EP1446528B1 - Sicherheitspapier und sicherheitsartikel - Google Patents

Sicherheitspapier und sicherheitsartikel Download PDF

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Publication number
EP1446528B1
EP1446528B1 EP01985333A EP01985333A EP1446528B1 EP 1446528 B1 EP1446528 B1 EP 1446528B1 EP 01985333 A EP01985333 A EP 01985333A EP 01985333 A EP01985333 A EP 01985333A EP 1446528 B1 EP1446528 B1 EP 1446528B1
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EP
European Patent Office
Prior art keywords
fibres
security
paper
article according
security article
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP01985333A
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English (en)
French (fr)
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EP1446528A1 (de
Inventor
Jakob Grob
Birger Tiberg
Christoph Kocher
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Landqart AG
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Landqart AG
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Priority to AT01985333T priority Critical patent/ATE324489T1/de
Publication of EP1446528A1 publication Critical patent/EP1446528A1/de
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Publication of EP1446528B1 publication Critical patent/EP1446528B1/de
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/40—Agents facilitating proof of genuineness or preventing fraudulent alteration, e.g. for security paper
    • D21H21/44—Latent security elements, i.e. detectable or becoming apparent only by use of special verification or tampering devices or methods
    • D21H21/48—Elements suited for physical verification, e.g. by irradiation

Definitions

  • the present invention relates to security paper and security articles in general, the forgery of which shall be hampered or rendered impossible through one or more security elements.
  • the present invention relates to security articles characterised by at least one security element comprising at least one photoluminescent segment which is characterised by a linearly polarised photoluminescence and/or linearly polarised absorption.
  • the present invention also relates to a method to produce such security articles and a method to use the latter.
  • security elements can be employed, which have the purpose to prevent or stifle forgery of those objects by unauthorised persons (R. van Renesse “Optical Document Security” (1997), Artech House, Boston).
  • security elements are also used to mark the authenticity or validity of object, or generally to enable or facilitate the identification of objects.
  • security threads or security strips which can consist of, among other things, a metal coated polymer, in security paper, especially for the application in banknotes and similar documents. When such security threads or strips are, for example, embedded in the security paper and the paper is subsequently printed, the thread or strips cannot be readily discerned in reflective light but immediately appear as a dark image when the document is viewed in transmitted light.
  • the areas printed with different colours are so small or so close together that they cannot be distinguished by the naked eye and, therefore, appear to the viewer as one uniform colour.
  • the microprint or the different colours can only be recognised with the aid of a magnifying glass or a microscope.
  • a similar security element is disclosed in GB-A-1,095,286 where the microprinted areas are letters or patterns.
  • Another security paper is described in US-A-4,897,300.
  • multiple security threads which are printed with different luminescent dyes are embedded in the security paper. The latter are colourless or have the colour of the paper and are, therefore, not or only hardly visible to the viewer. When excited, however, for example through irradiation with ultraviolet (UV) light, the security threads luminesce.
  • UV ultraviolet
  • the document describes security elements or segments incorporated into a paper or the like, which security elements show either linearly polarised photoluminescence or linearly polarised absorption. These security elements provide security paper and security articles in general which are characterised by secure, easily recognisable security elements. The document additionally describes security paper and security articles in general, the identification of which is enabled or facilitated through such security elements and it also describes the development of methods for the production of these security articles and the use of the latter.
  • US-A-6,035,914 discloses fluorescent dichroic fibers randomly incorporated within a media to provide an improved method for authentication and counterfeiting protection.
  • the dichroism is provided by an alignment of fluorescent molecules along the length of the fibers.
  • the fluorescent fibers provide an authentication mechanism of varying levels of capability.
  • the authentication signature depends on four parameters; the x,y position, the dichroism and the local environment. The availability of so many non-deterministic variables makes production of counterfeit articles (e.g., currency, credit cards, etc.) essentially impossible.
  • Counterfeit-resistant articles, an apparatus for authenticating articles, and a process for forming counterfeit-resistant media are also disclosed.
  • GB-A-2300596 discloses a composite material for counterfeit proof security documents, which has a transparent substrate incorporating fluorescent components which fluoresce UV light at different visible colours, where components are in form of coatings on substrate or are incorporated in it.
  • the security feature specifically comprises a transparent or translucent substrate and two fluorescent components which fluoresce UV light at different visible colours and a UV light absorber, e.g. given as titanium dioxide, the UV light absorber may be in the substrate or as a layer, and serves to prevent UV light entering the material.
  • the term security element relates to a, for example, shaped object that can have a variety of shapes, for example, but not only, fibre, thread, rod, tape, film, windows and/or combinations thereof.
  • the security element can be homogeneous and continuous and can be structured or patterned and can comprise multiple individual elements, zones or pixels.
  • security article relates to objects, the forgery of which shall be hampered or rendered impossible through one or more security elements, or the authenticity or validity of which shall be marked through one or more security elements, which shall be identified by one or more security elements; for example, but not limited to banknotes, checks, stocks, bonds, identification cards, passports, drivers licenses, tickets, stamps, bank cards, credit cards.
  • security article shall include woven such as textiles and non-woven articles such as paper or foil.
  • security paper relates to security articles which substantially are made from paper. It particularly but not exclusively relates to non-woven, flat, fibre-containing data carriers.
  • the object is achieved by the technical features given in the characterising portion of the main claim. More particularly, the object is achieved by embedding the photoluminescent segment in a paper or paper-like structure composed of 30 to 99 percent in dry weight paper-fibres and 70 to 1 percent in dry weight filler and optionally further additives, complementing to 100 percent in total, wherein the filler has high scattering properties and/or high absorption properties in the spectral range used in particular for irradiation and/or also for detection of the photoluminescence.
  • additives may be the ones conventionally used for paper like e.g. binder, resin, surfactants, colorants, antifoaming agent, and additives to e.g. provide desired surface/printing properties etc.
  • the paper or paper-like structure is additionally substantially free of brightener and/or additives which itself have fluorescent properties in particular which itself show linearly polarised photoluminescence and/or linearly polarised absorption. In other words, such substances should not be excessively present in the matrix.
  • additives commonly used in the production of paper which comprise chromophores with fluorescent properties when irradiated with ultraviolet irradiation.
  • binders with particular resins exhibiting such properties detrimental to the present application.
  • many of the brighteners commonly used in the production of paper or paper-like structures are based on dyes which comprise chromophores which themselves have fluorescent properties. These additionally hamper the efficiency of the security elements.
  • One particular class of brighteners commonly used are stilbene-based brighteners which have pronounced fluorescent properties, and therefore these brighteners should not be present to the extend that they interfere with the desired security feature. If such substances are present in the matrix of the security article, this matrix exhibits a very bright appearance when irradiated with ultraviolet irradiation leading to a low contrast between the matrix and the security elements. Additionally, transfer between these fluorescent chromophores and the security elements may lead to a destruction of the polarisation efficiency as macroscopically detectable when e.g. looking at the irradiated security elements e.g. through a rotating polarization filter or observing the security elements in linearly polarised light.
  • the security article is characterised in that the filler has high scattering properties and/or high absorption properties in the spectral range used in particular for irradiation and/or also for detection.
  • the filler should be chosen such as to absorb as much of the incident polarised or not polarised radiation as possible.
  • titanium dioxide in its rutile and/or in its anatase modification proves to be of use as well as zinc oxides. A particularly pronounced beneficial effect is achieved when employing titanium dioxide in its rutile-modification.
  • the paper-fibres at least partially comprise synthetic-fibres like for example polypropylene-fibres, polyethylene-fibres, aramide-fibres, polyacrylonitrile-fibres and/or at least partially comprise natural raw material based fibres selected from the group of wood-fibres, cotton-fibres, grass-fibres, cellulose-fibres, viscose-fibres, lyocell-fibres, rayon-fibres.
  • synthetic-fibres like for example polypropylene-fibres, polyethylene-fibres, aramide-fibres, polyacrylonitrile-fibres and/or at least partially comprise natural raw material based fibres selected from the group of wood-fibres, cotton-fibres, grass-fibres, cellulose-fibres, viscose-fibres, lyocell-fibres, rayon-fibres.
  • At least one of the security segments characterised by linearly polarised absorption.
  • irradiation with e.g. ultraviolet light of rotating polarisation for example provided by an ultraviolet lamp which is covered by a rotating polarisation filter
  • the bright/dark effect can be observed very easily while using as little instrumentation as possible.
  • the security segment is characterised by a dichroic ratio of 2 or more in absorption and/or emission, preferably of 5 or more in absorption and/or emission, and even more preferably by dichroic ratio of 10 or more in absorption and/or emission.
  • dichroic ratios of more than 5 are useful.
  • the security segments may have various shapes such as fibres, threads, rods, tapes, films, windows, or a combinations thereof, and may be either be homogeneously distributed within the paper or paper-like matrix or may also be provided in particular arrangements to further beneficially enhance the bright/dark effect. Also possible are stripes extending substantially across the entire security article.
  • the security segment can be excited to photoluminesce through exposure to electromagnetic irradiation of a wavelength between 200 and 500 nm.
  • electromagnetic irradiation is particularly useful as sources for providing such light are quite cheap and may be used without any human noticing it unless some of these particular security elements with particular dyes are being brought near such light.
  • the carrier material carrying the photoactive dye must allow an incorporation of the dye leading to a macroscopic polarisation effect.
  • the carrier allows an oriented incorporation/embedding of the dye which means that it should usually have some structural orientational order which may be achieved by stretching for example.
  • this high orientational order is measurable e.g. by wide-angle x-ray diffraction, where the order should be characteriseable by a half width at half height of less than 25 degrees, preferably of less than 15 degrees, and even more preferably of less than 10 degrees.
  • the security segments may be made of a polymer carrier, preferably polyethylene, polypropylene, polycarbonate, polyester, polyamide, polyacrylonitrile, polyvinyl alcohol, aramide, or other materials e.g. used in the field of textile fibres, or mixtures thereof, dyed with a photoluminescent dye.
  • said security segments may be made of a cellulose-based carrier dyed with a photoluminescent dye.
  • This carrier is of particular advantage as fibres or other security elements made of such carrier provide surface properties allowing for firm and easy embedding into a common, cellulose-based paper matrix.
  • Cellulose-based elements shows the same behaviour with respect to hydrogen bonding as the material being used for the paper matrix, thus ensuring tight attachment to this particular paper matrix.
  • security segment may be made of viscose, or lyocell.
  • the elements may e.g. be in the form of fibres with a length of 0.5 to 25 mm, preferably of 1.0 to 10 mm at 1 to 50 dtex, preferably at 5 to 20 dtex, which fibres may be incorporated/embedded into a paper matrix.
  • security elements in the form of threads/stripes extending over substantially the entire security article with a width in the range of 0.5 to 20 mm and a thickness of in the range of 5 ⁇ m to 100 ⁇ m.
  • textile fibres with more than 1 dtex.
  • lyocell-fibres as obtained by the NMMO-process, such as those manufactured by for example Lenzing.
  • Particularly distinct effects can be achieved if the fibres are as little distorted as possible and show as little fibrillation as possible.
  • a high transparency of the fibres is of advantage as well.
  • the security elements may also be patterned or otherwise modified after the dying/stretching process, for example to destroy the polarisation effect in certain regions. This may be achieved by methods like local heating such that the structural order in the heated region gets lost due to melting leading to isotropic distribution of dye in these regions(so called embossing). Another possibility is to irradiate selected regions of the dyed security elements with high-energy (ultraviolet) irradiation leading to destruction of the chromophores and subsequent bleaching of the irradiated regions. Both methods allow the design of particular forms, stripes, characters, logos, etc. on the security elements adding to the securing effect of such elements.
  • the paper or paper-like structure is composed of 80 to 97 percent in dry weight fibres and 20 to 3 percent in dry weight filler and optionally additives, complementing to 100 percent in total.
  • the present invention additionally concerns the application of a security article as described above for objects the forgery of which shall be made difficult or impossible, for objects the authenticity and/or validity of which shall be marked, for objects the identification of which shall be enabled and/or facilitated and/or for an object selected from the group consisting of banknotes, checks, stocks, bonds, identification cards, passports, drivers licenses, tickets, stamps, bank cards and credit cards.
  • the present invention also concerns processes for the production of security articles, characterised in that at least one security segment is dyed with a photoluminescent dye prior or after its structural orientation, and is then embedded in a paper-like matrix.
  • the security element/segment may subsequently also be treated in certain regions to selectively modify or erase the polarisation effect in these regions.
  • security elements in the paper-like matrix may be achieved by using conventional paper-making techniques. It is, however, also possible to introduce the security elements only in certain layers, preferentially in the surface layers of the security article (e.g. multi-layer paper or data carrier) to prevent that a large number of security elements is buried within the security article without substantially giving rise to the desired polarisation effects.
  • a multi-layer paper may for example be produced by laminating 2 flow boxes immediately behind the 2 vats/cylinders, where only one of them comprises polarising fibres. It may additionally be possible to incorporate fibres in a particular coating covering a security article.
  • the present invention is based on our finding that photoluminescent materials which are characterised by linearly polarised photoluminescence or linearly polarised absorption or both and can be made in a form according to the present invention, can be employed to produce security elements that can be used for the production of security paper and security articles in general.
  • security paper and other security articles according to the present invention are characterised by a high security against counterfeiting and are characterised by authenticity marks that can easily be recognised.
  • such materials can be brought in an appropriate shape and be used for the production of security elements that can be employed for the production of security papers and other security articles.
  • the security element can have a variety of shapes, for example, but not only, fibre, thread, rod, tape, film and/or combinations thereof. Further, security elements in more complex shapes can be used, for example, but not only, logos, letters, figures, numbers, etc.
  • a significant characteristic for a security article according to the present invention is that the security element comprises at least one photoluminescent segment which is characterised by a linearly polarised photoluminescence or that the security element comprises at least one segment which is characterised by a linearly polarised absorption, and that the security element is embedded in the security article.
  • the shape and the size of these segments can vary from case to case and that the measurement of absorption and emission polarization can be performed with a variety of experimental set-ups, for example conventional spectrometers, microscopic methods, etc. If, for example, a fibre based on the some photoluminescent material of a diameter of 0.5 mm and a length of 20 cm that is formed into a circle is considered to be a combination of many segments, because polarization measurements exhibit a strong positional dependence. Of course, also this element exhibits optical effects, analogous to the ones described above and according to the present invention, which can be described by a combination of individual segments.
  • the security elements in security articles according to the present invention comprise one or more luminescent dyes in suitable concentration and of suitable properties, i.e. which cause the polarization characteristics according to the present invention.
  • dyes usually dyes only have anisotropic polarisation characteristics in absorption or emission if also the underlying chromophore is structurally anisotropic.
  • Suitable luminescent dyes can, for example, be found in EP-A-0 889 350 and EP-A-0 933 655 and in the patent applications and publications cited therein.
  • dyes can be used: 1,4-Bis(5-phenyl-2-oxazolyl)benzene (POPOP, Fluka 15150), 4,4'-Bis(2-benzoxazolyl)stilbene (Uvitex OB ONE, Aldrich 368590), Pergasol Flavin 7G (available also under the trade name Pergasol Gelb GA from Ciba Speciality Chemicals or under the trade name Solophenylflavin 7 GFF; C I Direct yellow 96), Tinopal ABP liquid (particularly suitable for cellulose based elements and for elements based on polar synthetic carrier, also available under the trade name Blankophor P, Bayer, Leverkusen; C I fluorescent brightener 220), , Oxonol 595 (Aldrich 44052-3), Keystone Fluorescent Yellow 10G (available through Keystone Aniline Corp, Chicago, IL 606112).
  • POPOP 1,4-Bis(5-phenyl-2-oxazolyl)benzene
  • azo-dyes such as Congo Red and Sudan Red B are particularly suitable for the described effect in absorbance.
  • the choice of these dyes for particular carrier materials for the security elements can be made by the person skilled in the art based on the usual consideration of the compatibility/polarity of the dye and the carrier.
  • additional suitable dyes can for example be found in the field of laser dyes and dyes for fluoroimmunoassays.
  • Suitable luminescent dyes can be found among optical brighteners as used in textile or paper industry. Many optical brighteners have polarisation characteristics as requested according to the present invention and can therefore be used for dying the security elements. Possible products are for example Blankophor (R) P (liquid), which is a derivative of 4,4'-Diamino-stilbene-2,2'-disulfonic acid (available from Bayer, Leverkusen). This optical brightener gives blue fluorescent effects and is particularly suited for dying elements based on cellulose, namely lyocell, rayon or viscose threads, fibres, etc and those based on polar synthetic polymers such as aramide, polyamide, polyvinyl alcohol and the like.
  • Blankophor (R) P liquid
  • R 4,4'-Diamino-stilbene-2,2'-disulfonic acid
  • This optical brightener gives blue fluorescent effects and is particularly suited for dying elements based on cellulose, namely lyocell, rayon or viscose threads, fibres, etc
  • optical brightener is Uvitex OB-One, which is a 4,4'-bis(benzoxazol-2yl)stilbene (available from Ciba Speciality Chemicals). This optical brightener also gives blue fluorescent effects after excitation in the ultraviolet range and is particularly useful for dying elements based on a less polar polymer carrier (polypropylene, polyethylene etc.).
  • Stilbene based textile dyes or other textile dyes are generally given by stilbene based textile dyes or other textile dyes.
  • the stilbene unit leads to the anisotropic absorption or emission properties due to its anisotropic geometry.
  • other dyes used in textile industry with an anisotropic chromophore not based on the stilbene-unit can be advantageously used.
  • One particular dye used in textile industry which is particularly useful for dying security elements based on cellulose, namely lyocell, rayon or viscose, is available under the name Pergasol Gelb 8 GA, which is a stilbene-dye (available from Ciba Speciality Chemicals).
  • this dye can be excited in the ultraviolet range leading to emission of yellow radiation. Absorption as well as emission can be polarised.
  • Suitable dyes are inorganic transition metal-ion dyes which also have polarised absorption and/or emission properties.
  • the material does not have some surface layer/coating which disturbs or even annihilates the polarisation effects when a dye is incorporated/embedded/adsorbed or which prevents or hampers oriented embedding/adsorption.
  • final coatings are quite common, and these may have to be washed off prior to the dying process.
  • the so-called avivage should preferably be removed if the used material interferes with the desired orientation effect.
  • these layers may contain brighteners, colorants and other additives which can have the same detrimental effect as the brighteners and additives possibly present in the matrix of the security article.
  • Carrier material for the security elements is a carrier material for the security elements
  • the carrier material carrying the dye must allow an incorporation of the dye leading to a macroscopic polarisation effect, which can be observed by the naked eye or by a particular detector.
  • the carrier allows an oriented incorporation/embedding of the dye which in turn means that it should usually have some structural orientational order which may be achieved by stretching for example.
  • This high orientational order is measurable e.g. by wide-angle x-ray diffraction, where the order should be characteriseable by a half width at half height of less than 20 degrees, preferably of less than 15 degrees, and even more preferably of less than 10 or even 7 degrees.
  • Another possible mechanism allowing for oriented adsorption of the dye on the surface of the security carrier may be a particularly orientationally structured surface of said carrier.
  • polystyrene resin suitable in the context of the present invention and also generally for producing elements with polarised emission or absorption are the following:
  • the carrier polymer allows for the fabrication of blends comprising at least one PL dye and at least one carrier polymer by melt-mixing, which can be shaped by melt-processing. Production of the polymer carrier can however also be carried out by different methods like solution casting or spinning.
  • semicrystalline polyolefins such as polyethylene polypropylene, for example, are useful as carrier polymer in preferred embodiments of the present invention.
  • LLDPE linear low-density polyethylene
  • security elements can be manufactured, according to the present invention, that exhibit unusually high dichroic ratios in absorption.
  • Other examples of semicrystalline or amorphous polymers that are preferably used as carrier polymer in preferred embodiments of the present invention, are polyvinylidene halides, polyesters, and polyamides, polyacrylonitriles, polyvinylalcohols, aramides, polycarbonates and so forth, and mixtures thereof.
  • copolymers can be used as the carrier polymer, for example ethylene/propylene copolymers and so forth.
  • the molecular weight of the carrier polymer employed may vary within wide limits.
  • Polymers having lower molecular weights have, as a rule, good melt processing characteristics. At the other hand, it is well known in the art, that the maximal achievable draw ratio usually increases with molecular weight. As another rule, linear polymers are used by preference on account of their high degree of orientability. The one skilled in the art should be deemed capable of selecting the right carrier polymer, depending on the envisaged application and the dye employed.
  • the orientation within the polymer can e.g. be achieved by drawing after or during the production process of the fibres/threads.
  • the dye can be incorporated into these fibres either prior to drawing or after, and the dye can either be introduced into the fibre by a diffusion or a solution process.
  • oriented polypropylene e.g. isotactic polypropylene, Polysciences; polypropylene Fina 3374; REO Flock&Faser, e.g. roh Stamms, 5mm, 17dtex
  • polyvinyl-alcohol e.g. Aldrich 36, 315-4 98-99 %, Mw 85000-146000
  • aramide fibres or threads are being used in lengths of between 0.5 to 20 mm, preferably of 1 to 5 mm, at 1 to 50 dtex, preferably at between 5 and 20 dtex.
  • cellulose based structures with suitable orientation include among others cellophane, lyocell, viscose, rayon etc. Viscose threads with lengths between 1 to 10 mm at 2 to 20 dtex are suitable.
  • products like Bocell Alkzo Nobel
  • Fortisan CERMAV
  • Tencel fibre and cut CERMAV
  • Flax Ramie
  • viscose polymeric all CERMAV.
  • certain Bocell, Fortisan, and Tencel fibres show high orientation and were found to be suitable for the present applications.
  • lyocell-fibres/threads as manufactured by Lenzing . These are available under the trade name Lenzing-Lyocell and show a high degree of orientation at little fibrillation and little crumpling. These fibres can be easily dyed leading to polarised absorption and/or polarised emission of the adsorbed/incorporated dyes and can therefore be used not only for the incorporation into the security articles according to the present invention but also for many other applications. These other applications may for example be in the field of cloth, textiles, garments, woven and non-woven labels, films, credit cards, etc.
  • the fibres should preferably be transparent in the visible range, and that the fibres should be free from defects and distortions such as kinks as much as possible.
  • the straight segments should be longer than the typical length for the detection of the polarisation effect. So in case of observation by the naked eye, which usually allows a resolution of about 10 ⁇ m, the majority of the straight segments should preferably be longer than this unit. If this is not the case, the bright/dark effect may not be readily recognised by the naked eye.
  • such fibres should be highly oriented (wide-angle x-ray scattering have width at half height of less than 10 degrees), should have a clean, i.e. smooth surface, should be free from defects and kinks i.e. should be straight, should have a length between 3 to 5 mm and a thickness in the range of 10 to 40 dtex, preferably of in the range of 17 dtex. It is also possible to mix natural carriers with polymeric substances as mentioned above and to extrude them together into their final form of a thread, rod, tape, film, etc.
  • the dyed security elements may be treated after the dying process by methods like embossing and/or by bleaching out certain regions using high-energy a radiation destroying the chromophores in these regions (so-called patterning).
  • the surface of polymer based fibres/threads or also the surface of polymer coated natural raw material based elements can be modified.
  • cellulose based fibres usually do not need this surface treatment as for example for the embedding of such fibres into common cellulose-based paper hydrogen bonding possibilities are inherently available in this carrier. Principally this is sometimes necessary to allow a better interaction (e.g. via hydrogen bonds) between the surface of the fibre/thread and the surrounding matrix of the security article/paper.
  • Possible methods of modification are fluorination (carried out in the liquid or in the gas phase), etching with sodiumnaphthalinate (immersion in a solution) or plasma-surface modification and the like.
  • Suitable methods for the preparation of security elements for the application according to the present invention can, for example, be found in EP-A-0 889 350 and EP-A-0 933 655 and in the Patent applications and publications cited therein.
  • the security elements or segments of such security elements for the application in security articles according to the present invention can be produced by the anisotropic deformation of ductile mixtures.
  • the dying can be carried out either prior to the deformation of the security elements to introduce the structural order necessary for the dyed security elements to exhibit polarising properties or the dye can be introduced into or onto the oriented carrier of the security element. Principally, different dying processes are possible, of which the particularly useful are diffusion based dying processes and solvent based dying processes.
  • the dye is dissolved in a suitable solvent (the choice of the solvent or mixture of solvents depending on the polarity of the dye and of the fibre/thread to be treated), the fibres are subsequently added and this mixture is then either kept still or stirred and/or heated and/or refluxed for a certain period of time.
  • a suitable solvent the choice of the solvent or mixture of solvents depending on the polarity of the dye and of the fibre/thread to be treated
  • the fibres are subsequently added and this mixture is then either kept still or stirred and/or heated and/or refluxed for a certain period of time.
  • the fibres/threads may have to be dried for several hours e.g. in vacuo prior to the dying process. After that the fibres/threads are removed (e.g. by using a filter) and washed once or repeatedly with either the same solvent or another solvent.
  • solvents like toluene, benzene, N-Methylpyrrolidone, xylene and the like or mixtures of these solvents can be used for the dying processes.
  • solvents like toluene, benzene, N-Methylpyrrolidone, xylene and the like or mixtures of these solvents can be used for the dying processes.
  • polar dyes and cellulose based matrices water can be used advantageously as the solvent but also other polar solvents are possible.
  • Another possible dying mechanism can be vapour deposition of the dye.
  • Lyocell Lenzing fibres water can be used and the dying process is preferably carried out that elevated temperatures like above 80 degrees Celsius washing the isolated dyed fibres two to three times using water of about the same temperature.
  • the resulting fibres show a high degree of polarisation in absorption as well as emission and can therefore be used also for other purposes than for incorporating/embedding into security articles/papers as claimed within this application.
  • security papers which comprise at least one security element that is comparable with the one disclosed here, apart, of course, from the linearly polarised photoluminescence, absorption or both.
  • security papers can be made, into which one or multiple photoluminescent threads or strips with properties according to the present invention are embedded. If a multitude of such threads or strips are used, they can, according to a preferred embodiment of the present invention, also exhibit different emission colours and can be arranged in certain patterns, for example, with a specific arrangement of their polar axis'.
  • the security elements are integrated into the substrate in the form of fibres. Also in this latter embodiment the use of security elements with different emission colours can be advantageous, and the fibres can exhibit different shapes; for example, they can be straight or curled, which leads to different optical effects.
  • the fibres which can be used in the present context are synthetic fibres as well as natural raw material based fibres.
  • natural raw material based fibres e.g. wood- based-fibres (chemical wood pulp), cotton-fibres, grass-fibres, cellulose-fibres, viscose-fibres, lyocell-fibres, rayon-fibres, and mixtures of these fibres can be used.
  • wood- based-fibres chemical wood pulp
  • cotton-fibres e.g. wood- based-fibres (chemical wood pulp)
  • cotton-fibres e.g. wood- based-fibres (chemical wood pulp)
  • grass-fibres e.g., grass-fibres
  • cellulose-fibres e.g., cellulose-fibres
  • viscose-fibres e.g., lyocell-fibres
  • the fibres are preferably milled to a length in the range of 0.4 to 4 mm, preferably to a length of in the range of 0.6 to 1.2 mm.
  • fillers can be used for the paper-like structure to carry the security element. Usually fillers are added due to their low price, and to produce certain properties like opacity, stiffness, printing properties etc. E.g. titanium dioxide either in its rutile or in its anatase modification as well as zinc oxide can be used, as well as zinc sulphide, lithopone (zinc sulphide and barium sulfate), caoline, silicates, carbonates and the like. To enhance the particular polarisation effects or rather not to disturb the polarising effects due to the security elements, the filler can be chosen such as to absorb as much of the incident polarised or not polarised radiation as possible.
  • titanium dioxide in its rutile or at anatase modification as well as zinc sulphide prove to be particularly useful.
  • rutile is used as filler or at least added to the filler in a sufficient amount of usually 1 to 2 % (this percentage, as mentioned above, sometimes preferentially being higher in case of the additional presence of certain resins, brighteners and the like in the matrix)
  • the paper-like structure appears completely dark when irradiated with ultraviolet irradiation which means that the incident light is completely absorbed by this filler.
  • organic or other inorganic ultraviolet absorbers into the matrix to achieve the same results, i.e. to eliminate all irradiated ultraviolet irradiation which is not harvested by a particular fibre. This leads to two effects which are particularly advantageous in this context:
  • the counts per second in the visible range are below 40 between 400 and 450 nm, below 40 to 15 in the range of 450 to 550 nm and below 15 between 550 and 700 nm.
  • This criterion can be used to adjust the content of e.g. rutile-filler.
  • the desired black appearance of the paper-like structure when irradiated with light thus increasing the contrast between the paper matrix and the security elements can be achieved very efficiently by the incorporation of organic substances commonly known as 'uv-absorbers' into or onto the paper matrix.
  • organic substances commonly known as 'uv-absorbers' into or onto the paper matrix.
  • Such substances can typically be found among the classes of benzophenones, benzotriazenes and benzotriazoles and are, eg., commercialised by Ciba Speciality Chemicals under the trade names 'Tinuvin' and 'Chimassorb'.
  • any other organic substance capable of undergoing the transition known to be responsible for the uv absorbing properties in the above-mentioned classes of uv absorbers are suitable.
  • any other substance showing considerable absorbance in the wavelength regime of interest can be considered suitable, such as common dyes and stains, eg. azo-derivatives or polymethin-derivatives.
  • the paper-matrix may contain other additives like e.g. binder, colorants, resins, surfactants, detergents, anti-foaming agents, etc which may be necessary in the production process of for particular properties of the paper matrix. These additional components are however minor components. Their possible influence on the general appearance of the paper matrix when irradiated with ultraviolet light or other light used for the excitation of the dye incorporated in the security elements has been discussed above.
  • the security article shall be a paper or paper-like article, it can be produced according to standard paper production technology. However, if dyed fibres have to be incorporated, these fibres should be added to the pulp just prior to starting the actual paper production process, i.e. after the milling process, in order to minimise introduction of defects into the security elements. Also possible is the incorporation of security elements in the form of threads according to the present invention by using a process as described in EP-A-59056.
  • the dying process should be carried out in case of polypropylene-fibres above 40 degrees Celsius, i.e. typically in arranged between 40 to 50 degrees Celsius. Usually rinsing does not seem to be necessary.
  • Example 3 Dying of lyocell/viscose fibres
  • the dying process improves for temperatures above 80 degrees Celsius and should be carried out at 90 to 95 degrees Celsius.
  • the rinsing process should also be carried out at elevated temperature of at least 80 to 90 degrees Celsius, and in the case of the brightener should be repeated at least twice.
  • Example 5 Dying of uniaxially oriented polypropylene films with Uvitex OB ONE
  • Example 6 Production of Poly(propylene)films with Uvitex OB ONE by melt-processing techniques
  • Poly(propylene) (i-PP Fina 3374, pellets) is blended with 0.05% w/w Uvitex OB ONE (Aldrich 368590) in a twin-screw extruder at a temperature of 180 °C.
  • the polymer/dye blend is extruded and melt-processed into a foil. Subsequent uniaxial tensile deformation of stripes of this film at 130 °C yields a product with the described effect with high contrast in fluorescence.
  • Example 7 Dying of Viscose fibres with Tinopal ABP liquid
  • Tinopal ABP liquid (Ciba special chemicals) are mixed with 110 ml water and heated to 80 °C.
  • a bundle of viscose fibres (Fortisan, Akzo) are immersed in the solution and the mixture is kept for 30 min. The bundle is subsequently removed from the solution, thoroughly washed with water and dried at ambient.
  • the obtained blend films exhibit the described effect with good contrast in fluorescence.
  • Poly(propylene) (i-PP Fina 3374) is blended with 0.5% w/w (Keystone Yellow 10G, Keystone Aniline Corp., Chicago; K Y 10G) in a twin-screw extruder at a temperature of 180 °C.
  • the extruded polymer/dye blend is melt-processed into a foil. Subsequent uniaxial tensile deformation of stripes from that foil at 130 °C yields a product exhibiting the described effect with recognisable contrast in fluorescence.
  • Example 9 Production of Poly(ethylene) films with Keystone Yellow 10G and Uvitex OB One
  • Poly(ethylene) (LLDPE, Dowlex 2340) is blended with 0.5% w/w (Keystone Yellow 10G, Keystone Anliline Corp., Chicago ; K Y 10G) and 0.05% w/w Uvitex OB ONE (Uvi, Aldrich 368590) in a twin-screw extruder at a temperature of 180 °C.
  • the extruded polymer/dye blend is melt-processed into a foil. Subsequent uniaxial tensile deformation of stripes from that foil at 130 °C yields a product exhibiting the described effect with good contrast in fluorescence.
  • Oxonol 595 (Aldrich 44052-3) are dissolved in 50 ml water. The solution is heated to 80 °C. A bundle of viscose fibres (Bocell, Akzo) are added and kept for 10 min. The bundle is subsequently removed from the solution, washed with water and dried at ambient. The obtained fibres exhibit the described effect with good contrast in absorbance (colourless to blue) as well as with recognisable contrast in photoluminescence (dark to dull red).
  • Example 12 Production of Poly(vinylalcohol) / Congo Red blend film
  • the quality of the dyed security elements is 1 to12 shall be summarised as follows:
  • Example No Matrix Dye(s) Effect Production method Quality 1 PP fibres Uvitex OB One PL Diffusion dying ++ 2 Viscose fibres Blankophor P PL Direct dying ++ 3 Viscose fibres Pergasolgelb 8GA PL/Abs Direct dying ++ 4 PP fibres POPOP PL Diffusion dying ++ 5 PP film uniaxially Uvitex OB ONE PL Diffusion dying +++ 6 PP Uvitex OB ONE PL Melt processing +++ 7 Viscose fibres Tinopal ABP liq PL Direct dying ++ 8 PP K Y 10G PL Melt processing + 9 LLDPE Uvi/K Y 10 G PL Melt processing ++ 10 Viscose fibres Congo Red Abs Direct dying +++ 11 Viscose fibres Oxonol 595 Abs/PL Direct dying ++ 12 PVA Congo Red Abs Solution casting +++
  • This pulp is then used in a standard paper production process using a cylinder mould machine or a foudrinier technique.
  • the paper produced has a basis weight of approx. 60 to 120 g/m2.
  • the paper shows pronounced bright/dark effect of the incorporated fibres.
  • a pulp according to one of the example is 13 or 14 or mixtures of these examples is used in a paper production process involving 2 cylinders.
  • One of the cylinder is running with a pulp without dyed fibres while the other one contains dyed fibres.
  • the two webs individually produced by the two cylinders are joined immediately behind the cylinder to form a laminate, one side of which shows the polarisation effects according to the invention, while the other side does not.
  • a pulp according to one of the examples 13 or 14 or mixtures of these examples is used in a paper production process involving 3 cylinders.
  • the three webs individually produced by the three cylinders are joined or couched immediately behind the cylinder to form a laminate, the top and the bottom side shows the polarisation effects according to the invention, while the centre ply does not.
  • example 15 - 16 - 17 can also be created whilst one of the middle layer shows the polarisation effects according to the invention, and not the top or bottom layer. This can be a special hidden security feature.

Claims (21)

  1. Sicherheitsartikel mit mindestens einem Sicherheitselement, umfassend mindestens ein photolumineszentes Segment mit linear polarisierter Photolumineszenz und/oder linear polarisierter Absorption,
    dadurch gekennzeichnet, dass
    das photolumineszente Segment mindestens teilweise in ein Papier oder eine papierartige Struktur eingebunden ist, das/die sich aus 30 bis 99 Gew.-% des Trockengewichts Fasern und 70 bis 1 Gew.-% des Trockengewichts Füllstoff und optional Zusatzstoffen zusammensetzt, die sich zusammen zu 100 % insgesamt ergänzen, wobei der Füllstoff hohe Streuungseigenschaften und/oder hohe Absorptionseigenschaften in dem spektralen Bereich aufweist, der für die Bestrahlung und/oder Erkennung der Photolumineszenz verwendet wird.
  2. Sicherheitsartikel nach Anspruch 1, dadurch gekennzeichnet, dass das Papier oder die papierartige Struktur im Wesentlichen frei von Aufhellern und/oder von Zusatzstoffen ist, die an sich fluoreszierende Eigenschaften aufweisen, insbesondere die selber linear polarisierte Photolumineszenz und/oder linear polarisierte Absorption zeigen.
  3. Sicherheitsartikel nach Anspruch 2, dadurch gekennzeichnet, dass das Papier oder die papierartige Struktur im Wesentlichen frei von Stilbenbasierten Aufhellern und/oder Zusatzstoffen ist.
  4. Sicherheitsartikel nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Füllstoff Titandioxid in seiner Anatas-Form enthält oder im Wesentlichen daraus besteht, oder aus Zinkoxid oder insbesondere aus Titandioxid in seiner Rutil-Form besteht.
  5. Sicherheitsartikel nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass 0,5 bis 5 %, vorzugsweise 1 bis 2 % des Füllstoffs Titandioxid in seiner Rutil-Form sind.
  6. Sicherheitsartikel nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Absorptionseigenschaften des Füllstoffs mindestens teilweise von einer oder mehr organischen Substanzen herrührt, wobei diese organischen Substanzen vorzugsweise aus der Gruppe der Azo-Derivate, Benzophenone, Benzotriazole, Polymethin-Derivate oder Benzotriazole oder Mischungen daraus ausgewählt ist.
  7. Sicherheitsartikel nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Fasern mindestens teilweise synthetische Fasern umfassen, die aus der Gruppe der Polyethylen-Fasern, Polypropylen-Fasern, Aramid-Fasern, Polyamid-Fasern, Polyacrylnitril-Fasern ausgewählt sind, und/oder dass die Fasern mindestens teilweise natürliches Rohmaterial umfassen, das aus der Gruppe der Holzfasern, Baumwollfasern, Grasfasern, Zellulosefasern, Viskosefasern, Lyocellfasern, Rayonfasern ausgewählt ist.
  8. Sicherheitsartikel nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass mindestens eines der Sicherheitssegmente durch linear polarisierte Absorption gekennzeichnet ist.
  9. Sicherheitsartikel nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Sicherheitssegment durch ein dichroisches Verhältnis von 2 oder mehr in der Absorption und/oder Emission, vorzugsweise von 5 oder mehr in der Absorption und/oder Emission, und insbesondere durch ein dichroisches Verhältnis von 10 und mehr in der Absorption und/oder Emission gekennzeichnet ist.
  10. Sicherheitsartikel nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Sicherheitssegment eine Form aufweist, die aus der Gruppe ausgewählt ist, die aus Faser, Faden, Stab oder einer Kombination daraus besteht.
  11. Sicherheitsartikel nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Sicherheitssegment durch die Bestrahlung mit elektromagnetischer Strahlung mit einer Wellenlänge zwischen 200 und 500 nm zur Photolumineszenz angeregt werden kann.
  12. Sicherheitsartikel nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Sicherheitssegment aus einem Polymerträger hergestellt ist, vorzugsweise aus Polyethylen, Polypropylen, Polycarbonat, Polyvinylalkohol oder Aramid, das mit einem photolumineszenten Farbstoff gefärbt ist.
  13. Sicherheitsartikel nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass das Sicherheitssegment aus einem Zellulose-basierten Träger hergestellt ist, der mit einem photolumineszenten Farbstoff gefärbt ist.
  14. Sicherheitsartikel nach Anspruch 13, dadurch gekennzeichnet, dass das Sicherheitssegment aus einer Zellulosefaser oder einer Lyocellfaser mit einer Länge zwischen 0,5 und 25 mm, vorzugsweise zwischen 1,0 und 5 mm bei 1 bis 40 dtex, vorzugsweise bei 5 bis 20 dtex hergestellt ist.
  15. Sicherheitsartikel nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Papier oder die papierartige Struktur aus 70 bis 97 Gew.-% des Trockengewichts Papierfasern und aus 30 bis 3 Gew.-% des Trockengewichts Füllstoff und optional Zusatzstoffen, die sich zusammen zu 100 % insgesamt ergänzen, besteht.
  16. Verwendung des Sicherheitsartikels nach einem der vorhergehenden Ansprüche für Objekte, deren Fälschung schwer oder unmöglich gemacht werden soll.
  17. Verwendung des Sicherheitsartikels nach Anspruch 1 - 15 für Objekte, deren Echtheit und/oder Gültigkeit markiert werden soll.
  18. Verwendung des Sicherheitsartikels nach Anspruch 1 - 15 für Objekte, deren Identifizierung möglich und/oder einfacher gemacht werden soll.
  19. Verwendung des Sicherheitsartikels nach Anspruch 1 - 15 für ein Objekt, das aus der Gruppe ausgewählt ist, die aus Banknoten, Schecks, Wertpapieren, Obligationen, Ausweisen, Pässen, Führerscheinen, Fahrscheinen, Briefmarken, Scheckkarten und Kreditkarten besteht.
  20. Verfahren zur Herstellung eines Sicherheitsartikels mit mindestens einem Sicherheitselement, das mindestens ein photolumineszentes Segment mit linear polarisierter Photolumineszenz und/oder linear polarisierter Absorption nach Anspruch 1 - 15 umfasst, gekennzeichnet durch das mindestens teilweise Einbinden des photolumineszenten Segments in ein Papier oder eine papierartige Struktur, das/die sich aus 30 bis 99 Gew.-% des Trockengewichts Fasern und 70 bis 1 Gew.-% des Trockengewichts Füllstoff und optional Zusatzstoffen zusammensetzt, die sich zusammen zu 100% insgesamt ergänzen, wobei der Füllstoff hohe Streuungseigenschaften und/oder hohe Absorptionseigenschaften in dem spektralen Bereich aufweist, der für die Bestrahlung und/oder Erkennung der Photolumineszenz verwendet wird, und wobei mindestens ein Sicherheitssegment vor oder nach seiner strukturellen internen Ausrichtung mit einem photolumineszenten Färbstoff gefärbt und dann in eine papierartige Matrix eingebunden ist.
  21. Verfahren nach Anspruch 20, dadurch gekennzeichnet, dass die Fasern der Pulpe erst kurz vor dem eigentlichen Papierherstellungsprozess zugesetzt werden.
EP01985333A 2001-11-22 2001-11-22 Sicherheitspapier und sicherheitsartikel Expired - Lifetime EP1446528B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT01985333T ATE324489T1 (de) 2001-11-22 2001-11-22 Sicherheitspapier und sicherheitsartikel

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2001/013588 WO2003044276A1 (en) 2001-11-22 2001-11-22 Security paper and security articles

Publications (2)

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EP1446528A1 EP1446528A1 (de) 2004-08-18
EP1446528B1 true EP1446528B1 (de) 2006-04-26

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DE (1) DE60119177T2 (de)
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Cited By (1)

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EP2517889A1 (de) 2011-04-27 2012-10-31 Mitsubishi HiTec Paper Europe GmbH Wärmeempfindliches Aufzeichnungsmaterial mit Authentifikationsmerkmal

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DE10342253A1 (de) * 2003-09-11 2005-04-07 Giesecke & Devrient Gmbh Flächiges Sicherheitselement
EP1769484B1 (de) * 2004-07-21 2019-02-27 Landqart AG Sicherheitsmerkmal und verfahren zu dessen herstellung
GB0417422D0 (en) * 2004-08-05 2004-09-08 Suisse Electronique Microtech Security device
AT504704B1 (de) * 2006-06-14 2008-12-15 Chemiefaser Lenzing Ag Fasern enthaltender gegenstand
KR100971055B1 (ko) 2007-12-14 2010-07-20 한국조폐공사 비파괴 분석이 가능한 보안용지 및 이의 진위식별 방법
FR2937058B1 (fr) * 2008-10-10 2012-01-06 Arjowiggins Procede de fabrication d'un document de securite.
ITMO20090201A1 (it) * 2009-08-03 2011-02-04 Cavallini Eugenio Proprieta Al 70 Metodo anticontraffazione applicato a prodotti cartacei e prodotto cartaceo inglobante un codice di autenticazione anticontraffazione
WO2011073354A1 (de) 2009-12-18 2011-06-23 Construction Research & Technology Gmbh Verfahren zur qualitativen und quantitativen identifizierung von massengütern
US20110305919A1 (en) * 2010-06-10 2011-12-15 Authentix, Inc. Metallic materials with embedded luminescent particles
FR3004471B1 (fr) 2013-04-11 2015-10-23 Arjowiggins Security Element de securite comportant une structure de masquage contenant un melange de charges nanometriques.
FR3004470B1 (fr) 2013-04-11 2015-05-22 Arjowiggins Security Element de securite comportant un pigment interferentiel et une charge nanometrique.

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US6035914A (en) * 1993-10-22 2000-03-14 Martin Marietta Energy Systems Inc. Counterfeit-resistant materials and a method and apparatus for authenticating materials
GB2299036A (en) * 1995-03-22 1996-09-25 Coated Papers Limited Coated Paper
GB2300596B (en) * 1995-05-10 1998-11-04 Portals Ltd Composite material having fluorescent features
DE19829004A1 (de) * 1998-06-30 2000-01-05 Giesecke & Devrient Gmbh Sicherheitspapier
CA2344198C (en) * 1998-09-25 2007-05-01 Landqart Security paper and other security items

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Publication number Priority date Publication date Assignee Title
EP2517889A1 (de) 2011-04-27 2012-10-31 Mitsubishi HiTec Paper Europe GmbH Wärmeempfindliches Aufzeichnungsmaterial mit Authentifikationsmerkmal
EP2517888A1 (de) 2011-04-27 2012-10-31 Mitsubishi HiTec Paper Europe GmbH Wärmeempfindliches Aufzeichnungsmaterial mit Authentifikationsmerkmal
DE102011018852A1 (de) 2011-04-27 2012-10-31 Mitsubishi Hitec Paper Europe Gmbh Wärmeempfindliches Aufzeichnungsmaterial mit Authentifikationsmerkmal

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EP1446528A1 (de) 2004-08-18
DE60119177T2 (de) 2007-02-15
WO2003044276A1 (en) 2003-05-30

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