DE102013011403A1 - Glass bottle with counterfeit protection - Google Patents

Abstract

The present invention relates to a glass bottle which is closed with a closure, wherein on and / or on the closure a seal made of thermosetting polymer is attached, which is preferably in contact with the glass bottle, wherein the seal non-destructive of the closure and / or the Glass is removable and the seal comprises means for detecting the originality of the glass bottle, means for recording the entry of thermal energy and / or means for detecting the exceeding of a defined temperature.

Description

The present invention relates to a glass bottle which is closed with a closure.

Fine wines are traded at enormously high prices. For the buyer of a fine wine there are high risks that he might buy a fake bottle or store an original bottle under conditions that have damaged the wine. Such noble wines are often regarded as an investment. Ultimately, the buyer has little other way to check the quality of the bottle than to open it. This completes the purchase. An examination before the purchase can not be made.

Various methods are known from the prior art, which provide a tamper evidence of the bottle or the label, but still allow forgery possibilities, for example, by refilling the original bottle with a fake wine, or the sale of thermally superimposed wine.

Anti-counterfeiting devices for wine bottles are for example out CN 202518596 . CN 202464386 . CN 202557987 . CN 202400409 . CN 102582945 . CN 202346084 and CN 2806357 known.

It is therefore an object of the present invention to provide a counterfeit protection for glass bottles, especially wine bottles, which overcomes the disadvantages of the prior art. In particular, a glass bottle is to be provided which prevents counterfeiting possibilities by refilling the original bottle, which characterizes and ensures the refill protection and thus the wine bottle by means of a tamper-evident marker and / or makes a thermal overlay of the bottle contents detectable.

This object is achieved by a glass bottle which is closed with a closure, wherein on and / or on the closure, a seal made of thermosetting polymer is attached, which is preferably in contact with the glass bottle, wherein the seal non-destructive of the closure and / or the glass is removable and the seal comprises means for detecting the originality of the seal and thus the glass bottle and / or means for recording the entry of thermal energy and / or means for detecting the exceeding of a defined temperature. In a particularly preferred embodiment, the glass bottle is filled with contents, for example wine.

It is preferably provided that the closure is a cork.

It is further contemplated that the thermoset polymer is an acrylic polymer, preferably a modified acrylic polymer. Suitable thermoset polymers are for example commercially available under the brand name Permabond ^® UV681 or UV683 Permabond Engineering Additives Ltd. known.

In one embodiment, it is provided that the seal has at least one through hole. This through-hole is preferably formed already in the manufacture of the seal by providing a spacer made of polytetrafluoroethylene or the like, around which the liquid polymer is applied. After solidification of the polymer, the spacer can be removed and thereby the through hole can be formed.

In a further embodiment it is provided that the means for recognizing the originality with an armed eye visually visible particles, such as color code containing particles, natural structures, such as diatoms, and / or marking agents that require a detection device for detection, such as chemical markers, Stokes Pigments or anti-Stokes pigments.

According to the invention, it is preferably provided that the means for indicating the input of thermal energy comprises a porous material which contains a component releasable by thermal diffusion and triggering a color effect on release, and / or contains a material which decomposes by thermal energy and a in the material contained and releases a color effect triggering component.

It is particularly preferred that the material is microporous and / or inorganic or organic.

It is also preferred that the component itself or by reaction with a compound partner triggers a color effect.

Finally, it is preferably provided that the means for detecting the exceeding of a defined temperature contains an irreversibly thermochromic compound and / or a microencapsulated colorant.

According to the invention it has surprisingly been found that the proposed glass bottle has a security system that allows both the detection of counterfeiting and recognizing a thermal superimposition of the glass bottle contents, preferably wine.

It is essential that the seal is constructed of a thermosetting polymer material. This is applied to and / or on the closure, preferably a cork, and preferably also in contact with the glass of the bottle. The seal is connected to the closure material and / or the glass and can not be removed without destroying. Furthermore, it was surprisingly found that the sealing material can be added to various security and recording features that allow further protection against counterfeiting and verification of the thermal overlay of the glass bottle contents. These safety and recording features are a means for detecting the originality of the seal and the bottle, means for recording the input of thermal energy, and / or means for detecting the exceeding of a defined temperature of the glass bottle.

seal

The seal is made of a thermosetting polymer, which can be introduced in liquid form, for example in a recess between the closure (cork) and the bottle edge of the glass bottle and thereby firmly connects with the closure and in particular the glass. Alternatively or additionally, the seal may also include a sheet of thermosetting polymeric material which may be placed in the aforesaid recess between the closure and the rim of the bottle and which may then be connected to the closure and the glass via liquid thermosetting polymer to be added.

Preferably, the seal may include a through-hole to allow gas exchange of the glass bottle contents over the closure (cork). If an inserted plate made of thermosetting material is used, this could be provided with decorative elements, such as embossing or engraving.

Preferably, the seal may be raised, flush or recessed. Preferably, its intrinsic color may be colored or monochromatic, preferably white or colorless, more preferably colorless.

Thermosets, also called duromers, are plastics that can not be deformed after they have hardened. These are hard, glass-like polymer materials that are three-dimensionally firmly cross-linked by chemical valence bonds. It is particularly preferred that the thermoset only releases a very low heat energy when it is cured or requires no heat for curing, since this could possibly impair the function of the security and recording features contained therein. Also, the thermoset material should preferably be resistant to the conditions of storage of the glass bottle and have neither optical nor mechanical change over the storage period.

Particularly preferred as the sealing material, a thermosetting polymer is used, which is adjusted in its mechanical properties so that it shatters during removal or punctiform mechanical stress, such as when using a corkscrew into many small items, so that the closure can not be removed without destroying the seal.

As thermoset materials according to the invention preferably those materials can be used which cure under UV irradiation, such as modified acrylic polymers, which are known from the repair of car glass panes and in particular have an excellent connection to the glass and the required long-term stability.

Means of recognizing originality

The seal of the glass bottle according to the invention has a means of detecting the originality. In the context of the present invention, a means of recognizing originality is to be understood as meaning a means of checking whether the closure of the glass bottle is still an original closure. Such means of recognizing originality may include, for example, visibly-visible particles with the armed eye, such as particles containing a color code, such as those shown in FIG EP 1 003 146 A2 is described. Furthermore, it can be provided that this means contains labeling means which require a detection device for detection. Such markers may be, for example be chemical markers, as it is from the DE 102008060675 A1 is known, Stokes or anti-Stokes pigments or similar substances. All agents can be used alone or in combination.

Means for recording the input of thermal energy

The recording of the energy input into the contents of the glass bottle, for example a wine bottle, is also of particular importance. This energy input provides information about how much thermal energy was absorbed and possibly damaged the contents of the glass bottle. Such a means may in a first embodiment comprise a porous, preferably microporous or mesoporous, material in which is embedded a component which is releasable by thermal energy. This component can trigger a color effect directly or by reaction with another substance present in the sealing material.

In a second embodiment, this agent may comprise a material, inorganic or organic, which is decomposed by registered thermal energy and releases a component contained in this material. These embodiments may be used alone or in combination, with the first embodiment being preferred.

High demands are placed on the components used in these agents with regard to their long-term stability, so that preferably inorganic compounds are used or inorganic reactions are carried out.

An example of a means of recording the thermal energy input is the formation of "Berliner Blau", a reaction of ferric salts with potassium hexacyanidoferrate (II): ⁴ Fe ³⁺ + 3 [Fe ^{+ II} (CN) ₆ ] ^4- → Fe ^{+ III} [Fe ^{+ III} Fe ^{+ II} (CN) ₆ ] ₃

The iron compound may be present in a microporous polyester material, wherein the potassium hexacyanidoferrate (II) may be embedded in the sealing material. The iron slowly migrates out of the microporous polyester material by thermal processes and reacts with the potassium hexacyanidoferrate (II) to form a blue compound. The discoloration that occurs is proportional to the amount of iron diffused, which in turn is proportional to the thermal energy input. By appropriate calibration of the system in climatic chambers, a correlation with a real storage can be ensured.

The detection of the thermal energy input can be done by visual comparison with a reference scale or by measuring the discoloration with a suitable and appropriately calibrated photometer. Such a photometer could also be used, with a corresponding detector, to study the recognition of originality using appropriate means there.

Means for detecting the exceeding of a defined temperature

When storing wine bottles, it is known in the art that even the short-term exceeding a limit temperature, the z. B. at about 40 ° C, the wine is damaged. The detection of exceeding this temperature can be displayed according to the invention by a clear color change of the sealing material.

It may be provided that this color change is achieved either by the use of irreversible thermochromic compounds or microencapsulated colorant. Preference is given here microencapsulated colorants, since the Umschlagtemperatur can be set more accurately.

Microencapsulated colorants are dyes or pigments provided with a shell of a polymer or wax. The coating hides the color of the colorant. At the desired temperature, the encapsulant melts or decomposes so that the colorant becomes visible. Alternatively, a reactive colorant can be used in which a part of the colorant is incorporated in the base material of the seal and the other part is present in microencapsulated form. When the limit temperature is exceeded, the coating melts / decomposes and the two reactants form a colored compound.

Typical wrapping materials are paraffins and low molecular weight polymers, such as low molecular weight polyethylene (Fischer-Tropsch wax). Processes for the microencapsulation of substances are known to the person skilled in the art and are used industrially.

Further advantages and features of the invention will become apparent from the following detailed description of embodiments with reference to a figure showing the arrangement of a seal 1 on a glass bottle according to the invention 2 shows.

Example:

For the production of the seal the following recipe is used: Pemabond UV683 99.450% Anti-Stokes crystal based on Erbium doped Gadoliniukmoxisulfid 0.010% Microencapsulated red pigment (mp: 40 ° C) prepared according to A 0.240% Fe mod. Molecular sieve type A produced according to B 0.300% Kaliumhexacyanidoferrat (II) 0.05%

The permabond is placed in a container and the remaining substances dispersed with a Disolver with cooling. The temperature should not exceed 30 ° C.

To seal a corked wine bottle, add exactly 1.5 ml of the solution prepared above to the cork using a metering pump. Due to the surface tension of the solution, a lenticular drop forms. This is cured by means of UV light. The seal applied to the glass bottle is shown in the figure.

The exceeding of the maximum storage temperature can be easily recognized by the color change of the slightly honey-colored seal to red with the unaided eye.

The originality marker can be recognized by its visible fluorescence when excited with a laser at 980 nm. Alternatively, the decay behavior of the flourescene can be examined with a suitable detector such as the BRANDPROOF ^® F detector from Polysecure GmbH, resulting in a higher level of safety.

The thermal energy input is determined by visually comparing the color of the seal with a calibrated color gamut. This was created by storage trials of the sealing material under controlled conditions.

A Preparation of the microencapsulated pigment

Red iron oxide (Bayferrox 120) is placed in a hot mixer (eg from Thyssen Henschel) and, while the mixer is running, molten paraffin having a melting point of 40 ° C. is sprayed in. The ratio of pigment to wax is 70:30. The pigment particles are coated with a wax layer. The mixture is carried out until the particles have reached a size of about 20-30 microns. Thereafter, these are transferred to a cooling mixer and cooled to room temperature. Finally, a 20% solution of bleached shellac (1% based on the pigment) dissolved in methanol sprayed and the methanol was removed in vacuo.

B Preparation of the Fe Modified Molecular Sieve

Molekeular sieve A is occupied by ion exchange in acidic FeCl3 solution with Fe ions. Subsequently, the molecular sieve is washed with distilled water until no more iron is detectable on the surface. The product is dried in vacuo.

The features of the invention disclosed in the foregoing description, in the claims and the drawings may be essential both individually and in any combination for the realization of the invention in its various embodiments.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• CN 202518596 [0004]
• CN 202464386 [0004]
• CN 202557987 [0004]
• CN 202400409 [0004]
• CN 102582945 [0004]
• CN 202346084 [0004]
• CN 2806357 [0004]
• EP 1003146 A2 [0023]
• DE 102008060675 A1 [0023]

Claims (9)

Glass bottle sealed with a closure, with a thermosetting polymer seal affixed to and / or on the closure preferably in contact with the glass bottle, the seal being non-destructively removable from the closure and / or the glass, and the seal comprises means for detecting the originality of the seal or the glass bottle and / or means for recording the entry of thermal energy and / or means for detecting the exceeding of a defined temperature. Glass bottle according to claim 1, characterized in that the closure is a cork. Glass bottle according to claim 1 or 2, characterized in that the thermosetting polymer is an acrylic polymer, preferably a modified acrylic polymer. Glass bottle according to one of the preceding claims, characterized in that the seal has at least one through hole. Glass bottle according to one of the preceding claims, characterized in that the means for detecting the authenticity with an armed eye visually visible particles, such as a color code containing particles, natural structures, such as diatoms and / or marking agents, which require a detection device for detection, such as chemical markers , Stokes pigments or anti-Stokes pigments. A glass bottle according to any one of the preceding claims, characterized in that the means for indicating the thermal energy input comprises a porous material containing a thermal diffusion-releasable and color-releasing component, and / or containing a material which permeates decomposes thermal energy and releases a component contained in the material and triggering a color effect. Glass bottle according to claim 6, characterized in that the material is microporous and / or inorganic or organic. Glass bottle according to one of claims 6 and 7, characterized in that the component itself or by reaction with a compound partner triggers a color effect. Glass bottle according to one of the preceding claims, characterized in that the means for detecting the exceeding of a defined temperature contains an irreversibly thermochromic compound and / or a microencapsulated colorant.

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