CARDS

Abstract: Secure cards consisting essentially of a card base having an overlying thermally transferred topcoat, with a thermal transfer image in a dye-receptive surface of the card base and the topcoat typically of a polymethyl methacrylate composition, frequently show severe image fading after relative short periods of time when kept and carried in normal PVC pouches. To improve protection against such fading, the present topcoat comprises at least one barrier layer which is formed of a polymer composition having a Tg>70 DEG C, and which is resistant to the formation of microscopic cracks in the topcoat under tensile bending that is insufficient to cause macroscopic permanent deformation.

Description: CARDS The invention relates to secure cards having images formed by thermal transfer printing on at least one side, and especially to thermally transferable protective topcoats for securing such images Thermal transfer pπnting is a process in which one or more thermally transferable dyes are caused to transfer from selected areas of a dyesheet to a receiver by thermal stimuli, thereby to form an image Using a dyesheet comprising a thin substrate supporting a dyecoat containing one or more uniformly spread dyes, printing is effected by heating selected discrete areas of the dyesheet while the dyecoat is pressed against a dye-receptive surface of a receiver sheet, thereby causing dye to transfer to corresponding areas of the receiver The shape of the image transferred is determined by the number and locations of the discrete areas which are subjected to heating Full colour pπnts can be produced by pπnting with different coloured dvecoats sequentially in like manner, and the different coloured dvecoats are usually provided as discrete uniform panels arranged in a repeated sequence along a ribbon-shaped dyesheet High resolution photograph-like prints can be produced by thermal transfer pπnting using appropπate pπnting equipment, such as a programmable thermal pπnt head or laser pπnter. controlled by electronic signals deπved from a video, computer, electronic still camera, or similar signai generating apparatus A typical thermal print head has a row of tiny selectiveiv energizable heaters, spaced to pπnt six or more pixels per millimetre, often with two heaters per pixel Laser pπnters require absorbers to conveπ the laser radiation to heat, usually in or under the dyecoat, and similarly produce the print by transferring dyes to the receiver pixel by pixel The transfer mechanism is believed to depend very much on the conditions under which pπnting is earned out Thus for example, when using a thermal head, the dyesheet and receiver are pressed together between the head and a platen roller, giving conditions favouring diffusion of the dyes from the dyesheet directly into the receiver, virtually precluding any sublimation Where a small gap is provided between the dyesheet and receiver, as favoured in some laser driven printers for example, the transfer mechanism appears to be exclusively sublimation However, in both cases the dyes are mobile molecules which can diffuse into and out of the receiver when warmed, or in the presence of vaπous lyophilic liquids In paπicular, grease from a finger holding a pπnt can lead to migration of the dye to the surface, making the print seem dirty or causing smearing of the dyes, and plasticisers in plastic pouches can cause havoc with unprotected thermal transfer images. Particularly bad in this respect is dioctylphthalate. commonly used as a plasticiser in polyvinyl chloride. For many years various protective covers have been proposed to protect thermal transfer prints against abrasion, loss of dyes by migration to the surface, and protection against UN-induced fading, for example. Very thin covers are generally preferred, typically 4 μm, which are difficult to handle without some form of support, and in the past it has been proposed first to prepare a donor sheet comprising a temporary carrier base sheet having a surface coated with a layer of transparent thermally transferable cover material, then thermally transferring the coating onto the printed receiver and removing the carrier, thereby leaving the transferred material to form a topcoat. The transfer can be effected simultaneously over the whole print, and the carrier is then removed after the transfer is complete. Alternatively, transfer may be progressive, e.g. using heated rollers or a thermal head to transfer the topcoat line by line, and it is then generally more convenient to remove the carrier progressively as it emerges from the rolls or thermal head. It has been recognised that polymeric compositions having higher Tg values generally provide better protective coatings, but higher Tg values can lose some of the advantages of the lower Tg materials. Thus for example, good barrier materials of high Tg are not always good adhesives, and to overcome this problem, complex coatings consisting of a plurality of layers of differing functions have previously been proposed. Thus for example, multilayer polymeric coatings comprising a layer of barrier material, laminated to a layer of more adhesive material on one side for providing better adhesion to the receiver, and on the other a layer of a less adhesive material to assist in its release from the carrier, has been described in US 4,977, 136. Because a thermal transfer image corresponds to the electronic signal fed to the thermal head, laser printer or other thermal transfer driving means, each image can be readily customised as required, and this has been made use of in producing wallet size cards with personalised images These include, for example, credit cards, driving licences and identification cards, all of which can have images incorporating electronic photographs, signatures and/or personal data to provide a card unique to the user. Such cards are frequently earned in plastic pouches, but plasticisers in the pouches are a particular problem because they are generally good solvents for thermal transfer dyes A heavily plasticised PVC pouch, for example, can extract virtually all the colour from an unprotected image, and it has become the custom to protect such images with a thermally transferred polymer topcoat, typically of a polymethyl methacrylate based formulation, usually containing a small loading of filler The topcoat makes the card more secure by giving the image some degree of protection against abrasion and attack by plasticisers, and cards having such protective topcoats are referred to herein as secure cards, to distinguish them from cards having no topcoat However, presently used topcoats only provide a degree of protection We have seen many examples of cards showing severe fading of the image with use, particularly in the more heavily printed areas After microscopic examination of the failing cards, we believe we have found a cause for such failure, and provide herein a means for improving the useful lifespan of protected cards Thus we found that when the above known cards are flexed, e 'i by subjecting them to unconstrained hand bending without permanent deformation, microscopic cracks formed in the topcoat over both the heavily printed areas and lightly pπnted areas According to one aspect of the invention, a method for manufactuπng secure cards, each consisting essentially of a card base and a topcoat, compπses forming a thermal transfer image in a dve-receptive surface of the card base, and thermally transferπng the topcoat onto the image-containing surface, wherein to improve protection against plasticiser degradation of the thermal transfer image, the topcoat comprises at least one barπer layer which is formed of a polymer composition having a Tg>70°C, and which is resistant to the formation of microscopic cracks in the topcoat under tensile bending that is insufficient to cause macroscopic permanent deformation A preferred method is one wherein the level of tensile bending is that achieved by suppoπmg the ends of the secure card, flexing the card to displace by 2 cm the portion of the card equidistant from its supported ends, and repeating to complete 100 such displacements, and wherein the microscopic cracks are of a size to be visible when viewed at a magnification of 400x In practice, this may be achieved by prepaπng a plurality of sample secure cards of which each is topcoated with a different barrier layer composition, flexing each card as above, selecting a thus flexed sample card for which no cracks were evident in the surface of the topcoat, and carrying out the manufacture of secure cards using a topcoat composition corresponding to that used in the selected sample. In more detail, we prefer to carry out these steps as below Sample card preparation We prefer to prepare the sample secure cards by coating a PET film carrier with a layer of the topcoat barrier composition being tested. This is then placed in contact with a PVC card having a pre-printed thermal transfer image diffused into its contacted surface, and the foil and card passed together through a hot roller laminator unit. The PET carrier is then peeled from the card leaving the barrier coating adhered as a topcoat overlying the image. An alternative way to prepare the sample secure cards is to pass the foil and card through a printer, the thermal heads then providing the heat for transferring the topcoat barrier composition, but for this, the foil requires a heat resistant backcoat to protect the thermoplastic PET carrier from the high temperatures generated by the thermal head. Sample card flexing Flexing of the cards can be carried out rigorously by mounting the short edges of the sample cards in an ISO 7816- 1 1987 (E) test rig, and flexing the card by activating the rig. The ISO 7816-1 1987 (E) test method is designed to examine for macroscopic failure in cards after 1,000 bendings, but does also provide an appropriate standard rig for evaluating microscopic crack resistance in the present context when the cards are flexed for the smaller number of cycles detailed above. In this standard test, the card is held by its ends between two jaws and one of the jaws is moved to bend the card repeatedly at a rate of 30 bendings per minute. For its macro-failure testing, the test also prescribes that the card be held along its sides (as provided by its longer edges) and similarly bent repeatedly but with a deflection of only 1 cm. We have on occasions experimented with the flexing regimes by adding this further stressing, but found it to be unnecessary for the present purposes. In the various cases tested, we found generally that those samples which passed the test would survive further flexing in either direction, but those that failed the test would crack after a very small amount of flexing, with the number of cracks increasing with further flexing. While it is true that the more cracks there are, the more easily they can be seen, we found no difficulty in seeing the cracks when these were present after the limited number of bendings specified above However, because of the manner in which such flexing tests are generally uncπtical in how the samples are stressed, we have found that consistent data can be obtained very simply by carrying out essentially the same test manually, as follows Each of the sample secure cards produced as above, is supported in turn by its two short ends between the fingers and thumb of one hand, and the middle of the card gently raised and lowered by the other hand The displacement at the middle is similarly about 2 cm from its undisplaced position, and the middle is displaced 50 times in each direction thus bending the card 100 times as before Flexing the cards in both directions provides compressive as well as tensile bending Both appear to contribute to the formation of microscopic cracks, but tests to evaluate their relative contnbutions have indicated that the tensile bending causes more damage than compressive bending Sample card evaluation Irrespective of the method used to provide the flexing, we examine each flexed topcoat sample at 400x magnification using Nomarski differential interference contrast to show up surface features Those which have visible cracks fail the test, whilst those without cracks visible at the 400x magnification, pass We have found consistently that secure cards with a well adhered topcoat of a composition giving a pass in the above test, have provided better protection against pouch plasticisers than the previously used polymethyl methacrylate compositions The sheet base of the card can be a homogeneous sheet of a dye receptive polymer composition Typical of such sheets is polyvinylchloride sheet loaded with a white filler to show off the coloured image formed of thermally transferred dyes diffused into it Thus in this case, the material of the dye-receptive surface extends throughout the sheet base More typical are laminates of white filled polyvinylchloride sandwiched between clear layers of vinylchloπde/vinvl acetate copolymer. which are currently commercially available for the manufacture of secure cards by other methods This copolymer is more receptive than polyvinylchloride to most thermal transfer dyes, and such laminates are preferred materials for use as the sheet bases in the secure cards of the present invention According to a further aspect of the invention, we provide a transfer foil comprising a carrier sheet and a coating layer of a thermally transferable barrier composition for transfer onto a thermal transfer image formed in a receiver surface, thereby to form a topcoat for providing protection against plasticiser degradation of the image, wherein the barrier composition has a Tg>70°C, and comprises a polymer resistant to the formation of microscopic cracks under tensile bending that is insufficient to cause macroscopic permanent deformation. A preferred barrier composition is one formulated to minimise stress concentration by the use of unsuitable fillers. Previously known topcoats generally have a light loading of filler particles which are large compared to the thickness of the topcoat polymer, e.g. being about 10 μm and irregular in shape, they stand proud of a 4 μm polymer matrix to improve abrasion resistance and may also have a non-blocking effect to assist mechanical handling. However, microscopic observation of such topcoats after use, reveals cracks radiating from such fillers, and we prefer to use a topcoat compositions wherein the barrier layer composition is free from filler particles whose smallest diameter is greater than the thickness of the barrier layer. The topcoat preferably consists of a single layer which is formed of the barrier layer composr on, but alternatively can be a composite of two or more layers, this being especially beneficial when using barrier layers r f a particularly high Tg. For example, the high Tg barrier polymer of the invention may also have an associated layer of lower Tg polymer which is located on its outer surface such that when transferred onto the image-containing surface of a card, the layer of low Tg polymer lies between the barrier layer and the card in order to improve the adhesion between them. We have found that polymethyl methacrylate homopolymers, such as are presently used for topcoat foils, tend to crack when subjected to the tensile stresses described above; and this, we believe, is the reason that conventional secure cards having a thermal transfer image and kept in PVC pouches, tend to loose the quality of the image with the passage of time as the dye becomes leached out by the pouch plasticiser through cracks formed by flexing of the card during normal handling in use. Similarly, we have found that copolymers of methacrylate esters with various comonomers will readily form cracks, and suffer from the same fate. However, the addition of an acrylate ester to the methylmethacrylate as a co-monomer, even as a minor amount, provides a copolymer having resistance to cracking when flexed, and hence giving superior resistance to leaching of the dyes forming the image, by pouch plasticiser. The amount of acrylate ester that can be added as co-monomer is limited by the need to keep the Tg maintained above 70°C. Moreover, we have found that this beneficial effect occurs when acrylate esters are copoiymerised with other commoners whose homopolymers we have found to crack readily when flexed. For example, parahydroxystyrene/butyl acrylate copolymer provides a much stronger barrier than parahydroxystyrene/methylmethacrylate copolymer, or parahydroxystyrene/ styrene copolymer. A preferred transfer foil is thus one wherein the polymer of the barrier composition is a copolymer of an acrylate ester. Particularly preferred are copolymers of methyl methacrylate and ethyl acrylate. and copolymers of parahydroxystyrene and butyl acrylate Another class of compounds that we have found to be particularly effective are the polyesters, especially those which contain an alicyclic diol or dicarboxylic acid residue. Of those we tested, Vylon GK-640 gave particularly good resistance to cracking, and there was no visible dye migration seen, even after prolonged thermal accelerated ageing (as described in the Examples hereinafter. This is believed to be a copolymer of terephthalic acid, isophthalic acid, ethylene glycol and 1 ,4-cyclohexylenedimethanol. The barrier layer of the transfer foil can contain some particuiate fillers, but for the reasons discussed above, we prefer that it be free from filler particles whose smallest diameter is greater than the thickness of the barrier layer. The transfer foil comprises a carrier sheet and coating layer of thermally transferable topcoat barrier composition, and this carrier sheet can be any sheet or coated sheet able to withstand the transfer temperatures. Paper can be used, but the thicker the sheet, the more transfer energy is required, and we prefer to use polymer films, such as PET film, typically less than 30 μm thick according to the manner in which the barrier composition is to be transferred. In connection with the preparation of the test samples, we discussed two methods for transferring the barrier composition. For these we prefer to use a carrier sheet of about 12 μm when using a hot roller laminator unit, but a heat-resistant back-coated film of 4-6 μm thickness is preferred when using a thermal head. To assist in release of the cover material from a thermoplastic carrier sheet, we prefer that the latter be primed with a cross-linked resin, to prevent fusion between the carrier and the transferring cover material. Such primes, applied effectively in known manner, remain on the carrier as it is stripped off. Other coatings featuring one or more of the many known release agents or releasing binders, can be provided instead or in addition to the cross-linked prime, but with such materials there is a chance that at least some will transfer with the cover material. This can be undesirable in a number of applications, especially those requiring lamination of the print to a security cover sheet; in the passports, driving licences, medical cards and security passes referred to above, for example. In general, therefore, we prefer to coat the transferable cover material directly onto the primed surface of the carrier base sheet of the transfer foil. The transfer foil can be separate from the dyesheet used to prepare the image, although it is often convenient to have this packaged in a form which enables it to be used in the same apparatus as that which prints the image. To have the dyesheet ribbon and the present transfer foil as separate entities, whether used in the same apparatus or not, enables a first printed card to be covered with topcoat while a further image is being formed on a second card, thereby saving time. However, a preferred transfer foil is one which is incorporated into a dyesheet ribbon, suitably that used to form the image, comprising a substrate supporting different coloured dvecoats provided as discrete uniform print-size panels arranged in a repeated sequence along the ribbon, the carrier sheet of the transfer foil being provided by a part of the dyesheet substrate between repeated sequences of the dyecoat panels. Thus each sequence of print-size coloured dyecoats also has a further print-size panel of the thermally transferable topcoat barrier composition. According to a further aspect of the invention, there is provided a secure card consisting essentially of a card base having a thermal transfer image in a dye-receptive surface, and a thermally transferred topcoat overlying the image- containing surface; wherein to improve protection against plasticiser degradation of the thermal transfer image, the topcoat comprises at least one barrier layer which is formed of a polymer composition having a Tg>70°C, and which is resistant to the formation of microscopic cracks in the topcoat under tensile bending that is insufficient to cause macroscopic permanent deformation. According to a further aspect of the invention, a method for providing improved protection against plasticiser degradation of a thermal transfer image formed in a dye-receptive surface of a card, comprises thermally transferring onto the image containing surface, a topcoat of a polymer composition having a Tg>70°C, and which is resistant to the formation of microscopic cracks in the topcoat under tensile bending which is insufficient to cause macroscopic permanent deformation. Example 1 Three coating compositions were prepared based on the following polymers. Polymer Tg melting temp yield strain Product name °£ _°£ % A poly(bisphenolA carbonate) 162 220-230 6 Makrolon 5905 (Mobay/Bayer) B phenoxy resin 98 180 4 UCAR PKHH (Union Carbide) C poly(methylmethacrylate) 105 Neocryl B81 1 (Zeneca) The solutions were made up using the following solvents. Polymer solids solvent ° o w/w solution A poly(bisphenol A carbonate) 7 5 100% methyl ene dichloride B phenoxy resin 15 99% methyl ethyl ketone, 1 % water C poly(methylmethacrylate) 15 100% methyl ethyl ketone To prepare the transfer foils, the above solutions were hand coated by Meier bar onto pre-backcoated and subbed 6 μm PET film carriers, each to give a wet coat thickness of approx 12 μm. In the case of solution A two coatings were applied with oven drying between applications The coatings were then dried in oven at 80°C for 60 seconds. Preparation Samples of the above transfer foils were each placed in contact with a PVC card having a pre-printed thermal transfer image diffused into its contacted surface, and the foil and card passed together through a hot roller laminator unit. The lamination temperatures as measured by wax indicator strip at the card surface were >1 16°C & <122°C in each case. The PET carriers were then peeled from the cards leaving the polymer coatings adhered as topcoats overlying the images. Flex resistance test This was a simple manual test wherein each card in turn was supported by its two ends between the fingers and thumb of one hand, and the middle of the card gently raised and lowered by the other hand. The displacement at the middle was approximately 2 cm in each direction, and the middle was displaced 100 times in each direction. After flexing, the three topcoats were examined at 400x magnification using Nomarski differential interference contrast to show up surface features. The polymethyl methacrylate topcoat of sample C was clearly seen to have cracked and thus fail the test, whereas no cracks were seen in either of samples A (polycarbonate) or B (phenoxy resin). Evaluation of flex cracking criteria All three topcoated cards were placed in commercial plasticised PVC pouches containing approximately 24 wt% of di-octyl phthalate plasticiser. The PVC of each pouch was held against the topcoat of the secure card lodged inside it, by weighting it with a small steel plate (approximately 25 x 50 x 3 mm) weighing about 30 g. Each card, with its pouch and weight was then placed on a flat surface in an oven maintained at 50 +/- 2°C for five days, to provide thermally accelerated ageing. The PVC pouch was then removed, and the image examined by eye and optical microscope at 200x and 500x magnification using DIC and dark field illumination for evidence of dye migration and/or loss. The PVC pouch was also examined for transferred dye. The polymethyl methacrylate topcoated sample (C) exhibited considerable dye loss. This was observed under the microscope as white dye-free regions extending from the cracks. No dye migration was detected in either of samples A (polycarbonate) or B (phenoxy resin). The PVC pouches were then replaced on samples A and B, and the cycle repeated for a further five days, but no dye migration was observed in either case. Example 2 A variety of other polymer compositions were examined in essentially the same manner as that described in Example 1. The results are expressed in tabular form below Tg Visible Visible migration or °C cracks loss after 10 days Dolvester Vylon ST5020 79 no no Vylon GK-640 79 no no Dynapol L912 103 no no Dynapol L206/1 66 no yes Vylon GK880 84 no no acrvlic Elvacite 2009 87 no no Elvacite 2010 98 no no Elvacite 2013 80 yes yes PMMA-high MW 105 yes yes Diakon MG 102 105 yes yes competative product yes yes polvsulphones Udel 190 no no " (over adhesive layer) no no polycarbonate Lexan 121 150 no no acetal Vinylec E 105 no no Vinylec K 105 no S-Lec PVAA BL-3 95 no no PPHS coplvmer Lyncure CBA >100 no no Lyncure CST50 >100 yes yes Lyncure CMM >100 yes yes phenoxv phenoxy/Estane 60/40 no no " (over adhesive layer) no no chlorinated PVC Genclor S 100 yes yes Temprite 563 130 yes yes polvstvrene Polysciences 125-250 KDa 100 yes cellulosic CAB 551-0.2 101 yes yes no topcoat n/a total (@ 1 day) In the above table, "Vylon" is a trade name of Toyobo, "Dynapol" is a trade name of Huels AG, "Elvacite" is a trade name of ICI Acrylics, "Vinylec" is a trade name of Chisso, "Lyncure" is a trade name of Maruzen Chemical Co, "Genclor" is a trade name of ICI C&P, "Temprite" is a trade name of BF Goodrich, "CAB 551-0.2" is a trade name of Eastman, and "Udel" is a trade name of Amoco. The results in the table illustrate the correlation between the formation of visible cracks on flex testing, and the onset of dye migration within 10 days under the conditions of thermally accelerated ageing. Those which did exhibit cracking ("yes" in the "Visible cracks" column) fail the flex test, and fall outside the criteria for the barrier materials according to the present invention. Of those that passed, Vylon GK-640, Vylon ST5020, Elvacite 2009 and Lyncure CBA, all adhere well to PVC cards, are robust to flexing, and give particularly good resistance to plasticiser induced dye migration. These materials are preferred. The two Vylon compositions are both believed to be polyesters containing alicyclic residues of dibasic acid or diol. Elvacite 2009 is a copolymer of methyl methacrylate and ethyl acrylate, and Lyncure CBA is a copolymer of parahydroxystyrene and butyl acrylate.

Claims: CLAIMS 1. A method for manufacturing secure cards, each consisting essentially of a card base and a topcoat, by forming a thermal transfer image in a dye-receptive surface of the card base and thermally transferring the topcoat onto the image-containing surface; wherein to improve protection against plasticiser degradation of the thermal transfer image, the topcoat comprises at least one barrier layer which is formed of a polymer composition having a Tg>70°C, and which is resistant to the formation of microscopic cracks in the topcoat under tensile bending that is insufficient to cause macroscopic permanent deformation. 2. A method as claimed in claim 1, wherein the level of tensile bending is that achieved by supporting the ends of the secure card, flexing the card to displace by 2 cm the portion of the card equidistant from its supported ends, and repeating to complete 100 such displacements; and wherein the microscopic cracks are of a size to be visible when viewed at a magnification of 400x. 3. A method as claimed in claim 1, wherein the card comprises a laminate of white filled polyvinylchloride sandwiched between clear layers of vinylchloride/vinyl acetate copolymer, at least one of which layers provides the image containing surface onto which the topcoat is transferred. 4. A method as claimed in claim 1, wherein the barrier layer composition is free from " filler particles whose smallest diameter is greater than the thickness of the barrier layer. 5 A method as claimed in claim 1, wherein the topcoat consists of a single layer which is formed of the barrier layer composition. 6. A method as claimed in claim 1, wherein the polymer of the barrier composition is a copolymer of an acrylate ester. 7 A transfer foil comprising a carrier sheet and a coating layer of a thermally transferable barrier composition for transfer onto a thermal transfer image formed in a receiver surface, thereby to form a topcoat for providing protection against plasticiser degradation of the image, wherein the barrier composition has a Tg>70°C, and comprises a polymer resistant to the formation of microscopic cracks under tensile bending that is insufficient to cause macroscopic permanent deformation. 8 A transfer foil as claimed in claim 7, wherein the polymer of the barrier composition is a copolymer of an acrylate ester. 9. A transfer foil as claimed in claim 7, wherein the polymer of the barrier composition is a copolymer of methyl methacrylate and ethyl acrylate. 10. A transfer foil as claimed in claim 7, wherein the polymer of the barrier composition is a copolymer of parahydroxystyrene and butyl acrylate. 11. A transfer foil as claimed in claim 7, wherein the polymer of the barrier composition is a polyester containing an alicyclic diol or dicarboxyiic acid residue. 12 A transfer foil as claimed in claim 11 , wherein the polyester is a copolymer of terephthalic acid, isophthalic acid, ethylene glycol and 1,4-cyclohexylenedimethanol. 13 A transfer foil as claimed in claim 7, wherein the barrier layer composition is free from filler particles whose smallest diameter is greater than the thickness of the barrier layer. 14 A transfer foil as claimed in claim 7, which is incorporated into a dyesheet ribbon comprising a substrate supporting different coloured dyecoats provided as discrete uniform print-size panels arranged in a repeated sequence along the ribbon, the carrier sheet of the transfer foil being provided by a part of the dyesheet substrate between repeated sequences of the dyecoat panels. 15. A secure card consisting essentially of a card base having a thermal transfer image in a dye-receptive surface, and a thermally transferred topcoat overlying the image-containing surface; wherein to improve protection against plasticiser degradation of the thermal transfer image, the topcoat comprises at least one barrier layer which is formed of a polymer composition having a Tg>70°C, and which is resistant to the formation of microscopic cracks in the topcoat under tensile bending that is insufficient to cause macroscopic permanent deformation.

Inventors: ADKINS KELVIN PATRICK, HANN RICHARD ANTHONY, JENNO GARY JOHN, ADKINS, KELVIN, PATRICK, HANN, RICHARD, ANTHONY, JENNO, GARY, JOHN
Applicants: ADKINS KELVIN PATRICK, HANN RICHARD ANTHONY, ICI PLC, JENNO GARY JOHN, ADKINS, KELVIN, PATRICK, HANN, RICHARD, ANTHONY, IMPERIAL CHEMICAL INDUSTRIES PLC, JENNO, GARY, JOHN
Application year: 1995
Main classification: B42D15
IPC codes: B32B7, B32B27, B41M5, B41M7, B42D15