FI121335B - Procedure for securing the authenticity of a glassware - Google Patents

Description

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BACKGROUND OF THE INVENTION Field of the Invention

The present invention relates to a label verifying the authenticity of a glass product. In particular, the invention relates to a novel method for verifying the authenticity of a glass product by creating areas substantially integrated into the glass material during manufacture which, when irradiated with ultraviolet or infrared light, exhibit characteristic fluorescence in the glass.

Description of the Related Art

Counterfeiting is a common problem all over the world. Counterfeit products 15 are themselves a loss for businesses and it is estimated that around 5% of all world trade is in counterfeit products, corresponding to an annual revenue of around € 200 billion. For example, counterfeiting accounts for about 5% of watches, 6% of medicines, 5% of perfumes, 12% of toys, 33% of music and 50% of video products. In certain areas, such as medicines and medical instruments, counterfeiting poses a direct risk to health and life. It is clear, therefore, that 20 manufacturers of valuable products in particular need effective methods to ensure the authenticity of their products.

In particular, to ensure the authenticity of glass products, it would be advantageous to employ a method where the authentication mark used to check the authenticity is embedded within the glass, whereby counterfeiting without knowledge of the melting and manufacturing of glass products and expensive investment in manufacturing is impossible.

Several different methods have been developed for product safety marking and the most commonly used methods of protection are listed in Table I.

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The most common protection methods currently used in products are listed in Table I.

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Table I currently existing protection methods of use ___ Sequence Technology (% brand owners products) J__Viivakoodi__79 1_ ^ 2__Turvamerkintä__66,7_ _3__Turvalanka__ 54,2_ _4__Hologrammi__53,8_ _5__Turvapaperit__52,0_ _6__Turvamuste__50_ _7__Turvatiimi___ _8__Magneettiset tekniikat__36,4_ _9_EAS 3_E6_ __Erilaiset merkinnät__30,0_ 10 11 I 23 ~ RFID , 8

The protection methods mentioned in the table would be suitable for use in coating, sticker or packaging 5 of a glass product, but not as a solution buried in the glass product since such a solution must withstand the manufacturing temperature of the glass product, typically at least + 800 ° C.

Fluorescent materials have been used in product safety labels. The fluorescent material is characterized by the wavelength and fluorescence discharge time of the fluorescent radiation. The fluorescence of the visible region 10 can be produced in the desired pattern. Such a method is described, for example, in US patent application 2004/0169847,

Fluorescent-based shielding methods have also been described in patents and patent applications WO 87/06197, EPO 889446, WO 89/00319 and US 5,990,197. However, it is not known that the method has been used for protecting glass products - because and such a compound does not withstand the temperatures required for the manufacture of glass.

The most closely controlled fluorescence spectrum is currently obtained using quantum dots. The material of quantum dots is usually CdSe and has the special property that the emission spectrum depends on the size of the material. Thus, by controlling the size of the quantum dots, the emission spectrum of the 3 materials can be adjusted as desired. This protection technology is patented in U.S. Patent No. 6,692,031. However, this publication does not mention the use of quantum dots buried inside a glass.

The glass product can be provided with a security or identification mark by typing a 2-5 dimensional bar code on the hedgehog laser. However, such an inscription may also be produced on a finished glass article.

WO 01/90013 A1, Schott Gias, November 29, 2001, discloses a method for marking glass material. In the method, the molten glass material is doped with a tracer that emits 10 electromagnetic rays of wavelength outside the visible light range. Tracers used in the process include, for example, lead oxide, zinc oxide and / or oxides of rare-earth metals such as cerium oxide and ytterbium oxide. The method can also change the composition of the actual glass material and thus affect the emission spectrum. According to the publication, the tracer can also be applied only to the dotted area of the glass object or to the surface of the glass object.

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US 6,211,526 to Huston et al., April 3, 2001, discloses a luminescence based method for tagging objects for identification. The method comprises doping a luminescent material in a glass matrix, such as manganese doped zinc sulfide, europium or cerium. The known method of the publication monitors the color (wavelength) and lifetime of radiation emitted from the tag material, which is characteristic of the tag material used. The marker material may be made as a coating or may be mixed with various base materials such as glass or glazing during the manufacturing process.

EP 1 178 429 A2, Angstrom Technologies Inc, 06.02.2002, discloses a method for verifying the authenticity of a paragraph. In the method, the body is labeled with a fluorescent substance which, when exposed to electromagnetic radiation, emits electromagnetic radiation. The wavelength, intensity, life span and / or regional distribution of the emitted radiation are utilized to verify authenticity. In one embodiment of the method, the fluorescent tracer is doped in the article during manufacture.

From US 2005/0143249 A1, Ross et al., June 30, 2005, a method for marking paragraphs is known. In the method, the glass matrix is doped with a fluorescent agent, the doped glass 4 is ground, and the powders are further used to label articles. The properties of the emitted radiation, such as wavelength and lifetime, from the label material depend on the fluorescent material used and the composition of the glass matrix, which makes it very difficult to falsify the security marking.

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From US 2003/0177941 A1, Barbera-Guillem, 25.09.2003, a method is known in which the fluorescent material used for the security marking of a piece contains quantum dots (semiconductor nanocrystals) whose emission wavelength depends on the crystal size.

10 There is a need for a method whereby a glass article can, at the manufacturing stage, be provided with a security marking which ensures the authenticity of the glass product. The security marking should preferably be provided in an integrated manner at a low cost. In addition, the security marking should be easily variable so that different products can be given a different security marking.

SUMMARY OF THE INVENTION The method of the present invention generates a security tag on glass by utilizing the fluorescence in glass of certain elements, such as rare earth metals. Fluorescence can also be achieved by utilizing quantum dots. Fluorescence can be seen in 20 finished glasses when the glass is irradiated with light of correct wavelength and sufficient energy,

The present invention is based on the idea that during the manufacture of a glass product its surface can be doped so that the composition of the glass changes locally, thereby providing a characteristic fluorescent spot on the glass whose fluorescence fingerprint depends on both the composition of the glass and the alloy. Fluorescence fingerprinting is very difficult to replicate.

The fluorescence fingerprint consists of both the characteristic wavelength of the fluorescence and the time at which the fluorescence disappears

The characteristic wavelength of fluorescence produced by rare earth metals in glass depends on the composition of the 30 glass, the content of rare earth, the ratio of earth metals and the excipients present in the glass. By providing a fluorescent spot on the surface of the glass product during the manufacture of the cargo product 5, other elements can be introduced into the glass at the same time, which alter the local composition of the glass and thereby contribute to the fluorescence wavelength.

The fluorescence decay time (the time after which the fluorescence can no longer be detected by the detector) 5 also depends on the composition of the glass and the concentration and density of the fluorescent substance in the glass.

The fluorescent region of the present invention may be produced on glass, for example, by a spray pyrolysis process known to those skilled in the art, using the flame spray process described in patent FI98832, or by the sol-gel process.

More specifically, the invention is characterized in what is set forth in the characterizing part of claim 1. According to the invention, the emission region is achieved by spraying the emitting agent on the surface of a molded glass object by a flame spraying process.

Using the present method, excellent fluorescence fingerprint control is achieved. This can easily create a different fingerprint on different glass products and make counterfeiting of the glass product difficult and expensive.

Representative examples are described below with reference to the accompanying drawings.

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Brief Description of the Drawings

Figure 1 shows an inscription according to the invention created on a glass product.

Figure 2 illustrates the production of a security label on a glass ampoule during its manufacture.

Figure 3 illustrates the production of a security marking on a glass utility or art object during its manufacturing process (blow molding).

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DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a method for verifying the authenticity of a glass product based on producing at least a locally fluorescent spot whose fluorescence fingerprint depends on both the composition of the glass and at least locally applied material to the glass which dissolves or diffuses to a limited depth. The process can be used on a variety of glass materials such as soda glass, borosilicate glass, crystal, semicrystalline and quartz glass. The method can be used for a variety of glass products such as flat glass, packaging glass, operating glass, art glass and technical glassware. The method can also be used for glazed products such as glazed ceramic products.

According to the method, a two-component fluorescence fingerprint created in a glass product can be detected by irradiating the glass with a suitable wavelength so that the glass begins to fluoresce at its characteristic wavelength. This is the first component of the fingerprint. Another component of the fingerprint is the fluorescence lifetime, which can be detected by removing irradiation and then measuring the fluorescence decay time. Both the characteristic wavelength and the lifetime of the fluorescence depend on the glass material used and the materials introduced into the glass surface during the production of the fluorescent region.

The fluorescent agent may be, for example, an oxide of lanthanide, such as oxide of erbium, prasecdime, neodymium, samarium or thium. The fluorescent agent may also be, for example, oxide of ytterbium or cerium. The fluorescent agent may also be a quantum dot, whereby the fhiorescence wavelength depends solely on the size of the quantum dot.

The concentration of fluorescent material in the glass is typically about 0.01 to 5% by weight.

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To produce a fluorescent region on a glass surface at a temperature above the cooling limit of the glass typically comprises the steps of applying the fluorescent agent or compound thereof to the glass surface together or separately from other glass composition controlling agents and allowing the fluorescent agent to dissolve and diffuse into the glass. The composition of the glass can be controlled by other substances, for example, so that the fluorescent substances are clustered in the glass, which also produces unusual 7 fluorescence wavelengths due to the interaction of fluorescent substances in the cluster, for example, erbium ions.

5 Examples

The invention will now be described in more detail by way of Examples and with reference to Figures 1-4.

Example 1; safety label on glass ampoules used by the pharmaceutical industry 10

Referring to Figure 1, the fluorescent region 102 produced on glass product 101 emits electromagnetic radiation 103 at a wavelength λΐ when irradiated with electromagnetic radiation 105 having a wavelength λ2 different from that of electromagnetic radiation 103. There may be several emission wavelengths. For example, irradiation of S1O2-Al2O3 doped with erbium at 1480 15 nm, emits glass at 1530 nm, 980 nm. 835 nm, 660 nm and 540 nm. The emission wavelength depends on the glass matrix where the fluorescent material is. Thus, for example, the emission wavelength of the samarium is about 590 nm in a glass matrix rich in phosphorus, aluminum and alkali metal but about 680 nm in a glass matrix rich in phosphorus, aluminum and silicon.

The fluorescent region 102 shown in Fig. 1 may be produced in a glass ampoule for use in the pharmaceutical industry during its manufacture.

Referring to Fig. 2, glass ampoule 201 for use in the pharmaceutical industry is made of borosilicate or quartz glass tubing 202 by cutting a piece 203 of glass tubing 202 of appropriate length, which is sealed at one end 204 by a heating flame 205 and generally graphite tool 206. The temperature of the glass during processing is about 700-1700 ° C, depending on the composition of the glass. The other end of the glass ampoule may be processed as desired at the same time or at different stages. For example, a thread may be machined there for the cap.

Once the bottom of the vial has been machined, the surface of the glass 207 is sprayed with oxides of rare earth, such as erbium and / or samarium, as small particles 208, typically having an average 8 aerodynamic diameter of less than 100 nm. Such particles can easily be produced and sprayed on the surface of a hot ampoule using, for example, the flame spraying method 209 described in patent FI98832. generating a flame 210 by means of hydrogen gas 211 and oxygen 212. Flame is atomized by atomization nozzle 213 at the end of flame stroke 209 containing dissolved salts 215 of rare earth and other substances. Raw materials undergo flame 210 evaporation-condensation reaction and generate small oxide particles 208.

Example 2; Referring to FIG. 3, a glass utility or art object is often made by blow-blasting or blowing (semi-automatic), in the mouth-blasting of the glass whip 301 to the start of the blowing whip 302, i.e. the post 303. As the piece of glass cools during machining, it is sometimes heated in a reheat furnace, i.e. drum 305.

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During machining, a rare earth metal such as erbium and / or samarium oxide is injected onto the surface 306 of the glass object as small particles 307 typically having an average aerodynamic diameter of less than 100 nm. Such particles can easily be produced and sprayed on the surface of a hot ampoule using, for example, the flame spray method 308 described in FI98832 25. At the same time as rare earth metals, the same method can be used to inject aluminum oxide or the like locally.

Typically, when using flame injection method 308, the method generates flame 309 with hydrogen gas 310 and oxygen 311. The flame is atomized by atomization nozzle 312 at the end 30 of the flame gun 308, which contains dissolved salts 314 of the rare earths and other substances 94. In the flame 309, the raw materials undergo a volatilization-condensation reaction and generate small oxide particles 307.

Further glass is then collected on the surface of the glass article from the glass bath 301 and the piece is shaped into its final shape by a mold 315. The security tag 316 remains inside the final glass article 317, 10

Claims (4)

A method for verifying the authenticity of a glass object, comprising: producing, at least at some point, a surface of a glass object which, when irradiated with electromagnetic radiation at 5 wavelengths, emits a characteristic radiation having at least one emission wavelength and / or that the emission region is achieved by spraying the emitting agent onto the surface of the glass object by means of a flame spray process. A method as claimed in claim 1, characterized in that the emitting region is achieved by flame spraying on a glass member of a lanthanide group. A method as claimed in claim 1, characterized in that the emitting region is achieved by spraying quantum dots on the glass. A method as claimed in claims 1 to 3, characterized in that the emission wavelength and / or its disappearance time is controlled by flame spraying on the glass a substance modifying the composition of the basic glass.