# Patent

## Title
Colour laser marking of articles and security document precursors

## Abstract

A method of color laser marking an article having a polymeric foil with at least one colorless layer containing an infrared absorber, a polymeric binder and a color forming compound; including the steps of:—laser marking the colorless layer with an infrared laser using a first laser operation mode to generate a blue or cyan color; and—laser marking the same colorless layer with an infrared laser using a second laser operation mode to generate a black color, wherein the first laser operation mode applies less energy to the colorless layer than the second laser operation mode. Also disclosed is an article, such as a security document, including a polymeric foil and a colorless layer containing laser marked graphical data having a blue or cyan color and laser marked information having a black color.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
The present application is the U.S. National Phase of PCT/EP2011/071842, filed Dec. 6, 2011, claiming the benefit of European Patent Application No. 10193892.6, filed Dec. 7, 2010, and U.S. Provisional Patent Application No. 61/420,783, filed Dec. 8, 2010; the disclosures of the ‘842, ‘892 and ‘783 applications are incorporated by reference.


TECHNICAL FIELD
This invention relates to methods for colour laser marking articles, especially security document precursors, and to the resulting laser marked articles and security documents.
BACKGROUND ART
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.
EP739748 A1(3M) discloses a laser-imageable direct write medium comprising an infrared dye in photoreactive association with a leuco dye, in which irradiation of the medium at a wavelength absorbed by said infrared dye converts said leuco dye to the corresponding dye. In example 6, such a leuco dye forms a cyan dye colour in combination with a black colour derived from the reduction of silver behenate.
U.S. Pat. No. 6,017,972 (M A HANNACOLOR) discloses the controlled color laser marking of plastics using pulsed and continuous wave lasers and Q-switched lasers.
US 2010099556 (ZINK IMAGING) discloses that the time and temperature of heating of color-forming layers can be controlled by using a laser in a pulsed mode with appropriate choices of laser power and pulse length.
JP 61-175077 and the corresponding U.S. Pat. No. 4,742,042 (MITSUBISHI PAPER MILLS) discloses a thermosensitive recording material containing a colorless dye precursor and a developer which, upon being heated, reacts with said dye precursor to develop color, wherein said thermosensitive recording layer contains as sensitizer a compound selected from a group consisting of p-benzylbiphenyl, diaryl esters of adipic acid, and the developer is bis(3-allyl-4-hydroxyphenyl)sulfone.
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 recording material more complex and expensive and would require an extra laser, making also the apparatus for producing the security card more complex and expensive. If a white background for the security document is desired, then usually three spectrally separated infrared absorbers are selected to produce a CMY-image. Adding a fourth black colour forming layer would make it very difficult to have four infrared absorbers with minimal overlap in their absorption spectrum and thus minimal colour contamination.
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.
SUMMARY OF INVENTION
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 articles as described herein.
It is a further object of the present invention to provide security documents having an improved image quality and which are more difficult to falsify.
Further advantages and embodiments of the present invention will become apparent from the following description.
Definitions
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
A pulsed laser has adjustable variable parameters that govern laser energy characteristics, such as pulse content, pulse duration and pulse frequency. A laser beam remains a certain time, called the dwell time, at a certain position, called a pixel. Energy is applied to the pixel during this dwell time, for example, in the form of a number of pulses of a certain laser power.
The method of colour laser marking, according to the present invention, an article having a polymeric foil with at least one colourless layer containing an infrared absorber, a polymeric binder and a single colour forming compound selected from the group consisting of a leuco dye and a colourless dye-precursor;
including the steps of:

    
    
        laser marking a blue or cyan colour in the colourless layer with an infrared laser using a first laser operation mode; and
        laser marking a black colour in the same colourless layer with an infrared laser using a second laser operation mode,
    
    


wherein the second laser operation mode is a pulsed mode, and
wherein the energy applied for laser marking a blue or cyan pixel is smaller than for laser marking a black pixel.
The colourless layer includes an infrared absorber which is capable of converting the infrared radiation 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.
In a preferred embodiment of the method of colour laser marking an article according to the present invention, the same laser is used in two different laser operation modes to laser mark a colourless layer containing an infrared absorber, a polymeric binder and a colour forming compound, thereby producing both a black coloured marking and a blue or cyan coloured marking in one and the same colourless layer. The laser operation mode to generate the blue or cyan coloured marking in the colourless layer applies less energy than the laser operation mode used to generate the black coloured marking. By being able to use the same laser, the apparatus for manufacturing the article or security document is not only less costly but can also be made more compact.
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.
A semiconductor laser is particularly preferred because the device is compact and inexpensive. Most semiconductor lasers are laser diodes, which are pumped with an electrical current in a region where a n-doped and a p-doped semiconductor material meet. However, there are also optically pumped semiconductor lasers, where carriers are generated by absorbed pump light. Optically pumped semiconductor lasers have the advantage of unique wavelength flexibility, different from any other solid-state based laser. The fundamental near-IR output wavelength is determined by the structure of the gain chip (e.g. the semiconductor InGaAs), and can be set anywhere between about 920 nm and about 1150 nm. This allows a perfect match between the laser emission wavelength and the infrared dye absorption maximum.
The infrared laser is most preferably a solid state Q-switched laser. 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 one embodiment, the first and second laser operation modes are both a pulsed mode.
In more preferred embodiment, the first laser operation mode is a continuous wave mode and the second laser operation mode is a pulsed mode. Preferably, the continuous wave mode is modulated to apply different energy levels to the article resulting in different optical densities of cyan or blue.
Infrared lasers are widely commercially available. An example of a solid state Q-switched laser is the MatrixTM 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.
Articles and Security Documents
The article according to the present invention includes a transparent polymeric foil and a colourless layer containing laser marked graphical data having a blue or cyan colour and laser marked information having a black colour.
In one preferred embodiment, the article is a security document. The security document is preferably 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.
The transparency of the polymeric foil is required so that the infrared laser light can reach the colourless layer and that information and graphical data can be observed in and underneath the laser marked colourless layer(s).
In a preferred embodiment, the transparent polymeric foil is a biaxially stretched polyester foil, preferably a biaxially stretched polyethylene napthalate foil, most preferably a biaxially stretched polyethylene terephthalate foil. The advantage of such a PET-C foil is that it 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 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.
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 Layers
The article according to the present invention has at least one colourless layer including at least:
a) an infrared absorber;
b) a colour forming compound; and
c) a polymeric binder. The security document may further include d) a thermal acid generating compound.
The colourless layer(s) 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 transparent polymeric foil including a subbing layer.
The dry thickness of the colourless 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 article or security document according to present invention contains at least one colourless 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 article according to present invention is preferably a multi-coloured article containing at least three colourless 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 layers. This also allows having, for example, a pure white background in a security document.
In addition to the colourless layer containing laser marked graphical data having a blue or cyan colour and laser marked information having a black colour, preferably the article or security document contains two other colourless layers for forming a magenta respectively a yellow image or for forming a red respectively a green image, since most colour management systems for producing colour images are based on either a CMY or RGB colour reproduction.
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-FGLeuco-dye+H-donorColoured Dye

wherein FG represents a fragmenting group.
A preferred H-donor-FG compound includes an ester group as part of its chemical structure (the rest of the compound is represented by the group T) which by laser heating forms a carboxylic acid group:




A more preferred H-donor-precursor includes a carbonate group, e.g. a tBOC group, as part of its chemical structure (the rest of the compound is represented by the group T) which by laser heating forms a phenol group:




Preferred carbonate groups are given on page 8 of EP 605149 A (JUJO PAPER). In a preferred embodiment, the H-donor-FG compound contains 2 carbonate groups.
The most preferred H-donor-FG compound is:




The synthesis of compound HDP (CASRN 129104-70-7) is given on page 31 of EP 605149 A (JUJO PAPER) for the compound (19).
In addition to the H-donor, the fragmentation of the H-donor-FG compound above also leads to the formation of a compound having a melting temperature lower than room temperature (20° C.). In the present invention the formation of such a compound is used as an additional security feature. After producing a security document by the method of colour laser marking according to the present invention wherein a biaxially stretched polyethylene terephthalate polymeric foil is used as overlay, the compound having a melting temperature lower than room temperature will disturb a second laser marking (falsification of the security document) by the formation of visible blisters in laser marked areas.
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-donorColoured 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-precursor 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 layer of the method of colour laser marking an article 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 layer of the method of colour laser marking an article 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 method of colour laser marking an article 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 vinylacetate 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.
Polymeric Foils and Supports
In the present invention, the colourless layer containing an infrared absorber, a polymeric binder and a colour forming compound is coated on a transparent polymeric foil, preferably a transparent polymeric foil, optionally provided with a subbing layer.
The transparent polymeric foil may be laminated onto a support to form a security document wherein the colourless layer is sandwiched between the transparent polymeric foil and the support. Additional foils and layers, e.g. other colourless 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 multi-coloured security document, preferably at least three colourless layers are present between the transparent polymeric foil and the support for forming e.g. the CMYK colours.
In a preferred embodiment, the security document 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 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.
Suitable polymeric foils include cellulose acetate propionate or cellulose acetate butyrate, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyamides, polycarbonates, polyimides, polyolefins, polyvinylchlorides, polyvinylacetals, polyethers and polysulphonamides.
In the most preferred embodiment, the polymeric foil is a biaxially stretched polyethylene terephthalate foil (PET-C foil) to be very durable and resistant to scratches and chemical substances.
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 of the security document is more easily readable and that a colour image is more appealing by having a white background.
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 and cast coated paper Resin coated paper supports, such as polyethylene coated paper and polypropylene coated paper, are considered to be polymeric supports.
Polymeric supports include cellulose acetate propionate or cellulose acetate butyrate, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyamides, polycarbonates, polyimides, polyolefins, poly(vinylacetals), poluyvinylchlorides, polyethers and polysulphonamides.
Also synthetic paper can be used as a polymeric support, for example, SynapsTM 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 TeslinTM may be used as support.
Polyester supports and especially polyethylene terephthalate supports are preferred because of their excellent properties of dimensional stability. When 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 according to the present invention, 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 a transparant 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 according to the present invention, 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 polyethylene terephthalate foils and supports.
The polyethylene terephthalate is 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 polyethylene terephthalate and biaxially oriented films thereof of 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, kinegramsTM, 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.


EXAMPLES
Materials
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 BayhydrolTM 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 TospearlTM 120 from Momentive Performance materials.
PEA-sol is a 10 wt % (50/50) aqueous/ethanol dispersion of PEA.
DowfaxTM 2A1 from Pilot Chemicals C is a Alkyldiphenyloxide disulfonate (4.5% wt %).
DOW-sol is a 2.5 wt % solution of DowfaxTM 2A1 in isopropanol.
SurfynolTM 420 from Air Products is a non ionic surfactant.
Surfynsol is a 2.5 wt % solution of SurfynolTM 420 in iso propanol.
MEK is an abbreviation used for methylethylketon.
UCAR is an abbreviation for a 25 wt % solution in MEK of UCARTM VAGD UCARTM 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 BaysilonTM 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.
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.
Example 1
This example illustrates the formation of a black coloured marking and a blue or cyan coloured marking in one and the same colourless layer using a pulsed mode for both the first and second laser operation modes in the method. (this is the Muhlbauer experiment)
Preparation of PET-C Foil PET1
A coating composition SUB-1 was prepared by mixing the components according to Table 1 using a dissolver.










TABLE 1







Components of SUB-1
wt %



















deionized water
76.66



CCE
18.45



resorcinol
0.98



PAR-sol
0.57



PEA-sol
0.68



DOW-sol
1.33



Surfynsol
1.33










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.










TABLE 2







Components of COL-1
wt %



















Baysilon
1.20



MEK
6.71



UCAR
56.96



IR-1
29.20



HDP
3.08



CVL
2.85










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.
Preparation of Security Document Precursor SDP-1
The security film SF-1 was then laminated onto a 500 μm opaque PETG core from WOLFEN to deliver the security document precursor SDP-1. 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
After lamination, a test image containing a wedge with different grey-levels (ten squares of 7×9 mm) was laser marked on the security document precursor SDP-1 through the PET-C foil using a Rofin RSM Powerline E laser (10 W) with settings 33 ampere and 44 kHz.
The optical density of each square, including the non-laser marked square 1, was measured and is given in Table 3.











TABLE 3







Square
Optical density
Colour of square









1
0.33
blue



2
0.37
blue



3
0.45
blue



4
0.65
blue



5
0.92
blue



6
1.13
blue



7
1.26
blue



8
1.39
neutral black










From Table 3, it can be seen that greyscale levels of a blue color can be made for producing images and a neutral black color can be made for producing alphanumeric data. The squares 9 and 10 exhibited blisters.
Example 2
This example illustrates that the formation of a blue or cyan coloured marking in the colourless layer is also possible using a continuous wave mode for the first laser operation mode of the method colour laser marking an article in accordance with the invention.
Evaluation and Results
The same security document precursor SDP-1 of Example 1 was exposed at 1064 nm using an optical pumped semiconductor laser OPSL-1064 available from COHERENT.
The 0.6 mm diameter output beam from the OPSL-1064 laser beam was passed through a 5× beam expander. The beam was then 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 1000 mm/s. The spot size was about 100 μm. The optical density was measured and is shown in Table 4.










TABLE 4







Power (W)
Optical density



















2
—



4
0.28



6
0.44



8
0.70



10
0.94










From Table 4, it should be clear that no optical density was visible at 2 W laser power. The squares marked with a laser power between 4 and 10 W all exhibited a blue colour. No black colour could be observed in continuous wave mode even when the line speed was reduced to 250 mm/s for a laser power of 10 W and blisters were observed.

## Claims

1. A method of colour laser marking an article having a polymeric foil with at least one colourless layer containing an infrared absorber, a polymeric binder and a single colour forming compound selected from the group consisting of a leuco dye and a colourless dye-precursor;
including the steps of:
laser marking a blue or cyan colour in the colourless layer with an infrared laser using a first laser operation mode; and
laser marking a black colour in the same colourless layer with an infrared laser using a second laser operation mode,
wherein the second laser operation mode is a pulsed mode, and
wherein the energy applied for laser marking a blue or cyan pixel is smaller than for laser marking a black pixel.

2. The method according to claim 1 wherein the single colour forming compound is crystal violet lactone.

3. The method according to claim 2 wherein the colourless layer includes 4,4′-Bis(tert-butoxycarbonyloxy) diphenylsulfone as hydrogen donor precursor.

4. The method according to claim 1 wherein the colourless layer includes 4,4′-Bis(tert-butoxycarbonyloxy) diphenylsulfone as hydrogen donor precursor.

5. The method according to claim 1 wherein the first laser operation mode is a continuous wave mode.

6. The method according to claim 1 wherein the first laser operation mode is a pulsed mode.

7. The method according to claim 1 wherein the infrared laser utilized in the first and the second laser operation mode is the same laser.

8. The method according to claim 7 wherein the laser is an optically pumped semiconductor laser or a solid state Q-switched laser.

9. The method according to 1 wherein the polymeric foil is a biaxially stretched polyethylene terephthalate foil.

10. An article including a polymeric foil and a colourless layer containing an infrared absorber, a polymeric binder and a single colour forming compound selected from the group consisting of a leuco dye and a colourless dye-precursor, wherein the article includes in one and the same colourless layer a laser marked image having a blue or cyan colour and laser marked information having a black colour.

11. The article according to claim 10 wherein the single colour forming compound is crystal violet lactone.

12. The article of claim 10 wherein the polymeric foil is a biaxially stretched polyethylene terephthalate foil.

13. The article according to claim 10 wherein the article is a multi-coloured article containing at least three colourless layers containing different infrared absorbers and colour forming compounds.

14. The article according to 10 wherein the article is a security document.

15. The article according to claim 14 which is selected from the group consisting of a passport, a personal identification card and a product identification document.

16. The article according to claim 15 wherein the product identification document is attached to the packaging material of the product or to the product itself.