Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
  • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
  • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
  • B42D25/30—Identification or security features, e.g. for preventing forgery
  • B42D25/333—Watermarks
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
  • B41M3/10—Watermarks
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/0029—Formation of a transparent pattern using a liquid marking fluid
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
  • B41M5/52—Macromolecular coatings
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
  • B41M7/02—Dusting, e.g. with an anti-offset powder for obtaining raised printing such as by thermogravure ; Varnishing
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
  • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
  • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
  • B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
  • B41M5/508—Supports
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
  • B41M5/52—Macromolecular coatings
  • B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
  • B41M7/0045—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using protective coatings or film forming compositions cured by mechanical wave energy, e.g. ultrasonics, cured by electromagnetic radiation or waves, e.g. ultraviolet radiation, electron beams, or cured by magnetic or electric fields, e.g. electric discharge, plasma

Definitions

• the present invention relates to a method for the preparation of an improved carrier of information, and to ID cards cut from it.
• ID card identification cards
• cards involved in the electronic transfer of money include bank cards, pay cards, credit cards and shopping cards.
• Different types of security cards authorize access to the bearer of the card to particular areas such as a company (employee ID card), the military, a public service, the safe department of a bank, etc.
• identity cards For long time national states have issued identity cards to establish the national identity of their civilians.
• Still other types of identification cards include social security cards, membership cards of clubs and societies, and driver's licence cards.
• ID cards usually contain information referring both to the authority issuing the card on the one hand and to the owner of the card.
• the first type of information may be general information such as a name and/or logo of the issuing authority, or security marks, such as a watermark and security print, e.g a repeating monochrome pattern or a gradually changing colour pattern which are difficult to counterfeit.
• the second type includes e.g. the unique card number, personal data such as a birth day, a photo of the owner, and a signature.
• the card can further contain hidden information and therefore contain a magnetic strip or an electronic chip ("smart cards").
• a large set of ID cards are usually prepared on a large carrier of information such as a web or sheet by a step and repeat process, after which the information carrier is cut into multiple items with the appropriate dimensions each representing a personal ID card.
• Smart cards and ID cards have now the standardized dimensions of 85.6 mm x 54.0 mm x 0.76 mm.
• the card is protected by a plastic sheet material such as by lamination of the card to a plastic sheet or, as it is usually the case by lamination between two plastic sheets.
• a "security seal” is best explained by describing what happens if an attempt is made to pull a plastic sheet material from the surface of a card bonded to the plastic. If a "security seal” exists, all or at least portions of the adhered surface will be removed from the card together with the plastic sheet material. Accordingly, a "security seal” is normally established between the information-bearing surface of the card or document and the plastic. Under such circumstances, removal of the plastic should also remove substantial portions of the information-bearing surface of the card to render the card unusable for alteration purposes.
• Adhesives or adhesive systems which can provide "security seals" are described in e.g. U.S. Pat. Nos. 3,582,439, 3,614,839 and 4,115,618. According to US 4,322,461 a security seal can be provided by applying heat-sealable polymers so as to obtain a sealed envelop-type pouch.
• the present invention extends the teaching on verification marks, and particularly on watermarks.
• the ID cards which can be cut from the information carrier are tamper proof.
• a previously opaque porous receiving layer comprising a pigment and a binder can be rendered substantially transparent i.e. that the resulting layer comprising at least three components is substantially transparent, despite the fact that a layer containing at least two of the three components is opaque.
• a substantially transparent porous receiving layer comprising a pigment and a binder can be rendered opaque upon penetration by a varnish or lacquer despite the fact that a layer containing at least two of the components is transparent.
• an information carrier comprising: a rigid sheet or web support; an opaque porous receiving layer capable of being rendered substantially transparent by penetration by a lacquer, said receiving layer containing a pigment and a binder; an image provided onto and/or in said receiving layer; a cured pattern of a varnish provided onto said receiving layer provided with said image or onto and/or in said receiving layer provided with said image if said varnish is incapable of rendering said receiving layer transparent; and a cured layer of said lacquer provided on said receiving layer provided with said image and said cured pattern of said varnish, said lacquer having rendered said parts of said receiving layer in contact therewith substantially transparent, wherein said cured pattern of said varnish forms an opaque watermark.
• an information carrier comprising: a rigid sheet or web support; an opaque porous receiving layer capable of being rendered substantially transparent by penetration by a varnish, said receiving layer containing a pigment and a binder; an image provided onto and/or in said receiving layer; a cured pattern of said varnish provided in said receiving layer provided with said image; and a cured layer of a lacquer provided onto said receiving layer provided with said image and said cured pattern of said varnish, or onto and/or in said receiving layer provided with said image and said cured pattern of said varnish if said lacquer is incapable of rendering said receiving layer transparent, said varnish having rendered said parts of said receiving layer in contact therewith substantially transparent, wherein said cured pattern of said lacquer forms a substantially transparent watermark.
• an information carrier comprising: a rigid sheet or web support; a transparent porous receiving layer capable of being rendered substantially opaque by penetration by a lacquer, said receiving layer containing a pigment and a binder; an image provided onto and/or in said receiving layer; a cured pattern of a varnish provided onto said receiving layer provided with said image, or onto and/or in said receiving layer provided with said image if said varnish is incapable of rendering said receiving layer opaque; and a cured layer of said lacquer provided on said receiving layer provided with said image and said cured pattern of said varnish, said lacquer having rendered said parts of said receiving layer in contact therewith substantially opaque, wherein said cured pattern of said varnish forms a transparent watermark.
• an information carrier comprising: a rigid sheet or web support; a transparent porous receiving layer capable of being rendered substantially opaque by penetration by a varnish, said receiving layer containing a pigment and a binder; an image provided onto and/or in said receiving layer; a cured pattern of said varnish provided in said receiving layer provided with said image; and a cured layer of a lacquer provided onto said receiving layer provided with said image and said cured pattern of said varnish, or onto and/or in said receiving layer provided with said image and said cured pattern of said varnish if said lacquer is incapable of rendering said receiving layer opaque, said varnish having rendered said parts of said receiving layer in contact therewith substantially opaque, wherein said cured pattern of said lacquer forms a substantially opaque watermark.
• Objects of the present invention are also realized by a method for producing a carrier of information, said method comprising the following steps, in order,
• Objects of the present invention are also realized by a method for producing a carrier of information, said method comprising the following steps, in order,
• Objects of the present invention are also realized by a method for producing a carrier of information, said method comprising the following steps, in order,
• Objects of the present invention are also realized by a method for producing a carrier of information, said method comprising the following steps, in order,
• the terms "opaque” or “non-transparent” layer refers to a layer where less than 10% of the incident visible light is allowed to pass through the layer.
• a “substantially transparent” layer at least 50% of the incident visible light, preferably more than 65% and particularly preferably more than 75%, passes through the layer.
• the refractive index as a specific number, being the average of the range for possible refractive indices (e.g. 1.51 for polyvinylalcohol with a refractive index range of 1.49 to 1.53) if a range of refractive indices is present for the particular material.
• the terms "on”, “onto” and “in” have very precise meanings with respect to a layer: “on” means that penetration of the layer may or may not occur, “onto” means at least 90% on the top of i.e. there is no substantial penetration into the layer, and “in” means that penetration into the respective layer or layers occurs.
• “on” means that penetration of the layer may or may not occur
• “onto” means at least 90% on the top of i.e. there is no substantial penetration into the layer
• “in” means that penetration into the respective layer or layers occurs.
• the curable varnish and lacquer compositions used in the present invention may have similar compositions.
• the term “varnish” has therefore been used to designate the curable composition, which is applied pattern-wise in the present invention
• lacquer has been used to designate the composition, which is applied overall.
• the lacquer may not necessarily contain a cellulose derivative.
• watermark as used in disclosing the present invention means a localized modification of the structure and opacity of a layer so that a pattern or design can be seen when the information carrier is held to the light.
• security print as used in disclosing the present invention means a concretely recognizable design, or an abstract periodically-repeating monochrome or multichrome pattern, or a gradually changing colour pattern, which gradually changes in hue and/or density of the colours, and is in this way difficult to counterfeit.
• the security print may further contain, for example, a logo, name or abbreviation of the issuing authority of the information carrier.
• the digitally stored information is printed onto said porous receiving layer by means of ink jet printing.
• the application of the printed information and of the cured watermark is repeated multiple times according to a fixed pattern over the area of the information carrier, and finally the finished assemblage is cut into a set of multiple identification (ID) cards.
• ID identification
• the support for use in the present invention can be transparent, translucent or opaque, and can be chosen from paper type and polymeric type supports well-known from photographic technology.
• Paper types include plain paper, cast coated paper, polyethylene coated paper and polypropylene coated paper.
• Polymeric supports include cellulose acetate propionate or cellulose acetate butyrate, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyamides, polycarbonates, polyimides, polyolefins, poly(vinylacetals), polyethers and polysulfonamides.
• Other examples of useful high-quality polymeric supports for the present invention include opaque white polyesters and extrusion blends of polyethylene terephthalate and polypropylene.
• Polyester film supports and especially polyethylene terephthalate are preferred because of their excellent properties of dimensional stability.
• a subbing layer may be employed to improve the bonding of the receiving layer to the support.
• 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 support is colored or whitened polyvinyl chloride or polyethylene terephthalate.
• the receiving layer is porous and contains a binder and a pigment.
• the binder can be chosen from a list of compounds well-known in the art including hydroxyethyl cellulose; hydroxypropyl cellulose; hydroxyethylmethyl cellulose; hydroxypropyl methyl cellulose; hydroxybutylmethyl cellulose; methyl cellulose; sodium carboxymethyl cellulose; sodium carboxymethylhydroxethyl cellulose; water soluble ethylhydroxyethyl cellulose; cellulose sulfate; polyvinyl alcohol; vinylalcohol copolymers; polyvinyl acetate; polyvinyl acetal; polyvinyl pyrrolidone; polyacrylamide; acrylamide/acrylic acid copolymer; polystyrene, styrene copolymers; acrylic or methacrylic polymers; styrene/acrylic copolymers; ethylene-vinylacetate copolymer; vinylmethyl ether/maleic acid copolymer; poly(2-acrylamido-2-methyl propane sulf
• a preferred binder for the practice of the present invention is a polyvinylalcohol (PVA), a vinylalcohol copolymer or modified polyvinyl alcohol.
• the polyvinyl alcohol is a silanol modified polyvinyl alcohol.
• Most useful commercially available silanol modified polyvinyl alcohols can be found in the POVAL R polymer series, trade name of Kuraray Co., Japan.
• This R polymer series includes the grades R-1130, R-2105, R-2130, R-3109, which differ mainly in the viscosity of their respective aqueous solutions.
• the silanol groups are reactive to inorganic substances such as silica or alumina.
• R-polymers can be easily crosslinked by changing the pH of their aqueous solutions or by mixing with organic substances and can form water resistant films.
• the pigment may be chosen from the inorganic pigments well-known in the art such as silica, talc, clay, hydrotalcite, kaolin, diatomaceous earth, calcium carbonate, magnesium carbonate, basic magnesium carbonate, aluminosilicate, aluminum trihydroxide, aluminum oxide (alumina), titanium oxide, zinc oxide, barium sulfate, calcium sulfate, zinc sulfide, satin white, boehmite (alumina hydrate), zirconium oxide or mixed oxides.
• the main pigment is chosen from silica, aluminosilicate, alumina, calcium carbonate, alumina hydrate, and aluminum trihydroxide.
• aluminum oxide examples include ⁇ -Al 2 O 3 types, such as NORTON E700, available from Saint-Gobain Ceramics & Plastics, Inc, ⁇ -Al 2 O 3 types, such as ALUMINUM OXID C from Degussa, Other Aluminum oxide grades, such as BAIKALOX CR15 and CR30 from Baikowski Chemie; DURALOX grades and MEDIALOX grades from Baikowski Chemie, BAIKALOX CR80, CR140, CR125, B105CR from Baikowski Chemie; CAB-O-SPERSE PG003 tradeamrk from Cabot, CATALOX GRADES and CATAPAL GRADES from from Sasol, such as PLURALOX HP14/150; colloidal Al 2 O 3 types, such as ALUMINASOL 100; ALUMINASOL 200, ALUMINASOL 220, ALUMINASOL 300, and ALUMINASOL 520 trademarks from Nissan Chemical Industries or NALCO 8676 trademark from OND
• a useful type of alumina hydrate is ⁇ -AlO(OH), also called boehmite, such as, in powder form, DISPERAL, DISPERAL HP14 and DISPERAL 40 from Sasol, MARTOXIN VPP2000-2 and GL-3 from Martinswerk GmbH.; Liguid boehmite alumina systems, e.g. DISPAL 23N4-20, DISPAL 14N-25, DISPERAL AL25 from Sasol.
• Patents on alumina hydrate include EP 500021, EP 634286, US 5,624,428, EP 742108, US 6,238,047, EP 622244, EP 810101, etc..
• Useful aluminum trihydroxides include Bayerite, or ⁇ -Al(OH) 3 , such as PLURAL BT, available from Sasol, and Gibbsite, or ⁇ -Al(OH) 3 , such as MARTINAL grades from Martinswerk GmbH, MARTIFIN grades, such as MARTIFIN OL104, MARTIFIN OL 107 and MARTIFIN OL111 from Martinswerk GmbH , MICRAL grades, such as MICRAL 1440, MICRAL 1500; MICRAL 632; MICRAL 855; MICRAL 916; MICRAL 932; MICRAL 932CM; MICRAL 9400 from JM Huber company; HIGILITE grades, e.g.
• HIGILITE H42 or HIGILITE H43M from Showa Denka K.K.
• HYDRAL GRADES such as HYDRAL COAT 2, HYDRAL COAT 5 and HYDRAL COAT 7, HYDRAL 710 and HYDRAL PGA, from Alcoa Industrial Chemicals.
• a useful type of zirconium oxide is NALCO OOSS008 trademark of ONDEO Nalco, acetate stabilized ZrO2, ZR20/20, ZR50/20, ZR100/20 and ZRYS4 trademarks from Nyacol Nano Technologies.
• Useful mixed oxides are SIRAL grades from Sasol, colloidal metaloxides from Nalco such as Nalco 1056, Nalco TX10496, Nalco TX11678.
• Silica as pigment in receiving elements is disclosed in numerous old and recent patents, e.g. US 4,892,591, US 4,902,568, EP 373573, EP 423829, EP 487350, EP 493100, EP 514633, etc..
• Different types of silica may be used, such as crystalline silica, amorphous silica, precipitated silica, gel silica, fumed silica, spherical and non-spherical silica, calcium carbonate compounded silica such as disclosed in US 5,281,467, and silica with internal porosity such as disclosed in WO 00/02734.
• the use of calcium carbonate in receiving layers is described in e.g. DE 2925769 and US 5,185,213.
• the use of alumino-silicate is disclosed in e.g. DE 2925769.
• the main pigment can be chosen from organic particles such as polystyrene, polymethyl methacrylate, silicones, melamine-formaldehyde condensation polymers, ureaformaldehyde condensation polymers, polyesters and polyamides. Mixtures of inorganic and organic pigments can be used. However, most preferably the pigment is an inorganic pigment.
• the pigment must be present in a sufficient coverage in order to render the receiving layer sufficiently opaque and porous.
• the lower limit of the ratio by weight of the binder to the total pigment in the receiving layer is preferably about 1:50, most preferably 1:20, while the upper limit thereof is about 2:1, most preferably 1:1. If the amount of the pigment exceeds the upper limit, the strength of the receiving layer itself is lowered, and the resulting image hence tends to deteriorate in rub-off resistance and the like. On the other hand, if the binder to pigment ratio is too great, the ink-absorbing capacity of the resulting receiving layer is reduced, and so the image formed may possibly be deteriorated.
• the refraction indices of the pigment on the one hand, and of the UV-curable composition, which penetrates the opaque porus receiving layer (see description lateron) on the other hand should match each other as closely as possible. The closer the match of the refraction indices the better the transparency which will be obtained after impregnation of the receiver layer with the photopolymerizable composition.
• Inorganic pigments with a refractive index in the range from 1.45 to 1.55 are preferred.
• the most preferred pigment is a silica type, more particularly an amorphous silica having a average particle size ranging from 1 ⁇ m to 15 ⁇ m, most preferably from 2 to 10 ⁇ m.
• a most useful commercial compound is the amorphous precipitated silica type SIPERNAT 570, trade name from Degussa Co. It is preferably present in the receiving layer in an amount ranging from 5 g/m 2 to 30 g/m 2 . It has following properties:
• the refractive index of a typical UV-curable lacquer composition is about 1.47 to 1.49 it is clear that there is good match with the refractive index of this particular silica type, and good transparency will be obtained, but may not be obtained if another component is present.
• a receiving layer containing a porous alumina pigment such as MARTINOX GL-1 does not become substantially transparent on impregnation with the typical UV-curable compositions with a refractive index of 1.47 to 1.49 because its refractive index is 1.6.
• a layer with this pigment exhibits a strong improvement in adhesion between support and ink jet receiving layer upon impregnation with a UV-curable composition.
• the binder also may have an effect on the opacity of the receiving layer.
• a binder will render the receiving layer more transparent, on the condition that there is a good match of the refractive index of the binder with the refractive index of the pigment.
• a combination of the above-mentioned silica pigment SIPERNAT 570 with polyvinylalcohol (refractive index 1.49 to 1.53) produces an opaque layer, since there is a poor match between the refraction indices.
• the refractive index in the case of a range of refractive indices being present for a particular material we define the refractive index as a specific number, being the average of the range for possible refractive indices (e.g. 1.46 for SIPERNAT 570, 1.51 for polyvinylalcohol and 1.48 for the typical UV-curable lacquer mentioned earlier with a refractive index range of 1.47 to 1.49).
• the difference in refractive index of SIPERNAT 570 and polyvinylalcohol is 0.05, while the difference in refractive index of SIPERNAT 570 and the typical UV-curable lacquer is only 0.02.
• an opaque receiving layer containing a pigment and a binder can be rendered substantially transparant by a lacquer if the difference in refractive index of the pigment and the lacquer is no more than 0.04, and more preferably no more than 0.02.
• the binder may also have an effect on the opacity of the receiving layer. This results in the following possible situations:
• a cationic substance acting as mordant may be present in the receiving layer.
• Such substances increase the capacity of the layer for fixing and holding the dye of the ink droplets.
• a particularly suited compound is a poly(diallyldimethylammonium chloride) or, in short, a poly(DADMAC). These compounds are commercially available from several companies, e.g. Aldrich, Nalco, CIBA, Nitto Boseki Co., Clariant, BASF and EKA Chemicals.
• DADMAC copolymers such as copolymers with acrylamide, e.g NALCO 1470 trade mark of ONDEO Nalco or PAS-J-81, trademark of Nitto Boseki Co., such as copolymers of DADMAC with acrylates, such as Nalco 8190, trademark of ONDEO Nalco; copolymers of DADMAC with SO 2 , such as PAS-A-1 or PAS-92, trademarks of Nitto Boseki Co., copolymer of DADMAC with maleic acid, e.g.
• PAS-410 trademark of Nitto Boseki Co., copolymer of DADMAC with diallyl(3-chloro-2-hydroxypropyl)amine hydrochloride, eg. PAS-880, trademark of Nitto Boseki Co., dimethylamine-epichlorohydrine copolymers, e.g.
• Nalco 7135 trademark of ONDEO Nalco or POLYFIX 700, trade name of Showa High Polymer Co.
• other POLYFIX grades which could be used are POLYFIX 601, POLYFIX 301, POLYFIX 301A, POLYFIX 250WS, and POLYFIX 3000 ;
• NEOFIX E-117 trade name of Nicca Chemical Co., a polyoxyalkylene polyamine dicyanodiamine, and REDIFLOC 4150, trade name of EKA Chemicals, a polyamine;
• MADQUAT methacryloxyethyltrimethylammonium chloride
• CYPRO 514/515/516, SUPERFLOC 507/521/567 cationic acrylic polymers, such as ALCOSTAT 567, trademark of CIBA, cationic cellulose derivatives such as CELQUAT L-200, H-100, SC-240C, SC-230M, trade names of Starch & Chemical Co., and QUATRISOFT LM200, UCARE polymers JR125, JR400, LR400, JR30M, LR30M and UCARE polymer LK; fixing agents from Chukyo Europe: PALSET JK-512, PALSET JK512L, PALSET JK-182, PALSET JK-220, WSC-173, WSC-173L, PALSET JK-320, PALSET JK-320L and PALSET JK-350; polyethyleneimine and copolymers, e.g.
• LUPASOL trade name of BASF AG
• triethanolamine-titaniumchelate e.g. TYZOR, trade name of Du Pont Co.
• copolymers of vinylpyrrolidone such as VIVIPRINT 111, trade name of ISP, a methacrylamido propyl dimethylamine copolymer; with dimethylaminoethylmethacrylate such as COPOLYMER 845 and COPOLYMER 937, trade names of ISP
• vinylimidazole e.g.
• LUVIQUAT CARE, LUVITEC 73W, LUVITEC VPI55 K18P, LUVITEC VP155 K72W, LUVIQUAT FC905, LUVIQUAT FC550, LUVIQUAT HM522, and SOKALAN HP56 all trade names of BASF AG; polyamidoamines, e.g. RETAMINOL and NADAVIN, trade marks of Bayer AG; phosphonium compounds such as disclosed in EP 609930 and other cationic polymers such as NEOFIX RD-5, trademark of Nicca Chemical Co.
• the receiving layer may further contain well-known conventional ingredi ⁇ nts, such as surfactants serving as coating aids, hardening agents, plasticizers, whitening agents and matting agents.
• surfactants may be any of the cationic, anionic, amphoteric, and non-ionic ones as described in JP-A 62-280068 (1987).
• surfactants are N-alkylamino acid salts, alkylether carboxylic acid salts, acylated peptides, alkylsulfonic acid salts, alkylbenzene and alkylnaphthalene sulfonic acid salts, sulfosuccinic acid salts, ⁇ -olefin sulfonic acid salts, N-acylsulfonic acid salts, sulfonated oils, alkylsulfonic acid salts, alkylether sulfonic acid salts, alkylallylethersulfonic acid salts, alkylamidesulfonic acid salts, alkylphosphoric acid salts, alkyletherphosphoric acid salts, alkylallyletherphosphoric acid salts, alkyl and alkylallylpolyoxyethylene ethers, alkylallylformaldehyde condensed acid salts, alkylallylethersulfonic acid salts, alkyl
• Useful cationic surfactants include N-alkyl dimethyl ammonium chloride, palmityl trimethyl ammonium chloride, dodecyldimethylamine, tetradecyldimethylamine, ethoxylated alkyl guanidine-amine complex, oleamine hydroxypropyl bistrimonium chloride, oleyl imidazoline, stearyl imidazoline, cocamine acetate, palmitamine, dihydroxyethylcocamine, cocotrimonium chloride, alkyl polyglycolether ammonium sulphate, ethoxylated oleamine, lauryl pyridinium chloride, N-oleyl-1,3-diaminopropane, stearamidopropyl dimethylamine lactate, coconut fatty amide, oleyl hydroxyethyl imidazoline, isostearyl ethylimidonium ethosulphate, lauramidopropyl PEG-d
• These surfactants are commercially available from DuPont and 3M.
• the concentration of the surfactant component in the receiving layer is typically in the range of 0.1 to 2 %, preferably in the range of 0.4 to 1.5 % and is most preferably 0.75 % by weight based on the total dry weight of the layer.
• the receiving layer may be crosslinked to provide such desired features as waterfastness and non-blocking characteristics.
• the crosslinking is also useful in providing abrasion resistance and resistance to the formation of fingerprints on the element as a result of handling.
• crosslinking agents also known as hardening agents - that will function to crosslink film forming binders. Hardening agents can be used individually or in combination and in free or in blocked form.
• a great many hardeners, useful for the present invention are known, including formaldehyde and free dialdehydes, such as succinaldehyde and glutaraldehyde, blocked dialdehydes, active esters, sulfonate esters, active halogen compounds, isocyanate or blocked isocyanates, polyfunctional isocyanates, melamine derivatives, s-triazines and diazines, epoxides, active olefins having two or more active bonds, carbodiimides, zirconium complexes, e.g.
• BACOTE 20 ZIRMEL 1000 or zirconium acetate, trademarks of MEL Chemicals, titanium complexes, such as TYZOR grades from DuPont, isoxazolium salts subsituted in the 3-position, esters of 2-alkoxy-N-carboxy-dihydroquinoline, N-carbamoylpyridinium salts, hardeners of mixed function, such as halogen-substituted aldehyde acids (e.g.
• mucochloric and mucobromic acids onium substituted acroleins and vinyl sulfones and polymeric hardeners, such as dialdehyde starches and copoly(acroleinmethacrylic acid), and oxazoline functional polymers, e.g. EPOCROS WS-500, and EPOCROS K-1000 series, and maleic anhydride copolymers, e.g. GANTREZ AN119
• the receiving layers and the optional supplementary layers of the present invention may also comprise a plasticizer such as ethylene glycol, diethylene glycol, propylene glycol, polyethylene glycol, glycerol monomethylether, glycerol monochlorohydrin, ethylene carbonate, propylene carbonate, tetrachlorophthalic anhydride, tetrabromophthalicanhydride, urea phosphate, triphenylphosphate, glycerolmonostearate, propylene glycol monostearate, tetramethylene sulfone, n-methyl-2-pyrrolidone, n-vinyl-2-pyrrolidone.
• a plasticizer such as ethylene glycol, diethylene glycol, propylene glycol, polyethylene glycol, glycerol monomethylether, glycerol monochlorohydrin, ethylene carbonate, propylene carbonate, tetrachlorophthalic anhydride, tetrabromo
• the receiving layers and optional extra layers of the present invention may also comprise ingredients to improve the lightfastness of the printed image, such as antioxidants, UV-absorbers, peroxide scavengers, singlet oxygen quenchers such as hindered amine light stabilizers, (HALS compounds) etc.
• Stilbene compounds are a preferred type of UV-absorber.
• the curable varnish and lacquer compositions used in the information carriers, according to the present invention may have similar compositions. However, to avoid confusion, we have somewhat arbitrarily designated the term “varnish” to the curable composition which is applied pattern-wise in the invention, and the term “lacquer” to the composition which is applied overall.
• the lacquer may not necessarily contain a substantial quantity of a cellulose derivative.
• the varnish and lacquer may in principle be thermally curable compositions or electron beam curable compositions, but far most preferably, they are both photopolymerizable compositions which are cured after application by means of UV light.
• the essential ingredients of a typical UV-curable photopolymerizable composition to be applied on top of the receiving layer are a monomer and a photoinitiator.
• Suitable monomers include the monomers disclosed in DE-OS Nos. 4005231, 3516256, 3516257, 3632657 and US 4,629,676, unsaturated esters of polyols, particularly such esters of the ⁇ -methylene carboxylic acids, e.g.
• divinyl succinate divinyl adipate, divinyl phthalate, divinyl butane-1,4-disulphonate; and unsaturated aldehydes, e.g. sorbaldehyde (hexadienal).
• the photopolymerizable composition may also comprise polymers and/or oligomers comprising two or more different polymerizable functions, e.g. acrylated epoxies, polyester acrylates, urethane acrylates, etc..
• Suitable compounds include n-octylacrylate, decylacrylate, decylmethacrylate, stearylacrylate, stearylmethacrylate, cyclohexylacrylate, cyclohexylmethacrylate, phenylethylacrylate, phenylethylmethacrylate.
• the most preferred compounds comprise one or more (meth)acrylate functional groups.
• photopolymerizable compounds containing one or more (meth)acrylate groups are reactive multifunctional monomers as disclosed in EP 502562.
• Suitable photoinitiators are a wide variety of compounds or compound combinations which are known for this purpose. Examples are benzoin ethers, benzil ketals, polycyclic quinones, benzophenone derivatives, triarylimidazolyl dimers, photosensitive trihalomethyl compounds, for example trichloromethyl-s-triazines. Preference is given to 2,3-bisarylquinoxalines, as described in US-A 3,765,898, and 2-aryl-4,6-bistrichloromethyl-s-triazines.
• the amount of photoinitiator or photoinitiator combination is generally between 1 and 25% by weight, preferably between 5 and 15% by weight.
• the UV curable composition may also contain a minor amount of a heat polymerization inhibitor which prevents premature polymerization before the UV curing step.
• a heat polymerization inhibitor which prevents premature polymerization before the UV curing step.
• examples of such inhibitors include p-methoxyphenol, hydroquinone, aryl- or alkyl substituted hydroquinone, t-butylcatechol, pyrogallol, copper (I) chloride, phenothiazine, chloranil, naphtylamine, ⁇ -naphtol, 2,6-di-t-butyl-p-cresol, etc.
• a preferred polymerization inhibitor is 2-methyl hydroquinone.
• the heat polymerization inhibitors are preferable used in an amount of 0.001 to 5 parts by weight per 100 parts of monomer.
• the composition may also contain
• AIBN dicumyl peroxide - benzoyl peroxide - t-butyl peroxide - VAZO compounds (from DuPont Co.), e.g. VAZO 52 - LUPEROX (from Atofina Co.), e.g. 233, 10, 11, 231, 101, - hydroperoxides, and peresters.
• the varnish and lacquer compositions may also contain a colorant, which may be a soluble dye or a pigment.
• the method for producing an information carrier comprises following steps, in order,
• the rigid sheet or web support may be optionally preprinted with a so-called security print.
• the spectral characteristics of the inks of the security print are preferably chosen so that they are difficult to copy by means of a commercial colour copier.
• This security print can be applied by any known printing technique, e.g. letterpress, lithographic printing, gravure printing, silk screen printing, etc.
• a preferred technique is driographic printing being a waterless variant of lithographic printing whereby no fountain solution is applied to the printing press.
• the security print is repeatedly applied over multiple areas of the web or sheet by a step and repeat process thus giving rise to multiple identical items.
• These multiple identical items are distributed over the support according to a fixed pattern, e.g. a rectangular grid.
• This receiving layer may be coated onto the support by any conventional coating technique, such as dip coating, knife coating, extrusion coating, spin coating, slide hopper coating and curtain coating.
• this layer be printed with a digitally stored set of information, for example, by means of ink jet printing.
• Other printing techniques using toner particles can however also be used.
• this digitally stored information is personalized information different for each individual item present on the information carrier.
• this personalized information may be a unique individual card number assigned to the future bearer of the card, or the expiry date of the validity of the card, or personal data of the future bearer, e.g. a birth day, and/or a photo.
• the ink jet printing step is repeated over multiple areas of the support in register with the security print pattern when present, thereby providing each item with different personalized information.
• ink jet printing it may be performed by any known technique known in the art.
• a continuous droplet stream is created by applying a pressure wave pattern. This process is known as continuous ink jet printing.
• the droplet stream is divided into droplets that are electrostatically charged, deflected and recollected, and into droplets that remain uncharged, continue their way undeflected, and form the image.
• the charged deflected stream forms the image and the uncharged undeflected jet is recollected.
• several jets are deflected to a different degree and thus record the image (multideflection system).
• the ink droplets can be created "on demand” (“DOD” or “drop on demand” method) whereby the printing device ejects the droplets only when they are used in imaging on a receiver thereby avoiding the complexity of drop charging, deflection hardware, and ink recollection.
• DOD on demand
• the ink droplet can be formed by means of a pressure wave created by a mechanical motion of a piezoelectric transducer (so-called “piezo method”), or by means of discrete thermal pushes (so-called “bubble jet” method, or “thermal jet” method).
• Ink compositions for ink jet typically include following ingredients: dyes or pigments, water and/or organic solvents, humectants such as glycols, detergents, thickeners, polymeric binders, preservatives, etc.. It will be readily understood that the optimal composition of such an ink is dependent on the ink jetting method used and on the nature of the substrate to be printed.
• the ink compositions can be roughly divided in :
• a curable varnish composition is applied on top of the receiving layer provided with an image in a predetermined pattern, and is cured, preferable by UV light, so that the layer underneath said predetermined pattern remains non-transparent.
• One way to obtain a non-transparency underneath the pattern is by curing the varnish composition before it can substantially penetrate into the receiving layer.
• Another way is to select a varnish, capable of penetrating into the receiving layer, but with a refractive index that differs sufficiently from the refractive index of the pigment, so that it is not capable of rendering the receiving layer transparent.
• the application and curing of the varnish is repeated over multiple areas of the information carrier in register with the multiple different items already present consisting of optional security print and personalized information.
• step (5) the thus obtained assemblage is overall covered by coating, printing, spraying or jetting of a curable lacquer composition, preferably UV-curable as explained above.
• this lacquer is allowed to penetrate all areas of the receiving layer not covered by the predetermined pattern of the varnish. These areas on penetration by the lacquer gradually change to transparent.
• the predetermined pattern of the varnish forms a non-transparent watermark on a transparent background.
• This watermark can have any form, e.g. a concrete design or alphanumerical character, or a geometrical figure, or an abstract design.
• step (6) the thus obtained assemblage is subjected to a second curing step, preferable UV-curing.
• the method comprises an additional step (5bis), performed between steps (5) and (6), of laminating a protective foil on top of the assemblage before the final curing step.
• Apparatuses for UV-curing are well-known to those skilled in the art and are commercially available.
• the curing proceeds with medium pressure mercury vapour lamps with or without electrodes, or pulsed xenon lamps.
• These ultraviolet sources usually are equipped with a cooling installation, an installation to remove the produced ozone and optionally a nitrogen inflow to exclude air from the surface of the product to be cured during radiation processing.
• An intensity of 40 to 240 W/cm in the 200-400 nm region is usually employed.
• An example of a commercially available ultraviolet medium-pressure electrodeless mercury vapour lamp is the model VPS/I600 curing system of Fusion UV systems Ltd., UK.
• a pulsed xenon flash lamp is commercially available from IST Strahlentechnik GmbH, Nürtingen, Germany.
• the substantial non-penetration of the receiving layer by the varnish and the thorough penetration by the lacquer can be realized by controlling the penetration time and/or the viscosity of the composition.
• the time between the application of the varnish and its curing is chosen to be so short that the varnish is unable to penetrate substantially, while the lacquer is given ample time to penetrate.
• Such a difference in penetration rates between the varnish and the lacquer could, for example, be realized by using a varnish with a significantly higher viscosity than that of the lacquer used.
• the affinity of the particle ink type used may play a role in the penetration speed. For instance, a hydrophobic oil-based ink will penetrate more slowly into a fairly hydrophilic receiving layer, such as a silica containing layer, than would an aqueous hydrophilic ink.
• a negative image is obtained with respect to the first embodiment.
• a method for producing a carrier of information comprising the following steps, in order,
• a transparent watermark is obtained on an opaque background which is the reverse of what is obtained with the first embodiment i.e. an opaque watermark on a transparent background.
• the opaque background can be realised by selecting a lacquer capable of penetrating into the receiving layer, but with a refractive index that differs too much from the refractive index of the pigment, so that it is not capable of rendering the receiving layer transparent.
• the method preferably comprises the additional step (7) or (7') of cutting the finished assemblage by known cutting means into a set of multiple ID cards, each carrying optional security print, watermark, and personalized information.
• Most types of ID cards have now the standardized dimensions of 85.6 mm x 54.0 mm x 0.76 mm. This final thickness can be reached by thermal lamination of one or more polymeric foils, e.g. PVC foils.
• the finished ID card can serve as an identity card, a security card, a driver's licence card, a social security card, a bank card, a membership card, a time registration card, a pay card and a credit card, etc.
• the finished ID card may comprise additional security elements or information carriers such as a hologram, a magnetic strip, or a chip ("smart cards").
• the receiving layer may be transparent and rendered substantially opaque i.e. having a transmission of less than 10% by penetration of the varnish or by penetration of the lacquer ensuring that the lacquer or varnish respectively have no effect on the transparency of the receiving layer.
• the same considerations as regards the refractive index of the ingredients apply in these embodiments.
• a dispersion A was prepared by mixing following ingredients:
• the thus prepared ink receiver composition was coated on a white opaque polyvinyl chloride support, having a thickness of 165 ⁇ m, which was printed before by means of driographic printing with gradually changing colour patterns, serving as security print.
• the wet coating thickness of this ink receiving layer was 60 ⁇ m.
• After drying the ink receiving layer was printed by means of EPSON STYLUS COLOR 900 ink jet printer with a set of digitally stored personal information, like photo, name, address, birthday, birth place, identification number, etc..
• the obtained image containing assemblage was then locally, in a predetermined pattern, e.g.
• the underlying driographic security print was only clearly revealed in those where no pattern-wise UV screen printed varnish was present.
• the non-transparent design formed by the cured varnish represented a watermark.
• a white opaque polyvinyl chloride support having a thickness of 165 ⁇ m, which was printed before by means of driographic printing with gradually changing colour patterns serving as security print, was coated with the ink receiver composition as described in ex. 1.
• the wet coating thickness of this ink receiving layer was 60 ⁇ m. After drying the ink receiving layer was printed by means of an EPSON STYLUS COLOR 900 ink jet printer with a set of digitally stored personal information (photo, name and address, birthday and - place, identification number, etc.).
• the assemblage was subjected to UV-light by means of a DRSE-120 conveyer provided with VPS/1600 UV lamp (240 W/cm - speed 20 cm/sec.).
• the assemblage was covered integrally by means of a coating knife with an Akzo Nobel Inks UVF00106-405 UV-curable flexo lacquer (viscosity 220 mPa.s at 20°C) at a coating thickness of 60 ⁇ m, instantly followed by laminating a transparent protective PET-foil (thickness 100 ⁇ m) on top of the UV-curable lacquer layer.
• a transparent protective PET-foil thickness 100 ⁇ m

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• 2003
  • 2003-09-04 EP EP03102696A patent/EP1398175B1/de not_active Expired - Fee Related

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