SECURITY DOCUMENT WITH A TRANSPARENT PATTERN AND A PROCESS FOR PRODUCING A SECURITY DOCUMENT WITH A TRANSPARENT PATTERN
A security document comprising a plurality of self-supporting polymeric films and layers therebetween and thereon, said plurality of self-supporting polymeric films comprising a non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having a permanent transparent pattern; and a process for producing a security document with a permanent transparent pattern comprising the step of: image-wise application of heat optionally supplemented by the application of pressure to a security document precursor comprising a plurality of self-supporting polymeric films and layers therebetween and thereon, said plurality of self-supporting polymeric films comprising a non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam.
This application claims the benefit of U.S. Provisional Application No. 60/908,526 filed Mar. 28, 2007, U.S. Provisional Application No. 60/908,536 filed Mar. 28, 2007, U.S. Provisional Application No. 60/908,542 filed Mar. 28, 2007 and U.S. Provisional Application No. 60/975,300 filed Sep. 26, 2007, which are all incorporated by reference. In addition, this application claims the benefit of European Application No. 07104953.0 filed Mar. 28, 2008, European Application No. 07104947.2 filed Mar. 28, 2007, European Application No. EP 07104948.0 filed Mar. 28, 2007, European Application No. 07104950.6 filed Mar. 28, 2007, PCT Application No. PCT/EP07/060359 filed Oct. 1, 2007, PCT/EP07/060218 filed Sep. 26, 2007, PCT/EP07/060380 filed Oct. 1, 2007 and PCT/EP07/060373 filed Oct. 1, 2007, which are all also incorporated by reference.
FIELD OF THE INVENTIONThe present invention concerns a security document with a transparent pattern and a process for producing a security document with a transparent pattern.
BACKGROUND OF THE INVENTIONThe field of security documents encompasses not only personalized documents such as passports, driving licenses, health cards, identity cards (ID cards) and admission documents such as visa's and entry tickets, but also the authentification and identification of goods to avoid counterfeiting, tampering and fraud such as lottery tickets, share certificates, transaction documents, labels on luggage and the packaging of pharmaceuticals and high value products in general.
The term “identity card” encompasses cards requiring bearer identification and range from passports to national identity cards to establish the national identity of their civilians to cards involved in the electronic transfer of money such as bank cards, pay cards, credit cards and shopping cards to security cards authorizing access to the bearer of the card to particular areas such as a company (employee ID card), the military, a public service, the safe deposit departments of banks, etc. to social security cards to membership cards of clubs and societies.
Permanent transparent patterns, examples of which are so-called watermarks and so-called pseudo-watermarks, are desirable for documents for anti-falsification, security and traceability applications e.g. banknotes, share certificates, tickets, credit cards, identity documents and labels for luggage and packages. Permanent transparent patterns in a paper support, such as so-called watermarks, can be realized during the manufacturing process.
EP-A 0 203 499 discloses a method of applying a “pseudo watermark to paper, which method comprises the steps of preparing a sheet or roll of paper containing a suitable amount of a thermally sensitive material, and subsequently applying heat to a part of the surface of the paper in a manner to cause a region of the paper to become semi-translucent.
GB 1489084A discloses a method of producing a simulated watermark in a paper sheet, wherein the sheet is impregnated in the desired watermark pattern by a transparentising composition which is itself fluent, and which is polymerisable upon being activated by radiation to yield an insoluble resin matrix having a refractive index approximating to that of the paper, and the composition is cured in situ by irradiating the sheet with activating radiation.
U.S. Pat. No. 3,453,358 discloses in a method of forming clear images in opaque pressure coalescible films which includes the steps of forming an image in such film, and stabilizing the image by fixing a densifying agent in the pores of the film, the improvement in that method which comprises subjecting the densified and stabilized film to a post-treatment which substantially completely collapses and destroys the porous nature of the coalescible coating on the film to permanently encapsulate the densifying agent and to render more transparent those areas of the film in which less than a maximum amount of densifying agent has been deposited.
EP 0 436 178A2 discloses a polymeric shaped article characterized in that said article is comprised of a continuous oriented polymer matrix having dispersed therein microbeads of a cross-linked polymer which are at least partially bordered by void space, said microbeads being present in an amount of 5-50% by weight based on the weight of said oriented polymer, said void space occupying 2-60% by volume of said article. EP 0 436 178A2 further discloses that said cross-linked polymer preferably comprises polymerizable organic material which is a member selected from the group consisting of an alkenyl aromatic compound having the general formula Ar-C(—R)═CH2 wherein Ar represents an aromatic hydrocarbon radical, or an aromatic halohydracarbon radical of the benzene series and R is hydrogen or the methyl radical; acrylate-type monomers including monomers of the formula CH2═C(—R′)—C(—OR)═O wherein R is selected from the group consisting of hydrogen and an alkyl radical containing from about 1 to 12 carbon atoms and R′ is selected from the group consisting of hydrogen and methyl; copolymers of vinyl chloride and vinylidene chloride, acrylonitrile and vinyl chloride, vinyl bromide, vinyl esters having the formula CH2═CH—O—C(—R)═O wherein R is an alkyl radical containing from 2 to 18 carbon atoms; acrylic acid, methacrylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, oleic acid, vinylbenzoic acid; the synthetic polyester resins which are prepared by reacting terephthalic acid and dialkyl terephthalics or ester-forming derivatives thereof, with a glycol of the series HO(CH2)nOH, wherein n is a whole number within the range of 2-10 and having reactive olefinic linkages within the polymer molecule, the hereinabove described polyesters which include copolymerized therein up to 20 percent by weight of a second acid or ester thereof having reactive olefinic unsaturation and mixtures thereof, and a cross-linking agent selected from the group consisting of divinylbenzene, diethylene glycol dimethacrylate, diallyl fumarate, diallyl phthalate and mixtures thereof.
U.S. Pat. No. 5,660,925 discloses an authenticatible, tamper-indicating label, comprising: a normally opaque, transparentizable microporous film having first and second major surfaces, a first indicia proximate said first surface a second indicia on said first surface, and an adhesive proximate said first surface; wherein said microporous film can be changed from an opaque state to a transparent state by application of a first liquid that is not a solvent for said first and second indicia to said microporous film to thereby sufficiently fill the pores of said microporous film to cause said film to become transparent; wherein when said microporous film is in its opaque state, said first and second indicia are not visually perceptible when said label is viewed from said second surface, and when said microporous film is in its transparent state, at least said first indicia is visually perceptible when said label is viewed from said second surface, thereby providing an indication of the authenticity of said label; and wherein application of a second liquid that is a solvent for said second indicia causes at least a portion of said second indicia to migrate through said microporous film to said second major surface, thereby providing a permanent visually perceptible indication of tampering. U.S. Pat. No. 5,660,925 discloses the realization of temporary transparency not permanent transparency.
U.S. Pat. No. 5,928,471 discloses a method of making a continuous roll of banknote paper on a paper making machine, said banknote paper having a low porosity and having a plurality of discrete transparentised regions repeating along the length of the paper, and also having a plurality of discrete areas repeating along the length of the paper which are at least partly of a lower grammage than surrounding areas, so as to provide lighter and darker areas in said areas which are enhanced by said transparentised regions, said method comprising the steps of: (a) continuously depositing an aqueous fibrous suspension onto a support surface to form continuous wet paper sheet; (b) forming in the wet paper sheet a series of discrete areas repeating along the length of the sheet which are at least partly of a lower grammage than surrounding areas; (c) draining liquid from said wet paper sheet to form a continuous unfinished porous absorbent sheet; (d) printing a plurality of locations in said unfinished porous sheet with a transparentising resin to provide transparentised regions which cooperate with the discrete lower grammage areas to enhance the visibility thereof, which transparentising resin is absorbed into the sheet; (e) passing said unfinished porous sheet having the discrete printed transparentised regions through a surface sizing impregnating device so as to impregnate said porous sheet with surface sizing, such that the surface sizing surrounds the transparentised regions; (f) drying the resulting sized porous sheet to form a dried porous sheet; (g) calendering said dried porous sheet; and (h) reeling the resulting sheet into a roll of finished banknote paper.
US 2005/0116463A1 discloses a process for producing a security feature, in particular on print media, in particular passes and identity cards, plastic payment cards, credit cards, memory cards etc, wherein the substrate (1, 1a, 1b) includes at least one change-over substance which by virtue of irradiation with light of a given wavelength (λ, λ1, λ2) experiences an irreversible change in color from a starting color to a final color, characterized in that the substrate when in the initial condition is so irradiated by a controlled light beam of that wavelength (λ, λ1, λ2), in particular a laser beam, that due to the change in color caused thereby in the change-over substance an image which can be recognized especially with the naked eye is produced on the substrate (1).
US 2005/0104365A1 discloses a security substrate comprising at least one oriented, high melt-strength polypropylene foam layer and at least one security element with a preferred security element being an embossment which provides a substantially transparent region with substantially transparent meaning at least about 20 percent, preferably at least 30 percent, of 400 to 700 nm wavelength light passing through a 1-mm thick region. US 2005/0104365A1 fails to define the term “foam”. Therefore, the term “foam” as used in disclosing the invention of US 2005/0104365A1 has the meaning in plain English i.e. is a substance that is formed by trapping many gas bubbles in a liquid or solid. US 2005/0104365A1 discloses in comparative examples that microvoided materials gave very poor transparency upon embossment.
WO 2004/043708A discloses a laminated security document comprising: a transparent or translucent support layer; a first security layer provided on one side of the support layer; a second security layer provided on the opposite side of the support layer; the first and second security layers having security regions which together form a composite security image or device to indicate an authentic security state; a first tamper evident means provided between the support layer and the first security layer; a second tamper evident means provided between the support layer and the second security layer; wherein upon exposure of the security document to predetermined conditions to laminate the document, at least one of the tamper evident means is arranged to destruct or otherwise affect at least one of the security layers to indicate an unauthentic security state.
U.S. Pat. No. 4,526,803 discloses a method for electrostatically transparentizing a portion of a substrate, comprising: selecting finely divided, electrostatically chargeable particles of a material having transparentizing characteristics for a preselected substrate; electrostatically depositing said finely divided transparentizing particles onto a predetermined area of the substrate; heating the transparentizing particles to form a molten transparentizing material at the predetermined area; and transparentizing the substrate at the predetermined area by flowing the molten transparentizing material into the substrate at the predetermined area and allowing the material to solidify therein to form a substrate having a transparentized area and an opaque area.
EP-A 0 618 079 discloses a thermal dye transfer system comprising a thermal dye transfer receptor element in intimate contact with a thermal dye donor sheet, said receptor element comprising a substrate having on at least one surface thereof in contact with said dye transfer donor sheet, an opaque dye receptive receiving layer comprising a thermally transparentizable microporous polymer layer having insufficient pigment to provide an optical density of more than 0.2.
JP 2005-271321A1 discloses the giving of a matt finish to the surface of a recording paper by using a thermal head by heating the protective layer to form a transparent watermark pattern as a result of the different glossiness in accordance with thermal energy given.
However, in all of these disclosures, except for paper, the transparentization has been realized in layers laminated to or applied to the support. Therefore, the prior art fails to teach the realization of a permanent transparent pattern in a polymer self-supporting film itself or a means of obtaining a permanent transparent pattern in a self-supporting polymer film.
ASPECTS OF THE INVENTIONIt is therefore an aspect of the present invention to provide a security document having a permanent transparent pattern.
It is therefore a further aspect of the present invention to provide a process for producing a security document with a permanent transparent pattern.
Further aspects and advantages of the invention will become apparent from the description hereinafter.
SUMMARY OF THE INVENTIONIt has been surprisingly found that a permanent transparent pattern can be obtained by image-wise application of heat to an axially stretched non-transparent film comprising as a continuous phase polypropylene having dispersed therein calcium carbonate; a linear polyester matrix having uniformly dispersed therein a high polymer having a higher glass transition point than that of the linear polyester; a linear polyester matrix having uniformly dispersed therein a crystalline polymer having a higher melting point than that of the linear polyester; a linear polyester matrix having uniformly dispersed therein a high polymer having a higher glass transition point than that of the linear polyester and a crystalline polymer having a higher melting point than that of the linear polyester; and a linear polyester having uniformly dispersed therein a pigment causing microvoiding.
Furthermore, experiments have surprisingly shown that a transparent pattern can be realized in a security document precursor complete except for the provision of one or more security features or in one or more sub-elements from which the multilayered entity is produced. Furthermore, if the pattern, according to the present invention, is produced in a sub-element or even in a foil used to produce such a sub-element, subsequent lamination processes using pressure and/or heat do not degrade the pattern, according to the present invention, despite being possibly subject to multiple lamination processes e.g. lamination to an adhesive foil such as a polyethylene or PETG-foil followed by lamination of the resulting laminate with other foils thereby realizing a sub-element followed by laminating different sub-elements together to produce the precursor of a security document or the security document itself.
Aspects of the present invention are realized by a security document comprising a plurality of self-supporting polymeric films and layers therebetween and thereon, said plurality of self-supporting polymeric films comprising a non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having a permanent transparent pattern.
Aspects of the present invention are also realized by a process for producing a security document with a permanent transparent pattern comprising the step of: image-wise application of heat optionally supplemented by the application of pressure to a security document precursor comprising a plurality of self-supporting polymeric films and layers therebetween and thereon, said plurality of self-supporting polymeric films comprising a non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam.
Preferred embodiments of the present invention are disclosed in the detailed description of the invention.
DETAILED DESCRIPTION OF THE INVENTION DefinitionsThe term voids or microvoids, as used in disclosing the present invention, means microcells, minute closed cells, cavities or pores or cellulation, which, for example, can be formed in an oriented polymeric film during stretching as the result of a void-initiating particle initiated by particles that are immiscible with the polymer matrix. The voids or microvoids can be unfilled or filled with air or a vapour of some sort. Even if initially unfilled the voids or microvoids may over time become filled with air or a vapour of some sort.
The term “opaque”, means a percentage opacity to visible light of greater than 90% as determined according to ASTM D589-97 or according to opacity test T425m-60 as published by TAPPI, 360 Lexington Avenue, New York, USA. Alternative measures of opacity are optical density and the transmittance of visible light. For example YUPO synthetic paper would generally be regarded as opaque and has an optical density of 1.25 as measured with a MacBeth TR924 densitometer with a visible filter. “Opaque PETG” foils containing ca. 10% by weight of titanium dioxide with a thickness of 500 μm from FOLIENWERK WOLFEN GMBH was determined by measurement with an ULTRASCAN spectrophotometer to have a transmittance of 0.3% corresponding to an optical density of 2.52. “Opaque PETG” foils containing ca. 6% by weight of titanium dioxide with thicknesses of 500 μm and 50 μm with had an optical density of 2.52 and 50 μm from FOLIENWERK WOLFEN GMBH and AMCOR respectively were determined by measurement with an ULTRASCAN spectrophotometer to have transmittances of 1.0 to 1.6% and 21.5% respectively corresponding to optical densities of 1.8 to 2.0. Therefore foils with an optical density greater than 0.65 may be regarded as substantially opaque.
The term film, as used in disclosing the present invention, is an extruded sheet of a particular composition or a sheet consisting of a multiplicity of films with the same or different compositions produced by co-extrusion of liquids with the same or different compositions in contact with one another. The term film is also applied to axially and biaxially stretched films. The terms film and foil are used interchangeably in the present disclosure.
The term “axially stretched”, as used in disclosing the present invention, is a generic term referring to the axial stretching process and includes the possibility of stretching in one or more directions.
The term foam, as used in disclosing the present invention, means a substance that is formed by trapping many gas bubbles in a liquid or solid such as resulting from the incorporation of a chemical or physical blowing agent as disclosed in US 2005/0104365A1, WO 02/00982A1 and U.S. Pat. No. 6,468,451.
The term “security document precursor”, as used in disclosing the present invention, means any sub-configuration which can be directly used for producing a security document i.e. whose use enables a security document to be produced.
The term dicarboxylate monomer unit in a linear polyester, as used in disclosing the present invention, means a monomer unit derived either from a dicarboxylic acid or an ester thereof.
The term dimethylene aliphatic monomer unit in a linear polyester, as used in disclosing the present invention, means a monomer unit derived from a dimethylene aliphatic diol or an ether thereof, wherein the term aliphatic includes alicylic.
The term linear polyester, as used in disclosing the present invention, means a polyester comprising hydrocarbon dimethylene and dicarboxylate monomer units.
The term linear aromatic polyester, as used in disclosing the present invention, means a polyester comprising aliphatic dimethylene and aromatic dicarboxylate monomer units.
The term density, as used in disclosing the present invention, means the weight of a 100 mm×100 mm piece of film with a thickness measured in contact with an inductive probe with ball tip 3 mm in diameter divided by its volume. This value assumes that the surfaces of the piece of film are flat and parallel to one another. This value corresponds to the apparent density values reported in EP-A 0 496 323 and WO 2005/105903A.
The term thermally transparentizable, as used in disclosing the present invention, means capable upon the application of heat of providing an optical density difference of at least 0.2 as measured by a densitometer with a visible filter in the transmission mode e.g. using a MacBeth TR924 densitometer.
The term amorphous high polymer, as used in disclosing the present invention, means a polymer with a high molecular weight (sometimes arbitrarily designated as higher than 10,000) and a degree of crystallinity of less than 10%.
The degree of crystallinity can be determined by several experimental techniques including: (i) x-ray diffraction, with the degree of crystallinity=Ic/(Ic+KxIa), where Ic and Ia are the integrated intensities scattered over a suitable angular interval by the crystalline and the amorphous phases respectively and Kx is a calibration constant; (ii) calorimetry, with the degree of crystallinity=Δhfus/Δhfus,c, where hfus is the specific enthalpy of fusion of the sample and Δhfus,c is the specific enthalpy of fusion of the completely crystalline polymer; (iii) density measurements, with the degree of crystallinity=ρc(ρ−ρa)/[ρ(ρc−ρa)], where ρ, ρc and ρa are the densities of the sample, of the completely crystalline polymer and of the completely amorphous polymer, respectively; and (iv) infra-red spectroscopy (IR), with the degree of crystallinity=(1/acρl)log10(I0/I), where I0 and I are the incident and transmitted intensities respectively at the frequency of the absorption band due to the crystalline portion, ac is the absorptivity of the crystalline material and l is the thickness of the sample.
The term crystalline high polymer, as used in disclosing the present invention, means a polymer with a high molecular weight (sometimes arbitrarily designated as higher than 10,000) with a degree of crystallinity of at least 10%.
The term inorganic opacifying pigment, as used in disclosing the present application, means a pigment capable of opacifying (i.e. rendering more opaque) which includes substantially white inorganic pigments having a refractive index of at least 1.4 and below 2.0 and pigments, which as a dispersion in a polymer are capable upon stretching of causing opacity due to microvoiding.
The term whitening agent, as used in disclosing the present invention, means a white/colourless organic compound which exhibits a blue luminescence under the influence of ambient UV-light.
The term “support”, as used in disclosing the present invention, means a “self-supporting material” so as to distinguish it from a “layer” which may be coated as a solution or dispersion, evaporated or sputtered on a support, but which itself is not self-supporting. It also includes an optional conductive surface layer and any treatment necessary for, or layer applied to aid, adhesion.
The term “watermark”, as used in disclosing the present invention, means a transparent image in a non-transparent background or a non-transparent image in a transparent background. A watermark may be detectible in transmission and/or reflection e.g. by holding the foil up to the light.
The term overprintable, as used in disclosing the present invention, means capable of being overprinted by conventional impact and/or non-impact printing processes.
The term conventional printing processes, as used in disclosing the present invention, includes but is not restricted to ink-jet printing, intaglio printing, screen printing, flexographic printing, offset printing, stamp printing, gravure printing, dye transfer printing, thermal sublimation printing and thermal and laser-induced processes.
The term pattern, as used in disclosing the present invention, means a non-continuous layer which can be in any form of lines, squares, circles or any random configuration.
The term layer, as used in disclosing the present invention, means a (continuous) coating covering the whole area of the entity referred to e.g. a support.
The term “non-transparent film”, as used in disclosing the present invention, means a film capable of providing sufficient contrast to a transparent image to make the image clearly perceptible. A non-transparent film can be an “opaque film”, but need not necessarily be completely opaque in that there is no residual translucence i.e. no light penetration through the film. Optical density in transmission as measured with a MacBeth TR924 densitometer through a visible filter can provide a measure of the non-transparency of a film. ISO 2471 concerns the opacity of paper backing and is applicable when that property of a paper is involved that governs the extent to which one sheet visually obscures printed matter on underlying sheets of similar paper and defines opacity as “the ratio, expressed as a percentage, of the luminous reflectance factor of a single sheet of the paper with a black backing to the intrinsic luminous reflectance factor of the same sample with a white reflecting backing. 80 g/m2 copy paper, for example, is white, non-transparent and has an optical density of 0.5 as measured with a MacBeth TR924 densitometer through a yellow filter according to ISO 5-2 and metallized films typically have an optical density ranging from 2.0 to 3.0.
The term transparent, as used in disclosing the present invention, means having the property of transmitting at least 50% of the incident visible light without substantially diffusing it and preferably at least 70% of the incident visible light without substantially diffusing it.
The term flexible, as used in disclosing the present invention, means capable of following the curvature of a curved object such as a drum e.g. without being damaged.
The term “colorant”, as used in disclosing the present invention, means dyes and pigments.
The term “dye”, as used in disclosing the present invention, means a colorant having a solubility of 10 mg/L or more in the medium in which it is applied and under the ambient conditions pertaining.
The term “pigment” is defined in DIN 55943, herein incorporated by reference, as an inorganic or organic, chromatic or achromatic colouring agent that is practically insoluble in the dispersion medium under the pertaining ambient conditions, hence having a solubility of less than 10 mg/L therein.
Security DocumentAspects of the present invention are realized by a security document comprising a plurality of self-supporting polymeric films and layers therebetween and thereon, said plurality of self-supporting polymeric films comprising a non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having a permanent transparent pattern.
A non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having a permanent transparent pattern can be used as a substitute for PET, PETG, PC, PP, Teslin or PVC in a security card i.e. to replace the material which provides the body of a security document.
Security documents conventionally comprise multilayered entities, the sub-layers being coatings, prints, adhesive layers and thin plastic foils. Security printing techniques are used such as offset, intaglio and screen printing.
Often the sub-elements of the final multilayer entities are produced using coatings, prints, adhesive layers and thin plastic foils by coating, printing, lamination, coextrusion and other conventional techniques and these sub-elements are laminated together to produce a final multilayered entity to which further security features may be applied.
According to a first embodiment of the security document, according to the present invention, said non-transparent self-supporting polymeric film exclusive of foam and having said permanent transparent pattern is an outermost polymeric film of said security document.
According to a second embodiment of the security document, according to the present invention, said non-transparent axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern is an outermost polymeric film of said security document and said self-supporting polymeric film exclusive of foam and having said permanent transparent pattern is provided with a transparentizable overprintable layer i.e. suitable for impact or non-impact printing e.g. ink-jet printing. Transparentizable porous layers transparentized by the application of a liquid with an appropriate refractive index, which can also be applied image-wise, are as disclosed in EP-A 1 362 710 and EP-A 1 398 175. This transparentizable overprintable layer can be provided over at least one of alphanumeric characters, an embossed pattern, an optionally embossed hologram and a continuous, half-tone or digital image on a surface of the non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern.
According to a third embodiment of the security document, according to the present invention, the non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern is provided on at least one side with a transparent or translucent overprintable layer i.e. suitable for impact or non-impact printing. This transparent overprintable layer can be provided over at least one of alphanumeric characters, an embossed pattern, an optionally embossed hologram, a continuous image, a half-tone image and digital image on a surface of the non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern.
Transparentization of part of the transparentizable porous receiving layer can itself produce an image or the non-transparentized area of the opaque porous receiving layer can itself represent an image. The permanent transparent pattern can, for example, be part of a banknote, a share certificate, a ticket, a credit card, an identity document or a label for luggage and packages. Moreover, an additional security feature can be provided by relative positioning of the transparency/watermark in the transparentized layer and the permanent transparent pattern in the support.
According to a fourth embodiment of the security document, according to the present invention, said non-transparent axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern is an outermost polymeric film of said security document and said self-supporting polymeric film exclusive of foam and having said permanent transparent pattern is provided with an ink-jet receiving layer. Typical receiving layers are either porous in the case of aqueous or solvent inks or pastes to enable rapid drying to the touch or are non-porous in the case of phase-change inks or curable inks e.g. radiation curable inks. Porous receiving layers typically comprise at least one pigment such as silica or alumina; at least one binder, such as an ammonium salt of a styrene-acrylate-acrylic acid terpolymer; a surfactant e.g. an anionic surfactant such as an aliphatic sulphonate; optionally a levelling agent, such as polydimethylsiloxane, and optionally a mordant.
According to a fifth embodiment of the security document, according to the present invention, an outermost polymeric film of said security document is a non-transparent microvoided axially stretched self-supporting polymeric film.
According to a sixth embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern constitutes the core of said security document.
According to a seventh embodiment of the security document, according to the present invention, a biaxially stretched polyester film is the outermost film on both sides of the security document, with at least one of said biaxially stretched polyester films being transparent.
According to an eighth embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern comprises a polymer as a continuous phase and dispersed uniformly therein an amorphous high polymer with a higher glass transition temperature than the glass transition temperature of said continuous phase and/or a crystalline high polymer with a melting point higher than said glass transition phase of said continuous phase, with an amorphous high polymer being at least partially crosslinked being preferred.
According to a ninth embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern is a biaxially stretched film.
According to a tenth embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern comprises a polyolefin as continuous phase, with isotactic polypropylene or isotactic poly(4-methylpentene) being preferred.
According to an eleventh embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern comprises a linear polyester as continuous phase and in said continuous phase linear polyester matrix is uniformly dispersed from 5 to 35% by weight of the film, preferably 7 to 30% by weight and particularly preferably 9 to 25% by weight, of a high polymer, the high polymer being an amorphous high polymer having a higher glass transition point than the glass transition temperature of the linear polyester and/or a crystalline high polymer having a higher melting point than the glass transition temperature of the linear polyester.
According to a twelfth embodiment of the security document, according to the present invention, said pattern is a watermark.
According to a thirteenth embodiment of the security document, according to the present invention, said security document further comprises an embedded chip.
According to a fourteenth embodiment of the security document, according to the present invention, said security document further comprises an embedded chip and said embedded chip has contact surfaces.
According to a fifteenth embodiment of the security document, according to the present invention, said security document is an identity card.
According to a sixteenth embodiment of the security document, according to the present invention, said security document is an identity card and said identity card has a format according to ISO 7810.
According to a seventeenth embodiment of the security document, according to the present invention, said security document further comprises an embedded chip and said security document is an identity card according to ISO 7816 and/or ISO 14443.
According to an eighteenth embodiment of the security document, according to the present invention, said permanent transparent pattern is visible in transmission i.e. with transmitted light in the wavelength range 400 to 700 nm.
According to a nineteenth embodiment of the security document, according to the present invention, the pattern is visible in reflection i.e. with reflected light in the wavelength range 400 to 700 nm.
According to a twentieth embodiment security document, according to the present invention, the pattern has an optical density difference in respect of the background of at least 0.15, preferably at least 0.25, particularly preferably at least 0.35 and especially preferably at least 0.45.
According to a twenty-first of the security document, according to the present invention, the pattern has an optical density difference in respect of the background of at least 15%, preferably at least 25%, particularly preferably at least 35% and especially preferably at least 45%.
According to a twenty-second embodiment of the security document, according to the present invention, the pattern is detectable by touch.
According to a twenty-third embodiment of the security document, according to the present invention, the pattern is detectable by change in gloss.
According to a twenty-fourth embodiment of the security document, according to the present invention, the non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam is white i.e. non-transparent axially stretched self-supporting film providing the background for the pattern is white.
According to a twenty-fifth embodiment of the security document, according to the present invention, the non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam is coloured.
According to a twenty-sixth embodiment of the security document, according to the present invention, the non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam further contains at least one colorant.
According to a twenty-seventh embodiment of the security document, according to the present invention, the non-transparent self-supporting microvoided polymeric film exclusive of foam and having said permanent transparent pattern is exclusive of foaming agent and/or decomposition products of a foaming agent.
According to a twenty-eighth embodiment of the security document, according to the present invention, the non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern comprises a polymer as a continuous phase and dispersed uniformly therein an amorphous high polymer with a higher glass transition temperature than the glass transition temperature of the continuous phase and/or a crystalline high polymer with a melting point higher than the glass transition phase of the continuous phase and inorganic opacifying pigment as particles all having a refractive index of at least 2.0 in a total concentration of between 0.5 and 5% by weight of the film.
According to a twenty-ninth embodiment of the security document, according to the present invention, the non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern is provided with at least one of alphanumeric characters, an embossed pattern, an optionally embossed hologram, a continuous image, a half-tone image and a digital image.
According to a thirtieth embodiment of the security document, according to the present invention, the non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern is provided with a subbing layer. This subbing layer makes it possible to improve wettability and adhesive property of the polymeric film and preferably comprises a polyester resin, a polyurethane resin, a poly(ester urethane) resin or an acrylic resin.
According to a thirty-first embodiment of the security document, according to the present invention, the non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern has a thickness in the range from about 12 μm to about 500 μm, with from about 15 μm to about 300 μm being preferred, from about 25 μm to about 200 μm being particularly preferred and from about 50 μm to about 150 μm being especially preferred.
The permanent transparent pattern can itself represent an image or the non-transparentized area of the film can represent an image. The permanent transparent pattern can, for example, be part of a banknote, a share certificate, a ticket, a credit card, an identity card, an identity document or a label for luggage and packages and be one of a large number of security features rendering falsification as difficult as possible. Such additional security features include security printing, holograms, luminescing beads and luminesing threads. The permanent transparent pattern in a non-transparent microvoided axially stretched self-supporting polymeric film can can be one of the foils comprised in multiplex laminate.
The non-transparent microvoided axially-stretched polymeric film may further contain other ingredients such as antioxidants, light stabilizers, UV-absorbers and flame retardants.
The extruded film has a thickness of approximately 10 μm to approximately 6000 μm, with a thickness of approximately 100 to approximately 5000 μm being preferred, a thickness of approximately 200 μm to approximately 3000 μm being particularly preferred and a thickness of approximately 500 μm to approximately 2000 μm being especially preferred.
Non-Transparent Microvoided Axially-Stretched Polymeric Film Exclusive of FoamThe non-transparent microvoided axially-stretched polymeric film exclusive of foam is produced by orienting the film by stretching e.g. in the machine direction or in a direction perpendicular to the machine direction (the transversal direction). Preferably the non-transparent microvoided axially-stretched film is biaxially stretched. Biaxial stretching is realized by orienting the film by first stretching in one direction (e.g. in the machine direction=MD) and then stretching in a second direction [e.g. perpendicularly to the machine direction=TD (transversal direction)]. This orients the polymer chains thereby increasing the density and crystallinity. Longitudinal orientation can be carried out with the aid of two rolls running at different speeds corresponding to the desired stretching ratio by setting the surface speed V2 of the rotating rollers relative to the extrusion speed V1 so that the stretching ratio is V2/V1. The longitudinal stretching ratio should be sufficient to create voids.
Any longitudinal stretching operations known in the art to produce axially and biaxially oriented polyester film may be used. For instance, the combined film layers are passed between a pair of infra red heaters which heats the layers to a temperature above the glass transition temperature of the polyester (about 80° C. for polyethylene terephthalate) in the region where the stretching occurs. The temperatures at which stretching is carried out should be close to the glass transition temperature of the continuous phase polymer in order to improve opacity. Furthermore, the stretching temperatures should be below the glass transition temperature of the amorphous high polymer or melting point of the crystalline high polymer. In the case of polyethylene terephthalate, the longitudinal stretching is generally carried out at from about 80 to about 130° C. During longitudinal stretching opacity is realized as a result of the voids produced in the film extending longitudinally from each particle of dispersed polymer.
Transverse stretching is carried out at an angle substantially 90° to the direction of longitudinal stretching, with the angle being typically between about 70° and 90°. For transverse stetching use is generally made of an appropriate tenter frame, clamping both edges of the film and then drawing toward the two sides by heating the axially stretched film optionally with at least one primer layer thereon by, for example, passing through hot air heaters which heat the film above the glass transition temperature of the continuous phase. Transverse stretching at or below 30° C. above the glass transition temperature of the continuous phase, with a temperature at or below 20° C. above the glass transition temperature of the continuous phase preferred and a temperature at or below 10° C. above the glass transition temperature of the continuous phase being particularly preferred. In the case of polyethylene terephthalate and its copolymers, the transverse stretching is carried out at from about 80 to about 170° C., with from about 90 to about 160° C. being preferred and from about 85 to about 150° being particularly preferred. The transverse stretching of the film causes the voids to extend transversely.
The production of the biaxially stretched polymeric film, according to the present invention, is preferably produced by longitudinally stretching the thick film at a stretching tension>2.5 N/mm2, with a stretching tension>5.0 N/mm2 being preferred and a stretching tension>7.0 N/mm2 being particularly preferred. After optional intermediate quenching the longitudinal stretching is followed by transverse stretching at an angle substantially 90° to the first stretching process to at least twice the initial length at a stretching tension of >2.5 N/mm2, with a stretching tension of >4.0 N/mm2 being preferred, at a temperature preferably at or below 30° C. above the glass transition temperature of the continuous phase and preferably at or below 20° C. above the glass transition temperature of the continuous phase. The realizable stretching tension increases with decreasing stretching temperature.
Longitudinal and transverse stretching may be performed simultaneously e.g. with an apparatus produced by Brückner.
The production process may further comprise, as a further step, a thermal fixation step to counter shrinkage.
The longitudinal stretching ratio is generally in the range from about 2 to about 6, with a range from about 2.5 to about 5 being preferred and a range from about 3 to about 4 being particularly preferred. The high the stretching ratio, the higher the opacity.
The optional transverse stretching ratio is generally in the range from about 2 to about 6, with a range from about 2.5 to about 5 being preferred and a range from about 3 to about 4 being particularly preferred. The opacity increases at higher stretching rates and also at lower transverse stretching temperatures.
The axially or biaxially stretched film is passed through a second set of hot air heaters which blow hot air at a temperature of between 160 and 240° C. onto the film layers to heat-set or thermofix the film layers. The heat-set temperature must be sufficient to obtain crystallization of the polyester but care must be taken not to overheat the layers since the voids can collapse. On the other hand increasing the heat-set temperature improves the dimensional stability of the film. An appropriate mix of properties can be obtained by varying the heat-set temperature. The preferred heat-set or thermofixation temperature in the case of polyethylene terephthalate is at least 140° C. and preferably at least 150° and particularly preferably at least 175° C.
Before or after longitudinal stretching a first subbing layer, called a primer layer, may be applied to the non-voided polyester layer by a coating means such as an air knife coating system. The first subbing layer is for example formed from a (meth)acrylate copolymer, a poly(meth)acrylate, a polyurethane, a sulphonated polyester, a styrene-(meth)acrylate copolymer or a chloride containing copolymer such as vinylidene chloride copolymer in latex form having some hydrophilic functionality through the presence of a copolymerized unsaturated carboxylic acid which is applied as an aqueous dispersion.
Transparentization of part of the transparentizable porous receiving layer can itself produce an image or the non-transparentized area of the opaque porous receiving layer can itself represent an image. The permanent transparent pattern can, for example, be part of a banknote, a share certificate, a ticket, a credit card, an identity document or a label for luggage and packages.
The non-transparent microvoided axially stretched self-supporting polymeric film, used in the present invention, can be produced by a process comprising the steps of: i) mixing a linear polyester, a high polymer being an amorphous high polymer having a glass transition temperature higher than the glass transition temperature of the linear polyester and/or a crystalline high polymer having a melting point higher than the glass transition temperature of the linear polyester, optionally together with <3% by weight of the film of an inorganic opacifying pigment and also optionally together with ≦0.5% by weight of the film of a whitening agent in a kneader or an extruder, ii) forming the mixture produced in step i) in a thick film followed by quenching to room temperature, iii) longitudinally stretching the thick film at a stretching tension of >2.5 N/mm2 at a temperature between the glass transition temperature of the amorphous high polymer and the glass transition temperature of the linear polyester or between the melting temperature of the crystalline high polymer and the glass transition temperature of the linear polyester to at least twice the initial length and iv) optionally laterally stretching the thick film at a stretching tension of >2.5 N/mm2 at a temperature between the glass transition temperature of the amorphous high polymer and the glass transition temperature of the linear polyester or between the melting temperature of the crystalline high polymer and the glass transition temperature of the linear polyester to at least twice the initial length. Steps iii) and iv) of this process can be performed simultaneously and the process may further comprise a thermal relaxation step.
Before or after longitudinal stretching a first priming layer, otherwise known as a subbing layer or a primer layer, may be applied to the non-voided polyester layer by a coating means such as an air knife coating system. The first subbing layer is for example formed from a (meth)acrylate copolymer, a poly(meth)acrylate, a poly-urethane, a sulphonated polyester or a chloride containing copolymer such as vinylidene chloride copolymer in latex form having some hydrophilic functionality through the presence of a copolymerized unsaturated carboxylic acid which is applied as an aqueous dispersion. Alternatively layers of adhesive may be applied by coating, printing e.g. gravure printing or lamination.
Optical Density of the Film Due to MicrovoidsThe optical density of the film measured in transmission with a visible filter due to microvoids is obtained by measuring the optical density of the film without void-producing ingredients as a function of film thickness to provide comparative values. The optical density of a film measured in transmission with a visible filter due to voids is then obtained by biaxially stretching a composition to which has been added the void-inducing ingredient and subtracting the measured optical density measured in transmission with a visible filter from the optical density measured in transmission with a visible filter for the film composition without void-inducing ingredient for the film thickness expected on the basis of the longitudinal and transverse drawing ratios.
Linear PolyesterIf the continuous phase of the axially stretched polymeric film is a polyester, the axially stretched self-supporting film including the permanent transparent pattern provided by the present invention can replace axially stretched polyester films in security document configurations without loss of mechanical functionality such as bending and wear properties. Conventional adhesive layers can be used with the axially stretched polyester film including the permanent transparent pattern such as polyethylene, polyurethane adhesives and PETG and lamination temperatures between 120 and 150° C. can be used. Axially stretched polyester film including the permanent transparent pattern can be laminated to axially stretched poly(ethylene terephthalate) without adhesive layer from a temperature of 180° C. and directly to PETG from a temperature of 160° C.
According to a thirty-second embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern comprises a linear polyester as continuous phase, with the linear polyester preferably comprising at least one aromatic polyester resin being preferred and a linear polyester having monomer components consisting essentially of at least one aromatic dicarboxylic acid and at least one aliphatic diol being particularly preferred. Upon heating, e.g. during mixing in an extruder, the different linear polyester resins present will undergo metathesis, condensing and decondensing so as to evolve upon sufficiently long heating into a single resin.
If the continuous phase of the microvoided film is a polyester matrix, it can comprise any polyester and preferably comprises poly(ethylene terephthalate) or a copolymer thereof. Suitable polyesters include those produced from aromatic, aliphatic, or cyclo-aliphatic dicarboxylic acids or their esters, the dicarboxylate group having 4-20 carbon atoms, and aliphatic (including alicyclic) glycols or ethers thereof, the aliphatic dimethylene groups having 2-24 carbon atoms, and mixtures thereof. Examples of suitable aromatic dicarboxylates include terephthalate, isophthalate, phthalate, naphthalene dicarboxylates and sodiosulfoisophthalate. Examples of suitable aliphatic dicarboxylates include succinate, glutarate, adipate, azelaiate (from azelaic acid), sebacate, fumarate, maleiate (from maleic acid) and itaconate. Examples of suitable alicylic dicarboxylate are 1,4-cyclohexane-dicarboxylate, 1,3-cyclohexane-dicarboxylate and 1,3-cyclopentane-dicarboxylate. Examples of suitable aliphatic dimethylenes include ethylene, propylene, methylpropylene, tetramethylene, pentamethylene, hexamethylene, neopentylene [—CH2C(CH3)2—CH2], 1,4-cyclohexane-dimethylene, 1,3-cyclohexane-dimethylene, 1,3-cyclopentane-dimethylene, norbornane-dimethylene, —CH2CH2(OCH2CH2)n—, where n is an integer with 1 to 5 being preferred, and mixtures thereof.
Such polyesters are well known in the art and may be produced by well-known techniques, for example, those described in U.S. Pat. No. 2,465,319 and U.S. Pat. No. 2,901,466.
Preferred continuous matrix polymers are those having repeat units from terephthalic acid or naphthalene dicarboxylic acid and at least one glycol selected from ethylene glycol, 1,4-butanediol, neopentyl glycol, 2-endo, 3-endo norbornane dimethanol and 1,4-cyclohexanedimethanol. Poly(ethylene terephthalate), which may be modified by small amounts of other monomers, is especially preferred. Other suitable polyesters include liquid crystal copolyesters formed by the inclusion of a suitable amount of a co-acid component such as stilbene dicarboxylic acid. Examples of such liquid crystal copolyesters are those disclosed in U.S. Pat. No. 4,420,607, U.S. Pat. No. 4,459,402 and U.S. Pat. No. 4,468,510.
According to a thirty-third embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern comprises as continuous phase a linear polyester having a number average molecular weight in the range of 10,000 to 30,000.
According to a thirty-fourth embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern comprises as continuous phase a linear polyester having an inherent viscosity determined in a 0.5 g/dL solution of 60 wt % phenol and 40 wt % ortho-dichlorobenzene at 25° C. of at least 0.45 dl/g with an inherent viscosity of 0.48 to 0.9 dl/g being preferred, an inherent viscosity of 0.5 to 0.85 dl/g being particularly preferred and an inherent viscosity of 0.55 to 0.8 dl/g being especially preferred.
According to a thirty-fifth embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern comprises as continuous phase a linear polyester comprising poly(ethylene terephthalate) or a copolymer thereof.
According to a thirty-sixth embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern comprises as continuous phase a linear polyester having aromatic dicarboxylate monomer units selected from the group consisting of terephthalate, isophthalate and naphthalene dicarboxylates.
According to a thirty-seventh embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern comprises as continuous phase a linear polyester in which at least 1 mole % of the aromatic dicarboxylate monomer units in the linear polyester are isophthalate monomer units, with at least 3 mole % being preferred and at least 5 mole % being particularly preferred.
According to a thirty-eighth embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern comprises as continuous phase a linear polyester in which 30 mole % or less of the aromatic dicarboxylate acid monomer units in the linear polyester are isophthalate monomer units, with 20 mole % or less being preferred, 18 mole % or less being particularly preferred and 15% or less being especially preferred.
According to a thirty-ninth embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern comprises as continuous phase a linear polyester in which the aliphatic dimethylene monomer units are selected from the group consisting of ethylene, tetramethylene and 1,4-cyclohexane-dimethylene.
According to a fortieth embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern comprises as continuous phase a linear polyester are neopentylene or 1,4-cyclohexanedimethylene monomer units, with at least 3 mole % being preferred and at least 5 mole % being particularly preferred.
According to a forty-first embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern comprises as continuous phase a linear polyester comprising 30 mole % or less of the aliphatic dimethylene monomer units in the linear polyester are neopentylene or 1,4-cyclohexanedimethylene monomer units, with 20 mole % or less being preferred, 18 mole % or less being particularly preferred and 15% or less being especially preferred.
According to a forty-second embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern comprises as continuous phase a linear polyester further comprising an electroconductivity enhancing additive e.g. a metallic salt which ionizes in the melt giving enhanced electroconductivity such as magnesium acetate, manganese salts and cobalt sulphate. Suitable salt concentrations are about 3.5×10−4 moles/mole polyester. Enhanced polyester melt viscosity enables improved pinning of the melt on the chilling roller maintained at a temperature of 5 to 25° C. (preferably 15 to 30° C.) to cool the extrudate thereby enabling higher stretching forces to be realized and hence enhanced void-forming and a higher degree of opacification.
According to a forty-third embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern comprises as continuous phase a linear polyester having a glass transition temperature from 40 to 150° C., preferably from 50 to 120° C. and particularly preferably from 60 to 100° C.
According to a forty-fourth embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern comprises as continuous phase a linear polyester blend comprising poly(ethylene terephthalate) and poly(1,4-cyclohexylene dimethylene terephthalate).
Amorphous High PolymerThe amorphous high polymer used in the non-transparent microvoided axially stretched self-supporting polymeric film, used in the present invention, has a glass transition temperature higher than the glass transition temperature of the continuous phase in which it is dispersed e.g. a linear polyester. Poly(ethylene terephthalate), for example, has a glass transition temperature of ca 80° C.
The glass transition temperatures and refractive indices for various amorphous high polymers are given in the table below:
According to a forty-fifth embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern comprises a linear polyester as continuous phase and dispersed therein is an amorphous high polymer which is at least partially crosslinked e.g. at least partially crosslinked poly(methyl methacrylate) or at least partially crosslinked copolymers of acrylonitrile and styrene.
According to a forty-sixth embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern comprises a linear polyester as continuous phase and dispersed therein is an amorphous high polymer having a degree of crosslinking of at least 10%.
According to a forty-seventh embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern comprises a linear polyester as continuous phase and dispersed therein is an amorphous high polymer comprising at least one chain-polymerized block.
According to a forty-eighth embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern comprises a linear polyester as continuous phase and dispersed therein is an amorphous high polymer selected from the group consisting of a polymethylmethacrylate, a SAN polymer, and a copolymer of acrylonitrile, butadiene and styrene.
According to a forty-ninth embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern comprises a linear polyester as continuous phase and dispersed therein is an amorphous high polymer comprising at least one chain-polymerized block and the at least one chain-polymerized block is selected from the group consisting of polystyrene, styrene copolymers, SAN-polymers, polyacrylates, acrylate-copolymers, polymethacrylates and methacrylate-copolymers.
According to a fiftieth embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern comprises a linear polyester as continuous phase and dispersed therein is an amorphous high polymer comprising at least one chain-polymerized styrene copolymer block selected from the group consisting of SAN-polymers, ABS-polymers and SBS-polymers.
The SAN polymer additive of the present composition is a known class of polymer consisting essentially of a random copolymer of a styrenic monomer component, including styrene as well as an alpha-lower alkyl-substituted styrene or mixtures thereof and an acrylonitrilic monomer component including acrylonitrile as well as an alpha-lower alkyl substituted acrylonitrile or mixtures thereof. By lower-alkyl is meant a straight or branched chain alkyl group of 1 to 4 carbon atoms exemplified by the methyl, ethyl, isopropyl and t-butyl groups. In readily available SAN polymers, the styrene component is generally styrene, alpha-straight chain alkyl substituted styrene, typically alpha-methyl-styrene, or mixtures thereof with styrene being preferred. Similarly in the readily available SAN polymers, the acrylonitrile component is generally acrylonitrile, alpha-methyl-acrylonitrile or mixtures thereof with acrylonitrile being preferred.
In the SAN polymer the styrene component is present in a major weight proportion, i.e. in a weight proportion of greater than 50%, typically about 65% to about 90%, especially about 70% to about 80%, based on the combined weight of the styrene component and the acrylonitrile component. The acrylonitrile component is present in a minor proportion, i.e. in a weight proportion of less than 50%, typically about 10% to about 35% especially about 20% to 30% based on the combined weight of the styrene monomer component and the acrylonitrile monomer component. Styrene-acrylonitrile copolymers are currently commercially available with an acrylonitrile content of 15 to 35% by weight, with 18 to 32% by weight being preferred and 21 to 30% by weight being particularly preferred.
The SAN polymer class is more particularly identified and described in R. E. Gallagher, U.S. Pat. No. 3,988,393, issued Oct. 26, 1976 (especially at Column 9, lines 14-16 and in Claim 8), in “Whittington's Dictionary of Plastics”, Technomic Publishing Co., First Edition, 1968, page 231, under the section headed “Styrene-Acrylonitrile Copolymers (SAN)”, and R. B. Seymour, “Introduction to Polymer Chemistry”, McGraw-Hill, Inc., 1971, page 200, (last two lines) to page 201 (first line). The preparation of a SAN polymer by copolymerization of styrene and acrylonitrile is more particularly described in the “Encyclopedia of Polymer Science and Technology”, John Wiley and Sons, Inc., Vol. 1, 1964, pages 425-435.
According to a fifty-first embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern comprises a linear polyester as continuous phase and dispersed therein is a SAN polymer.
According to a fifty-second embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern comprises a linear polyester as continuous phase and dispersed therein is a SAN polymer having a concentration of AN-monomer units of 15 to 35% by weight.
According to a fifty-third embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern comprises a linear polyester as continuous phase and dispersed therein is a SAN polymer in a concentration of at least 5% by weight of the film, with at least 10% by weight of the film being preferred and at least 12% by weight being particularly preferred.
According to a fifty-fourth embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern comprises a linear polyester as continuous phase and dispersed therein is a SAN polymer in a concentration of 35% by weight or less with a concentration of 25% by weight or less being preferred and a concentration of 20% by weight or less being particularly preferred.
According to a fifty-fifth embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern comprises a linear polyester as continuous phase and dispersed therein is a non-crosslinked SAN polymer having a number average molecular weight in the range of 30,000 to 100,000, preferably in the range of 32,000 to 80,000, particularly preferably in the range of 35,000 to 70,000 and especially preferably in the range of 40,000 to 60,000. Typical SAN-polymers have number averaged molecular weights of 45,000 to 54,000 and polymer dispersities (Mw/Mn) of 1.2 to 2.5.
According to a fifty-sixth embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern comprises a linear polyester as continuous phase and dispersed therein is a non-crosslinked SAN polymer having a weight average molecular weight in the range of 50,000 to 200,000, preferably in the range of 75,000 to 150,000. The higher the molecular weight of the SAN polymer, the larger the size of the dispersed SAN polymer particles.
According to a fifty-seventh embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern comprises a linear polyester as continuous phase and dispersed therein are amorphous high polymer particles having a diameter of less than 10 μm, with particles having a number average particle size of 0.5 to 5 μm being preferred and particles with an average particle size of 1 to 2 μm being particularly preferred. The smaller the particles size, the higher the opacity.
According to a fifty-eighth embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern comprises is exclusive of a polyether such as polyethylene oxide. Such polyethers decrease the density and may decompose producing additional non-uniformly distributed voids.
According to a fifty-ninth embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern is exclusive of a cellulose ester.
Crystalline High PolymerThe crystalline high polymer used in the non-transparent microvoided axially stretched self-supporting polymeric film, used in the present invention, has a melting point higher than the glass transition temperature of the continuous phase polymer in which it is dispersed e.g. a linear polyester. Crystalline high polymers with sufficiently high melting points include polyethylene, polypropylene and poly(4-methyl-1-pentene).
According to a sixtieth embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern comprises a linear polyester as continuous phase and dispersed therein are crystalline high polymer particles having a number averaged particle size of 0.5 to 12 μm, with 1 to 7 μm being preferred and 2 to 5 μm being particularly preferred.
According to a sixty-first embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern comprises a linear polyester as continuous phase and dispersed therein are crystalline high polymer particles selected from polyethylene, polypropylene and poly(4-methyl-1-pentene) particles, with poly(4-methyl-1-pentene) particles being preferred.
The melting points and refractive indices for various polyethylenes and polypropylenes are given in the table below:
According to a sixty-second embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern further comprises at least one inorganic opacifying pigment, with an inorganic opacifying agent selected from the group consisting of silica, zinc oxide, zinc sulphide, lithopone, barium sulphate, calcium carbonate, titanium dioxide, aluminium phosphates and clays being preferred. The titanium dioxide may have an anatase or rutile morphology and may be stabilized by alumina oxide and/or silicon dioxide. The aluminium phosphate can be an amorphous hollow pigment e.g. the Biphor™ pigments from BUNGE.
The refractive indices of these pigments are given in the table below:
According to a sixty-third embodiment of the security document, according to the present invention, the non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern further comprises ≦5% by weight of inorganic opacifying pigment each with a refractive index of less than 2.0, with less than ≦3% by weight of inorganic opacifying pigment each with a refractive index of less than 2 being preferred.
According to a sixty-fourth embodiment of the security document, according to the present invention, the non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern further comprises ≦5% by weight of inorganic opacifying pigment with less than ≦3% by weight being preferred.
According to a sixty-fifth embodiment of the security document, according to the present invention, the non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern comprises a polymer as a continuous phase and dispersed uniformly therein an amorphous high polymer with a higher glass transition temperature than the glass transition temperature of the continuous phase and/or a crystalline high polymer with a melting point higher than the glass transition phase of the continuous phase and inorganic opacifying pigment as particles all having a refractive index of at least 2.0 in a total concentration of between 0.5 and 5% by weight of the film.
According to a sixty-sixth embodiment of the security document, according to the present invention, the non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern further comprises at least one inorganic opacifying pigment and the concentration of inorganic opacifying pigment is ≧1% by weight.
According to a sixty-seventh embodiment of the security document, according to the present invention, the non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern further comprises an inorganic opacifying pigment having a number averaged particle size of 0.1 to 10 μm, with 0.2 to 2 μm being preferred and 0.2 to 1 μm being particularly preferred.
Addition of an inorganic opacifying pigment has the advantage of stabilizing the orientation of the polyester, so that the non-transparent microvoided axially stretched self-supporting polymeric film can be stabilized at temperatures of 175° C. without substantially affecting the opacity of the non-transparent microvoided axially stretched self-supporting polymeric film. Without the presence of an inorganic opacifying pigment, such as BaSO4, thermofixing of the polyester is possible, but only at the expense of some of the opacity of the non-transparent microvoided axially stretched self-supporting polymeric film. Moreover, pigments with a refractive index below 2.0 do not of themselves provide substantial opacity due to the small refractive index differences between the pigment and the polymer matrix.
Titanium dioxide particles dispersed in polymer films have been found not to induce microvoiding upon stretched the films.
Whitening AgentAccording to a sixty-eighth embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern further comprises a whitening agent, with a concentration of ≦0.5% by weight of the film being preferred, a concentration of ≦0.1% by weight being preferred particularly preferred, a concentration of ≦0.05% by weight being especially preferred and a concentration of ≦0.035% by weight being especially particularly preferred.
According to a sixty-ninth embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern further comprises a whitening agent selected from the group consisting of bis-benzoxazoles e.g. bis-benzoxazolyl-stilbenes and bis-benzoxazolyl-thiophenes; benzotriazole-phenylcoumarins; naphthotriazole-phenylcoumarins; triazine-phenylcoumarins and bis(styryl)biphenyls.
Suitable whitening agents are:
According to a seventieth embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern further comprises a flame retardant.
According to a seventy-first embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern further comprises a flame retardant selected from the group consisting of: brominated compounds; organophosphorus compounds; melamine; melamine-derivatives, e.g. melamine salts with organic or inorganic acids such as boric acid, cyanuric acid, phosphoric acid or pyro/poly-phosphoric acid, and melamine homologues such as melam, melem and melon; metal hydroxides e,g. aluminium hydroxide and magnesium hydroxide; ammonium polyphosphates and zinc borate e.g. with a composition of xZnO.yB2O3.zH2O such as 2ZnO.3B2O3.3.5H2O.
Suitable flame retardants include:
According to a seventy-second embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern further comprises an antioxidant.
According to a seventy-third embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern further comprises an antioxidant selected for the group consisting of organotin derivatives, sterically hindered phenols, sterically hindered phenol derivatives and phosphites.
Suitable antioxidants include:
According to a seventy-fourth embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern further comprises a light stabilizer.
According to a seventy-fifth embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern further comprises a hindered amine light stabilizer.
Suitable light stabilizers include:
According to a seventy-sixth embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern further further comprises a UV-absorber.
According to a seventy-seventh embodiment of the security document, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having said permanent transparent pattern further comprises an UV-absorber selected from the group consisting of benzotriazole derivatives and triazine derivatives.
Suitable UV-absorbers include:
Aspects of the present invention are realized by a process for producing a security document with a permanent transparent pattern comprising the step of: image-wise application of heat optionally supplemented by the application of pressure to a security document precursor comprising a plurality of self-supporting polymeric films and layers therebetween and thereon, said plurality of self-supporting polymeric films comprising a non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam.
According to a first embodiment of the process, according to the present invention, at least one outermost polymeric film of said security document precursor is said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam.
According to a second embodiment of the process, according to the present invention, said non-transparent microvoided self-supporting polymeric film exclusive of foam constitutes the core of said security document precursor.
According to a third embodiment of the process, according to the present invention, said non-transparent microvoided self-supporting polymeric film exclusive of foam further comprises at least one inorganic opacifying pigment.
According to a fourth embodiment of the process, according to the present invention, said non-transparent microvoided self-supporting polymeric film exclusive of foam comprises a polymer as a continuous phase and dispersed uniformly therein an amorphous high polymer with a higher glass transition temperature than the glass transition temperature of said continuous phase and/or a crystalline high polymer with a melting point higher than said glass transition phase of said continuous phase.
According to a fifth embodiment of the process, according to the present invention, said non-transparent microvoided self-supporting polymeric film exclusive of foam is a biaxially stretched film.
According to a sixth embodiment of the process, according to the present invention, said non-transparent microvoided self-supporting polymeric film exclusive of foam comprises a polyolefin as continuous phase, with.
According to a seventh embodiment of the process, according to the present invention, isotactic polypropylene or isotactic poly(4-methylpentene) being preferred.
According to an eighth embodiment of the process, according to the present invention, said non-transparent microvoided self-supporting polymeric film exclusive of foam comprises a linear polyester as continuous phase.
According to a ninth embodiment of the process, according to the present invention, said non-transparent microvoided self-supporting polymeric film exclusive of foam comprises a linear polyester as continuous phase and wherein in said continuous phase linear polyester matrix is uniformly dispersed from 5 to 35% by weight of said film of a high polymer, said high polymer being an amorphous high polymer having a higher glass transition temperature than the glass transition temperature of said linear polyester and/or a crystalline high polymer having a higher melting point than the glass transition temperature of said linear polyester.
According to a tenth embodiment of the process, according to the present invention, said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam further comprises a whitening agent.
According to an eleventh embodiment of the process, according to the present invention, said non-transparent microvoided self-supporting polymeric film exclusive of foam comprises a linear polyester as continuous phase and wherein said linear polyester has monomer components consisting essentially of at least one aromatic dicarboxylic acid and at least one aliphatic diol.
According to a twelfth embodiment of the process, according to the present invention, said security document further comprises an embedded chip, contact chip, combi chip or antenna.
According to a thirteenth embodiment of the process, according to the present invention, said security document further comprises an embedded chip having contact surfaces.
According to a fourteenth embodiment of the process, according to the present invention, said security document is an identity card.
According to a fifteenth embodiment of the process, according to the present invention, said security document is an identity card which has a format according to ISO 7810.
According to a sixteenth embodiment of the process, according to the present invention, said security document further comprises an embedded chip and is an identity card according to ISO 7816 or ISO 14443.
According to a seventeenth embodiment of the process, according to the present invention, said non-transparent microvoided self-supporting polymeric film exclusive of foam is exclusive of foaming agent and/or decomposition productions of a foaming agent.
According to an eighteenth embodiment of the process, according to the present invention, said image-wise applied heat is provided by a digital or an analogue process. Digital processes provide the possibility of a personalized watermark e.g. with the number of a chip incorporated in a security document, whereas analogue processes provide a non-personalized security feature. Attempts to modify the watermark in a security document would be immediately detectible due to the effect of the heat upon the layer configurations on the outermost surfaces of the security document, e.g. local melting, and delamination on the side of the non-transparent microvoided axially stretched self-supporting polymeric film nearer to the heat source as a result of the surface deformation accompanying the transparentization effect.
According to a nineteenth embodiment of the process, according to the present invention, said image-wise applied heat is provided by a digital process in which said digital image-wise heating process uses a laser beam or a thermal head. Heating processes using a laser beam may require the uniform incorporation into the non-transparent microvoided axially stretched self-supporting polymeric film of a substance capable of efficiently converting absorbed light into heat.
According to a twentieth embodiment of the process, according to the present invention, said image-wise applied heat is provided by an analogue process in which said image-wise heating process uses a heated stamp or an infrared image.
The transparentization realized upon obtaining a permanent transparent pattern, according to the present invention, increases with decreasing film thickness, with thicknesses of 100 μm or less being preferred. Optical density changes of at least 0.4 can be readily realized or up to 40% without significant changes in film thickness. Moreover, the transparentization effect realized by the process for obtaining a permanent transparent pattern, according to the present invention, results from a combination of heat supplied by a heat source, the pressure between the heat source and the film and the time the heat source is applied. The heat has to be applied for at least 1 ms either continuously or non-continuously. Heating with a thermal head can be with a single heat pulse, but multiple short heating pulses are preferred to avoid overheating of the heating elements. When a thermal head is used a foil can be used between the thermal head and the non-transparent microvoided axially stretched self-supporting polymeric film during the heating process e.g. a 6 μm thick PET-film can be interposed between the non-transparent microvoided film and the thermal head to prevent possible contamination of the thermal head. Thermal head printers, such as the DRYSTAR-printers supplied by AGFA-GEVAERT N.V., can be used to produce the permanent transparent pattern of the present invention e.g. as personalized watermarks.
This transparentization effect is accompanied by a relief pattern, which can be detected by touch i.e. in a tactile manner. This relief pattern is more pronounced the higher the temperature of the heat source, this embossing effect increasing with temperature between 110° C. and 190° C., and the higher the contact pressure. The tactile relief obtained by applying a hot stamp to a non-transparent microvoided axially stretched self-supporting polymeric film is much more pronounced than that obtained using a thermal head.
The degree of transparency realized depends upon the stamp/thermal head printing conditions: time, temperature and pressure. The thermofixation history of the material is also important. The heated-induced transparentization of the non-transparent microvoided axially stretched self-supporting polymeric film can be carried out before or after the optional application of a layer, such as an ink-jet receiving layer and before or after transparentization. The relative positioning of the transparentized areas and transparency in the support can be of value as an additional security measure.
According to a twenty-first embodiment of the process, according to the present invention, According to a fourteenth embodiment of the process for obtaining a permanent transparent pattern, according to the present invention, the heat is applied non-continuously.
According to a twenty-second embodiment of the process, according to the present invention, a transparent overprintable layer is provided on the film prior to the image-wise application of heat.
According to a twenty-third embodiment of the process, according to the present invention, a transparent overprintable layer is provided on the film after the image-wise application of heat.
INDUSTRIAL APPLICATIONThe security documents, according to the present invention, can be used in security and anti-counterfeiting applications e.g. in tickets, labels, tags, an ID-card, a bank card, a legal document, banknotes and packaging and can also be integrated into packaging.
The invention is illustrated hereinafter by way of comparative examples and invention examples. The percentages and ratios given in these examples are by weight unless otherwise indicated.
- Subbing layer Nr. 01 on the emulsion side of the support:
- Ingredients used in the EXAMPLES:
- MAGNUM 8391: an ABS-resin with a Vicat softening temperature of 95° C., from DOW CHEMICAL
- TPX® DX820: a high rigidity poly(4-methylpentene) from MITSUI CHEMICAL
- BARIUM SULPHATE: NEOBRK/renol white, a masterbatch from CLARIANT GmbH containing 50% by weight barium sulphate and 50 wt % polyester
- TITANIUM DIOXIDE: Renol-white/PTX 506, a masterbatch from CLARIANT GmbH containing 65% by weight TiO2 and 35 wt % polyester
The PET-types and SAN-types used for producing the extrudates used in producing of the films of COMPARATIVE EXAMPLES 1 to 3 are given in Table 1. The PET, titanium dioxide and UVITEX OB-one in the weight percentages given in Table 1 were mixed and then dried at 150° C. for 4 hours under vacuum (<100 mbar), the mixtures then melted in a PET-extruder and extruded through a sheet die and cooled to produce the extrudates of COMPARATIVE EXAMPLES 1 to 3.
The extrudates of COMPARATIVE EXAMPLES 1 to 3 were then longitudinally stretched with an INSTRON apparatus in which the extrudate was heated in an oven mounted on the apparatus under the conditions given in Table 2 to yield the longitudinally stretched films of COMPARATIVE EXAMPLES C1/LS1, C1/LS2 and C1/LS3. The optical densities of the films of COMPARATIVE EXAMPLES C1/LS1, C2/LS1 and C3/LS1 were measured with a MacBeth TR924 densitometer in transmission mode with a visible filter are also given in Table 2 together with the film thicknesses.
Transversal stretching was then performed on the longitudinally stretched films with a stretch time of 30 s and stretching speed of 1000%/min under the conditions given in Table 3. Finally the films were thermally fixated at 175° C. for 1 minute giving the substantially opaque films of COMPARATIVE EXAMPLES C1/LS1/BS1, C2/LS1/BS1 and C3/LS1/BS1.
The optical densities of the films of COMPARATIVE EXAMPLES C1/LS1/BS1, C2/LS1/BS1 and C3/LS1/BS1 were measured with a MacBeth TR924 densitometer in transmission mode with a visible filter are also given in Table 3 together with the film thicknesses.
The films of COMPARATIVE EXAMPLES 1/LS1/BS1, 2/LS1/BS1 and 3/LS1/BS1 were each mounted in an Instron 4411 apparatus and were heated at various temperatures between 120 and 190° C. for 5 seconds with a soldering iron in the upper clamp making contact with the film at a pressure of 0.5 N/mm2. The optical densities (OD) of the film after the tests were measured in transmission with a MacBeth TR924 densitometer with a visible filter and and the film thicknesses were also measured. The results are summarized below in Tables 4 and 5 respectively.
Within experimental error no transparentization was observed upon heating the films of COMPARATIVE EXAMPLES 1/LS1/BS1, 2/LS1/BS1 and 3/LS1/BS1. This shows that there is no transparentization of the contribution to the non-transparency due to the presence of titanium dioxide i.e. there is no micro-void formation.
COMPARATIVE EXAMPLE 4The 1083 μm thick extrudate of COMPARATIVE EXAMPLE 4 with a composition of 2% by weight of titanium dioxide, 100 ppm UVITEX OB-one and 98% by weight of PET02 was produced as described for COMPARATIVE EXAMPLES 1 to 3 and had an optical density measures with a MacBeth TR924 densitometer in transmission mode with a visible filter of 1.35.
The extrudate was stretched longitudinally as described for COMPARATIVE EXAMPLES 1 to 3 under the conditions given in Table 6. The thickness values were measured by averaging measurements obtained by contacting the upper surface at 16 different positions at a measuring force of 0.8N using a SONY U30A thickness gauge with a resolution of 1 μm, an accuracy of 2 μm and a contact ball 3 mm in diameter.
Transversal stretching was then performed on the longitudinally stretched films with a stretch time of 30 s and stretching speed of 1000%/min under the conditions given in Table 7. The measured thickness and measured optical density with the MacBeth TR924 densitometer in transmission mode with a visible filter are also given in Table 7.
Since there is no contribution to the optical density from void-forming upon biaxial stretching for the composition of COMPARATIVE EXAMPLE 4 as can be seen from COMPARATIVE EXAMPLE 1 to 3, the dependence of optical density upon film thickness can be used to provide a baseline with which to assess the contribution of void-forming to the optical density for those compositions based upon aromatic polyesters with 2% by weight of the same titanium dioxide pigment which form voids upon biaxial stretching.
The Beer-Lambert relationship does not hold for pigmented films with light-scattering pigments such as titanium dioxide. If the film thickness is smaller than the average free path-length of the scattered light, light will escape after scattering otherwise the light does not escape and in fact interferes with further scattered light providing for a quasi-exponential dependence of optical density upon film thickness. The situation is too complex to be able to be described theoretically and hence the only possible approach is to measure the actual optical density observed at particular film thicknesses. The above-mentioned optical density appear to a fair approximation to be linearly dependent upon the logarithm of the film thickness in the layer thickness range 1084 to 120 μm giving the following relationship:
OD=0.891 log[thickness in μm]−1.3727
This relationship provides the optical density attributable to a 2% by weight concentration of the titanium dioxide pigment used as a function of film thickness.
INVENTION EXAMPLES 1 to 11The ca. 1100 μm thick extrudates of INVENTION EXAMPLES 1 to 11 all with 2% by weight of titanium dioxide and 15% by weight of SAN 06 were produced by mixing the ingredients in Table 8 in the proportions given in Table 8 and then drying the mixture at 150° C. for 4 hours under vacuum (<100 mbar) before melting in a PET-extruder, extrusion through a sheet die and cooling to produce the extrudates of INVENTION EXAMPLES 1 to 11 having a density of ca. 1.3 g/mL as summarized in Table 8.
Longitudinal stretching was carried out for each extrudate as described in COMPARATIVE EXAMPLES 1 to 3 under the conditions given in Table 9. The expected thickness is the thickness based on the extrudate thickness and longitudinal as observed for non-voided films.
Optical density measurements were carried out on the longitudinally stretched extrudates and the results are given in Table 10. The expected OD is obtained by substituting the expected thickness into the expression derived in COMPARATIVE EXAMPLE 4.
Longitudinal stretching was accompanied by a decrease in density due to void-forming, this decrease in density clearly increasing as the proportion of PET04 increased i.e. surprisingly indicates that an increase in the isophthalic acid unit concentration in the aromatic polyester favours increased void-forming in the film. The increase in optical density due to void forming was in the range of 15 to 32%.
Transversal stretching was then performed on the longitudinally stretched films with a stretch time of 30 s and stretching speed of 1000%/min under the conditions given in Table 11. The density, measured thickness, the expected thickness, i.e. thickness if no void-forming on the basis of the extrudate thickness and the longitudinal and transversal stretch ratios, the measured optical density with the MacBeth TR924 densitometer in transmission mode with a visible filter, the expected optical density, i.e. the optical density calculated using the relationship disclosed in COMPARATIVE EXAMPLE 4 using the theoretical layer thickness values, and the difference between the observed optical density and the optical density expected due to a 2% by weight concentration of the particular titanium dioxide pigment used, ΔOD, are also given in Table 11.
Transversal stretching reduced the density of the films still further with again the density decrease being greater as the proportion of PET04 increased. This again surprisingly indicates that an increase in the isophthalic acid unit concentration in the aromatic polyester favoured increased void-forming in the film. The decrease in density is smaller than would be expect simply based on the measured thicknesses compared with the expected thicknesses for non-voided films.
The results of Table 11 show that at approximately the same stretching temperature the contribution to the optical density of biaxially stretched films clearly increases to over 70% as the concentration of PET04 in the composition increases i.e. the concentration of isophthalic acid units in the polyester increases to the concentration of 10 mole % of the aromatic dicarboxylic acid in PET04 itself.
The presence of void-forming was demonstrated for several of the biaxially stretched films by clamping the films in an Instron 4411 apparatus and observing the changes in film thickness and optical density upon contacting the films with a soldering iron for 5 s at 150° C. The results of these experiments are given in Table 12.
The results of Table 12 show that at approximately the same stretching temperature the contribution to the optical density of biaxially stretched films clearly increases as the concentration of PET04 in the composition increases i.e. the concentration of isophthalic acid units in the polyester increases to the concentration of 10 mole % of the aromatic dicarboxylic acid in PET04 itself.
The ca. 1100 μm thick extrudates of INVENTION EXAMPLES 12 to 16 all with 2% by weight of titanium dioxide were produced as described for INVENTION EXAMPLES 1 to 11 with 15% by weight of SAN or 15% by weight of ABS (MAGNUM 8391) and different weight ratios of TO4 and PET04 as summarized in Table 13.
Stretching in the length direction was carried out for each extrudate as described in COMPARATIVE EXAMPLES 1 to 3 under the conditions given in Table 14. The expected thickness is the thickness based on the extrudate thickness and longitudinal as observed for non-voided films.
Transversal stretching was then performed on the length-stretched films with a stretch time of 30 s and stretching speed of 1000%/min as described in COMPARATIVE EXAMPLES ! to 3 under the conditions given in Table 15. The measured thickness, the expected thickness, i.e. thickness if no void-forming on the basis of the extrudate thickness and the longitudinal and transversal stretch ratios, the measured optical density with the MacBeth TR924 densitometer in transmission mode with a visible filter, the expected optical density, i.e. the optical density calculated using the relationship disclosed in COMPARATIVE EXAMPLE 4 using the theoretical layer thickness values, and the difference between the observed optical density and the optical density expected due to a 2% by weight concentration of the particular titanium dioxide pigment used, ΔOD, are also given in Table 15.
The elasticity (Young's) modulus and yield stress of the biaxially stretched extrudates were measured for INVENTION EXAMPLES 13/LS1/BS1, 13/LS1/BS2 and 13/LS2/BS1 and the results are summarized in Table 16 below:
The presence of void-forming was demonstrated for the biaxially stretched film of INVENTION EXAMPLE 12/LS1/BS1 by clamping the film in an Instron 4411 apparatus and observing the change in film thickness and optical density upon contacting the film with a soldering iron for 5 s at 150° C. The results of these experiments are given in Table 17.
The results of Table 17 show that at approximately the same stretching temperature the contribution to the optical density of biaxially stretched films clearly increases as the concentration of PET04 in the composition increases i.e. the concentration of isophthalic acid units in the polyester increases to the concentration of 10 mole % of the aromatic dicarboxylic acid in PET04 itself.
The presence of void-forming was also demonstrated for the biaxially stretched films of INVENTION EXAMPLES 15/LS1/BS1 and 16/LS1/BS1 by clamping the films in an Instron 4411 apparatus and observing the changes in film thickness and optical density upon contacting the film with a soldering iron for 5 s at various temperatures. The results of these experiments are given in Tables 18 and 19.
Reductions in optical density at 150° C. of 0.19, 0.42 and 0.60 were observed for the films of INVENTION EXAMPLE 12/LS1/BS1, 15/LS1/BS1 and 16/LS1/BS1 respectively corresponding to 26, 38 and 50%.
INVENTION EXAMPLES 17 to 19The ca. 1100 μm thick extrudates of INVENTION EXAMPLES 17 to 19 all with 2% by weight of titanium dioxide and 15% by weight of SAN 06 were produced as described for EXAMPLES 1 to 11 with different weight ratios of TO4 and PET04 as summarized in Table 20.
Stretching in the length direction was carried out for each extrudate as described in COMPARATIVE EXAMPLES 1 to 3 under the conditions given in Table 21. The expected thickness is the thickness based on the extrudate thickness and longitudinal as observed for non-voided films.
Transversal stretching was then performed on the length-stretched films with a stretch time of 30 s and stretching speed of 1000%/min as described in COMPARATIVE EXAMPLES 1 to 3 under the conditions given in Table 22. The measured thickness, the expected thickness, i.e. thickness if no void-forming on the basis of the extrudate thickness and the longitudinal and transversal stretch ratios, the measured optical density with the MacBeth TR924 densitometer in transmission mode with a visible filter, the expected optical density, i.e. the optical density calculated using the relationship disclosed in COMPARATIVE EXAMPLE 4 using the theoretical layer thickness values, and the difference between the observed optical density and the optical density expected due to a 2% by weight concentration of the particular titanium dioxide pigment used, ΔOD, are also given in Table 22.
The results of Table 22 show that at approximately the same stretching temperature the contribution to the optical density of biaxially stretched films clearly increases as the concentration of PET04 in the composition increases i.e. the concentration of isophthalic acid units in the polyester increases to the concentration of 10 mole % of the aromatic dicarboxylic acid in PET04 itself.
INVENTION EXAMPLE 20The 1100 μm thick extrudate of INVENTION EXAMPLE 20 having a composition of 2% by weight of titanium dioxide, 100 ppm of UVITEX OB-one [ppm], 15% by weight of SAN 06 and 83% by weight of PET04 was produced as described for EXAMPLES 1 to 11. Stretching in the length direction was carried out for the extrudate as described in EXAMPLES 1 to 58 under four different sets of conditions as given in Table 23. The expected thickness is the thickness based on the extrudate thickness and longitudinal as observed for non-voided films.
Transversal stretching was then performed on the length-stretched films as described in COMPARATIVE EXAMPLES 1 to 3 under the conditions given in Table 24. The density, measured thickness and the expected thickness, i.e. thickness if no void-forming on the basis of the extrudate thickness and the longitudinal and transversal stretch ratios, are also given in Table 24.
Biaxial stretching reduced the density of the films with the density decrease being greater the lower the transversal stretching temperature. However, the decrease in density is smaller than would be expect simply based on the measured thicknesses compared with the expected thicknesses based on the extrudate thickness, longitudinal stretch ratio and transversal stretch ratio as observed for non-voided films. This can be partly explained by the combination of two effects: the decrease in the density due to void forming on the one hand being to a degree compensated by the increase in the crystallinity of the polyester matrix due to biaxial stretching on the other.
Table 25 gives the measured thickness, the expected thickness, i.e. thickness if no void-forming on the basis of the extrudate thickness and the longitudinal and transversal stretch ratios, the optical density measured with a MacBeth TR924 densitometer in transmission mode with a visible filter, the expected optical density, i.e. the optical density calculated using the relationship disclosed in COMPARATIVE EXAMPLE 4 using the theoretical layer thickness values, and the difference between the observed optical density and the optical density expected due to a 2% by weight concentration of the particular titanium dioxide pigment used, ΔOD, together with the temperature at which the transversal stretching was carried out.
It is clear from the results in Table 25, that the degree of void-forming, as indicated by the optical density not attributable to the 2% by weight of titanium dioxide present, increased with decreasing transversal stretch temperature regardless of the other conditions pertaining during the transversal stretch process.
Table 26 summarizes the stretch conditions, the thickness, expected thickness, optical density, expected optical density and non-attibutable increase in optical density as a result of void-forming for different films obtained at a stretch temperature of approximately 110° C.
The data in Table 26 shows that reducing the stretching time from 30 s to 10 s and increasing the stretching speed from 1000%/min to 2000%/min also promote void-forming.
The presence of void-forming was demonstrated for the biaxially stretched film of INVENTION EXAMPLE 20/LS3/BS1 by clamping the film in an Instron 4411 apparatus and observing the changes in film thickness and optical density upon contacting the film with a soldering iron for 5 s at various temperatures. The results of these experiments are given in Tables 27 and 28.
A reduction in optical density at 150° C. of 0.42 was observed for the film of INVENTION EXAMPLE 20/LS1/BS1 corresponding to 25% accompanied by a reduction of 26% in layer thickness.
INVENTION EXAMPLES 21 to 23The ca. 1100 μm thick extrudates of INVENTION EXAMPLES 21 to 23 of unpigmented dispersions of SAN 06 in aromatic polyester were produced as described for EXAMPLES 1 to 11 with different concentrations of SAN 06, TO4 and PET04 as summarized in Table 29.
Stretching in the length direction was carried out for each extrudate as described in COMPARATIVE EXAMPLES 1 to 3 under the conditions given in Table 30. The expected thickness is the thickness based on the extrudate thickness and longitudinal as observed for non-voided films.
Transversal stretching was then performed on the length-stretched films with a stretch time of 30 s and stretching speed of 1000%/min as described in COMPARATIVE EXAMPLES 1 to 3 under the conditions given in Table 31. The measured thickness, the expected thickness, i.e. thickness if no void-forming on the basis of the extrudate thickness and the longitudinal and transversal stretch ratios, the measured optical density with the MacBeth TR924 densitometer in transmission mode with a visible filter, the expected optical density, i.e. 0.05 the optical density of polyethylene terephthalate almost completely determined by refraction effects at the two sides of the film, and the difference between the observed optical density and the optical density expected due to the aromatic polyester, ΔOD, are also given in Table 31.
The results in Table 31 show strongly increased opacification optical densities of 1.28 and 1.29 due to void-forming for the films of INVENTION EXAMPLES 23/LS2/BS4 and 23/LS2/BS5 with a linear polyester matrix with 10 mole % isophthalate compared with an opacification optical density of 0.78 due to void forming for the film of INVENTION EXAMPLE 21/LS2/BS1 with a linear polyester matrix with 3 mole % isophthalate.
The presence of void-forming was demonstrated for the biaxially stretched films of INVENTION EXAMPLES 21/LS2/BS1, 22/LS1/BS1 and 22/LS2/BS1 and the INVENTION EXAMPLE 23 series by clamping the films in an Instron 4411 apparatus and observing the changes in film thickness and optical density upon contacting the film with a soldering iron for 5 s at various temperatures. The results of these experiments are given in Tables 32 and 33.
A reduction in optical density at 190° C. of 0.67, 0.85 and 0.88 was observed for the films of INVENTION EXAMPLES 21/LS2/BS1, 22/LS1/BS1 and 22/LS2/BS1respectively corresponding to 81, 86 and 85%. In the INVENTION 23 series the reduction in optical density at 190° C. varied between 0.84 and 1.01 corresponding to 64 to 84%.
These reductions in optical density were accompanied by a reduction of 13, 16 and 19% in layer thickness with 25 to 36% reduction in thickness being observed for the INVENTION EXAMPLE 23 series. These results show an extremely large reduction in optical density of up to 1.01 upon transparentizing polyester layers with 15 or 17 wt % SAN 06.
EXAMPLES 24 to 30The ca. 1100 μm thick extrudates of INVENTION EXAMPLES 24 to 30 with 2% by weight of titanium dioxide and 15% by weight of SAN 06 were produced as described for EXAMPLES 1 to 11 with different concentrations of PET02 and PET06 as summarized in Table 34.
Stretching in the length direction was carried out for each extrudate as described in COMPARATIVE EXAMPLES 1 to 3 under the conditions given in Table 35. The expected thickness is the thickness based on the extrudate thickness and longitudinal as observed for non-voided films.
Transversal stretching was then performed on the length-stretched film as described for COMPARATIVE EXAMPLES 1 to 3 with a stretch time of 30 s and stretching speed of 1000%/min under the conditions given in Table 36. The measured thickness, the expected thickness, i.e. thickness if no void-forming on the basis of the extrudate thickness and the longitudinal and transversal stretch ratios, the measured optical density with the MacBeth TR924 densitometer in transmission mode with a visible filter, the expected optical density and the difference between the observed optical density and the optical density expected due to the aromatic polyester, ΔOD, are also given in Table 36.
The results in Table 36 clearly show very substantial opacification, 69% of the optical density realized being due to void-forming with a matrix of a blend of PET and PETG rather than PET or a blend of PET with a polyester of terephthalic acid, isophthalic acid and ethylene glycol such as PET03, PET04 and PET05.
The presence of void-forming was demonstrated for the biaxially stretched films of INVENTION EXAMPLES 24/LS1/BS1, 25/LS1/BS2, 26/LS1/BS1, 28/LS1/BS1 and 29/LS1/BS1 by clamping the films in an Instron 4411 apparatus and observing the changes in film thickness and optical density upon contacting the film with a soldering iron for 5 s at various temperatures. The results of these experiments are given in Table 37.
A reduction in optical density at 170° C. varying from 0.413 for the film of INVENTION EXAMPLE 24/LS1/BS1 to 0.654 for the film of INVENTION EXAMPLE 29/LS1/BS1 corresponding to 41.6 to 61.7%. These reductions in optical density were accompanied by a reduction of 16 to 47.7% in layer thickness. These results show a large reduction in optical density of up to 0.654 upon transparentizing polyester layers with 15 wt % SAN 06 and 2 wt % TiO2.
EXAMPLES 31 and 32The ca. 1100 μm thick extrudates of INVENTION EXAMPLES 31 and 32 all with 2% by weight of titanium dioxide and 15% by weight of TPX 820 were produced by mixing the ingredients in Table 8 in the proportions given in Table 8 and then drying the mixture at 150° C. for 4 hours under vacuum (<100 mbar) before melting in a PET-extruder, extrusion through a sheet die and cooling to produce the extrudates of INVENTION EXAMPLES 31 and 32 summarized in Table 38 together with the isophthalate (IPA):terephthalate (TPA) ratio.
Longitudinal stretching was carried out for each extrudate as described in COMPARATIVE EXAMPLES 1 to 3 under the conditions given in Table 39. The expected thickness is the thickness based on the extrudate thickness and longitudinal as observed for non-voided films.
Transversal stretching was then performed on the length-stretched film as described for COMPARATIVE EXAMPLES 1 to 3 with a stretch time of 30 s and stretching speed of 1000%/min under the conditions given in Table 40. The measured thickness, the expected thickness, i.e. thickness if no void-forming on the basis of the extrudate thickness and the longitudinal and transversal stretch ratios, the measured optical density with the MacBeth TR924 densitometer in transmission mode with a visible filter, the expected optical density and the difference between the observed optical density and the optical density expected due to the aromatic polyester, ΔOD, are also given in Table 40.
The results in Table 40 clearly show very substantial opacification, 64% of the optical density realized being due to void-forming with a matrix of PET04 with TPX as crystalline dispersed phase with a particle size of ca. 10 μm. However, C5/LS1/BS1 exhibited an elasticity (Young's) modulus in the longitudinal direction of 1258 N/mm2 and a yield stress in the longitudinal direction of 26.4 N/mm2, which were substantially lower than for materials using SAN as opacity-producing agent.
Transparentization was investigated for the biaxially stretched film 32/LS1/BS1 by clamping the film in an Instron 4411 apparatus and observing the changes in optical density and film thickness upon contacting the film with a soldering iron for 5 s at 150° C., 5 s at 190° C. and 5 s at 210° C. at a pressure of 0.5N/mm2. The results of these experiments are given in Table 41, 42 and 43 respectively.
There was no significant transparentization even at 210° C. despite a 27.3% change in film thickness. Significant transparentization was only observed at 230° C. at which there was a 29% decrease in optical density and a 55% decrease in film thickness. Film thickness changes at 150° C. and 190° C. of 7.4% and 15.5% respectively coupled with no transparentization indicated an excellent temperature stability.
INVENTION EXAMPLES 33 and 34The 1095 μm thick extrudates of INVENTION EXAMPLES 33 and 34 with 2% by weight of titanium dioxide and 15% by weight of SAN 06 were produced by mixing the ingredients in Table 44 in the proportions given in Table 14 and then drying the mixture at 150° C. for 4 hours under vacuum (<100 mbar) before melting in a PET-extruder, extrusion through a sheet die and cooling to produce the extrudates of COMPARATIVE EXAMPLES 7 and 8 summarized in Table 44 together with the isophthalate (IPA):terephthalate (TPA) ratio.
Longitudinal stretching was carried out for the extrudate as described in COMPARATIVE EXAMPLES 1 to 3 under the conditions given in Table 45. The expected thickness is the thickness based on the extrudate thickness and longitudinal as observed for non-voided films.
Longitudinal stretching was accompanied by a decrease in density due to void-forming, which increased with decreasing temperature i.e. stretching force. However, whereas for the longitudinal stretching of the extrudate of INVENTION EXAMPLE 33 at a temperature of 93° C. the longitudinal stretching occurred without inhomogeneities in the stretched film, at a temperature of 82° C. inhomogeneities occurred as bumps at the edges of the stretched film.
Transversal stretching was then performed on the length-stretched film as described for COMPARATIVE EXAMPLES 1 to 3 with a stretch time of 30 s and stretching speed of 1000%/min under the conditions given in Table 46. The measured thickness, the expected thickness, i.e. thickness if no void-forming on the basis of the extrudate thickness and the longitudinal and transversal stretch ratios, the measured optical density with the MacBeth TR924 densitometer in transmission mode with a visible filter, the expected optical density and the difference between the observed optical density and the optical density expected due to the aromatic polyester, ΔOD, are also given in Table 46.
The results in Table 16 clearly show very substantial opacification, up to 66% of the optical density realized being due to void-forming with a matrix of polyester with an IPA/TPA ratio of 0.0637 with 15% by weight of SAN 06 as amorphous high polymer dispersed phase.
INVENTION EXAMPLES 35 to 39The ca. 1100 μm thick extrudates of INVENTION EXAMPLES 35 to 39 all with 2% by weight of titanium dioxide, SAN 06 and TPX 820 were produced by mixing the ingredients in the proportions given in Table 47 and then drying the mixture at 150° C. for 4 hours under vacuum (<100 mbar) before melting in a PET-extruder, extrusion through a sheet die and cooling to produce the extrudates of INVENTION EXAMPLES 1 to 5 summarized in Table 47 together with the isophthalate (IPA):terephthalate (TPA) ratio.
Longitudinal stretching was carried out for each extrudate as described in COMPARATIVE EXAMPLES 1 to 3 under the conditions given in Table 48. The expected thickness is the thickness based on the extrudate thickness and longitudinal as observed for non-voided films.
The results in Table 48 show with 15% by weight of a dispersed mixture of particles of isotactic poly(4-methyl-1-pentene) (PMP), a crystalline high polymer with a melting point above the glass transition temperature of the lineear polyester matrix, and particles of an acrylonitrile-styrene block copolymer (SAN), an amorphous high polymer with a glass transition temperature above that of the linear polyester matrix, that longitudinal stretching was possible without film inhomogeneity down to temperatures lower than 80° C., whereas this was not possible with 15% by weight of SAN for an identical polyester composition (IPA:TPA ratio=0.0637)(see INVENTION EXAMPLE 33). Moreover, although longitudinal stretching was possible with 15% by weight of PMP in the same polyester composition at temperatures below 80° C. (see INVENTION EXAMPLE 31), upon transversal stretching a film was obtained with substantially inferior elasticity (Young's) modulus in the longitudinal direction and yield stress in the longitudinal direction. This was not the case when mixtures of PMP and SAN were dispersed.
The tearing strength of the films of INVENTIVE EXAMPLES 38/LS1 and 39/LS1 with total PMP and SAN concentrations of 15% by weight and concentrations of PMP of 1 and 0.5% by weight respectively longitudinally stretched at stretching forces of 9.8 and 9.5 N/mm2 of 6.5 N/mm was approximately double the tearing strength of the film of INVENTION EXAMPLE 34/LS1 with 15% by weight of SAN in a polyester with the same composition longitudinally stretched at a stretching force of 9.3 N/mm2 of 3.4 N/mm.
Transversal stretching was then performed on the longitudinally stretched films as described for COMPARATIVE EXAMPLES 1 to 3 with a stretch time of 30 s and stretching speed of 1000%/min under the conditions given in Table 49. The density, measured thickness and the expected thickness, i.e. thickness if no void-forming on the basis of the extrudate thickness and the longitudinal and transversal stretch ratios, are also given in Table 49.
Transversal stretching resulted in films with densities in the range of 1.07 to 0.57 g/mL and ratios of measured thickness to expected thickness in the range of 1.43 to 2.12 indicating the presence of considerable microvoiding and excellent insulating properties.
Table 50 gives the measured thickness, the expected thickness, the measured optical density with the MacBeth TR924 densitometer in transmission mode with a visible filter, the expected optical density, i.e. the optical density calculated using the relationship disclosed in COMPARATIVE EXAMPLE 4 using the theoretical layer thickness values, and the difference between the observed optical density and the optical density expected due to a 2% by weight concentration of the particular titanium dioxide pigment used, ΔOD.
The results of Table 50 show that at approximately the same stretching temperature the contribution to the optical density of biaxially stretched films of microvoiding increases was extremely high for all the films.
The mechanical properties of the films 35/LS1/BS1, 36/LS1/BS1, 37/LS1/BS1, 38/LS2/BS1 and 39/LS1/BS1 are summarized in Table 21.
The transparentization of these films was investigated for several of the biaxially stretched films by clamping the films in an Instron 4411 apparatus and observing the changes in film thickness and optical density upon contacting the films with a soldering iron for 5 s at 150° C. and 190° C. The results of these experiments are given in Tables 51 and 52.
For similar changes in film thickness, the percentage decrease in optical density was much higher at PMP-concentrations of 0.5 and 1.0% by weight [37/LS1/BS1, 38/LS2/BS1 and 39/LS1/BS1] than at PMP-concentrations of 7.5 and 14% by weight [35/LS1/BS1 and 36/LS1/BS1].
Transparenization Experiments Performed Security Document Precursors Comprising a Plurality of Self-Supporting Polymeric Films and Layers Therebetween and Thereon INVENTION EXAMPLE 40A non-transparent microvoided film 240 μm thick was produced by biaxially stretching a 1100 μm thick extrudate with the composition given in Table 53 below:
to a thickness of 240 μm as given in Table 54 below:
The 240 μm thick non-transparent microvoided film was laminated with a 35 μm thick PETG non-transparent film from AMCOR on one side using a polyurethane adhesive layer and coated with a 12 μm thick receiving layer configuration on the other side, the receiving layer configuration having an optical density of ca. 0.41 comprising in order two gelatine layers pigmented with titanium dioxide, a receiving layer comprising dye DTR-precursors and a protective layer, producing a first security document precursor for use in realizing an ID-1 format as defined in ISO 7810.
A pattern of a letter M was realized in the 240 μm thick non-transparent microvoided film by placing a metal shape in contact with the side of the first security document precursor with the PETG film between two metal plates with silicone paper inbetween to prevent sticking in an OASYS OLA6/7 laminator from OASYS Technologies Ltd with settings such that a pressure of 32 units was applied and was maintained while the temperature was increased from room temperature to 180° C. over a period of 135 s, the temperature was held at 180° C. for 150 s and then was reduced to 155° C. over a period of 45 s. The pressure was then increased to 37 units and this pressure maintained while the temperature decreased from 155° to 50° C. over a period of 390 s. The whole cycle took 12 minutes. The transparentization of the 240 μm thick non-transparent microvoided film was accompanied by a detectable deformation in the PETG film.
The first security document precursor with a pattern in the 240 μm thick non-transparent microvoided film was then laminated on the side with the PETG film to a second security document precursor consisting of in order a 500 μm thick opaque PETG film from AMCOR, a 35 μm thick opaque PETG film from FOLIENWERK WOLFEN GMBH, a 63 μm thick biaxially oriented PET film and a 6 μm thick layer configuration consisting of two gelatine layers pigmented with titanium dioxide and a protective layer.
Lamination was carried out between two metal plates with silicone paper inbetween to prevent sticking in an OASYS OLA6/7 laminator from OASYS Technologies Ltd with settings such that a pressure of 30 units was applied and maintained during the whole lamination process while the temperature was increased from room temperature to 150° C. over a period of 100 s, then held at 150° C. for 150 s, then reduced to 50° C. over a period of 270 s. The whole cycle took 520 s. The deformation in the PETG film of the first security document precursor disappeared during the lamination process due to the melting of the PETG-film, but the pattern in the 240 μm thick non-transparent microvoided film remained clearly visible if viewed from the side of the first security card precursor with the layer configuration.
The first security document precursor with a pattern in the 240 μm thick non-transparent microvoided film was also laminated to a third security document precursor consisting of in order a 200 μm thick opaque PETG film from FOLIENWERK WOLFEN GMBH, a 35 μm thick opaque PETG film from AMCOR, a further sheet of the 240 μm thick non-transparent microvoided film and a 6 μm thick layer configuration consisting of two gelatine layers pigmented with titanium dioxide and a protective layer to provide a security document in an ID-1 format as defined in ISO 7810.
The security document in an ID-1 resulting from lamination of the first and third security card precursors was subjected to dynamic bending tests over the width and length of the security document. The card survived more than 50,000 bends using the dynamic bending test over the width according to ISO 10373:5.8 and more than 200,000 bends using the dynamic bending test over the length according to ISO 10373:5.8.
The present invention may include any feature or combination of features disclosed herein either implicitly or explicitly or any generalisation thereof irrespective of whether it relates to the presently claimed invention. In view of the foregoing description it will be evident to a person skilled in the art that various modifications may be made within the scope of the invention.
Having described in detail preferred embodiments of the current invention, it will now be apparent to those skilled in the art that numerous modifications can be made therein without departing from the scope of the invention as defined in the following claims.
All references, including publications, patent applications, and patents, cited herein are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein.
The use of the terms “a” and “an” and “the” and similar referents in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.
Preferred embodiments of this invention are described herein, including the best mode known to the inventors for carrying out the invention. Of course, variations of those preferred embodiments will become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intend for the invention to be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context.
Claims
1. A security document comprising a plurality of self-supporting polymeric films and layers therebetween and thereon, said plurality of self-supporting polymeric films comprising a non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam and having a permanent transparent pattern.
2. The security document according to claim 1, wherein said self-supporting polymeric film exclusive of foam and having said permanent transparent pattern is an outermost polymeric film of said security document.
3. The security document according to claim 2, wherein said self-supporting polymeric film exclusive of foam and having said permanent transparent pattern is provided on at least one side with a transparentizable overprintable layer.
4. The security document according to claim 1, wherein an outermost polymeric film of said security document is a non-transparent microvoided axially stretched self-supporting polymeric film.
5. The security document according to claim 1, wherein said non-transparent microvoided self-supporting polymeric film exclusive of foam and having said permanent transparent pattern constitutes the core of said security document.
6. The security document according to claim 1, wherein said non-transparent microvoided self-supporting polymeric film exclusive of foam and having said permanent transparent pattern further comprises at least one inorganic opacifying pigment.
7. The security document according to claim 1, wherein said non-transparent microvoided self-supporting polymeric film exclusive of foam and having said permanent transparent pattern comprises a polymer as a continuous phase and dispersed uniformly therein an amorphous high polymer with a higher glass transition temperature than the glass transition temperature of said continuous phase and/or a crystalline high polymer with a melting point higher than said glass transition phase of said continuous phase.
8. The security document according to claim 1, wherein said non-transparent microvoided self-supporting polymeric film exclusive of foam and having said permanent transparent pattern is a biaxially stretched film.
9. The security document according to claim 1, wherein said non-transparent microvoided self-supporting polymeric film exclusive of foam and having said permanent transparent pattern comprises a polyolefin as continuous phase.
10. The security document according to claim 1, wherein said non-transparent microvoided self-supporting polymeric film exclusive of foam and having said permanent transparent pattern comprises a linear polyester as continuous phase.
11. The security document according to claim 1, wherein said security document further comprises an embedded chip.
12. The security document according to claim 11, wherein said embedded chip has contact surfaces.
13. The security document according to claim 1, wherein said security document is an identity card.
14. The security document according to claim 13, wherein said identity card has a format according to ISO 7810.
15. The security document according to claim 11, wherein said security document is an identity card according to ISO 7816 and/or ISO 14443.
16. A process for producing a security document with a permanent transparent pattern comprising the step of: image-wise application of heat optionally supplemented by the application of pressure to a security document precursor comprising a plurality of self-supporting polymeric films and layers therebetween and thereon, said plurality of self-supporting polymeric films comprising a non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam.
17. The process according to claim 16, wherein at least one outermost polymeric film of said security document precursor is said non-transparent microvoided axially stretched self-supporting polymeric film exclusive of foam.
18. The process according to claim 16, wherein said non-transparent microvoided self-supporting polymeric film exclusive of foam constitutes the core of said security document precursor.
19. The process according to claim 16, wherein said non-transparent microvoided self-supporting polymeric film exclusive of foam further comprises at least one inorganic opacifying pigment.
20. The process according to claim 16, wherein said non-transparent microvoided self-supporting polymeric film exclusive of foam comprises a polymer as a continuous phase and dispersed uniformly therein an amorphous high polymer with a higher glass transition temperature than the glass transition temperature of said continuous phase and/or a crystalline high polymer with a melting point higher than said glass transition phase of said continuous phase.
20. The process according to claim 16, wherein said non-transparent microvoided self-supporting polymeric film exclusive of foam is a biaxially stretched film.
21. The process according to claim 16, wherein said non-transparent microvoided self-supporting polymeric film exclusive of foam comprises a polyolefin as continuous phase.
22. The process according to claim 16, wherein said non-transparent microvoided self-supporting polymeric film exclusive of foam comprises a linear polyester as continuous phase.
23. The process according to any of claims 16 to 22, wherein said image-wise applied heat is provided by a digital or an analogue process.
24. The process according to claim 23, wherein said digital image-wise heating process uses a laser beam or a thermal head.
25. The process according to claim 23, wherein said analogue image-wise heating process uses a heated stamp or an infrared image.
26. The process according to claim 16, wherein said security document further comprises an embedded chip.
27. The process according to claim 26, wherein said embedded chip has contact surfaces.
28. The process according to claim 16, wherein said security document is an identity card.
29. The security document according to claim 28, wherein said identity card has a format according to ISO 7810.
30. The security document according to claim 26, wherein said security document is an identity card according to ISO 7816 and/or ISO 14443.
Type: Application
Filed: Mar 18, 2008
Publication Date: Oct 2, 2008
Inventors: Ingrid Geuens (Emblem), Dirk Quintens (Westerlo)
Application Number: 12/050,660
International Classification: B42D 15/00 (20060101); B29C 43/52 (20060101);
