DE10316034A1 - Method for generating information, carrier body in which the information is generated, and use of such a carrier body - Google Patents

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

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

to Obtaining colored information, photochemical reactions are direct or indirectly part of everyday Life. Processes in the context of classic silver halide photography involve either wet chemical steps, such as developing and fixing in appropriate baths, or working with organic dye systems, e.g. for Polaroid instant photos, which, however, usually are not lightfast.

in the In the course of semiconductor development but also in computer-aided creation of prototypes (rapid prototyping, rapid tooling) has a variety on so-called photoresist materials or photoprepolymers Market established (Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, 2002 Electronic Release, Keyword photoresists). It is in the broadest sense so-called prepolymers, which are based on photochemical reactions polymerize, crosslink or harden and only in a subsequent one Step by washing out with solvents, like in photolithography, or with changing the z coordinate, like in rapid prototyping, as separate information from the background take off, writing in the x-y direction.

Around a comparatively high spatial resolution and hence a higher one To achieve data and information density, lasers are usually used used. Usual laser marking methods find in the production of ID cards, driving licenses, bank cards, credit cards or the like from plastic a large field of application.

From the DE 29 07 004 C2 is known to apply visually readable information on identity 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. This fact is according to DE 30 48 733 C2 used to put different colored information on ID 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 the DE 44 17 343 A1 It is known to laser-technically introduce a monochrome 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, punctiform 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, he produces a high depth of color, which makes it difficult to forge using common color copying and color printing techniques, but requires an apparatus-intensive process.

The 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.

Also in the DE 100 11 486 A1 describes a card-shaped data carrier and a method for producing the same, which enables the application of 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 alone. 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 The invention has for its object a method for generating to specify an information in and / or on a carrier body, which with simple Means one especially towards Light and moisture particularly high long-term durability having. Furthermore, one should be special for this procedure suitable carrier body provided as well a use of such a support body can be specified.

Regarding the According to the invention, this object is achieved by a number of im and / or held on the carrier body Starting materials in a localized section of the carrier body Laser irradiation set the reaction conditions 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 among other things is limited by the fact that color conversion reactions even without targeted and desired activation, e.g. by irradiated sunlight, continue uncontrolled. This activation can be done by statistical Suggestions one usually used dissociation reaction happen because in a dissociation reaction, where only one starting material is required, the necessary ones Reaction conditions for the decay of the molecule into simpler molecules, Atoms, ions or radicals are comparatively easy to reach. For example, fading due to photochemical decomposition, the until destruction both the information and the carrier body can occur. The concept to create a long-term resistant Information therefore represents a departure from such simple ones deinking an increase long-term stability The information can be obtained precisely by the probability for subsequent, statistical triggered Implementation processes are consequently reduced. This is achievable through a targeted increase in the complexity of the implementation reaction used with correspondingly higher, more difficult fulfillable Reaction conditions. For one increased accordingly complexity of the reaction processes it is therefore intended to use reaction types based on the Using a variety of starting materials or other complex Reaction parameters are based. The generation of a towards light and moisture resistant information instead of destructive processes or dissociation achieved through synthetic processes.

As Such synthesis reactions preferably involve additions, eliminations, Substitutions and especially redox and complex formation reactions into consideration. When adding atoms or atom groups to one Multiple bond attached. In the case of elimination as a reversal of the addition become one molecule Atoms or groups of atoms separated without others to take their place. The substitution is characterized by the replacement of an atom or group of atoms in a molecule other atoms or groups of atoms, with a covalent bond with a partner solved and subsequently one is made with another partner. The redox reaction is characterized by the electron donation of one partner (Reducing agent) and the electron absorption of the other partner (Oxidatiansmittel). In the case of complex formation reactions, a central atom or ion of several other atoms, ions or molecules, the so-called ligands, in spatial regular arrangement surround.

With these synthetic processes become comparatively demanding or complex requirements to the reaction conditions and to the reactants and.

As Reaction conditions in particular have a sufficiently high reaction temperature, a Release of reactive starting materials or activated molecular species in for the reaction of a sufficient number and / or a sufficiently high particle mobility the reaction partner has a special meaning. This can result in these reaction conditions be carried out by laser light that is spatially resolved thermal energy is introduced, which is the activation energy of the process. Due to the thermal energy mobility the starting materials in or on the carrier body improved and thus the The likelihood of reaction increases so much that a sufficient one Reaction turnover is reached. Irradiation also enables Laser light that reaction-inhibiting environments are broken up and thus making the starting materials available as reactants in the first place become.

Without the supply of energy, the starting materials held in the carrier body in order to generate durable information should not be able to induce a change in properties or substance. 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 complete reaction conversion to reach. Another A 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. Therefore, in principle, material mixtures or compounds of all elements of the periodic table which are capable of such "robust" use are considered as starting materials held in the carrier body. These criteria are preferably met by selected inorganic substance mixtures, since these migrate comparatively little in the carrier body and reactions with a change in material or properties usually only at high temperatures of several hundred degrees Celsius, such as inside a Bunsen burner flame.

to Detection of the properties caused by laser radiation or change of substance the change of the starting materials is expedient their absorption properties with respect to the wavelengths in the Ultraviolet to infrared range. For one The starting materials are advantageously particularly simple detection 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 several selected as needed Colored information or information becomes the raw materials the synthesis reactions of different color changes are preferably chosen such that the product of the respective synthesis reaction of a base color a CMYK color scheme for Cyan, magenta, yellow and contrast or black is associated. So that can with a suitable combination, mono or mixed colors can be created.

Around graphically particularly diverse The starting materials are color patterns and variations in the carrier body of synthesis reactions of different color changes, preferably in each other delimited volume segments held in the carrier body.

to Generation of different colored information and information in a carrier body with a comparatively high depth of color, especially with regard to towards one opposite forgeries and manipulations, especially safe laser marking, is next to the outer color Design in this regard Carrier body too an interior color design is appropriate. Therefore, the different Starting materials assigned to color reactions preferably in each other delimited layers in the carrier body.

Around a premature reaction of the starting materials without excitation Preventing laser radiation is conveniently one of these reactions protective device or measure provided. For this For this reason, at least one of the starting materials is preferably encapsulated in the carrier body provided, the encapsulation is advantageously chosen such that it is broken up by the laser radiation and the concerned Releases starting material as a reactant. The encapsulation is preferred for this designed such that it absorbs the laser radiation itself. This is one in time and place targeted generation of information guaranteed.

to targeted focusing of laser radiation directly on at least a starting material, especially if this alone or not insufficient for the absorption of the laser radiation is suitable, or for reduction of the required laser energy is preferably laser radiation in the carrier body absorbent auxiliary substances or layers embedded. As an absorbent Auxiliaries include, for example, a mica pigment that is under the designation "Iriodin" or "Mica" is commercially available, et al into consideration. As a result, that which is radiated onto the excipient Laser light over Interference or mirror effects are transferred to the selected raw material. this leads to at this point to a local temperature increase, a so-called hot spot or one is called Place, and thus to stimulate at least one starting material with usual se at least one other starting material so that they interact kick and enter 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, at higher concentrations, blackening due to finely divided platinum could be generated.

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 are to be labeled Commercial lasers with emissions from the 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 are particularly advantageous in the process as Basic components of the carrier body preferably materials that do not absorb laser radiation, such as paper, plastic films and / or a paint, adhesive and / or lacquer layer provided, the advantageously for tamper-proof Marking or for machine verification and simultaneous Validation of the documents, labeled or marked.

In particularly advantageous embodiment of the method held in and / or on the carrier body Starting materials preferably as an additional additive in film production processes, such as calendering, extrusion or film casting, or in papermaking introduced into the paper pulp and / or advantageously by coating processes, like painting, spraying, spraying, Coating, dipping, and / or by printing processes such as offset, steel engraving, Screen printing, flexographic printing, screen printing, indirect printing, thermal transfer printing, Electrophotography and ink-jet processes brought in and / or on the carrier body.

Regarding the Carrier body is solved the stated task, by placing a number of starting materials in and / or on it it is held that the reaction conditions for a synthesis reaction are laser-induced the source materials are adjustable.

As Basic components of the carrier body are preferably substances not absorbing the laser radiation, such as Paper, foils, in particular thermoplastics, and / or a layer of paint, adhesive and / or lacquer is provided.

to Detection of the properties caused by laser radiation or change of substance the change of the starting materials is expedient their absorption properties with respect to the wavelengths from Ultraviolet range over the visible range up to the infrared range. For a special one The starting materials are advantageously simple detection chosen so that they are going to a synthesis reaction changing their for human Color visible to the eye. For synthesis reactions under Color reactions are advantageously inorganic as starting materials Mixtures of substances used. These can be used in particular via redox or complex formation reactions generate intense colored information, which are particularly resistant to light and moisture etc. are and therefore also for the identification of value and / or security documents with a particularly high level of security against forgery are suitable. The colored information is in particular Word and picture symbols, such as inscriptions, logos or barcodes.

For one or several selected as needed single or multi-colored information, the starting materials in the carrier body are preferred chosen so that the product of the respective synthesis reaction is a base color a CMYK color scheme for Cyan, magenta, yellow and contrast or black is associated.

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 assignment to the color blue (“cyan”). Alternatively or cumulatively, for a product with the assignment to the color red (“magenta”) are preferably provided as starting materials Fe ₂ (SO ₄ ) ₃ and KSCN. 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, starting materials are preferably Cu ²⁺ and NH ₃ for the reaction to the tetraammine copper complex or the substances Co (NO ₃ ) ₂ and Al ₂ O ₃ and / or for a product associated with the color green as starting materials, preferably Co (NO ₃ ) ₂ and ZnO or the substances K ₂ CrO ₄ and C ₃ H ₇ OH.

Around graphically particularly diverse The starting materials are to enable color patterns and variations in the carrier body of synthesis reactions of different color changes, preferably in each other delimited volume segments held 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 that is particularly secure against counterfeiting and manipulation, in addition to the outer color design of the relevant carrier body, an inner color design is also expedient. The starting materials assigned to different color reactions are therefore preferably in layers which are delimited from one another held in the carrier body.

Around the laser radiation directly onto at least one starting material, in particular, if this alone is insufficient or insufficient for the absorption of the laser radiation is suitable to focus without the carrier body with too high laser energy to destroy, are preferred in the carrier body auxiliary substances or layers absorbing the laser radiation are embedded.

In particularly advantageous embodiment of the carrier body is in it for the assignment to contrast or black alternatively or cumulatively to the colors Blue ("cyan"), red ("magenta") and / or yellow ("yellow") as auxiliary substances, which the irradiated laser radiation via interference or mirror effects to a selected one Starting material transferred, preferably a mica pigment, such as "Iriodin", but also simply Titanium dioxide or carbon in the form of soot or advantageously also a color pigment such as phthalocyanine.

Around the carrier body in time and locally reliable and to be able to use it flexibly, are they in it for a synthesis reaction provided starting materials preferably at least partially encapsulated by an encapsulation that up to this reaction Inhibits excitation by laser radiation. In a particularly advantageous way The encapsulation is chosen in such a way that it is caused by the laser radiation is broken up and the starting material concerned only with the Release as a reactant releases. The encapsulation is preferred for this designed such that it absorbs the laser radiation itself.

For a belittling the activation energy, especially for redox reactions in the carrier body Starting materials, and in favor of the use of a comparative Low power lasers are preferred in the carrier body embedded catalytic particles.

use the carrier body equipped in this way can expediently be found in all areas, in the area of value and / or security documents, in the logistics area or ticketing and for Presentations. Therefore, the carrier body is preferred as ID, driving license, Credit or health card, ticket or foil used.

The Advantages achieved with the invention are in particular that constant information comes from the synthesis reaction of a number of starting materials be generated. In particular, there are typical ones known from the literature and sensitive detection reactions for subgroup metals to the Creation of particularly intense and more colored colors that are more resistant to environmental influences Use information. Especially by irradiating at least one Reactants with laser light enable reliable process control. The laser radiation ensures doing that just one for the desired Synthesis reaction sufficiently high reaction temperature is provided and / or that the irradiated substances move sufficiently strongly and / or to induce the release of reactive molecular species.

Of Furthermore, the carrier body allows through its in particular suitable equipment with encapsulations of particularly reactive starting materials, with auxiliaries or layers absorbing the laser radiation and / or a specifically controlled one with catalytically active particles Process management. So is in the carrier body, though the starting materials of a synthesis reaction at room temperature or are reactive with one another by rubbing, at least one of the Encapsulated starting materials in the carrier body reserved so that the synthesis reaction only by laser-induced Enables the encapsulation to be broken becomes. While a starting material that does not absorb laser radiation, or absorbs it only slightly indirectly via embedded in the carrier body the auxiliary substances or layers absorbing the laser radiation the laser radiation is activated by the laser radiation via interference or mirror effects of the auxiliaries or layers on the selected starting material focus and there is a hot spot due to the local temperature increase arises on which the starting material interacts with at least another starting material or brought to the monomolecular reaction becomes. Embedded in the carrier body Catalytic particles set the activation energy of the raw materials down.

Further allows the carrier body through the embedding of the starting materials of different synthetic reactions color changes in separate volume segments and / or layers a high degree of flexibility at desired graphic designs in the form of various color variations and Color patterns. The process for laser-induced in-situ generation of information in the carrier body thus enables a use for marking or labeling papers, foils and other plastic documents, in particular increases the security against forgery of a document marked in this way and can also be used for machine verification and simultaneous cancellation of documents, such as. of tickets. Thus the procedure in all areas of everyday Find life application where it is quick and localized Application and / or introduction of permanent word and / or picture symbols et al goes.

On embodiment the invention will be described in more detail below explained.

in the The following are various starting materials, their incorporation in and / or on a support body as well their laser initialization, which has a wavelength-specific effect over the UV-VIS-IR range allows described.

ever after application can the for a desired one Selected synthesis reaction Starting materials are precisely localized by means of various application or application processes matrix or layer-like in an inner and / or outer area one functioning as a carrier body disk to be brought. As the basis of the carrier body Basic components or composite materials are, for example, paper or plastic films, as well as between and / or applied to them Color, adhesive or lacquer layers are used. In a preferred one embodiment are the starting materials in film production as an additional Introduced additive. This applies in particular to the common film production processes, such as calendering, extruding and film casting. When making paper can also be used for selected the synthesis reaction Starting materials also as additional Work additive into the paper pulp. Incorporation in foils and papers has the advantage that when producing documents, such as cards and ID cards, in the production process itself no major intervention required are. Through various coating processes, such as painting, Spraying, spraying, coating, Diving, and / or by printing processes such as offset, steel engraving, Screen printing, flexographic printing, screen printing, indirect printing, thermal transfer printing, Electrophotography and ink-jet processes can be used for a desired synthesis reaction chosen Bring starting materials in and / or on the carrier body.

In a preferred embodiment is a screen printing varnish filled with the raw materials onto a opaque plastic film printed and overlaminated with several layers of plastic film. This procedure represents a particularly flexible embodiment because it creates internal prints when manufacturing composite materials, such as cards, ID cards made of all-plastic or paper-plastic compounds, are easy to do.

Of course in addition to those in the exemplary embodiment the complex formation and redox reactions mentioned below in the carrier body Other synthetic reactions are also conceivable, e.g. Eliminations in which part of the molecule is split off, with what also change its physical properties, or additions, at the new covalent bonds are formed and thus generate a "new" substance, or substitution reactions in which e.g. Ligands of a complex be replaced.

Example 1: Blue laser marking

A stoichiometric mixture of the inorganic starting materials from cobalt (II) nitrate with aluminum sulfate and a binder is printed on a plastic card using screen printing, for example. 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 are called the reaction to the cobalt spinel CoAl ₂ O ₃ , 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 focus 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 blue color impression.

The reaction to Thenards blue can be described with the following equation: Co (NO ₃ ) ₂ + Al ₂ O ₃ → CoAl ₂ O ₃ + 2 NO ₂ + ½ O ₂

In 1 is schematically one in a matrix 1 embedded pigment 2 , "Iriodin", shown that in its mica core 4 the incident laser light 6 absorbed and it as in 1 by lightning 8th is symbolized via interference effects to those at its interface 10 in the matrix 1 found inorganic starting materials Co (NO ₃ ) ₂ and Al ₂ O ₃ transferred. This creates at the interface 10 of the pigment 2 a hot spot 12 , 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 from 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 combined with other components to form a plastic card which is only covered with an NIR-permeable overlay film. When irradiated with a Nd : YAG laser occurs on the generated hot spot or the hot spot is the reaction to the zinc cobalt spinel ZnCo ₂ O ₄ , known in the literature as Rinmanns green. In the expanded formulation, the "iriodin" in turn serves as an auxiliary substance that absorbs the 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 is the green one Minimize or cover color impression.

The reaction to Rinmanns-Grün can be described with the following equation: 2 Co (NO ₃ ) ₂ + ZnO → ZnCo ₂ O ₄ + 4 NO ₂ + ½ O ₂

Example 3: Blue ("Cyane") laser marking

A stoichiometric Mixture of inorganic raw materials from pink manganese (II) sulfate with 2 potassium nitrate and 2 potassium hydroxide is in the embodiment added as an additive to an adhesive during hotmelt film production. Optionally includes the mixture still contains "iriodin" (<0.5 percent by weight). This film is in the embodiment subsequently assembled with other components to form a plastic card that only with a NIR-permeable overlay film is covered. When irradiated with a Nd: YAG laser occurs on the thereby generated hot spot or the hot spot which also acts as an oxidation melt known reaction to green-blue ("Cyan") Manganat. The "Iriodin" serves in the extended formulation in turn as the laser radiation absorbing Auxiliary to direct the laser radiation towards the raw materials focus and / or the laser energy required for the reaction to minimize. Excessive laser radiation usually leads to carbonization, which the green-blue ("Cyan") Minimize or cover the color impression can.

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 4a) Yellow laser inscription and b) Greens Laser Marking

• a) A stoichiometric mixture of the inorganic starting materials made of green chromium (III) oxide with 3 potassium nitrate and 2 potassium hydroxide is introduced into a matrix analogously to one of Examples 1 to 3. The use of "Iriodin" can be dispensed with in this exemplary embodiment, since Cr ³⁺ absorbs very well in the red spectral range. This results in the irradiation with a powerful dye or semiconductor laser with red emission (630 - 690 nm) generated hot spot or the hot spot the reaction to the yellow-orange ("yellow") dichromate (Cr ⁶⁺ ) also known as chromium oxidation melt. 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) As a color reaction from yellow to green, the reaction from yellow potassium chromate (Cr ⁶⁺ ) with propanol, which is present in many pressure additives at least in traces, to green chromium (III) oxide is also known as the "classic alcohol test" in the test tube 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 has to be minimized, for example by lamination, in order to rule out health risks which may arise from the toxic chromates.

In 2 is schematically one in a matrix 1 embedded pigment 2 , yellow chromate (Cr ⁶⁺ ), shown with the matrix 1 as a reducing agent 14 Contains traces of an alcohol (R-OH). The Lightning 8th symbolizes one by the irradiated laser light 6 induced hot spot 12 or a hot spot at the interface 10 of the pigment 2 (Cr ⁶⁺ ) to the 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 marking

• a) Iron in the oxidation state +3, for example iron (III) sulfate, forms a deep red ("magenta"), characteristic complex with thiocyanates even in the non-aqueous medium according to the equation: Fe ₂ (SO ₄ ) ₃ + 6 KSCN (+ 6 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 triturated with one another, so that the iron (III) sulfate is encapsulated and introduced into the matrix and only the laser radiation breaks up the encapsulation in order to stimulate the reaction with a change in color.
• b) Iron (II) sulfate does not require encapsulation. It becomes iron with potassium nitrate and potassium thiocyanate and water due to the laser effect oxidation level +3 oxidizes, 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 the oxidation state +2 shows with oxidation with saltpetre Oxidation level +3 after laser radiation in a blue fluorescent Environment a local limited red fluorescence.

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 each be combined with one another in different, delimited layers 16a-d , each of which represents a carrier body with a correspondingly reactive matrix, as in 3 shown. In the exemplary embodiment, a film composite structure with four differently doped layers 16a-d provided the bottom layer 16a with MnSO ₄ , KNO ₃ and KOH (Example 3), the second lowest layer 16b with Fe ₂ (SO ₄ ) ₃ and KSCN (Example 5), the third layer 16c from below with Cr ₂ O ₃ , KNO ₃ and KOH (example 4) and the top layer 16d is doped with "Iriodin". The respective synthesis reaction is initiated by irradiation with an Nd: YAG laser. For this purpose, the laser is applied to selected volume segments, for example by means of confocal optics 18a-d within each layer 16a-d (z coordinate) focused at certain positions (xy coordinates). Resolutions of approximately 10 μm in the xy direction and approximately 30 μm in the z direction are achieved. Due to the comparatively low focus sharpness in the z direction, every layer 16a-d individually scanned to match the selected volume segments 18a-d carry out the synthesis reaction. In the exemplary embodiment, the bottom layer 16a by converting MnSO ₄ with KNO ₃ and KOH, a color change to blue ("cyan") is achieved (example 3). In the second step, the laser is then applied to the second bottom layer 16b adjusted and focused on the desired xy positions within it. As a result of the irradiation by reaction of Fe ₂ (SO ₄ ) ₃ with KSCN, a color change to red (“magenta”) is produced (example 5). The same applies in the third layer 16c from below the reaction of Cr ₂ O ₃ , KNO ₃ and KOH in the selected volume segments 18c induced and thus the color change to yellow ("Yellow") achieved (Example 4). Finally, in the exemplary embodiment in the top layer doped with "Iriodin" 16d the locally resolved radiation. It is in the selected volume segments 18d Due to the local overheating, a gray to black color change is created, which represents the contrast. After the laser-induced labeling process, the film composite structure is perpendicular to the layers 16a-d considered, results from the overlaying of the individual colored volume segments 18a-d a full-color CMYK image through subtractive color mixing. The above-mentioned spatial resolutions enable images with a resolution of more than 600 dpi, which corresponds to the standard resolution of modern color printers.

1

matrix

2

pigment

4

mica core

6

irradiated laser light

8th

lightning

10

interface

12

hot-spot

14

reducing agent

16a-d

layer

18a-d

volume segments

Claims (31)

Method for generating information in and / or on a support body, at that for a number of starting materials held in and / or on the carrier body in a localized sub-area of the carrier body by laser radiation Reaction conditions are set, which are the starting materials induce a synthesis reaction. A method according to claim 1, in which as a synthesis reaction an addition, an elimination, a substitution, a redox reaction or a complex formation reaction is used. A method according to claim 1 or 2, in which as starting materials inorganic synthesis mixtures are used in the synthesis reaction. Method according to one of the preceding claims, which the starting materials are chosen so that they become a Synthesis reaction with color change be initiated. Method according to one of the preceding claims, in which the starting materials are selected in such a way that the product of the respective synthesis reaction is in each case a basic color CMYK color schemes is assigned. Method according to one of the preceding claims, in which starting materials from synthesis reactions of different property changes, in particular color changes, in mutually delimited volume segments ( 18a-d ) are held in the carrier body. Method according to one of the preceding claims, in which starting materials from synthesis reactions of different property changes, in particular color changes, in mutually delimited layers ( 16a-d ) are held in the carrier body. Method according to one of the preceding claims, which is held encapsulated at least one of the starting materials, wherein the encapsulation is chosen such that it is characterized by the Laser radiation is broken up. The method of claim 8, wherein the encapsulation so chosen is that it absorbs the laser radiation. Method according to one of the preceding claims, the in the carrier body Auxiliary materials or layers absorbing laser radiation are embedded are. Method according to one of the preceding claims, that in the carrier body for the synthesis reaction particles having a catalytic action are embedded. Method according to one of the preceding claims, that for laser irradiation is a laser with emissions from the UV to IR range is used. Method according to one of the preceding claims, an Nd: YAG laser with an emission wavelength of 1064 for laser irradiation nm is used. Method according to one of the preceding claims, which as the basic components of the carrier body Laser radiation non-absorbent materials such as paper, plastic films and / or a layer of paint, adhesive and / or lacquer are provided, the forgery-proof Marking or for machine verification and simultaneous Revaluation of documents, labeled or marked. Method according to one of the preceding claims, the one held in and / or on the carrier body Starting materials in the film or Paper making as an additional Additive introduced and / or by coating processes such as painting, Spraying, spraying, Coating, dipping, and / or by printing processes such as offset, steel engraving, Screen printing, flexographic printing, screen printing, indirect printing, thermal transfer printing, Electrophotography and ink-jet processes brought in and / or on the carrier body become. Carrier body, in particular for the Method according to one of the claims 1 to 15, in and / or on which a number of starting materials such it is held that the reaction conditions for a synthesis reaction are laser-induced the source materials are adjustable. Carrier body after Claim 16, in which laser radiation is the basic component of the carrier body non-absorbent materials such as paper, plastic films and / or a layer of paint, adhesive and / or lacquer are provided. Carrier body after Claim 16 or 17, in which as starting materials of the synthesis reaction inorganic mixtures are used. Carrier body after one of the claims 16 to 18, in which the starting materials are chosen such that the product the respective synthesis reaction of a basic color of a CMYK color scheme assigned. 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”). Carrier body according to Claim 19 or 20, in which Fe ₂ (SO ₄ ) ₃ and KSCN are provided as starting materials for a product with the assignment to the color red (“magenta”). Carrier body according to one of claims 19 to 21, in which Cr ₂ O ₃ , KNO ₃ and KOH are provided as starting materials for a product with the assignment to the color yellow. Carrier body according to one of claims 19 to 22, in which for a product with 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 ₄ and C ₃ H ₇ OH are available. Carrier body according to one of claims 16 to 23, in which starting materials from synthesis reactions of different property changes, in particular color changes, in mutually delimited volume segments ( 18a-d ) Support bodies are available. Carrier body according to one of claims 16 to 24, in which starting materials from synthesis reactions of different property changes, in particular color changes, in mutually delimited layers ( 16a-d ) are held in the carrier body. Carrier body after one of the claims 16 to 25, in which the laser radiation absorbing excipients or layers are embedded. Carrier body after Claim 26, in which for Assignment to contrast or black as a laser radiation absorbent auxiliary a mica or color pigment is available. Carrier body after one of the claims 16 to 27, in which at least one of the starting materials of a synthesis reaction is provided encapsulated, the encapsulation being selected in such a way that it is broken up by laser radiation. Carrier body after Claim 28, in which the encapsulation is selected such that it is the laser radiation absorbed. Carrier body after one of the claims 16 to 29 in which for the synthesis reaction catalytically active particles are embedded. Use of a carrier body according to one of claims 16 to 30 as a value and / or security document, such as ID, driver’s license, Credit or health card, or as a ticket or foil, etc.