WO2004087795A1 - Element d'authentification - Google Patents

Element d'authentification Download PDF

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Publication number
WO2004087795A1
WO2004087795A1 PCT/EP2004/003549 EP2004003549W WO2004087795A1 WO 2004087795 A1 WO2004087795 A1 WO 2004087795A1 EP 2004003549 W EP2004003549 W EP 2004003549W WO 2004087795 A1 WO2004087795 A1 WO 2004087795A1
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WO
WIPO (PCT)
Prior art keywords
film
additive
radiation
orientation
substrate
Prior art date
Application number
PCT/EP2004/003549
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English (en)
Inventor
John Raseburn
Original Assignee
Ucb, S.A.
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 Ucb, S.A. filed Critical Ucb, S.A.
Publication of WO2004087795A1 publication Critical patent/WO2004087795A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/01—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene

Definitions

  • the present invention relates to security features used to authenticate an article such as a security document comprising a substrate for example an orientated polymer film.
  • the applicant has found that additives which absorb radiation which are large linear molecules with a degree of conformational rigidity will when incorporated into a polymer film be preferentially oriented with the polymer chains when such a polymeric film is oriented. This effect leads to a change in the radiation absorption properties of the additives.
  • the additive preferably absorbs radiation in the non visible region (i.e. is colourless) such as IR or UV radiation, preferably UV radiation.
  • a biaxially oriented polymeric film suitable for use as a substrate to provide improved authentication, the film comprising from about 0.001 % to about 5% by weight of a colourless additive dispersed in at least one layer of the film; where the additive exhibits a detectable difference in the spectral response when illuminated with polarised IR or UV radiation for which the axis of polarisation is parallel with one of the principal orientation axes (MD or TD).
  • MD principal orientation axes
  • the additive may also be a modification and/or functionalisation of the polymer rather than an additive per se.
  • the additive preferentially aligns along one orientation axis of the film.
  • the polymer film is a thermoplastic or biopolymer film, more preferably a polyolefinic film (which may be a homo-, bi, ter or co-polymer and/or any mixture(s) thereof) and/or cellulosic film. More preferably the film comprises polypropylene, polyethylene, mixtures and/or (co)polymer(s) thereof. Most preferably the film is a polypropylene homopolymer.
  • the film may be a multilayer structure formed by any suitable method (such as co-extrusion and/or lamination) with one or more core or surface layers being as formed as described herein.
  • the film comprises biaxially oriented polypropylene (BOPP).
  • BOPP films may be prepared with substantially balanced physical properties, for example as can be produced using substantially equal machine direction and transverse direction stretch ratios or can be unbalanced where the film is significantly more oriented in one direction (MD or TD).
  • Sequential stretching can be used, in which heated rollers effect stretching of the film in the machine direction and a stenter oven is thereafter used to effect stretching in the transverse direction or simultaneous stretching, for example using the so-called double bubble process or a simultaneous draw stenter.
  • the heater rollers in the double-bubble process effect MD orientation by causing TD shrinkage rather than deliberately exerting an MD tension directly.
  • the action of the heat is to generate an MD shrinkage and therefore to exert an additional MD tension.
  • the machine direction and transverse direction stretch ratios are preferably in the range of from 4:1 to 10:1 , and more preferably from 6:1 to 8:1.
  • preferred additives are those which will be more preferentially oriented in one direction and so the ansiotropic spectra of the film will be more pronounced.
  • some degree of anisotropy may be re-introduced for example in either the MD or TD or locally (e.g. using a laser heat source) to reduce the orientation in one direction or region and thus partially unbalance the film to increase the anisotropic orientation of the additive.
  • the films used in accordance with the present invention can be of a variety of thicknesses according to the requirements of the packages which are to be produced. For example they can be from about 10 to about 120 microns thick, and preferably from about 14 to about 40 microns thick.
  • the additive is a material which absorbs and/or fluoresces in the UV (hereinafter referred to as a UV absorber or UV additive).
  • a UV absorber or UV additive Certain UV-additives have anisotropic UV- absorption and/or UV fluorescence. Substrates that incorporate such UV additives may thus indicate by their absorbance or fluorescence the preferred physical orientation of additive within the substrate under UV irradiation. The preferred orientation reflects the overall molecular orientation of the additive in the substrate and may arise from the processing history of the substrate. This anisotropic behaviour may be particularly apparent when the UV light is filtered thought an appropriate polarising device where the intensity of the absorption or fluorescence may be dependent on the relative orientations of the polarisation of the UV irradiation and a suitable reference direction in the substrate. In the case of a manufactured film, a convenient reference direction is often the machine direction (i.e. the direction by which the film is conveyed and culminating in its being wound onto a reel.)
  • the dichroic ratio measures the maximum absorption or fluorescence intensity obtained when transverse direction of the film sample is aligned with the principal direction of the polarisng filter divided by the maximum intensity of absorption or fluorescence when the machine direction of the film sample is aligned with the principal direction of the polarising filter.
  • the ratio of the two intensities is approximately unity.
  • the dichroic ratio is greater than unity.
  • the dichroic ratio is less than unity.
  • Suitable anisotropic UV additives may comprise long, 'rod' shaped molecules which are compatible with the film polymer so they may be distributed in the polymer melt. The action of stretching the film during orientation may cause the 'rods' to aligned preferentially in a particular direction. The 'rods' can then influence the passage of UV radiation through the film.
  • polarised UV light is passed through the film in a direction A (parallel to the direction of the long axis of the molecules) a specific spectra will be displayed In a UV spectrophotometer or the UV light will be transmitted.
  • polarised UV light is passed through the film in a direction B (with polarisation axis perpendicular to the direction of the long axis of the molecules in the plane of the web), a different spectrum is displayed or then the radiation will be partially absorbed.
  • the fluorescence of pigments can be controlled by direction the polarised UV light is applied i.e. in direction A full fluorescence observed, direction B partial fluorescence observed.
  • Detection of the anisotropic properties of the film additive would normally be covert using a laboratory based spectrophotometer (although a hand held detector could be used in the field).
  • the additive would not normally be detected by the user. This is advantageous as the counterfeiter would be unaware of the additive and even if the presence of the additive was detected it would be very difficult to mimic the ansiotropic effect by using any coating or printing techniques which might be available to a counterfeiter.
  • a localised change in the orientation of biaxially orientated polypropylene film can be achieved by the application of a continuous stream of laser energy (as described in the applicant's patent application WO 02/053473, incorporated herein by reference).
  • the present invention can uses a subtle change in film orientation as a possible to make the authentication feature even more covert, so as well as unbalanced films it is possible to use balanced films which if necessary have been slightly unbalanced only enough so the anisotropic absorption can be detected .
  • any localised modifications can not be viewed under normal lighting conditions. However when viewed between two sheets of Polaroid film, any changes in orientation can be observed.
  • tagents could be added to the base film material to indicate its degree of orientation.
  • the localised modification of orientation by the action of a continuous laser could be made detectable by adding suitable pigments that react to any orientation change.
  • Preferred UV-additives for use in the present invention may be selected from: polyenes, such as (trans, trans)-diphenyl butadiene, (trans, trans, trans)-diphenyl hexatriene, beta- carotene, vitamin A and its derivatives, cinnamoyl compounds and terpene resins; polycyclic aromatic hydrocarbons and their derivatives, such as fluorene, chrysene, perylene, phenanthrene, anthracene, and naphthalene; polyphenyl molecules, such as ortho- or para-terphenyl; heterocyclic compounds such as coumarins, rhodamines, fluorescein, flavins such as riboflavin (vitamin B 2 ) and amino acids such as tryptophan, phenylalanine and tyrosine, and derivatives of these susbtances such as methoxytryptophan; UV-absorbant polymers such as polyesters and
  • More preferred rod like UV additives which can be successfully dispersed in polypropylene to make BOPP films and used to determine the orientation with in the film using UV spectroscopy, comprise:
  • two or more rigid rod like species may be used as one of more UV absorber, UV fluorescent material, a material capable of Intermolecular non-radiative energy transfer (NRET) and/or a phosphorescent rnaterial.
  • NRET Intermolecular non-radiative energy transfer
  • UV absorbing rod species present in the film or article to be authenticated, each of which may exhibit a greater or lesser, or the same, orientational sensitivity as its counterpart, a more complicated UV absorption spectrum may be possible which can provide an enhanced means for authentication.
  • Some rod-like molecules fluoresce, i.e. when illuminated with UV light, the film appears to "glow". Both absorption and fluorescence are anisotropic, i.e. directionally-dependent, for molecules which themselves are anisotropic. Polarised UV illumination enables one to distinguish between bubble and stenter film via detection of the associated fluorescence, in an analogous fashion to the absorption method. With two or more UV fluorescent rod species present in said film or article, and where said species fluoresce at different wavelengths and which are isolated from one another on a molecular scale, a blend of fluorescence colours can occur. The intensity or colour of this blended light can be linked to orientation via appropriate detection.
  • a third or further UV absorbing species can be added to substantially block certain wavelengths in the applied illumination.
  • Fluorescence may offer sensitivity advantages with regards to detection, which facilitates the design of the hand-held device. However, fluorescence is most effective in mobile phases where the rigid rod molecules experience a weaker physical connection to their molecular environment relative to more rigid phases. In a more mobile phase, it is likely that sensitivity to the orientation of the surrounding polymer chains is lower.
  • NRET intermolecular non-radiative energy transfer
  • Phosphorescence refers to the "after-glow" effect which occurs with certain substances after an applied UV illumination has been switched off. It appears that rigid phases are more effective in this regard and phosphorescent materials may also be used in the present invention.
  • the present invention provides a means to distinguish BOPP film produced by the bubble process (known herein as bubble film) which is generally balanced (i.e. substantially the same orienting process conditions in MD and TD as the film is orientated simultaneously) from BOPP film produced by the stenter process which is generally unbalanced (i.e. MD and TD orienting process conditions are different, as the film is oriented sequentially).
  • bubble film encompasses any similar oriented film of similar properties made by different techniques (such as LISM) where the film is also oriented simultaneously.
  • the principle of the "Rigid Rods” verification system is to include ultra-violet (UV) absorbing molecules within base film, thus affording a unique analytical signature for either forensic or field-detection.
  • the molecules are preferably "rod-like", i.e. of an elongated and rigid nature, where rigid suggests that they do not easily change shape.
  • their principal axes align with the directions of the polymer molecular chains in the film. The latter are governed chiefly by the manufacturing process by which the made.
  • the "rods” are distributed evenly, such that they point in all directions within the film.
  • the "rods" will also be aligned chiefly in the transverse direction.
  • the distribution of rod directions can be evaluated. This enables identification of the origin of the film sample under scrutiny in terms of its associated manufacturing process (bubble or stenter). Because of both the inclusion of the UV rods within the body of the film, and also the unusual nature of the bubble process, this method offers a means of verifying a UCB film sample as originating from UCB in a way which cannot be easily counterfeited.
  • bubble and stenter process underlies the principle behind the Rigid-Rod Verification system.
  • film samples were produced in the laboratory by drawing a heated plaque in two perpendicular directions simultaneously.
  • the heated plaque was drawn first in one direction and then in a direction perpendicular to the first (sequential drawing).
  • Factors which may be used to select an optimal material for use in the present invention as a rigid rod are sensitivity to film processing history (orientation); stability with regard to extrusion and subsequent film storage; fluorescence efficiency and/or price and cost effectiveness.
  • DPBD was selected as a preferred material to use as rigid rod mainly on cost grounds. It will be appreciated that there will be many other suitable materials could be used as the rigid rod in the present invention.
  • Preferred materials feature an elongated molecular geometry, more preferably comprise aromatic moieties, most preferably are selected from phenanthrenes, fluorenes, fluoresceins, flavins and/or aromatic hard-resins.
  • the intensity of the detected UV absorbance or fluorescence is a function of the total number of "rigid rods" through which the UV light beam passes, thicker films would likely require a lower concentration for optimal detection. Hence, the concentration would be best tailored to the film thickness of the particular grade being manufactured. It is worth noting that the propensity to absorb or fluoresce UV light is not the same for all the candidate Rod species. It is then possible that a molecule which absorbs strongly could be used at a lower concentration than another.
  • the UV-active species used as additives in the present invention are preferably those which possess a marked anisotropy in its interaction with UV irradiation such that, when largely immobilised in a host substrate, irradiation of the substrate with UV light gives an absorption spectrum or a fluorescence intensity which is indicative of a preferred orientation of the guest molecule with respect to any of the principal directions attributable to the substrate, such as the machine direction, transverse direction or normal direction.
  • the security feature of the present invention may be incorporated directly into a suitable article and/or document or may be attached thereto (e.g. in a permanent or tamper evident manner) and/or is otherwise associated therewith as part of a security and/or authentication means.
  • a suitable article and/or document or may be attached thereto (e.g. in a permanent or tamper evident manner) and/or is otherwise associated therewith as part of a security and/or authentication means.
  • the term article includes but is not limited to printed matter such as documents.
  • Suitable articles which may be authenticated as described herein may comprise an integral part of a larger article and/or product (e.g. a high value article whose authenticity it is desired to check) where preferably that article or part thereof comprises a region of oriented polymer film .
  • the article may comprise for example a label and/or tag which is designed to be or attached to another article and/or for example comprise the packaging associated with another article.
  • An article of the present invention (in which the article and/or product to which the security article is attached, of which it is an integral part and/or with which it is associated), may preferably be one which would otherwise be susceptible to counterfeiting due to the high value, prestige and/or other importance associated with the article and/or product and/or where authentication of a genuine article and/or product is desired.
  • an article of the present invention comprises a security document and/or goods, such as one or more of; security tag, label, packaging, brand, trademark, logo, currency (such as bank note), cheque, share certificate, bond, stamp, passport, official document, ticket, security pass and the like.
  • security tag such as one or more of; security tag, label, packaging, brand, trademark, logo, currency (such as bank note), cheque, share certificate, bond, stamp, passport, official document, ticket, security pass and the like.
  • a film of the invention may package, wrap, be associated with, attached to and/or comprise an article selected from for example any of the following non-exhaustive list: antique objects; audio and/or visual goods for example blank and/or pre-recorded media in any format (e.g.
  • compact disks, audio tapes and/or video tapes chemical products for example pesticides, cleaning products, washing powders and/or detergents; tobacco products for example cigarettes, cigars, and/or tobacco goods; clothing articles for example leather articles; soft and/or alcoholic beverages for example wines or spirits; entertainment goods for example toys and/or computer games; foodstuffs for example tea, coffee, meats, fish, caviar and/or delicatessen produce, electrical and electronics parts for example computers and/or spare parts therefor, electronic objects and/or computer software, high technology machines and/or equipment; jewellery for example watches; leisure items for example binoculars and/or telescopes; perfumes and/or cosmetics for example shampoos, soaps, perfumes, deodorants, body lotions, creams, toothbrushes, toothpastes, razors and/or razor blades; products related to or for the treatment, diagnosis, therapy and/or prophylaxis of humans and/or animals, for example dental, medical and/or surgical equipment, blood transfusion pouches, medical infusion pouches, packaging for donated organ
  • optical glasses and/or sunglasses and/or pharmaceutical products
  • pharmaceutical products e.g. in any suitable form for application for example pills, tablets, syrups and/or lotions
  • military equipment for example guns, gun sights, ammunition, rockets, military clothing, foodstuffs, gas-masks, mines, grenades and/or ordnance
  • photographic industry goods for example cameras and/or pellicles
  • scientific instruments and spare parts therefor for example microscopes, chromatographic apparatus, spectrometric and/or nuclear magnetic resonance apparatus
  • machinery and spare parts for the transport industry for example parts for automotive, aerospace and/or aeronautical industry goods, cars, lorries/trucks, motorcycles, space vehicles, rocket ships, vehicle's windscreen stickers, tax discs, trains, coaches and buses, aeroplanes, tubes, trams, helicopters, deep sea exploration equipment, submarines, ships, boats, liners and/or merchant vessels
  • security documents and/or goods such as one or more of: security tag, label, packaging, brand, trademark, logo
  • An article made using the authentication means as described herein may comprise any other compatible security and/or authentication means in any compatible combination comprises, optionally in corresponding patterns the article: such as any of Moire inducing pattern, optical lens, Fresnel lens, multiple micro-lens, lenticular lens, distorting lens, metameric ink, micro-printing and polarising filter.
  • a further aspect of the invention broadly comprises a method of manufacturing a comprising the step of: applying an article and/or security document as described herein to the product as an integral part of the product, by attaching or associating the article to the product and/or by associating the article with the product.
  • Another aspect of the invention broadly comprises a method of authenticating a product comprising the steps of:
  • a still further aspect of the invention broadly comprises the use of UV absorbers, UV fluorescent materials, materials capable of intermolecular non-radiative energy transfer (NRET) and/or phosphorescent materials in a film and/or a method of the invention for the purpose of reflecting a preferred orientation distribution of the polymer chain trajectories in the film via approriate detection methods, i.e. UV absorption, UV fluorescence, dichroic UV absorption or dichroic UV fluorescence measurements, and thus betraying the manufacturing origin of the film in so far as it affects the orientation history of the film.
  • NRET intermolecular non-radiative energy transfer
  • Still other aspects of the invention broadly comprise: Use of a product, article, security document and/or authentication means as described herein to provide a means of authentication.
  • Figures 1 and 2 are plots of the force versus time used to draw oriented films of Examples 9 and 10 respectively.
  • Figures 3 and 4 show infra-red absorbance as a function of the angle between the beam polariser and direction 1 for Examples 9 and 10 respectively
  • Figure 5 shows the known UV absorption spectrum of DPBD dissolved in hexane
  • Figures 7 and 8 are plots of UV fluorescence as described in Examples 7 and 8
  • Figure 9 is a schematic depiction of the even distribution of molecular axes in the plane of a BOPP film made by the bubble process
  • Figure 10 is a Schematic depiction of the preferential distribution of molecular axes towards the transverse direction in a BOPP film made by the stenter process Examples
  • the examples were prepared as follows with reference to Table 1.
  • Each UV additive (as given in Table 1 , both available commercially from Aldrich Chemcials) was dispersed in a pure powdered polyproylene (PP) homopolymer to which 0.3% of an antioxidant was added.
  • the PP used was that available commercially without additives from Solvay SA under the trademark Eltex® P.
  • the antioxidant was that available commercially from Ciba Speciality Chemicals under the trademark Irganox B225.
  • the dispersions were prepared from an initial master batch (as specified in Table 1) using an air mixer. Subsequent mixing of the master batch with further quantities of polypropylene powder diluted the master batch sequentially to achieve the specified final concentration of UV absorber. Concentrations in units of g/kg denote the number of g of UV molecule in the number of kg of the homopolymer.
  • the diluted PP mixtures were subsequently melt-blended on a Prism Twin-Screw extruder to form granules from which solid plaques of polymer were produced in a heated press at 230°C, and then cast cold water to give sheets of cast PP film of thickness 1 mm.
  • These cast sheets were cut into small square sheets of dimensions 1 mm x 60 mm x 60 mm, and stretched on a laboratory biaxial stretching machine at a temperature of 160°C. At this temperature, the polypropylene was slightly below its melting temperature, so that stretching took place in the solid state, affording biaxially-oriented polypropylene sheets of thickness approx. 30 ⁇ m. Two distinct biaxial drawing regimes were used simultaneously or sequentially.
  • a temperature of 157° C was found to be the lowest temperature at which Eltex® P homopolymer could be drawn.
  • 165°C the differences in the characteristics of Examples drawn under simultaneous or sequential conditions were fewer to those Examples drawn at lower temperatures.
  • the example films were made by either drawing simultaneously or sequentially, in both cases the heating blowers were switched off a few seconds before stretching was applied, to prevent the film from melting in the vicinity of the blower outlet. Hence, for sequential draws, the second draw occurred at a lower temperature than the first.
  • Figures 1 and 2 illustrate the contrast in drawing forces for simultaneous and sequential experiments (respectively Examples 9 and 10).
  • the draw temperature was 157°C and the data acquisition rate was 20 Hz.
  • the sample was first drawn at constant width in the x-direction ('direction 1 ') and then at constant with in the y-direction ('direction 2'). It can be seen that comparatively dramatic drawing forces develop in the y-direction during the second draw, suggesting that the finished sample will be largely direction-2-oriented.
  • the FITR may be explained as follows.
  • two peaks were particularly useful.
  • the peak at -997 cm “1 was attributed to crystalline-only vibrations
  • the peak at ⁇ 972cm "1 was attributed to both crystalline and amorphous vibrations, but its intrinsic extinction coefficient may be different to that of the peak at 997 cm "1 .
  • Both of these vibrations were taken as being directed along the chain axis.
  • Figures 3 and 4 show infra-red absorbance as a function of the angle between the beam polariser and direction 1 for respectively Examples 9 (simultaneously-drawn) and Example 10 (sequentially-drawn).
  • a polarised UV beam could be usefully used for orientation analysis of the UV additives.
  • Samples with balanced biaxial orientation or unbalanced biaxial orientation can be made conveniently on the long-stretcher. Lower temperatures accentuate the difference in properties according to film direction in sequentially-drawn (unbalanced) samples. Approx. 0.01% of UV molecule in the polymer was found a particularly suitable concentration for UV analysis.
  • Example 7 DPBD (100g) was blended with 25 kg of isotactic PP homopolymer (BP Eltex P HV001 PF) and the blended material introduced at a 1 % addition level to the extrusion system for the core layer of a BOPP bubble line.
  • Samples from the process were obtained in which the finished film had been subjected to either a heat-setting process (i.e. thermally-induced relaxation of the film in its width (transverse) direction during its conveyance across heated rollers), or no heat-setting process.
  • UV absorption spectroscopy using a polarising filter revealed a UV dichroic ratio or 1.0 for non-heat-set film and 0.8 for heat-set film, thus affording a clear indication of distinct differences in the processing history of the two sample types.
  • Film samples obtained as described in Example 2 were examined using a proprietary UV fluorescence measurement device in which was incorporated a polarising filter for the purpose of polarising the exciting UV irradiation at a wavelength of 360 nm.
  • the fluorescence intensity was measured at a wavelength of 460 nm.
  • the polarising filter was rotated in 5 degree increments with respect to the transverse direction of the film samples.
  • Figure 7 is a plot of UV fluorescence intensity at 460 nm as a function of polariser angle for non-oriented BOPP film containing diphenylbutadiene (DPBD).
  • DPBD diphenylbutadiene
  • Figure 8 is a plot of UV fluorescence intensity at 460 nm as a function of polariser angle for oriented BOPP film containing diphenylbutadiene (DPBD).
  • Heat-setting at 135°C
  • the solid line is a sixth-order polynomial regression fit, applied as a guide to the eye.
  • Non-heat-set 1.01 , 0.97, 1.17; average 1.05 Heat-set 1.11 , 1.20, 1.18; average 1.16

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention concerne une pellicule de polypropylène orientée biaxialement (BOPP) contenant des absorbeurs UV rigides en forme de tige dispersés, compatibles avec le polymère, tels que (E,E)-1,4-diphénylbuta-1,3-diène (DPBD) ; (E,E)-1,6-diphénylhexa-1,3,5-triène (DPHT) ; et bêta-bêta-carotène (carotène) à des concentrations de 0,01 % en poids. Ces absorbeurs s'alignent de préférence le long d'un axe d'orientation de la pellicule, parmi deux, et permettent de détecter de façon cachée l'anisotropie dans la pellicule au moyen de la différence entre les spectres de fluorescence UV de la pellicule le long de chaque axe. Ainsi, il est possible de disposer d'un élément d'authentification cachée de la pellicule pouvant servir de substrat dans des applications de sécurité.
PCT/EP2004/003549 2003-04-02 2004-04-02 Element d'authentification WO2004087795A1 (fr)

Applications Claiming Priority (2)

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GB0307615A GB0307615D0 (en) 2003-04-02 2003-04-02 Authentication means
GB0307615.5 2003-04-02

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2292329A1 (fr) 2009-09-08 2011-03-09 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Substrat polymère doté d'une structure fluorescente, son procédé de fabrication et son utilisation
US8088848B2 (en) 2007-07-24 2012-01-03 Innovia Films Limited UV barrier film
US20120105783A1 (en) * 2010-11-02 2012-05-03 Arizona Board Of Regents On Behalf Of The University Of Arizona Patterned electronic and polarization optical devices
US9079374B2 (en) 2007-05-04 2015-07-14 Innovia Films Limited Sealable, peelable film
US9822229B2 (en) 2007-05-24 2017-11-21 Innovia Films Limited Low emissivity film
US10254453B2 (en) 2010-11-02 2019-04-09 Arizona Board Of Regents On Behalf Of The University Of Arizona Thin-film broadband and wide-angle devices for generating and sampling polarization states
EP3342589A4 (fr) * 2015-08-24 2019-05-01 Toppan Printing Co., Ltd. Feuille décorative
US11230631B2 (en) 2015-08-24 2022-01-25 Toppan Printing Co., Ltd. Decorative sheet, and transparent resin sheet
EP2388551B1 (fr) * 2008-04-28 2022-07-06 Innovia Films Limited Procédé d'authentification d'un film polymère

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US9822229B2 (en) 2007-05-24 2017-11-21 Innovia Films Limited Low emissivity film
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US8088848B2 (en) 2007-07-24 2012-01-03 Innovia Films Limited UV barrier film
EP2388551B1 (fr) * 2008-04-28 2022-07-06 Innovia Films Limited Procédé d'authentification d'un film polymère
EP2292329A1 (fr) 2009-09-08 2011-03-09 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Substrat polymère doté d'une structure fluorescente, son procédé de fabrication et son utilisation
US9597688B2 (en) 2009-09-08 2017-03-21 Ibidi Gmbh Polymer substrate with fluorescent structure, method for the production thereof and the use thereof
US8866997B2 (en) * 2010-11-02 2014-10-21 Arizona Board Of Regents On Behalf Of The University Of Arizona Patterned electronic and polarization optical devices
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US10254453B2 (en) 2010-11-02 2019-04-09 Arizona Board Of Regents On Behalf Of The University Of Arizona Thin-film broadband and wide-angle devices for generating and sampling polarization states
EP3342589A4 (fr) * 2015-08-24 2019-05-01 Toppan Printing Co., Ltd. Feuille décorative
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