Method for identifying and / or verifying security article

Abstract

The present invention relates to a method of identifying and / or verifying a security article, the method comprising probing and / or analyzing (120) in at least a portion of the security article one or more markers representative of the presence, content and / or morphological characteristics of a calcium carbonate filler of bio-based origin, and determining the identity and / or authenticity of the security article based at least on a comparison of the one or more markers with one or more reference information (130).

Description

Technical Field

[0001] This invention relates to methods for identifying and / or verifying safety products.

[0002] The present invention also relates to security elements to be integrated into a security file preferably suitable for implementing the identification and / or verification method, and the corresponding security file.

[0003] The present invention also relates to a security document preferably suitable for implementing the identification and / or verification method, preferably comprising an impression or a surface layer receiving the impression and an oil-based printing ink.

[0004] This invention relates more particularly to the field of secure documents.

[0005] “ Security Files "In particular, it refers to means of payment, such as banknotes (whether they are made of paper, polymers or mixtures thereof), checks, payment cards or restaurant vouchers, identity documents such as ID cards, visas, passports or driver's licenses, lottery tickets, transport tickets or tickets for cultural or sporting events, but also to packaging materials for additional packaging, the field of coated paper, and the field of luxury packaging materials and brand protection."

[0006] To prevent forgery or counterfeiting attempts targeting security documents, a known practice is to add security elements to the document's substrate, which may take the form of fibers, granules, patches, planchettes, films, knitted structures, or security threads.

[0007] Security documents are secured in particular by adding embedded security elements. These elements may be introduced during paper manufacturing, specifically in the form of fibers, particles, films, threads, or knitted structures, or after manufacturing, specifically in the form of films or patches, and may contain one or more levels of security features that enable the identification and / or verification of the security document.

[0008] The present invention also relates to security elements that have been integrated or are to be integrated into security files.

[0009] “ Safety elements "Specifically, this refers to security threads, security particles, security fibers, security panels, security foils, data protection films, and security patches. Such security elements are removable, pre-cut, or ready to be cut from the security document into which they are integrated. These security elements can be single-layered or multi-layered. They may contain one or more layers made of paper, polymers, or mixtures thereof."

[0010] The security document can also be made more secure by adding printed materials.

[0011] The present invention therefore also relates to ink.

[0012] Calcium carbonate in various crystalline forms is widely used in the paper, polymer, coating and printing ink industries, especially in security documents, security elements and / or printing inks.

[0013] It is used as a filler in powder form to significantly reduce material production costs. It helps to improve opacity and whiteness and is typically used in high proportions in various types of refined paper, creative paper, and writing and printing paper.

[0014] In the field of coated paper, it is customary to apply a coating with a high pigment content (usually more than 80% of the coating composition) to the surface of the paper, and calcium carbonate is also widely used here to develop printability, whiteness and opacity.

[0015] Calcium carbonate is also used in the manufacture of printing inks and some plastic films.

[0016] For all these applications, calcium carbonate is obtained through mining, and this extracted source of calcium carbonate is not renewable.

[0017] Documents disclosed by international applications WO2017 / 089148 and WO2018 / 234106 describe how security is achieved by utilizing the salt-forming properties of calcium carbonate that is integrally incorporated into the substrate or incorporated into the surface layer of the substrate to form patterns.

[0018] A method for using a spectrally detectable security feature marking substrate for anti-counterfeiting is also known from patent application US 2021 / 324584. This method includes the steps of: providing a substrate containing a salt-forming alkali metal or alkaline earth metal compound; applying a liquid treatment composition containing an acid to create a surface-modified region; and covering the region with an opaque layer. The authenticity of the product is verified by recording the spectrum of the substrate and comparing it with a spectral library to confirm the proportions of various compounds, particularly calcium carbonate (Example 1). This spectroscopic method allows for the identification of calcium carbonate in substrates from any mixed sources. It cannot distinguish between different sources of calcium carbonate.

[0019] In addition, an international application WO2014 / 033658 provides a method for verification by detecting the content of bio-based materials in a document containing at least a portion of synthetic hydrocarbon polymers derived from plant resources.

[0020] There is a need to further improve file security while maintaining an environmentally friendly path. Summary of the Invention

[0021] According to its first aspect, the present invention relates to a method for identifying and / or verifying a safety article, the method comprising recherche and / or analyzing one or more markers representing the presence, content, and / or morphological characteristics of a bio-based source of calcium carbonate filler in at least a portion of the safety article, and determining the identity and / or authenticity of the safety article at least based on a comparison of the one or more markers with one or more reference information.

[0022] the term" Bio-based calcium carbonate filler "Throughout this description and the entire following text, it should be understood that this refers to calcium carbonate fillers, particularly in granular or powder form, obtained from bio-based calcium carbonate, especially by grinding and / or micronizing the bio-based calcium carbonate. In accordance with various aspects of the invention, the bio-based calcium carbonate filler may comprise eggshell powder and / or seashell powder, particularly comprising at least one type of bio-based calcium carbonate, or a mixture of different types of bio-based calcium carbonate. Preferably, in accordance with various aspects of the invention, the particle size D50 of the bio-based calcium carbonate filler is between 1 and 100 μm, more preferably between 1 and 50 μm, and even more preferably between 1 and 10 μm. Preferably, in accordance with various aspects of the invention, the eggshell powder does not contain a membrane and / or egg white extending between the egg white and the eggshell." Types of bio-based calcium carbonate "In this and throughout the following description, it should be understood to refer to bio-based calcium carbonate obtained from sources selected from each of the following: eggshell powder or shell powder or eggshell powder derived from a particular bird or a particular family of birds (e.g., from hens, ducks, quails, pheasants, turkeys, ostriches, geese, pigeons and / or guinea fowl), or eggshell powder derived from mollusks or a particular family of mollusks (e.g., from oysters, mussels, Saint-Jacques, scallops, snails, clams, sea snails, clams, coques, razor clams, abalone, razor clams, limpets, scallops, praires and / or cherry clams)."

[0023] This approach constitutes an environmentally friendly alternative for verifying the safety of products. This is because bio-based calcium carbonate is derived from the value-added utilization of byproducts or waste.

[0024] Furthermore, this verification and identification can be carried out by various methods by determining the presence or content of bio-based calcium carbonate fillers and / or by determining morphological characteristics, which enables multiple levels of protection.

[0025] Safe products containing bio-based calcium carbonate fillers constitute an environmentally friendly and safe alternative. This is because the source of this bio-based calcium carbonate is derived from the value-added utilization of by-products or waste, which is not the case with carrière calcium carbonate fillers.

[0026] In this invention, the fact that the one or more markers specifically represent bio-based calcium carbonate fillers makes it possible to specifically identify or quantify calcium carbonate from such sources, whether it exists alone in the substrate or is mixed with mineral-derived calcium carbonate. Thus, the presence of bio-based calcium carbonate can be specifically identified in mixtures containing calcium carbonate from multiple sources.

[0027] The fact that bio-based calcium carbonate can be specifically identified makes it possible to conceive of new safety features based on such calcium carbonate sources. Therefore, safety features can be particularly acquired through the following means:

[0028] - The simple presence of bio-based calcium carbonate, unlike mineral-derived calcium carbonate, which cannot be identified by the markers of this invention or can be identified in a different manner by the markers of this invention, and / or

[0029] - A specific proportion of bio-based calcium carbonate, either alone in the substrate or mixed with mineral-derived calcium carbonate, relative to a specific bio-based proportion of total calcium carbonate, constitutes identification and / or verification information, and / or

[0030] - Identification or quantification of one or more types of calcium carbonate from bio-based sources.

[0031] Analysis and / or exploration

[0032] Preferably, the detection and analysis includes detection and analysis methods different from spectroscopic methods.

[0033] It can be performed without using spectroscopy, or as a variant, by combining spectroscopy with a different detection and analysis method than spectroscopy, particularly to quantify the ratio between the proportion of total calcium carbonate filler in the substrate (e.g., which can be determined by spectroscopy) and the proportion of bio-based calcium carbonate filler in the substrate (which can be determined by the methods described above).

[0034] Advantageously, the method includes incinerating at least a portion of the safety article prior to probing and / or analyzing one or more markers representing the presence and / or morphological characteristics of the bio-based calcium carbonate filler, the probing and / or analysis being based on the ash produced by the incineration. This makes it possible, in particular, to recover the filler solely from the ash, which is beneficial for the probing and analysis.

[0035] Preferably, the incineration temperature is selected to decompose the organic matter and retain the mineral fraction by protecting the bio-based calcium carbonate from possible thermal decomposition into CaO and CO2. Preferably, this temperature is less than or equal to 420°C. Above this temperature, the calcium carbonate can decompose. Such decomposition would be detrimental to the analysis.

[0036] As a variant, the method does not include an incineration step. In this case, the method preferably includes probing and / or analyzing one or more markers that represent the morphological characteristics of the bio-based calcium carbonate filler.

[0037] Preferably, the operation of probing and / or analyzing the one or more markers representing the morphological characteristics of the calcium carbonate filler is performed on a cross-section of at least a portion of the safety article. Such probing and / or analysis of the markers can be performed using microscopy, particularly electron microscopy. In practice, specific morphological structures (e.g., layered structures, porous and / or permeable structures, etc.) of bio-based calcium carbonate can be identified based on the cross-section of at least a portion of the safety article, and thus the identity and / or authenticity of the safety article can be determined at least based on a comparison of the one or more markers with one or more reference information.

[0038] markers

[0039] Preferably, the one or more markers include markers representing the content of bio-based material. The markers may be carbon-14 isotope content, determined according to standard ASTM D6866-22. This invention enables the addition of safety features to an article without altering its manufacturing process. An article containing bio-based calcium carbonate filler and thus loaded with carbon-14 isotopes can be used as a substitute for the same article containing petroleum fossil resources and therefore not containing carbon-14 isotopes.

[0040] “ Content of bio-based materials "This refers to the standard ASTM D6866-11:" Determining the Biobased Content of Solid, Liquid, and Gaseous Samples Using Radiocarbon Analysis The determined content.

[0041] Furthermore, this invention benefits from the presence of one or more markers, enabling easy and reliable identification and / or verification of safety articles. This is because, conventionally, marker elements used in identification and / or verification methods are introduced in trace amounts (typically less than 0.5%), meaning that the identification and / or verification of safety articles is sometimes imprecise and unreliable. The bio-based calcium carbonate used as the marker element is introduced in a much larger amount than conventional marker elements. Preferably, the content of the bio-based material is greater than 1%, more preferably greater than or equal to 2%, even more preferably greater than or equal to 10%, even more preferably greater than or equal to 50% or greater than or equal to 90%. The method for identifying and / or verifying this safety article becomes easier due to the presence of one or more marker elements present in large quantities, thereby improving the reliability of the method.

[0042] Calcium carbonate is a widely used compound in the paper industry and is therefore typically present initially in at least a portion of safety articles. In the context of this invention, the addition of bio-based calcium carbonate allows it not only to replace existing compounds (i.e., compounds necessary for the formulation of at least a portion of the safety article) but also to function as a marker element in methods for identifying and / or verifying the safety article. Therefore, it is unnecessary to add specific compounds (i.e., markers) that are only present for identifying and / or verifying the safety article.

[0043] The one or at least one of the reference information may contain a content of greater than 1%, more preferably greater than or equal to 2%, even more preferably greater than or equal to 10%, even more preferably greater than or equal to 50%, or greater than or equal to 90% of bio-based material. Preferably, the method includes incinerating a portion of the article as described above, and the one or at least one of the reference information corresponds to the content of a reference bio-based material in the ash, particularly the content of carbon-14 isotope. In ash "It is understood to refer to the substances remaining after incineration."

[0044] The method may include determining the carbon-14 isotope content in the ash after incineration of at least a portion of the article as described above, and determining the identity or authenticity of the article by comparing the determined carbon-14 isotope content with a reference carbon-14 isotope content or a range of carbon-14 isotope content.

[0045] As a variant or additionally, the marker or at least a portion of the markers represents one or more morphological features of a bio-based calcium carbonate filler derived from the grinding and / or micronization of eggshells and / or shells.

[0046] As a variant or additionally, the marker or at least a portion of the markers represents one or more morphological features of that portion or portion of the bio-based calcium carbonate filler. The one or more morphological features may represent the predetermined source of the bio-based calcium carbonate (particularly calcium carbonate derived from eggshells or shells). Additionally, the one or more morphological features may represent the type of bio-based calcium carbonate, particularly bird-type eggshells or mollusc-type shells.

[0047] The one or more morphological features may be one or more crystallographic, shape, and / or porous features of the calcium carbonate in the calcium carbonate filler.

[0048] The one or more markers may include one or more markers representing the following:

[0049] - The layered structure of calcium carbonate, which is a characteristic morphological structure of calcium carbonate derived from seashells, and / or

[0050] - Porous and / or permeable structures, particularly including channels through particles of bio-based calcium carbonate filler, which is characteristic of the morphological structure of calcium carbonate derived from eggshells.

[0051] In the case of one or more markers representing a layered structure, the markers may include one or more morphological features of the layered structure, particularly the average density and / or average thickness of the layers. Each type of shell contains a layered structure with its own characteristics. The determination of the morphological features indicating the shell type makes it possible to distinguish the type of shell from which all or part of the filling originates. The one or more markers can be used to distinguish the shells of oysters, mussels, Saint-Jacques, scallops, whelks, cockles, conches, clams, cockles, razor clams, abalone, razor clams, limpets, scallops, cockles, or cherry clams, more particularly the shells of Saint-Jacques, oysters, and mussels.

[0052] In the case of one or more markers representing a porous and / or permeable structure, the markers may include one or more characteristics of the porous structure, particularly porosity, pore shape, average pore size per unit area on a given plane, and / or pore density. Each type of bird forms an egg with a shell that exhibits a porous structure with its own characteristics. The one or more markers can be used to distinguish eggshell powder from different birds (particularly hens, quails, pheasants, turkeys, ostriches, geese, pigeons, or guinea fowl). One or more markers representing the presence of eggshell powder may be the presence of a porous structure with an average pore diameter between 20 nm and 500 nm, preferably between 40 nm and 400 nm, measured particularly by analyzing one or more images of a safety element or ash content.

[0053] The detection and / or analysis of markers representing morphological characteristics can be performed using microscopy, particularly electron microscopy, with or without pre-incineration. Unlike spectroscopic methods, which only allow elemental analysis of samples, microscopic analysis enables the acquisition of information about the sample's morphology, grain size, and crystallographic structure.

[0054] Therefore, the precise morphology of the calcium carbonate filler can be determined, and its identity or authenticity relative to the reference information can be inferred from this.

[0055] Preferably, the method includes probing and / or analyzing at least two markers, one of which represents the presence of the bio-based calcium carbonate, particularly the presence and / or content of the carbon-14 isotope as described above, and the other represents the morphological characteristics of the bio-based calcium carbonate filler, particularly the presence and / or morphological characteristics of the layered and / or porous structure.

[0056] The method may include detecting and / or analyzing one or more markers representing mixtures of at least two different types of bio-based calcium carbonate, particularly those derived from eggshells of different birds, shells of different mollusks, or mixtures of one or more types of eggshells and one or more types of shells. This allows for enhanced protection by increasing the possible level of security.

[0057] The steps of probing and / or analyzing at least a portion of the article may include determining the presence of bio-based calcium carbonate filler and probing and / or analyzing one or more markers representing the composition of the bio-based calcium carbonate filler (particularly the properties and / or mass proportions of the calcium carbonate filler), and determining the identity or authenticity of the article may include comparing the identified one or more markers with reference information, and inferring the identity and / or authenticity of the article when the one or more markers correspond to the reference information. Therefore, multiple levels of security are possible, ranging from simply determining the presence of bio-based calcium carbonate to determining its complex composition using one or more markers specific to the probing composition. This allows for multiple levels of security. For example, a first level may correspond to determining the presence of bio-based calcium carbonate, a second level to determining the nature of the overall source (eggshell or shell) of the calcium carbonate filler, and a third level to determining the bird or mollusc from which the calcium carbonate originates and its proportion.

[0058] This method may additionally include probing and / or analyzing the presence and / or mass proportion of compounds in the bio-based filler, particularly magnesium, silicon, sodium, aluminum, or chlorine. Eggshells may specifically contain magnesium, and seashells may contain silicon, sodium, aluminum, or chlorine.

[0059] The method may further include probing and / or analyzing the particle size distribution of the calcium carbonate filler, which represents the calcium carbonate filler obtained, particularly by grinding and / or micronization; and determining its identity and / or authenticity at least based on a comparison of the particle size distribution with one or more reference information, including information on the particle size distribution of the calcium carbonate filler or information on methods for obtaining reference calcium carbonate filler. This reference information may include a particle size D50 between 1 and 100 μm, more preferably between 1 and 50 μm, or even more preferably between 1 and 10 μm.

[0060] Reference Information

[0061] Reference information may include the presence of bio-based calcium carbonate, a reference content of bio-based calcium carbonate, a reference mass ratio of bio-based calcium carbonate or one or more types of bio-based calcium carbonate, a reference morphological characteristic of bio-based calcium carbonate or one or more types of bio-based calcium carbonate, information on reference values ​​or reference ranges representing the morphological characteristics of bio-based calcium carbonate or one or more types of bio-based calcium carbonate, and information on the presence of one or more types of bio-based calcium carbonate in the reference bio-based calcium carbonate filler and / or the mass ratio of each type of bio-based calcium carbonate in the reference bio-based calcium carbonate filler.

[0062] The method may include pre-determining reference information by at least probing and / or analyzing one or more markers on one or more reference articles whose identity and / or authenticity are known. The determination of this reference information may be performed by acquiring one or more images of the bio-based calcium carbonate filler of the one or more reference articles and analyzing the acquired images and / or learning, particularly via learning algorithms and / or neural networks, based on markers identified or analyzed on images of multiple reference articles.

[0063] The detection and / or analysis of markers in portions of the article, particularly directly in portions of the article or in the ash of portions of the article, is preferably performed using a microscope, particularly an optical microscope or preferably an electron microscope. This method may include acquiring one or more images of the portion of the article to be analyzed and / or the ash, particularly by an electron microscope, at a magnification that allows visualization of the calcium carbonate filler particles in the one or more images. Analysis of the substrate is preferably performed without a specific electromagnetic detector, for example, under white light.

[0064] It can also verify the presence of one or more additional conventional safety elements on the product.

[0065] Among these additional security elements, some can be detected by the eye under sunlight or artificial light without the use of special equipment. These security elements include, for example, colored fibers or boards, fully or partially metallized or printed security threads, secure knitted structures, security films, watermarks, optically variable elements (so-called "OVD"), and especially holograms. These security elements are referred to as Level 1 security elements.

[0066] Other types of additional safety elements can only be detected by relatively simple devices, such as lamps that emit light in the ultraviolet (UV) or infrared (IR) range. These safety elements include, for example, fibers, sheets, strips, threads, or particles. These safety elements may be visible to the naked eye or invisible, for example, emitting light when illuminated by a Wood lamp that emits light at a wavelength of 365 nm. These safety elements are referred to as Level 2 safety elements.

[0067] Other types of additional security elements require more sophisticated detection equipment to detect them. These security elements, for example, can generate specific signals when subjected to one or more external excitation sources simultaneously or asynchronously. Automated detection of these signals enables document verification when needed. These security elements include tracers in the form of, for example, active materials, particles, or fibers, which can generate specific signals when subjected to photoelectronic, electrical, magnetic, or electromagnetic excitation. These security elements are referred to as Level 3 security elements.

[0068] The security document or paper containing the security features according to the present invention may have a first level, a second level, or a third level of security features.

[0069] The analysis of the substrate is preferably performed using automated image analysis, for example, using a computer, particularly a computer connected to the microscope used for the analysis. This analysis can be performed using image analysis algorithms, particularly learning algorithms trained on images of identified and / or authentic articles. The method draws conclusions about identity and / or authenticity by comparing one or more acquired images with images acquired through another test performed on an identified and / or authentic reference article or a portion thereof.

[0070] Safety products

[0071] The investigation and / or analysis can be performed on the entire article or only a part of the article, especially on detachable or cut-off sections.

[0072] The security artifact can be a security document.

[0073] The portion of the security artifact on which it is probed and / or analyzed may be a security element integrated into a security document.

[0074] As a variant, the security artifact can be a security element specifically integrated into a security document.

[0075] This method may include, in particular, extracting the security element by separating or cutting it at least partially prior to the exploration and / or analysis. Specifically, the exploration and / or analysis may be based on a cross-section of the security element as described above.

[0076] Bio-based calcium carbonate fillers can be arranged locally within a safety element, particularly in a pre-defined pattern that is preferably detectable and, more particularly, visible. The method may include extracting portions of the safety element corresponding to the portion of the safety element intended to contain the bio-based calcium carbonate filler, and probing and / or analyzing one or more markers in said portions.

[0077] Safety elements (elément)

[0078] According to its second aspect, the invention also relates to safety elements to be integrated into a safety document particularly suitable for implementing the method according to the first aspect of the invention, which comprises a bio-based calcium carbonate filler.

[0079] These safety features constitute an environmentally friendly and safe alternative. This is because bio-based calcium carbonate is derived from the value-added utilization of by-products or waste.

[0080] The content of bio-based materials in the ash, as measured according to standard ASTM D6866-11, may be greater than 1%, preferably greater than or equal to 2%, even better than or equal to 10%, even better than or equal to 50% or greater than 90%.

[0081] At least a portion, and more preferably all, of the bio-based calcium carbonate filler may be porous and have an average pore diameter between 20 nm and 500 nm, more preferably between 40 nm and 400 nm, measured particularly by analyzing one or more images of safety elements or ash content. This porosity is particularly characteristic of eggshell powder. The calcium carbonate filler may be eggshell powder derived from a specific family or species of bird. Eggshell powder derived from a specific family or species of bird can be readily identified by observing the microstructure of the powder (particularly the shape of the pores), the ultrastructure of the powder, and its crystallographic properties, as illustrated in the following article by Yves Y. Nys et al.: Structure, propriétés et miné ralisation de la coquille de l' uf : rôle de la matrice organique dans le contrôle de sa fabrication . INRA Productions Animales, Paris: INRA, 2010, 23(2), pp.143-154. hal-02667365.

[0082] A portion of this bio-based calcium carbonate filler may have a layered morphological structure. This layered structure is particularly characteristic of shell powder. The calcium carbonate filler may be shell powder derived from a specific mollusc, possessing morphological characteristics specific to this type of shell, particularly the average density or average thickness of the layers.

[0083] Preferably, the bio-based calcium carbonate filler is integrated into the inner layer of the safety element, which has a surface protective layer.

[0084] This safety element may include printed material. When the calcium carbonate filler is integrated into the printed layer, the printing ink, when aqueous, preferably has a non-acidic pH, particularly a pH greater than or equal to 7.

[0085] The calcium carbonate filler can be uniformly dispersed in a substrate or locally arranged, particularly for forming at least partially opaque areas, especially in the form of patterns, which are preferably detectable, and particularly visible. This allows for simultaneous visual identification and identification according to the methods described above, making verification easier and improving security.

[0086] This bio-based calcium carbonate filler can be an opaque filler with safety features.

[0087] The safety element may include titanium dioxide filler. Preferably, the calcium carbonate filler is configured as an opaque filler to form the safety element with the titanium dioxide filler, particularly in the case of paper-type safety elements.

[0088] As a variant, this safety element is titanium dioxide-free, and the calcium carbonate filler is integrally integrated into the substrate to form an opaque filler for the substrate.

[0089] The fact that the opaque filler is formed, at least in part, from bio-based calcium carbonate makes it possible to reduce costs by limiting the use of expensive fillers such as titanium dioxide. Furthermore, this allows for a reduction in the environmental footprint without compromising opacity.

[0090] Preferably, the safety element comprises a paper layer or polymer that integrally contains bio-based calcium carbonate filler.

[0091] The bio-based calcium carbonate filler can be integrally integrated into a fiber layer, which in particular comprises cellulose and / or hemicellulose fibers and / or vessels extracted from broadleaf trees, especially at least one of the following species: birch, elm, chestnut, oak, eucalyptus, beech, styrax, purple oak, poplar, tulip tree, preferably eucalyptus. According to this second aspect, the invention also relates to a safety document comprising the safety elements described above. The safety document may include removable or separable portions containing the safety elements.

[0092] Security Files

[0093] According to its third aspect, the present invention also relates to a security document particularly suitable for implementing the identification and / or verification methods described above, comprising a multi-layer structure including at least one inner layer of the security document (particularly a paper security document), the inner layer comprising throughout a bio-based calcium carbonate filler, and a surface protective layer.

[0094] The bio-based material content in the ash of the document, as measured according to standard ASTM D6866-11, may be greater than 1%, preferably greater than or equal to 2%, even more preferably greater than or equal to 10%, even more preferably greater than or equal to 50% or greater than 90%.

[0095] At least a portion, preferably all, of the bio-based calcium carbonate filler may be porous and have an average pore diameter between 20 nm and 500 nm, more preferably between 40 nm and 400 nm, measured particularly by analyzing one or more images of safety elements or ash content. This porosity is particularly characteristic of eggshell powder. The calcium carbonate filler may be eggshell powder derived from a specific family or species of bird.

[0096] A portion of this bio-based calcium carbonate filler may have a layered morphological structure. This layered structure is particularly characteristic of shell powder. The calcium carbonate filler may be shell powder derived from a specific mollusc, possessing the morphological characteristics characteristic of that type of shell.

[0097] The bio-based calcium carbonate filler can be an opaque filler for the inner layer, and the layer placed on top of the inner layer is at least partially transparent, preferably completely transparent.

[0098] The inner layer may comprise a mixture of titanium dioxide filler and bio-based calcium carbonate filler. Preferably, the calcium carbonate filler is configured as an opaque filler for use together with the titanium dioxide filler to form the security document.

[0099] As a variant, the inner layer does not contain titanium dioxide, and the calcium carbonate filler is integrally integrated into the inner layer to form an opaque filler for the substrate.

[0100] The fact that bio-based calcium carbonate is used to form opaque fillers allows for cost reduction by limiting the use of expensive fillers such as titanium dioxide. Furthermore, this enables a reduction in environmental footprint without compromising opacity.

[0101] Preferably, the inner layer is a paper layer or polymer that integrally contains bio-based calcium carbonate filler.

[0102] The inner layer may contain at least partially derived synthetic hydrocarbon polymers, also known as bio-based polymers, derived from plant resources, particularly bio-based latex, in which bio-based calcium carbonate fillers are integrally integrated.

[0103] The inner layer may comprise a fibrous substrate, which in particular comprises cellulose and / or hemicellulose fibers and / or vessels extracted from broad-leaved trees, especially at least one of the following species: birch, elm, chestnut, oak, eucalyptus, beech, styrax, purple tree, poplar, tulip tree, preferably eucalyptus.

[0104] The inner layer preferably does not contain printed materials using ink with a pH value less than 6, preferably 7.

[0105] The inner layer may contain greater than 1% dry mass, more preferably greater than 2% dry mass, and even more preferably greater than 4% dry mass of bio-based calcium carbonate, relative to the total dry matter mass of the inner layer. The inner layer may contain less than 50% dry mass, more preferably less than 40% dry mass of bio-based calcium carbonate, relative to the total dry matter mass of the inner layer.

[0106] Preferably, the security document is contained in print on the outer protective layer.

[0107] According to its fourth aspect, the present invention also relates to a security document particularly suitable for implementing the identification and / or verification methods described above, comprising a surface layer and a print of ink on the surface layer, the print and / or the surface layer comprising a bio-based calcium carbonate filler, the print ink having a pH greater than or equal to 6, preferably greater than or equal to 7 when it is aqueous.

[0108] Preferably, the security document does not contain water-based printing ink with a pH less than 7 that comes into contact with the surface layer, which has a bio-based calcium carbonate filler.

[0109] The fact that this ink is not acidic or only slightly acidic allows it to avoid the salt-forming process of calcium carbonate, which would otherwise degrade the calcium carbonate.

[0110] The bio-based calcium carbonate filler can be integrally integrated into the surface layer or the printed material.

[0111] Preferably, the bio-based calcium carbonate filler is eggshell powder. The presence of the bio-based calcium carbonate filler in the form of eggshell powder in the printed layer or the printed matter makes it particularly easy to dry the ink due to the porous characteristics of the filler as described above.

[0112] The content of bio-based materials in the ash, as measured according to standard ASTM D6866-11, may be greater than 1%, preferably greater than or equal to 2%, preferably greater than or equal to 10%, and even more preferably greater than or equal to 50% or greater than 90%.

[0113] At least a portion, preferably all, of the bio-based calcium carbonate filler may be porous and have an average pore diameter between 20 nm and 500 nm, preferably between 40 nm and 400 nm, as described above, particularly measured by analyzing one or more images of safety elements or ash content.

[0114] The bio-based calcium carbonate filler can be the opaque filler of the printed layer or the printed material.

[0115] The surface layer and / or the printout may comprise a mixture of titanium dioxide filler and bio-based calcium carbonate filler. Preferably, the calcium carbonate filler is configured as an opaque filler for forming the surface layer or the printout together with the titanium dioxide filler.

[0116] As a variant, the calcium carbonate filler is integrally integrated into the surface layer and / or the print to form an opaque filler for the substrate, wherein the surface layer and / or the print does not contain titanium dioxide.

[0117] The surface layer may contain synthetic hydrocarbon polymers, also known as bio-based polymers, that are at least partially derived from plant resources, particularly bio-based latex.

[0118] The surface layer may comprise a fibrous substrate, which in particular comprises cellulose and / or hemicellulose fibers and / or vessels extracted from broad-leaved trees, especially at least one of the following species: birch, elm, chestnut, oak, eucalyptus, beech, styrax, purple tree, poplar, tulip tree, preferably eucalyptus.

[0119] The surface layer and / or the print may contain more than 1% dry mass, preferably more than 10% dry mass, even more than 20% dry mass, even more than 40% dry mass, even more than 60% dry mass of bio-based calcium carbonate filler relative to the total dry matter mass of the surface layer and / or the print.

[0120] ink

[0121] According to its fifth aspect, the present invention also relates to an oil-based printing ink (hereinafter referred to as "oil-based ink") comprising a bio-based calcium carbonate filler.

[0122] This oil-based ink may have a dynamic viscosity of 0.1-50 Pa·s, particularly 0.2-40 Pa·s, and preferably 2-40 Pa·s, under ambient pressure and temperature. In the context of this invention, ambient temperature refers to a temperature of 18-25°C.

[0123] The dynamic viscosity of oil-based inks can be measured using conventional methods. In particular, the selection of suitable measurement methods and equipment, taking into account the viscosity range of the compositions involved, is clearly within the capabilities of those skilled in the art.

[0124] For example, for inks with a dynamic viscosity significantly less than 2 Pa·s, the preferred measuring device is a Brookfield viscometer using an n°2 rotor rotating at 100 rpm (ISO 2555).

[0125] The dynamic viscosity can be adjusted according to the specific function associated with the ink, but it can also be adjusted according to the application method considered for treating the carrier surface with the ink.

[0126] For example, the ink according to the invention can be deposited on the surface of a carrier by offset printing, screen printing, gravure printing, letterpress printing, or lithographing. Preferably, the ink according to the invention is deposited on the surface of the carrier by gravure printing.

[0127] Therefore, under ambient temperature and pressure, the ink of this invention used is:

[0128] In offset printing, it can advantageously have a dynamic viscosity of 4-50 Pa·s.

[0129] In screen printing, it can advantageously have a dynamic viscosity of 0.1-10 Pa·s.

[0130] In gravure printing, a dynamic viscosity of 5-20 Pa·s can be advantageously achieved.

[0131] In letterpress printing, it can advantageously achieve a dynamic viscosity of 2-20 Pa·s, and

[0132] In offset printing, a dynamic viscosity of 10-20 Pa·s can be advantageously achieved.

[0133] Preferably, the ink is a gravure printing ink, especially a gravure printing ink dried by oxidation.

[0134] In addition to bio-based calcium carbonate filler, the ink may contain at least one coloring pigment. Preferably, the ink is a safety ink, which, together with the object on which the ink is printed, can form a safety article suitable for implementing the identification and / or verification methods described above.

[0135] Preferably, the bio-based calcium carbonate filler is eggshell powder. The presence of the bio-based calcium carbonate filler in the form of eggshell powder in the ink makes it particularly easier to dry the ink due to the porous nature of the filler as described above.

[0136] The content of bio-based materials in the ash, as measured according to standard ASTM D6866-11, may be greater than 1%, preferably greater than or equal to 2%, preferably greater than or equal to 10%, and even more preferably greater than or equal to 50% or greater than 90%.

[0137] At least a portion, preferably all, of the bio-based calcium carbonate filler may be porous and have an average pore diameter between 20 nm and 500 nm, preferably between 40 nm and 400 nm, as described above, particularly measured by analyzing one or more images of safety elements or ash content.

[0138] The ink may comprise a mixture of titanium dioxide filler and bio-based calcium carbonate filler. Preferably, the calcium carbonate filler is configured as an opaque filler for forming the ink together with the titanium dioxide filler.

[0139] As a variant, this ink does not contain titanium dioxide.

[0140] The ink may contain more than 1% by mass, preferably more than 10% by mass, and even more than 30% by mass of bio-based calcium carbonate relative to the total mass of the ink. Attached Figure Description

[0141] The invention can be better understood by reading the following detailed description of non-limiting embodiments of the invention and by referring to the accompanying drawings, in which:

[0142] [ Figure 1 ] Figure 1 This is a schematic diagram of an embodiment of the security document according to the present invention.

[0143] [ Figure 2 ] Figure 2 This is a flowchart of the steps of an embodiment of the identification and / or verification method.

[0144] [ Figure 3 ] Figure 3 Corresponding to photographs of eggshell powder at various magnifications,

[0145] [ Figure 4 ] Figure 4 Corresponding photographs of St-Jacques shell powder at various magnifications, and

[0146] [ Figure 5 ] Figure 5 This is a magnified photograph of mussel shell powder. Detailed Implementation

[0147] Figure 1 A security document 10 is shown, which includes a substrate 11 in which security elements 12 are integrated or added.

[0148] The security document 10 is, for example, a banknote and may have a rectangular shape. The substrate 11 may be fibrous. The security element 12, in the considered embodiments, may take the form of a security thread, patch, security fiber, security plate, security foil, data protection film, security patch, or security printing. Preferably, the security element is positioned on a clearly defined portion of the security document. It may be integrally integrated into the substrate 11, or in the form of a window, or formed as a part of the security document.

[0149] The security element itself may be removable or cuttable for verification or identification. As a variation, it may be located on a removable or cuttable area of ​​the security document; in particular, printed material 15 indicating the area to be cut for identification or verification may be present on the security document.

[0150] The safety element contains bio-based calcium carbonate filler, particularly in the form of eggshell or seashell powder, either distributed or locally in one of its layers or integrally on the surface (especially by printing).

[0151] This bio-based calcium carbonate filler may be derived from the grinding and / or micronization of a single type of bio-based calcium carbonate (particularly from the eggshells of a single bird species or the shells of a single type of mollusc). Alternatively, the bio-based calcium carbonate filler may comprise a mixture of at least two different types of bio-based calcium carbonate. Different types of bio-based calcium carbonate differ in their morphological characteristics, as will be evident in the examples below.

[0152] The substrate 11 of this document can be a fibrous or polymeric substrate, or a paper-polymer hybrid substrate. It can, for example, comprise a substrate made of a bio-based polymeric material, which may or may not contain reinforcing fibers.

[0153] As a variant, the security document does not contain specific security elements, but instead has an inner layer or printed surface containing bio-based calcium carbonate filler. In the case of a surface layer, the security document contains printing using non-acidic inks, which prevents the degradation of calcium carbonate. The calcium carbonate filler can be integrally integrated into the corresponding layer. In these cases, identification or verification can be performed on the entire security document or only a portion thereof by cutting a section of the security document or by removing a pre-cut section of the document.

[0154] In addition to its ability to identify or verify characteristic markers for documents or articles, this bio-based calcium carbonate filler can be used for its various properties. It can be used as an opaque filler to make layers of security elements or documents opaque or to form specific patterns. This opacity can be localized or generalized, depending on the distribution of the filler. It can be used in the case of eggshell powder due to its porous properties, which particularly facilitates ink drying or improves the properties of the substrate. It is also noteworthy that, under certain conditions, it can improve the mechanical properties of the substrate, especially in the case of eggshell powder at a mass ratio of 5% or greater.

[0155] In one variant, the invention also relates to oil-based inks, particularly gravure printing inks dried by oxidation, which can be used as safe inks and contain bio-based calcium carbonate fillers. This ink can have the dynamic viscosity described above and / or be deposited on the surface of a substrate by the printing method described above.

[0156] In addition to bio-based calcium carbonate fillers, the ink may also contain at least one coloring pigment.

[0157] The safety product may include additional safety features for additional first, second, or third level of safety.

[0158] Figure 2The block diagram illustrates the steps of an embodiment of the identification and / or verification method according to the present invention.

[0159] First, in order to perform an analysis of a safety article containing safety elements, in an optional first step 100, a predetermined portion of the safety document is extracted, particularly the safety elements or cuttable or detachable portions of the safety document, to provide the safety article to be analyzed. This first step is only necessary when the analysis is not performed on the entire safety document.

[0160] In the optional second step 110, the safety article is incinerated at a selected incineration temperature that allows the organic matter to decompose and preserves the mineral portion by protecting the bio-based calcium carbonate from possible thermal decomposition into CaO and CO2. Preferably, this temperature is less than or equal to 420°C.

[0161] In the third step 120, one or more markers representing bio-based calcium carbonate filler in the safety article or its ash (depending on whether a previous incineration step has been performed) are probed or analyzed.

[0162] The one or more markers may represent:

[0163] - The content of bio-based materials, particularly by analyzing the carbon-14 isotope content in the ash after incineration in step 110, which is determined according to standard ASTM D6866-22, and / or

[0164] - One or more morphological features of bio-based calcium carbonate fillers, particularly representing a predetermined type of bio-based calcium carbonate or a mixture of predetermined types of bio-based calcium carbonate. These one or more morphological features may be one or more crystallographic, ultrastructural, shape, and / or porosity characteristics of the calcium carbonate in the bio-based calcium carbonate filler.

[0165] The one or more markers may include one or more markers representing the following:

[0166] - The layered structure of calcium carbonate, a characteristic morphological feature of calcium carbonate derived from seashells, is particularly easily identifiable in microscopic images, and / or

[0167] - Porous structure, which is a characteristic morphological structure of calcium carbonate derived from eggshells, and can be easily identified in microscopic images.

[0168] In the case of one or more markers representing a layered structure, the markers may include one or more characteristics of the layered structure, particularly the average density and / or average thickness of the layers. Each type of shell contains a layered structure with its own characteristics. The determination of morphological characteristics indicating the shell type makes it possible to distinguish the type of shell from which all or part of the filling originates. The one or more markers can be used to distinguish the shells of oysters, mussels, Saint-Jacques, scallops, whelks, cockles, sea snails, clams, cockles, razor clams, abalone, razor clams, limpets, scallops, cockles, or cherry clams, and more particularly the Saint-Jacques shells of oysters and mussels.

[0169] In the case of one or more markers representing a porous structure, the markers may include one or more characteristics of the porous structure, particularly porosity, pore shape, average pore size per unit area on a given plane, and / or pore density. Each type of bird forms an egg with a shell that exhibits a porous structure with its own characteristics. These one or more markers can be used to distinguish eggshell powder from different birds (particularly hens, quails, pheasants, turkeys, ostriches, geese, pigeons, or guinea fowl). One or more markers representing the presence of eggshell powder may be the presence of a porous structure having an average pore diameter between 20 nm and 500 nm, more preferably between 40 nm and 400 nm, measured particularly by analyzing images of the powder.

[0170] When investigating or analyzing morphological features, it can be done with or without pre-incineration, particularly through visualization using an electron microscope or other microscopes. The analysis of morphological features can be based on a cross-section of the safety article. The analysis of morphological features can be performed by acquiring images, particularly using an electron microscope or optical microscope at a magnification that allows visualization of calcium carbonate particles, and by using computer image analysis algorithms to analyze the acquired images.

[0171] Step 120 may include probing or analyzing at least two of the markers, particularly the content of bio-based materials in the ash and one or more morphological characteristics.

[0172] The method may then include step 130 of identifying and / or verifying a safety article by comparing one or more probed or analyzed markers with one or more reference information. The reference information may include information regarding the presence of bio-based calcium carbonate, a reference content of bio-based calcium carbonate, a reference mass ratio of bio-based calcium carbonate or one or more types of bio-based calcium carbonate, a reference morphological characteristic of bio-based calcium carbonate or one or more types of bio-based calcium carbonate, information on reference values ​​or ranges of reference values ​​representing the morphological characteristics of bio-based calcium carbonate or one or more types of bio-based calcium carbonate, and information regarding the presence of that one or more types of bio-based calcium carbonate in a reference bio-based calcium carbonate filler and / or the mass ratio of each type of bio-based calcium carbonate in the reference bio-based calcium carbonate filler. This identification and / or verification may be automated by a computer using a learning algorithm trained from identified and / or verified reference articles.

[0173] Therefore, multiple levels of safety can be achieved, ranging from simply identifying the presence of bio-based calcium carbonate to determining its complex composition. This allows for multiple levels of safety. For example, the first level could correspond to identifying the presence of bio-based calcium carbonate, the second level to determining the nature of the overall source of the calcium carbonate filler (eggshell or shell), and the third level to determining the bird or mollusc from which the calcium carbonate originates and its proportion.

[0174] The method may further include probing and / or analyzing the particle size distribution of the calcium carbonate filler, which represents the calcium carbonate filler particularly by means of obtaining it through grinding and / or micronization; and determining its identity and / or authenticity at least based on a comparison of the particle size distribution with one or more reference information, which includes information on the particle size distribution of the calcium carbonate filler or information on the methods of obtaining the calcium carbonate filler.

[0175] Example 1 (Determination of bio-based material content in various calcium carbonate powders)

[0176] Carbon-14 isotope content was analyzed according to method ASTM D6866-22 to infer the bio-based material content in calcium carbonate powder samples from various sources. The sample composition and analytical results are given in the table below.

[0177]

[0178] As can be clearly seen from the table above, the bio-based material content according to method ASTM D6866-22 is a marker that adequately represents the bio-based origin of calcium carbonate powder. This is because mineral-derived or precipitated calcium carbonate has a bio-based material content of 1%, while calcium carbonate powder derived from biological materials has a bio-based material content of greater than 95%.

[0179] Example 2 (Mineral-derived calcium carbonate)

[0180] Below is a formulation example of a pigmented couche for coated paper, with a deposition rate of approximately 25 g / m³. 2 :

[0181] For a 4000L coating material:

[0182] Starch (Collofilm MS00): 185 kg dry weight

[0183] Kaolin 7A: 1437 kg dry weight

[0184] CaCO3 (Hydrocarb 90 from Omya): 1751 kg dry weight

[0185] Dispersant (Polysel S): 2 kg dry weight

[0186] Colorant (Violet BB 200%): 0.08% dispersion in 35L

[0187] Optical brightener (Globrite BBU liq): 11 kg dry weight

[0188] Adhesive (Latex DOW 950): 346 kg dry weight

[0189] Smoothing additive, calcium stearate (Nopcote C104): 21 kg dry weight

[0190] The viscosity of the coating material is adjusted downward by diluting it with water, with the goal of achieving a final dry extract of 50-52%.

[0191] In this formulation, the milled mineral calcium carbonate filler constitutes 47% of the coating material by dry weight and 85% of the total mineral fraction. The resulting coating material is incinerated at approximately 400°C, and the carbon-14 isotope content is analyzed according to method ASTM D6866-22 to infer the bio-based material content in the ash. The determined bio-based material content in the ash is less than 1% by mass.

[0192] Example 3 (Bio-based calcium carbonate)

[0193] This formulation is the same as that of Example 1, but the milled mineral calcium carbonate filler is replaced by an equivalent amount of eggshell powder obtained through micronization. The eggshell powder used has a particle size of less than 30 μm. The result is a lower whiteness of the coating, but the calcium carbonate source can be utilized in more natural coated paper series, for which it is common practice to provide a lower whiteness range of the blanc cassé type.

[0194] The coating material obtained from this combination can be deposited on the surface or as an internal layer. It is noted that due to the microporous structure of the eggshell powder, ink achieves better printing on this coating material and drying is improved. Furthermore, the coated paper can be verified by analyzing the ash content. For this purpose, the coating material was incinerated as described in Example 1 to infer the content of bio-based materials in the ash. The determined content of bio-based materials in the ash was approximately 99% by mass. This analysis of the bio-based material content thus constitutes a good way to verify / identify eggshell powder.

[0195] It was also determined that the eggshell powder contained identifiable magnesium, while this was not the case with mineral calcium carbonate.

[0196] The bio-based material content of the St-Jacques shell powder was also measured. The bio-based material content in the ash was determined to be approximately 99% by mass. This analysis of the bio-based material content thus constitutes a good way to verify / identify St-Jacques shell powder.

[0197] Furthermore, it was determined that shell powder (especially oyster shell powder) may contain identifiable silicon, sodium, aluminum, and / or chlorine, while this is not the case for mineral calcium carbonate.

[0198] Furthermore, it is known that birds produce eggs with shells of different structures, and that mollusks have shells of different structures. Therefore, by studying the morphological characteristics of calcium carbonate powder, one or more types of calcium carbonate in the ash can be inferred, thereby inferring the composition of the powder to be compared with reference information corresponding to identification or verification marks.

[0199] Example 4

[0200] The obtained paper has a basis weight of 80-85 g / m². 2 The composition of banknotes was studied on a formette.

[0201] In this study, the fibers were refined before introducing the mineral filler using conventional methods. All the papermaking boards used below were manufactured using the same method, with only the composition of the mineral filler varying according to the table below. The eggshell powder used had a particle size of less than 30 μm.

[0202]

[0203] Application standards:

[0204] - CIE Whiteness: ISO 11475:2017

[0205] - ISO whiteness: ISO 2470-1:2016

[0206] Yellowness index: DIN 6167

[0207] - L a and b ISO / CIE 11664-4:2019

[0208] - Opacity: ISO 2471:2008.

[0209] Handmade paperboard F33476 appears less white than handmade paperboard F33477, and its opacity is also lower (-1.6 points) for the same weight percentage of calcium carbonate used. This is related to the organic portion present in the eggshell, which does not contribute to the paper's opacity.

[0210] Both types of calcium carbonate produce less opacity compared to titanium dioxide. However, by replacing a significant portion of the titanium dioxide with eggshell powder, the whiteness level can be made close to that of the reference handmade paper template F33475 containing only titanium dioxide, with opacity only 2 points lower.

[0211] Example 5

[0212] In this study, for handmade paperboard F33510 to F33512, the mineral filler was introduced during the refining step, and for handmade paperboard F33513 to F33516, the mineral filler was introduced along with the fibers prior to the refining step. The eggshell powder used had a particle size of less than 30 μm.

[0213] Advantageously, the strong mechanical stress applied during the refining step allows for better dispersion of the mineral filler, and even further micronization of it.

[0214] Other manufacturing characteristics are the same.

[0215]

[0216] Therefore, it can be deduced that two parts of eggshell filler can be used to replace one part of TiO2 while maintaining the same level of opacity.

[0217] Example 6

[0218] Figure 3 The images show photographs of eggshell powder at various magnifications, taken with a scanning electron microscope.

[0219] Pore ​​200 is clearly visible in these photos. Mineralized calcium carbonate powder does not show any porosity.

[0220] Therefore, the presence of porous structures can be used to identify whether calcium carbonate powder originates from eggshells. The characteristics of these porous structures can also be determined, particularly the crystallographic structure or average pore size of the eggshell powder particles. These characteristics allow for the differentiation of various types of eggshells that form the powder.

[0221] Example 7

[0222] Figure 4 The images shown are photographs of St-Jacques shell powder at various magnifications, taken with a scanning electron microscope.

[0223] The layered structure is clearly visible in these photographs. These layers are not visible in mineral calcium carbonate powder.

[0224] Therefore, the presence of layered structures can be used to identify whether calcium carbonate powder originates from seashells.

[0225] Eggshell powder and seashell powder can also be distinguished by observing porous or layered structures, or by identifying mixtures and the proportions of various types within the mixture.

[0226] Example 8

[0227] Figure 5 The images show photographs of mussel shell powder at various magnifications, taken with a scanning electron microscope.

[0228] This layered structure differs from the layered structure of St-Jacques shell particles.

[0229] Therefore, the calcium carbonate powder from St. Jacques shells and mussel shells can be distinguished by analyzing their layered structure. The same applies to other shells with a different layered structure.

[0230] Example 9

[0231] In this study, several handmade papermaking plates were prepared. The only difference between these handmade papermaking plates lies in the composition of their powdered mineral fillers. Their optical properties are given in the table below.

[0232]

[0233] ΔE was calculated for each powder relative to a composition having 5% dry weight TiO2.

[0234] This table shows that St-Jacques shell powder is comparable to mineral calcium carbonate powder in terms of whiteness and opacity. Oyster shell powder has comparable whiteness to eggshell powder. However, oyster shell powder has a higher degree of opacity than mineral calcium carbonate, eggshell powder, and St-Jacques shell powder.

[0235] Example 10

[0236] Multiple handmade papermaking plates were prepared. These plates contained 5%–10% by mass of St-Jacques shell powder. A reference material containing 5% by mass of TiO2 was also prepared. Otherwise, this reference material was identical to the handmade papermaking plates. Their optical properties were determined.

[0237]

[0238] The corrected opacity corresponds to the opacity that takes into account the difference in basis weight. It corresponds to the opacity measured independently of the basis weight of the paperboard used for handmade papermaking.

[0239] This study shows that increasing the mass percentage of St-Jacques shell powder does not affect ISO whiteness or corrected opacity, which remains below the corresponding parameters of reference F33536.

[0240] Furthermore, using St-Jacques shell powder instead of TiO2 does not reduce the mechanical properties of the paper, because the tear index and the number of folds before breakage are on the same order of magnitude.

[0241] This invention is not limited to the embodiments just described. Other types of bio-based calcium carbonate besides those mentioned above can be used, as long as they are identifiable and have inherent properties different from those of mineral-derived calcium carbonate.

[0242] Example 11

[0243] Figure 6 A photograph of a cross-section of a safety device, taken using a scanning electron microscope, is shown. Specifically, [the image shows the image of the device]. Figure 6 The cross-section of the ink was used to detect bio-based calcium carbonate present in the ink.

[0244] The pores 300, indicating the presence of eggshell powder, are clearly identifiable in a photograph of the side (i.e., cross-section) of the safety product. The powder of mineral calcium carbonate does not exhibit any porosity.

[0245] Therefore, the presence of porous structures can be used to identify whether calcium carbonate powder originates from eggshells. The characteristics of these porous structures can also be determined, particularly the crystallographic structure and / or average pore size of the eggshell powder particles. These characteristics allow for the differentiation of various types of eggshells that form the powder.

[0246] Similar analyses can be performed by identifying the presence of layered structures indicative of shell powder. Likewise, the morphological characteristics of the shell powder, such as the average thickness of the layers and / or crystallographic structure, can be determined more precisely, thereby identifying the source in various types of shells.

[0247] This cross-sectional analysis thus allows for the precise identification of one or more sources of calcium carbonate in safety products, and, if necessary, the inference of verification or identification information.

Claims

1. A method for identifying and / or verifying a safety product, the method comprising detecting and / or analyzing (120) one or more markers representing the presence, content and / or morphological characteristics of a bio-based source of calcium carbonate filler in at least a portion of the safety product, and determining the identity and / or authenticity of the safety product at least based on a comparison of the one or more markers with one or more reference information (130).

2. The method of claim 1, wherein the detection and analysis includes detection and analysis methods different from spectroscopic methods.

3. The method according to claim 1 or 2, comprising, in particular, incinerating (110) at a temperature less than or equal to 420°C, prior to probing and / or analyzing (120) the one or more markers representing the presence and / or morphological characteristics of the bio-based calcium carbonate filler, the probing and / or analysis being performed based on the ash produced by the incineration.

4. The method according to claim 1 or 2, wherein the morphological characteristics of the calcium carbonate filler are detected and / or analyzed on at least a portion of the cross-section of the safety article.

5. The method according to claims 1-4, wherein the one or more markers include markers representing the content of bio-based material, said markers being particularly carbon-14 isotope content determined according to standard ASTM D6866-22.

6. The method of claim 5, wherein at least one of the one or more reference information comprises a content of more than 1%, more preferably more than or equal to 2%, more preferably more than or equal to 10%, more preferably more than or equal to 50%, or more than or equal to 90% of the bio-based material.

7. The method according to any one of the preceding claims, wherein the one marker or at least one of the plurality of markers represents one or more morphological features of the bio-based calcium carbonate filler or a portion thereof.

8. The method according to any one of the preceding claims, wherein the one or more markers comprise one or more markers representing a layered structure of calcium carbonate, the layered structure being a characteristic morphological structure of calcium carbonate derived from shells, particularly the average density and / or average thickness of the layers.

9. The method according to any one of the preceding claims, wherein the one or more markers comprise one or more markers representing a porous and / or permeable structure, the porous and / or permeable structure being a characteristic of the morphological structure of calcium carbonate derived from eggshells, particularly porosity, pore shape, average pore size per unit area on a given plane, and / or pore density.

10. The method according to any one of the preceding claims, comprising detecting and / or analyzing at least two markers, one of which represents the presence of the bio-based calcium carbonate, particularly the presence and / or content of the carbon-14 isotope, and the other represents the morphological characteristics of the bio-based calcium carbonate filler, particularly the presence and / or morphological characteristics of the layered or porous structure.

11. The method according to any one of the preceding claims includes detecting and / or analyzing one or more markers representing a mixture of at least two different types of bio-based calcium carbonate, particularly derived from eggshells of different birds, shells of different mollusks, or a mixture of one or more types of eggshells and one or more types of shells.

12. The method according to any one of the preceding claims, wherein the step of detecting and / or analyzing at least a portion of the article comprises determining the presence of a bio-based calcium carbonate filler and detecting and / or analyzing markers representing the composition of the bio-based calcium carbonate filler, particularly the properties of one or more types of calcium carbonate fillers in the composition of the bio-based calcium carbonate filler and their mass proportion in the composition of the bio-based calcium carbonate filler, and determining the identity or authenticity of the article comprises comparing the determined one or more markers with reference information, and inferring the identity and / or authenticity of the article when the one or more markers correspond to the reference information.

13. The method according to any one of the preceding claims, additionally comprising detecting and / or analyzing the presence and / or mass proportion of compounds present in the bio-based filler, particularly magnesium, silicon, sodium, aluminum or chlorine.

14. The method according to any one of the preceding claims, wherein the security article is a security document, particularly a banknote, which is particularly made of paper and / or polymers, packaging material or additional packaging material, coated paper, payment card, and the portion of the security article on which the probing and / or analysis is performed is particularly integrated into a security element of the security document, which is particularly removable, pre-cut or to be cut, or the security article is a security element particularly integrated into a security document.

15. A safety element (12) to be integrated into a safety document (10) particularly suitable for implementing the method according to any one of the preceding claims, comprising at least one bio-based calcium carbonate filler.

16. The safety element of claim 15, wherein the bio-based calcium carbonate filler comprises eggshell powder and / or seashell powder, particularly at least one type of bio-based calcium carbonate powder, or a mixture of different types of bio-based calcium carbonate powder.

17. A security document (10) particularly suitable for implementing the identification and / or verification methods described above, comprising a multi-layer structure including at least one inner layer of the security document, the inner layer comprising a bio-based calcium carbonate filler and a surface protective layer.

18. A security document (10) particularly suitable for implementing the identification and / or verification methods described above, comprising a surface layer and a print of ink on the surface layer, the print and / or the surface layer comprising a bio-based calcium carbonate filler, the print ink having a pH greater than or equal to 6, preferably greater than or equal to 7 when it is aqueous.

19. The security document of claim 17 or 18, wherein the layer comprising bio-based calcium carbonate filler comprises a mixture of titanium dioxide filler and bio-based calcium carbonate filler, the calcium carbonate filler being configured to form an opaque filler for the security document together with the titanium dioxide filler.

20. The security document according to any one of claims 17-19, wherein the bio-based calcium carbonate filler is integrally integrated into a layer comprising a synthetic hydrocarbon polymer, the synthetic hydrocarbon polymer being at least partially derived from plant resources, also referred to as a bio-based polymer, particularly a bio-based latex.

21. The security document according to any one of claims 17-20, wherein the bio-based calcium carbonate filler is integrally integrated into a layer comprising a fibrous substrate comprising cellulose and / or hemicellulose fibers and / or vessels extracted from broadleaf trees, particularly at least one of the following species: birch, elm, chestnut, oak, eucalyptus, beech, styrax, purple privet, poplar, tulip tree, preferably eucalyptus.

22. The security document according to any one of claims 18-21, wherein the layer containing bio-based calcium carbonate filler comprises more than 1% dry mass, more preferably more than 2% dry mass, and even more preferably more than 4% dry mass of bio-based calcium carbonate relative to the total dry matter mass of the inner layer.

23. Oil-based printing inks containing bio-based calcium carbonate fillers.

24. The ink according to claim 23, wherein the ink is a security ink, and the security ink together with the object on which the ink is printed forms a security article suitable for implementing the identification and / or verification methods as described above.

Images