Patent Application
20100260985
The invention relates to a method for producing a polymer layer composite that comprises a plurality of polymer layers and at least one polymer layer contains a laser-sensitive component, wherein first personalised information is applied to at least one of the polymer layers by means of an inkjet printing method as a coloured inkjet printed layer, wherein second personalised information is inscribed into the obtained polymer layer composite by means of laser engraving, and wherein the polymer layer with the coloured inkjet printed layer is joined to the other polymer layers. The invention also relates to a thus obtained polymer layer composite, a security and/or valuable document comprising a polymer layer composite of said type and to a method for producing a security and/or valuable document of said type.
Personalisation of a security and/or valuable document is a process, wherein personalised information, i.e. individual information for a certain person, which is intended as holder or owner of the security and/or valuable document, for instance picture information, such as passport photograph, finger print etc., sequences of characters, such as name, address, place of residence etc., is applied to or in the respective security and/or valuable document. This may take place for instance in the form of coloured or black & white imprints or laser engraving. Alternatively or additionally, this or other person-individual information may however also be stored in an electronic circuit integrated in the security and/or valuable document, and then the electronic circuit or the information contained therein can be read by authorised persons.
The personalisation can be made in a centralised manner or in a decentralised manner. In the centralised personalisation, the personalised information is determined and transmitted to a manufacturer of the security and/or valuable document. The latter then applies the personalised information in or on the security and/or valuable document during the production and completion thereof. In the decentralised personalisation, the manufacturer of the security and/or valuable document supplies a non-personalised blank to a location, which carries out the determination of the personalised information and applies it on or in the blank and thus complete the security and/or valuable document, if applicable complemented by the final application of an uppermost protective film.
From the documents DE 2 907 004 C2, DE 3 151 407 C1 and EP 0 219 011 B1, different methods for laser marking of security and/or valuable documents are known in the art. By such methods, personalised information can be integrated in internal layers of a security and/or valuable document and is thus protected very well against manipulations. However, by means of this method, the integration of coloured personalised information, such as e.g. of passport photographs, is not possible.
From the documents U.S. Pat. No. 6,685,312, U.S. Pat. No. 6,932,527, U.S. Pat. No. 6,979,141, U.S. Pat. No. 7,037,013, U.S. Pat. No. 6,022,429 and U.S. Pat. No. 6,264,296, different methods for producing security and/or valuable documents are known in the art, wherein an inkjet printed layer is applied to a completed blank and then if applicable by a protective paint or a protective paint, the inkjet printed layer is protected against mechanical and/or chemical damages or manipulations. These methods are therefore basically suited for the decentralised personalisation. By these methods, coloured personalised information can be applied to the security and/or valuable document, however in case of the decentralised arrangement a later application of a protective paint or protective film is required in an expensive manner. Further, the resulting very superficial arrangement does however not secure a sufficient security against manipulations of the personalised information, in particular when the latter is removed for unauthorised purposes and used elsewhere or replaced, and then the destruction of the protective paint or film only occurs and they can be replaced if applicable.
It is the technical object of the invention to provide a method for producing polymer layer composite for a security and/or valuable document, wherein coloured personalised information is protected with a high security against manipulations, and which can be carried out in a centralised manner.
For achieving this technical object, the invention teaches a method for producing a polymer layer composite that comprises a plurality of polymer layers and at least one polymer layer contains a laser-sensitive component, said method consisting of the following steps: A) first personalised information is applied to at least one of the polymer layers by means of an inkjet printing method as a coloured inkjet printed layer, B) the polymer layer with the coloured inkjet printed layer is then joined to the other polymer layers, the polymer layer with the coloured inkjet printed layer being arranged between two other polymer layers, C) second personalised information is inscribed into the polymer layer composite obtained in step B) by means laser of engraving.
It is achieved by the invention that first personalised information is integrated in colour in the security and/or valuable document and is not only imprinted. Thereby, a very high security against manipulation is obtained, since a manipulation will require a decomposition of the polymer layer composite without destruction of coloured inkjet printed layer, which is practically impossible.
Typically, the joining process is a lamination step, and the different polymer layers are basically materially joined with each other. It is therefore not necessary to apply a protective layer on the completed composite, which appreciably simplifies production.
In particular, the following is noted with regard to the joining process. As a matter of principle, the step of compilation of the different polymer layers precedes the joining process. The compilation can take place in all usual ways, continuously, quasi-continuously or discontinuously. In a so called roll-to-roll production (continuous compilation), all polymer layers can be guided in parallel to each other, so that only when inserting a roll, the accuracy of fit of all tracks is important. After inserting and starting, an automatic monitoring of the running accuracy of the tracks and an automatic correction is performed, so that the different polymer layers always move in a given defined position with regard to each other. Thereafter, a lamination of the positioned tracks takes place, for this purpose the lamination of rolls being a particularly efficient and fast method. Alternatively, the lamination of single sheets (discontinuous compilation) can also be used. A single sheet contains different sections of a polymer layer, which are assigned to different security and/or valuable documents, or consists thereof. Finally, document-wise individual lamination can be employed. Therein, for instance electronic circuits can be tested for proper operation, and inkjet printed layers can be tested for freedom of faults, and that before the respective polymer layers are compiled. Thereby, rejects are minimized, since only tested polymer layers are compiled and then joined with each other. There is no need to re-manufacture all polymer layers, if one of the polymer layers is faulty. When compiling quasi-continuously, individual layers of the polymer layer composite are joined at one position. The specialty is that the feed of roll as well as of single sheet can be made from a stack and that not only strictly parallel, but also a crosswise operation is possible.
In a further method, the compilation takes place in a combined roll-to-roll and single sheet process. Therein, an electronic inlay can be fed as a single sheet and the polymer cover layers can be fed from the roll.
When joining, the different polymer layers are connected to a monolithic composite. This lamination may take place at temperatures from 140 to 270° C., preferably 140 to 210° C., and pressures (specific pressure directly at the workpiece) from 1 to 10 bars, in particular 3 to 7 bars.
After step B) (and before or after step C)), an optical inspection may take place, in order to detect faults of joining. Further, the accuracy of fit of the different polymer layers can be examined.
After step B) or after step C), typically a separation of the security and/or valuable documents is carried out, if it is not a single-unit production anyway. Such a separation can be carried out by cutting or stamping.
In an improvement of the invention, one of the polymer layers contains an electronic circuitry (overlying or embedded), which may also include electronic circuits, and a third personalised information is stored in the electronic circuitry before, in particular immediately before, at the same time as or after step C). It is useful if this polymer layer has on the side of the electronic circuitry and/or on the side opposite to the electronic circuitry at least in the area of the chip a preferably opaque over-print. Thereby, the electronic circuitry can be protected against light irradiation, or a converter layer according to document EP 4106463 can be integrated.
The polymer layer with the laser-sensitive component and the polymer layer with the coloured inkjet printed layer may be identical or different, i.e. the inkjet printed layer may be applied to the polymer layer with the laser-sensitive component or to another polymer layer. The polymer layer with the electronic circuitry may, not necessarily however must be different from the polymer layer or the polymer layers with the inkjet printed layer and/or the laser-sensitive component.
In step A, a personalised coloured inkjet printed layer can be applied to two or more different polymer layers. It is also possible to apply coloured inkjet printed layers to both opposite sides of a polymer layer. The coloured inkjet printed layers on different polymer layers can, however not necessarily must respectively represent partial information of first personalised information and optionally be arranged complementarily and accurately to register with respect to each other. In other words, the different inkjet printed layers represent partial pictures of an overall picture.
In a particularly preferred variant of the invention, the first personalised information is the colour portion of personalised overall picture information, and the second personalised information is the black portion of the personalised overall picture information. Herein, the overall picture information is only produced by the inkjet printed layer as well as the laser engraving process, and the inkjet printed layer represents a first partial picture and the laser engraving represents a second partial picture of the overall picture information. It is understood that the partial pictures have to be produced or applied exactly to register with respect to each other.
Optionally, an optical inspection of the coloured inkjet printed layer or of the coloured inkjet printed layers and/or an electronic test of the electronic circuit can be made before step B), in particular immediately before step B).
One or several of the polymer layers may additionally be provided on one side or both sides with a printed layer, which has been applied by a non-inkjet printing technology. Thereto belong the classic printing methods such as relief printing (direct and indirect), lithographic printing in the versions offset printing, wet and waterless printing, screen printing (silkscreen), digital and in particular intaglio and photogravure.
The invention further relates to a polymer layer composite that can be obtained by the method according to the invention. It may be a web, a sheet or an individual card. A web and a sheet contain a plurality of fields and every field forms after separation a security and/or valuable document. Such a polymer layer composite comprises a plurality of polymer layers, between two polymer layers a coloured inkjet printed layer produced by means of inkjet printing with first personalised information being arranged, and in one of the polymer layers, containing a laser-sensitive component, second personalised information produced by means of laser engraving being arranged. The explanations with regard to the method described above apply in an analogous manner.
Typically, the first personalised information or the personalised overall picture information will be a picture representation, in particular a passport photograph of a person.
The second personalised information may contain a personalised sequence of characters or consist thereof. This may for instance be the name of the person, the date of birth, and/or the address etc. The second personalised information may however also comprise document-individual information, as for instance serial number or date of issue, or consist thereof.
The polymer layer composite may contain 9 to 15, 3 to 14, in particular 5 to 12 polymer layers or the polymer layer composite may consist of these layers. The polymer layers without the electronic circuitry have for instance a thickness in the range from 5 to 270 μm, preferably from 10 to 120 μm, most preferably 20 to 120 μm. The polymer layer with the electronic circuitry has for instance a thickness from 50 to 650 μm, for instance in the case of a chip module as an electronic circuitry from 150 to 650 μm, or in the case of a display module from 50 to 600 μm, or in the case of a thinned flex chip from 50 to 200 μm.
In principle, all polymer materials being common in the field of security and/or valuable documents can be used as materials for the polymer layers. The polymer materials may be, identical or different, based on a polymer material from the group consisting of “PC (polycarbonate, in particular bisphenol A polycarbonate), PET (polyethylene glycol terephthalate), PMMA (polymethyl methacrylate), TPU (thermoplastic polyurethane elastomers), PE (polyethylene), PP (polypropylene), PI (polyimide or poly-trans-isoprene), PVC (polyvinyl chloride) and copolymers of such polymers”. Preferred is the use of PC materials, and for instance for the polymer cover layer in particular so-called low-Tg materials can for instance be used, but not necessarily must be used, in particular for the polymer layer, on which the inkjet printed layer is arranged, and/or for the polymer layer, which is connected with the polymer layer that carries the inkjet printed layer, and that on the side with the inkjet printed layer. Low-Tg materials are polymers, the glass temperature of which is below 140° C. It is preferred that the basic of at least one of polymer layers to be connected contains identical or different groups being reactive with each other, and at a lamination temperature of less than 200° C. reactive groups of a first polymer layer react with each other and/or with reactive groups of a second polymer layer. Thereby the lamination temperature can be reduced, without the tight bond of the laminated layers being at risk. This is caused by that, in the case of the different polymer layers with reactive groups, because of the reaction of the respective reactive groups the different polymer layers cannot easily be delaminated anymore. There is a reactive coupling between the layers, so to speak a reactive lamination. Secondly, it is made possible that because of the lower lamination temperature a change of the coloured inkjet printed layer, in particular a colour change, is prevented. It is preferred that the glass temperature Tg of the at least one polymer layer before the thermal lamination is less than 120° C. (or even less than 110° C. or than 100° C.), and the glass temperature of this polymer layer after the thermal lamination by reaction of reactive groups of the basic polymer of the polymer layer with each other is at least by 5° C., preferably at least 20° C., higher than the glass temperature before the thermal lamination. Herein, not only a reactive coupling of the layers to be laminated with each other, rather an increase of the molecular weight and thus of the glass temperature by cross-linkage of the polymer within the layer and between the layers takes place. This additionally makes a delamination difficult, in particular since an attempt of manipulation at the necessary high delamination temperatures will irreversibly damage e.g. the colours and thus the document will be destroyed. Preferably the lamination temperature in step B) is, when using such polymer materials, less than 180° C., even better less than 150° C. The choice of suitable reactive groups is easy for the man skilled in the art of polymeric chemistry. Exemplary reactive groups are selected from the group consisting of “—CN, —OCN, —NCO, —NC, —SH, —Sx, -Tos, —SCN, —NCS, —H, epoxy (—CHOCH2), —NH2, —NN+, —NN—R, —OH, —COOH, —CHO, —COOR, -Hal (—F, —Cl, —Br, —I), -Me-Hal (Me=at least divalent metal, for instance Mg), —Si(OR)3, —SiHal3, —CH═CH2, and —COR″, wherein R may be an arbitrary reactive or non-reactive group, for instance —H, -Hal, C1-C20 alkyl, C3-C20 aryl, C4-C20 aralkyl, each branched or linear, saturated or unsaturated, optionally substituted, or corresponding heterocycles with one or several identical or different heteroatoms N, O, or S″. Other reactive groups are of course also possible. Thereto belong the reaction partners of the Diels-Alder reaction or of a metathesis. The reactive groups may be bound directly to the basic polymer or may be connected by a spacer group to the basic polymer. Spacer groups may be all spacer groups known to the man skilled in the art of polymeric chemistry. The spacer groups may also be oligomers or polymers, which mediate elasticity, thus a risk of breaking of the security and/or valuable document being reduced. The man skilled in the art is familiar with such elasticity-mediating spacer groups, which therefore do not need to be described here in more detail. Examples of spacer groups are selected from the group consisting of “—(CH2)n—, —(CH2—CH2—O)n—, —(SiR2—O)n—, —(C6H4)n—, —(C6H10)n—, C1-Cn alkyl, C3-C(n+3) aryl, C4-C(n+4) aralkyl, each branched or linear, saturated or unsaturated, optionally substituted, or corresponding heterocycles with one or several, identical or different heteroatoms O, N, or S” with n=1 to 20, preferably 1 to 10. With respect to further reactive groups or possibilities of modification, reference is made to the document “Ullmann's Encyclopaedia of Industrial Chemistry”, Wiley Verlag, electronic edition 2006. The term basic polymer denotes for the purpose of the above explanations a polymeric structure, which does not carry any reactive groups under the employed lamination conditions. They may be homopolymers or copolymers. However, polymers being modified with respect to the mentioned polymers are also comprised.
For producing the inkjet printed layer, in principle all conventional inks can be used. Preferred is the use of a preparation containing: A) 0.1 to 20 wt. % of a binding agent with a polycarbonate derivative based on a geminally disubstituted dihydroxydiphenyl cycloalkane, B) 30 to 99.9 wt. % of a preferably organic solvent or solvent mixture, C) 0 to 10 wt. %, referred to dry matter, of a colorant or colorant mixture, D) 0 to 10 wt. % of a functional material or of a mixture of functional materials, E) 0 to 30 wt. % additive and/or auxiliary substances, or of a mixture of such substances, the sum of the components A) to E) always being 100 wt. %, as an inkjet printing ink. Such polycarbonate derivatives are highly compatible with polycarbonate materials, in particular with polycarbonates based on bisphenol A, such as for instance Makrofol© films. Furthermore, the employed polycarbonate derivative has high-temperature stability and does not show any coloration at temperatures being typical for lamination, up to 200° C. and more, thereby the use of the low-Tg materials described above being not necessary. In particular, the polycarbonate derivative may contain functional carbonate structure units of Formula (I),
wherein R1 and R2 are independently from each other hydrogen, halogen, preferably chlorine or bromine, C1-C8 alkyl, C5-C6 cycloalkyl, C6-C10 aryl, preferred phenyl, and C7-C12 aralkyl, preferably phenyl-C1-C4 alkyl, in particular benzyl; m is an integer from 4 to 7, preferably 4 or 5; R3 and R4 are individually selectable for each X, independently from each other from hydrogen or C1-C6 alkyl; X is carbon and n is an integer greater than 20, such that at least at one atom X, R3 and R4 simultaneously mean alkyl. It is preferred that at 1 to 2 atoms X, in particular only at one atom X, R3 and R4 are simultaneously alkyl. R3 and R4 may in particular be methyl. The X atoms in alpha position with respect to the diphenyl-substituted C atom (C1) may not be dialkyl-substituted. The X atoms in beta position with respect to C1 may be disubstituted with alkyl. Preferred is m=4 or 5. The polycarbonate derivative may for instance be based on monomers, such as 4,4′-(3,3,5-trimethylcyclohexane-1,1-diyl)diphenol, 4,4′-(3,3-dimethylcyclohexane-1,1-diyl)diphenol, or 4,4′-(2,4,4-trimethylcyclopentane-1,1-diyl)diphenol. Such a polycarbonate derivative may for instance be produced from diphenols of the Formula (Ia) according to document DE 38 32 396.6, whose scope of disclosure is herewith explicitly integrated with its complete contents in the scope of disclosure of this description. A diphenol of the Formula (Ia), under formation of homopolycarbonates, as well as several diphenols of the Formula (Ia), under formation of copolycarbonates, can be used (meaning of the radicals, groups and parameters same as in Formula I).
Furthermore, the diphenols of the Formula (Ia) can also be used in a mixture with other diphenols, for instance with those of the Formula (Ib)
HO—Z—OH (Ib)
for producing high-molecular, thermoplastic, aromatic polycarbonate derivatives.
Suitable other diphenols of the Formula (Ib) are such, in which Z is an aromatic radical with 6 to 30 C atoms, which may comprise one or several aromatic nuclei, may be substituted and may contain aliphatic radicals or other cycloaliphatic radicals than those of the Formula (Ia) or heteroatoms as bridge members. Examples for the diphenols of the Formula (Ib) are: hydroquinone, resorcin, dihydroxydiphenyls, bi-(hydroxyphenyl)-alkanes, bis-(hydroxyphenyl)cycloalkanes, bis-(hydroxyphenyl)-sulfides, bis(hydroxyphenyl)-ethers, bis-(hydroxyphenyl)-ketones, bis-(hydroxyphenyl)-sulfones, bis-(hydroxyphenyl)-sulfoxides, alpha,alpha′-bis-(hydroxyphenyl)-diisopropylbenzenes and the nucleus-alkylated and nucleus-halogenated compounds thereof. These and other suitable diphenols are e.g. described in the documents U.S. Pat. Nos. 3,028,365, 2,999,835, 3,148,172, 3,275,601, 2,991,273, 3,271,367, 3,062,781, 2,970,131 and 2,999,846, in the documents DE-A 1 570 703, 2 063 050, 2 063 052, 2 211 956, the Fr-A 1 561 518 and in the monograph “H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964”, which herewith are explicitly integrated with their complete contents in the scope of disclosure of this application. Preferred other diphenols are for instance: 4,4′-dihydroxydiphenyl, 2,2-bis-(4-hydroxyphenyl)-propane, 2,4-bis-(4-hydroxyphenyl)-2-methylbutane, 1,1-bis-(4-hydroxyphenyl)-cyclohexane, alpha, alpha-bis-(4-hydroxyphenyl)-p-diisopropylbenzene, 2,2-bis-(3-methyl-4-hydroxyphenyl)-propane, 2,2-bis-(3-chloro-4-hydroxyphenyl)-propane, bis-(3,5-dimethyl-4-hydroxyphenyl)-methane, 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane, bis-(3,5-dimethyl-4-hydroxyphenyl)-sulfone, 2,4-bis-(3,5-dimethyl-4-hydroxyphenyl)-2-methylbutane, 1,1-bis-(3,5-dimethyl-4-hydroxyphenyl)-cyclohexane, alpha,alpha-bis-(3,5-dimethyl-4-hydroxyphenyl)-p-diisopropylbenzene, 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane and 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane. Particularly preferred diphenols of the Formula (Ib) are for instance: 2,2-bis-(4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane and 1,1-bis-(4-hydroxyphenyl)-cyclohexane. In particular, 2,2-bis-(4-hydroxyphenyl)-propane is preferred. The other diphenols may be used individually as well as in a mixture. The molar ratio of diphenols of the Formula (Ia) to the other diphenols of the Formula (Ib) also to be used if applicable, should be from 100 mol % (Ia) to 0 mol % (Ib) and 2 mol % (Ia) to 98 mol % (Ib), preferably from 100 mol % (Ia) to 0 mol % (Ib) and 10 mol % (Ia) to 90 mol % (Ib) and in particular from 100 mol % (Ia) to 0 mol % (Ib) and 30 mol % (Ia) to 70 mol % (Ib). The high-molecular polycarbonate derivatives from the diphenols of the Formula (Ia), if applicable in a combination with other diphenols, may be produced according to the known polycarbonate production method. The different diphenols may be linked to each other statistically as well as block-wise. The employed polycarbonate derivatives may be branched in a per se known manner. If a branching is desired, this can be achieved in a known manner by condensation of small amounts, preferably amounts between 0.05 and 2.0 mol % (referred to employed diphenols), at three- or more than three-functional compounds, in particular those with three or more than three phenolic hydroxyl groups. Some branching agents with three or more than three phenolic hydroxyl groups are: phloroglucin, 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-heptene-2,4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-heptane, 1,3,5-tri-(4-hydroxyphenyl)-benzene, 1,1,1-tri-(4-hydroxyphenyl)-ethane, tri-(4-hydroxyphenyl)-phenylmethane, 2,2-bis-[4,4-bis-(4-hydroxyphenyl)-cyclohexyl]-propane, 2,4-bis-(4-hydroxyphenyl-isopropyl)-phenol, 2,6-is-(2-hydroxy-5-methyl-benzyl)-4-methylphenol, 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)-propane, hexa-[4-(4-hydroxyphenyl-isopropyl)-phenyl]-ortho-terephthalic acid ester, tetra-(4-hydroxyphenyl)-methane, tetra-[4-(4-hydroxyphenyl-isopropyl)phenoxy]-methane and 1,4-bis-[4′,4″-dihydroxytriphenyl)-methyl]-benzene. Some of the other three-functional compounds are 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride and 3,3-bis-(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindole. As chain terminators for the per se known control of the molecular weight of the polycarbonate derivatives serve mono-functional compounds in usual concentrations. Suitable compounds are e.g. phenol, tert.-butylphenols or other alkyl-substituted phenols. For controlling the molecular weight, in particular small amounts of phenols of the Formula (Ic) are suitable.
wherein R is a branched C8 and/or C9 alkyl radical. Preferred is that in the alkyl radical R the portion of CH3 protons is between 47 and 89% and the portion of the CH and CH2 protons is between 53 and 11%; also preferred is R in an o and/or p position with respect to the OH group, and particularly preferred is an upper limit of the ortho portion of 20%. The chain terminators are in general preferred in amounts of 0.5 to 10, preferably 1.5 to 8 mol %, referred to the employed diphenols. The polycarbonate derivatives may preferably be produced in a per se known manner according to the phase boundary behaviour (comp. H. Schnell “Chemistry and Physics of Polycarbonates”, Polymer Reviews, Vol. IX, page 33ff., Interscience Publ. 1964). Herein, the diphenols of the Formula (Ia) are dissolved in an aqueous alkaline phase. For producing copolycarbonates with other diphenols, mixtures of diphenols of the Formula (Ia) and the other diphenols, for instance those of the Formula (Ib), are employed. For controlling the molecular weight, chain terminators e.g. of the Formula (Ic) may be added. Then, in presence of an inert, preferably polycarbonate-dissolving organic phase, a reaction with phosgene according to the method of the phase boundary condensation is carried out. The reaction temperature is between 0° C. and 40° C. The branching agents also used if applicable (preferably 0.05 to 2.0 mol %) may either be provided with the diphenols in the aqueous alkaline phase or added in a solution with the organic solvent before the phosgenation. Besides the diphenols of the Formula (Ia) and if applicable other diphenols (Ib), the mono- and/or bis-chlorocarbonic acid esters thereof can also be used, which are added in a solution with organic solvents. The amount of chain terminators and of branching agents depends on the molar amount of diphenolate radicals according to Formula (Ia) and if applicable Formula (Ib); when also using chlorocarbonic acid esters, the amount of phosgene can be reduced in a known manner. Suitable organic solvents for the chain terminators and if applicable for the branching agents and the chlorocarbonic acid esters are for instance methylene chloride, chlorobenzene an in particular mixtures of methylene chloride and chlorobenzene. If applicable, the employed chain terminators and branching agents can be dissolved in the same solvent. As an organic phase for the phase boundary polycondensation serves for instance methylene chloride, chlorobenzene and mixtures of methylene chloride and chlorobenzene. As an aqueous alkaline phase serves for instance NaOH solution. The production of the polycarbonate derivatives according to the phase boundary method can be catalysed in a conventional way by catalysts such as tertiary amines, in particular tertiary aliphatic amines such as tributylamine or triethylamine; the catalysts can be used in amounts from 0.05 to 10 mol %, referred to the moles of employed diphenols. The catalysts can be added before starting the phosgenation or during or also after the phosgenation. The polycarbonate derivatives can be produced according to the known method in a homogeneous phase, the so-called “pyridine method” and according to the known melt transesterification method by using for instance diphenylcarbonate instead of phosgene. The polycarbonate derivatives may be linear or branched, they are homopolycarbonates or copolycarbonates based on the diphenols of the Formula (Ia). By the arbitrary composition with other diphenols, in particular with those of the Formula (Ib), the polycarbonate properties can be varied in a favourable way. In such copolycarbonates, the diphenols of the Formula (Ia) are contained in amounts from 100 mol % to 2 mol %, preferably in amounts from 100 mol % to 10 mol % and in particular in amounts from 100 mol % to 30 mol %, referred to the total amount of 100 mol % of diphenol units, in polycarbonate derivatives. The polycarbonate derivative may be a copolymer containing, in particular consisting thereof, monomer units M1 based on the Formula (Ib), preferably bisphenol A, and monomer units M2 based on the geminally disubstituted dihydroxydiphenyl cycloalkanes, preferably of the 4,4′-(3,3,5-trimethylcyclohexane-1,1-diyl)diphenol, the molar ratio M2/M1 preferably being greater than 0.3, in particular greater than 0.4, for instance greater than 0.5. It is preferred that the polycarbonate derivative has a mean molecular weight (weight average) of at least 10,000, preferably of 20,000 to 300,000. The component B may in principle be essentially organic or aqueous. Essentially aqueous means that up to 20 wt. % of the component B) may be organic solvents. Essentially organic means that up to 5 wt. % water may be present in the component B). Preferably, the component B contains or consists of a liquid aliphatic, cycloaliphatic, and/or aromatic hydrocarbon, a liquid organic ester, and/or a mixture of such substances. The employed organic solvents are preferably halogen-free organic solvents. These may be in particular aliphatic, cycloaliphatic, aromatic hydrocarbons, such as mesitylene, 1,2,4-trimethylbenzene, cumene and solvent naphtha, toluene, xylene; (organic) esters, such as methyl acetate, ethyl acetate, butyl acetate, methoxypropyl acetate, ethyl-3-ethoxypropionate. Preferred are mesitylene, 1,2,4-trimethylbenzene, cumene and solvent naphtha, toluene, xylene, acetic acid methyl ester, acetic acid ethyl ester, methoxypropyl acetate, ethyl-3-ethoxy propionate. Particularly preferred are: mesitylene (1,3,5-trimethylbenzene), 1,2,4-trimethylbenzene, cumene (2-phenylpropane), solvent naphtha and ethyl-3-ethoxy propionate. A suitable solvent mixture comprises for instance L1) 0 to 10 wt. %, preferably 1 to 5 wt. %, in particular 2 to 3 wt. %, mesitylene, L2) 10 to 50 wt. %, preferably 25 to 50 wt. %, in particular 30 to 40 wt. %, 1-methoxy-2-propyl acetate, L3) 0 to 20 wt. %, preferably 1 to 20 wt. %, in particular 7 to 15 wt. %, 1,2,4-trimethylbenzene, L4) 10 to 50 wt. %, preferably 25 to 50 wt. %, in particular 30 to 40 wt. %, ethyl-3-ethoxy propionate, L5) 0 to 10 wt. %, preferably 0.01 to 2 wt. %, in particular 0.05 to 0.5 wt. %, cumene, and L6) 0 to 80 wt. %, preferably 1 to 40 wt. %, in particular 15 to 25 wt. %, solvent naphtha, the sum of the components L1) to L6) always being 100 wt. %. The polycarbonate derivative typically has a mean molecular weight (weight average) of at least 10,000, preferably from 20,000 to 300,000. The preparation may in particular comprise: A) 0.1 to 10 wt. %, in particular 0.5 to 5 wt. %, of a binding agent with a polycarbonate derivative based on a geminally disubstituted dihydroxydiphenyl cycloalkane, B) 40 to 99.9 wt. %, in particular 45 to 99.5 wt. %, of an organic solvent or solvent mixture, C) 0.1 to 6 wt. %, in particular 0.5 to 4 wt. %, of a colorant or colorant mixture, D) 0.001 to 6 wt. %, in particular 0.1 to 4 wt. %, of a functional material or of a mixture of functional materials, E) 0.1 to 30 wt. %, in particular 1 to 20 wt. %, additive and/or auxiliary substances, or of a mixture of such substances. As component C, if a colorant is to be provided, in principle any arbitrary colorant or colorant mixture can be used. Colorants are all colour-changing substances. This means, these may be dyes (a survey of dyes is found in Ullmann's Encyclopaedia of Industrial Chemistry, Electronic Release 2007, Wiley Verlag, chapter “Dyes, General Survey”), as well as pigments (a survey of organic and inorganic pigments is found in Ullmann's Encyclopaedia of Industrial Chemistry, Electronic Release 2007, Wiley Verlag, chapter “Pigments, Organic” or “Pigments, Inorganic”). Dyes should be soluble or (stably) dispersible or suspensible in the solvents of the component B. Further, it is advantageous, if the colorant is stable, in particular colour-stable at temperatures of 160° C. and more for a time of more than 5 min. It is also possible that the colorant is subjected to a given and reproducible colour change under the processing conditions and is selected correspondingly. Pigments must have, besides the temperature stability, in particular a very fine particle size distribution. In the practice of inkjet printing, this means that the particle size should not be higher than 1.0 μm, since otherwise blockings in the pressure head will occur. Usually, nano-scale solid pigments and soluble organic colorants have shown good results. The colorants may be cationic, anionic or also neutral. Examples for colorants that can be used for inkjet printing are: Brillantschwarz C.I. No. 28440, Chromogenschwarz C.I. No. 14645, Direkttiefschwarz E C.I. No. 30235, Echtschwarzsalz B C.I. No. 37245, Echtschwarzsalz K C.I. No. 37190, Sudanschwarz HB C.I. 26150, Naphtolschwarz C.I. No. 20470, Bayscript® Schwarz Flüssig, C.I. Basic Black 11, C.I. Basic Blue 154, Cartasol® Türkis K-ZL Flüssig, Cartasol® Türkis K-RL Flüssig (C.I. Basic Blue 140), Cartasol Blau K5R Flüssig. Suitable are further e.g. the commercially obtainable colorants Hostafine® Schwarz TS Flüssig (sold by Clariant GmbH Germany), Bayscript® Schwarz Flüssig (C.I. mixture, sold by Bayer AG Germany), Cartasol® Schwarz MG Flüssig (C.I. Basic Black 11, registered trademark of Clariant GmbH Germany), Flexonylschwarz® PR 100 (E C.I. No. 30235, sold by Hoechst AG), Rhodamin B, Cartasol® Orange K3 GL, Cartasol® Gelb K4 GL, Cartasol® K GL, or Cartasol® Rot K-3B. Further, as soluble colorants can be used anthraquinone, azo, quinophthalone, cumarin, methin, perinone, and/or pyrazole colorants, e.g. obtainable under the trade name Macrolex®. Further suitable colorants are described in the document Ullmann's Encyclopaedia of Industrial Chemistry, Electronic Release 2007, Wiley Verlag, chapter “Colorants Used in Ink Jet Inks”. Well soluble colorants will lead to an optimum integration in the matrix or the binding agent of the printing layer. The colorants can be added either directly as a dye or pigment or as a paste, a mixture of dye and pigment together with an additional binding agent. This additional binding agent should be chemically compatible with the additional components of the preparation. If such a paste is used as a colorant, the amount of the component B refers to the colorant without the other components of the paste. These other components of the paste must then be subsumed under the component E. When using so-called coloured pigments in the scale colours cyan-magenta-yellow and preferably also (soot-) black, full-tone colour images are possible. The component D comprises substances, which by using technical means can immediately be seen by the human eye or by using suitable detectors. These are materials familiar to the man skilled in the art (cf. also van Renesse, Optical Document Security, 3rd ed., Artech House, 2005), which are used for the protection of valuable and security documents. Thereto belong luminescent substances (dyes or pigments, organic or inorganic) such as e.g. photoluminophores, electroluminophores, anti-Stokes luminophores, fluorophores, but also magnetisable, photo-acoustically addressable or piezoelectric materials. Furthermore, Raman-active or Raman-amplifying materials can be used, same as so-called barcode materials. Here, too, the preferred criteria are either the solubility in the component B or for pigmented systems particle sizes<1 μm and temperature stability for temperatures>160° C. in the meaning of the explanations with regard to the component C. Functional materials can be added directly or via a paste, i.e. mixture with an additional binding agent, which is then a constituent of the component E, or the employed binding agent of the component A. The component E comprises the substances normally used for inks in ink jet printing, such as anti-foam agents, set-up agents, wetting agents, tensides, floating agents, drying agents, catalysers, (light) stabilisers, preservation agents, biocides, tensides, organic polymers for viscosity adjustment, buffer systems, etc. Set-up agents are for instance conventional set-up salts. An example is sodium lactate. As biocides may be used all commercially available preservation agents, which are used for inks. Examples are Proxel®GXL and Parmetol® A26. Tensides may be all commercially available tensides, which are used for inks. Preferred are amphoteric or non-ionic tensides. Of course, however, the use of special anionic or cationic tensides, which do not alter the properties of the dye, is also possible. Examples for suitable tensides are betaines, ethoxilated diols etc. Examples are the product series Surfynol® and Tergitol®. The amount of tensides is for instance selected such that the surface tension of the ink is in the range from 10 to 60 mN/m, preferably from 20 to 45 mN/m, measured at 25° C. A buffer system may be provided, which stabilises the pH value in the range from 2.5 to 8.5, in particular in the range from 5 to 8. Suitable buffer systems are lithium acetate, borate buffer, triethanolamine or acetic acid/sodium acetate. A buffer system will in particular be applied in the case of a substantially aqueous component B. For adjusting the viscosity of the ink, (if applicable water-soluble) polymers may be provided. These may be all polymers being suitable for conventional ink formulations. Examples are water-soluble starch, in particular with an average molecular weight from 3,000 to 7,000, polyvinylpyrolidone, in particular with an average molecular weight from 25,000 to 250,000, polyvinyl alcohol, in particular with an average molecular weight from 10,000 to 20,000, xanthan gum, carboxymethyl cellulose, ethylene oxide/propylene oxide block copolymer, in particular with an average molecular weight from 1,000 to 8,000. An example for the above block copolymer is the product series Pluronic®. The share of biocide, referred to the total amount of ink, may be in the range from 0 to 0.5 wt. %, preferably from 0.1 to 0.3 wt. %. The share of tenside, referred to the total amount of ink, may be in the range from 0 to 0.2 wt. %. The share of set-up agents, referred to the total amount of ink, may be from 0 to 1 wt. %, preferably from 0.1 to 0.5 wt. %. To the auxiliary agents also belong all other components, such as for instance acetic acid, formic acid or n-methyl pyrolidone or other polymers from the used dye solution or paste. With regard to substances, which are suitable as component E, reference is made for instance to Ullmann's Encyclopaedia of Chemical Industry, Electronic Release 2007, Wiley Verlag, chapter “Paints and Coatings”, section “Paint Additives”.
The laser-sensitive component may in principle be a polymer, which can per se be locally pyrolysed by laser irradiation and thus dyed black. The respective polymer layer may also consist of such a polymer. Suitable polymers are explained in the following in connection with laser-sensitive pigments. The laser-sensitive component may however also be a laser-sensitive pigment, which is mixed with the polymer material of the respective polymer layer and is distributed therein. As laser-sensitive pigments, all pigments that are known in the technological field of the security and/or valuable products can be used. They may for instance be formed from organic polymers, which have a high absorption of the laser radiation, for instance PET, ABS, polystyrene, PPO, polyphenylene sulfide, polyphenylene sulfone, polyimide sulfone. They may however also be for instance LCP's. Particularly suitable are micro-milled thermoplastic materials with a very high melting range of more than 300° C. The particle size is typically in the range from 0.01 to 100 μm, in particular 0.1 to 50 μm, preferably 1 to 20 μm. Further, the polymer particles may contain light sensitive filler materials or pigments, for instance in an amount of 0.1 to 90 wt. %, referred to the laser-sensitive pigment. They may also be electrically conductive pigments and/or effect pigments and/or dyes, as described above. They may however also be oxides, hydroxides, sulfides, sulfates or phosphates of metals, such as for instance Cu, Bi, Sn, Zn, Ag, Sb, Mn, Fe, Ni, or Cr. In particular basic Cu(II) hydroxide phosphate can be employed. For example, a product is mentioned that is formed by heating blue Cu(II)-orthophosphate (Cu3(PO4)2*3H2O) to 100 to 200° C. and has the chemical formula Cu3(PO4)2*Cu(OH)2. Further suitable copper phosphates are: Cu3(PO4)2*3Cu(OH)2, Cu3(PO4)2*2Cu(OH)2*2H2O, 4CuO* P2O5, 4CuO* P2O5* 3H2O, 4CuO* P2O5* 1.5H2O and 4CuO* P2O5*1.2H2O.
Suitable laser radiation for generating the second personalised information has a wave length in the range from 150 nm to 10,600 nm, in particular 150 nm to 1,100 nm. For instance CO2 lasers (10,600 nm), Nd:YAG lasers (1,064 nm or 532 nm), and pulsed UV lasers (excimer lasers) can be used. The energy density is in general in the range from 0.3 mJ/cm2 to 50 J/cm2, in particular in the range from 0.3 mJ/cm2 to 10 J/cm2.
Further printed layers may be provided on one or several of the polymer layers, said further printed layers being known from the field of the security and/or valuable documents. They may be arranged on one side or on both sides of the polymer layer(s) before joining. Such another printed layer may also be applied to the polymer layer with the coloured inkjet printed layer, also immediately above or below the inkjet printed layer and/or on the side of the polymer layer being opposite to the inkjet printed layer. Such printed layers may also comprise functional substances, as explained above with respect to component D).
During step B) it is also possible to integrate or apply for instance (arbitrary) diffraction structures, such as line patterns as known for instance from the documents DE 199 49 945 or 100 36 505.
The invention also relates to a security and/or valuable document containing a polymer layer composite according to the invention and optionally a layer or several layers based on paper, Teslin and other composite materials.
Examples for security and/or valuable documents are: identity cards, passports, ID cards, access control cards, visas, tickets, driver's licenses, vehicle documents, personalised valuable documents, credit cards, and personalised chip cards. Such security and/or valuable documents typically comprise at least a substrate, a printed layer and optionally a transparent cover layer. Substrate and cover layer themselves may be composed of a multitude of layers. A substrate is a carrier structure, to which the printed layer with information, images, patterns and the like is applied. As materials for a substrate, all conventional materials on a paper and/or (organic) polymer basis can be used. Such a security and/or valuable document comprises within the total multi-layer structure a polymer layer composite according to the invention. Besides the polymer layer composite according to the invention, at least one (additional) printed layer may be provided, which may be applied to an external surface of the polymer layer composite or to an additional layer connected with the polymer layer composite.
The invention finally relates to a method for producing a security and/or valuable document according to the invention, wherein the polymer layer composite is joined at the same time as or after joining the polymer layers to a layer or several further layers based on paper, Teslin and other composite materials, for instance by laminating or gluing.
In the following, the invention is explained in more detail with reference to embodiments representing examples only. There are:
In
In phase P1 the different polymer layers 1, 2, 3, 4, 5 extend in parallel to each other, to the layer 2 the application of an inkjet printed layer is carried out, optionally followed by an optical inspection of the inkjet printed layer. Further, optionally a test of the electronic circuit in the layer 3 is carried out. If applicable, a second inkjet printed layer can be applied to the layer 4, said second inkjet printed layer being identical to or different from the first inkjet printed layer, and optionally follows in this phase P1 an optical inspection of the second inkjet printed layer. Said inkjet printed layers can be applied independently from each other to one or the other side of the layers 2, 4. In phase P2, the different polymer layers 1, 2, 3, 4, 5 are compiled and joined by way of lamination. A fixation of the compiled layers to each other before lamination, may for instance be made by means of ultrasonic stitching, but also other stitching methods, such as glue stitching. The lamination may be carried out by all conventional lamination methods, for instance by means of press plates in a combined heating/cooling press or particularly advantageously by means of a roll lamination. In phase P3 optionally an optical inspection for proper joining is carried out. In phase P4 a laser engraving step with the second personalised information and optionally a subsequent optical inspection of the laser engraving is performed. For this purpose, one of the polymer layers 1, 2, 3, 4, 5 contains a laser-sensitive component, for instance a laser-sensitive pigment. In phase P5 follows an electronic personalisation by storage of personalised data in the electronic circuit. In phase P6 optionally an electronic test of the stored data is made.
In
In phase P1, the different polymer layers 1, 2, 3, 4, 5 extend in parallel to each other, to the layer 2 the application of an inkjet printed layer is carried out, and optionally follows in this phase P1 an optical inspection of the inkjet printed layer. Furthermore, optionally a test of the electronic circuitry in the sheets 3 is carried out. If applicable, a second inkjet printed layer can be applied to the layer 4, said second inkjet printed layer being identical to or different from the first inkjet printed layer, and optionally in this phase P1 an optical inspection of the second inkjet printed layer is also carried out. Said inkjet printed layers can be applied respectively independently from each other to one or the other side of the layers 2, 4. Same as in Example 1, the second inkjet printed layer may represent third personalised information, which is different from first personalised information. In phase P2, the different polymer layers 1, 2, 3, 4, 5 are compiled and joined by way of lamination. Here, it is particularly advantageous that the polymer layer 3 with the integrated optional electronic circuitries is used as the sheet 3. This permits a simple orientation of the tracks relative to the sheet. A fixation of the compiled layers with respect to each other may for instance be carried out by means of ultrasonic stitching, but also by other stitching methods, such as glue stitching. The lamination may be performed by all conventional lamination methods, for instance by means of press plates in a combined heating/cooling press or particularly advantageously by a roll lamination. In phase P3, optionally an optical inspection for proper joining takes place. In phase P4 follows a laser engraving process with the second personalised information. For this purpose, one of the polymer layers 1, 2, 3, 4, 5 contains a laser-sensitive component, for instance a laser-sensitive pigment. In phase P5 an electronic personalisation by storage of personalised data in the electronic circuit is made. In phase P6, optionally an electronic test of the stored data is made.
In the middle can be seen two opaque polymer layers 14, 15 with a thickness of 150 μm, and a chip 16 with an antenna 17 is applied to one polymer layer 14 and to the side directed toward the polymer. The chip 16 and the antenna 17 are overprinted with a first printed layer 18. Toward outside follow opaque and 100 μm thick polymer layers 19, 20, which on the respectively external side carry as a background a printed layer of a non-inkjet printing technology, for instance an iris in the flat printing method. Further, toward outside follow the 100 μm thick and transparent polymer layers 21, 22, which internally carry an inscription formed as a relief printing layer. The polymer layer 21 comprises an external fluorescent printed layer and the polymer layer 22 comprises an external printed layer with optically variable pigments as well as an inkjet printed layer with personalised information, for instance a passport photograph. The outermost polymer layers 23 and 24 are 50 μm thick and transparent. The polymer layer 23 contains a laser-sensitive component, for instance laser-sensitive pigments. In the polymer layer is inscribed personalised information by means of a laser.
| Number | Date | Country | Kind |
|---|---|---|---|
| 102007059747.0 | Dec 2007 | DE | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/DE08/02013 | 12/8/2008 | WO | 00 | 7/2/2010 |
