is introduced and second places into which no energy is introduced.
  • the non-energized points of the value or security product show no visually perceptible feature.
  • the security feature before the energy input also have a uniform, surface optically recognizable coloration, which can be achieved by uniform surface loading of at least one material layer, for example with particles containing dye, ink or pigment.
  • This contrast may consist in the fact that initially there is no color impression and is exposed locally by the energy input color or that a contrast arises between a first color at untreated areas and a second color at treated areas.
  • inks or pigments contained in particles are initially not or only slightly perceptible.
  • the energy input for example, contained in the particles dyes and / or pigments are released, for example by melting. This release can be perceived by the human eye.
  • the introduction of energy into the particles can otherwise lead to an optically perceptible contrast, for example by disturbing existing interference-generating mirror planes in the particles.
  • the binder is preferably made of or contains a polymer, and the polymer layers are or include PC and / or PET.
  • PC compatibility results from the large chemical similarity of the materials used.
  • PET material pairing with a colorant with, for example, a PET-containing binder is preferred.
  • PC is used which is formed with aromatic diols, more preferably diols from a group comprising bis (hydroxyphenyl) methane derivatives and geminally disubstituted bis (hydroxyphenyl) cycloalkanes, this preferred choice being for both Ma - Material of the polymer layers and for the binder for the preparation of the colorant layers applies.
  • Another advantage of the manufacturing method according to the present invention is its high cost efficiency, since the colorant layer is first provided on an intermediate carrier and then transferred from this to the polymer layer.
  • Such processes are typically referred to as (direct) transfer printing, sublimation printing, diffusion
  • the inventive method is also suitable for the production of a large number of security features (mass suitability).
  • the pattern can also be subsequently generated inside the document by Energy is introduced locally at least in part of the colorant layer.
  • this local energy feed serves to destroy the particles in order to release the dye contained therein and / or the pigment contained therein, so that the colorant layer is visible at the treated areas or converted into one of the previous different color state.
  • the particles are not visible to the naked eye, so that even the colorant layer is not visible to the naked eye.
  • the colorant layer can be white and, upon destruction, assume the color of the dye and / or pigment.
  • the energy feed serves to locally destroy the cover layer above the colorant layer, so that an area of the colorant layer underneath is recognizable from the outside.
  • the cover layer can fuse with this area of the colorant layer, so that the color penetrates to the outside and thus causes a local color according to the location and the color of the relevant area of the colorant layer. Since the colorant layer is arranged on the inside of the document, the security feature thus formed is particularly secure against counterfeiting or falsification.
  • the dye or the pigment of the colorant penetrates into the material of the adjacent polymer layers and thereby unfolds an intense color impression.
  • colorant particles containing dyes, inks or pigments are used to form the colorant layer.
  • the color particles may be formed in the form of core / shell color particles.
  • the paint particles can be damaged or destroyed in any way.
  • the color particles can be subjected to thermal energy, so that the color particles melt or at least melt their shell. Alternatively or additionally, the color particles can also burst.
  • the shell of the color particles can also be selectively removed (de-pointing, revealing), for example by thermal removal of the shell or by chemical dissolution or dissolution of the shell.
  • bursting color particles contain, for example, a liquid dye or a (liquid) ink in its interior (core).
  • the core may be formed by a (solid) pigment or a solid dye.
  • color particles including the pigment or dye of the core may be melted by the action of the energy.
  • the shell can be melted, or only the core melts.
  • a thermal action on the color particles preferably takes place directly by the direct action of energy on the color particles.
  • a chemical action on the color particles can be triggered by release of a chemical substance, preferably a chemical solvent. This chemical can then damage or destroy the shell.
  • the chemical may be contained in other (adjacent) particles, for example capsules, which contain a solvent for the shell of the color particles and which absorb the incident energy.
  • the color particles may be formed by a core and a shell surrounding the core.
  • the color particles are formed by porous particles, for example zeolite particles, which are either surrounded by a shell or which are not surrounded by a shell.
  • the colorant in this case may be contained in the pores of the porous paint particles in a solid state, and liquefied for its release. If the porous paint particles are surrounded by a shell, this is removed for release.
  • the dye or ink to be encapsulated is dispersed in droplets, for example, in a liquid in which it is insoluble, so that minute droplets are formed, or solid particles are dispersed in a liquid, so that forms a suspension.
  • pigment is initially charged as granules and coated with a shell material, for example with TiO 2 or with metal, for example Al, or with a polymer.
  • a shell material for example with TiO 2 or with metal, for example Al, or with a polymer.
  • liquid dye or an ink may be suspended in a liquid in which it is insoluble, so that minute droplets are formed.
  • These droplets or solid particles can be stabilized, for example, by means of suitable wetting agents or emulsifiers.
  • a process for the production of coated particles for the encapsulation of, for example, paints is disclosed in EP 0 505 648 A1, the disclosure of which is incorporated in full in the present application.
  • a hydrophobic material is coated with a resin by first providing an organic phase formed by a mixture of one or more hydrophobic liquids and / or hydrophobic solids with a self-dispersing resin, and by mixing the same then an aqueous phase is added so that the resin forms therein a dispersion with particle sizes of up to 0.1 ⁇ and the hydrophobic liquid and / or the hydrophobic solid coated. If a solid is to be coated, this is first in the desired particle size ße transferred, for example by grinding.
  • a solid dye (cyanine blue) is dispersed with a resin (polyurethane resin having terminal isocyanate groups) in a hydrophobic liquid (methyl ethyl ketone).
  • a resin polyurethane resin having terminal isocyanate groups
  • a hydrophobic liquid methyl ethyl ketone
  • An aqueous solution of an amine is then mixed with this dispersion and heated. Removal of the hydrophobic liquid produces an aqueous dispersion of coated color particles.
  • latex particles are first functionalized with polyelectrolytes, and then TiO 2 particles are deposited thereon by the latex particles being treated with a solution of (NH 4 ) 2 [TiF 6 ] and H 3 B0 3 / HCl in
  • the latex particles are subsequently removed, either by calcination of the TiO 2 layers in an air atmosphere or chemically by dissolving the template core with toluene, thus producing so-called nano-containers Applications have already been described, for example for Trans Porter medical agents, for self-healing processes of materials and the like.
  • porous particles can also be loaded (soaked) with a liquid dye or with an ink by mixing the liquid dye or the ink or a molten one
  • porous or non-porous particles may be coated with the liquid dye or the ink or molten colorant. The particles are then sheathed.
  • Suitable porous particles are inorganic materials such as, for example, zeolites or organic materials, such as, for example, polyurethane-based microfoams, or porous nanoparticles or inorganic microcontainers.
  • porous materials can be produced by spray pyrolysis. For this, reference is made to M. Hampden-Smith, T. Kodas, S. Haubrich, M. Oljaca, R. Einhorn, D. Williams, "Novel Particulate Production Processes to Create Unique Seeds". curity Materials ", in: Proc.
  • core / shell particles including hollow glass particles
  • Other manufacturing methods for core / shell particles are described in D.G. Shchukin, H. Möhwald, "Self-Repairing Coatings Containing Active Nanoreservoirs", in: www.small-journal.com (small), 2007, 3, No. 6, 926-943, Wiley-VCH Verlag, Weinheim the disclosure of this publication is incorporated in full in the present application, at least in respect of the production methods described therein.
  • the color particles can also be formed by OVI pigments (OVI: optically variable ink), in which the optically perceptible feature is caused by the interference layers contained therein.
  • OVI pigments OVI pigments
  • These particles are usually formed by mica platelets, which are thinly coated with metal oxide.
  • the colorant layer is formed in the form of pattern elements.
  • the pattern elements can advantageously be arranged in a grid, so that the pattern elements can be addressed specifically for example with a laser beam.
  • the color particles are preferably in the micrometer or sub-micron range, i. in the case of a substantially spherical or cubic or cuboid particle whose diameter or main diagonal in the nanometer or micrometer range, preferably in the range of 0.05 to 500 ⁇ , more preferably from 0.1 to 100 ⁇ and most preferably from 0.5 to 50 ⁇ .
  • the color particles may also have platelet or needle shape. Also in this case is their thickness or needle diameter in the micrometer range, preferably in the range of 0.05 to 500 ⁇ , more preferably from 0.1 to 100 ⁇ and most preferably from 0.5 to 50 ⁇ .
  • the size dimension in longitudinal extension, i. parallel to the platelet plane or needle length, is preferably 0.5 ⁇ to 500 ⁇ , preferably 1 to 100 ⁇ and most preferably 5 to 50 ⁇ .
  • the particles which may contain colorants are contained in one color or one ink, ie the color or ink is suitable to be printed in a printing process or transferred in another method on the intermediate carrier and from there to the polymer layer.
  • the color or ink is suitable to be printed in a printing process or transferred in another method on the intermediate carrier and from there to the polymer layer.
  • all customary colors or inks can be used, as long as they are chemically compatible with PC or PET and have an affinity or adhesion to these polymers. This is achieved, for example, with a PC-based binder for PC polymer layers.
  • the PC derivatives are highly compatible with PC materials, in particular with PC based on bisphenol A.
  • the PC derivative used is resistant to high temperatures and shows no discoloration at lamination typical temperatures up to 200 ° C and more.
  • the PC derivative may contain functional carbonate structural units represented by the following formula (I):
  • R 1 and R 2 independently of one another, are hydrogen, halogen, preferably chlorine or bromine, C 1 -C 8 -alkyl, C 5 -C 6 -cycloalkyl, C 6 -C 10 -aryl, preferably phenyl, and C 7 -C 12 -aralkyl, preferably phenyl-C 1 -C 4 -alkyl, especially benzyl;
  • m is an integer from 4 to 7, preferably 4 or 5;
  • R 3 and R 4 are individually selectable for each X, independently of one another is hydrogen or CC 6 alkyl;
  • X is carbon and n is an integer greater than 20, with the proviso that on at least one atom X, R 3 and R 4 are simultaneously alkyl.
  • X, R 3 and R 4 may be simultaneously alkyl at 1 to 2 atoms, in particular only at one atom.
  • R 3 and R 4 may be in particular methyl.
  • the X atoms in the ⁇ -position to the diphenyl-substituted C atom (C1) may not be dialkyl-substituted.
  • the X atoms in the ⁇ -position to C1 can be disubstituted with alkyl.
  • m 4 or 5.
  • the PC derivative can be prepared, for example, on the basis of monomers, such as 4,4 ' - (3,3,5-trimethylcyclohexane-1,1-diyl) diphenol, 4,4 ' - (3, 3-dimethylcyclohexane-1,1-diyl) diphenol, or 4,4 ' - (2,4,4-trimethylcyclopentane-1,1-diyl) diphenol.
  • monomers such as 4,4 ' - (3,3,5-trimethylcyclohexane-1,1-diyl) diphenol, 4,4 ' - (3, 3-dimethylcyclohexane-1,1-diyl) diphenol, or 4,4 ' - (2,4,4-trimethylcyclopentane-1,1-diyl) diphenol.
  • Such a PC derivative can, for example, according to DE-A 38 32 396 from
  • Diphenols of the formula (Ia) are prepared, the disclosure content of which is hereby incorporated in full in the disclosure content of this application. It is possible to use both a diphenol of the formula (Ia) to form homopolycarbonate and also a number of diphenols of the formula (Ia) to give copolycarbonate (meaning of radicals, groups and parameters, as in formula I).
  • diphenols of the formula (Ia) can also be used in admixture with other diphenols, for example those of the formula (Ib): HO - Z - OH (Ib), for the preparation of high molecular weight, thermoplastic, aromatic PC derivatives.
  • Suitable other diphenols of the formula (Ib) are those in which Z is an aromatic radical having 6 to 30 C atoms, which may contain one or more aromatic nuclei, may be substituted, and aliphatic radicals or cycloaliphatic radicals other than those of the formula (II) Ia) or heteroatoms may contain as bridge members.
  • diphenols of the formula (Ib) are hydroquinone, resorcinol, dihydroxydiphenyls, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) -cycloalkanes, bis (hydroxyphenyl) sulfides, bis (hydroxyphenyl) ethers, bis - (hydroxyphenyl) - ketones, bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) sulfoxides, a, a'-bis (hydroxyphenyl) - diisopropylbenzenes and their ring-alkylated and ring-halogenated compounds.
  • diphenols of the formula (Ib) are hydroquinone, resorcinol, dihydroxydiphenyls, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) -cycloalkanes, bis (hydroxyphenyl) sulfides, bis (hydroxyphenyl) ethers, bis
  • Preferred other diphenols are, for example: 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis ( 4-hydroxyphenyl) cyclohexane, ⁇ , ⁇ -bis (4-hydroxyphenyl) -p-diisopropylbenzene, 2,2-bis (3-methyl-4-hydroxyphenyl) -propane, 2,2-bis (3-methyl) chloro-4-hydroxyphenyl) -propane, bis (3,5-dimethyl-4-hydroxyphenyl) -methane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) -propane, bis (3, 5-dimethyl-4-hydroxyphenyl) sulfone, 2,4-bis (3,5-dimethyl-4-hydroxyphenyl) -2-
  • Diphenols of the formula (Ib) are, for example, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3 , 5-dichloro-4-hydroxyphenyl) -propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) -propane and 1,1-bis (4-hydroxyphenyl) -cyclohexane.
  • 2,2-bis (4-hydroxyphenyl) propane is preferred.
  • the other diphenols can be used both individually and in a mixture.
  • the molar ratio of diphenols of the formula (Ia) to the other diphenols of the formula (Ib) which may optionally be used should be between 100 mol% (Ia) to 0 mol% (Ib) and 2 mol% (Ia) 98 mol% (Ib), preferably between 100 mol% (Ia) to 0 mol% (Ib) and 10 mol% (Ia) to 90 mol% (Ib) and in particular between 100 mol% (Ia ) to 0 mol% (Ib) and 30 mol% (Ia) to 70 mol% (Ib).
  • the high molecular weight PC derivatives of the diphenols of the formula (Ia), optionally in combination with other diphenols, can be prepared by the known PC production methods.
  • the various diphenols can be linked together both statistically and in blocks.
  • the PC derivatives used can be branched in a manner known per se. If the branching is desired, this can in known manner by condensing small amounts, preferably amounts of 0.05 to 2.0 mol% (based on diphenols), of trifunctional or more than trifunctional compounds, especially those with three or more than three phenolic hydroxyl groups.
  • Some branching agents having three or more than three phenolic hydroxyl groups are phloroglucinol, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene-2, 4,6-dimethyl-2,4,6-tri - (4-hydroxyphenyl) heptane, 1, 3,5-tri (4-hydroxyphenyl) benzene, 1,1,1-tri (4-hydroxyphenyl) ethane, tri- (4-hydroxyphenyl) -phenylmethane .
  • Some of the other trifunctional compounds are 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride and 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole
  • Monofunctional compounds in customary concentrations are suitable for the molecular weight of the PC derivatives Suitable compounds are, for example, phenol, tert-butylphenols or other alkyl-substituted phenols
  • Suitable regulators for the molecular weight are, in particular, small amounts of phenols of the formula (Ic):
  • R represents a branched C 8 and / or C 9 alkyl radical.
  • the proportion of CH 3 protons is preferably between 47 and 89% and the proportion of CH and CH 2 protons between 53 and 11%; also preferably R is in the o- and / or p-position to the OH group, and more preferably the upper limit of the ortho-portion is 20%.
  • the chain terminators are generally used in amounts of 0.5 to 10, preferably 1, 5 to 8 mol%, based on diphenols used.
  • the PC derivatives can preferably be prepared in a manner known per se according to the phase boundary behavior (compare H. Schnell in: Chemistry and Physics of Polycarbonates, Polymer Reviews, Vol. IX, page 33ff., Interscience Publ.
  • the diphenols of the formula (Ia) are dissolved in an aqueous alkaline phase.
  • mixtures of diphenols of the formula (Ia) and the other diphenols, for example those of the formula (Ib), are used.
  • chain terminators of, for example, the formula (Ic) can be added.
  • organic phase is reacted with phosgene by the method of interfacial condensation.
  • the reaction temperature is in the range of 0 ° C to 40 ° C.
  • the branching agents optionally used may be initially charged with the diphenols in the aqueous alkaline phase or may be added in the organic solvent before phosgenation.
  • the branching agents optionally used may be initially charged with the diphenols in the aqueous alkaline phase or may be added in the organic solvent before phosgenation.
  • Diphenols (Ib) may also be used with their mono- and / or bis-chloroformates are added, which are added dissolved in organic solvents.
  • the amount of chain terminators and of branching agents then depends on the molar amount of diphenolate radicals corresponding to formula (Ia) and optionally formula (Ib); When using chloroformates the amount of phosgene can be reduced accordingly in a known manner.
  • Suitable organic solvents for the chain terminators and optionally for the branching agents and the chloroformates are, for example, methylene chloride, chlorobenzene and in particular mixtures of methylene chloride and chlorobenzene.
  • the chain terminators and branching agents used can be dissolved in the same solvent.
  • methylene chloride, chlorobenzene and mixtures of methylene chloride and chlorobenzene serve as the organic phase for the interfacial polycondensation.
  • the aqueous alkaline phase used is, for example, NaOH solution.
  • the preparation of the PC derivatives by the phase interface method can in the usual way by catalysts such as tertiary amines, in particular tertiary aliphatic amines such as tributylamine or
  • Triethylamine be catalyzed; the catalysts can be used in amounts of 0.05 to 10 mol%, based on moles of diphenols used.
  • the catalysts can be added before the beginning of the phosgenation or during or after the phosgenation.
  • the PC derivatives can be prepared by the known process in a homogeneous phase, the so-called "pyridine process” and by the known melt transesterification process using, for example, diphenyl carbonate instead of phosgene.
  • the PC derivatives may be linear or branched, they are homopolycarbonates or
  • the PC properties can be varied in a favorable manner.
  • the diphenols of the formula (Ia) are present in amounts of from 100 mol% to 2 mol%, preferably in amounts of from 100 mol% to 10 mol% and in particular in amounts of from 100 mol% to 30 mol% %, based on the total amount of 100 mol% of diphenol units, contained in PC derivatives.
  • the PC derivative can be
  • Copolymer comprising, in particular consisting thereof, monomer units M1 based on the formula (Ib), preferably bisphenol A, and monomer units M2 based on the geminally disubstituted Dihydroxydiphenylcycloalkans, preferably the 4,4 ' - (3,3,5-trimethylcyclohexane-1 , 1-diyl) diphenol, wherein the molar ratio M2 / M1 is preferably greater than 0.3, in particular greater than 0.4, for example greater than 0.5. It is preferred if the PC derivative has a weight average molecular weight of at least 10,000, preferably from 20,000 to 300,000. In principle, component B may be substantially organic or aqueous.
  • Substantially aqueous means that up to 20% by weight of component B) can be organic solvents.
  • Substantially organic means that up to 5% by weight of water may be present in component B).
  • Component B preferably contains one or consists of a liquid aliphatic, cycloaliphatic and / or aromatic hydrocarbon, a liquid organic ester and / or a mixture of such substances.
  • the organic solvents used are preferably halogen-free organic solvents.
  • aliphatic, cycloaliphatic, aromatic hydrocarbons such as mesitylene, 1, 2,4-trimethylbenzene, cumene and solvent naphtha, toluene, xylene; (organic) esters, such as methyl acetate, ethyl acetate, butyl acetate, methoxypropyl acetate, ethyl 3-ethoxypropionate.
  • organic esters such as methyl acetate, ethyl acetate, butyl acetate, methoxypropyl acetate, ethyl 3-ethoxypropionate.
  • mesitylene, 1, 2,4-trimethylbenzene, cumene and solvent naphtha, toluene, xylene methyl acetate, ethyl acetate, methoxypropyl acetate.
  • Ethyl 3-ethoxypropionate is particularly suitable.
  • a suitable solvent mixture comprises, for example, L1) 0 to 10% by weight, preferably 1 to 5
  • Wt .-% in particular 2 to 3 wt .-%, mesitylene, L2) 10 to 50 wt .-%, preferably 25 to 50 wt .-%, in particular 30 to 40 wt .-%, 1-methoxy-2 propanol acetate, L3) 0 to 20
  • Wt .-% preferably 1 to 20 wt .-%, in particular 7 to 15 wt .-%, 1, 2,4-trimethylbenzene, L4) 10 to 50 wt .-%, preferably 25 to 50 wt .-%, in particular 30 to 40% by weight, ethyl 3-ethoxypropionate, L5) 0 to 10% by weight, preferably 0.01 to 2% by weight, in particular 0.05 to 0.5% by weight, of cumene , and L6) 0 to 80 wt .-%, preferably 1 to 40 wt .-%, in particular 15 to 25 wt .-%, solvent naphtha, wherein the sum of the components L1 to L6 always gives 100 wt .-%.
  • component C are in the first process variant in or on particles contained dyes and / or pigments, especially in core / shell particles contained dyes and / or pigments, and in the second process variant, the free dyes and / or pigments (not contained in particles ) used.
  • any desired dye or pigment can be used in both variants.
  • Dyes and pigments are all colorants (for a review of dyes, see Ullmann's Encyclopedia of Industrial Chemistry, Electronic Release 2007, Wiley Publishing, Chapter “Dyes, General Survey”, for an overview of organic and inorganic pigments see Ullmann's Encyclopedia of Industrial Chemistry, Electronic Release 2007, Wiley Verlag, chapter “Pigments, Organic” or “Pigments, Inorganic”).
  • Dyes should be in the solvents of the component B be soluble or (stable) dispersible or suspendable. Furthermore, it is advantageous if the colorant is stable at temperatures of 160 ° C. and more for a period of more than 5 minutes, in particular color-stable. It is also possible that the colorant undergoes a predetermined and reproducible color change under the processing conditions and is selected accordingly.
  • pigments In addition to the temperature stability, light stability and climatic resistance, pigments must be present in particular in the finest particle size distribution. For inkjet printing, this means in practice that the particle size should not exceed 1, 0 ⁇ , otherwise blockages in the print head are the result. As a rule, nanoscale solid-state pigments and dissolved dyes have proven their worth.
  • the dyes and pigments can be cationic, anionic or even neutral.
  • dyes and pigments which can be used in ink-jet printing are mentioned: Brilliant Black Cl No. 28440, Chromogen Black Cl No. 14645, Direct deep black E Cl No. 30235, true black salt B Cl No. 37245, true black salt K Cl No. 37190, Sudan Black HB Cl 26150 , Naphtol Black Cl No. 20470, Bayscript® Black Liquid, Cl Basic Black 1 1, Cl Basic Blue 154, Cartasol® Turquoise K-ZL liquid, Cartasol® Turquoise K-RL liquid (Cl Basic Blue 140), Cartasol Blue K5R liquid.
  • Cartasol® Orange K3 GL, Cartasol® Yellow K4 GL, Cartasol® K GL, or Cartasol® Red K-3B Furthermore, as soluble dyes anthraquinone, azo, quinophthalone, coumarin, methine, perinone, and / or pyrazole, for example, under the name Macrolex® available, find use. Other suitable dyes and pigments are described, inter alia, in the reference Ullmann 's Encyclopedia of Industrial Chemistry, Electronic Release 2007, Wiley Verlag, chapter "Colorants Used in Ink Jet Inks". Well-soluble dyes lead to an optimal integration into the matrix or the binder of the print layer.
  • the dyes and pigments can either be added directly or as a paste, a mixture of dye and pigment together with another binder.
  • This additional binder should be chemically compatible with the other components of the formulation. If such a paste is used as component B, its quantity refers to the dye or the pigment without the other components of the paste.
  • component E When using so-called Colored pigments in the scale colors cyan-magenta-yellow and preferably also (soot) - black, solid color images are possible.
  • the dyes and / or pigments are dispersed together with titanium dioxide, for example, together in a suitable means, so that the dyes and / or pigments bind to and store the titanium dioxide particles and form with these microparticles.
  • the dyes and / or pigments can also be dispersed together with lipids in a suitable liquid medium so that the lipids form micelles into which the dyes and / or pigments are incorporated. Methods of making the color particles are given above.
  • Component D comprises substances that can be seen directly by the human eye or by the use of suitable detectors using technical aids.
  • materials known to those skilled in the art (see also van Resse in: Optica! Document security, 3rd ed., Artech House, 2005), which are used to secure value and security documents.
  • luminescent substances include photoluminophores, electroluminophores, Antistokes luminophores, fluorophores, but also magnetizable, photoacoustically addressable or piezoelectric materials and metal particles, magnetic particles, thermochromic particles, electrochromic particles and other substances.
  • Raman-active or Raman-reinforcing materials can be used, as well as so-called barcode materials.
  • the preferred criteria are either the solubility in component B or pigmented systems particle sizes ⁇ 1 ⁇ and a temperature stability for temperatures> 160 ° C and light resistance and climatic resistance in the sense of the comments on component C.
  • Functional materials can be added directly or a paste, ie a mixture with a further binder, which then forms a constituent of component E, or the binder of component A.
  • the component E comprises in inks for inkjet printing usually established substances such as antifoaming agents, adjusting agents, wetting agents, Surfactants, superplasticizers, dryers, catalysts, (light) stabilizers, preservatives, biocides, surfactants, organic polymers for viscosity adjustment, buffer systems, etc.
  • Suitable setting agents are customary setting salts. An example of this is sodium lactate.
  • Biocides are all commercially available preservatives. agents which are used for inks in question. Examples are Proxel®GXL and Parmetol® A26.
  • Suitable surfactants are all commercially available surfactants which are used for inks. Preferred are amphoteric or nonionic surfactants.
  • surfactants which do not alter the properties of the dye or pigment.
  • suitable surfactants are betaines, ethoxylated diols, etc. Examples are the product series Surfynol® and Tergitol®.
  • the amount of surfactants is particularly selected when used for ink-jet printing, for example, provided that the surface tension of the ink is in the range of 10 to 60 mN / m, preferably 20 to 45 mN / m, measured at 25 ° C.
  • a buffer system can be set up which stabilizes the pH in the range from 2.5 to 8.5, in particular in the range from 5 to 8.
  • Suitable buffer systems are lithium acetate, borate buffer, triethanolamine or acetic acid / sodium acetate.
  • a buffer system will be considered in particular in the case of a substantially aqueous component B.
  • To adjust the viscosity of the ink (possibly water-soluble) polymers can be provided. Here all suitable for conventional ink formulations polymers come into question.
  • Examples are water-soluble starch, in particular having an average molecular weight of from 3,000 to 7,000, polyvinylpyrrolidone, in particular having an average molecular weight of from 25,000 to 250,000, polyvinyl alcohol, in particular having an average molecular weight of from 10,000 to 20,000, xanthan gum, carboxy-methylcellulose, ethylene oxide / Propylene oxide block copolymer, in particular with a mean molecular weight of 1, 000 to 8,000.
  • An example of the latter block copolymer is the product series Pluronic®.
  • the proportion of biocide, based on the total amount of ink may be in the range of 0 to 0.5% by weight, preferably 0.1 to 0.3% by weight.
  • the proportion of surfactant may range from 0 to 0.2% by weight.
  • the proportion of adjusting agents based on the total amount of ink, 0 to 1 wt .-%, preferably 0.1 to 0.5 wt .-%, be.
  • the auxiliaries also include other components, such as, for example, acetic acid, formic acid or n-methylpyrrolidone or other polymers from the dye solution or paste used.
  • component E reference is additionally made, for example, to Ullmann's Encyclopedia of Chemical Industry, Electronic Release 2007, Wiley Verlag, chapter “Paints and Coatings", section “Paint Additives”.
  • a heat-resistant carrier material of the intermediate carrier is used in film form, for example of polyethylene terephthalate, polyamide or polyimide, preferably from Polyethylene terephthalate.
  • the support may additionally comprise a release layer on the side of the support on which the colorant is temporarily applied, for example a layer of cross-linked acrylic polymer.
  • the carrier may be formed on the opposite side with a protective layer, for example of silicone, to prevent adhesion of heating and pressure elements.
  • the carrier material may be in the form of a band, in particular a circumferential band.
  • a drum or a flat film or plate are also conceivable instead of a circulating belt, which are coated with a coating of the carrier and the release layer material.
  • the band or the drum can advantageously be formed circumferentially in order to be able to continuously carry out the application of the colorant (process step (a)) and the subsequent transfer to the polymer film (process step (b)).
  • the thus provided with the colorant intermediate carrier can be used in a conventional apparatus for transfer printing as a color carrier, in particular as a ribbon.
  • any coating method in particular a printing method, with which screened patterns can also be produced.
  • the intermediate carrier can be coated by means of a doctor blade, roller coating, injection, casting, dispenser, transfer printing or other printing method, for example with an offset printing method.
  • a digital printing method in particular a non-impact printing method, since digital printing methods have a very high flexibility with regard to the selected motif, the motif in this case preferably already being formed on the intermediate carrier. Therefore, the colorant can be applied in a further preferred embodiment of the present invention, in particular by means of a Tintenstrahltigverfah- rens (inkjet method) or xerographic printing process on the intermediate carrier.
  • the above-described ink composition is particularly suitable for ink-jet printing. If another method is used, the ratio of the individual components of the colorant is adapted to the coating technique. In the case of a xerographic printing process, the colorant is to be provided in the form of a toner.
  • the colorant is applied to the intermediate carrier in the two-dimensional arrangement (for the provision according to process step (a) according to both process variants) in which it is finally to be transferred to the polymer layer, although a mirror-inverted Arrangement on the subcarrier is chosen to the right side pattern on the
  • a plurality of colorants are used to form multicolor colorant layers, for example of different pattern element types or different colorant layer areas, on one surface of the polymer layer, for example, to form a multicolor pattern, or if multiple patterns are to be formed on different surfaces thereof or of different polymer layers
  • Structures with optionally screened colorant can be formed several times successively on the intermediate carrier and then each transferred to a polymer layer. After transferring the colorant from the intermediate carrier to the polymer film, the intermediate carrier can be cleaned again before colorant is again applied to the intermediate carrier for a further polymer film. Alternatively, an unused area of a colorant-coated subcarrier is used.
  • the generation of a rastered image of the pattern to be generated on the intermediate carrier means that individual structural elements corresponding to the colorant layer areas to be formed are generated, which are separated from one another, preferably spaced from one another.
  • the colorant layer on the intermediate carrier can not be generated rastered.
  • the colorant layer may be formed on the intermediate carrier in a non-patterned areal uniform shape (screened or not screened).
  • a non-patterned areal uniform shape screened or not screened.
  • either the entire colorant layer or only a part thereof can be transferred to the polymer surface.
  • a part is transferred, for example, by means of this suitable plunger under additional heat.
  • Such a device corresponds to a conventional thermal printhead. If the entire colorant layer is transferred from the subcarrier to the polymer surface, patterning subsequently occurs upon activation.
  • a pattern for example representing an information, can already be formed on the intermediate carrier and then transferred to the surface of the polymer layer. the.
  • this pattern can then only be subsequently made perceptible, since the respective colors do not yet emerge.
  • the intermediate carrier After the colorant has been applied in the optionally screened arrangement on the intermediate carrier, this is brought into contact with the polymer layer.
  • the intermediate carrier and the polymer layer are pressed together.
  • either the entire surface of the polymer layer can be brought into simultaneous contact with the intermediate carrier, or individual parts of the intermediate carrier are brought into contact with corresponding portions of the polymer layer one after the other.
  • the pattern can already be generated, which is finally to be formed on the polymer layer.
  • pressure and heat can be applied to the temporary composite of the intermediate carrier and the polymer film, but the pressure and the temperature must not be so high that the core containing the dye and / or the pigment / Shell particles / particles are impaired according to the first method variant.
  • the colorant layer can either be applied on one side to a surface of a polymer layer, or one colorant layer can be applied to the two surfaces of a polymer layer or to a plurality of polymer layers intended for a value or security product, either on one side and / or on both sides.
  • the intermediate carrier between two transfer processes of the colorant on the polymer layers in each case again loaded with the colorant by this optionally rastered is applied to the intermediate carrier, or it is a new range of loaded with colorant intermediate carrier available.
  • the colorant layer on the polymer layer can be formed by pattern element matrices, which are identical in each case. Or different types of matrices can be formed in each case, which differ, for example, in the arrangement and / or in the type of the pattern elements, for example of their color. For example, first pattern elements that are red upon introduction of energy on a first surface, second pattern elements that are green upon introduction of energy, on a second surface, and third pattern elements that appear blue upon introduction of energy may be formed on a third surface. At least two of these surfaces may in this case be opposed surfaces of the same polymer layer.
  • the first pattern formed with the first pattern elements, the Second patterns formed with the second pattern elements and the third pattern formed with the third pattern elements can each be print separations of the same overall pattern, for example the face image of a person, and formed in register over one another, so that they give the overall pattern.
  • Each of these print extracts includes a partial information of the information stored throughout the print image.
  • multiple patterns may be formed in different spaced-apart pattern planes in the value or security document, which are parallel to one another.
  • At least two types of pattern elements differing by different dyes and / or pigments can be formed in a regular arrangement on a surface of the at least one polymer layer.
  • the pattern elements can accordingly in method step (b) of both variants of the method according to the invention in a grid arrangement on the
  • Polymer layer (s) are transmitted in the pattern elements of different colors, for example in the colors of the CMYK color space, are evenly distributed.
  • a single transfer operation can be carried out from the intermediate carrier to the surface of the polymer layer, when all the pattern elements of the different types have first been applied together to the intermediate carrier.
  • several transfer operations are made by successively each pattern elements of a type formed on the subcarrier and then these are each transmitted from the intermediate carrier to the surface of the polymer layer.
  • the pattern elements of different types may alternate in a particular order.
  • a planar, in particular honeycomb-shaped, arrangement of pattern elements in which alternating cyano, magenta, yellow and black pattern elements alternate along rows.
  • the pattern elements formed with free dye or pigment when viewed with the naked eye, give a dark (black-brown) area without texture (pattern).
  • the pattern elements formed with dye and / or pigment, which is integrated into particles give the color impression predetermined by the structure of the particles. Only by activating individual pattern elements in these process variants with their own colors, the desired pattern results.
  • energy is locally introduced into certain pattern elements at the locations of a specific color predetermined by the pattern in order to desired color impression, possibly as a result of a color mixture of several pattern elements, each with a specific color to obtain.
  • the pattern formed with the colorant layer or the fully coated surface may cover the surface of the polymer layer completely or only partially in a field on the polymer layer or the entire polymer layer.
  • Polymer layers further processed to the value or security product according to the invention are further processed to the value or security product according to the invention.
  • a conventional lamination method can be used.
  • the value or security product may be prepared by extruding the corresponding polymeric material together with color particles.
  • the color particles are preferably arranged on the inside in the value or security product and remain there completely or at least largely integrated invisibly until they are activated.
  • the colorant layer is hidden within the value or security product by the cover layer.
  • local energy for example heat energy
  • energy by means of electromagnetic radiation and / or mechanical energy is additionally applied to the colorant layer by means of a suitable energy source.
  • the colorant layer is activated, and the dye and / or the pigment diffuses into the polymer material.
  • the energy source in order to be able to selectively apply energy to individual regions of the colorant layer, ie not to impinge on adjacent colorant layer regions, the energy source must be designed to be focusable.
  • An advantage of electromagnetic radiation for energy input is that it can be applied in a spatially resolved manner. Another advantage is that it contains, via its energy (wavelength, frequency), further information that can be used to address particular colors of the desired pattern and to specifically control activation therefor.
  • chen for example, by adjusting the wavelength of the electromagnetic radiation to the dyes and / or pigments of the respective colorant can be achieved.
  • the dyes and / or pigments or particles which contain these substances may additionally contain an electromagnetic radiation-absorbing sensitizer, thereby advantageously enabling the absorption of the colorant layer areas to be targeted.
  • the radiated electromagnetic radiation must be tuned without special demands being placed on the materials of the dyes and / or pigments with regard to their spectral sensitivity.
  • a laser can be used which, for example, can be absorbed by radiation locally supplying heat, resulting in a local temperature increase of all or only of colorant layer areas of one type
  • a local mechanical pressure on the colorant layer may also be applied be exercised areas, for example, with a thermal print head, which additionally supplies local heat.
  • an ultrasound generator sonotrode
  • these are selectively destroyed, so that the dye contained therein and / or pigment contained therein are released and thus the desired color is produced at the site of activation.
  • the cover of the cover layer is at least fused, destroyed and / or pierced, so that an existing thereunder area of the colorant layer is visible, such as by local fusing with the cover.
  • the cover layer may be formed, for example, of Ti0 2 .
  • the size of the TiO 2 particles is preferably so small that just just an opaque layer is present, ie the particle diameter of the TiO 2 particles should be greater than half the wavelength of the visible
  • the overlying (for example, adjacent to the polymer layer) cover layer is opaque. It can be any color, including white, gray and black. Preferably, it is white, because this results in a very good contrast of the pattern formed before the remaining surface of the cover layer.
  • the cover layer may be opaque in itself, ie the material, in particular polymer, of the cover layer may have been made opaque by suitable dyes and / or pigments. Or the cover layer has at least one opaque layer, which also has the required opacity by means of suitable dyes and / or pigments.
  • This layer preferably lies in a stack together with the at least one polymer layer bearing the colorant layer on the colorant layer, since, when the energy is introduced into the cover, this leads to a connection of the colorant to the cover.
  • the cover may cover the entire surface of the security or value product, or only a part thereof, namely in particular the part corresponding to the area occupied by the colorant layer.
  • the perceptible pattern is formed.
  • the energy is very particularly preferably introduced by means of a process into the colorant layer which does not require any direct contact between the energy source and the colorant layer for this purpose
  • Non-contact method For example, the introduction of energy by means of electromagnetic radiation is particularly suitable. In order to enable a local introduction of energy into individual colorant layer areas, laser radiation can therefore advantageously be used. Any laser radiation that leads to absorption in the colorant layer or in adjacent material is suitable, for example, by an IR radiation emitting laser, such as Nd: YAG (fundamental wavelength or frequency multiplied: 1064 nm, 532 nm, 355 nm, 266 nm ) or a C0 2 laser (10.6 ⁇ ). For radiation emission in the visible spectral range, gas lasers, for example argon and krypton ion lasers, or diode lasers can be used.
  • Excimer lasers for example F 2 : 157 nm, ArF: 193 nm, KrF: 248 nm, XeCl: 308 nm, XeF 351 nm
  • the laser is focused on the targeted introduction of energy.
  • the non-contact method it is possible, in particular, to process document blanks which, apart from the security method which can be produced by the method according to the invention, feature essentially all other security features already included.
  • the pattern is located inside the document blank.
  • a personalization of a document for example an identity card blank
  • an internal arrangement of the colorant layer ensures that the pattern can not be falsified or falsified without further ado, because in addition the internal pattern would have to be accessed, which is difficult to achieve without exposing the pattern.
  • a very accurate positioning of the energy source is required. Since the individual pattern elements are not exactly recognizable in advance in the presence of a matrix of alternating pattern elements of different colors, an adjustment can first be made, for example, in order to determine the position of the pattern elements relative to one another. For this, the position of at least two pattern elements in the pattern is to be determined. For the adjustment, for example, energy is introduced into at least two pattern elements and the color and the position of the activated pattern elements are determined optically. By means of these color marks, the identity and the position of all other pattern elements of the pattern can then be derived.
  • a pattern for the energy input can then be determined, according to which the pattern elements are converted into colored dots. If the surface of the polymer layer on which the colorant layer is formed is exposed after activation, those colorant layer regions into which no energy has been introduced and which are therefore not fixed can be subsequently removed again from the at least one surface of the respective polymer layer. This achieves a better contrast of the pattern and thus an improved pattern quality.
  • unchanged color particles ie color particles which are not involved in the pattern formation
  • the fixation can be effected, for example, by irradiation of the value or security product by means of an electromagnetic radiation which has a different photon energy (wavelength) than the electromagnetic radiation used for the activation without the previously produced optically perceptible color impression being changed.
  • the matrix in which the color particles are located are chemically changed in such a way that colorant can no longer escape from the unaltered color particles.
  • One possibility of chemical modification is to chemically crosslink the matrix.
  • the matrix contains chemical compounds which can be crosslinked.
  • the colorant that does not form the pattern can be bleached.
  • Polymeric layer can also be formed in the form of a part of a motif, the other part of which is produced in a conventional manner.
  • the motif part for example a surface half of the motif
  • the motif part produced according to the invention only after the joining and joining of the polymer layers by subsequent activation is made visible.
  • a motif provided in the finished value or security document for example a coat of arms, to be present only partially in a raw document and to be provided with the further motif part only when the document issuing the document.
  • the value or security product is preferably produced from a polymer layer provided with a colorant layer, furthermore further polymer layers on which no colorant layers are present, moreover in the case of the second method variant of a cover layer and finally, if appropriate, outside protective coatings or protective films.
  • the protective coatings or protective films are used for outside protection against damage (scratches) and for enclosing otherwise outside mounted security features in the interior of the product to protect against tampering. Furthermore, on the outside, a diffractive film can be attached.
  • the value or security product can be produced from the document materials, in particular by lamination. In addition to the PC and / or PET layers, the product may also include layers of other materials, such as other polymers or paper or paperboard.
  • the document is preferably produced from 3 to 12, preferably 4 to 10 films, it being possible for the individual films to consist of the same material or of different materials.
  • the lamination of PC in a hot / cold lamination press is made in a first step at 170 to 200 ° C and a pressure of 50 to 600 N / cm 2 and in a second step with cooling to about room temperature and under the same pressure.
  • the lamination of PET takes place at a higher temperature, for example at 220 ° C.
  • the polymer films typically have a thickness of from 25 to 150 ⁇ m, preferably from 50 to 100 ⁇ m.
  • the value or security product can also be produced in a different way than by lamination, for example by extrusion.
  • the value or security product can have at least one further security feature that is either individualizing or not individualizing.
  • Other security features include mottled fibers, guilloches, watermarks, embossed prints, a security thread, microfilm, tilting images, holograms, optically variable pigments, luminescent colors, transmitted light register and the like.
  • the document may also comprise electronic components, for example an RFID circuit with antenna and RFID
  • Figure 1 shows a security document with a security feature made in accordance with the invention in a schematic isometric view
  • FIG. 3A shows the process sequence according to the invention according to the first variant of the method in a schematic form
  • Fig. 3A Applying colorant to an intermediate carrier, for example in rastered form
  • Fig. 3B transferring colorant present on the intermediate carrier from the intermediate carrier onto a surface of a polymer film to form, for example, in a grid arranged pattern elements on the polymer film
  • 3C forming pattern elements on a polymer layer, schematic section through the polymer layer with the brought pattern elements with four types of particulate colorants
  • FIG. 3D first alternative: activation of the pattern elements, schematic section through a laminate of the polymer film from FIG. 3C with further polymer films in which the pattern elements have been activated by means of energy supply
  • Fig. 3D ' second alternative: activating some pattern elements, schematic section through the polymer film with partially activated pattern elements
  • Fig. 3E ' removing non-activated pattern elements;
  • FIG. 4A shows the process sequence according to the invention according to the second variant of the method in a schematic form
  • 4A forming the laminate with pattern elements on the polymer layer and the cover layer arranged above, schematic section through the laminate
  • Fig. 4B activating some pattern elements, schematic section through the laminate, in which the cover has been partially destroyed by means of energy supply;
  • Fig. 5A shows the autopositioning for activating the pattern elements
  • Fig. 5B shows the autopositioning for activating the pattern elements
  • Fig. 5A forming a grid of four types of pattern elements, shown in a schematic plan view
  • Fig. 5B activation of two marker pattern elements
  • FIG. 1 shows a grid of four types of pattern elements in a schematic plan view in which only two types of pattern elements have been activated.
  • the embodiment of an identity card 600 shown in FIG. 1 in each case has a standard format for the card, for example the format ID 1 according to ISO / IEC 7810.
  • the card may be produced as a laminate of a plurality of polymer films consisting of PC and / or PET can and make single layers of the card. Some of these layers may be colored opaque with pigments, for example, to hide the card from an internal electronic device.
  • the card is formed of a polymer film as a substrate.
  • the card has a front side 601 and a rear side (not shown). You can, for example, have a thickness of 800 ⁇ .
  • the card may include a plurality of security features, such as a face image 610 of the person to whom the card is associated, a data field 620 in which, for example, that person's data is shown in plain text, and other security features that are not shown.
  • the card 600 has a security feature 160, which has been activated in accordance with the invention.
  • a reproduction of the face image 150 of the holder of the card in the form of a pattern is reproduced as representative of any differently designed marking.
  • Other representations may be formed by any other pattern.
  • the facial image 610 may be formed by the security feature that has been activated in accordance with the invention. In this case, no further field 160 would be provided.
  • the device is suitable for producing in a document blank 600 a multicolored pattern 150, for example from pattern elements 110 (FIG. 3C).
  • the device has three lasers 2 ', 2 ", 2"', three primary mirrors 3 ', 3 ", 3"', a secondary mirror 4, further imaging optics (not shown), a control unit 5 and a computer 6.
  • the computer 6 stores, for example, input data, for example an image file, from which a halftone image can be formed.
  • the raw data for the programming of the control unit 5 are then generated from the halftone image.
  • the control unit in turn controls the secondary mirror 4, so that the laser beam is guided over the surface of the document blank 600 to be activated.
  • the control device also controls the lasers 2 ', 2 ", 2"' or respectively a modulator (not shown) associated with the lasers. With these modulators, the intensity of the laser beams L can be individually modulated. With the data provided by the controller, the device can be controlled to generate pattern elements 110 of the pattern 150 in the document blank.
  • the laser beams emanating from the lasers pass through the primary mirrors 3 ', 3 ", 3"', then strike the secondary mirror 4 and are deflected by the latter onto the document blank.
  • the laser beams may be passed line by line across the document surface, with the intensity of the beams being tuned by modulation to the desired beam intensity to be formed at a location on the document surface.
  • the laser beams may, for example, be focused on the surface in order to obtain the smallest possible beam diameter.
  • the pattern 150 is produced by activating the document blank 600 by means of the laser, in which the laser beam L in the document blank strikes the colorant layer 100 (FIG. 3D). This is activated by the action of the laser beam, so that, for example, contained therein colorant is released and thus perceived by a viewer. Before activation, the colorant is hidden, for example, in color particles in that the shell largely shields the colorant.
  • FIG. 3 the inventive method in the first process variant is shown in a schematic form:
  • a colorant layer 100 in the form of regularly arranged pattern elements 1 10 different types A, B, C, D, i. with different colors, are applied in a printing field 120 to a surface 310 of a commercially available PC film 300 as a polymer layer, for example based on bisphenol A (FIG. 3C).
  • colorant is screened onto an intermediate carrier 200 (FIG. 3A).
  • the intermediate carrier is a film of PET with a release layer applied thereon.
  • the colorants are printing inks, in which respective dyes are integrated into particles (first process variant). These are, for example, dyes included in titanium dioxide particles. In the present case, four dyes are selected, namely a yellow, a red, a green and a blue dye, with which respective colorants and with these the corresponding pattern element types A, B, C, D are formed.
  • These particulate dyes are dispersed in a dye formulation containing as binder, for example, a PC derivative, preferably based on a geminally disubstituted bis (hydroxyphenyl) cycloalkane.
  • a solvent for the binder and other additives usually added to printing inks are included.
  • These inks are printed on the subcarrier 200 by means of, for example, an ink jet printer 400 having four printheads 410 (ink A), 420 (ink B), 430 (ink C), 440 (ink D) for each one of the four printing inks Size and with the arrangement of on the surface 310 of the PC film 300 to be formed pattern elements 1 10 are formed.
  • the size of the pattern elements is for example 30 ⁇ .
  • all the structures on the intermediate carrier which correspond to the pattern elements to be formed on the PC film, ie all four pattern element types A, B, C, D, are generated in a laterally reversed arrangement.
  • a grid is formed from which a pattern element arrangement, such as that shown in Fig. 6, can be generated.
  • the structures produced on the surface of the intermediate carrier are transferred to this surface of the PC film, forming a colorant layer 100 in the form of the pattern element arrangement ( Fig. 3C).
  • the PC film is pressed by means of a pressure roller 220 against the intermediate carrier belt (FIG. 3B). This results in a grid arrangement of the pattern elements with the four different colorants A, B, C, D on the polymer film surface. Because of the use of titanium dioxide, the pattern elements 110 are white to gray and have no recognizable coloration. An observer sees the print field 120, in which the pattern elements lie, because of their small size therefore pale gray.
  • Polymer films 320, 330, 340 are combined into a stack 350.
  • the printed surface 310 of the PC film 300 is arranged inside the stack (FIG. 3D).
  • the stack is then further processed in a conventional hot / cold lamination process into a laminate which after completion is a value or security document 600.
  • the result is a monolithic composite of the individual layers, i. the original surfaces are no longer recognizable after lamination.
  • the colorant layer 100 is retained during lamination, i. the dye does not diffuse out.
  • the now internal pressure field 120 also appears slightly gray or white.
  • the pattern elements 110 are treated with a focused laser beam L (method step (c)).
  • the device is used, in which the laser beam is focused on the pattern plane in which the pattern elements are located and moved over the pressure field 120.
  • the deflection unit 4 for the laser beam is present (FIG. 2).
  • the laser is, for example, a Nd: YAG laser.
  • Targeted laser treatment activates individual pattern elements by releasing dye. This diffuses into adjacent polymer layers 300, 320 and locally develops an intensive coloring of the material. In the present case all pattern elements have been activated (FIG. 3D).
  • the PC film 300 is not collated with other polymer layers and laminated but processed separately.
  • the colorant layer 100 in the form of the pattern elements 110 remains on the surface 310 of the PC film (FIG. 3D ').
  • a subsequent method step only a part of the pattern elements is activated, namely the pattern elements of the type B (red) and the type D (blue).
  • the laser device in turn serves for this purpose.
  • the yellow pattern elements (A) and the green pattern elements (C) remain inactive.
  • the non-activated pattern elements are removed from the surface (FIG. 3E ').
  • an adhesive film is pressed onto the surface (not shown) so that the non-activated pattern elements adhere to it.
  • the print field 120 appears as a mixed color of red and blue thus violet.
  • a colorant layer 100 in the form of pattern elements 110 is again formed on a PC film 300 (FIG. 4A).
  • printing inks containing the free dyes are used for this purpose.
  • four inks are used with yellow, red, green, blue dyes.
  • the pattern elements have a size and are formed in an arrangement on the surface 310 of the PC film, which correspond to those of the first example.
  • the print field 120 formed with the pattern elements appears dark brown to an observer.
  • the printing inks contain a PC derivative as binding agent, for example based on a geminally disubstituted bis (hydroxyphenyl) -cycloalkane, and a solvent for the binder and other additives which are usually added to printing inks.
  • a PC derivative as binding agent for example based on a geminally disubstituted bis (hydroxyphenyl) -cycloalkane
  • a solvent for the binder and other additives which are usually added to printing inks.
  • patterns corresponding to the pattern elements are first formed on an intermediate carrier 200, and the printing ink of these structures is then transferred from the intermediate carrier surface 210 to the surface 310 of the PC film 300 (corresponding to FIGS. 3A, 3B).
  • the structures may be formed by a pattern or by a full colorant layer.
  • this PC film 300 is combined with further polymer films 320, 330, 340, for example also PC films, to form a stack 350 (FIG. 4A).
  • a cover layer in the form of a cover film 360 having a cover layer 362 on a surface 361, which is opaque white, for example by titanium dioxide.
  • This covering layer is formed by a white printing layer, for example by means of an offset printing process.
  • the surface 310 of the PC film 300 provided with the pattern elements is accordingly between see the PC film and the cover film 360 arranged inside.
  • the stack is then further processed into a laminate in a conventional hot / cold lamination process. The result is a monolithic composite of the individual layers, ie the original surfaces are no longer recognizable after lamination.
  • the pattern elements are retained during lamination.
  • the now inner pressure field 120 is not visible due to the cover. At this point, the document appears white.
  • the covering layer 362 is treated with a focused laser beam L via individual pattern elements 110.
  • the aforementioned laser treatment device is used.
  • the targeted laser treatment causes the covering layer to be locally melted.
  • the dye in the underlying pattern elements diffuses into the adjoining PC film 300 and into the cover film 360 in the z direction, where it locally develops an intensive coloration of the material.
  • only pattern elements of the colors A (yellow) and C (green) have been activated (FIG. 4B). This results in a changed color impression in the print field 120.
  • the print field appears by the mixture of the yellow and green pattern elements in a light green color.
  • white By activating the pattern elements 1 10 of the types A and C, for example in strips, white can be formed in addition to light green stripes. Similarly, other patterns can be created.
  • the first and second examples are repeated using PET as the material for the polymer layers to be provided with the colorant layers 100. The same results, especially for the attempted delamination of the laminate.
  • 5A shows the colorant layer 100 in the form of pattern elements 110 on the surface 310 of a PC film 300 in the coding of its respective colors.
  • the print field 120 there are four pattern element types, namely yellow (A), red (B), green (C) and blue (D) pattern elements.
  • These pattern elements are arranged systematically in a square array in a printing field 120: two pattern element types A and B, and C and D, respectively, are formed in one of two consecutive arrangement types of the pattern elements.
  • a first row yellow pattern elements A and red pattern elements B and in a second row green pattern elements C and blue pattern elements D are each arranged alternately to each other.
  • the first and second rows also alternate with each other.
  • the pattern elements 110 do not yet show these colors before they are activated.
  • the colorant can be incorporated in titanium dioxide particles, so that the pattern elements appear white or gray.
  • pattern elements are activated on an experimental basis in order to determine their type.
  • the yellow pattern element (A) on the top left and the blue pattern element (D) on the bottom right have been activated and thus made visible. From this determination, it is possible to infer the absolute position of all the pattern elements of a respective type from the knowledge of the arrangement of the pattern element types relative to one another, so that a targeted activation of certain pattern elements is possible after this calibration.
  • a red pattern element (B) is located to the left and right of a yellow pattern element (A) and a green pattern element (C) below and above a yellow pattern element and a blue pattern element (D) below and above a red pattern element
  • yellow pattern elements (A) and red pattern elements (B) are located in a first row
  • green pattern elements (C) and blue pattern elements (D) are located in an underlying second row offset from the first row.
  • the further rows down represent repetitions of the first and the second row.
  • a pattern 150 that may represent information, such as the encoded value of a patterned document.
  • a pattern can also be individualizing for a value or security document 600 and, for example, reproduce the facial image of a person.
  • the generation of a pattern can be achieved in a variety of ways:
  • the pattern is already generated during the transfer of the colorant to the intermediate carrier.
  • the entire colorant is transferred from the intermediate carrier to the polymer layer and then also preferably fully activated on the polymer layer.
  • the pattern is formed only by partial transfer of the colorant areas corresponding to the pattern on the intermediate carrier to the polymer layer.
  • the intermediate carrier is preferably coated over its full area with the colorant.
  • Polymer layer formed colorant layer is then preferably fully activated.
  • the pattern is first generated by selective activation on the polymer layer.
  • the colorant is first preferably over the entire surface of the intermediate carrier and then also preferably over the entire surface of the intermediate carrier transferred to the polymer layer.
  • facial image 160 inventive security feature

Landscapes

  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Electromagnetism (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Laminated Bodies (AREA)
  • Credit Cards Or The Like (AREA)
  • Printing Methods (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)

Abstract

L'invention concerne un procédé permettant la production économique d'un signe de sécurité (160), particulièrement protégé contre la contrefaçon et la falsification, d'un produit de valeur ou de sécurité (600). Ce signe de sécurité (160) est formé par au moins un motif (150). Ce procédé comprend les étapes suivantes : (a) préparation d'un support intermédiaire (200) pourvu d'une matière colorante, cette dernière contenant des particules renfermant respectivement au moins un colorant et/ou au moins un pigment, ainsi qu'un liant polymère ; (b) transfert respectivement d'au moins une partie de la matière colorante du support intermédiaire (200) à une surface (310) d'une couche polymère (300), ce qui entraîne la formation d'une couche de matière colorante (100) sur la couche polymère (300) respective, cette dernière étant produite à partir d'au moins un matériau sélectionné dans un groupe comprenant le polycarbonate et le polyéthylène téréphtalate; et (c) apport local d'énergie au moins dans une partie de la couche de matière colorante (100) pour libérer ledit au moins colorant et/ou ledit au moins pigment des particules de façon à former le motif (150) sur la couche polymère (300) respective.
EP14771544.5A 2013-09-18 2014-09-17 Procédé de production d'un signe de sécurité d'un produit de valeur ou de sécurité Active EP3046777B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE201310218751 DE102013218751A1 (de) 2013-09-18 2013-09-18 Verfahren zum Herstellen eines Sicherheitsmerkmals eines Wert- oder Sicherheitsprodukts sowie Verfahren zum Herstellen eines derartigen Produkts
PCT/EP2014/069787 WO2015040055A1 (fr) 2013-09-18 2014-09-17 Procédé de production d'un signe de sécurité d'un produit de valeur ou de sécurité et procédé de fabrication d'un tel produit

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EP3046777A1 true EP3046777A1 (fr) 2016-07-27
EP3046777B1 EP3046777B1 (fr) 2017-11-08

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JP (1) JP6487926B2 (fr)
DE (1) DE102013218751A1 (fr)
WO (1) WO2015040055A1 (fr)

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JP2016538164A (ja) 2016-12-08
EP3046777B1 (fr) 2017-11-08
JP6487926B2 (ja) 2019-03-20
WO2015040055A1 (fr) 2015-03-26

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