EP1479797A1 - Fibre photoluminescente, papier fiduciaire et d'autres articles de sécurité - Google Patents

Fibre photoluminescente, papier fiduciaire et d'autres articles de sécurité Download PDF

Info

Publication number
EP1479797A1
EP1479797A1 EP03405361A EP03405361A EP1479797A1 EP 1479797 A1 EP1479797 A1 EP 1479797A1 EP 03405361 A EP03405361 A EP 03405361A EP 03405361 A EP03405361 A EP 03405361A EP 1479797 A1 EP1479797 A1 EP 1479797A1
Authority
EP
European Patent Office
Prior art keywords
fibres
photoluminescent
fibre
paper
security
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.)
Withdrawn
Application number
EP03405361A
Other languages
German (de)
English (en)
Inventor
Jakob Grob
Klaus Franken
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Landqart AG
Original Assignee
Landqart AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Landqart AG filed Critical Landqart AG
Priority to EP03405361A priority Critical patent/EP1479797A1/fr
Priority to AT04732265T priority patent/ATE484612T1/de
Priority to ES04732265T priority patent/ES2354215T3/es
Priority to EP04732265A priority patent/EP1631705B1/fr
Priority to PCT/CH2004/000287 priority patent/WO2004104277A1/fr
Priority to DE602004029570T priority patent/DE602004029570D1/de
Publication of EP1479797A1 publication Critical patent/EP1479797A1/fr
Withdrawn legal-status Critical Current

Links

Images

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/0004—General aspects of dyeing
    • D06P1/0012—Effecting dyeing to obtain luminescent or phosphorescent dyeings
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/253—Formation of filaments, threads, or the like with a non-circular cross section; Spinnerette packs therefor
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • D01F6/06—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins from polypropylene
    • 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
    • D21H15/00—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution
    • D21H15/02—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution characterised by configuration
    • 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 a photoluminescent fibre for the incorporation into a security article.
  • the present invention relates to photoluminescent, i.e. fluorescent or phosphorescent fibres which are to be embedded in paper like structures like for example banknote paper etc..
  • the present invention also relates to security articles comprising such photoluminescent fibres and to a method to produce such security articles and to a use of the latter.
  • security elements in particular in the form of photoluminescent fibres can be employed, which have the purpose to prevent or stifle forgery of those objects by unauthorised persons.
  • 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.
  • WO 00/19016 describes such novel security elements based on their dichroic properties.
  • the document describes security elements or segments incorporated into a paper or the like, which security elements show either linearly polarised photoluminescence and/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.
  • security article relates articles which substantially are made from paper from a synthetic material. It particularly but not exclusively relates to non-woven, flat, fibre-containing data carriers. In particular cotton containing paper as it is heavily being used in the field of banknotes is a possible security article.
  • the security article may also be a more complex article like a passport, a banknote etc..
  • the polar axis of a linear polarizer or analyzer is the direction of the electrical field vector of the light that is transmitted by the polarizer films.
  • the polar axis of a photoluminescent fibre or other object is the direction of the electrical field vector of the light that is emitted or absorbed by the respective segment, photoluminescent fibre, or other object.
  • segment is used for a part of an object, in particular of a photoluminescent fibre, for which the characteristic degree of polarization and polar axis for absorption and emission can be determined in appropriate manner.
  • the degree of emission polarization (also referred to as degree of polarization in emission) is expressed as the emission dichroic ratio (also referred to as dichroic ratio in emission).
  • the emission dichroic ratio is defined as the ratio of the integrated emission spectra measured through a linear polarizer (analyzer) with its polar axis parallel and perpendicular to the polar axis of the investigated segment, using unpolarized excitation light.
  • the degree of absorption polarization (also referred to as degree of polarization in absorption) is expressed as the absorption dichroic ratio (also referred to as dichroic ratio in absorption).
  • the absorption dichroic ratio is defined as the ratio of the absorption measured with incident light linearly polarised parallel and perpendicular to the polar axis of the investigated segment or photoluminescent fibre, and is measured at the wavelength used for excitation.
  • the excitation wavelength is defined as the wavelength that is used for optical excitation (to generate photoluminescence) of the security element or its photoluminescent segments, respectively.
  • absorption and emission relate to optical processes.
  • the object of the present invention to overcome the problems of the prior art photoluminescent fibres and security articles.
  • the invention relates to photoluminescent fibres for the incorporation into a security article.
  • a problem of such photoluminescent fibres is that if incorporated into a matrix material like for example into paper or paper like structures, the major part of the fibres is buried in the matrix material and not close to the surface of the corresponding security article. Since the actual aim of such a photoluminescent fibre is to be seen upon irradiation, this means that most of the fibre does not give rise to the desired effect.
  • Anisotropic basically means that two principal axes are of different length.
  • fibres with such anisotropic cross-sections not only have the tendency to align with and be arranged more closely to the surface of the corresponding security article into which they are incorporated, but they also align such that the large principal axis of the cross-section is substantially parallel to the surface of the security article. This means that on the one hand the fibres are more effective due to their increased closeness to the surface, but also their visibility is particularly pronounced since the wide side faces the viewer.
  • such a photoluminescent fibre shows a ratio of the lengths of the short principal axis to the long principal axis of the anisotropic cross-section in the range of 1:1.5 to 1:100. It is also possible to choose that ratio to be in the range of 1:2 to 1:50, preferably in the range of 1:2 to 1:25 or 1:5 to 1:25 and most preferably in the range of 1:2 to 1:15 or 1:8 to 1:15. Typically, ratios of about 1:8 have proven to be useful and effective.
  • the anisotropic cross-section can have various shapes, and it may for example be of substantially oval, polygonal, rectangular, triangular or lens-type shape.
  • the photoluminescent fibre is characterised in that the short principal axis is between 5-20 ⁇ m, preferably between 10-15 ⁇ m long, and in that the long principal axis is between 50 - 150 ⁇ m, preferably between 75 - 125 ⁇ m long.
  • the short principal axis is between 5-20 ⁇ m, preferably between 10-15 ⁇ m long
  • the long principal axis is between 50 - 150 ⁇ m, preferably between 75 - 125 ⁇ m long.
  • the fibres can preferably be embedded 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.
  • 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 photoluminescent fibres.
  • 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 extent 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 photoluminescent fibres. Additionally, in the case of linearly polarised absorption or linearly polarised fluorescence, transfer between these fluorescent chromophores and the photoluminescent fibres may lead to a destruction of the polarisation efficiency as macroscopically detectable when e.g. looking at the irradiated photoluminescent fibres e.g. through a rotating polarization filter or observing the photoluminescent fibres 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.
  • the photoluminescent fibre is characterised by linearly polarised absorption and/or linearly polarised fluorescence.
  • 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 photoluminescent fibre 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 photoluminescent fibres 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 photoluminescent fibre 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 photoluminescent fibres with particular dyes are being brought near such light.
  • carrier materials which are particularly suitable for forming said photoluminescent fibres if they are to show linearly polarised absorption and/or linearly polarised emission (fluorescence).
  • 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 photoluminescent fibres 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 photoluminescent fibres may be made of a cellulose-based carrier dyed with a photoluminescent dye.
  • This carrier is of particular advantage as fibres or other photoluminescent fibres made of such carrier provide surface properties allowing for firm and easy embedding into a common, cellulose-based paper matrix.
  • Cellulose-based fibres 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.
  • photoluminescent fibre may be made of viscose, or lyocell.
  • the fibre 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.
  • the particular shape of the cross-section of the fibres can be obtained by using correspondingly shaped extrusion nozzles.
  • textile fibres with more than 1 dtex are particularly well suited due to their high degree of orientation and due to their ease with respect or dying. 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, 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 fibre with anisotropic cross-section is dyed with a photoluminescent dye preferably prior or after its structural orientation, and is then embedded in a paper-like matrix.
  • the photoluminescent fibre/segment may subsequently also be treated in certain regions to selectively modify or erase the polarisation effect in these regions.
  • Figure 1 a shows a photoluminescent fibre 1 according to the state-of-the-art.
  • Such fluorescent or phosphorescent fibres are widely being used to be incorporated into a paper or paper-like structures to render them security papers.
  • Articles provided with such photoluminescent fibres 1 in their matrix reveal, if irradiated with corresponding electromagnetic radiation, generally in the UV-range, the fibres, which are otherwise invisible. To enhance the effects, normally these fibres 1 are coloured differently.
  • these fibres generally have a quasi-circular cross-section 3 and may be tilted or straight (see in particular segment 2).
  • a photoluminescent fibre 1 is incorporated into a security article 4 like for example a banknote paper
  • the fibres, which form part of the pulp out of which the paper is made are arranged randomly within the matrix. This means that generally only a small fraction 5 of the fibres 1 is close to one of the two surfaces 6 or 7, while a large fraction 8 of the fibres is buried within the matrix of the security article 4. This on the one hand makes sure that the fibres are well fixed to the matrix of the security article 4, but on the other hand the visibility of the fluorescence effect is hampered due to the fact that most of the fibres is buried within the paper structure.
  • the alignment of fibres within such a structure 4 can be influenced by changing the cross-section of such a fibre 12. If the fibre 12 is allowed to have an anisotropic cross-section, ie a cross-section which shows a long principal axis and a short principal axis, such fibres align as is displayed in figure 3.
  • the fibres 12 not only align close to the surfaces 6 or 7 of the security article 4 due to the paper production process, but they also align such that their maximum width is exposed to the surface, and therefore to the viewer. This means that the large principal axes of the anisotropic cross-sections are generally aligned substantially parallel to the surfaces 6,7.
  • Figure 2a)-h) show different possible anisotropic cross-sectional shapes.
  • the ratio of the short principal axis 10 to the long principal axis 11 has always be chosen in the range of 1:2 to 1:4. However, it has to be noted that this ratio may well exceed these values and for example be 1:8, as is realised when the short side of a rectangular shape (cf e.g. figure 2b) is in the range of 10 to 15 ⁇ m while the long side of the rectangular shape is about 100 ⁇ m.
  • the length is preferably chosen to be around 3 mm or 3.5 mm.
  • the present invention is additionally based on the finding that photoluminescent materials which are characterised by linearly polarised photoluminescence or linearly polarised absorption or both and can be made in a form, can be employed to produce photoluminescent fibres that can be used for the production of security paper and security articles in general.
  • photoluminescent materials which are characterised by linearly polarised photoluminescence or linearly polarised absorption or both and can be made in a form, can be employed to produce photoluminescent fibres that can be used for the production of security paper and security articles in general.
  • problems may arise when embedding the photoluminescent fibres into paper or some other security article due to the fact that this matrix may reduce or disturb the efficiency of the photoluminescence effects that can be observed.
  • 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.
  • linearly polarised absorption of such fibres leads to the situation that linearly polarised excitation light which, for example, can be generated by an external light source in combination with a linear polarizer, is absorbed unequally strong by the fibre; depending on the orientation of the polar axis of the excitation light and the polar axis of the fibre.
  • segment is used for a part of an fibre for which the characteristic degree of polarization and polar axis for absorption and emission can be determined in appropriate manner. It is obvious to the one skilled in the art that 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 photoluminescent fibres in security articles according to the present invention comprise one or more luminescent dyes in suitable concentration and of suitable properties, i.e. which if desired also cause the polarization characteristics.
  • dyes usually 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 European Patent Applications 97111229.7 and 98101520.9 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 fibres 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 fibres is:
  • 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 fibres 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.
  • semicrystalline polyolefins such as polyethylene polypropylene, for example
  • LLDPE linear low-density polyethylene
  • security elements can be manufactured, according to the present invention, that exhibit unusually high dichroic ratios in absorption.
  • 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. Usually, 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 fibres for the application according to the present invention can, for example, be found in European Patent Applications 97111229.7 and 98101520.9 and in the Patent applications and publications cited therein.
  • the fibres or segments of such fibres 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 fibres are embedded. If a multitude of such fibres are used, they can, also exhibit different emission colours and can be arranged in certain patterns, for example, with a specific arrangement of their polar axis'.
  • 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:
  • Another advantage of using rutile as filler is due to the black appearance of the paper-like structure when irradiated with light thus increasing the contrast between the paper matrix and the security elements.
  • the amount of e.g. rutile effectively necessary to achieve the above effect may depend on other substances possibly present in the matrix. These are substances which themselves have fluorescent effects in the sense that they absorb ultraviolet light and subsequently emit visible light leading to a bright appearance of the matrix. Usually 1 to 2% w/w of rutile are sufficient to provide the requested ultraviolet-dullness.
  • 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 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.
  • the quality of the dyed security elements according to example is 1 to 12 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 +++
  • 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/m 2 .
  • 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.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Paper (AREA)
  • Credit Cards Or The Like (AREA)
  • Artificial Filaments (AREA)
  • Pens And Brushes (AREA)
  • Control Of Combustion (AREA)
  • Inspection Of Paper Currency And Valuable Securities (AREA)
EP03405361A 2003-05-22 2003-05-22 Fibre photoluminescente, papier fiduciaire et d'autres articles de sécurité Withdrawn EP1479797A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP03405361A EP1479797A1 (fr) 2003-05-22 2003-05-22 Fibre photoluminescente, papier fiduciaire et d'autres articles de sécurité
AT04732265T ATE484612T1 (de) 2003-05-22 2004-05-12 Photolumineszierende faser, sicherheitspapier und andere sicherheitsartikel
ES04732265T ES2354215T3 (es) 2003-05-22 2004-05-12 Fibra fotoluminiscente, papel de seguridad y otros artículos de seguridad.
EP04732265A EP1631705B1 (fr) 2003-05-22 2004-05-12 Fibre photoluminescente, papier fiduciaire et d'autres articles de securite
PCT/CH2004/000287 WO2004104277A1 (fr) 2003-05-22 2004-05-12 Fibre photoluminescente, papier de securite et autres articles de securite
DE602004029570T DE602004029570D1 (de) 2003-05-22 2004-05-12 Photolumineszierende faser, sicherheitspapier und andere sicherheitsartikel

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP03405361A EP1479797A1 (fr) 2003-05-22 2003-05-22 Fibre photoluminescente, papier fiduciaire et d'autres articles de sécurité

Publications (1)

Publication Number Publication Date
EP1479797A1 true EP1479797A1 (fr) 2004-11-24

Family

ID=33041146

Family Applications (2)

Application Number Title Priority Date Filing Date
EP03405361A Withdrawn EP1479797A1 (fr) 2003-05-22 2003-05-22 Fibre photoluminescente, papier fiduciaire et d'autres articles de sécurité
EP04732265A Expired - Lifetime EP1631705B1 (fr) 2003-05-22 2004-05-12 Fibre photoluminescente, papier fiduciaire et d'autres articles de securite

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP04732265A Expired - Lifetime EP1631705B1 (fr) 2003-05-22 2004-05-12 Fibre photoluminescente, papier fiduciaire et d'autres articles de securite

Country Status (5)

Country Link
EP (2) EP1479797A1 (fr)
AT (1) ATE484612T1 (fr)
DE (1) DE602004029570D1 (fr)
ES (1) ES2354215T3 (fr)
WO (1) WO2004104277A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007143762A1 (fr) * 2006-06-14 2007-12-21 Lenzing Aktiengesellschaft Article contenant des fibres
EP2024541A1 (fr) * 2006-05-25 2009-02-18 Kolon Industries, Inc. Filament pour câble pneumatique, faisceau de filaments, fil torsadé et câble de pneumatique comprenant ledit filament
WO2011073442A1 (fr) * 2009-12-18 2011-06-23 Universiteit Gent Fibres codées
WO2012095005A1 (fr) * 2011-01-11 2012-07-19 上海柯斯造纸防伪技术有限公司 Fibre anti-contrefaçon, papier anti-contrefaçon contenant la fibre anti-contrefaçon et leur procédé de fabrication
CN105408533A (zh) * 2013-07-30 2016-03-16 东丽株式会社 碳纤维束及耐燃化纤维束
WO2018124832A1 (fr) * 2016-12-29 2018-07-05 코오롱인더스트리 주식회사 Fibre lyocell, agrégat de non-tissé comprenant celle-ci, et feuille de masque de soin comprenant celui-ci
CN108589287A (zh) * 2018-04-03 2018-09-28 四川大学 一种荧光棉花纤维的原位制备方法
EP3385429A1 (fr) * 2017-04-03 2018-10-10 Lenzing Aktiengesellschaft Tissu de fibres de cellulose non tissé ayant des particules de diffusion de rayonnement connectés aux fibres

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EA201170723A1 (ru) * 2008-12-09 2012-02-28 Шанхай Кос Секьюрити Пэйпэ Текнолоджи Ко., Лтд. Защитное волокно и защитная бумага, содержащая защитное волокно
RU2017117187A (ru) 2014-10-31 2018-11-30 Клокс Текнолоджиз Инк. Фотоактивируемые волокна и тканые материалы
WO2020152505A1 (fr) * 2019-01-25 2020-07-30 Unity Pulp And Papers Private Limited Préparation de nouveaux fils de sécurité et son application pour un processus anti-contrefaçon
CN115976859A (zh) * 2022-11-29 2023-04-18 深圳全棉时代科技有限公司 感光变色棉纱及其制备方法与面料、混合染料

Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2089293A (en) * 1934-08-08 1937-08-10 Ici Ltd Safety paper
GB763240A (en) * 1952-07-18 1956-12-12 Firestone Tire & Rubber Co Improvements in synthetic plastic filaments and method of making same
DE3511884A1 (de) * 1985-04-01 1986-10-02 Weise-Richter, Helga, 8125 Huglfing Chemiefaser und verfahren zu deren herstellung
US4655788A (en) * 1984-06-22 1987-04-07 Michel Jalon Security fibers and other materials made luminescent by a dyeing process, processes for their manufacture and their applications
US4954398A (en) * 1988-02-16 1990-09-04 Eastman Kodak Company Modified grooved polyester fibers and process for production thereof
DE4133977A1 (de) * 1991-10-14 1993-04-15 Cassella Ag Verfahren zum faerben von fasern mit pigmenten
GB2299036A (en) * 1995-03-22 1996-09-25 Coated Papers Limited Coated Paper
GB2300596A (en) * 1995-05-10 1996-11-13 Portals Ltd Fluorescent security feature for cheques and banknotes
US5989389A (en) * 1992-11-11 1999-11-23 Ab Tumba Bruk Method of producing visible, continuous streaks and/or delimited fields in paper
WO1999063144A1 (fr) * 1998-06-01 1999-12-09 Isotag Technologies, Inc. Composition pour enduction de fibres comportant un marqueur invisible et procede de fabrication d'une telle composition
WO1999063145A1 (fr) * 1998-06-01 1999-12-09 Isotag Technologies, Inc. Fibres contenant des compositions de marquage et polymeres reticules
US6035914A (en) * 1993-10-22 2000-03-14 Martin Marietta Energy Systems Inc. Counterfeit-resistant materials and a method and apparatus for authenticating materials
WO2000019016A1 (fr) * 1998-09-25 2000-04-06 Landqart Papier de securite et autres articles de securite
EP1039017A2 (fr) * 1999-03-23 2000-09-27 Rinke Etiketten Karl Rinke GmbH & Co. KG Procédé de production de textiles ayant une fluorescence localisée
US20020160188A1 (en) * 2001-02-21 2002-10-31 Tam Thomas Y-T. Security articles
WO2003054259A1 (fr) * 2001-12-20 2003-07-03 Honeywell International Inc. Articles de securite contenant des colorants physiques multi-sensibles

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2089293A (en) * 1934-08-08 1937-08-10 Ici Ltd Safety paper
GB763240A (en) * 1952-07-18 1956-12-12 Firestone Tire & Rubber Co Improvements in synthetic plastic filaments and method of making same
US4655788A (en) * 1984-06-22 1987-04-07 Michel Jalon Security fibers and other materials made luminescent by a dyeing process, processes for their manufacture and their applications
DE3511884A1 (de) * 1985-04-01 1986-10-02 Weise-Richter, Helga, 8125 Huglfing Chemiefaser und verfahren zu deren herstellung
US4954398A (en) * 1988-02-16 1990-09-04 Eastman Kodak Company Modified grooved polyester fibers and process for production thereof
DE4133977A1 (de) * 1991-10-14 1993-04-15 Cassella Ag Verfahren zum faerben von fasern mit pigmenten
US5989389A (en) * 1992-11-11 1999-11-23 Ab Tumba Bruk Method of producing visible, continuous streaks and/or delimited fields in paper
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
GB2300596A (en) * 1995-05-10 1996-11-13 Portals Ltd Fluorescent security feature for cheques and banknotes
WO1999063144A1 (fr) * 1998-06-01 1999-12-09 Isotag Technologies, Inc. Composition pour enduction de fibres comportant un marqueur invisible et procede de fabrication d'une telle composition
WO1999063145A1 (fr) * 1998-06-01 1999-12-09 Isotag Technologies, Inc. Fibres contenant des compositions de marquage et polymeres reticules
WO2000019016A1 (fr) * 1998-09-25 2000-04-06 Landqart Papier de securite et autres articles de securite
EP1039017A2 (fr) * 1999-03-23 2000-09-27 Rinke Etiketten Karl Rinke GmbH & Co. KG Procédé de production de textiles ayant une fluorescence localisée
US20020160188A1 (en) * 2001-02-21 2002-10-31 Tam Thomas Y-T. Security articles
WO2003054259A1 (fr) * 2001-12-20 2003-07-03 Honeywell International Inc. Articles de securite contenant des colorants physiques multi-sensibles

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2024541A1 (fr) * 2006-05-25 2009-02-18 Kolon Industries, Inc. Filament pour câble pneumatique, faisceau de filaments, fil torsadé et câble de pneumatique comprenant ledit filament
EP2024541A4 (fr) * 2006-05-25 2014-12-24 Kolon Inc Filament pour câble pneumatique, faisceau de filaments, fil torsadé et câble de pneumatique comprenant ledit filament
JP2009540140A (ja) * 2006-06-14 2009-11-19 レンツィング アクチェンゲゼルシャフト 繊維含有物品
WO2007143762A1 (fr) * 2006-06-14 2007-12-21 Lenzing Aktiengesellschaft Article contenant des fibres
WO2011073442A1 (fr) * 2009-12-18 2011-06-23 Universiteit Gent Fibres codées
RU2590538C2 (ru) * 2011-01-11 2016-07-10 Шанхай Кос Секьюрити Пэйпэ Текнолоджи Ко., Лтд Защитное волокно, защищенная от подделывания бумага, содержащая защитное волокно, и способ их изготовления
WO2012095005A1 (fr) * 2011-01-11 2012-07-19 上海柯斯造纸防伪技术有限公司 Fibre anti-contrefaçon, papier anti-contrefaçon contenant la fibre anti-contrefaçon et leur procédé de fabrication
CN105408533A (zh) * 2013-07-30 2016-03-16 东丽株式会社 碳纤维束及耐燃化纤维束
WO2018124832A1 (fr) * 2016-12-29 2018-07-05 코오롱인더스트리 주식회사 Fibre lyocell, agrégat de non-tissé comprenant celle-ci, et feuille de masque de soin comprenant celui-ci
JP2020504791A (ja) * 2016-12-29 2020-02-13 コーロン インダストリーズ インク リヨセル繊維、これを含む不織繊維集合体およびこれを含むマスクパックシート
EP3564417A4 (fr) * 2016-12-29 2020-09-02 Kolon Industries, Inc. Fibre lyocell, agrégat de non-tissé comprenant celle-ci, et feuille de masque de soin comprenant celui-ci
EP3385429A1 (fr) * 2017-04-03 2018-10-10 Lenzing Aktiengesellschaft Tissu de fibres de cellulose non tissé ayant des particules de diffusion de rayonnement connectés aux fibres
WO2018184926A1 (fr) * 2017-04-03 2018-10-11 Lenzing Aktiengesellschaft Tissu de fibres de cellulose non tissées avec des particules de diffusion de rayonnement connectées par des fibres
CN108589287A (zh) * 2018-04-03 2018-09-28 四川大学 一种荧光棉花纤维的原位制备方法

Also Published As

Publication number Publication date
WO2004104277A1 (fr) 2004-12-02
EP1631705A1 (fr) 2006-03-08
EP1631705B1 (fr) 2010-10-13
ES2354215T3 (es) 2011-03-11
ATE484612T1 (de) 2010-10-15
DE602004029570D1 (de) 2010-11-25

Similar Documents

Publication Publication Date Title
EP1631705B1 (fr) Fibre photoluminescente, papier fiduciaire et d'autres articles de securite
EP1446528B1 (fr) Papier infalsifiable et articles infalsifiables
US20030194578A1 (en) Security articles comprising multi-responsive physical colorants
BRPI0613053A2 (pt) fio e mÉtodo para fabricar o mesmo, papel impeditivo de falsificaÇço utilizando o fio, material impresso impeditivo de falsificaÇço, e mÉtodo para julgar a autenticidade utilizando os mesmos
KR20100013560A (ko) 특수 파장에 따라 색이 변하는 보안색사가 내재된보안용지와 이를 이용한 제조방법
BRPI0719827B1 (pt) folha de segurança, fita de segurança feita de papel, documento de segurança, artigo a autenticar e processos de fabricação de uma folha de segurança e de autenticação de uma folha de segurança.
FR2925535A1 (fr) Feuille de securite comprenant un substrat fibreux comportant au moins un filigrane
US20160325579A1 (en) Silk fibroin security fibers containing security markers and a process for the preparation thereof
EP1233106B1 (fr) Papier de sécurité et autres articles de sécurité
WO2006008931A1 (fr) Moyen d’identification et article fourni avec ce moyen
KR101234552B1 (ko) 근적외선 발광 특성을 가지는 위조방지용 시트
KR100945471B1 (ko) 보안용형광실을 이용한 보안용지
KR101450614B1 (ko) 약품 변색 기능을 가지는 보안 요소를 갖는 보안용지 및 그 제조 방법
KR20160069955A (ko) 셀룰로오스 섬유를 포함한 보안사와 이를 이용한 보안용지
KR100346056B1 (ko) 형광 색사의 제조 방법
US11649563B2 (en) Use of 4-bora-3a,4a-diaza-s-indacenes for the production of fluorescent fibres
CN115667603A (zh) 防伪性和识别性提高的防伪织物
JPH1193096A (ja) 蛍光発色する繊維状物、及びこれを使用した偽造防止用紙、及び偽造防止印刷物
EP3090080A1 (fr) Fibres de sécurité en fibroïne de soie contenant des marqueurs de sécurité et leur procédé de préparation
KR20110043803A (ko) 전기방사에 의한 위조방지용 부직포 섬유, 이의 제조방법 및 이를 이용한 보안제품
KR101430234B1 (ko) 이중식별이 가능한 보안사, 그의 제조방법 및 그를 이용한 위폐방지용품
RU2671745C2 (ru) Бумага, содержащая фибриллированные синтетические волокна
RU2698693C2 (ru) Бумага, содержащая синтетические волокна
RU148594U1 (ru) Защитная полимерная профилированная нить, многослойное изделие и устройство для ввода нити
RO126417B1 (ro) Hârtie securizată şi procedeu de obţinere a acesteia

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK

AKX Designation fees paid
REG Reference to a national code

Ref country code: DE

Ref legal event code: 8566

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20050525