EP2396172A1 - Procédé amélioré de production d'un composite multicouche laminé - Google Patents

Procédé amélioré de production d'un composite multicouche laminé

Info

Publication number
EP2396172A1
EP2396172A1 EP10702440A EP10702440A EP2396172A1 EP 2396172 A1 EP2396172 A1 EP 2396172A1 EP 10702440 A EP10702440 A EP 10702440A EP 10702440 A EP10702440 A EP 10702440A EP 2396172 A1 EP2396172 A1 EP 2396172A1
Authority
EP
European Patent Office
Prior art keywords
vicat softening
thermoplastic
layer
poly
softening temperature
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Withdrawn
Application number
EP10702440A
Other languages
German (de)
English (en)
Inventor
Matthias Grötsch
Georgios Tziovaras
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Deutschland AG
Original Assignee
Bayer MaterialScience AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Bayer MaterialScience AG filed Critical Bayer MaterialScience AG
Priority to EP10702440A priority Critical patent/EP2396172A1/fr
Publication of EP2396172A1 publication Critical patent/EP2396172A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2519/00—Labels, badges
    • B32B2519/02—RFID tags

Definitions

  • the present invention relates to a method for producing a laminated layer composite in which at least one base layer and at least one further layer, between which a component is located, are laminated in two stages from two thermoplastic materials having different Vicat softening temperatures B / 50 to form a laminate.
  • the invention furthermore relates to a layer structure suitable for this process, to a laminated layer composite produced by this process, and to a security and / or value document containing such a laminated layer composite.
  • ID cards represent security and / or value documents of increasing interest.
  • Such ID cards usually contain a plurality of layers, which may preferably consist of identical or different thermoplastic materials.
  • Such ID cards may also have in their construction a component, preferably an electronic component, such as e.g. a chip and an antenna included.
  • Such electronic components are preferably arranged in the middle part of an ID card.
  • Em such middle part of an ID card has in its simplest case at least one base layer on which the component is applied, and at least one but preferably several further layer (s) which are to embed the component in the thermoplastic or the plastics (intermediate layers ), and optionally at least one cover layer on said further layer (s).
  • These layers are preferably processed by means of Lammieren to an inseparable layer composite.
  • the further layer (s) (interlayer (s)) is (are) punched out, so that the recess eliminates the component to be embedded (see Fig. 1).
  • FIG. 1 shows schematically a layer structure with a component to be embedded in the form of a chip (1) and an antenna (2), a base layer (3) to which this component is applied, three intermediate layers (4) which together approximate the height of the Have chips and are punched around the chip, and a cover view (5).
  • a small gap is created in which the softened material is pressed during the laminating process using the laminating pressure P (see FIG. 2). This leads to a destruction of the connection between antenna and chip.
  • the additional step of punching out the intermediate layers is disadvantageous, since the size of the punched-out surface must be matched to the component to be integrated in each case and makes standardized large-scale production more difficult.
  • FIG. 1 shows schematically a layer structure with a component to be embedded in the form of a chip (1) and an antenna (2), a base layer (3) to which this component is applied, three intermediate layers (4) which together approximate the height of the Have chips and are punched around the chip, and a cover view (5).
  • FIG. 3 shows schematically a layer structure with a component to be embedded in the form of a chip (1) and an antenna (2), a base layer (3) to which this component is applied, two intermediate layers (4) which together approximate the height of the Have chips and are not punched around the chip, and a cover view (5).
  • Lamimerdrucks P is pressed. This also leads to a destruction of the connection between the antenna and the chip.
  • Laminated composite with embedded component in which the functionality of the component is not destroyed or significantly reduced by the lamination process.
  • the object of the present invention was to find and provide a method for producing a laminated layer composite with an integrated component, wherein the functionality of the component is not destroyed or significantly reduced by the lamination process.
  • a layer structure comprising at least one base layer of a thermoplastic, polymeric Mate ⁇ al having a Vicat softening temperature B / 50 (Bas i s) and applied to this base layer component, at least one further layer of a thermoplastic polymer Mate ⁇ al , with a Vicat softening temperature B / 50 ( s ct ⁇ cht) less than the Vicat softening temperature B / 50 (B a s i s) and optionally at least one cover layer of a thermoplastic polymer Mate ⁇ al is laminated in a two-stage lamination process, wherein the first lamination at a temperature above the Vicat softening temperature B / 50 (Shi ch t), which is at most 5 ° C above the Vicat softening temperature B / 50 (Bas i s) , and the second lamination at a temperature above the Vicat softening temperature B / 50 (BaS i s) is performed.
  • the present invention accordingly provides a process for producing a laminated layer composite, characterized in that a layer structure comprising
  • thermoplastic polymeric Mate ⁇ al having a lower Vicat softening temperature B / 50 (see Ch i ch t) as the thermoplastic polymeric matenal of the base layer optionally at least one cover layer of a thermoplastic, polymeric Mate ⁇ al,
  • thermoplastic, polymeric material having a lower Vicat softening temperature B / 50 ( Schi tt ) ,
  • the lamination temperature of the second step b) of the process according to the invention is preferably higher than the lamination temperature of the first step a).
  • the method according to the invention has the advantage that only a further layer (s) are softened in the first laminating layer by using a termoplastic plastic with a lower Vicat softening temperature B / 50 for the further layer (s), and that they are gapless To put the component to be embedded before the base layer is softened in the second step to form the entire layer composite. As a result, no destruction of the functionality of the component according to the prior art method can take place.
  • 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 Vicat softening temperature B / 50 (Sch , Cht) is at least 5 ° C lower, preferably at least 10 ° C lower than the Vicat softening temperature B / 50 (B s i s) -
  • the component may, for example and preferably, be at least one electronic component or at least one (volume) hologram.
  • the electronic component (s) may, for example, be integrated circuits, thick-film circuits, circuits comprising a plurality of discrete active and passive electronic components, sensors, chip modules, displays, batteries, coils, capacitors, printed conductors and / or contact points.
  • thermoplastic polymeric material for both the base layer and the further layer (s) may independently preferably be at least one thermoplastic selected from polymers of ethylenically unsaturated monomers and / or polycondensates of bifunctional reactive compounds and / or Polyaddition products of bi-functional reactive compounds, act.
  • thermoplastic of the layer (s) containing at least one thermoplastic and the layer (s) containing at least one thermoplastic and at least one laser-sensitive additive may be the same or different.
  • thermoplastics are polycarbonates or copolycarbonates based on diphenols, poly- or copolyacrylates and poly- or co-polyethacrylates such as, by way of example and preferably, polymethyl methacrylate (PMMA), poly- or copolymers with styrene, by way of example and preferably polystyrene (PS) or polystyrene-acrylonitrile (SAN).
  • PMMA polymethyl methacrylate
  • PS polystyrene
  • SAN polystyrene-acrylonitrile
  • thermoplastic polyurethanes as well as polyolefins, as exemplified and preferably
  • Polypropylene types, or polyolefins based on cyclic olefins for example, TOPAS ®, Hoechst
  • polyvinyl chloride poly- or copolycondensates of terephthalic acid, such as for example and preferably poly- or copolyethylene terephthalate (PET or CoPET), glycol-modif ⁇ participatedes PET (PETG), glycolic modified poly- or copolycyclohexanedimethylene terephthalate (PCTG) or poly- or copolybutylene terephthalate (PBT or CoPBT), poly- or copolycondensates of
  • Naphthalenedicarboxylic acid such as by way of example and preferably polyethylene glycol naphthalate (PEN), poly- or copolycondensate (s) of at least one cycloalkyldicarboxylic acid, such as by way of example and preferably polycyclohexanedimethanolcyclohexanedicarboxylic acid (PCCD), polysulfones (PSU) or mixtures of the foregoing.
  • PEN polyethylene glycol naphthalate
  • PCCD polycyclohexanedimethanolcyclohexanedicarboxylic acid
  • PSU polysulfones
  • thermoplastics are polyurethanes, polycarbonates or copolycarbonates or blends comprising at least one polyurethane, polycarbonate or copolycarbonate. Particular preference is given to polycarbonates or copolycarbonates Blends comprising at least one polycarbonate or copolycarbonate. Preferred blends are those comprising at least one polycarbonate or copolycarbonate and at least one poly- or copolycondensate of terephthalic acid, naphthalenedicarboxylic acid or a cycloalkyldicarboxylic acid, preferably
  • Cyclohexanedicarboxylic acid Very particular preference is given to polycarbonates or copolycarbonates, in particular having average molecular weights M w of from 500 to 100,000, preferably from 10,000 to 80,000, more preferably from 15,000 to 40,000 or blends thereof with at least one poly- or copolycondensate of terephthalic acid average molecular weights M w from 10,000 to 200,000, preferably from 26,000 to 120,000.
  • polyisocyanates or copolycondensates of terephthalic acid polyalkylene terephthalates are suitable in preferred embodiments of the invention.
  • 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 (Kunststoff-Handbuch, Vol. VIII, p. 695 ff, Karl Hanser Verlag, Kunststoff 1973 ).
  • Preferred polyalkylene terephthalates contain at least 80 mol%, preferably 90 mol%
  • Terephthalic acid residues based on the dicarboxylic acid component, and at least 80 mol%, preferably at least 90 mol% of ethylene glycol and / or butanediol-1,4- and / or 1,4-cyclohexanedimethanol radicals, based on the diol component.
  • the preferred polyalkylene terephthalates may contain up to 20 mol% of radicals of other aromatic dicarboxylic acids having 8 to 14 carbon atoms or aliphatic
  • Dicarboxylic acids having 4 to 12 carbon atoms such as radicals of phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic, adipic, sebacic, azelaic, cyclohexanediacetic.
  • the preferred polyalkylene terephthalates in addition to ethylene or butanediol-l, 4-glycol radicals up to 80 mol% of other aliphatic diols having 3 to 12 carbon atoms or cycloaliphatic
  • Diols having 6 to 21 carbon atoms for.
  • 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.
  • trihydric or trihydric alcohols or 3- or 4-basic carboxylic acids as z.
  • preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and -propane and pentaerythritol.
  • branching agent based on the acid component
  • branching agent based on the acid component
  • polyalkylene terephthalates which have been prepared solely from terephthalic acid and its reactive derivatives (for example their dialkyl esters) and ethylene glycol and / or 1,4-butanediol and / or 1,4-cyclohexanedimethanol radicals, and mixtures of these polyalkylene terephthalates.
  • Preferred polyalkylene terephthalates are also copolyesters which consist of at least two of the abovementioned acid components and / or of at least two of the abovementioned
  • Alcohol components are prepared, 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 parts by weight) at 25 ° C.
  • the blend of at least one polycarbonate or copolycarbonate with at least one poly- or copolycondensate of terephthalic acid is a blend of at least one polycarbonate or copolycarbonate with poly- or copolybutylene terephthalate or glycol-modified poly- or
  • Such a blend of polycarbonate or copolycarbonate with poly- or copolybutylene terephthalate or glycol-modified poly- or copolycyclohexanedimethylene terephthalate may preferably be one having from 1 to 90% by weight of polycarbonate or copolycarbonate and from 99 to 10% by weight of polyisocyanate or polycarbonate Copolybutylene terephthalate or glycol-modified poly- or Copolycyclohexandimethylenterephthalat, preferably with 1 to 90 wt .-% polycarbonate and 99 to 10 wt .-% polybutylene terephthalate or glycol-modified polycyclohexanedimethylene terephthalate, wherein the proportions add up to 100 wt .-%.
  • Such a blend of polycarbonate or copolycarbonate with poly- or copolybutylene terephthalate or glycol-modified poly- or copolycyclohexanedimethylene terephthalate may be particularly preferably of such a blend with 20 to 85
  • polycarbonate or copolycarbonate and 80 to 15% by weight of poly- or copolybutylene terephthalate or glycol-modified poly- or copolycyclohexanedimethylene terephthalate preferably with 20 to 85% by weight of polycarbonate and 80 to 15% by weight of polybutylene terephthalate or glycol modified polycyclohexanedimethylene terephthalate, wherein the proportions add up to 100 wt .-%.
  • such a blend can be obtained
  • Polycarbonate or copolycarbonate with poly- or copolybutylene terephthalate or glycol-modified poly- or Copolycyclohexandimethylenterephthalat to such with 35 to 80 wt .-% polycarbonate or copolycarbonate and 65 to 20 wt .-% poly- or Copolybutylenterephthalat or glycol-modified poly- or Copolycyclohexandimethylenterephthalat , preferably with 35 to 80 wt .-% polycarbonate and 65 to 20 wt .-% polybutylene terephthalate or glycol-modified polycyclohexanedimethylene terephthalate, wherein the proportions add to 100 wt .-%.
  • these may be blends of polycarbonate and glycol-modified polycyclohexanedimethylene terephthalate in the abovementioned compositions.
  • 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 or copolycarbonates can be carried out, inter alia, 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. As an example, let's just say quick,
  • production of the polycarbonates or copolycarbonates can be carried out in a known manner by the phase boundary process.
  • Diphenols in the presence of an inert organic solvent or solvent mixture which forms a second phase.
  • oligocarbonates are condensed with the aid of suitable catalysts to high molecular weight, dissolved in the organic phase, polycarbonates.
  • the organic phase is finally separated and the polycarbonate isolated from it by various work-up steps.
  • the preparation of the polycarbonates or copolycarbonates can also be carried out in a known manner by the melt transesterification process.
  • Suitable diphenols may be, for example, dihydroxyaryl compounds of the general formula (I)
  • dihydroxyaryl compounds examples include dihydroxybenzenes, dihydroxydiphenyls, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) -cycloalkanes, bis (hydroxyphenyl) -aryls, bis-
  • Preferred dihydroxyaryl compounds are, for example, resorcinol, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis (3, 5-dimethyl-4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) diphenylmethane , 1,1-bis (4-hydroxyphenyl) -1-phenyl-ethane, 1,1-bis (4-hydroxyphenyl) -l- (1-naphthyl) -ethane, 1,1-bis- (4-hydroxyphenyl) -1- hydroxyphenyl) -1- (2-naphthyl) ethane, 2,2-bis (4-hydroxyphenyl) -propane, 2,2-bis (3-methyl-4-hydroxyphenyl) -propane, 2,2-bis - (3,5-dimethyl-4-hydroxyphenyl) -propane, 2,2-bis (4-hydroxyphenyl) -1-phenyl-propane, 2,2-bis
  • R 1 and R 2 independently of one another are hydrogen, halogen, preferably chlorine or bromine,
  • n is an integer from 4 to 7, preferably 4 or 5
  • R 3 and R 4 are individually selectable for each X, independently hydrogen or QC 6 -
  • Preferred alkyl radical for the radicals R 3 and R 4 in formula (Ia) is methyl.
  • the X atoms in the alpha position to the diphenyl-substituted C atom (CI) are preferably not dialkyl-substituted, whereas alkyl disubstitution in the beta position to CI is preferred.
  • a most preferred dihydroxydiphenylcycloalkane of Formula I (Ia) is 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (Formula (Ia-I) where R 1 and R 2 are H).
  • Such polycarbonates can be prepared according to EP-A 359 953 from dihydroxydiphenylcycloalkanes of the formula (Ia).
  • dihydroxyaryl compounds are resorcinol, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) -diphenyl-methane, 1,1-bis- (4-hydroxyphenyl) -l-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, l Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1'-bis (4-hydroxyphenyl) -3,3,
  • Both a dihydroxyaryl compound to form homopolycarbonates and various dihydroxyaryl compounds to form copolycarbonates can be used. It is possible to use either a dihydroxyaryl compound of the formula (I) or (Ia) with the formation of
  • Homopolycarbonates and a plurality of dihydroxyaryl compounds of formula (I) and / or (Ia) are used to form copolycarbonates.
  • the various dihydroxyaryl compounds can be linked to one another both statistically and in blocks.
  • the molar ratio of dihydroxyaryl compounds of the formula (Ia) to the other dihydroxyaryl compounds of the formula (I) which may be used is preferably between 99 mol% (Ia) and 1 mol -% (I) and 2 mol% (Ia) to 98 mol% (I), preferably between 99 mol o / o (Ia) to 1 mol% (I) and 10 mol% (Ia) to 90 Mol% (I) and in particular between 99 mol% (Ia) to 1 mol% (I) and 30 mol% (Ia) to 70 mol% (I).
  • 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 for the preparation according to the melt transesterification process may be, for example, diaryl carbonates of the general formula (II)
  • R, R 'and R are independently the same or different and represent hydrogen, linear or branched Ci-C 34 alkyl, C 7 -C 34 - alkylaryl or C 6 -C 34 -ATyI further, R and -COO-R'"whereR" is hydrogen, linear or branched C r C 34 alkyl, C 7 -C 34 alkylaryl or C 6 -C 34 aryl.
  • Preferred diaryl carbonates are, for example, diphenyl carbonate, methylphenyl phenyl carbonates and di (methylphenyl) carbonates, 4-ethylphenyl phenyl carbonate, di (4-ethylphenyl) carbonate, 4-n-propylphenyl phenyl carbonate, di- (4-n-propylphenyl) carbonate, 4-iso-propylphenyl-phenyl-carbonate, di- (4-iso-propylphenyl) -carbonate, 4-n-butylphenyl-phenyl-carbonate, di- (4-n-propylphenyl) carbonate butylphenyl) carbonate, 4-iso-butylphenyl phenyl carbonate, di (4-iso-butylphenyl) carbonate, 4-tert-butylphenyl phenyl carbonate, di (4-tert-butylphenyl) carbonate, 4 -n-penty
  • 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.
  • R A is linear or branched Ci-C 34 -alkyl, C 34 -alkoxy, C 7 -C 34 alkylaryl, C 6 -C 34 -aryl or -COO-R 0, wherein R D is hydrogen linear or branched Ci-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 hydrogen, linear or branched C, -C 34 alkyl, C 7 -C 34 alkylaryl or C 6 -C 34 aryl.
  • Such MonohydroxyarylENSen are, for example, 1-, 2- or 3-methylphenol, 2,4-dimethylphenol 4-ethylphenol, 4-n-propylphenol, 4-iso-propylphenol, 4-n-butylphenol, 4- lSoButylphenol, 4-tert-butylphenol , 4-n-pentylphenol, 4-n-hexylphenol, 4-iso-octylphenol, 4-n-nonylphenol, 3-pentadecylphenol, 4-cyclohexylphenol, 4- (l-methyl-1-phenylethyl) -phenol, 4-phenylphenol , 4-phenoxyphenol, 4- (1-naphthyl) -phenol, 4- (2-naphthyl) -phenol, 4-t-tylphenol,
  • "Cio-C 25 -alkyl-substituted aryl” is preferably a phenyl or
  • Naphtyl radical which is substituted by Ci O -C 25 alkyl.
  • Such monohydroxyaryl compounds are, for example, n-decyl, n-undecyl, n-dodecyl, n-t-decyl, n-pentadecyl, n-hexadecyl, n-heptadecyl or n-octadecylphenol.
  • the phenols can carry these substituents m o-, m-, or p-position.
  • Particularly preferably suitable polycarbonates or copolycarbonates can be used for the further layer (s) (s) having a Vicat softening temperature nied ⁇ geren B / 50 (Sch ic h t) of more than 80 mol%, in particular more than 90 mol%, based to the total amount of chain terminators used, end groups of general formula (III), wherein R A is linear or branched C 10 -C 25 alkyl, C 10 -C 2 5-alkoxy or C 10 -C 25 alkyl-substituted aryl and R B and R c are independently the same or different and represent hydrogen, linear or branched C 10 -C 25 -alkyl, C 0 - containing C 25 alkoxy or C O -C 25 alkyl-substituted aryl.
  • R A is linear or branched C 10 -C 25 alkyl, C 10 -C 2 5-alkoxy or C 10 -C 25 alkyl-substituted ary
  • suitable polycarbonates or copolycarbonates for the further layer (s) with a lower Vicat Softening temperature B / 50 can also be up to 40 mol%, based on the total amount of chain terminators used, the end groups of other chain terminators of the general formula (III) are formed.
  • the measurement of the respective proportion of end groups can be determined e.g. determine by NMR spectroscopy about integration of aliphatic protons.
  • a more detailed analysis is the alkaline total saponification of the polycarbonate or copolycarbonate followed by HPLC analysis, with prior appropriate calibration with the pure substance, e.g. 4-n-pentadecylphenol is made.
  • the chain terminators of the general formula (III) are used in the preparation of the polycarbonates or copolycarbonates preferably in a total amount of 0.1 to 10 mol%, based on moles
  • Suitable branching agents may be compounds having three or more functional groups, preferably those having three or more hydroxyl groups. Usually trisphenols, quarterphenols or acid chlorides of tri- or tetracarboxylic acids are used, or mixtures of polyphenols or acid chlorides.
  • Suitable compounds having three or more phenolic hydroxyl groups are, for example, phloroglucinol, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -hepten-2, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) heptane, 1, 3,5-tri- (4-hydroxyphenyl) -benzene, 1,1,1-tris (4-hydroxyphenyl) -ethane, tri- (4-hydroxyphenyl) -phenylmethane, 2,2-bis (4,4-bis (4-hydroxyphenyl) cyclohexyl] propane, 2,4-bis (4-hydroxyphenyl-isopropyl) -phenol and tetra (4-hydroxyphenyl) -methane.
  • Suitable compounds having three and more functional groups are, for example, 2,4-dihydroxybenzoic acid, trimesic acid (trichloride), cyanuric trichloride and 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole.
  • Preferred branching agents are 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole and
  • thermoplastic polymeric materials may be mixed with various additives.
  • additives serves to extend service life or color (stabilizers), to simplify processing (e.g., demulsifiers, flow aids, antistatic agents), or to tailor polymer properties to particular loads
  • additives can be added individually or in any desired mixtures or several different mixtures of the polymer melt, namely directly in the isolation of the polymer or after melting of granules in a so-called Compounding.
  • the additives or their mixtures may be added as a solid, ie as a powder, or as a melt of the polymer melt.
  • Another type of dosing is the use of masterbatches or mixtures of masterbatches of the additives or additive mixtures.
  • laser-sensitive write-on additives can be added by laser engraving.
  • laser-sensitive additives are for example so-called laser marking additives in question, i. those from an absorber in the wavelength range of the laser to be used, preferably in the wavelength range of ND: YAG lasers (neodymium-doped yttrium-aluminum-garnet lasers).
  • laser marking additives and their use in molding compositions are described, for example, in WO-A 2004/50766 and WO-A 2004/50767 and are described by the
  • DSM under the brand name Micabs ® commercially offered.
  • suitable absorbers carbon black, coated layer silicates such as, for example, in DE-A-described 195 22 397 and commercially available under the brand names Lazerflair ®, antimony-doped tin oxide such as described in US 6,693,657 and commercially available under the brand names of Mark-it TM, and phosphorus-containing tin-copper mixed oxides such as in WO-A
  • Laser-sensitive additives are preferred for laser engraving inscription from dark to light background.
  • Particularly preferred laser-sensitive additives in the context of the invention are black pigments.
  • a most preferred laser-sensitive additive is carbon black.
  • fillers may be added to the thermoplastic polymeric materials.
  • the filler may be, for example and preferably, at least one color pigment and / or at least one other filler for producing a translucency of the filled layers, such as e.g. e.g. Conventional inorganic pigments, especially metals or metal oxides such as aluminum oxides, silicic acid, titanites, and alkaline metal salts such as carbonates or sulfates of calcium or barium, particularly preferably a white pigment, most preferably titanium dioxide, zirconium dioxide or barium sulfate, in a preferred embodiment to titanium dioxide ,
  • the fillers mentioned are preferably used in amounts of from 2 to 45% by weight, more preferably from 5 to 30% by weight, based on the total weight of filler and thermoplastic, of the thermoplastics prior to shaping into the plastic film, which, for example by extrusion or coextrusion added.
  • the layer structure for the process according to the invention comprises at least one cover layer and the thermoplastic, polymeric material of the cover layer has a Vicat softening temperature B / 50 ( DeCkschi cht) , which is higher than the Vicat softening temperature
  • the Vicat softening temperature B / 50 (DeCks c h ic h t) is at least 5 ° C higher, preferably at least 10 0 C higher than the Vicat softening temperature B / 50 (s Ch ic h t) -
  • the layer structure to be laminated is produced in such a way that films made of the respective thermoplastic, polymeric materials with the respective thermoplastic, polymeric materials with the respective thermoplastic, polymeric materials with the respective thermoplastic, polymeric materials with the respective thermoplastic, polymeric materials with the respective thermoplastic, polymeric materials with the respective thermoplastic, polymeric materials with the respective thermoplastic, polymeric materials with the respective thermoplastic, polymeric materials with the respective thermoplastic, polymeric materials with the respective thermoplastic, polymeric materials with the respective
  • Vicat softening temperatures B / 50 formed a corresponding Fohenstapel and this is then laminated according to the invention in two stages.
  • the component to be embedded is applied to the film for producing the base layer prior to formation of the film stack.
  • the component may, prior to formation of the film stack on the film for the production of the base layer by means of known measures, such. Lamimeren, welding, clamping, press-fitting, gluing and / or printing to avoid changing the position during the lamination process.
  • the component can also be placed without fixing on the base layer.
  • Softening temperature B / 50 (Sch , c ht) is and a maximum of 5 0 C above, but preferably below the Vicat softening temperature B / 50 (Bas is ) hudes, applied, by which the further (s) layer (s) containing at least one polycarbonate or Copolacarbonat with a lower Vicat softening point B / 50 (sc h ic ht) softens (soften). Since base and top layer (s) do not soften at this temperature or not yet completely, it comes to a gentle
  • the layer structure at a temperature above, preferably 5 to 50 0 C, more preferably 10 to 40 0 C, most preferably 20 to 35 0 C above the Vicat softening temperature B / 50 (Bas i s) halls laminated (cf., schematic representation m Fig. 5).
  • the Lamimerdruck is in the first lamination for gentle flow preferably 2 to 100 N / cm 2 , in the second
  • Laminiersch ⁇ tt during heating and cooling preferably 100 to 400 N / cm 2 .
  • a pressure of 10 to 30 N / cm 2 is particularly preferred in the first lamination for gentle flow, and a pressure of 150 to 350 N / cm 2 in the second lamination cycle during heating and cooling.
  • the lamination time can preferably be between a few minutes and more than one hour. Preferably, depending on the number to be laminated
  • Foils in the foil stack a lamination time of 1 to 30 minutes.
  • 4 shows schematically a foil stack with a base layer (3), a component to be embedded in the form of a chip (1) and an antenna (2), two intermediate layers (4) which together have approximately the height of the chip (1) and a cover layer (5), which in the first step of the inventive method with pressurization with a first laminating pressure P at a temperature T above the Vicat softening temperature B / 50 (Sch ic h t) and at most 5 0 C above, but preferably below the Vicat Softening temperature B / 50 ( B asis) is laminated.
  • FIG. 5 schematically shows the film stack laminated according to FIG. 4, which is laminated in the second step of the method according to the invention with pressurization with a second laminating pressure P at a temperature T above the Vicat softening temperature B / 50 (BaS i s) .
  • Further subject of the present invention is a layer structure containing
  • thermoplastic polymeric material having a lower Vicat softening temperature B / 50 ( Schig h ) than the thermoplastic polymeric material of the base layer
  • thermoplastic, polymeric Mate ⁇ al optionally at least one cover layer of a thermoplastic, polymeric Mate ⁇ al,
  • thermoplastic, polymeric Mate ⁇ al with medi gerer Vicat softening temperature B / 50 (Sch ic h t ) wherein at least one component is contained between the base layer and the further layer of a thermoplastic, polymeric Mate ⁇ al with medi gerer Vicat softening temperature B / 50 (Sch ic h t ) .
  • the layer structure is preferably a film stack of corresponding films and the electronic component between the film for producing the base layer and the - optionally first - further layer, wherein the component may be attached to the base layer or not.
  • the respective films can be made of the aforementioned thermoplastic, polymeric
  • Mate ⁇ ahen be prepared by extrusion or coextrusion. These methods are known to the person skilled in the art and adequately described in the literature.
  • the thickness of the suitable films is preferably 5 to 1000, ⁇ m, more preferably 5 to 850.
  • the foils can be smooth on one side or both sides or matt or structured on one or both sides.
  • a further subject of the present invention is therefore a laminated layer composite obtainable by the process according to the invention.
  • the layers in the layer composite or layer structure according to the invention may consist of the same or different materials. Even though layers consist predominantly of the same thermoplastic, polymeric material, they are nevertheless different layers for the purposes of the present invention, when incorporated in e.g. be applied in separate steps, contain different additives or have different properties.
  • At least one layer means that the layer composite or layer structure according to the invention can have one or more such layers.
  • the laminated layer composite according to the invention can be part of security and / or value documents.
  • the security and / or value document may be, for example, data carriers in the form of cards and identity cards, e.g. Smart ID cards, smart cards in general, EC cards, credit cards, insurance cards, passports, RFID tags, driving licenses etc act.
  • data carriers in the form of cards and identity cards, e.g. Smart ID cards, smart cards in general, EC cards, credit cards, insurance cards, passports, RFID tags, driving licenses etc act.
  • layers which provide UV protection, protection against mechanical damage - e.g. Scratch-resistant coatings - etc. have.
  • layers can also be subsequently applied to the laminated layer composite according to the invention. This can be done for example by gluing or another laminating step.
  • Example 1 Preparation of a polycarbonate granulate for the preparation of the further layer (s) with low Vicat softening temperature B / 50fSrhi ⁇ -hn
  • the organic phase was acidified after separating the aqueous phase with phosphoric acid and washed neutral with distilled water and salt-free. After solvent exchange against chlorobenzene, the product was extruded at 290 0 C and 80 revolutions / min at 0.1 mbar via a Ausdampffextruder and granulated through a granulator.
  • Example 2 Compounding of a Masterbatch for the Production of the Base Layer Containing a Thermoplastic Plastic and a White Pigment as Filler
  • a masterbatch was compounded with the following composition and then granulated:
  • Example 1 Each film from the granules according to Example 1, the masterbatch of Example 2 and pure polycarbonate Makrolon ® 3108 Fa. Bayer Material Science AG were extruded.
  • the respective polycarbonate films had a width of 350 mm.
  • the melt reached the casting roll and then the cooling roll, the rolls having the temperature mentioned in Tab. 1. Subsequently, the film was transported through a trigger and then wound up.
  • Example 1 From the granules according to Example 1 films of thickness of 100 microns were prepared. From the masterbatch according to Example 2 foils of thickness of 105 microns and 150 microns were prepared.
  • Example 4 Production of a laminated layer composite according to the invention
  • the further layers were realized with transparent material, the base and cover layers with white material in order to be able to recognize the Matenal flow in microscopic images.
  • the film stack was then laminated in a first Lammier Colour at a temperature of 140 0 C and a pressure of 15 N / cm 2 for 10 minutes in the press. Then the press was heated to a temperature of 180 0 C and exposed to the vorlammATOR layer structure in a second step for 2 minutes at a pressure of 300 N / cm 2. Subsequently, the laminated layer composite was cooled at a pressure of 300 N / cm 2 to a temperature of 40 0 C and finally removed from the press.
  • the further layers were realized with transparent material, the base and cover layers with white material in order to be able to recognize the material flow in microscopic images.
  • the film stack was then laminated in a first Lammiersch ⁇ tt at a temperature of 140 0 C and a pressure of 15 N / cm 2 for 10 minutes in the press. Then the press was heated to a temperature of 180 0 C and exposed to the vorlammATOR layer structure in a second step for 2 minutes at a pressure of 300 N / cm 2. Subsequently, the laminated layer composite was cooled at a pressure of 300 N / cm 2 to a temperature of 40 0 C and finally removed from the press.
  • the base and top coats were pressed into the die gap during the lamimer process.
  • Antenna was stretched greatly and the connection between antenna and chip was torn and no longer functional.

Landscapes

  • Laminated Bodies (AREA)

Abstract

La présente invention concerne un procédé de production d'un composite multicouche laminé, selon au moins une couche de base (3) et au moins une autre couche de base (4), qui sont réalisées dans deux matières thermoplastiques ayant des températures de ramollissement Vicat B/50 différentes et entre lesquelles est intercalé un composant (1), sont laminées pour obtenir un composite multicouche. L'invention concerne également une structure en couche adaptée à ce procédé, un composite multicouche produit selon ce procédé et un document de sécurité et/ou de valeur contenant un tel composite multicouche laminé.
EP10702440A 2009-02-13 2010-01-30 Procédé amélioré de production d'un composite multicouche laminé Withdrawn EP2396172A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP10702440A EP2396172A1 (fr) 2009-02-13 2010-01-30 Procédé amélioré de production d'un composite multicouche laminé

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP09002025A EP2218579A1 (fr) 2009-02-13 2009-02-13 Procédé amélioré destiné à la fabrication d'un composite stratifié laminé
EP10702440A EP2396172A1 (fr) 2009-02-13 2010-01-30 Procédé amélioré de production d'un composite multicouche laminé
PCT/EP2010/000566 WO2010091796A1 (fr) 2009-02-13 2010-01-30 Procédé amélioré de production d'un composite multicouche laminé

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EP2396172A1 true EP2396172A1 (fr) 2011-12-21

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EP10702440A Withdrawn EP2396172A1 (fr) 2009-02-13 2010-01-30 Procédé amélioré de production d'un composite multicouche laminé

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BR (1) BRPI1007980A2 (fr)
CA (1) CA2752100A1 (fr)
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EP2441589A1 (fr) 2010-10-14 2012-04-18 Bayer Material Science AG Document de sécurité et/ou de valeur contenant un convertisseur électromécanique
EP2455228A1 (fr) 2010-11-18 2012-05-23 Bayer Material Science AG Document de sécurité et/ou de valeur contenant un convertisseur électromécanique
CN104896211B (zh) * 2015-04-28 2017-06-20 南京林业大学 高性能木基复合压力输送管及制备方法
JP6358311B2 (ja) * 2016-11-17 2018-07-18 東洋製罐株式会社 積層フィルムの立体成形方法
EP3501819A1 (fr) * 2017-12-22 2019-06-26 Covestro Deutschland AG Feuilles en matière plastique pour document d'id à luminosité des hologrammes estampés améliorée
EP3623148A1 (fr) * 2018-09-14 2020-03-18 Covestro Deutschland AG Procédé de fabrication d'un laminé comportant des composants électroniques et / ou des unités fonctionnelles
EP3890971B1 (fr) 2018-12-03 2024-08-28 Covestro Deutschland AG Feuilles en matière plastique à température de ramollissement vicat plus élevée dans les structures stratifiées
CN117642290A (zh) * 2021-07-14 2024-03-01 科思创德国股份有限公司 适合于快速层压的膜结构

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WO2010091796A1 (fr) 2010-08-19
TW201041738A (en) 2010-12-01
EP2218579A1 (fr) 2010-08-18
CA2752100A1 (fr) 2010-08-19

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