WO2011151117A1

WO2011151117A1 - Method for labelling a substrate

Info

Publication number: WO2011151117A1
Application number: PCT/EP2011/056897
Authority: WO
Inventors: Bernd Grünler; Arnd Schimanski; Andreas Pfuch; Kerstin Horn; Oliver Beier
Original assignee: Innovent E.V.
Priority date: 2010-06-04
Filing date: 2011-05-02
Publication date: 2011-12-08
Also published as: DE102010022701B4; DE102010022701A1; EP2576230A1; US20130074449A1

Abstract

The invention relates to a method for labelling a substrate, in which method at least one luminescent dye is deposited as a first identification feature in at least one transparent marker layer or in at least one functional layer on a surface of the substrate or on a layer which is situated on the surface, wherein the transparent marker layer or the functional layer is provided with a structure in a further step for producing a second identification feature by local destruction, in particular thermally. According to the invention, the deposition of the at least one marker layer or functional layer takes place by means of chemical gas-phase deposition using a flame or a plasma, by means of a sol-gel method or electrochemically.

Description

Method for identifying a substrate

The invention relates to a method for identifying a substrate according to the features of the preamble of claim 1.

Product piracy is a problem that causes significant economic damage to manufacturers of original products, especially for high quality products (cosmetics, medicines, watches, lenses, car windows, etc.).

Especially with counterfeit drugs, the consumer is seriously affected because counterfeit drugs can be ineffective at best and in the worst case dangerous or even life-threatening. For such product groups there is therefore a need for an effective

Counterfeit protection.

The labeling of product packaging, such as container glass or plastic packaging, by means of laser marking has long been known. This type of marking is easily verifiable by eye, but also relatively easy to fake.

Furthermore, the admixture of fluorescent dyes in polymers for the production of device housings and components is known. With these dyes, it is possible to set a defined color point or color value, which can be read by means of a detector. With different colors thereby different production times are coded.

From WO 02/26507 AI a method and an apparatus for

Personalization of luminescent authenticity features on data carriers of any kind, in particular plastic cards known. In a first

Process step becomes a luminescent authenticity feature in the

Card composite introduced or applied to the card composite. In one second method step, the authenticity feature is personalized with a high-energy beam (eg a laser beam). Here, the intensity and / or wavelength of the beam is selected so that a local bleaching of the structure of the authenticity feature takes place. As a result, the structure of the authenticity feature is locally changed so that when luminescent illumination of the authenticity feature inscribed by personalization lettering is recognizable as a negative image.

DE 10 2006 038 270 A1 describes a security and / or value document with a pattern of radiation-modified components. The security and / or value document comprises a substrate and a printing layer arranged on the substrate. First parts of the document have a non-radiation-modified component or a low-radiation-modified component. Second parts of the document contain a radiation-modified component or more radiation-modified

Component, wherein the radiation-modified component differs from the non-radiation-modified component exclusively by radiation-induced structural differences. The first subregions are indistinguishable from the second subregions with the human eye. However, the first partial regions can be distinguished from the second partial regions by means of apparatus for measuring.

From DE 10 2005 025 095 Al a data carrier and a method for its production are known. The data carrier, in particular a value document or security paper, comprises a substrate and a coating applied to the substrate into which markings in the form of patterns, letters, numbers or images are introduced by the action of laser radiation. The coating contains a layer absorbing the laser radiation and a printing layer arranged above the absorbing layer and at least partially transparent to the laser radiation. The printed substrate is pressed during or after the printing of the at least partially permeable layer. The invention has for its object to provide a method for identifying a substrate, with which an improved protection against plagiarism is achieved.

The object is achieved by a method having the features of claim 1.

Advantageous embodiments of the invention are the subject of the dependent claims.

In a method for identifying a substrate, at least one luminescent dye is deposited in at least one transparent marker layer or in at least one functional layer on a surface of the substrate or on an on-surface layer as a first identification feature. The transparent marker layer or the functional layer is provided with a structure in a further step for generating a second identification feature by local destruction of the dye, in particular thermally.

According to the invention, the deposition of the at least one marker layer or functional layer takes place by means of chemical vapor deposition

Use of a flame or a plasma, by a sol-gel method or electrochemically. A process of deposition by means of chemical

Gas phase deposition using a flame or a plasma is commonly referred to as PACVD (plasma activated chemical vapor deposition). Such processes run both in low pressure and under

Normal pressure conditions.

The first identifier may encode desired information about the selected luminescent dye. Luminescent dyes emit light as a result of external excitation, for example by irradiation with light of the visible spectrum or in the ultraviolet range in the case of photoluminescence. Photoluminescent dyes are in particular phosphorescent and / or fluorescent. Both fluorescence and phosphorescence are Forms of luminescence (cold glow). Fluorescence ends relatively quickly after the end of irradiation (usually within one millionth of a second). In the case of phosphorescence, however, afterglow can occur over fractions of a second up to hours.

To generate a second identification feature of the luminescent dye is destroyed locally. In this case, for example, one or more alphanumeric characters, symbols or logos or one- or two-dimensional barcodes are introduced into the dye-containing layer. The combination of both features results in a particularly high security against counterfeiting.

Special luminescent dyes are not visible in the absence of UV radiation or at low intensities and accordingly do not affect the appearance of the product. Nor is the second identification feature in the luminescent layer recognizable under such conditions. Only upon excitation of the luminescent layer, for example by irradiation with ultraviolet light, for example from a scanner, both identification features are visible. The scanner is then preferably designed so that it can not only make the identification features visible, but also recognize them.

Alternatively to a luminescent dye, a thermochromic and / or electrochromic and / or photochromic and / or gasochromic switching dye can be deposited. Switching dyes change their color depending on a temperature (thermochromic), an electric field or a current flow (electrochromic), an excitation with light, in particular light of certain wavelengths (photochromic) or in the presence of a certain gas (gasochromic).

Similarly, loaded with the dye Nanozeolithe can be deposited. Nanozeolites are nanoscale particles of a species-rich family of chemically complex silicate minerals, the zeolites. These minerals can be up to about Save 40 percent of its dry weight of water, which is given off when heated again. In damp air, the water can be absorbed without affecting the structure of the mineral. Zeolites are formed from a microporous framework structure of AIO ₄ and SiCV tetrahedra. The aluminum and silicon atoms are interconnected by oxygen atoms. This results in a structure of uniform pores and / or channels in which substances can be adsorbed. Zeolites can therefore be used as sieves, since only those molecules which have a smaller kinetic diameter than the pore openings of the zeolite structure adsorb in the pores. In the present case, the dyes are embedded in the pores of the nanozeolites.

In particular, organic fluorescent dyes are suitable, since they are temperature-sensitive and can easily be destroyed thermally.

The deposition by chemical vapor deposition using a flame or a plasma is preferably such that from a

Working gas, a plasma jet or a flame is generated, wherein at least one precursor material is supplied to the working gas and / or the plasma jet or the working gas and / or the flame and reacted in the plasma jet or the flame. At least one reaction product of at least one of the precursors is deposited on the substrate as a marker layer or functional layer. The dye is either dissolved or dispersed in a liquid medium or contained in the nanozeolites. The dissolved or dispersed dye or nano zeolites with the dye are added separately or together with the working gas or the plasma jet or the flame

Precursor supplied.

In the case of dispersion, organic dyes are preferably used, in particular chemically more stable organic dyes. The dispersed dye is preferably by means of a peristaltic pump in the

Working gas, the flame or the plasma jet metered. In the sol-gel coating, a precursor is dissolved in a solvent and admixed with a catalyst, for example an acid. This sol is applied to the surface to be coated and dried, so that the crosslinking begins. The resulting network is called a gel. After drying, a temperature of the layer can be carried out, wherein the layer is completely crosslinked. A temperature for temperature control of the layer is preferably selected as a function of the decomposition temperature of the dye, ie lower than the decomposition temperature, so as not to destroy the dye during the temperature control. For example, the temperature of the layer at a temperature of at least 300 ° C. The layer thus produced is mechanically stable.

The deposition of at least one further marker layer or functional layer is preferably carried out by means of chemical vapor deposition using a flame or a plasma, by means of a sol-gel method or electrochemically.

The sol-gel coating may be followed by a previous chemical vapor deposition from the flame or the plasma.

Particularly preferably, the deposition is carried out by means of chemical vapor deposition using a flame or a plasma at atmospheric pressure, in particular as a normal pressure plasma process. By working at atmospheric pressure, a time-consuming process step of evacuating a process chamber as well as apparatuses for vacuum generation, such as vacuum pumps and process chamber are saved in a particularly advantageous manner. As a result, the method can be integrated into a process chain without great effort, which involves production and compensation of the substrate. The local destruction takes place by thermal entry into the layer containing the luminescent dye. The heat input raises the temperature in a locally limited area above the decomposition temperature of the luminescent dye and destroys the luminescence property locally. Ie. by the localized energy input, in particular the

Heat input, a decomposition energy for decomposition of the luminescent dye is reached or exceeded, whereby the luminescence property is locally destroyed.

The local destruction preferably takes place by means of a laser. This simplifies the labeling, since the laser is usually used anyway for labeling or engraving. With the laser a pinpoint thermal destruction of the dyes is possible. The laser can be focused so that the dye in the marker layer or functional layer can be destroyed even if there are one or more other layers over it which were later deposited without damaging these further layers. If necessary, the laser can be tuned to an absorption wavelength of the respective dye.

Likewise, the local destruction can be done by means of a flame or a plasma. Particularly suitable for this purpose are atmospheric-pressure plasma jets which can be positioned at high spatial resolution.

Similarly, the local destruction can be done by means of a plasma micro-stamp. For this plasma sources are used, in which so-called cold discharges ignite in cavities that are temporarily formed between a printing plate (stamp or roller) and the surface of the coated substrate. These treat the surface locally. These discharges are dielectric barrier and high frequency discharges.

As the luminescent dye, a fluorescent dye, in particular, an organic fluorescent dye, is preferably used because it can be easily destroyed by heating. Preferably, such a fluorescent dye is used which emits light only when excited with an aid such as UV light and otherwise invisible.

In a preferred embodiment, a transparent or translucent substrate, in particular an optical glass, for example a lens, in particular a spectacle lens, is characterized at a locally limited location of the substrate with the first and second identification feature.

In a further preferred embodiment, a transparent or translucent substrate, such as a watch glass or a car window, at a localized location of the substrate with the first and second

Identification feature marked.

In a particularly preferred embodiment, a transparent or translucent substrate, in particular a container with the first and second identification feature is characterized. The substrate may for example consist of glass or a transparent plastic.

In this case, the deposition of the marker layer or the functional layer can take place at the end of a process for producing the container, for example with a manufacturer of the container. The local destruction can then take place in a process for filling the container, not necessarily at the manufacturer of the container, but at the manufacturer of a product that is filled into the container.

The first identifier is used, for example, by selecting the luminescent dye to code a production lot or a production date of the container. Different colors of the luminescent dye can, for example, code different production batches. By means of the second identification feature can then a Product batch or a filling date of a product filled in the container. This allows a follow-up of the production chain.

The marking of the container with the identification features can

for example, on the ground or on the vessel walls.

Embodiments of the invention will be explained in more detail below.

Using an atmospheric pressure plasma, a silicon dioxide layer was applied as a marker layer to a glass substrate. As a result of this PACVD process (plasma activated chemical vapor deposition), a layer with a thickness of approximately 200 nm was achieved. By adding a fog containing a fluorescent dye into the plasma jet, particles of this dye were incorporated into the matrix of the marker layer.

The silicon dioxide coating by means of atmospheric pressure plasma was carried out using an organosilicon precursor, for example

Hexamethyldisiloxane (HMDSO). The plasma torch was operated at a power of 350W. The substrate was moved at a distance of 10 mm from the burner at a travel speed of 100 mm / s to 200 mm s. The plasma torch was meandered over the substrate, the

Grid spacing was 3 mm. The fluorescent dye selected was Blue-Violet LC-Fluorescent Dye 1 from Synthon Chemicals GmbH & Co. KG.

The thus-coated substrate was irradiated with a laser, whereby the laser was rastered over the surface of the substrate. As a result, the fluorescence effect of the layer was destroyed locally in the area scanned by the laser. In this case, a C0 ₂ laser of wavelength 10.6 μιη with a

Focal length of 200 mm, a focus diameter of 300 μιη and a power of 18.5 W used. Another dye, in particular a luminescent dye and / or a thermochromic and / or electrochromic and / or photochromic and / or gasochromic switching dye, can be deposited as the first identification feature in the marker layer or in a functional layer.

The second identification feature can be destroyed by other means, in particular thermally. For example, a flame or a plasma, in particular a plasma microstamp, can be used for this purpose.

Similarly, loaded with the dye Nanozeolithe be deposited in the marker layer or functional layer.

The deposition can be carried out alternatively to the atmospheric pressure plasma process by other methods, for example by chemical vapor deposition using a flame, by a sol-gel method or by electrochemical deposition.

Claims

PATENT APPLICATIONS

A method for identifying a substrate, wherein at least one luminescent dye in at least one transparent marker layer or in at least one functional layer on a surface of the

Substrate or deposited on a surface located on the surface layer as a first identification feature, wherein the transparent marker layer or the functional layer is provided in a further step for generating a second identification feature by local destruction, in particular thermally, with a structure

characterized in that the deposition of the at least one marker layer or functional layer by means of chemical vapor deposition using a flame or a plasma, by means of a sol-gel method or electrochemically.

2. The method according to claim 1, characterized in that the deposition of at least one further marker layer or functional layer by means of chemical vapor deposition using a flame or a plasma, by means of a sol-gel process or electrochemically.

3. The method according to claim 1 or 2, characterized in that the

Deposition by means of chemical vapor deposition using a flame or a plasma under atmospheric pressure.

4. The method according to any one of the preceding claims, characterized

characterized in that the local destruction by means of a laser, a flame or a plasma takes place, wherein the heat input, the temperature in a local area over the Decomposition temperature of the luminescent dye is raised and the luminescence property is destroyed locally limited.

5. The method according to claim 4, characterized in that the local

Destruction by means of a plasma micro-stamp done.

6. The method according to any one of the preceding claims, characterized in that a fluorescent dye is used as the luminescent dye.

7. The method according to any one of the preceding claims, characterized in that a transparent or translucent substrate, in particular a container is characterized.

8. The method according to claim 7, characterized in that the deposition of the marker layer or the functional layer takes place at the end of a process for producing the container and that the local destruction takes place in a process for filling the container.

9. The method according to claim 8, characterized in that the first

Identification feature is used by selecting the luminescent dye for coding a production batch or a production date of the container, and that by means of the second identification feature a product batch or a filling date of a product filled in the container is encoded.