WO2004089638A1

WO2004089638A1 - Method for generating an item of information, supporting body, inside of which the item of information is generated, and use of a supporting body of this type

Info

Publication number: WO2004089638A1
Application number: PCT/EP2004/003218
Authority: WO
Inventors: Hermann Hecker; Manfred Paeschke; Oliver Muth
Original assignee: Bundesdruckerei Gmbh
Priority date: 2003-04-07
Filing date: 2004-03-26
Publication date: 2004-10-21
Also published as: CA2519404A1; CN1767953A; ATE343482T1; DE502004001851D1; EP1610956B1; DE10316034A1; EP1610956A1

Abstract

A method for generating an item of information in a supporting body should, by using simple means, produce an item of information that is stable over a long period of time and, in particular, with regard to light and moisture. To this end, the reaction conditions for a number of reactants contained in the supporting body are set in a localized partial area of the supporting body by laser irradiation, whereby the reaction conditions set are those that cause the reactants to enter into a synthesis reaction.

Description

description

Method for generating information, carrier body in which the information is generated, and use of such a carrier body

The invention relates to a method for generating information. It further relates to a carrier body in which the information is generated and to the use of such a carrier body.

To achieve colored information, photochemical reactions are a direct or indirect part of everyday life. Processes in the context of classic silver halide photography include either wet chemical work steps, such as developing and fixing in appropriate baths, or working with organic dye systems, such as for Polaroid instant photos, which, however, are usually not lightfast.

In the course of semiconductor development but also in the computer-aided creation of prototypes (rapid prototyping, rapid tooling), a large number of so-called photoresist materials or photoprepolymers have established themselves on the market (Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, 2002 Electronic Release, keyword photo - resists). In the broadest sense, these are so-called prepolymers that polymerize, crosslink or harden due to photochemical reactions and only in a subsequent step by washing out with solvents, such as in photolithography, or by changing the z-coordinate, such as in rapid prototyping , separate from the background as separate information, writing in the xy direction.

Lasers are generally used to achieve a comparatively high Orls resolution and thus also a higher data and information density in the above-mentioned methods. Usual laser marking methods find a large field of application in the production of ID cards, driving licenses, bank cards, credit cards or the like from plastic. From DE 29 07 004 C2 it is known to apply visually readable information to identification cards by means of laser radiation. The information becomes visible through carbonization and / or carbonization of the plastic material, the information standing out in black or gray against a background of a different color, for example opaque or transparent. Other colors cannot be created with it. Laser marking is more secure than other marking methods against counterfeiting or manipulation, because it can also be carried out subsequently in layers on the inside.

In addition, it is also known to engrave using laser radiation, in particular it is possible to locally remove individual layers of a multilayer card body. According to DE 30 48 733 C2, this fact is used to apply differently colored information to identity cards. A multi-layer card body is used, the layers of which are of different colors. The local removal of individual layers by laser radiation makes the underlying different colored layer visible. However, this method for labeling card-shaped data carriers may have the disadvantage that the surface of the data carrier is damaged by the removal.

From DE 44 17 343 A1 it is known to laser-introduce a single-color portion and / or gray and black portion of an image part into an identification card and to apply a complementary color image portion above it, in particular in the thermal transfer process, with respect to the image. In the latter, point-shaped electrodes of a thermal printer line are heated in an electrically controlled manner, so that the color layer of a color film or multicolor color film introduced between the thermal printer line and the top layer melts and / or evaporates at points and is deposited on the top layer. The different processing of the card with high-tech devices produces a high depth of color, which makes it difficult to counterfeit by means of widespread color copying and color printing techniques, but requires an apparatus-intensive process. DE 199 55 383 A1 describes a method for applying colored information to an object by means of laser radiation with at least two different wavelengths, the color of the layer being adjustable by wavelength-selective bleaching of individual organic pigments as a result of subtractive color mixing.

DE 100 11 486 A1 also describes a card-shaped data carrier and a method for producing the same, which makes it possible to apply colored information by means of laser processing without damaging the surface of the data carrier. In this case, a layer is completely bleached out locally by the laser radiation, so that the layer alone is at least almost transparent in the laser writing spot. In this way, an originally black, gray or dark brown stain can be set red, blue or green, depending on which of the laser-sensitive layers in the sandwich structure are bleached.

The invention is based on the object of specifying a method for generating information in and / or on a carrier body which, with simple means, has a particularly high long-term resistance to light and moisture. Furthermore, a carrier body that is particularly suitable for this method is to be provided and the use of such a carrier body is to be specified.

With regard to the method, this object is achieved according to the invention by setting the reaction conditions for a number of starting materials held in and / or on the carrier body in a localized partial area of the carrier body that cause the starting materials to undergo a synthesis reaction.

The invention is based on the consideration that, in previous systems, the long-term stability of the information is limited, inter alia, by the fact that color conversion reactions continue uncontrolled even without specific and intentional activation, for example by irradiated sunlight. This activation can take place through statistical suggestions of a commonly used dissociation reaction, since at a dissociation reaction, in which only one starting material is required, the necessary reaction conditions for the decomposition of the molecule into simpler molecules, atoms, ions or radicals are comparatively easy to achieve. For example, fading due to photochemical decomposition, which can lead to the destruction of both the information and the carrier body, can occur. The concept for generating long-term information is therefore a departure from such simple decolorization processes. An increase in the long-term stability of the information can be achieved precisely by consistently reducing the likelihood of subsequent, statistically triggered implementation processes. This can be achieved through a targeted increase in the complexity of the reaction used with correspondingly higher, more difficult to achieve reaction conditions. For a correspondingly increased complexity of the reaction processes, the use of reaction types is therefore provided which are based on the use of a plurality of starting materials or other complex reaction parameters. The generation of information that is resistant to light and moisture is achieved instead of destructive processes or dissociation through synthetic processes.

Such synthesis reactions are preferably additions, eliminations, substitutions and in particular redox and complex formation reactions. During the addition, atoms or groups of atoms are attached to a multiple bond. In the process of elimination as a reversal of the addition, atoms or groups of atoms are separated from one molecule without others taking their place. The substitution is characterized by the replacement of an atom or an atomic group in a molecule by other atoms or atomic groups, whereby a covalent bond with one partner is released and then one is linked with another partner. The redox reaction is characterized by the electron donation of one partner (reducing agent) and the electron absorption by the other partner (oxidizing agent). In complex formation reactions, a central atom or ion is surrounded by several other atoms, ions or molecules, the so-called ligands, in a spatially regular arrangement. These synthetic processes place comparatively demanding or complex demands on the reaction conditions and on the reactants and.

A particularly high reaction temperature, a release of reactive starting materials or activated molecular species in sufficient numbers for the reaction and / or a sufficiently high particle mobility of the reactants are particularly important as reaction conditions. These reaction conditions can be achieved by introducing thermal energy that is spatially resolved by laser light, which provides the activation energy of the process. The mobility of the starting materials in or on the carrier body is improved by the thermal energy and the reaction probability is increased so much that a sufficient reaction conversion is achieved. In addition, irradiation with laser light enables reaction-inhibiting environments to be broken up and the raw materials to be made available as reactants in the first place.

Without the supply of energy, it should not be possible to induce the starting materials held in the carrier body to produce durable information to change properties or substances. Your statistical reaction probability should, for example, be reduced compared to the reaction partners of a bleaching process. Under normal environmental conditions, however, the activation energy necessary to generate reactive molecular species from the starting materials should not be achieved, nor should the reactive molecular species be present under normal conditions in sufficient local concentration to initiate a reaction or even one to achieve complete reaction sales. A further condition for suitable starting materials is an inertness towards the carrier body itself, so that it is not permanently changed by the starting materials and thereby possibly damaged or made unusable. In principle, material mixtures or compounds of all elements of the periodic table which are capable of such a “robust” use are therefore considered as starting materials held in the carrier body. These criteria are preferably met in particular by selected inorganic substance mixtures, since these migrate comparatively little in the carrier body and reactions with changes in substance or properties usually only occur at high temperatures of several hundred degrees Celsius, such as inside a Bunsen burner flame.

In order to detect the change in properties or substance of the starting materials caused by laser radiation, it is expedient to change their absorption properties with respect to the wavelengths in the ultraviolet to infrared range. For a particularly simple detection, the starting materials are advantageously chosen such that they are caused to undergo a synthesis reaction with a change in color. Colored information is therefore preferably generated.

For one or more colored information or information selected as required, the starting materials of the synthesis reactions of different color changes are preferably chosen such that the product of the respective synthesis reaction is assigned to a basic color of a CMYK color scheme for cyan, magenta, yellow and contrast or black. With a suitable combination, mono or mixed colors can be created.

In order to enable graphically particularly diverse color patterns and variations in the carrier body, the starting materials for synthesis reactions of different color changes are preferably kept in separate volume segments in the carrier body.

In order to generate differently colored information and information in a carrier body with a comparatively high color depth, in particular also with regard to laser inscription which is particularly secure against counterfeiting and manipulation, an inner color design is also useful in addition to the outer color design of the carrier body in question. Therefore, the starting materials assigned to different color reactions are preferably kept in separate layers in the carrier body. In order to prevent premature reaction of the starting materials without excitation by laser radiation, a protective device or measures preventing this reaction is expediently provided. For this reason, at least one of the starting materials is preferably kept encapsulated in the carrier body, the encapsulation advantageously being chosen such that it is broken up by the laser radiation and releases the relevant starting material as a reaction partner. For this purpose, the encapsulation is preferably designed such that it absorbs the laser radiation itself. This ensures that information is generated in a targeted manner in terms of time and location.

In order to focus the laser radiation directly on at least one starting material, in particular if this alone is not or only insufficiently suitable for absorbing the laser radiation, or to reduce the required laser energy, auxiliary substances or layers absorbing the laser radiation are preferably embedded in the carrier body. Examples of absorbing auxiliaries are a mica pigment which is commercially available under the names "Iriodin" or "Mica", i.a. into consideration. As a result, the laser light irradiated onto the auxiliary substance is transferred to the selected starting substance via interference or mirror effects. At this point, this leads to a local temperature increase, a so-called hot spot or a hot point, and thus to an excitation of at least one starting material with usually at least one further starting material, so that they interact and initiate a synthesis reaction.

In order to reduce the activation energy of the reactants, preferably catalytically active particles are embedded in the carrier body. This makes it possible, depending on the selected starting materials, to use a comparatively low laser energy or even a comparatively low-power laser. The catalytic elements can in particular come from the 8th subgroup, the so-called platinum metals. Finely divided platinum, rhodium, palladium or mixtures thereof can catalyze redox reactions, in particular, analogously to their use in exhaust gas catalysts. A decomposition of a platinum complex would also be conceivable, such as a decomplexation of the orange-red (CH ₃ ) ₃ Ptl. By decomposing the (CH ₃ ) ₃ Ptl, elemental platinum could be obtained as a catalyst or even generate blackening at higher concentrations due to finely divided platinum.

For a particularly simple generation of information in a carrier body with a low equipment and technical outlay and for a high spatial resolution and thus also to achieve a higher data and information density, preferably all commercially available lasers for labeling documents with emissions from UV to IR range can be used, e.g. with emissions of 190 nm for photolithography or with emissions of 10 μm for packaging labeling with a CO ₂ laser. In a particularly advantageous embodiment of the labeling, an Nd: YAG laser with an emission of 1064 nm is used.

In a particularly advantageous embodiment, the method preferably provides, as basic components of the carrier body, substances which do not absorb laser radiation, such as paper, plastic films and / or a coloring, adhesive and / or lacquer layer, which are advantageously used for tamper-proof identification or for machine verification and simultaneous cancellation of the documents are labeled or marked.

In a particularly advantageous embodiment of the process, the starting materials held in and / or on the carrier body are preferably introduced into the paper pulp as an additional additive in film production processes, such as calendering, extruding or film casting, or during paper production and / or advantageously by coating processes, such as brushing, Spraying, spraying, coating, dipping, and / or by means of printing processes such as offset, steel engraving, gravure printing, flexographic printing, screen printing, indirect printing, thermal transfer printing, electrophotography and ink-jet processes in and / or on the carrier body.

With regard to the carrier body, the stated object is achieved by holding a number of starting materials in and / or on it in such a way that the reaction conditions for a synthesis reaction of the starting materials can be set in a laser-induced manner. The basic components of the carrier body are preferably provided as materials which do not absorb laser radiation, such as paper, foils, in particular thermoplastic materials, and / or a coloring, adhesive and / or lacquer layer.

In order to detect the change in properties or substance of the starting materials caused by laser radiation, it is expedient to change their absorption properties with respect to the wavelengths from the ultraviolet range through the visible range to the infrared range. For a particularly simple detection, the starting materials are advantageously selected such that they are caused to undergo a synthesis reaction changing their color, which is visible to the human eye. Inorganic reactions are advantageously used as starting materials for synthesis reactions involving a color reaction. These can be used to generate intense colored information that is particularly resistant to light and moisture, among other things, via redox or complexation reactions. are and are therefore also suitable for the identification of valuable and / or security documents with a particularly high level of security against forgery. Word and symbols, such as inscriptions, logos or barcodes, can be generated as colored information.

For one or more single- or multi-colored pieces of information selected as required, the starting materials in the carrier body are preferably selected such that the product of the respective synthesis reaction is assigned to a basic color of a CMYK color scheme for cyan, magenta, yellow and contrast or black.

In order to be able to use the carrier body in a particularly versatile manner, the carrier body is expediently equipped for the generation of permanent, intensive colored information. MnSO ₄ , KNO ₃ and KOH are preferably provided as starting materials for a product with the color blue (“cyan”). Alternatively or cumulatively, for a product with the color red (“magenta”) are preferred Fe ₂ (SO ₄ ) ₃ and KSCN are available as starting materials. As an alternative or in addition to the colors blue (“cyan”) and / or red (“magenta”), Cr ₂ O ₃ , KNO ₃ and KOH are preferably kept as starting materials for a product with the assignment to the color yellow (“yellow”) , To increase the variety of colored information, in the carrier body for a product with the assignment to the color blue as starting materials, Cu ²⁺ and NH ₃ for the reaction to the tetraammine copper complex or the substances Co (NO ₃ ) ₂ and Al _{2 are} preferred O ₃ and / or for a product associated with the color green, preferably Co (NO ₃ ) ₂ and ZnO or the substances K ₂ CrO and C ₃ H ₇ OH as starting materials.

In order to enable graphically particularly diverse color patterns and variations in the carrier body, the starting materials for synthesis reactions of different color changes are preferably held in separate volume segments in the carrier body.

In order to generate differently colored information in a carrier body with a comparatively high color depth, in particular also with regard to laser inscription which is particularly secure against counterfeiting and manipulation, an inner color design is also useful in addition to the outer color design of the relevant carrier body. Therefore, the starting materials assigned to different color reactions are preferably kept in separate layers in the carrier body.

In order to focus the laser radiation directly on at least one starting material, in particular if this alone is not or only insufficiently suitable for the absorption of the laser radiation, without destroying the carrier body with excessive laser energy, auxiliary substances or laser absorbing agents are preferably in the carrier body layers embedded.

In a particularly advantageous embodiment of the carrier body for the assignment to contrast or black, alternatively or cumulatively to the colors blue ("cyan"), red ("magenta") and / or yellow ("yellow") as an auxiliary agent, which radiates the irradiated Laser radiation is transferred via interference or mirror effects to a selected starting material, preferably a mica pigment such as "Iriodin", but also simply titanium dioxide or carbon in the form of carbon black or advantageously also a color pigment such as phthalocyanine.

In order to be able to use the support body reliably and flexibly in terms of time and location, the starting materials provided in it for a synthesis reaction are preferably at least partially encapsulated by an encapsulation which inhibits this reaction until excitation by laser radiation. In a particularly advantageous manner, the encapsulation is selected in such a way that it is broken up by the laser radiation and only releases the relevant starting material as a reaction partner when it is broken up. For this purpose, the encapsulation is preferably designed such that it absorbs the laser radiation itself.

To reduce the activation energy, in particular for redox reactions of the starting materials held in the carrier body, and in favor of the use of a comparatively low-power laser, preferably catalytically active particles are embedded in the carrier body.

The carrier body equipped in this way can expediently be used in all areas in which valuable and / or security documents are concerned, in the logistics area or ticketing and for presentations. The carrier body is therefore preferably used as identification, driving license, credit or health card, ticket or film.

The advantages achieved with the invention consist in particular in that constant information is generated precisely by the synthesis reaction of a number of starting materials. In particular, typical and sensitive detection reactions for subgroup metals known from the literature can be used to generate particularly intensive colored information which is resistant to environmental influences. Reliable process control is made possible precisely by irradiating at least one reactant with laser light. Laser irradiation ensures that a reaction temperature that is sufficiently high for the desired synthesis reaction is provided and / or that the irradiated substances are sufficient. accordingly moved and / or caused to release reactive molecular species.

Furthermore, due to its particularly suitable configuration with encapsulations of particularly reactive starting materials, with auxiliaries or layers absorbing the laser radiation and / or with particles having a catalytic action, the carrier body permits a specifically controlled process control. Thus, when the starting materials of a synthesis reaction are already reactive at room temperature or by rubbing with one another, at least one of the starting materials is held encapsulated in the carrier body so that the synthesis reaction is only made possible by laser-induced breaking of the encapsulation. While a starting material that does not or only slightly absorb the laser radiation is activated indirectly by the laser radiation by means of auxiliary substances or layers absorbing the laser radiation embedded in the carrier body, by focusing the laser radiation on the selected starting material via interference or mirror effects of the auxiliary substances or layers and there The local temperature increase creates a hot spot at which the starting material is made to interact with at least one other starting material or to undergo a monomolecular reaction. Catalytically active particles embedded in the carrier body reduce the activation energy of the starting materials.

Furthermore, by embedding the starting materials of synthesis reactions of different color changes in different volume segments and / or layers, the carrier body enables a high degree of flexibility in the desired graphic designs in the form of diverse color variations and color patterns. The method for laser-induced in-situ generation of information in the carrier body thus enables use for marking or lettering papers, foils and other plastic documents, in particular increases the security against forgery of a document identified in this way and can furthermore be used for machine verification and simultaneous validation of Documents such as tickets. Thus, the method can be used in all areas of daily life, in which it is a question of the rapid and locally targeted application and / or introduction of permanent word and / or symbols, among other things. An embodiment of the invention is explained in more detail below.

Various starting materials, their installation in and / or on a carrier body and their laser initialization, which enables a wavelength-specific effect over the UV-VIS-IR range, are described below.

Depending on the application, the starting materials selected for a desired synthesis reaction can be brought into an inner and / or outer area of a data carrier acting as a carrier body in a precise, matrix-like or layer-like manner by means of various insertion or application methods. The basic components or composite materials on which the carrier body is based are, for example, paper or plastic films, and also between and / or colored, adhesive or lacquer layers applied to them. In a preferred embodiment, the starting materials are introduced as an additional additive during film production. This applies in particular to the common film production processes such as calendering, extruding and film casting. In papermaking, the starting materials selected for the synthesis reaction can also be incorporated into the paper pulp as an additional additive. The incorporation into foils and papers has the advantage that in the production of documents, such as cards and IDs, no major interventions are necessary in the production process itself. Various coating processes, such as brushing, spraying, spraying, coating, dipping, and / or printing processes, such as offset, steel engraving, gravure printing, flexographic printing, screen printing, indirect printing, thermal transfer printing, electrophotography and ink-jet processes can be used to achieve the desired synthesis reaction Bring selected starting materials into and / or onto the carrier body.

In a preferred embodiment, a screen printing varnish that is highly filled with the starting materials is printed onto an opaque plastic film and overlaminated with several layers of plastic film. This procedure represents a particularly flexible embodiment, since it makes it easy to produce internal prints when manufacturing composite materials such as cards, ID cards made of all-plastic or paper-plastic compounds. Of course, in addition to the complex formation and redox reactions of the starting materials held in the carrier body mentioned in the exemplary embodiment, other synthesis reactions are also conceivable, such as eliminations in which part of the molecule is split off, which also changes its physical properties, or additions in which new covalent bonds are formed and thus generate a “new” substance, or substitution reactions in which, for example, ligands of a complex are exchanged.

Example 1: Blue laser inscription A stoichiometric mixture of the inorganic starting materials from cobalt (II) nitrate with aluminum sulfate and a binder is printed on a plastic card, for example by screen printing. Optionally, the mixture also contains "Iriodin"(<0.5 percent by weight). This plastic card can then be laminated with an NIR-permeable overlay film. When irradiated with an Nd: YAG laser, the hot spot or the generated thereby occurs are called the reaction to the cobalt spinel CoAl ₂ θ _{3ι known} in the literature as Thenards blue. The "Iriodin" is used in the extended recipe as an auxiliary agent that absorbs the laser radiation in order to transfer the laser radiation to the starting materials and thus to to focus the starting materials and / or to minimize the laser energy required for the reaction. Excessive laser radiation usually leads to carbonization, which can minimize or mask the blue color impression.

The reaction to Thenards blue can be described with the following equation: Co (NO ₃ ) ₂ + AI ₂ O ₃ → CoAI ₂ O ₃ + 2 NO ₂ + O ₂

FIG. 1 schematically shows a pigment 2, “iriodin”, embedded in a matrix 1, which absorbs the irradiated laser light 6 in its mica core 4 and, as symbolized in FIG. 1 by a flash 8, interferes with its other effects Transfer of inorganic starting materials Co (NO ₃ ) ₂ and Al ₂ O _{3 located} in the interface 1. This creates a hot spot 12 at the interface 10 of the pigment 2, so that the reaction described in Example 1 is initiated with a change in color. Example 2: Green laser marking

A stoichiometric mixture of the inorganic starting materials of 2 cobalt (II) nitrate with 1 zinc oxide is added in the exemplary embodiment in film production, for example in the calendering process, as an additive. Optionally, the mixture also contains proportions of "Iriodin"(<0.5 percent by weight). In the exemplary embodiment, this film is then joined together with other components to form a plastic card which is only covered with an NIR-permeable overlay film. When irradiated with a Nd. The demAG laser causes the reaction to the zinc-cobalt spinel ZnCo ₂ O _{ι known} in the literature as Rinmanns-Green at the hot spot or hot spot generated thereby. The “Iriodin” in turn serves as an extended formulation the auxiliary material absorbing laser radiation in order to focus the laser radiation on the starting materials and / or to minimize the laser energy required for the reaction. Excessive laser radiation usually leads to carbonization, which can minimize or mask the green color impression.

The reaction to Rinmanns-Grün can be described with the following equation: 2 Co (NO ₃ ) ₂ + ZnO → ZnCo ₂ O + 4 NO ₂ + ^Λ O ₂

Example 3: Blue ("Cvane") laser marking A stoichiometric mixture of the inorganic starting materials from pink manganese (II) sulfate with 2 potassium nitrate and 2 potassium hydroxide is added as an additive to an adhesive in hot melt film production. Optionally, this contains Mixture still shares in "Iriodin"(<0.5 percent by weight). In the exemplary embodiment, this film is then joined together with other components to form a plastic card which is only covered with an NIR-permeable overlay film. When irradiated with an Nd: YAG laser, the reaction to the green-blue ("cyan") manganate, which is also known as the oxidation melt, occurs at the hot spot or hot spot thereby generated. The "Iriodin" in turn serves as an extended formulation the auxiliary material absorbing laser radiation in order to focus the laser radiation on the starting materials and / or to minimize the laser energy required for the reaction. Excessive laser radiation usually leads to carbonization, which can minimize or mask the green-blue ("cyan") color impression. The reaction to the green-blue ("cyan") manganate can be described with the following equation: MnSO ₄ + 2 KNO ₃ + 2 KOH → K ₂ MnO ₄ + 2 KNO ₂ + H ₂ SO ₄

Example 4 a) Yellow ("Yellow") laser marking and b) Green laser marking a) A stoichiometric mixture of the inorganic starting materials from green chromium (III) oxide with 3 potassium nitrate and 2 potassium hydroxide is analogous to one of Examples 1 to 3 in a matrix. The use of “iriodin” can be dispensed with in this exemplary embodiment, since Cr ³⁺ absorbs very well in the red spectral range. Upon irradiation with a powerful dye or semiconductor laser with red emission (630 - 690 nm), the reaction to the yellow-orange ("yellow") dichromate (also known as chromium oxidation melt) occurs at the hot spot or hot spot thereby generated. Cr ⁶⁺ ) a.

The redox reaction to the yellow-orange (“yellow”) dichromate can be described with the following equation: Cr ₂ O ₃ + 3 KNO ₃ + 2 KOH → K ₂ Cr ₂ O ₇ + 3 KNO ₂ + H ₂ O

b) The reaction from yellow potassium chromate (Cr ⁶⁺ ) with propanol, which is at least present in traces in many pressure additives, to green chromium (III) is suitable as a color reaction from yellow to green, also known as the "classic alcohol test" in the test tube. -oxide according to the equation: 2 K ₂ CrO ₄ + 3 C ₃ H ₇ OH → Cr ₂ O ₃ + 3 C ₃ H ₆ O + 4 KOH + H ₂ O When implemented in a carrier body, the mobility of the system is, for example, complete Minimize lamination in order to exclude health hazards that can arise from the toxic chromates.

FIG. 2 schematically shows a pigment 2, yellow chromate (Cr ⁶⁺ ) embedded in a matrix 1, the matrix 1 containing 14 traces of an alcohol (R-OH) as a reducing agent. The flash 8 symbolizes a hot spot 12 induced by the irradiated laser light 6 or a hot spot at the interface 10 of the pigment 2 (Cr ⁶⁺ ) to matrix 1. There the alcohol is oxidized to an aldehyde (R-HO) and the Cr ⁶⁺ reduced to green Cr ³⁺ according to the equation described in Example 4b).

Example 5: Red (“magenta”) laser inscription a) Iron in the oxidation state +3, for example iron (III) sulfate, forms a deep red (“magenta”), characteristic complex according to the equation with thiocyanates even in the non-aqueous medium :

Fe ₂ (SO ₄ ) ₃ + 6 KSCN (+ β H ₂ O) → 2 [Fe (SCN) ₃ (H ₂ O) ₃ ] + 3 K ₂ SO ₄ The complex formation already takes place when the starting materials are rubbed together, so that the iron (III) sulfate is encapsulated and introduced into the matrix and only the laser radiation breaks the encapsulation in order to stimulate the reaction with a change in color.

b) Iron (II) sulfate does not require encapsulation. It is oxidized with potassium nitrate and potassium thiocyanate and water by laser action to iron with the oxidation level +3, which immediately reacts to the deep red ("magenta"), characteristic complex according to the equation:

2 FeSO ₄ + KNO ₃ + 6 KSCN + 4 H ₂ O → 2 [Fe (SCN) ₃ (H ₂ O) ₃ ] + KNO ₂ + 2 K ₂ SO ₄

+ 2 KOH

Example 6: Red fluorescent laser marking

Europium with oxidation level +2 shows a localized red fluorescence when oxidized with saltpetre to oxidation level +3 after laser irradiation in a blue fluorescent environment.

The redox reaction can be described with the following equation: 2 Eu ²⁺ + KNO ₃ + H ₂ O → 2 Eu ³⁺ + KNO ₂ + 2 OH ^"

Example 7: Multi-colored laser marking

Furthermore, the starting materials presented in Examples 3, 4 and 5 for their laser-induced characteristic color reactions can in each case be combined with one another in different, delimited layers 16a-d, each of which represents a carrier body with a correspondingly reactive matrix, as shown in FIG. 3 , In the exemplary embodiment, a film composite structure with four different differently doped layers 16a-d are provided, the bottom layer 16a with MnSO ₄ , KNO ₃ and KOH (example 3), the second bottom layer 16b with Fe ₂ (SO) ₃ and KSCN (example 5), the third layer 16c from below is doped with Cr ₂ O ₃ , KNO ₃ and KOH (example 4) and the top layer 16d with "Iriodin". The respective synthesis reaction is initiated by irradiation with an Nd: YAG laser confocal optics, focused on selected volume segments 18a-d within the respective layer 16a-d (z-coordinate) at specific positions (xy-coordinates), with resolutions of approximately 10 μm in the xy-direction and approximately 30 μm in z Due to the comparatively low focus sharpness in the z direction, each layer 16a-d is scanned individually in order to carry out the synthesis reaction on the selected volume segments 18a-d setting of MnSO ₄ with KNO ₃ and KOH a color change to blue ("cyan") was achieved (example 3). In the second step, the laser is then set on the second lowest layer 16b and focused on the desired xy positions within it. As a result of the irradiation by reaction of Fβ ₂ (SO ₄ ) ₃ with KSCN, a color change to red (“magenta”) is produced (example 5). Analogously, in the third layer 16c, the reaction of Cr ₂ θ ₃ , KNO, from below ₃ and KOH induced in the selected volume segments 18c and thus the color change to yellow ("Yellow") achieved (Example 4). Finally, in the exemplary embodiment, the locally resolved irradiation is carried out in the top layer 16d doped with “Iriodin”. In the selected volume segments 18d, a gray to black color change is generated by the local overheating, which represents the contrast. If the film composite structure after the laser-induced loading Looking at the writing process perpendicular to the layers 16a-d, the overlaying of the individual colored volume segments 18a-d results in a full-color CMYK image through subtractive color mixing. The spatial resolutions mentioned above make images with a resolution of more than 600 dpi possible, which means corresponds to the standard resolution of modern color printers. LIST OF REFERENCE NUMBERS

1 matrix

pigment

Irradiated laser light

lightning

10 interface 2 hot spot 4 reducing agent 6a-d layer 8a-d volume segments

Claims

Expectations

1. A method for generating information in and / or on a carrier body, in which for a number of starting materials held in and / or on the carrier body in a localized partial area of the carrier body

Laser irradiation, the reaction conditions are set which cause the starting materials to undergo a synthesis reaction.

2. The method according to claim 1, in which an addition, an elimination, a substitution, a redox reaction or a complex formation reaction is used as the synthesis reaction.

3. The method according to claim 1 or 2, in which inorganic substance mixtures are used as starting materials for the synthesis reaction.

4. The method according to any one of the preceding claims, wherein the starting materials are selected such that they are caused to undergo a synthesis reaction with a color change.

5. The method according to any one of the preceding claims, in which the starting materials are selected such that the product of the respective synthesis reaction is assigned to a base color of a CMYK color scheme.

6. The method according to any one of the preceding claims, in which starting materials from synthesis reactions of different property changes, in particular color changes, are kept in separate volume segments (18a-d) in the carrier body.

7. The method according to any one of the preceding claims, in which starting materials from synthesis reactions of different property changes, in particular color changes, are kept in separate layers (16a-d) in the carrier body.

8. The method according to any one of the preceding claims, in which at least one of the starting materials is held encapsulated, the encapsulation being selected such that it is broken up by the laser radiation.

9. The method according to claim 8, wherein the encapsulation is chosen such that it absorbs the laser radiation.

10. The method according to any one of the preceding claims, in which auxiliary substances or layers absorbing the laser radiation are embedded in the carrier body.

11. The method according to any one of the preceding claims, in which catalytically active particles are embedded in the carrier body for the synthesis reaction.

12. The method according to any one of the preceding claims, in which a laser with emissions from the UV to IR range is used for laser irradiation.

13. The method according to any one of the preceding claims, in which an Nd: YAG laser with an emission wavelength of 1064 nm is used for laser irradiation.

14. The method according to any one of the preceding claims, are provided in the basic components of the carrier body, the laser radiation non-absorbing substances, such as paper, plastic films and / or a coloring, adhesive and / or lacquer layer, which are for tamper-proof identification or for machine Verification and simultaneous devaluation of documents, labeled or marked.

15. The method according to any one of the preceding claims, in which the starting materials held in and / or on the carrier body are introduced as an additional additive in film or paper production and / or by coating processes, such as brushing, spraying, spraying, coating, dipping, and / or by Printing processes such as offset, steel engraving, gravure printing, Flexographic printing, screen printing, indirect high pressure, thermal transfer printing, electrophotography and ink jet processes can be brought into and / or onto the carrier body.

16. Carrier body, in particular for the method according to one of claims 1 to 15, in and / or on which a number of starting materials are provided in such a way that the reaction conditions for a synthesis reaction of the starting materials can be set in a laser-induced manner.

17. A carrier body according to claim 16, in which the base components of the carrier body are provided with the laser radiation non-absorbing substances such as paper, plastic films and / or a coloring, adhesive and / or lacquer layer.

18. A carrier body according to claim 16 or 17, in which inorganic substance mixtures are used as starting materials for the synthesis reaction.

19. Support body according to one of claims 16 to 18, in which the starting materials are chosen such that the product of the respective synthesis reaction in each case. is assigned to a basic color of a CMYK color scheme.

20. Carrier body according to claim 19, in which MnSO ₄ , KNO ₃ and KOH are provided for a product with the assignment to the color blue (“cyan”).

21. Carrier body according to claim 19 or 20, in which for a product with the assignment to the color red ("magenta") are provided as starting materials Fβ ₂ (SO) ₃ and KSCN.

22. Carrier body according to one of claims 19 to 21, in which Cr ₂ θ ₃ , KNO ₃ and KOH are provided as starting materials for a product with the assignment to the color yellow.

23. Support body according to one of claims 19 to 22, in which for a product with the assignment to the color blue as starting materials Cu ²⁺ and NH ₃ or the substances Co (NO ₃ ) ₂ and Al ₂ O ₃ and / or for a Product with the assignment to the color green as raw materials Co (NO ₃ ) ₂ and ZnO or the substances K ₂ CrO and C ₃ H7OH are available.

24. Carrier body according to one of claims 16 to 23, in which starting materials of synthesis reactions of different property changes, in particular color changes, are kept in separate volume segments (18a-d) of the carrier body.

25. Carrier body according to one of claims 16 to 24, in which starting materials of synthesis reactions of different property changes, in particular color changes, are kept in separate layers (16a-d) in the carrier body.

26. Carrier body according to one of claims 16 to 25, in which auxiliary substances or layers absorbing the laser radiation are embedded.

27. A carrier body according to claim 26, in which a mica or color pigment is provided for the assignment to contrast or black as an auxiliary substance which absorbs the laser radiation.

28. Support body according to one of claims 16 to 27, in which at least one of the starting materials of a synthesis reaction is held encapsulated, the

Encapsulation is selected such that it is broken up by the laser radiation.

29. Carrier body according to claim 28, wherein the encapsulation is selected such that it absorbs the laser radiation.

30. Support body according to one of claims 16 to 29, in which catalytically active particles are embedded for the synthesis reaction.

1. Use of a carrier body according to one of claims 16 to 30 as

Value and / or security document, such as ID, driver's license, credit or health card, or as a ticket or film, etc.