Patent Grant
8786651
This invention relates to methods for colour laser marking security document precursors.
Security cards are widely used for various applications such as identification purposes (ID cards) and financial transfers (credit cards). Such cards typically consist of a laminated structure consisting of various paper or plastic laminates and layers wherein some of them may carry alphanumeric data and a picture of the card holder. So called ‘smart cards’ can also store digital information by including an electronic chip in the card body.
A principal objective of such security cards is that they cannot be easily modified or reproduced in such a way that the modification or reproduction is difficult to distinguish from the original.
Two techniques frequently used for preparing security documents are laser marking and laser engraving. In literature, laser engraving is often incorrectly used for laser marking. In laser marking, a colour change is observed by local heating of material, while in laser engraving material is removed by laser ablation.
US 2005001419 (DIGIMARK) discloses a colour laser engraving method and a security document including an opaque surface layer and one or more coloured sub-layers. A laser provides openings in the surface layer to expose the colour of the sub-layer thereby creating colour images and text.
WO 2009/140083 (3M) discloses methods to generate a colour image in a multilayer article containing at least one thermally activatable layer coated from a composition including a non-linear light to heat converter, a leuco dye, a thermal acid generator and a solvent. A colour image is formed in the colour forming layer upon activation with non-linear light beam radiation (300-1500 nm).
U.S. Pat. No. 7,158,145 (ORGA SYSTEMS) discloses a three-wavelength system (440, 532 and 660 nm) for applying coloured information to a document by means of wavelength-selective bleaching of chromophoric particles in a layer close to the surface.
U.S. Pat. No. 4,720,449 (POLAROID) discloses a thermal imaging method for producing colour images on a support carrying at least one layer of a colourless compound, such as di- or triarylmethane, by direct application of heat or by conversion of electromagnetic radiation into heat. The laser beam may have different wavelengths, typically in a range above 700 nm with at least about 60 nm apart so that each imaging layer may be exposed separately to convert a colourless triarylmethane compound into a coloured form, such as yellow, magenta, cyan or black, by controlling the focusing depth of the laser beam source to each colour forming layer. The colour forming compositions include di- or triarylmethane compounds, infrared absorbers, acidic substances and binders.
U.S. Pat. No. 4,663,518 (POLAROID) discloses a laser printing method for activating heat sensitive image forming dyes in three different layers on a support to provide an identification card containing a coloured pictorial image of the card holder, coloured text and machine readable digital code.
In conventional printing techniques, such as offset and inkjet printing, four colours (CMYK) are normally used to obtain optimal image quality and colour gamut. The colour laser marking systems described for producing security documents generally use three colours: cyan, magenta and yellow (CMY). The black colour (K) produced by colour addition of the three other colours (CMY) tends to be a brownish black colour rather than the desired neutral black colour. Adding a fourth layer to produce a neutral black colour makes the apparatus for producing the security card more complex and expensive since this requires an extra laser.
Therefore, it would be desirable to have a secure colour laser marking system for producing security documents with improved image quality (neutral black colour) without increasing the complexity of the laser marking apparatus or the recording material.
In order to overcome the problems described above, preferred embodiments of the present invention provide a simple and cost-effective method of colour laser marking security document precursors as defined herein.
It is a further object of the present invention to provide security documents having an improved image quality and which are much more difficult to falsify.
It was surprisingly found that by using an infrared laser in two different output modes, i.e. pulsed mode and continuous wave mode, two different greyscale images could be made in a black colour, respectively in a colour different from black, e.g. a cyan or a magenta colour.
This has the advantage that a four coloured image, for example a CMYK-coloured image, can be laser marked in a security document precursor by using only three different infrared lasers at three different wavelengths instead of four different infrared lasers at four different wavelengths. This not only reduces the cost of the laser apparatus and the security document precursor, but also drastically simplifies their construction.
Further advantages and embodiments of the present invention will become apparent from the following description.
The term “graphical data” as used in disclosing the present invention means any graphical representation, e.g. a picture of a person, a drawing, etc.
The term “information” as used in disclosing the present invention means any alphanumeric data, e.g. name, place of birth, date of birth, etc.
The term “image” as used in disclosing the present invention means any graphical data and information. The image on a security document preferably varies at least partially from one security document to another one.
The term “security document” as used in disclosing the present invention means a document which contains the required image, e.g. a valid passport or identification card, and is ready for use.
The term “security document precursor” as used in disclosing the present invention means a document not containing all the required components of the security document, e.g. a layer or a security feature, and/or not containing the required image of the security document.
The term “visible spectrum” as used in disclosing the present invention means the electromagnetic spectrum from 400 nm to 700 nm.
The term “polymeric foil” as used in disclosing the present invention, means a self-supporting polymer-based sheet, which may be associated with one or more adhesion layers e.g. subbing layers. Foils are generally manufactured through extrusion.
The term “support” as used in disclosing the present invention, means a self-supporting polymer-based sheet, which may be transparent but is preferably opaque and which may be associated with one or more adhesion layers e.g. subbing layers. Supports are generally manufactured through extrusion.
The term “layer”, as used in disclosing the present invention, is considered not to be self-supporting and is manufactured by coating it on a support or a polymeric foil.
“PET” is an abbreviation for polyethylene terephthalate.
“PETG” is an abbreviation for polyethylene terephthalate glycol, the glycol indicating glycol modifiers which are incorporated to minimize brittleness and premature aging that occur if unmodified amorphous polyethylene terephthalate (APET) is used in the production of cards.
“PET-C” is an abbreviation for crystalline PET, i.e. a biaxially stretched polyethylene terephthalate. Such a polyethylene terephthalate support or foil has excellent properties of dimensional stability.
The definitions of security features correspond with the normal definition as adhered to in the “Glossary of Security Documents—Security features and other related technical terms” as published by the Consilium of the Council of the European Union on Aug. 25, 2008 (Version: v.10329.02.b.en) on its website: http://www.consilium.europa.eu/prado/EN/glossaryPopup.html.
The term “alkyl” means all variants possible for each number of carbon atoms in the alkyl group i.e. for three carbon atoms: n-propyl and isopropyl; for four carbon atoms: n-butyl, isobutyl and tertiary-butyl; for five carbon atoms: n-pentyl, 1,1-dimethyl-propyl, 2,2-dimethylpropyl and 2-methyl-butyl etc.
The term “substituted” in, for example substituted alkyl, means that the substituent on alkyl contains at least one atom different from carbon or hydrogen. The substituent may be a single atom (e.g. a halogen) or a group of atoms containing at least one atom different from carbon or hydrogen (e.g. an acrylate group).
The term “chlorinated ethylene”, as used in disclosing the present invention, means ethylene substituted with at least one chlorine atom e.g. vinyl chloride, vinylidene chloride, 1,2-dichloro-ethylene, trichloroethylene and tetrachloroethylene. Trichloroethylene and tetrachloroethylene are all much more difficult to polymerize than vinyl chloride or vinylidene chloride.
A leuco dye is a well-known colour forming compound whose molecules can acquire two forms, one of which is colourless. An example of a leuco dye is crystal violet lactone, which in its lactone form is colourless, but when it is protonated becomes intensely violet.
Methods of Colour Laser Marking
In the present invention, the method of colour laser marking a security document precursor including at least:
a) a polymeric foil;
b) at least one colourless colour forming layer for generating a colour different from black containing at least an infrared absorber, a colour forming compound and a polymeric binder; and
c) a laser markable polymeric support or a laser markable layer for generating a black colour; comprises the steps of:
(1) laser marking the colourless colour forming layer with an infrared laser used in continuous wave mode to generate a colour different from black; and
(2) laser marking the lasermarkable polymeric support or the lasermarkable layer with the same infrared laser but used in a pulsed mode to generate a black colour.
The colourless colour forming layer includes an infrared absorber which is capable of converting the infrared light of the infrared laser into heat which triggers the colour formation reaction. Hence, the laser emission wavelength of the infrared laser preferably matches the absorption maximum of the infrared dye within 40 nm, more preferably within 25 nm.
Preferably, the infrared laser used in the method of colour laser marking an article according to the present invention is an optically pumped semiconductor laser or a solid state Q-switched laser. Such lasers are widely commercially available. An example of a solid state Q-switched laser is the Matrix™ 1064 laser from COHERENT emitting at 1064 nm and capable of producing an average power of 7 Watt at a pulse repetition rate of 10 kHz.
Q-switching is a technique by which a laser can be made to produce a pulsed output beam. The technique allows the production of light pulses with extremely high peak power, much higher than would be produced by the same laser if it were operating in a continuous wave (constant output) mode, Q-switching leads to much lower pulse repetition rates, much higher pulse energies, and much longer pulse durations.
In the present invention, the pulsed output is used for lasermarking the lasermarkable polymeric support or the lasermarkable layer to generate a black colour. By modulating the light pulses, different optical densities of grey to black are obtained. In the same manner, by modulating the continuous wave mode, different optical densities of a colour different from black, e.g. cyan, magenta, yellow, red, green or blue, are obtained on lasermarking the colourless colour forming layer. For obtaining no optical density, i.e. minimum optical density Dmin, the laser beam is deflected.
Security Documents and Precursors
The security document precursor includes preferably at least:
a) a transparent biaxially stretched polyethylene terephthalate foil;
b) at least one colourless colour forming layer for generating a colour different from black containing at least an infrared absorber, a colour forming compound and a polymeric binder; and
c) a lasermarkable polymeric support or a lasermarkable layer for generating a black colour;
wherein the polymeric support is selected from the group selected from polycarbonate, polyvinyl chloride, polystyrene, polystyrene-acrylonitrile-butadiene and copolymers thereof;
and wherein the lasermarkable layer includes:
The security document precursor contains at least one colourless colour forming layer, but preferably contains two, three or more colourless colour forming layers for producing a multi-coloured security document. Most preferably the security document includes three colourless colour forming layers containing different infrared absorbers and colour forming compounds.
In one preferred embodiment, the three colourless colour forming layers containing different infrared absorbers and colour forming compounds are turned into three at least partially coloured layers having either a cyan, a magenta or a yellow colour.
In another preferred embodiment, the three colourless colour forming layers containing different infrared absorbers and colour forming compounds are turned into three at least partially coloured layers having either a red, a green or a blue colour.
Having either CMY- or RGB-coloured layers has the advantage that a well-established colour management system can be used for producing colour images based on either a CMY or RGB colour reproduction.
The infrared absorber not only delivers the heat for the colour forming action, but also has the advantage that there is no or minimal absorption in the visible spectrum and thus there is no or minimal interference with the colours formed by the one or more colourless colour forming layers. This allows a security document to have a pure white background.
In a preferred embodiment, the security document obtained from laser marking the security document precursor is selected from the group consisting of a passport, a personal identification card and a product identification document.
The security document preferably also contains electronic circuitry, more preferably the electronic circuitry includes a RFID chip with an antenna and/or a contact chip. The security document is preferably a “smart card”, meaning an identification card incorporating an integrated circuit. In a preferred embodiment the smart card includes a radio frequency identification or RFID-chip with an antenna.
The security document preferably has a format as specified by ISO 7810. ISO 7810 specifies three formats for identity cards: ID-1 with the dimensions 85.60 mm×53.98 mm, a thickness of 0.76 mm is specified in ISO 7813, as used for bank cards, credit cards, driving licences and smart cards; ID-2 with the dimensions 105 mm×74 mm, as used in German identity cards, with typically a thickness of 0.76 mm; and ID-3 with the dimensions 125 mm×88 mm, as used for passports and visa's. When the security cards include one or more contactless integrated circuits then a larger thickness is tolerated, e.g. 3 mm according to ISO 14443-1.
In another preferred embodiment, the security document is a product identification document which is attached to the packaging material of the product or to the product itself. The product identification document according to the present invention not only allows to verify the authenticity of the product, but to maintain the attractive look of a product (packaging) due to the enhanced image quality by making neutral black laser markings in colour images possible.
Colourless Colour Forming Layers
The security document precursor used in the laser marking method according to the present invention contains at least one colourless colour forming layer for generating a colour different from black including at least:
a) an infrared absorber;
b) a colour forming compound; and
c) a polymeric binder.
The at least one colourless colour forming layer can be coated onto the polymeric foil by any conventional coating technique, such as dip coating, knife coating, extrusion coating, spin coating, slide hopper coating and curtain coating. Preferably the colourless colour forming layer is coated with a slide hopper coater or a curtain coater, more preferably coated onto the polymeric foil including a subbing layer.
The dry thickness of the colourless colour forming layer is preferably between 5 and 40 g/m2, more preferably between 7 and 25 g/m2, and most preferably between 10 and 15 g/m2.
The security document precursor used in the laser marking method according to present invention contains at least one colourless colour forming layer containing an infrared absorber, a polymeric binder and a colour forming compound, but preferably contains two, three or more colourless colour forming layers for producing a multi-coloured security document.
The security document precursor used in the laser marking method according to present invention is preferably a multi-coloured article containing at least three colourless colour forming layers containing different infrared absorbers and colour forming compounds
The infrared absorber not only delivers the heat for the colour forming action, but also has the advantage that there is no or minimal absorption in the visible spectrum and thus there is no or minimal interference with the colours formed by the one or more colourless colour forming layers.
The infrared absorber not only delivers the heat for the colour forming action, but also has the advantage that there is no or minimal absorption in the visible spectrum and thus there is no or minimal interference with the colours formed by the one or more colourless colour forming layers. This also allows having, for example, a pure white background in a security document.
Colour Forming Compounds
Colour forming compounds are colourless or slightly yellowish compounds which react into a coloured form.
The colour forming compound is preferably present in the colourless colour forming layer in an amount of 0.5 to 5.0 g/m2, more preferably in an amount of 1.0 to 3.0 g/m2.
For performing the method of colour laser marking according to the present invention, the following reaction mechanisms and the colour forming compounds involved are suitable to form a coloured dye.
1. Fragmentation of a Colourless Dye-Precursor
The reaction mechanism can be represented by:
Colourless dye-FGDye
wherein FG represents a fragmenting group.
Such a reaction mechanism is explained in more detail by U.S. Pat. No. 5,243,052 (POLAROID) disclosing the colour formation by fragmentation of a mixed carbonate ester of a quinophthalone dye and a tertiary alkanol containing not more than about 9 carbon atoms.
The fragmentation of a colourless dye-precursor may be catalyzed or amplified by acid generating agents. The dyes G-(18) to G-(36) disclosed by U.S. Pat. No. 6,100,009 (FUJI) are catalyzed or amplified by polymeric acid generating agents based on A-(1) to A-(52), which are also suitable as acid generating agents in the present invention.
Another preferred colourless dye-precursor is the leuco dye-precursor (CASRN104434-37-9) shown in EP 174054 A (POLAROID) which discloses a thermal imaging method for forming colour images by the irreversible unimolecular fragmentation of one or more thermally unstable carbamate moieties of an organic compound to give a visually discernible colour shift from colourless to coloured.
The fragmentation of a leuco dye-precursor may be a two-step reaction mechanism represented by:
Leuco-dye-FG[Leuco-dye]
Coloured Dye
wherein FG represents a fragmenting group.
The fragmentation of a colourless leuco dye-precursor may be catalyzed or amplified by acids and acid generating agents. The leuco dye-precursors G-(1) to G-(17) disclosed by U.S. Pat. No. 6,100,009 (FUJI) are catalyzed or amplified by polymeric acid generating agents based on A-(1) to A-(52), which are also suitable as acid generating agents in the present invention.
2. Protonation of a Leuco Dye after Fragmentation of a H-donor-Precursor
The reaction mechanism can be represented by:
Leuco-dye+H-donor-RGLeuco-dye+H-donor
Coloured Dye
wherein RG represents a rearranging group.
A preferred H-donor-RG compound is capable of forming a compound having an allyl substituted phenol group as part of its chemical structure (the rest of the compound is represented by the group T) by laser heating:
Preferred H-donor-RG compounds include 4-hydroxy-4′-allyloxy diphenylsulfone and 4,4′-diallyloxy diphenylsulfone whereof the synthesis is disclosed by EP 1452334 A (RICOH).
In contrast to the H-donor-FG compound of reaction mechanism 2, no compound having a melting temperature lower than room temperature (20° C.) is produced by the rearrangement of the H-donor-precursor to a hydrogen donor. Consequently, the security feature of blister formation as possible with the H-donor-FG compound cannot be produced by the H-donor-RG compounds.
The colour formation according to the mechanisms 2 and 3 above are two-component reactions involving a leuco dye and a hydrogen donor-precursor, i.e. a ‘H-donor-FG compound’ or ‘H-donor-RG compound’, while the first reaction mechanism are one-component reactions. The advantage of using a two-component reaction for the colour formation is that the stability, especially the shelf-life stability, can be enhanced. The probability of undesired colour formation due to environment heating is decreased by going from a single step reaction to a two step reaction involving the formation of the H-donor followed by a reaction of the formed H-donor with the leuco dye.
The preferred colour formation mechanism is the protonation of a leuco dye after fragmentation of the H-donor since it includes both advantages of the blister formation security feature and the enhanced shelf-life stability.
In a preferred embodiment of the colourless layer, a combination is used of 4,4′-Bis(tert-butoxycarbonyloxy)diphenylsulfone (CASRN 129104-70-7) as the H-donor-FG compound with the leuco dye crystal violet lactone (CASRN 1552-42-7).
3. Protonation of a Leuco Dye after a Re-arrangement in a H-Donor-Precursor
The reaction mechanism can be represented by:
Leuco-dye+H-donor-RGLeuco-dye+H-donor
Coloured Dye
wherein RG represents a rearranging group.
A preferred H-donor-RG compound is capable of forming a compound having an allyl substituted phenol group as part of its chemical structure (the rest of the compound is represented by the group T) by laser heating:
Preferred H-donor-RG compounds include 4-hydroxy-4′-allyloxy diphenylsulfone and 4,4′-diallyloxy diphenylsulfone whereof the synthesis is disclosed by EP 1452334 A (RICOH).
In contrast to the H-donor-FG compound of reaction mechanism 2, no compound having a melting temperature lower than room temperature (20° C.) is produced by the rearrangement of the H-donor-precursor to a hydrogen donor. Consequently, the security feature of blister formation as possible with the H-donor-FG compound cannot be produced by the H-donor-RG compounds.
The colour formation according to the mechanisms 2 and 3 above are two-component reactions involving a leuco dye and a hydrogen donor-precursor, i.e. a ‘H-donor-FG compound’ or ‘H-donor-RG compound’, while the first reaction mechanism is an one-component reaction. The advantage of using a two-component reaction for the colour formation is that the stability, especially the shelf-life stability, can be enhanced. The probability of undesired colour formation due to environment heating is decreased by going from a single step reaction to a two step reaction involving the formation of the H-donor followed by a reaction of the formed H-donor with the leuco dye.
The preferred colour formation mechanism is the protonation of a leuco dye after fragmentation of the H-donor since it includes both advantages of the blister formation security feature and the enhanced shelf-life stability.
In a preferred embodiment of the colourless layer, a combination is used of 4,4′-Bis(tert-butoxycarbonyloxy)diphenylsulfone (CASRN 129104-70-7) as the H-donor-FG compound with the leuco dye crystal violet lactone (CASRN 1552-42-7).
Infrared Absorbers
The infrared absorber used in the colourless colour forming layer of the colour laser marking method according to the present invention, can be an infrared dye, an infrared organic pigment and an inorganic infrared pigment, but preferably the infrared absorber is an infrared dye.
The advantage of using infrared dyes is that the absorption spectrum of an infrared dye tends to be narrower than that of an infrared pigment. This allows the production of multicoloured articles and security documents from precursors having a plurality of colourless layers containing different infrared dyes and colour forming compounds. The infrared dyes having a different λmax can then be addressed by infrared lasers with corresponding emission wavelengths causing colour formation only in the colourless layer of the addressed infrared dye.
Suitable examples of infrared dyes include, but are not limited to, polymethyl indoliums, metal complex IR dyes, indocyanine green, polymethine dyes, croconium dyes, cyanine dyes, merocyanine dyes, squarylium dyes, chalcogenopyryloarylidene dyes, metal thiolate complex dyes, bis(chalcogenopyrylo)polymethine dyes, oxyindolizine dyes, bis(aminoaryl)polymethine dyes, indolizine dyes, pyrylium dyes, quinoid dyes, quinone dyes, phthalocyanine dyes, naphthalocyanine dyes, azo dyes, (metalized) azomethine dyes and combinations thereof.
Suitable inorganic infrared pigments include ferric oxide, carbon black and the like.
A preferred infrared dye is 5-[2,5-bis[2-[1-(1-methylbutyl)benz[cd]indol-2(1H)-ylidene]ethylidene]cyclopentylidene]-1-butyl-3-(2-methoxy-1-methylethyl)-2,4,6(1H,3H,5H)-pyrimidinetrione (CASRN 223717-84-8) represented by the Formula IR-1:
The infrared dye IR-1 has an absorption maximum λmax of 1052 nm making it very suitable for a Nd-YAG laser having an emission wavelength of 1064 nm.
The infrared red absorber is preferably present in the colourless colour forming layer in an amount of 0.05 to 1.0 g/m2, more preferably in an amount of 0.1 to 0.5 g/m2.
Thermal Acid Generating Compounds
The fragmentation of a colourless dye-precursor in the colourless colour forming layer of the colour laser marking method according to the present invention may be catalyzed or amplified by acids and acid generating agents.
Suitable thermal acid generating agents may be the polymeric acid generating agents based the ethylenically unsaturated polymerizable compounds A-(1) to A-(52) disclosed by U.S. Pat. No. 6,100,009 (FUJI) and herein incorporated as a specific reference.
Suitable non-polymeric acid generating agents are the compounds A-(1) to A-(52) disclosed by U.S. Pat. No. 6,100,009 (FUJI) lacking the ethylenically unsaturated polymerizable group.
The thermal acid generating agent is preferably present in the amount of 10 to 20 wt %, more preferably 14 to 16 wt % based on the total dry weight of the colourless layer.
Polymeric Binders
In principle any suitable polymeric binder that does not prevent the colour formation in the colourless layer of the colour laser marking method according to the present invention may be used. The polymeric binder may be a polymer, a copolymer or a combination thereof.
In a preferred embodiment, especially where the colourless layer includes a hydrogen donor-precursor and a leuco dye as the colour forming compound, the polymeric binder is a polymer or a copolymer of a chlorinated ethylene. The polymeric binder preferably includes at least 85 wt % of a chlorinated ethylene and 0 wt % to 15 wt % of vinyl acetate both based on the total weight of the polymeric binder. The polymeric binder preferably includes vinyl chloride as the chlorinated ethylene, and optionally vinylidene chloride as a second chlorinated ethylene.
In the most preferred embodiment of the invention, the polymeric binder includes at least 90 wt % of vinyl chloride based on the total weight of the polymeric binder.
The polymeric binder preferably includes at least at least 95 wt % of vinyl chloride and vinyl acetate based on the total weight of the polymeric binder.
The polymeric binder is preferably present in the colourless colour forming layer in an amount of 5 to 30 g/m2, more preferably in an amount of 7 to 20 g/m2.
In the most preferred embodiment, the colourless layer in the method of colour laser marking an article according to the present invention includes 4,4′-Bis(tert-butoxycarbonyloxy)diphenylsulfone as hydrogen donor-precursor and crystal violet lactone as the colour forming compound and a copolymer of a chlorinated ethylene as polymeric binder.
Lasermarkable Polymeric Supports
The lasermarkable polymeric support of the colour laser marking method according to the present invention is preferably selected from the group consisting of polycarbonate, polyvinyl chloride, polystyrene, polystyrene acrylonitrile butadiene and copolymers thereof.
Laser marking produces a colour change from white to black in a lasermarkable support through carbonization of the polymer caused by local heating. Patent literature and other literature contain contradictory statements regarding the necessity of specific “laser additives” for one polymer or another. This is presumably because particular additives which are regularly added to plastics for other purposes (for example as a filler, for colouring or for flame retardation) can also promote the laser marking result. The literature particularly frequently mentions polycarbonate, polybutylene terephthalate (PBT) and Acrylonitrile Butadiene Styrene (ABS) as “lasermarkable even without additive”, but additives are often added even in the case of these polymers in order to improve the lasermarkability further.
Lasermarkable Layers
In the colour laser marking method according to the present invention, the lasermarkable layer preferably includes:
Laser additives, such as carbon black, are used in so minute concentration that they have practically no contribution to the colour of the lasermarkable layer.
The advantage of using a lasermarkable layer coated on a support instead of a lasermarkable support, is that a support can be used which has better physical properties than the lasermarkable supports, such as for example a higher flexibility than a polycarbonate support.
Suitable supports for the lasermarkable layer include those disclosed above in the next section on “Polymeric Foils”. The support is preferably a polyethylene terephthalate glycol support (PETG) or a polyethylene terephthalate support (PET), more preferably a biaxially stretched polyethylene terephthalate support (PET-C), which may be transparent or opaque.
Suitable polymers include polycarbonate (PC), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyvinyl chloride (PVC), polystyrene (PS) and copolymers thereof, such as e.g. aromatic polyester-carbonate and acrylonitrile butadiene styrene (ABS). A mixture of two or more of these polymers may also be used.
In order to promote and to support the colour change in polymeric materials, various additives have been developed. As a result of the addition of a “laser additive”, a substance which absorbs the laser light and converts it to heat, the heat input and the carbonization can be improved. This is the case even for polymers such as polycarbonate which carbonize readily on their own. Lasermarkable plastics which are difficult to laser-treat include polyethylene, polypropylene, polyamide, polyoxymethylene, polyester, polymethyl methacrylate, polyurethane or a copolymer thereof.
Suitable laser additives include antimony metal, antimony oxide, carbon black, mica (sheet silicate) coated with metal oxides and tin-antimony mixed oxides. Suitable laser additives are additives based on various phosphorus-containing mixed oxides of iron, copper, tin and/or antimony as disclosed in WO 2006/042714 (TICONA).
In a preferred embodiment of the security document precursor, the lasermarkable layer contains carbon black particles as laser additive. This avoids the use of heavy metals, which are less desirable from an ecology point of view, in manufacturing these security documents, but may also cause problems for persons having a contact allergy based on heavy metals.
Suitable carbon blacks include Pigment Black 7 (e.g. Carbon Black MA8™ from MITSUBISHI CHEMICAL), Regal™ 400R, Mogul™ L, Elftex™ 320 from CABOT Co., or Carbon Black FW18, Special Black 250, Special Black 350, Special Black 550, Printex™ 25, Printex™ 35, Printex™ 55, Printex™ 90, Printex™ 150T from DEGUSSA.
The use of these laser additives may lead to an undesired background colouring of the security document. For example, a too high concentration of carbon black in a lasermarkable layer based on polycarbonate leads to grey security documents. If a white background is requested for the security document, then a white pigment may be added to the composition for manufacturing the lasermarkable layer. Preferably a white pigment with a refractive index greater than 1.60 is used. A preferred pigment is titanium dioxide.
However, most white pigments with a refractive index greater than 1.60, such as titanium dioxide, also have a high specific density resulting in problems of dispersion stability of the lasermarkable compositions used for making the lasermarkable layer. Both problems of white background and dispersion stability were solved in the present invention by using a dispersion of carbon black particles having a small average size and present in a low concentration.
The numeric average particle size of the carbon black particles is preferably between 5 nm and 250 nm, more preferably between 10 nm and 100 nm and most preferably between 30 nm and 60 nm. The average particle size of carbon black particles can be determined with a Brookhaven Instruments Particle Sizer BI90plus based upon the principle of dynamic light scattering. The measurement settings of the BI90plus are: 5 runs at 23° C., angle of 90°, wavelength of 635 nm and graphics=correction function.
For avoiding grey background colouring of security document, carbon black is preferably present in a concentration of less than 0.1 wt %, more preferably in the range 0.005 to 0.03 wt %, based on the total weight of the lasermarkable polymer(s).
Polymeric Foils
In the present invention, the colourless colour forming layer containing an infrared absorber, a polymeric binder and a colour forming compound is preferably coated on the polymeric foil, but may also be coated on the laser markable support.
If an opaque laser markable support or laser markable layer is used, then the polymeric foil is transparent so that the infrared light of the laser can reach the colourless colour forming layer.
If an opaque polymeric foil is used, then the laser markable support or laser markable layer is transparent so that the infrared light of the laser can reach the colourless colour forming layer.
The polymeric foil and/or the laser markable support may be provided with a subbing layer for improving the adhesion and coating quality.
The polymeric foil is preferably a biaxially stretched polyethylene terephthalate foil.
In a preferred embodiment, the polymeric foil is a transparent polymeric foil.
In a more preferred embodiment, the polymeric foil is a transparent biaxially stretched polyethylene terephthalate foil, optionally provided with a subbing layer.
In the present invention, the colourless colour forming layer containing an infrared absorber, a polymeric binder and a colour forming compound is preferably coated on a biaxially stretched polyethylene terephthalate foil, optionally provided with a subbing layer.
The transparency of the biaxially stretched polyethylene terephthalate foil is required so that the infrared laser light can reach the colourless colour forming layer and that information and graphical data, e.g. security print and guilloches, can be observed in and underneath the laser marked colourless colour forming layer(s).
Another advantage of using a biaxially stretched polyethylene terephthalate foil as the polymeric foil is that is very durable and resistant to mechanical influences (flexion, torsion, scratches), chemical substances, moisture and temperature ranges. This is especially useful for security documents such as identification cards and credit cards for which the average daily usage has lately augmented substantially from less than 1 time per week to 4 times per day. The card body has to withstand not only this increased usage, but also the associated storage conditions. Cards are no longer safely tucked away in cabinets at home or seldom-opened wallets, but are now loosely put away in pockets, purses, sport bags etc.—ready for immediate use. PVC (polyvinylchloride) is the most widely used material for plastic cards but has low durability of the card body, resulting in an effective lifetime of only 1-3 years, much lower than the lifetime of the often expensive chips included in the card. Other materials like Teslin™ and ABS are only suitable for very low-end or single-use cards. PC (polycarbonate) can be used for longer-life and more secure ID cards, but has a high production cost and a low resistance to torsion, scratching and chemicals.
The biaxially stretched polyethylene terephthalate foil (PET-C foil) should be sufficiently thick to be self-supporting, but thin enough so that it is possible to include other layers, foils and support within the format as specified for security documents, e.g. by ISO 7810 for identity cards. The thickness of the PET-C foil is preferably between 10 μm and 200 μm, more preferably between 10 μm and 100 μm, most preferably 30 μm and 65 μm.
The transparent polymeric foil with the at least one colourless colour forming layer may be laminated onto a support, e.g. the lasermarkable polymeric support or the support coated with the lasermarkable layer for generating a black colour, to form a security document precursor wherein the colourless colour forming layer is sandwiched between the transparent polymeric foil and the support. Additional foils and layers, e.g. other colourless colour forming layers having different infrared absorbers and colour forming compounds, may be included between the support and the transparent polymeric foil. In the case of a fully coloured security document, at least three colourless colour forming layers are present between the polymeric foil and the support so that e.g. CMYK colours can be formed.
In a preferred embodiment, the security document precursor is symmetrical, i.e. the same layers and foils are present on both sides of the support. This has the advantages that both sides can be full colour laser marked and that possible curl due to an asymmetric construction of the security document is effectively prevented.
In order to comply with the format as specified by ISO 7810 for security documents, the polymeric foil and the support have a thickness of between about 6 μm and about 250 μm, more preferably between about 10 μm and about 150 μm, most preferably between about 20 μm and about 100 μm.
In the case of a lasermarkable layer, the support can be transparent, translucent or opaque, and can be chosen from paper type and polymeric type supports well-known from photographic technology.
In a preferred embodiment the support is an opaque support. The advantage of an opaque support, preferably of a white colour, is that any information on the security document is more easily readable and that a colour image is more appealing. The support preferably is a single component extrudate, but may also be co-extrudate. Examples of suitable co-extrudates are PET/PETG and PET/PC. Paper type supports include plain paper, cast coated paper, polyethylene coated paper and polypropylene coated paper.
Suitable polymeric supports for a lasermarkable layer and polymeric foils include cellulose acetate propionate or cellulose acetate butyrate, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyamides, polycarbonates, polyimides, polyolefins, poly(vinylacetals), polyvinylchlorides, polyethers and polysulphonamides. Also synthetic paper can be used as a polymeric support, for example, Synaps™ synthetic paper of Agfa-Gevaert NV. Other examples of useful high-quality polymeric supports for the present invention include opaque white polyesters and extrusion blends of polyethylene terephthalate and polypropylene. Also Teslin™ may be used as support.
Polyester film supports for a lasermarkable layer and polymeric foils and especially polyethylene terephthalate are preferred because of their excellent properties of dimensional stability. When such a polyester is used as the support material, a subbing layer may be employed to improve the bonding of layers, foils and/or laminates to the support.
In a preferred embodiment of the security document precursor, the support is polyvinyl chloride, polycarbonate or polyester, with coloured or whitened polyvinyl chloride, polycarbonate or polyester being preferred. The polyester support is preferably polyethylene terephthalate support (PET) or polyethylene terephthalate glycol (PETG).
Instead of a coloured or whitened support, an opacifying layer can be coated onto the support. Such opacifying layer preferably contains a white pigment with a refractive index greater than 1.60, preferably greater than 2.00, and most preferably greater than 2.60. The white pigments may be employed singly or in combination. Suitable white pigments include C.I. Pigment White 1, 3, 4, 5, 6, 7, 10, 11, 12, 14, 17, 18, 19, 21, 24, 25, 27, 28 and 32. Preferably titanium dioxide is used as pigment with a refractive index greater than 1.60. Titanium oxide occurs in the crystalline forms of anatase type, rutile type and brookite type. In the present invention the rutile type is preferred because it has a very high refractive index, exhibiting a high covering power.
In one embodiment of the security document precursor, the support is an opacified polyvinyl chloride, an opacified polycarbonate or an opacified polyester.
The manufacturing of PET-C foils and supports is well-known in the art of preparing suitable supports for silver halide photographic films. For example, GB 811066 (ICI) teaches a process to produce biaxially oriented films of polyethylene terephthalate.
The polyethylene terephthalate supports and foils are preferably biaxially stretched with a stretching factor of at least 2.0, more preferably at least 3.0 and most preferably a stretching factor of about 3.5. The temperature used during stretching is preferably about 160° C.
Methods to obtain opaque biaxially oriented polyethylene terephthalate supports and foils have been disclosed in, e.g. US 2008238086 (AGFA).
Subbing Layers
The polymeric foil and support may be provided with one or more subbing layers. This has the advantage that the adhesion between a layer, such as the colourless layer, and the polymeric foil or support is improved. The transparent polymeric foil preferably includes a subbing layer whereon the colourless layer is coated.
Useful subbing layers for this purpose are well known in the photographic art and include, for example, polymers of vinylidene chloride such as vinylidene chloride/acrylonitrile/acrylic acid terpolymers or vinylidene chloride/methyl acrylate/itaconic acid terpolymers.
The application of subbing layers is well-known in the art of manufacturing polyester supports for silver halide photographic films. For example, the preparation of such subbing layers is disclosed in U.S. Pat. No. 3,649,336 (AGFA) and GB 1441591 (AGFA);
Suitable vinylidene chloride copolymers include: the copolymer of vinylidene chloride, N-tert.-butylacrylamide, n-butyl acrylate, and N-vinyl pyrrolidone (e.g.70:23:3:4), the copolymer of vinylidene chloride, N-tert.-butylacrylamide, n-butyl acrylate, and itaconic acid (e.g. 70:21:5:2), the copolymer of vinylidene chloride, N-tert.-butylacrylamide, and itaconic acid (e.g. 88:10:2), the copolymer of vinylidene chloride, n-butylmaleimide, and itaconic acid (e.g. 90:8:2), the copolymer of vinyl chloride, vinylidene chloride, and methacrylic acid (e.g. 65:30:5), the copolymer of vinylidene chloride, vinyl chloride, and itaconic acid (e.g. 70:26:4), the copolymer of vinyl chloride, n-butyl acrylate, and itaconic acid (e.g. 66:30:4), the copolymer of vinylidene chloride, n-butyl acrylate, and itaconic acid (e.g. 80:18:2), the copolymer of vinylidene chloride, methyl acrylate, and itaconic acid (e.g.90:8:2), the copolymer of vinyl chloride, vinylidene chloride, N-tert.-butylacrylamide, and itaconic acid (e.g. 50:30:18:2). All the ratios given between brackets in the above-mentioned copolymers are ratios by weight.
In a preferred embodiment, the subbing layer has a dry thickness of no more than 2 μm or preferably no more than 200 mg/m2.
Organic Solvents
For coating the laser markable colourless layer, one or more organic solvents may be used. The use of an organic solvent facilitates the dissolution of the polymeric binder and specific ingredients such as the infrared dye.
A preferred organic solvent is methylethylketon (MEK) because it combines a high solubilizing power for a wide range of ingredients and it provides, on coating the colourless layer, a good compromise between the fast drying of the colourless layer(s) and the danger of fire or explosion thereby allowing high coating speeds.
Other Security Features
To prevent forgeries of identification documents, different means of securing are used. One solution consists in superimposing lines or guilloches on an identification picture such as a photograph. In that way, if any material is printed subsequently, the guilloches appear in white on added black background. Other solutions consist in adding security elements such as information printed with ink that reacts to ultraviolet radiation, micro-letters concealed in an image or text etc.
The security document according to the present invention may contain other security features such as anti-copy patterns, guilloches, endless text, miniprint, microprint, nanoprint, rainbow colouring, 1D-barcode, 2D-barcode, coloured fibres, fluorescent fibres and planchettes, fluorescent pigments, OVD and DOVID (such as holograms, 2D and 3D holograms, Kinegrams™, overprint, relief embossing, perforations, metallic pigments, magnetic material, Metamora colours, microchips, RFID chips, images made with OVI (Optically Variable Ink) such as iridescent and photochromic ink, images made with thermochromic ink, phosphorescent pigments and dyes, watermarks including duotone and multitone watermarks, ghost images and security threads.
A combination of the security document according to the present invention with one of the above security features increases the difficulty for falsifying the document.
All materials used in the following examples were readily available from standard sources such as ALDRICH CHEMICAL Co. (Belgium) and ACROS (Belgium) unless otherwise specified. The water used was deionized water.
CCE is Bayhydrol™ H 2558, a anionic polyester urethane (37.3%) from BAYER.
Resorcinol from Sumitomo Chemicals.
Par is a dimethyltrimethylolamine formaldehyde resin from Cytec industries.
PAR-sol is a 40 wt % aqueous solution of Par.
PEA is Tospearl™ 120 from Momentive Performance materials.
PEA-sol is a 10 wt % (50/50) aqueous/ethanol dispersion of PEA.
Dowfax™ 2A1 from Pilot Chemicals C is a Alkyldiphenyloxide disulfonate (4.5% wt %).
DOW-sol is a 2.5 wt % solution of Dowfax™ 2A1 in isopropanol.
Surfynol™ 420 from Air Products is a non ionic surfactant.
Surfynsol is a 2.5 wt % solution of Surfynol™ 420 in isopropanol.
MEK is an abbreviation used for methylethylketon.
UCAR is an abbreviation for a 25 wt % solution in MEK of UCAR™ VAGD.
UCAR™ VAGD is a medium molecular weight copolymer of 90% vinyl chloride, 4% vinyl acetate and 6% vinylalcohol, provided by Dow Chemical.
Baysilon is a 1 wt % solution in MEK of the silicon oil Baysilon™
Lackadditive MA available from BAYER.
HDP is the hydrogen donor-precursor CASRN 129104-70-7 prepared according to the synthesis given on page 31 of EP 605149 A (JUJO PAPER) for the compound (19).
CVL is crystal violet lactone is CASRN 1552-42-7 available from Pharmorgana:
DMF is dimethylformamide.
DMA is dimethylacetamide.
THF is tetrahydrofuran.
Makrofol™ DE 1-4 is a translucent extrusion film based on Makrolon™ (polycarbonate) from BAYER.
IR-1 is a 0.15 wt % solution in MEK of the infrared dye CASRN 223717-84-8 and was prepared as described below.
The synthesis of intermediate INT-5 was carried out in a cascade mode without purification of the intermediates INT-1, INT-2, INT-3 and INT-4 as described below:
Intermediate INT-1
To a solution of butyl isocyanate (1.03 eq.) in toluene (70 mL/mol) at 50° C. was added 2-amino-1-methoxy propane (1.00 eq.) over a 2 hour period. After stirring for 30 minutes, excess toluene and reagent were distilled off at 85° C./50 mbar and at 85° C./20 mbar respectively. The mixture was allowed to reach atmospheric pressure under nitrogen.
Intermediate INT-2
To the warm residue (INT-1) were consecutively added: acetic acid (140 mL/mol), malonic acid (1.00 eq.) and acetic anhydride (2.00 eq.). Under stirring the reaction mixture was gently warmed to 90° C. After stirring for 2.5 hours at 90° C., methanol (70 mL/mol) was added and the mixture was refluxed for 45 minutes. Subsequently, the solvents were removed at 100° C./70 mbar. After cooling to 30° C., methyl t. butyl ether (MTBE) (300 mL/mol) was added. This mixture was extracted 3× with a 5% NaCl solution in water and 2× with a satured NaCl solution in water. The MTBE was distilled off at 95° C./70 mbar. The remaining water was azeotropically removed with toluene. The mixture was allowed to reach room temperature under nitrogen at atmospheric pressure.
Intermediate INT-3
To the residue (INT-2) were consecutively added under a nitrogen blanket at room temperature: cyclopentanone (1.10 eq.), ammoniumacetate (0.07 eq.) and methanol (150 mL/mol). After refluxing for 4.5 hours, methanol was distilled off at 50 mbar. Remaining methanol and water were azeotropically removed with toluene. After cooling to room temperature, toluene (0.108 kg/mol) was added. This solution was filtered on a stainless steel filter covered with silica (30 g/mol). The reactor and the filter cake were washed with toluene (4×50 mL/mol). This solution of INT-3 was directly used in the next step
Intermediate INT-4
To the toluene solution of INT-3 at room temperature was added acetic acid (1.00 eq.). Under a nitrogen blanket, DMF-DMA (1.13 eq.) was quickly (10 minutes) added at 10° C. After 5 minutes, n. hexane (830 mL/mol) was added, followed by another portion of n. hexane (415 mL/mol) after 30 minutes. After stirring for at least 1 hour (crystallisation) INT-4 is collected by filtration. After washing with n. hexane/toluene (100 mL/mol) and n. hexane (3×125 mL/mol), the product INT-4 was digested with n. hexane (500 mL/mol), filtered and dried at 25° C. for 24 hours.
Intermediate INT-5
To a suspension of INT-4 in ethyl acetate (320 mL/mol) under nitrogen at room temperature was added DMF-DMA (3.49 eq.) in one portion. The mixture was heated to 65° C. and stirred at 65° C. for 25 minutes. While quickly cooling to 15° C., a mixture of MTBE (640 mL/mol) and n. hexane (160 mL/mol) was added. After stirring for 15 minutes, the product was filtered and consecutively washed with ethylacetate/MTBE 80/20 (200 mL/mol), ethylacetate/n. hexane 80/20 (200 mL/mol), ethylacetate/n. hexane 50/50 (200 mL/mol) and n. hexane (200 mL/mol). The rather unstable product (INT-5) was dried at 25° C. for 24 hours.
The synthesis of intermediate INT-7 was carried out in a cascade mode without purification of the intermediate INT-6 as described below:
Intermediate INT-6
To a nitrogen blanketed solution of 1.8-Naphtholactam (1.00 eq.) in sulfolane (250 mL/mol) at 70° C. were added potassium iodide (0.20 eq.) and dimethylaminopyridine (DMAP) (0.135 eq.).
To this mixture was added potassium hydroxide (KOH) (0.60 eq.) and 2-bromo pentane (0.50 eq.).
After 1 hour at 70-75° C. another portion of KOH (0.60 eq.) and 2-bromo pentane (0.50 eq.) were added, while distilling of the pentene side product. This was repeated 2 times. After cooling the reaction mixture was diluted with MTBE (1 L/mol) and washed with water. The water layer was extracted again with MTBE. The combined extracts were washed consecutively with a 15% NaCl solution in water, a 10% NaCl solution in water containing 4% HCl, a 15% NaCl solution in water containing 1% NaHCO3 and a 25% NaCl solution in water. The MTBE was distilled off and the remaining water was azeotropically removed with toluene. The crude INT-6 (oil) was used a such.
Intermediate INT-7
To nitrogen blanketed solution of INT-6 (1.00 eq.) in THF (100 mL/mol) at room temperature was added methyl magnesium chloride (1.28 eq.) over 45 minutes (55-60° C.). After stirring for 1 hour at 55° C., the reaction mixture was added to a mixture of HCl (3.9 eq.) in ice water (3.66 kg/mol). After distillative removal of the THF, the aqueous solution was filtered and added to a solution of KI (2.00 eq.) in water (2.1 L/mol). After crystallisation, crude INT-7 was filtered and consecutively washed with water (2.55 L/mol) and ethyl acetate (2.55 L/mol) and dried at 40° C. Yield: 76%
IR-absorber IR-1
To a stirred suspension of INT-5 (1.00 eq.) in methyl acetate (4 L/mol) at 50° C., was added in portions INT-7 (2.10 eq.) over 5 minutes. After stirring for 1 hour at 55° C., 2 extra portions of INT-7 (each 0.016 eq.) were added. After stirring for 2.5 hours at 55° C., the reaction mixture was cooled to room temperature. Crude IR-1 was isolated by filtration and washed with ethyl acetate (4 L/mol).
After digestion in water (to remove salts) (4 L/mol), filtering and washing on the filter with water (2 L/mol) and MTBE (1.5 L/mol) the product was dried at 40° C. Yield=92%.
Measurement Methods
1. Optical Density
The optical density was measured in reflection using a spectrodensitometer Type Macbeth TR924 using a visual filter.
This example illustrates the formation of black and blue coloured markings of different optical densities by using the same infrared laser in a pulsed mode respectively a continuous wave mode.
Preparation of PET-C Foil PET1
A coating composition SUB-1 was prepared by mixing the components according to Table 1 using a dissolver.
A 1100 μm thick polyethylene terephthalate sheet was first longitudinally stretched and then coated with the coating composition SUB-1 to a wet thickness of 10 μm. After drying, the longitudinally stretched and coated polyethylene terephthalate sheet was transversally stretched to produce a 63 μm thick sheet PET1, which was transparent and glossy.
Preparation of Colourless Colour forming Layer
A coating composition COL-1 was prepared by mixing the components according to Table 2 using a dissolver.
The coating composition COL-1 was coated with an Elcometer™ Bird Film Applicator (from ELCOMETER INSTRUMENTS) on the subbed PET-C support PET1 at a coating thickness of 100 μm and subsequently dried for 2 minutes at 20° C. on the film applicator and for a further 15 minutes in an oven at 75° C. to deliver the security film SF-1. A second security film SF-1 was prepared in the same manner.
Preparation of Security Document Precursor SDP-1
A security document precursor SDP-1 was prepared by laminating the security films SF-1 with the colourless colour forming layer facing the black & white lasermarkable 100 μm Makrofol™ DE 1-4 in laminate construction as given by Table 3. The lamination was performed using an Oasys™ OLA6/7 plate laminator with the settings: LPT=115° C., LP=40, Hold=210 sec, HPT=115° C., HP=40 and ECT=50° C.
Evaluation and Results
The security document precursor SDP-1 was exposed at 1064 nm using a Matrix™ 1064 laser from COHERENT in three different modes: no beam, continuous wave mode and pulsed mode. No beam means that the laser beam was deflected and did not reach the security document precursor SDP-1. The beam was focused at the surface of SDP-1 with a 163 mm focal length f-theta scan lens in a galvanometer scanner assembly scanning at a line speed of 200 mm/s. The spot size was about 100 μm. The optical density was measured and is given by Table 4.
From Table 4, it should be clear that the same intermediate optical density of about 0.7 could be obtained in a different colour depending on laser operation mode used.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10193893 | Dec 2010 | EP | regional |
The present application is the U.S. National Phase of PCT/EP2011/071161, filed Nov. 28, 2011, claiming the benefit of European Patent Application No. 10193893.4, filed Dec. 7, 2010, and U.S. Provisional Patent Application No. 61/424,088, filed Dec. 17, 2010; the disclosures of the '161, '893 and '088 applications are incorporated by reference.
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP2011/071161 | 11/28/2011 | WO | 00 | 5/16/2013 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2012/076354 | 6/14/2012 | WO | A |
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