EP2441589A1 - Document de sécurité et/ou de valeur contenant un convertisseur électromécanique - Google Patents
Document de sécurité et/ou de valeur contenant un convertisseur électromécanique Download PDFInfo
- Publication number
- EP2441589A1 EP2441589A1 EP10187563A EP10187563A EP2441589A1 EP 2441589 A1 EP2441589 A1 EP 2441589A1 EP 10187563 A EP10187563 A EP 10187563A EP 10187563 A EP10187563 A EP 10187563A EP 2441589 A1 EP2441589 A1 EP 2441589A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- security
- value document
- electromechanical transducer
- elastomer
- thermoplastic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
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
- B42D25/40—Manufacture
- B42D25/45—Associating two or more layers
- B42D25/455—Associating two or more layers using heat
-
- 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
- B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
- B42D25/373—Metallic materials
-
- 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
- B42D25/20—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof characterised by a particular use or purpose
- B42D25/23—Identity cards
-
- 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
- B42D25/20—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof characterised by a particular use or purpose
- B42D25/29—Securities; Bank notes
-
- 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
-
- 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
- B42D25/351—Translucent or partly translucent parts, e.g. windows
-
- 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
- B42D25/40—Manufacture
- B42D25/45—Associating two or more layers
- B42D25/465—Associating two or more layers using chemicals or adhesives
- B42D25/47—Associating two or more layers using chemicals or adhesives using adhesives
Definitions
- the present invention relates to a security and / or value document with an electromechanical transducer as a novel security element, a method for its production and the use of such an electromechanical transducer as a security element in security and / or value documents.
- identification documents In the market of security and / or value documents, in particular identification documents (ID documents) there is a need for continuous improvement of the security features used and development of new security features to always be one step ahead of potential counterfeiters.
- the security features should be designed so that a counterfeit is technically difficult and purely visually as easy to identify.
- Plastic-based security and / or value documents, in particular identification documents, such as e.g. ID cards are now produced as multilayer composites by means of lamination.
- the appropriate security features are introduced, which must therefore be designed so that they withstand the laminating process parameters nondestructive.
- no weaknesses in the multi-layer composite must be introduced by the security features, which would enable a non-destructive subsequent opening of the composite again.
- Level 1 security features can be perceived quickly, they are disadvantageous in that sufficiently complex counterfeits can result with limited effort.
- Level 3 security features can only be counterfeited at extremely high cost, but their identification can usually be at least partially destroyed Document can not be avoided. Accordingly, the focus is on the improvement of Level 2 security features.
- the object underlying the present invention was to find a novel security feature to improve the security against forgery of security and / or value documents.
- Electromechanical converters convert electrical energy into mechanical energy and vice versa. They are described in the literature as part of sensors, actuators and generators (cf., eg US-A 2004/0263028 and EP-A 2,182,559 ).
- electromechanical transducers containing two electrodes and a layer arranged therebetween with at least one elastomer or a polymeric piezoelectric material are suitable as a security feature for improving the security against forgery of security and / or value documents.
- Such electromechanical transducers can be used as a safety feature, on the one hand, in order to prevent the introduction of electrical energy, e.g. by means of a "reader” a tactile feedback, z.b. by vibration or other movement.
- they offer the possibility of introducing mechanical energy, i. For example, by simply bending the security and / or value document or pressing a button that is not visible, to generate electrical energy that makes visible hidden information, for example in the form of an EL, OLED or PLED-based arrangement.
- the subject of the present invention is accordingly a security and / or value document, characterized in that it comprises at least one electromechanical transducer comprising at least two electrodes and at least one polymer layer arranged between the electrodes, wherein the polymer layer comprises at least one elastomer or one polymeric piezoelectric Contains material.
- the elastomer (s) of the polymer layer are so-called electroactive polymers. Electroactive polymers are deflected when activated by electrical energy. Such an electroactive polymer acts as an insulating dielectric between two electrodes and may be deflected upon application of a voltage difference between the two electrodes.
- the elastomers used in the invention may be those which are pre-stressed.
- the pre-stress of a electroactive polymer may be described in one or more directions as the change in dimension in this direction after pre-stress relative to the dimension in that direction prior to pre-stressing.
- the pre-stress may include elastic deformation of the electroactive polymer, and may be generated, for example, by stretching the electroactive polymer under tension and fixing it to one or more of the edges while tensioned.
- the pre-stress improves the conversion between electrical and mechanical energy.
- pre-stress can improve the dielectric strength of the electroactive polymer, allowing for greater deflection and thus providing greater mechanical work when electrical energy is converted into mechanical energy.
- the pre-stress may result in more charge being applied to the electrodes, resulting in more generated electrical energy per cycle of deflection.
- Suitable elastomers which can be used according to the invention are all substantially insulating polymers or rubbers (or a combination thereof) which deform in response to an electrostatic force or whose deformation leads to a change in the electric field.
- Elastomers which can be used according to the invention are preferably silicone elastomers, acrylate elastomers, polyurethanes, thermoplastic elastomers, copolymers comprising polyvinylidene fluoride (PVDF), pressure-sensitive adhesives, fluoroelastomers, polymers comprising silicone and acrylate components, and mixtures of these.
- PVDF polyvinylidene fluoride
- polymers comprising silicone and acrylate components may include, for example, copolymers including silicone and acrylate components, polymer blends comprising a silicone elastomer, and an acrylate elastomer.
- Particularly preferred elastomers are polyurethane elastomer, silicone elastomer, acrylate elastomers and / or polymers comprising silicone and acrylate components.
- a suitable silicone elastomer is Dow Corning ® HS3 (Dow Coming of Wilmington, Delaware) is supplied.
- An example of a suitable fluoro-silicone is Dow Corning® 730 (Dow Corning, Wilmington, Delaware).
- Another suitable silicone elastomer is NuSil CF19-2186 (NuSil Technology Carpenteria, CA),
- thermoplastic elastomer is styrene-butadiene-styrene (SBS) block copolymer.
- Suitable examples of acrylate elastomers are, for example, those from the 4900 VHB acrylate series (3 M Corp., St. Paul, MN). Suitable acrylate elastomers can be prepared from any monoethylenically unsaturated monomer (or combination of monomers) which is homopolymerizable to form a polymer having a glass transition temperature of at most about 0 ° C.
- Preferred monoethylenically unsaturated monomers include isooctyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, dodecyl acrylate, hexyl acrylate, isononyl acrylate, isooctyl methacrylate and 2-ethylhexyl methacrylate.
- Any of the monomers may also contain one or more halogens, such as eg fluorine.
- the acrylate elastomer is one comprising mixtures of aliphatic acrylates, especially containing at least one branched acrylate, which are photocured during fabrication. The elasticity of the acrylate elastomer results from a combination of branched aliphatic groups and the crosslinking between the acrylate polymer chains.
- Suitable polyurethane elastomers can be prepared by reacting a polyisocyanate A) and / or a polyisocyanate prepolymer B) with at least one difunctional or polyfunctional isocyanate-reactive compound C) in the presence of a catalyst D) which is customary in polyurethane chemistry.
- Suitable polyisocyanates A) are, for example, 1,4-butylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2,2,4 and / or 2,4,4-trimethylhexamethylene diisocyanate, the isomeric bis (4, 4'-isocyanatocyclohexyl) methanes or mixtures thereof of any isomer content, 1,4-cyclohexylene diisocyanate, 4-isocyanatomethyl-1,8-octane diisocyanate (nonane triisocyanate), 1,4-phenylene diisocyanate, 2,4- and / or 2,6-toluene diisocyanate, 1,5-naphthylene diisocyanate, 2,2'- and / or 2,4'- and / or 4,4'-diphenylmethane diisocyanate, 1,3- and / or 1,4-
- Component A) may preferably be a polyisocyanate or a polyisocyanate mixture having an average NCO functionality of 2 to 4 with exclusively aliphatically or cycloaliphatically bonded isocyanate groups.
- the polyisocyanate prepolymers which can be used as component B) can be obtained by reacting one or more diisocyanates with one or more hydroxy-functional, in particular polymeric, polyols, if appropriate with addition of catalysts and auxiliaries and additives.
- components for chain extension such as, for example, with primary and / or secondary amino groups (NH 2 and / or NH-functional components) for the formation of the polyisocyanate prepolymer.
- the polyisocyanate prepolymer as component B) may preferably be obtainable from the reaction of polymeric polyols and aliphatic diisocyanates.
- Hydroxy-functional, polymeric polyols for the conversion to the polyisocyanate prepolymer B) may be, for example, polyester polyols, polyacrylate polyols, polyurethane polyols, polycarbonate polyols, polyether polyols, polyester polyacrylate polyols, polyurethane polyacrylate polyols, polyurethane polyester polyols, polyurethane polyether polyols, polyurethane polycarbonate polyols and / or polyester polycarbonate polyols. These can be used to prepare the polyisocyanate prepolymer individually or in any mixtures with each other.
- Suitable polyester polyols for the preparation of the polyisocyanate prepolymers B) may be polycondensates of di- and optionally tri- and tetraols and di- and optionally tri- and tetracarboxylic acids or hydroxycarboxylic acids or lactones.
- free polycarboxylic acids it is also possible to use the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols for the preparation of the polyesters.
- diols examples include ethylene glycol, butylene glycol, diethylene glycol, triethylene glycol, polyalkylene glycols such as polyethylene glycol, furthermore 1,2-propanediol, 1,3-propanediol, butanediol (1,3), butanediol (1,4), hexanediol (1,6 and isomers, neopentyl glycol or hydroxypivalic acid neopentyl glycol esters or mixtures thereof, with hexanediol (1,6) and isomers, butanediol (1,4), neopentyl glycol and hydroxypivalic acid neopentyl glycol ester being preferred.
- polyalkylene glycols such as polyethylene glycol, furthermore 1,2-propanediol, 1,3-propanediol, butanediol (1,3), butanediol (1,4)
- polyols such as trimethylolpropane, glycerol, erythritol, pentaerythritol, trimethylolbenzene or trishydroxyethyl isocyanurate or mixtures thereof.
- phthalic acid isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexanedicarboxylic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, tetrachlorophthalic acid, maleic acid, fumaric acid, itaconic acid, malonic acid, suberic acid, 2-methylsuccinic acid, 3,3-diethylglutaric acid and / or 2, 2-dimethyl succinic acid are used.
- the acid source used may also be the corresponding anhydrides.
- the mean functionality of the polyol to be esterified is ⁇ 2
- monocarboxylic acids such as benzoic acid and hexanecarboxylic acid.
- Preferred acids are aliphatic or aromatic acids of the abovementioned type. Particular preference is given to adipic acid, isophthalic acid and phthalic acid.
- Hydroxycarboxylic acids which may be co-used as reactants in the preparation of a hydroxyl-terminated polyester polyol include hydroxycaproic acid, hydroxybutyric acid, hydroxydecanoic acid or hydroxystearic acid, or mixtures thereof.
- Suitable lactones are caprolactone, butyrolactone or homologs or mixtures thereof. Preference is given to caprolactone.
- hydroxyl-containing polycarbonates for example polycarbonate, preferably polycarbonate, can be used.
- polycarbonate preferably polycarbonate
- they may have a number average molecular weight M n of from 400 g / mol to 8000 g / mol, preferably from 600 g / mol to 3000 g / mol.
- M n number average molecular weight
- These can be obtained by reaction of carbonic acid derivatives, such as diphenyl carbonate, dimethyl carbonate or phosgene, with polyols, preferably diols.
- diols examples include ethylene glycol, 1,2- and 1,3-propanediol, 1,3- and 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, 1,4-bishydroxymethylcyclohexane, 2 Methyl 1,3-propanediol, 2,2,4-trimethylpentane-1,3-diol, dipropylene glycol, polypropylene glycols, dibutylene glycol, polybutylene glycols, bisphenol A or lactone-modified diols of the type mentioned above or mixtures thereof.
- the diol component then preferably contains from 40% by weight to 100% by weight of hexanediol, preferably 1,6-hexanediol and / or hexanediol derivatives.
- hexanediol derivatives are based on hexanediol and may have ester or ether groups in addition to terminal OH groups.
- Such derivatives are obtainable, for example, by reaction of hexanediol with excess caprolactone or by etherification of hexanediol with itself to give di- or trihexylenglycol.
- the amount of these and other components are chosen such that the sum does not exceed 100% by weight, in particular 100% by weight.
- Hydroxyl-containing polycarbonates especially polycarbonate polyols, are preferably linearly constructed.
- polyether polyols can be used to prepare the polyisocyanate prepolymers B).
- polytetramethylene glycol polyethers as obtainable by polymerization of tetrahydrofuran by means of cationic ring opening are suitable.
- suitable polyether polyols may be the addition products of styrene oxide, ethylene oxide, propylene oxide, butylene oxide and / or epichlorohydrin to di- or polyfunctional starter molecules.
- starter molecules for example, water, butyldiglycol, glycerol, diethylene glycol, trimethylolpropane, propylene glycol, sorbitol, ethylenediamine, triethanolamine, or 1,4-butanediol or mixtures thereof can be used.
- Preferred components for the preparation of the polyisocyanate prepolymers B) are polypropylene glycol, polytetramethylene glycol polyethers and polycarbonate polyols or mixtures thereof, with polypropylene glycol being particularly preferred.
- polymeric polyols having a number average molecular weight M n of 400 g / mol to 8000 g / mol, preferably from 400 g / mol to 6000 g / mol and particularly preferably from 600 g / mol to 3000 g / mol can be used.
- These preferably have an OH functionality of from 1.5 to 6, particularly preferably from 1.8 to 3, very particularly preferably from 1.9 to 2.1.
- short-chain polyols can also be used in the preparation of the polyisocyanate prepolymers B).
- ester diols of the stated molecular weight range, such as ⁇ -hydroxybutyl- ⁇ -hydroxy-caproic acid ester, ⁇ -hydroxyhexyl- ⁇ -hydroxybutyric acid ester, adipic acid ( ⁇ -hydroxyethyl) ester or terephthalic acid bis ( ⁇ -hydroxyethyl) ester.
- monofunctional isocyanate-reactive hydroxyl-containing compounds for the preparation of the polyisocyanate prepolymers B).
- monofunctional compounds are ethanol, n-butanol, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, 2-ethylhexanol, 1-octanol, 1-dodecanol or 1-hexadecanol or mixtures from that.
- polyisocyanate prepolymers B it is possible to react diisocyanates with the polyols at a ratio of the isocyanate groups to hydroxyl groups (NCO / OH ratio) of 2: 1 to 20: 1, for example 8: 1.
- NCO / OH ratio ratio of the isocyanate groups to hydroxyl groups
- urethane and / or allophanate structures can be formed.
- a proportion of unreacted polyisocyanates can then be separated off.
- Thin-film distillation may be used for this purpose, for example, products having low residual monomers having residual monomer contents of, for example, ⁇ 1 percent by weight, preferably ⁇ 0.5 percent by weight, more preferably ⁇ 0.1 percent by weight, being obtained.
- the reaction temperature may be from 20 ° C to 120 ° C, preferably from 60 ° C to 100 ° C, amount.
- stabilizers such as benzoyl chloride, isophthaloyl chloride, dibutyl phosphate, 3-chloropropionic acid or methyl tosylate may be added during the preparation.
- NH 2 - and / or NH-functional components can be used in addition to the chain extension in the preparation of the polyisocyanate prepolymers B).
- Suitable components for chain extension are organic di- or polyamines.
- compounds which, in addition to a primary amino group, also have secondary amino groups or, in addition to an amino group (primary or secondary), OH groups for the preparation of the polyisocyanate prepolymers B).
- primary / secondary amines such as diethanolamine, 3-amino-1-methylaminopropane, 3-amino-1-ethylaminopropane, 3-amino-1-cyclohexylaminopropane, 3-amino-1-methylaminobutane, alkanolamines such as N-aminoethylethanolamine, ethanolamine , 3-aminopropanol, neopentanolamine.
- amines having an isocyanate-reactive group such as methylamine, ethylamine, propylamine, butylamine, octylamine, laurylamine, stearylamine, isononyloxypropylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, N-methylaminopropylamine, diethyl (methyl) aminopropylamine, morpholine, piperidine, or suitable substituted derivatives thereof, amide amines from diprimary amines and monocarboxylic acids, monoketim of diprimary amines, primary / tertiary amines, such as N, N-dimethylaminopropylamine.
- an isocyanate-reactive group such as methylamine, ethylamine, propylamine, butylamine, octylamine, laurylamine, stearylamine, isononyloxypropylamine, di
- the polyisocyanate prepolymers or mixtures thereof used as component B) may preferably have an average NCO functionality of 1.8 to 5, particularly preferably 2 to 3.5 and very particularly preferably 2 to 3.
- Component C) is a compound having at least two isocyanate-reactive functional groups.
- component C) may be a polyamine or a polyol having at least two isocyanate-reactive hydroxy groups.
- component C it is possible to use hydroxy-functional, in particular polymeric, polyols, for example polyether polyols or polyester polyols.
- Suitable polyols have already been described above in connection with the preparation of the prepolymer B), so that reference is made to avoid repetition thereof.
- component C) is a polymer having 2 to 4 hydroxy groups per molecule, most preferably a polypropylene glycol having 2 to 3 hydroxy groups per molecule.
- polyether polyols preferably have a polydispersity of 1.0 to 1.5 and an OH functionality of greater than 1.9, and particularly preferably greater than or equal to 1.95.
- Such polyether polyols can be prepared in a manner known per se by alkoxylation of suitable starter molecules, in particular using double metal cyanide catalysts (DMC catalysis). This method is for example in the patent US 5,158,922 and the publication EP 0 654 302 A1 described.
- DMC catalysis double metal cyanide catalysts
- the reaction mixture for the polyurethane can be obtained by mixing components A) and / or B) and C).
- the ratio of isocyanate-reactive hydroxy groups to free isocyanate groups is preferably from 1: 1.5 to 1.5: 1, more preferably from 1: 1.02 to 1: 0.95.
- At least one of the components A), B) or C) has a functionality of ⁇ 2.0, preferably ⁇ 2.5, preferably ⁇ 3.0 in order to introduce branching or crosslinking into the polymer element.
- the term "functionality" in component A) and B) refers to the average number of NCO groups per molecule and in component C) to the average number of OH--, NH or NH 2 groups per molecule.
- This branching or crosslinking brings about better mechanical properties and better elastomeric properties, in particular also better elongation properties, which is advantageous when using the dielectric elastomers in security and / or value documents according to the invention.
- the obtained polyurethane polymer may preferably have a maximum stress of ⁇ 0.2 MPa, especially from 0.4 MPa to 50 MPa, and a maximum elongation of ⁇ 100%, especially ⁇ 120%.
- the polyurethane may have a stress of from 0.1 MPa to 1 MPa, for example from 0.1 MPa to 0.8 MPa, in particular from 0.1 MPa to 0.3 MPa (determination according to ASTM D 412).
- the polyurethane may have a Young's modulus at an elongation of 100% from 0.1 MPa to 10 MPa, for example from 1 MPa to 8 MPa (determined according to ASTM D 412).
- the polyurethane polymer obtained is a dielectric elastomer having a volume resistivity according to ASTM D 257 of ⁇ 10 12 to ⁇ 10 17 ohm cm. It is also possible that the polyurethane polymer has a dielectric constant according to ASTM 150-98 of ⁇ 5 and a dielectric breakdown field strength according to ASTM 149-97a of ⁇ 100 V / ⁇ m. Basically, a maximum dielectric constant and a maximum dielectric breakdown field strength are desired in order to optimize the serviceability of the polymer.
- the elastomers may contain one or more additives to enhance various properties.
- additives are crosslinkers, thickeners, solvents, thixotropic agents, stabilizers, antioxidants, preferably nonvolatile antioxidants, light stabilizers, emulsifiers, surfactants, adhesives, plasticizers, water repellents, pigments, fillers and leveling agents.
- these additives are added to the reaction mixture for the preparation of the polyurethane in addition to the components A), B), C) and D).
- Preferred solvents are methoxypropyl acetate and ethoxypropyl acetate.
- Preferred flow control agents are polyacrylates, in particular amine resin-modified acrylic copolymers.
- the additives improve the ability of the elastomer to convert between mechanical energy and electrical energy.
- the additives may improve any polymer property or parameter related to the ability of the parameter to convert between mechanical energy and electrical energy, such as e.g. dielectric breakdown strength, maximum stress, dielectric constant, modulus of elasticity, properties associated with viscoelastic behavior, properties associated with creep, response time, and activation voltage.
- fillers can regulate the dielectric constant of the polymer element.
- the reaction mixture comprises fillers to increase the dielectric constants, such as fillers with a high dielectric constant.
- these are ceramic fillers, in particular barium titanate, titanium dioxide and piezoelectric ceramics such as quartz or lead zirconium titanate, as well as organic fillers, in particular those having a high electrical polarizability, for example phthalocyanines.
- a high dielectric constant can also be achieved by introducing electrically conductive fillers below the percolation threshold.
- Examples of these are carbon black, graphite, single-walled or multi-walled carbon nanotubes, electrically conductive polymers such as polythiophenes, polyanilines or polypyrroles, or mixtures thereof.
- electrically conductive polymers such as polythiophenes, polyanilines or polypyrroles, or mixtures thereof.
- those types of carbon are of interest, which have a surface passivation and therefore at low concentrations below the percolation threshold, although the dielectric constant increase and still do not lead to an increase in the conductivity of the polymer.
- a plasticizer may improve the functioning of the electromechanical transducer by reducing the modulus of elasticity of the elastomer and / or increasing the dielectric breakdown strength of the elastomer.
- Suitable Plasticizers include High Molecular Weight Hydrocarbon Oils, High Molecular Weight Hydrocarbon Fats, Pentalyne® H, Piccovar® AP Hydrocarbon Resins, Admex® 760, Plastolein® 9720, Silicone Oils, Silicone Greases, Floral® 105, Silicone elastomers, nonionic surfactants, and the like. Combinations of these materials may also be used.
- the polymeric piezoelectric materials may be, for example, fluorinated polymers, such as PVDF (polyvinylidene fluoride) or copolymers with VDF such as the VDF / TrFE copolymers (vinylidene fluoride-trifluoroethylene copolymers), or so-called ferroelectrets.
- PVDF polyvinylidene fluoride
- VDF vanadium-silicon
- TrFE copolymers vinylene fluoride-trifluoroethylene copolymers
- ferroelectrets are ferroelectrets. Ferroelectrets are for example in Physics Today, February 2004, 37 - 43 or ChemPhysChem, 2005, 6, 1014-1025 described.
- Ferroelectrets are polymer materials with a void structure that can store electrical charges for long periods of time.
- the previously known ferroelectrets have a cellular cavity structure and are formed either as foamed polymer films or as multilayer systems of polymer films or polymer fabrics. If electrical charges are distributed according to their polarity on the different surfaces of the cavities, each charged cavity represents an electric dipole. If the cavities are deformed, this causes a change in the dipole size and leads to a flow of current between external electrodes.
- the ferroelectrets can exhibit a piezoelectric activity comparable to that of other piezoelectrics.
- Materials suitable for ferroelectrets include polymers selected from the group consisting of polycarbonate, perfluorinated or partially fluorinated polymers, and co-polymers, such as e.g. Polytetrafluoroethylene (PTFE), perfluoroethylene-propylene copolymer (FEP), perfluoroalkoxy polymers (PFA), polyesters, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide, polyetherimide, polyether, polymethyl (meth) acrylate, cyclo-olefin polymers, cyclo -Olefin copolymers (COC) and / or polyolefins, such as Polypropylene. With these materials, good to very good piezo activities can be achieved.
- PTFE Polytetrafluoroethylene
- FEP perfluoroethylene-propylene copolymer
- PFA perfluoroalkoxy polymers
- polyesters polyethylene tere
- Such piezoelectric behavior can be found, for example, in closed cell foams, such as e.g. foamed, closed-pore polypropylene (PP) are observed.
- closed cell foams such as e.g. foamed, closed-pore polypropylene (PP) are observed.
- PP closed-pore polypropylene
- Such polypropylene ferroelectrets may have a piezoelectric coefficient of several hundred picocoulombs per Newton.
- Gerhard et al. (2007 Annual Report on Electrical Insulation and Dielectric Phenomena, pages 453-456 ) describes, for example, a three-layer ferroelectret in which a Polytetrafluoroethylene film, which has been provided by mechanical or laser-based drilling with a plurality of uniform, continuous recesses, is disposed between two uniform fluoroethylene propylene films.
- Other suitable multi-layer ferrules and their preparation are, for example, in WO 2010/066348 A2 described.
- FEP perfluoroethylene-propylene copolymer
- the electromechanical transducer can also contain more than two electrodes and in each case a polymer layer arranged therebetween comprising at least one elastomer or a polymeric piezoelectric material.
- Such stack structures may offer the advantage, for example, of enhancing haptic feedback due to the greater mechanical forces that can be generated therewith.
- the thickness of the polymer layer containing the elastomer (s) or polymeric piezoelectric material (s) may preferably be in the range of 1 ⁇ m to 150 ⁇ m, with thicknesses below 100 ⁇ m, e.g. between 20 and 100 microns are preferred for use in particularly thin security and / or value documents.
- the polymer layer between the electrodes contains at least one elastomer.
- the polymer layer between the electrodes may again be advantageous and preferred for the polymer layer between the electrodes to contain at least one polymeric piezoelectric material.
- the electrode materials may be conductive materials known to those skilled in the art.
- fillers for polymers filled with conductive fillers include metals, conductive carbon-based materials, such as carbon black, carbon nanotubes (CNTs), or conductive ones Oligo- or polymers, in question.
- the filler content of the polymers is above the percolation threshold, which is characterized in that the conductive fillers form continuous electrically conductive paths.
- the filled with conductive fillers polymers are elastomers.
- suitable electrode materials are, for example, elastic electrode materials, such as conductive oligomers or polymers or polymers filled with conductive fillers.
- the basic structure and the production of electromechanical transducers is known to the skilled person and, for example, in US-A 2004/0263028 or EP-A 2,182,559 described.
- the thickness of the electromechanical transducer as a whole may preferably be in the range of 10 .mu.m and 200 .mu.m, with thicknesses below 150 .mu.m, such as between 30 and 120 .mu.m, being preferred for use in particularly thin security and / or value documents.
- the electromechanical converter may preferably be located in the security and / or value document according to the invention between at least two thermoplastic resin layers.
- the electromechanical converter may preferably be located between at least two filled thermoplastic resin layers in the security and / or value document according to the invention.
- the filled thermoplastic resin layers can each independently of one another preferably be a translucent, white, black or colored layer filled with fillers.
- the filled thermoplastic synthetic layers are particularly preferably independent of each other of translucent or white filled layers.
- Suitable fillers are preferably such translucent or white-colored filled plastic layers preferably contain titanium dioxide, zirconium dioxide, barium sulfate or glass fibers as pigments and / or fillers.
- Other suitable filled thermoplastic plastic layers those from Teslin ® in question.
- the filled thermoplastic polymer layers are preferably those with a transmission in the visible wavelength range from 380 nm to 780 nm of less than 50%, preferably less than 35%, particularly preferably less than 25%, in very particularly preferred embodiments less than 15 %.
- the security and / or valuable document may contain at least one further plastic layer which contains laser-sensitive additives, wherein these plastic layer (s) are not located between the optionally filled thermoplastic layers.
- laser-sensitive additives are for example so-called laser marking additives in question, ie those from an absorber in the wavelength range of the laser to be used, preferably in Wavelength range of ND: YAG lasers (neodymium-doped yttrium aluminum garnet lasers).
- ND: YAG lasers neodymium-doped yttrium aluminum garnet lasers
- Such laser marking additives and their use in molding compositions are, for example, in WO-A 2004/50766 and WO-A 2004/50767 described and are commercially available from the Fa. DSM under the trade name Micabs ®.
- Further absorbers which are suitable as laser-sensitive additives are carbon black, coated sheet silicates, such as, for example, in US Pat DE-A-195 22 397 described and commercially available under the trade name Lazerflair ® , antimony doped tin oxide such as in US 6,693,657 and commercially available under the brand name Mark-it TM and phosphorus-containing tin-copper mixed oxides such as in WO-A 2006/042714 described. It is preferred if the particle size of the laser-sensitive additive is in the range of 100 nm to 10 ⁇ m, and particularly advantageous if it is in the range of 500 nm to 2 ⁇ m. A most preferred laser-sensitive additive is carbon black.
- the security and / or value document according to the invention may comprise one or more further additional layer (s), preferably plastic layers, in particular preferably thermoplastic synthetic layers, via which, for example, further information is introduced into the security or value document, preferably identification document.
- Such information may be obtained, for example, by means of at least one method selected from printing methods such as e.g. Screen, ink-jet, offset or laser printing processes, etc., or engraving processes, e.g. Laser engraving, or coating methods such as e.g. Doctoring, dipping, etc., optionally with the aid of masking, etc., to one or more ingredients used in the preparation of the document, e.g. Foils have been applied.
- the information may be of a decorative or individualizing nature, e.g. Show names, addresses, photos etc.
- the plastic layer (s) providing the information are preferably not located between the optionally present filled layers.
- the information is preferably located on the respective outward-facing side of the layer (s).
- the multilayer structure according to the invention may comprise one or more additional additional layer (s), preferably plastic layers, which are e.g. serve the protection of the security and / or value document. This may be e.g. scratch resistant, antistatic and / or IR reflective finished layers.
- additional additional layer preferably plastic layers, which are e.g. serve the protection of the security and / or value document. This may be e.g. scratch resistant, antistatic and / or IR reflective finished layers.
- the layers according to the invention preferably plastic layers, particularly preferably thermoplastic plastic layers, preferably each have a thickness of from 20 ⁇ m to 850 ⁇ m, it being possible for the individual plastic layers to have the same or different layer thicknesses.
- layer thicknesses of 50 ⁇ m to 600 ⁇ m are particularly preferred.
- the security and / or value document according to the invention is an identification document, preferably an ID card, such as an ID card. an identity card, passport, driving license, bank card, credit card, insurance card, other identity card etc ..
- thermoplastic resin layers contained in the multilayer structure according to the invention preferably contain at least one thermoplastic.
- thermoplastics for the plastic layers are independently thermoplastics selected from polymers of ethylenically unsaturated monomers and / or polycondensates of bifunctional reactive compounds in question.
- thermoplastics for the plastic layers are independently thermoplastics selected from polymers of ethylenically unsaturated monomers and / or polycondensates of bifunctional reactive compounds in question.
- said plastic layers may comprise at least one thermoplastic plastic selected from the aforementioned groups.
- thermoplastics are polycarbonates or copolycarbonates based on diphenols, poly- or copolyacrylates and poly- or co-polyethacrylates such as, by way of example and by way of preference, polymethyl methacrylate, poly- or copolymers with styrene such as, by way of example and preferably, transparent polystyrene or polystyrene-acrylonitrile (SAN), transparent thermoplastic polyurethanes, and polyolefins, such as for example and preferably transparent polypropylene types, or polyolefins based on cyclic olefins (for example, TOPAS ®, Hoechst) or polyolefin based materials such as Teslin ®, poly- or copolycondensates of terephthalic acid, such as for example and preferably poly- or copolyethylene terephthalate (PET or CoPET), glycol-modified PET (PETG) or poly- or copolybut
- polycarbonates or copolycarbonates in particular having average molecular weights M w from 500 to 100,000, preferably 10,000 to 80,000, particularly preferably 15,000 to 40,000 or blends containing at least one such polycarbonate or copolycarbonate.
- the blend is a blend of polycarbonate or copolycarbonate with poly- or copolybutylene terephthalate.
- a blend of polycarbonate or copolycarbonate with poly- or copolybutylene terephthalate may preferably be one having from 1 to 90% by weight of polycarbonate or copolycarbonate and from 99 to 10% by weight of poly- or copolybutylene terephthalate, preferably from 1 to 90% by weight .-% polycarbonate and 99 to 10 Wt .-% polybutylene terephthalate, wherein the proportions add up to 100 wt .-%.
- Such a blend of polycarbonate or copolycarbonate with poly- or copolybutylene terephthalate is particularly preferably one with 20 to 85% by weight of polycarbonate or copolycarbonate and 80 to 15% by weight of poly- or copolybutylene terephthalate, preferably with 20 to 85 Wt .-% polycarbonate and 80 to 15 wt .-% polybutylene terephthalate, wherein the proportions add up to 100 wt .-%.
- polycarbonate or copolycarbonate with polybutylene glycol or copolybutylene terephthalate it is most preferred that it contains 35 to 80% by weight polycarbonate or copolycarbonate and 65 to 20% by weight poly- or copolybutylene terephthalate, preferably 35 to 80% by weight 80 wt .-% polycarbonate and 65 to 20 wt .-% polybutylene terephthalate, wherein the proportions add up to 100 wt .-%.
- Particularly suitable polycarbonates or copolycarbonates in preferred embodiments are aromatic polycarbonates or copolycarbonates.
- the polycarbonates or copolycarbonates may be linear or branched in a known manner.
- polycarbonates can be carried out in a known manner from diphenols, carbonic acid derivatives, optionally chain terminators and optionally branching agents. Details of the production of polycarbonates have been laid down in many patents for about 40 years. By way of example, let's look at this Quick, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Volume 9, Interscience Publishers, New York, London, Sydney 1964 , on D. Freitag, U. Grigo, PR Müller, H. Nouvertne ', BAYER AG, "Polycarbonates” in Encyclopedia of Polymer Science and Engineering, Volume 11, Second Edition, 1988, pages 648-718 and finally up Dres. U. Grigo, K. Kirchner and PR Müller “Polycarbonates” in Becker / Braun, Plastics Handbook, Volume 3/1, polycarbonates, polyacetals, polyesters, cellulose esters, Carl Hanser Verlag Kunststoff, Vienna 1992, pages 117-299 directed.
- Suitable diphenols may be, for example, dihydroxyaryl compounds of the general formula (I) HO-Z-OH (I) wherein Z is an aromatic radical having 6 to 34 carbon atoms, which may contain one or more optionally substituted aromatic nuclei and aliphatic or cycloaliphatic radicals or alkylaryl or heteroatoms as bridge members.
- dihydroxyaryl compounds are resorcinol, 4,4'-dihydroxydiphenyl, bis- (4-hydroxyphenyl) -diphenyl-methane, 1,1-bis- (4-hydroxyphenyl) -1-phenyl-ethane, bis- (4-hydroxyphenyl) 1- (1-naphthyl) ethane, bis (4-hydroxyphenyl) -1- (2-naphthyl) ethane, 2,2-bis (4-hydroxyphenyl) -propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) -propane, 1,1-bis (4-hydroxyphenyl) -cyclohexane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1'-bis (4-hydroxyphenyl) -3-diisopropyl
- dihydroxyaryl compounds are 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.
- a most preferred copolycarbonate can be prepared using 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and 2,2-bis (4-hydroxyphenyl) -propane.
- Suitable carbonic acid derivatives may be, for example, diaryl carbonates of the general formula (II) wherein R, R 'and R "are each, independently of one another or different, hydrogen, linear or branched C 1 -C 34 -alkyl, C 7 -C 34 -alkylaryl or C 6 -C 34 -aryl, R furthermore also -COO-R ', where R'"is hydrogen, linear or branched C 1 -C 34 alkyl, C 7 -C 34 alkylaryl or C 6 -C 34 aryl.
- diaryl compounds are diphenyl carbonate, 4-tert-butylphenyl-phenyl carbonate, di (4-tert-butylphenyl) carbonate, biphenyl-4-yl-phenyl carbonate, di- (biphenyl-4-yl) -carbonate, 4- (1-methyl-1-phenylethyl) phenyl phenyl carbonate, di- 4- (1-methyl-1-phenylethyl) phenyl] carbonate and di (methyl salicylate) carbonate.
- one or more monohydroxyaryl compound (s) may be used as a chain terminator for controlling or changing the end groups, which was not used to prepare the diaryl carbonate (s) used.
- These may be those of the general formula (III), in which R A is linear or branched C 1 -C 34 -alkyl, C 7 -C 34 -alkylaryl, C 6 -C 34 -aryl or -COO-R D , where R D is hydrogen, linear or branched C 1 - C 34 alkyl, C 7 -C 34 alkylaryl or C 6 -C 34 aryl, and R B , R C independently of one another are identical or different for hydrogen, linear or branched C 1 -C 34 -alkyl, C 7 -C 34 -alkylaryl or C 6 -C 34 -aryl.
- Suitable branching agents may be compounds having three or more functional groups, preferably those having three or more hydroxyl groups.
- Preferred branching agents are 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole and 1,1,1-tri- (4-hydroxyphenyl) -ethane.
- Suitable poly- or copolycondensates of terephthalic acid in preferred embodiments of the invention are polyalkylene terephthalates.
- Suitable polyalkylene terephthalates are, for example, reaction products of aromatic dicarboxylic acids or their reactive derivatives (for example dimethyl esters or anhydrides) and aliphatic, cycloaliphatic or araliphatic diols and mixtures of these reaction products.
- Preferred polyalkylene terephthalates can be prepared from terephthalic acid (or its reactive derivatives) and aliphatic or cycloaliphatic diols having 2 to 10 carbon atoms by known methods ( Plastics Handbook, Vol. VIII, p. 695 ff, Karl-Hanser-Verlag, Kunststoff 1973 ).
- Preferred polyalkylene terephthalates contain at least 80 mole%, preferably 90 mole% terephthalic acid residues, based on the dicarboxylic acid component, and at least 80 mole%, preferably at least 90 mole% ethylene glycol and / or 1,4-butanediol residues, based on the diol component.
- the preferred polyalkylene terephthalates may contain up to 20 mol% of residues of other aromatic dicarboxylic acids having 8 to 14 carbon atoms or aliphatic dicarboxylic acids having 4 to 12 carbon atoms, such as, for example, phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid . 4,4'-diphenyldicarboxylic acid, succinic, adipic, sebacic, azelaic, cyclohexanediacetic.
- the preferred polyalkylene terephthalates may contain up to 20 mol% of other aliphatic diols having 3 to 12 C atoms or cycloaliphatic diols having 6 to 21 C atoms, eg. B.
- the polyalkylene can be prepared by incorporation of relatively small amounts of trihydric or trihydric alcohols or 3- or 4-basic carboxylic acids, as z. B. in the DE-OS 19 00 270 and the U.S. Patent 3,692,744 are described to be branched.
- preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and -propane and pentaerythritol.
- not more than 1 mol% of the branching agent, based on the acid component, is used.
- polyalkylene terephthalates which have been prepared solely from terephthalic acid and its reactive derivatives (eg their dialkyl esters) and ethylene glycol and / or butane-1,4-diol, and mixtures of these polyalkylene terephthalates.
- Preferred polyalkylene terephthalates are also copolyesters which are prepared from at least two of the abovementioned acid components and / or from at least two of the abovementioned alcohol components; particularly preferred copolyesters are poly (ethylene glycol / butanediol-1,4) terephthalates.
- the polyalkylene terephthalates preferably used as a component preferably have an intrinsic viscosity of about 0.4 to 1.5 dl / g, preferably 0.5 to 1.3 dl / g, each measured in phenol / o-dichlorobenzene (1: 1 wt . Parts) at 25 ° C.
- the optional translucent plastic layers, and any additional thermoplastic layers present at least one polycarbonate or copolycarbonate.
- the multilayer structure can have a monolithic layer composite in the regions in which the plastic layers are in direct contact with one another.
- a monolithic layer composite offers special protection against subsequent, non-destructive separation of the layer composite.
- plastics of the individual plastic layers are identical or similar plastics or plastic mixtures, in particular in the case of a monolithic layer composite, individual layers are to be understood as meaning those parts of the layer composite which differ from one another in the production of the multilayer composite Components, eg various films, contributed to the layer composite.
- an intermediate layer formed of an adhesive may be present on at least one side, preferably on both sides of the electromechanical transducer, between the electromechanical transducer and the nearest thermoplastic layer.
- Such an intermediate layer can protect the electromechanical transducer against destruction, in particular at elevated lamination temperatures in the production of the security and / or value document.
- the security and / or value document according to the invention may preferably contain electrical connections for contacting the electromechanical converter and / or at least one induction coil and / or at least one inverter and / or at least one voltage converter.
- these components are - if any - between the same thermoplastic layers of plastic as the electromechanical transducer.
- Electrical connections for contacting are in particular present in such embodiments of the invention, in which the electromechanical transducer is to provide a tactile feedback when applied to a power supplier, such as a reader.
- At least one inverter and electrical connections for contacting are present in particular in such embodiments of the invention, in which the electromechanical transducer by mechanical stress, eg bending the security and / or value document or pressing one or more hidden keys, electrical energy to supply an internal consumption , such as an EL device to provide an OLED structure and / or a PLED structure, the illumination of which, if appropriate, a hidden information can be made visible.
- At least one voltage converter and electrical connections for contacting are present in particular in those embodiments of the invention in which different voltages must be converted into each other, for example, alternating current into direct current.
- Voltage transformers may also be capable of converting low AC voltages to high DC voltages.
- At least one induction coil and electrical connections for contacting are present in particular in such embodiments of the invention, the contactless, ie without extrenen to contact Voltage devices to be operated.
- the security and / or value document according to the invention may also contain one or more other voltage suppliers, such as batteries, which would preferably also be located between the same thermoplastic layers of plastic as the electromechanical transducer.
- the security and / or value document according to the invention can, in preferred embodiments, contain an EL arrangement, an OLED structure and / or a PLED structure.
- the translucent plastic layers, and all additionally present transparent plastic layers contain at least one polycarbonate or copolycarbonate, preferably at least one polycarbonate.
- thermoplastic resin films used in steps (a) and (b) may be provided with an adhesive layer on the side facing the electromechanical transducer, or between at least one of those used in steps (a) and (b) thermoplastic plastic films and the electromechanical transducer a film of an adhesive material are placed.
- Both of the thermoplastic resin films used in steps (a) and (b) may be provided with an adhesive layer on the side facing the electromechanical transducer, or between both the thermoplastic resin films used in steps (a) and (b) and the electromechanical transducer in each case a film of an adhesive material are placed.
- adhesive films for example, those of thermoplastic polyurethane or EVA (ethylene vinyl acetate) are suitable.
- EVA ethylene vinyl acetate
- adhesive coatings for example, those based on polyurethane or acrylate adhesives are suitable. Such adhesives are known to the person skilled in the art.
- Latent reactive adhesives are known in the art.
- Preferred latently reactive adhesives are those which have an aqueous dispersion containing a di- or polyisocyanate with a melting or softening temperature of> 30 ° C and an isocyanate-reactive polymer.
- such an aqueous dispersion has a viscosity of at least 2000 mPas.
- the isocyanate-reactive polymer in this dispersion is a polyurethane, which are composed of crystallizing polymer chains which, when measured by means of thermomechanical analysis (TMA) at temperatures below + 110 ° C, preferably at temperatures below + 90 ° C. , partially or completely recrystallize.
- TMA thermomechanical analysis
- the measurement by TMA is carried out analogously to ISO 11359 Part 3 "Determination of the Penetration Temperature”.
- the di- or polyisocyanate is one selected from the group consisting of dimerization products, trimerization products and urea derivatives of TDI (tolylene diisocyanate) or IPDI (isophorone diisocyanate).
- Such latent reactive adhesives are for example in DE-A 10 2007 054 046 described.
- an additional increase in the security against forgery of the security and / or value document can be achieved in that no water vapor and / or air can diffuse into the interior beyond the edges of the layer structure and thus no longer cause subsequent delamination being able to lead.
- Such layer structures can no longer be separated indestructively.
- the thermoplastic resin film used in step (b) and / or at least one of the adhesive layers and / or at least one of the adhesive films may have recesses at the locations where the electromechanical transducer is located. This can for example serve to protect the electromechanical transducer or allow the electromechanical transducer sufficient mobility in the horizontal and / or vertical direction.
- the recesses are preferably selected such that the electromechanical converter in the security and / or value document according to the invention is not completely enclosed by thermoplastic material and / or adhesive.
- the security and / or value document according to the invention between the electromechanical transducer and the thermoplastic material and / or adhesive such a distance that the electromechanical transducer can expand at least in one direction, preferably in more than one direction.
- the preparation can be carried out such that between the two thermoplastic films from step (a) and (b), a further thermoplastic film, optionally with recesses at the one or more places on which or the electromechanical transducers or are , wherein the thermoplastic of this film has a Vicat softening temperature B / 50 (intermediate layer) which is smaller than the Vicat softening temperature B / 50 of the plastic compositions of the thermoplastic resin films used in steps (a) and (b).
- the first lamination step is at a temperature above the Vicat softening temperature B / 50 (interlayer) and below the Vicat softening temperature B / 50 of the plastic compositions of those used in steps (a) and (b) thermoplastic resin films
- the second lamination step is carried out at a temperature above the Vicat softening temperature B / 50 of the plastic compositions of the thermoplastic resin films used in steps (a) and (b).
- the recesses are preferably selected such that the electromechanical transducer in the security and / or value document according to the invention is not completely enclosed by thermoplastic material and / or adhesive. Particularly preferably, in the security and / or value document according to the invention between the electromechanical transducer and the thermoplastic material and / or adhesive such a distance that the electromechanical transducer can expand at least in one direction, preferably in more than one direction.
- the Vicat softening temperature B / 50 of a thermoplastic in the context of the invention is the Vicat softening temperature B / 50 according to ISO 306 (50 N, 50 ° C./h).
- the present invention furthermore relates to the use of an electromechanical transducer which comprises at least two electrodes and at least one polymer layer arranged between the electrodes, the polymer layer containing at least one elastomer or at least one polymeric piezoelectric material as security feature in a security and / or value document ,
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Business, Economics & Management (AREA)
- Accounting & Taxation (AREA)
- Finance (AREA)
- Laminated Bodies (AREA)
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP10187563A EP2441589A1 (fr) | 2010-10-14 | 2010-10-14 | Document de sécurité et/ou de valeur contenant un convertisseur électromécanique |
EP11767450.7A EP2627519A1 (fr) | 2010-10-14 | 2011-10-11 | Document de sécurité et/ou de valeur contenant un transducteur électromécanique |
PCT/EP2011/067703 WO2012049160A1 (fr) | 2010-10-14 | 2011-10-11 | Document de sécurité et/ou de valeur contenant un transducteur électromécanique |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP10187563A EP2441589A1 (fr) | 2010-10-14 | 2010-10-14 | Document de sécurité et/ou de valeur contenant un convertisseur électromécanique |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2441589A1 true EP2441589A1 (fr) | 2012-04-18 |
Family
ID=43825401
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP10187563A Withdrawn EP2441589A1 (fr) | 2010-10-14 | 2010-10-14 | Document de sécurité et/ou de valeur contenant un convertisseur électromécanique |
EP11767450.7A Withdrawn EP2627519A1 (fr) | 2010-10-14 | 2011-10-11 | Document de sécurité et/ou de valeur contenant un transducteur électromécanique |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP11767450.7A Withdrawn EP2627519A1 (fr) | 2010-10-14 | 2011-10-11 | Document de sécurité et/ou de valeur contenant un transducteur électromécanique |
Country Status (2)
Country | Link |
---|---|
EP (2) | EP2441589A1 (fr) |
WO (1) | WO2012049160A1 (fr) |
Citations (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1900270A1 (de) | 1968-01-04 | 1969-11-06 | Rhodiaceta | Neue thermoplastische Formmassen |
DE2407674A1 (de) | 1973-03-30 | 1974-10-10 | Tokyo Kosei Kaken Co | Fahrbare vorrichtung zum schleifen und reinigen von boeden |
DE2407776A1 (de) | 1974-02-19 | 1975-09-04 | Licentia Gmbh | Schaltung zur regelung der betriebsspannung fuer die transistor-zeilenendstufe eines fernsehempfaengers |
DE2715932A1 (de) | 1977-04-09 | 1978-10-19 | Bayer Ag | Schnellkristallisierende poly(aethylen/alkylen)-terephthalate |
US4654546A (en) | 1984-11-20 | 1987-03-31 | Kari Kirjavainen | Electromechanical film and procedure for manufacturing same |
US5158922A (en) | 1992-02-04 | 1992-10-27 | Arco Chemical Technology, L.P. | Process for preparing metal cyanide complex catalyst |
EP0634732A1 (fr) * | 1993-07-16 | 1995-01-18 | Idmatics S.A. | Carte souple équipée d'un dispositif de contrôle de validité |
EP0654302A1 (fr) | 1993-11-23 | 1995-05-24 | ARCO Chemical Technology, L.P. | Catalyseur amélioré à base de complexe de cyanure métallique double |
DE19522397A1 (de) | 1995-06-23 | 1997-01-02 | Merck Patent Gmbh | Lasermarkierbare Kunststoffe |
US6693657B2 (en) | 2001-04-12 | 2004-02-17 | Engelhard Corporation | Additive for YAG laser marking |
WO2004050766A1 (fr) | 2002-12-04 | 2004-06-17 | Dsm Ip Assets B.V. | Additif absorbeur de lumiere laser |
US20040263028A1 (en) | 1999-07-20 | 2004-12-30 | Sri International | Electroactive polymers |
WO2006042714A1 (fr) | 2004-10-15 | 2006-04-27 | Ticona Gmbh | Matieres moulables marquables au laser ; produits obtenus a partir de ces matieres et procede de marquage au laser |
DE102007048102A1 (de) * | 2007-10-06 | 2009-04-09 | Leonhard Kurz Gmbh & Co. Kg | Sicherheitselement zur Kennzeichnung eines Sicherheitsdokuments und Verfahren zu seiner Herstellung |
DE102007054046A1 (de) | 2007-11-13 | 2009-06-18 | Bayer Materialscience Ag | Latentreaktive Klebstoffe für Identifikations-Dokumente |
EP2182559A1 (fr) | 2008-10-30 | 2010-05-05 | Bayer MaterialScience AG | Convertisseur d'énergie à base de solutions de polyuréthane |
WO2010066348A2 (fr) | 2008-12-13 | 2010-06-17 | Bayer Materialscience Ag | Composite à deux couches ou multicouche à ferroélectret et procédé de fabrication dudit composite |
WO2010091796A1 (fr) | 2009-02-13 | 2010-08-19 | Bayer Materialscience Ag | Procédé amélioré de production d'un composite multicouche laminé |
-
2010
- 2010-10-14 EP EP10187563A patent/EP2441589A1/fr not_active Withdrawn
-
2011
- 2011-10-11 EP EP11767450.7A patent/EP2627519A1/fr not_active Withdrawn
- 2011-10-11 WO PCT/EP2011/067703 patent/WO2012049160A1/fr active Application Filing
Patent Citations (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3692744A (en) | 1968-01-04 | 1972-09-19 | Rhodiaceta | Injection molded branched polyesters |
DE1900270A1 (de) | 1968-01-04 | 1969-11-06 | Rhodiaceta | Neue thermoplastische Formmassen |
DE2407674A1 (de) | 1973-03-30 | 1974-10-10 | Tokyo Kosei Kaken Co | Fahrbare vorrichtung zum schleifen und reinigen von boeden |
DE2407776A1 (de) | 1974-02-19 | 1975-09-04 | Licentia Gmbh | Schaltung zur regelung der betriebsspannung fuer die transistor-zeilenendstufe eines fernsehempfaengers |
DE2715932A1 (de) | 1977-04-09 | 1978-10-19 | Bayer Ag | Schnellkristallisierende poly(aethylen/alkylen)-terephthalate |
US4654546A (en) | 1984-11-20 | 1987-03-31 | Kari Kirjavainen | Electromechanical film and procedure for manufacturing same |
US5158922A (en) | 1992-02-04 | 1992-10-27 | Arco Chemical Technology, L.P. | Process for preparing metal cyanide complex catalyst |
EP0634732A1 (fr) * | 1993-07-16 | 1995-01-18 | Idmatics S.A. | Carte souple équipée d'un dispositif de contrôle de validité |
EP0654302A1 (fr) | 1993-11-23 | 1995-05-24 | ARCO Chemical Technology, L.P. | Catalyseur amélioré à base de complexe de cyanure métallique double |
DE19522397A1 (de) | 1995-06-23 | 1997-01-02 | Merck Patent Gmbh | Lasermarkierbare Kunststoffe |
US20040263028A1 (en) | 1999-07-20 | 2004-12-30 | Sri International | Electroactive polymers |
US6693657B2 (en) | 2001-04-12 | 2004-02-17 | Engelhard Corporation | Additive for YAG laser marking |
WO2004050767A1 (fr) | 2002-12-04 | 2004-06-17 | Dsm Ip Assets B.V. | Composition d'ecriture par laser |
WO2004050766A1 (fr) | 2002-12-04 | 2004-06-17 | Dsm Ip Assets B.V. | Additif absorbeur de lumiere laser |
WO2006042714A1 (fr) | 2004-10-15 | 2006-04-27 | Ticona Gmbh | Matieres moulables marquables au laser ; produits obtenus a partir de ces matieres et procede de marquage au laser |
DE102007048102A1 (de) * | 2007-10-06 | 2009-04-09 | Leonhard Kurz Gmbh & Co. Kg | Sicherheitselement zur Kennzeichnung eines Sicherheitsdokuments und Verfahren zu seiner Herstellung |
DE102007054046A1 (de) | 2007-11-13 | 2009-06-18 | Bayer Materialscience Ag | Latentreaktive Klebstoffe für Identifikations-Dokumente |
EP2182559A1 (fr) | 2008-10-30 | 2010-05-05 | Bayer MaterialScience AG | Convertisseur d'énergie à base de solutions de polyuréthane |
WO2010066348A2 (fr) | 2008-12-13 | 2010-06-17 | Bayer Materialscience Ag | Composite à deux couches ou multicouche à ferroélectret et procédé de fabrication dudit composite |
WO2010091796A1 (fr) | 2009-02-13 | 2010-08-19 | Bayer Materialscience Ag | Procédé amélioré de production d'un composite multicouche laminé |
Non-Patent Citations (9)
Title |
---|
"Kunststoff-Handbuch", vol. VIII, 1973, KARL-HANSER-VERLAG, pages: 695 FF |
CHEMPHYSCHEM, vol. 6, 2005, pages 1014 - 1025 |
D. FREITAG; U. GRIGO; P. R. MÜLLER; H. NOUVERTNE: "Encyclopedia of Polymer Science and Engineering", vol. 11, 1988, article "Polycarbonates", pages: 648 - 718 |
DRES. U. GRIGO; K. KIRCHNER; P. R. MÜLLER: "Kunststoff-Handbuch, Band 3/1, Polycarbonate, Polyacetale, Polyester, Celluloseester", 1992, CARL HANSER VERLAG, article "Polycarbonate", pages: 117 - 299 |
GERHARD ET AL., ANNUAL REPORT CONFERENCE ON ELECTRICAL INSULATION AND DIELECTRIC PHENOMENA, 2007, pages 453 - 456 |
PHYSICS TODAY, February 2004 (2004-02-01), pages 37 - 43 |
SCHNELL: "Polymer Reviews", vol. 9, 1964, INTERSCIENCE PUBLISHERS, article "Chemistry and Physics of Polycarbonates" |
VON R. A. P. ALTAFIM ET AL., JOURNAL OF APPLIED PHYSICS, vol. 106, 2009, pages 014106 |
VORONINA ET AL., APPLIED PHYSICS A: MATERIALS SCIENCE & PROCESSING, vol. 90, 2008, pages 615 - 618 |
Also Published As
Publication number | Publication date |
---|---|
WO2012049160A1 (fr) | 2012-04-19 |
EP2627519A1 (fr) | 2013-08-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2586073A2 (fr) | Transducteur électromécanique, procédé de production et utilisation | |
US12084583B2 (en) | Dielectric ink composition | |
US5977685A (en) | Polyurethane elastomer actuator | |
TWI546192B (zh) | 卡片用核芯片 | |
DE102017223703A1 (de) | Verpackungsmaterial für Energiespeichervorrichtungen, Verpackungsgehäuse für Energiespeichervorrichtungen und Energiespeichervorrichtungen | |
EP2870189A1 (fr) | Procédé de fabrication d'un système de films de polyuréthane diélectriques multicouches | |
EP2459611B1 (fr) | Convertisseur électromécanique doté d'un élément polymère basé sur un mélange en polyisocyanate et de pré-polymères fonctionnels avec de l'isocyanate et sur une liaison dotée d'au moins deux groupes hydroxy réactifs à isocyanate | |
EP2867281A1 (fr) | Film de polyuréthane diélectrique | |
EP2284919A1 (fr) | Procédé de fabrication d'un convertisseur électromécanique | |
EP2244489A1 (fr) | Procédé de fabrication d'un convertisseur électromécanique | |
WO2016193061A1 (fr) | Convertisseur électromécanique constitué d'un électrode extensible, réversible et cycliquement stable et procédé de fabrication de celle-ci | |
WO2014131895A1 (fr) | Procédé de fabrication d'un système de film de polyuréthane diélectrique multicouches | |
EP2218579A1 (fr) | Procédé amélioré destiné à la fabrication d'un composite stratifié laminé | |
EP3890971A1 (fr) | Films en plastique à température de ramollissement vicat élevée dans des structure en couches | |
JP6408124B2 (ja) | フィルム巻層体及びその製造方法 | |
DE102010016499A1 (de) | Flächige Piezogeneratormodule und Verfahren zu ihrer Herstellung | |
EP2441589A1 (fr) | Document de sécurité et/ou de valeur contenant un convertisseur électromécanique | |
EP3037449A1 (fr) | Polyuréthane modifié dipolaire, son procédé de fabrication et utilisation destiné à fabrication de feuilles élastomères de coulée à base de polyuréthane électroactif | |
EP4232297A1 (fr) | Structure en couches avec gravure en tant qu'élément de sécurité visible | |
EP2455228A1 (fr) | Document de sécurité et/ou de valeur contenant un convertisseur électromécanique | |
WO2016193062A1 (fr) | Additif polymère non lié pour augmenter la constante diélectrique de polymères de polyurethane électriquement actifs | |
EP2697317A1 (fr) | Procédé de sérigraphie à l'aide d'une encre d'impression réagissant pour devenir un polymère polyuréthane | |
EP2368935B1 (fr) | Composite à couches de polymère ayant une adhérence des couches améliorée | |
EP3934907A1 (fr) | Structure à couches servant à fabriquer une charnière, en particulier pour la fabrication d'une couverture de livre multicouche | |
WO2015173126A1 (fr) | Films diélectriques eap à bas point de transition vitreuse et à base de polyester-polyols |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN |
|
18W | Application withdrawn |
Effective date: 20121006 |