EP4370333A1

EP4370333A1 - Special polymer layers for faster laminability of multilayer structures

Info

Publication number: EP4370333A1
Application number: EP22747684.3A
Authority: EP
Inventors: Heinz Pudleiner; Georgios Tziovaras; Wieland Hovestadt; Stefan Janke; Kira PLANKEN
Original assignee: Covestro Deutschland AG
Current assignee: Covestro Deutschland AG
Priority date: 2021-07-14
Filing date: 2022-07-11
Publication date: 2024-05-22
Also published as: EP4119344A1; WO2023285356A1; CN117677499A; US20240308191A1

Abstract

The invention relates to a multilayer structure (MS) comprising (SI) at least one first polymer layer (SI) comprising ≥ 95% by weight, preferably ≥ 98% by weight, particularly preferably ≥ 99% by weight, based on the total weight of the polymer layer (SI), of a polymer (PI) selected from the group consisting of a polycarbonate, a co-polycarbonate or mixtures thereof having a Vicat softening temperature ≥ 149°C, preferably ≥ 160°C, further preferably ≥ 170°C; more preferably ≥180°C, determined according to ISO 306:2004 (50N; 50°/h); (S2) at least one further polymer layer (S2) having a Vicat softening temperature < 149°C, preferably ≤ 140°C, more preferably ≤ 130°C, determined according to ISO 306:2004 (50N; 50°/h), preferably in a range from 120°C to 148°C; (S3) optionally at least one third polymer layer (S3) having a Vicat softening temperature ≥ 149°C, preferably ≥ 160°C, further preferably ≥ 170°C; more preferably ≥ 180°C, determined according to ISO 306:2004 (50N; 50°/h). The invention further relates to a process for producing a multilayer structure (MS) and to a security document comprising such a multilayer structure according to the invention.

Description

Special polymer layers for faster lamination of multi-layer structures

The invention relates to a multilayer structure comprising at least two layers (S1) and (S2) and optionally further layers (S3), wherein at least one outer layer (S1) or (S3) contains a polymer (PI) or (P3) which has a Vicat softening point > 149°C. Furthermore, the invention relates to a method for producing the multi-layer structure (MA), the use of the multi-layer structure (MA) for the production of laminates or security documents and the security document containing the multi-layer structure (MA).

The lamination of polymer films is interesting in many areas of application. When laminating different polymer films, problems of air inclusions, bubble formation or other deformations of the laminates occur again and again for a wide variety of reasons. The incompatibility of the polymer materials plays a major role here, as do the properties of the polymers used. Furthermore, there is a great need in the production of laminates on the one hand to produce a durable product, on the other hand to be flexible in the choice of materials and also to carry out the lamination as quickly as possible. Therefore, there is a great and long-lasting need in the industry to generate the complex production of laminates as quickly and efficiently as possible.

It was therefore an object of this invention to minimize at least one of the problems mentioned. Furthermore, it was an object of the invention to find and use a combination of materials which, on the one hand, enables complex laminates to be built into the layer structure, which is also relevant in particular for security documents, and, on the other hand, enables cost-efficient and rapid production.

Surprisingly, it was found that the combination of features from claim 1 solves these problems.

A first subject matter of the invention relates to a multi-layer structure (MA), comprising

(51) at least one first polymer layer (S1) which is >95% by weight, preferably >98% by weight, particularly preferably >99% by weight, based on the total weight of the polymer layer (S1) a polymer (PI) selected from the group consisting of a polycarbonate, a co-polycarbonate or mixtures thereof, which has a Vicat softening point > 149°C, preferably > 160°C, more preferably > 170°C; more preferably > 180°C, determined according to ISO 306:2004 (50N; 50°/h);

(52) at least one further polymer layer (S2) which has a Vicat softening point <149° C., preferably <140° C., more preferably <130° C. determined according to ISO 306:2004 (50N; 50°/h). in a range of 120 to 148 °C;

(53) optionally at least one third polymer layer (S3) which has a Vicat

softening point >149°C, preferably >160°C, more preferably >170°C; more preferably >180°C, determined according to ISO 306:2004 (50N; 50°/h). The multi-layer structure (MA) is preferably a component of a security document or the security document itself, in particular the data page of a passport or an identity card or other ID cards.

Depending on which substrate or base is to be processed into a laminate with the multi-layer structure (MA), the multi-layer structure (MA) either only has the two layers (Sl) and (S2), with the polymer layer (Sl) being an outside of the resulting Laminate forms, or additionally the third polymer layer (S3). The use of the third polymer layer (S3) can help to protect heat-sensitive layers in the laminate that are located between the substrate and the multi-layer structure (MA) or the substrate itself from excessive temperatures during the lamination process.

The polymer (PI) is preferably selected from the group consisting of aliphatic or aromatic polycarbonates or co-polycarbonates.

Aromatic polycarbonates or co-polycarbonates are preferably suitable as polycarbonates or co-polycarbonates.

The polycarbonates or co-polycarbonates can be linear or branched in a known manner.

These polycarbonates or co-polycarbonates can be produced in a known manner from diphenols, carbonic acid derivatives, chain terminators if appropriate and branching agents if appropriate. Details of the production of polycarbonates and co-polycarbonates have been laid down in many patent specifications for about 40 years. An example is Schnell, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Volume 9, Interscience Publishers, New York, London, Sydney 1964, on D. Freitag, U. Grigo, P. R. Müller, H. Nouvertne', BAYER AG, "Polycarbonates" in Encyclopedia of Polymer Science and Engineering, Volume 11, Second Edition, 1988, pages 648-718 and finally to Drs. U. Grigo, K. Kirchner and P. R. Müller "Polycarbonate" in Becker/Braun, Kunststoff- Handbuch, Volume 3/1, Polycarbonate, Polyacetal, Polyester, Celluloseester, Carl Hanser Verlag Munich, Vienna 1992, pages 117-299. In the "Encyclopedia of Polymer Science and Technology", John Wiley & Sons, Inc., by Daniel J. Brunelle, the article "Polycarbonates" on pages 1 to 33 not only describes the production of suitable polycarbonates or co-polycarbonates described in particular in Table 3 on pages 10 to 13 aromatic polycarbonates based on bisphenols.

Suitable diphenols can be, for example, dihydroxyaryl compounds of the general formula (I),

HO-Z-OH (I) where Z is an aromatic radical having 6 to 34 carbon atoms, which can contain one or more optionally substituted aromatic nuclei and aliphatic or cycloaliphatic radicals or alkylaryls or heteroatoms as bridge members.

Examples of suitable dihydroxyaryl compounds are: dihydroxybenzenes, dihydroxydiphenyls, bis(hydroxyphenyl) alkanes, bis(hydroxyphenyl) cycloalkanes, bis(hydroxyphenyl) aryls, bis(hydroxyphenyl) ketones, bis(hydroxyphenyl) sulfones, Bis(hydroxyphenyl) sulfoxides and their nucleus-alkylated and nucleus-halogenated compounds.

These and other suitable other dihydroxyaryl compounds are described, for example, in DE-A 3 832 396, FR-A 1 561 518, in H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964, pp. 28 et seq.; p.102 ff. and in D.G. Legrand, J.T. Bendler, Handbook of Polycarbonate Science and Technology, Marcel Dekker New York 2000, p. 72 et seq.

Examples of preferred dihydroxyaryl compounds are 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)- 1 -( 1 - naphthyl)-ethane, l,l-bis-(4- hydroxyphenyl)-1-(2-naphthyl)ethane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)-1-phenylpropane , 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 2,4-bis(3,5-dimethyl-4- hydroxyphenyl)-2-methylbutane, l,l-bis(4-hydroxyphenyl)cyclohexane, l,l-bis(3,5-dimethyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(4- hydroxyphenyl)-4-methylcyclohexane, 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, 1,1'-bis(4-hydroxyphenyl)-3-diisopropylbenzene, l,l'-bis(4-hydroxyphenyl)-4-diisopropylbenzene, l,3-bis[2-(3,5-dimethyl-4-hydroxyphenyl)-2-propyl]benzene, bis( 4-hydroxyphenyl) sulfone, bis(3,5-dimethyl-4-hydroxy phenyl) sulfone and 2,2',3,3'-tetrahydro-3,3,3',3'-tetramethyl-1,r-spirobi[1H-indene]-5,5'-diol or mixtures of at least two of these.

Particularly preferred dihydroxyaryl compounds are resorcinol, 4,4'-dihydroxydiphenyl, bis(4-hydroxyphenyl)diphenylmethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 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, l,l-bis(4-hydroxyphenyl)cyclohexane, l,l-bis(3,5-dimethyl-4-hydroxyphenyl)cyclohexane, l,l- Bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1'-bis(4-hydroxyphenyl)-3-diisopropylbenzene and 1,1'-bis(4-hydroxyphenyl)- 4-diisopropylbenzene or mixtures of at least two of these.

Very particularly preferred dihydroxyaryl compounds are 4,4'-dihydroxydiphenyl and 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane.

Both a dihydroxyaryl compound to form homopolycarbonates and different dihydroxyaryl compounds to form co-polycarbonates can be used. Both one dihydroxyaryl compound of formula (I) or (Ia) (formula shown below) to form homopolycarbonates and several one dihydroxyaryl compounds of formula (I) and/or (Ia) to form co-polycarbonates can be used. The various dihydroxyaryl compounds can be linked to one another either randomly or in blocks. In the case of co-polycarbonates of dihydroxyaryl compounds of the formula (I) and (Ia), the molar ratio of dihydroxyaryl compounds of the formula (Ia) to the other dihydroxyaryl compounds of the formula (I) that may also be used is preferably between 99 mol % of (Ia). 1 mol% (I) and 2 mol% (Ia) to 98 mol% (I), preferably between 99 mol% (Ia) to 1 mol% (I) and 10 mol% (Ia). 90% by moles of (I) and in particular between 99% by moles of (Ia) to 1% by moles of (I) and 30% by moles of (Ia) to 70% by moles of (I).

A very particularly preferred co-polycarbonate can be prepared using 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and dihydroxyaryl compounds of the formula (Ia) and (I).

Suitable carbonic acid derivatives can be, for example, diaryl carbonates of the general formula (II), wherein

R, R 'and R "are independently identical or different for hydrogen, linear or branched Ci-C34-alkyl, C ₆ -C34-alkylaryl or G, -CA- aryl, R can also mean -COO-R", where R" represents hydrogen, linear or branched Ci-C34-alkyl, C ₆ -C34-alkylaryl or G-CA-aryl.

Preferred diaryl carbonates are, for example, diphenyl carbonate, methylphenyl phenyl carbonate and di-(methylphenyl) carbonate, 4-ethylphenyl phenyl carbonate, di-(4-ethylphenyl) carbonate, 4-n-propylphenyl phenyl carbonate, di- (4-n-propylphenyl) carbonate, 4-isopropylphenyl phenyl carbonate, di(4-isopropylphenyl) carbonate, 4-n-butylphenyl phenyl carbonate, di(4-n-butylphenyl). )-carbonate, 4-iso-butylphenyl-phenyl-carbonate, di-(4-iso-butylphenyl)-carbonate, 4-tert-butylphenyl-phenyl-carbonate, di-(4-tert-butylphenyl)-carbonate, 4- n-pentylphenyl phenyl carbonate, di-(4-n-pentylphenyl) carbonate, 4-n-hexylphenyl phenyl carbonate, di-(4-n-hexylphenyl) carbonate, 4-iso-octylphenyl phenyl carbonate, di(4-iso-octylphenyl) carbonate, 4-n-nonylphenyl phenyl carbonate, di(4-n-nonylphenyl) carbonate, 4-cyclohexylphenyl phenyl carbonate, di(4-cyclohexylphenyl). )-carbonate, 4-( 1 -methyl- 1 -phenylethyl)-phenyl -phenyl -carbonate, di-[4-( 1 -methyl- l-phenylethyl)-phenyl] -carbonate, biphenyl -4-yl-phenyl- approx carbonate, di-(biphenyl-4-yl)-carbonate, 4- ( 1 -Naphthyl)phenyl phenyl carbonate, 4-(2-Naphthyl)phenyl phenyl carbonate, Di[4-( 1 -naphthyl)phenyl] carbonate, Di[4-(2- naphthyl)phenyl] carbonate, 4-phenoxyphenyl phenyl carbonate, di(4-phenoxyphenyl) carbonate, 3-pentadecylphenyl phenyl carbonate, di(3-pentadecylphenyl) carbonate, 4-tritylphenyl phenyl carbonate , Di(4-tritylphenyl) carbonate, Methyl salicylate phenyl carbonate, Di(methyl salicylate) carbonate, Ethyl salicylate phenyl carbonate, Di(ethyl salicylate) carbonate, n-Propyl salicylate phenyl carbonate, Di( n-propyl salicylate carbonate, iso-propyl salicylate phenyl carbonate, di(iso-propyl salicylate) carbonate, n-butyl salicylate phenyl carbonate, di(n-butyl salicylate) carbonate, iso-butyl salicylate phenyl carbonate , di(iso-butyl salicylate) carbonate, tert-butyl salicylate phenyl carbonate, di(tert-butyl salicylate) carbonate, di(phenyl salicylate) carbonate and di(benzyl salicylate) carbonate.

Particularly preferred 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. Diphenyl carbonate is very particularly preferred.

Both a diaryl carbonate and various diaryl carbonates can be used.

To control or change the end groups, one or more monohydroxyaryl compound(s) can additionally be used as chain terminators, for example, which were not used to prepare the diaryl carbonate(s) used. These can be those of the general formula (III), in which

R ^A is linear or branched Ci-C34-alkyl, C ₆ -C34-alkylaryl, GG-aryl or -COO- R ^D where R ^D is hydrogen, linear or branched Ci-C34-alkyl, C7-C34- alkylaryl or GG -aryl, and

R ^B , R ^c , independently of one another, are identical or different for hydrogen, linear or branched Ci-C34-alkyl, C7-C34-alkylaryl or GG-aryl.

Preferred monohydroxyaryl compounds are 1-, 2- or 3-methylphenol, 2,4-dimethylphenol, 4-ethylphenol, 4-n-propylphenol, 4-isopropylphenol, 4-n-butylphenol, 4-isobutylphenol, 4-tert-butylphenol, 4-n-pentylphenol, 4-n-hexylphenol, 4-iso-octylphenol, 4-n-nonylphenol, 3- Pentadecylphenol, 4-cyclohexylphenol, 4-(1-methyl-1-phenylethyl)-phenol, 4-phenylphenol, 4-phenoxyphenol, 4-(1-naphthyl)-phenol, 4-(2-naphthyl)-phenol, 4- tritylphenol, methyl salicylate, ethyl salicylate, n-propyl salicylate, iso-propyl salicylate, n-butyl salicylate, iso-butyl salicylate, tert-butyl salicylate, phenyl salicylate and benzyl salicylate.

4-tert-butylphenol, 4-iso-octylphenol and 3-pentadecylphenol are particularly preferred.

Suitable branching agents can be compounds with three or more functional groups, preferably those with three or more hydroxyl groups.

Examples of suitable compounds having three or more phenolic hydroxyl groups are phloroglucinol, 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-heptene-2,4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl)-heptane, l,3,5-tri-(4-hydroxyphenyl)-benzene, l,l,l-tri-(4-hydroxyphenyl)-ethane, tri-(4-hydroxyphenyl)-phenylmethane, 2,2-bis(4,4-bis(4-hydroxyphenyl)cyclohexyl]propane, 2,4-bis(4-hydroxyphenylisopropyl)phenol and tetra(4-hydroxyphenyl)methane.

Examples of other suitable compounds having three or more functional groups are 2,4-dihydroxybenzoic acid, trimesic acid (trichloride), cyanuric acid 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 1,1,1-tri(4-hydroxyphenyl)ethane.

Furthermore, the polymer layer (S1) can contain additives, such as fillers, dyes, pigments, UV stabilizers and other additives, as also explained further below in connection with the polymer layer (S3).

The first polymer layer (S1) preferably has a transparency in the visible wavelength range, preferably in the range from >70% to <99%, preferably from >80% to <95%, particularly preferably >90% to <93%, determined according to ISO 13468-2:2006-07 on.

The further polymer layer (S2) preferably has transparency in the visible wavelength range, preferably in the range from >70% to <99%, preferably from >80% to <95%, particularly preferably >88% to <93%, determined according to ISO 13468 -2:2006-07 on.

In a preferred embodiment of the multilayer structure (MA), the polymer layer (S2) contains at least one polymer (P2) selected from the group consisting of a polycarbonate, a mixture or blend of a polycarbonate and a copolyester or mixtures of at least two of these .

Suitable diphenols can be, for example, dihydroxyaryl compounds of the general formula (I) as already indicated above for the diphenols for the polymer (PI). Therefore, for all statements on the diphenols at this point, reference is made to the statements above, which apply equally to the diphenols of the polymer (P2). Both a dihydroxyaryl compound to form homopolycarbonates and different dihydroxyaryl compounds to form co-polycarbonates can be used. Both one dihydroxyaryl compound of the formula (I) or (Ia) to form homopolycarbonates and one or more dihydroxyaryl compounds of the formula (I) and/or (Ia) to form copolycarbonates can be used. The various dihydroxyaryl compounds can be linked to one another either randomly or in blocks. In the case of co-polycarbonates of dihydroxyaryl compounds of the formula (I) and (Ia), the molar ratio of dihydroxyaryl compounds of the formula (Ia) to the other dihydroxyaryl compounds of the formula (I) that may also be used is preferably between 99 mol % of (Ia). 1 mol% (I) and 2 mol% (Ia) to 98 mol% (I), preferably between 99 mol% (Ia) to 1 mol% (I) and 10 mol% (Ia). 90% by moles of (I) and in particular between 99% by moles of (Ia) to 1% by moles of (I) and 30% by moles of (Ia) to 70% by moles of (I).

In addition to the examples of suitable dihydroxyaryl compounds listed for (PI), the following are particularly suitable for forming polymer (P2): bis(hydroxyphenyl) ether, bis(hydroxyphenyl) sulfides, l,r-bis(hydroxyphenyl)diisopropylbenzenes, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, bis(4-hydroxyphenyl) ether, bis(4-hydroxyphenyl)- sulfide, particularly preferably 2,2-bis(4-hydroxyphenyl)propane, and their nucleus-alkylated and nucleus-halogenated compounds, and mixtures of at least two of these.

For suitable carbonic acid derivatives of the general formula (II) and the chain terminators of the general formula (III), reference is also made at this point to the statements relating to the polymer (PI), which applies equally to the polymer (P2).

The polymer layer (S2) contains the polymer (P2) preferably in a range from 50 to 100% by weight, more preferably in a range from 70 to 98% by weight, more preferably in a range from 80 to 95% by weight. % based on the total weight of the polymer layer (S2).

Furthermore, the polymer layer (S2) can contain additives, such as fillers, dyes, pigments, UV stabilizers and other additives, as explained below.

In a preferred embodiment of the multilayer structure (MA), the polymer layer (S3) contains at least one polymer (P3) selected from the group consisting of a polycarbonate, a copolycarbonate and mixtures of at least two of these. The polymer (P3) is preferably selected from the same group of polycarbonates or co-polycarbonates as the polymer (PI). The polymer (P3) is preferably the same as the polymer (PI).

For the general structure of the polymer (P3), reference is made to the statements, components and other information on the polymer (PI), which are equally applicable to the polymer (P3). Even if the components are basically the same can be selected by selection some different components, the polymer (P3) may have a different structure than the polymer (PI).

The further polymer layer (S3) preferably contains the polymer (P3) in an amount in a range from >80 to 100% by weight, preferably in a range from >90 to 99% by weight, particularly preferably from >95 to 98% % by weight, based on the total weight of the polymer layer (S3). Furthermore, the polymer layer (S3) can contain additives, such as fillers, dyes, pigments, UV stabilizers and other additives, as explained below.

The polymer layer (S3) preferably has the same composition of polymers as the polymer layer (S1). The polymer (P3) is preferably identical to the polymer (PI). The polymer layer (S3) is preferably identical to the polymer layer (S1).

The polymer layer (S3) is preferably used when the substrate onto which the multilayer structure (MA) is to be laminated contains a polymer which has a similar melting point to the polymer composition of the polymer (P3).

The polymer layer (S3) preferably has a transparency in the visible wavelength range, preferably in the range from >70% to <99%, preferably from >80% to <95%, particularly preferably

> 88% to < 93%, determined according to ISO 13468-2:2006-07.

In a preferred embodiment of the multilayer structure (MA), the polymer (PI) or the polymer (P3) is a polycarbonate or co-poly carbonate of the formula (Ia), (1-2), (1-3) or (1-4). ), where (Ia) wherein

R ¹ and R ² are independently hydrogen, halogen, preferably chlorine or bromine,

Ci-Cs-alkyl, G-G-cycloalkyl. G-Cio-Aryl. preferably phenyl, and C7-C12 aralkyl, preferably phenyl-Ci-C4-alkyl, in particular benzyl, m is an integer from 4 to 7, preferably 4 or 5,

R ³ and R ⁴ can be selected individually for each X, independently of one another hydrogen or Ci-G,- alkyl and X is carbon, with the proviso that on at least one atom X, R ³ and R ⁴ are simultaneously alkyl, or in which R ⁵ is a C 1 -C 10 alkyl radical, aralkyl radical or aryl radical, preferably a methyl radical or phenyl radical, very particularly preferably a methyl radical.

The one or more polycarbonate or co-polycarbonate based on diphenols of the polymer layer (S1) or (S3) preferably has an _Mw (weight-average molecular weight, determined by size exclusion chromatography (SCE) after prior calibration with polycarbonate calibration substances) of at least 10,000 g/mol, preferably from 15,000 g/mol to 300,000 g/mol, particularly preferably 17,000 to 36,000 g/mol, very particularly preferably 17,000 to 34,000 g/mol. on. The polymers (PI) or (P3) can be linear or branched, they can be homopolycarbonates or copolycarbonates.

The at least one polycarbonate or co-polycarbonate based on diphenols of at least the polymer (PI) or polymer (P3) preferably comprises a carbonate structural unit of the formula (1-1).

These polycarbonates or co-polycarbonates can be produced in a known manner from diphenols, carbonic acid derivatives, chain terminators if appropriate and branching agents if appropriate. Details of the production of polycarbonates have been laid down in many patent specifications for about 40 years. As an example here only on H. Schnell, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Volume 9, Interscience Pubbshers, 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 to Drs. U. Grigo, K. Kirchner and PR Müller "Polycarbonate" in Becker/Braun, Kunststoff-Handbuch, volume 3/1, polycarbonates, polyacetals, polyesters, cellulose esters, Carl Hanser Verlag Munich, Vienna 1992, pages 117-299. In the "Encyclopedia of Polymer Science and Technology", John Wiley & Sons, Ine., by Daniel J. Brunelle, in the article "Polycarbonates" on pages 1 to 33, not only the production of suitable polycarbonates or co-polycarbonates is described, but especially in Table 3 on pages 10 to 13 describes aromatic polycarbonates based on bisphenols. Starting products for the realization of poly carbonate structural units according to formula (1-1) are dihydroxydiphenylcycloalkanes of the formula (I-la)

(I-la) wherein

X, R ¹ , R ² , R ³ , R ⁴ and m have the meaning given for the formula (1-1). Starting products for the realization of polycarbonate structural units of the formula (1-2), (1-3) and/or (1-4) are dihydroxydiphenylcycloalkanes of the formula (I-2a), (I-3a) and/or (I-4a)

(l-2a) (l-3a) (l-4a) where R ⁵ is a C 1 -C 4 -alkyl radical, aralkyl radical or aryl radical, preferably a methyl radical or phenyl radical, very particularly preferably a methyl radical. The radicals R ¹ and R ² in formula (I-la) are preferably hydrogen.

In formula (I-1a), preference is given to alkyl on 1-2 atoms X, in particular on only one atom X, R ³ and R ⁴ simultaneously.

Preferred alkyl residue in formula (I-la) for R ³ , R ⁴ is methyl; the X atoms in the alpha position to the diphenyl-substituted C atom (Cl) are preferably not dialkyl-substituted, and at least one X atom in the beta-position to Cl is preferably alkyl disubstituted. In a preferred embodiment of the multi-layer structure (MA), the polycarbonate or the co-polycarbonate is partially produced from the starting materials selected from the group consisting of: or mixtures of at least two of these.

In formula (I-la), preference is given to dihydroxydiphenylcycloalkanes having 5 and 6 ring carbon atoms in the cycloaliphatic radical (m=4 or 5 in formula (I-la)), for example the diphenols of the formulas (I-lb) to (I -ld), particular preference being given to 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (formula (I-lb) where R ¹ and R ² are H). According to EP 0359953 A1, the polycarbonates can be prepared from diphenols of the formula (I-1a).

Both a diphenol of the formula (I-la) with the formation of homopolycarbonates and several diphenols of the formula (I-la) with the formation of co-polycarbonates can be used.

At least one of the polymer layers (S1), (S2) and/or (S3) of the multilayer structure (MA) can also have at least one filler. The filler is preferably at least one color pigment and/or at least one other filler for producing translucency in the filled layers, particularly preferably a white pigment, very particularly preferably titanium dioxide, zirconium dioxide or barium sulfate, in a preferred embodiment titanium dioxide.

Filling at least one polymer layer (S1), (S2) or (S3) of the multilayer structure (MA) with at least one such filler can improve the visibility of the inscription or images introduced, thereby further increasing perception of the improved sharpness and resolution.

The fillers mentioned are preferably used in amounts of 2 to 45% by weight, particularly preferably 5 to 30% by weight, based on the total weight of the respective polymer layer (S1), (S2) or (S3) containing the filler contains, which can be done for example by extrusion or coextrusion added. In particular, these are the polymer layers (S2) or less preferably (S3). The polymer layer (SI) preferably contains 0 to 1% by weight, more preferably 0.01 to 0.5% by weight, particularly preferably 0.05 to 0.1% by weight of a filler from the list as mentioned above , based on the total weight of the polymer layer (Sl). The polymer layers (S1), (S2) and (S3) are preferably free of fillers.

The multi-layer structure (MA) according to the invention comprising at least one polymer layer (S1) and a further polymer layer (S2) and optionally a third polymer layer (S3) can, for example and preferably, by means of coextrusion of the layers contained, lamination of the layers contained or extrusion lamination, i.e. extruding the layer ( en) containing at least a first polymer layer (S1) and a further polymer layer (S2) and optionally a third polymer layer (S3). The variants of coextrusion and extrusion are preferred. The production of the multilayer structure (MA) by means of coextrusion of at least the polymer layers (S1) and (S2) and optionally (S3) is very particularly preferred.

Accordingly, preference is given to a coextruded multilayer structure (MA) comprising at least one further polymer layer (S2) containing at least one blend of at least one or more poly- or copolycondensate(s) of an aromatic and/or cycloalkyl dicarboxylic acid and aliphatic, cycloaliphatic and/or araliphatic diols with 2 to 16 carbon atoms with one or more polycarbonate or co-polycarbonate (s), characterized in that the proportion of polycarbonate or co-polycarbonate (s) in this blend in a range from> 50 wt .-% to < 90% by weight, preferably in a range from >60% by weight to <80% by weight, very particularly preferably in a range from >60% by weight to <75% by weight, and that the or the Poly- or copolycondensate(s) of an aromatic and/or cycloalkyl dicarboxylic acid and aliphatic, cycloaliphatic and/or araliphatic diols having 2 to 16 carbon atoms a proportion of 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol and/or 2,2, 4,4-tetr amethyl-1,3-cyclobutanediol in a range from >20 to <80 mol%, preferably in a range from >25 to <75 mol% and particularly preferably in a range from >25 to <70 mol% on the diol component have at least one or more poly- or copolycondensate(s) of an aromatic and/or cycloalkyl dicarboxylic acid and aliphatic, cycloaliphatic and/or araliphatic diols having 2 to 16 carbon atoms with one or more poly- or co-polycarbonate(s) , characterized in that the proportion of polycarbonate or co-polycarbonate(s) in this blend is in a range from >50% by weight and up to <90% by weight, preferably in a range from >60% by weight and to <80% by weight very particularly preferably in a range from >60% by weight to <70% by weight, and that the poly- or copolycondensate(s) of an aromatic and/or cycloalkyl dicarboxylic acid and aliphatic, cycloaliphatic and/or araliphatic diols having 2 to 16 carbon atoms n Proportion of 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol and/or 2,2,4,4-tetramethyl-1,3-cyclobutanediol in a range from 30 to 80 mol %, preferably in a range from 30 to 75 mol% and particularly preferably in a range from 32 to 68 mol% based on the diol component, and a first polymer layer (Sl), this first polymer layer (Sl) one or more poly- or copolycondensate (s) one aromatic and/or cycloalkyl Contains dicarboxylic acid and aliphatic, cycloaliphatic and/or araliphatic diols having 2 to 16 carbon atoms.

Optionally, the coextruded multilayer structure (MA) contains a third polymer layer (S3), this third polymer layer containing one or more poly- or copolycondensate(s) of an aromatic and/or cycloalkyl dicarboxylic acid and aliphatic, cycloaliphatic and/or araliphatic diols with 2 to 16 Includes carbon atoms and the layers are arranged so that the two polymer layers (Sl) and (S3) form the outer layers of the coextruded multilayer structure (MA).

The multi-layer structure (MA) according to the invention, regardless of whether it is extruded or laminated, is outstandingly suitable as a component for security documents, preferably identification documents and/or bank cards. The multi-layer structure (MA) is particularly suitable for labeling using laser engraving. When using the multi-layer structure (MA), a high degree of sharpness and high quality of the elements applied by means of laser engraving are achieved. Personalizing lettering and/or images can preferably be introduced into one of the polymer layers (S1), (S2) or (S3) by means of laser engraving. The multi-layer structure (MA) is particularly preferably suitable for identification documents in the form of glued or laminated layer composites in the form of plastic cards, such as ID cards, passports, driver's licenses, credit cards, bank cards, cards for access control or other identification documents, etc. Preferred identification documents are in the context according to the present invention, multi-layer, flat documents with security features such as chips, photographs, biometric data, etc. These security features can be visible from the outside or at least can be queried. Such an identification document preferably has a size between that of a bank card and that of a passport. Such an identification document can also be part of a document consisting of several parts, such as a plastic identification document in a passport, which also contains paper or cardboard parts.

The multi-layer structure (MA) shows good adhesion of the individual polymer layers in layer structures, such as in security documents, with high resolution, clarity, transparency, flatness and low warpage, even at high fading temperatures.

Furthermore, the multi-layer structure (MA), in particular as a component in security documents, preferably identification documents and/or bank cards, has very good chemical resistance, in particular to acetone and artificial skin defects. The durability of security documents containing the multi-layer structure (MA) is better than that of conventional cards, which can be seen by looking at all the parameters mentioned together.

In a preferred embodiment of the multilayer structure (MA), the polycarbonate or the co-polycarbonate contains the starting compound (Ib) in a range from 10% by weight to 90% by weight, preferably in a range from 15 to 85% by weight, based on the total weight of the polycarbonate or the co-polycarbonate or the polycarbonate or the co-polycarbonate has a molar ratio of (Ib) to other bisphenol A derivatives in a range from 1:10 to 10:1, preferably in a range from 1:5 to 5:1.

In a preferred embodiment of the multi-layer structure (MA), the complete multi-layer structure (MA) has at least one, preferably at least two, particularly preferably all of the following properties:

(A) a thickness in a range from 10 to 500 μm, preferably in a range from 20 to 400 μm, particularly preferably in a range from 30 to 200 μm, very particularly preferably in a range from 50 to 100 μm;

(B) a flatness in a range from 5 to 40 mm, preferably in a range from 10 to 30 mm for a 500 mm*600 mm layer structure;

(C) a vertical deviation in the thickness of the multilayer structure (MA) in a range from >0.002 to <0.020 mm, more preferably in a range from >0.003 to <0.015 mm, most preferably in a range from >0.005 to <0, 01 mm over the entire surface of the multi-layer structure (MA);

(D) a layer thickness tolerance of 4 to 20%, more preferably 5 to 15%, particularly preferably 6 to 10%, based on the nominal layer thickness of the multilayer structure (MA);

(E) heat resistance up to a temperature of 350°C, more preferably up to 380°C;

(F) a transparency in a range from 20 to 98%, preferably from 50 to 95%, particularly preferably from 60 to 90%, measured according to ISO 13468-2:2006-07;

The multilayer structure (MA) preferably has at least one, preferably a combination of properties selected from the group consisting of (A); (B); (C); (D); (E); (F); (A) and (B);

(A) and (C); (A) and (D); (A) and (E); (A) and (F); (B) and (C); (B) and (D); (B) and (E);

(B) and (F); (C) and (D); (C) and (E); (C) and (F); (D) and (E); (D) and (F); (E) and (F);

(A) and (B) and (C); (A) and (B) and (D); (A) and (B) and (E); (A) and (B) and (F); (A) and (C) and (D); (A) and (C) and (E); (A) and (C) and (F); (A) and (D) and (E); (A) and

(D) and (F); (A) and (E) and (F); (B) and (C) and (D); (B) and (C) and (E); (B) and (C) and (F); (B) and (D) and (E); (B) and (D) and (F); (B) and (E) and (F); (C) and (D) and (E); (C) and (D) and (F); (C) and (E) and (F); (D) and (E) and (F); (A) and (B) and (C) and (D); (A) and (B) and (C) and (E); (A) and (B) and (C) and (F); (A) and (B) and (D) and (E); (A) and

(B) and (D) and (F); (A) and (B) and (E) and (F); (A) and (C) and (D) and (E); (A) and (C) and (D) and (F); (A) and (C) and (E) and (F); (A) and (D) and (E) and (F); (B) and (C) and (D) and (E); (B) and (C) and (D) and (F); (B) and (C) and (E) and (F); (A) and (B) and (C) and (D) and (E); (A) and (B) and (C) and (D) and (F); (A) and (B) and (C) and (E) and (F); (A) and (B) and (D) and (E) and (F); (A) and (C) and (D) and (E) and (F); (B) and (C) and (D) and (E) and (F); (A) and (B) and (C) and (D) and (E) and (F).

The flatness mentioned in the property (B) can be determined by measuring the height deviation of a 500*600mm piece of the multi-layer structure (MA) with a ruler when the piece is placed on a flat surface such as a table. The flatness is preferably determined on both sides of the flat multi-layer structure (MA). The values of the flatness measurements on both sides of the multilayer structure (MA) are preferably in the stated range of property (B). The flatness values on one side of the (MA) preferably deviate by no more than 10%, preferably no more than 5%, from the flatness values of the opposite side of the (MA), with the side of the (MA) having the higher Values form the basis for determining the deviation.

One of the polymer layers (S1) or (S3) preferably has at least one, preferably both, of the following properties:

(G) a thickness in a range from 5 to 100 μm, preferably in a range from 6 to 50 μm, more preferably in a range from 7 to 40 μm, most preferably in a range from 10 to 30 μm;

(H) a transparency in a range from 20 to 98%, preferably from 50 to 95%, particularly preferably from 60 to 90%, measured according to ISO 13468-2:2006-07.

The polymer layer (S2) preferably has at least one, preferably both, of the following properties:

(I) a thickness in a range from 20 to 100 μm, preferably in a range from 25 to 90 μm, particularly preferably in a range from 30 to 80 μm, very particularly preferably in a range from 40 to 70 μm.

(J) a transparency in a range from 20 to 98%, preferably from 50 to 95%, particularly preferably from 60 to 90%, measured according to ISO 13468-2:2006-07.

One of the polymer layers (S1), (S2), (S3) or (S4), particularly preferably the polymer layer (S2), preferably contains a laser-sensitive additive, preferably a black pigment, particularly preferably carbon black. The polymer layer, which contains the laser-sensitive additive, can be easily personalized using laser engraving.

The inscription of plastic foils by means of laser engraving is referred to in the professional world and also in the following as laser inscription. Accordingly, in the following under the term "laser inscribed" to be understood as inscribed by means of laser engraving. The laser engraving process is known to those skilled in the art and should not be confused with printing using laser printers.

Examples of laser-sensitive additives are so-called laser marking additives, i.e. those made 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). Such 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 commercially available from DSM under the brand name Micabs™. Absorbers that are also suitable as laser-sensitive additives are carbon black and phosphorus-containing tin-copper mixed oxides, as described, for example, in WO-A 2006/042714.

The laser-sensitive additive can be contained in the polymer layers (S1) and/or (S2) and/or (S3) in an amount of 0.5 to 180 ppm, preferably 1 to 160 ppm, particularly preferably 5 to 120 ppm. In the context of the invention, ppm is to be understood as meaning ppm by weight, unless otherwise stated.

It is preferred if the particle size of the laser-sensitive additive is in the range from 100 nm to 10 μm, and it is particularly advantageous if it is in the range from 50 nm to 2 μm.

The optional addition of laser-sensitive additives, preferably black pigments, particularly preferably carbon black, in the polymer layers (S1) and/or (S2) and/or (S3) does not impair the transparency of the multilayer structure (MA).

Another subject matter of the invention relates to a method for producing a multi-layer structure (MA) with a first outer side (AS1) and a second outer side (AS2) lying opposite the outer side (AS1), comprising the steps i) providing at least one first polymer layer (S1) ; ii) providing at least one further polymer layer (S2); iii) optionally providing at least one third polymer layer (S3); iv) forming a laminate from a separate polymer layer (S1), (S2) and optionally (S3) at a temperature (TI) of >150°C, preferably >180°C, more preferably >200°C, very particularly preferably >210°C; wherein at least one of the outer sides (AS1) or (AS2) is formed by one of the polymer layers (S1) or (S3), each of which contains or consists of a polymer (PI) or (P2), each having a Vicat softening point >149°C, preferably >160°C, more preferably >170°C; more preferably >180°C, determined according to ISO 306:2004 (50N; 50°/h). The polymer layers (S1), (S2) and optionally (S3) in steps i), ii) and optionally iii) can be provided in any way that the person skilled in the art would select for lamination to produce the multilayer structure (MA). The provision preferably takes place in a continuous lamination system.

The sequence of layers (S1) to (S3) before step iv) is preferably selected from the group consisting of: a first polymer layer (S1) as the outside (AS1) followed by a further polymer layer (S2); a first polymer layer (Sl) as the outside (AS1) followed by two identical further polymer layers (S2); a first polymer layer (Sl) as the outside (AS1) followed by two different further polymer layers (S2); a first polymer layer (Sl) as the outside (AS1) followed by at least one further polymer layer (S2) followed by a third polymer layer (S3); a first polymer layer (Sl) as the outside (AS1) followed by at least one further polymer layer (S2) followed by a first polymer layer (Sl); and combinations of at least two of these.

The formation of the laminate in step iv) can be done in any way that one skilled in the art would choose for a lamination at a temperature (TI) of at least 150°C and preferably at most 300°C. The lamination preferably takes place in the form of a roll lamination, in which the polymer layers provided from steps i) to iii) are guided over at least two opposite rollers or rollers, also called a pair of rollers. At least one of the at least two rolls or rollers is heated to a temperature (TI). The roll lamination preferably takes place over two pairs of rolls connected in series, of which each of the 4 rolls can be heated individually. A cooling station is preferably located between and/or behind the pairs of rollers, which is cooled to a temperature significantly below (TI). The cooling stations are preferably brought to a temperature in a range from 10 to 100.degree. C., preferably from 15 to 80.degree. C., particularly preferably from 20 to 50.degree. The polymer layer (S1), which is on the outside (AS1), then comes into contact with the heated cylinders or rollers. Depending on which polymer layer forms the second outer layer (AS2), the second roll or roll can also be heated, heated less than the first roll or roll or not heated at all. If the second cylinder or roller also has a temperature (T2) above 150° C., the polymer layer that forms the outside (AS2) is selected from a polymer layer (S1) or (S3). The contact surface of the rollers on the outer sides (AS1) and (AS2) is preferably 1 to 100 mm, preferably 2 to 50 mm, particularly preferably 3 to 20 mm.

All properties, compositions, dimensions and configurations of the multilayer structure (MA) according to the invention can also be used in connection with the method for producing the multilayer structure (MA) and are not mentioned again here to avoid repetition.

In a preferred embodiment of the method, the heat input into the respective polymer layer (S1), (S2) or (S3) in step iv) is >50 J/s*m ² , preferably >60 J/s*m ² . more preferably >80 J/s*m ² . this specification is made in Joule (J)/second (s) * square meter (m ² ).

In a preferred embodiment of the method, the heat is applied to the respective polymer layer S1), (S2) or (S3) in step iv) to reach the temperature (TI) starting from 23° C. within <15 seconds, preferably from < 10 seconds, more preferably <5 seconds, in particular in a range from 5 to 10 seconds.

In a preferred embodiment of the method, the polymer layer (S1) or the polymer layer (S3) contains at least one polymer (PI) or (P3) selected from the group consisting of a polycarbonate, a co-polycarbonate or a mixture of at least two of these.

In a preferred embodiment of the method, the polymer layer (S2) contains at least one polymer (P2) selected from the group consisting of a polycarbonate, a mixture or blend of a polycarbonate and a copolyester or a mixture of at least two of these.

Another subject matter of the invention relates to a laminate, in particular a security document, containing a multi-layer structure (MA) according to the invention or a multi-layer structure (MA) obtainable by the method according to the invention.

All properties, compositions, dimensions and configurations of the multilayer structure (MA) according to the invention or its production method can also be used in connection with the security document and are not mentioned again here to avoid repetition.

The security document is preferably an identification document, such as an ID card or a passport, and/or a bank card containing at least one multi-layer structure (MA).

The security document according to the invention, preferably an identification document, can have further additional layers, for example at least one polymer layer (S4), via which, for example, further information is preferably included in the security document Identification document and/or bank card are brought in. The polymer layer (S4) preferably contains the polymer (P2) in an amount in a range from 50 to 100% by weight, more preferably in a range from 70 to 98% by weight, particularly preferably in a range from 80 to 95% % by weight, based on the total weight of the polymer layer (S4). The polymer layer (S4) can likewise have additives, as already mentioned for the polymer layers (S1) and (S2), preferably in the same amounts as stated there.

The polymer layer (S4) preferably has a transparency in the visible wavelength range, preferably in the range from >70% to <99%, preferably from >80% to <95%, particularly preferably >88% to <93%, determined according to ISO 13468- 2:2006-07 on.

Such additional information can be, for example, personalizing portraits or non-personalizing general information that is contained in the same form, for example, in every security document of the same type, preferably an identification document and/or bank card.

Such layers can, for example, be introduced into the security document, preferably identification document and/or bank card, from foils or polymer layers previously equipped with this information using conventional printing methods, preferably inkjet or laser printing, particularly preferably color printing.

Films or polymer layers that can be printed by means of ink-jet printing processes are known per se to the person skilled in the art and can also be the polymer layers (S4), for example. In particularly preferred embodiments, plastic films or polymer layers (S4) colored white or translucent by means of fillers such as titanium dioxide, zirconium dioxide, barium sulfate etc. are used to improve the visibility of the printed information.

For polymer layers to be printed by means of laser printing, in particular by means of color laser printing, those of the polymer layers (S1) or polymer layers (S4) according to the invention described above that have a specific surface resistance of 10 ⁷ to 10 ¹³ W, preferably 10 ⁸ to 10 ¹² W, are particularly suitable. The specific surface resistance in W is determined according to DIN IEC 60093 (1993).

This can preferably be a polymer layer of type (S1), in which the plastic before layer production to achieve the specific surface resistance, for example, an additive selected from tertiary or quaternary, preferably quaternary ammonium or phosphonium salts of a partially or perfluorinated organic acid or quaternary ammonium or phosphonium hexafluorophosphates, preferably a partially or perfluorinated alkyl sulfonic acid, preferably a perfluoroalkyl sulfonic acid was added. These additives can be contained in particular in the polymer layer (S1), but also to a small extent in the polymer layers (S2) and/or (S3). Preferred suitable quaternary ammonium or phosphonium salts are:

Perfluoroctansulfonsäuretetrapropylammoniumsalz, Perfluorbutansulfonsäuretetrapropylammoniumsalz, Perfluoroctansulfonsäuretetrabutylammoniumsalz, Perfluorbutansulfonsäuretetrabutylammoniumsalz, Perfluoroctansulfonsäuretetrapentylammoniumsalz, Perfluorbutansulfonsäuretetrapentylammoniumsalz, Perfluoroctansulfonsäuretetrahexylammoniumsalz, Perfluorbutansulfonsäuretetrahexylammoniumsalz, Perfluorbutansulfonsäuretrimethylneopentylammoniumsalz, Perfluoroctansulfonsäuretrimethylneopentylammoniumsalz, Perfluorbutansulfonsäuredimethyldineopentylammoniumsalz, Perfluoroctansulfonsäuredimethyldineopentylammoniumsalz, N-Methyl-tripropylammoniumperfluorbutylsulfonat, N-Ethyl-tripropylammoniumperfluorbutylsulfonat, Tetrapropylammoniumperfluorbutylsulfonat, Diisopropyldimethylammoniumperfluorbutylsulfonat, Diisopropyldimethylammoniumperfluoroctylsulfonat, N-Methyl-tributylammoniumperfluoroctylsulfonat Cyclohexyldiethylmethylammoniumperfluoroctylsulfonat, Cyclohexyltrimethylammoniumperfluoroctylsulfon at, and the corresponding phosphonium salts. The ammonium salts are preferred.

It is also possible with preference to use one or more of the abovementioned quaternary ammonium or phosphonium salts, ie mixtures as well.

The perfluorooctanesulfonic acid tetrapropylammonium salt, the perfluorooctanesulfonic acid tetrabutylammonium salt, the perfluorooctanesulfonic acid tetrapentylammonium salt, the perfluorooctanesulfonic acid tetrahexylammonium salt and the perfluorooctanesulfonic acid dimethyldiisopropylammonium salt and the corresponding perfluorobutanesulfonic acid salts are very particularly suitable.

Perfluorobutanesulfonic acid dimethyldiisopropylammonium salt (diisopropyldimethylammonium perfluorobutylsulfonate) is particularly preferably used as an additive.

The salts mentioned are known or can be prepared by known methods. The salts of the sulfonic acids can be prepared, for example, by combining equimolar amounts of the free sulfonic acid with the hydroxy form of the corresponding cation in water at room temperature and evaporating the solution. Other manufacturing processes are described, for example, in DE-A 1 966 931 and NL-A 7 802 830. The salts mentioned are preferably used in amounts of from 0.001 to 2% by weight, preferably from 0.1 to 1% by weight, based on the total weight of the respective polymers (PI), (P2) or (P3), the polymers (PI), ( P2) or (P3) added before shaping to give the multilayer structure (MA) according to the invention, which can preferably be carried out by extrusion or coextrusion.

The multilayer structure (MA) according to the invention is preferably used for the accelerated production of a laminate, which preferably within 15 seconds, more preferably within 10 seconds, particularly preferably within 5 seconds, in particular in a range from 5 to 10 seconds, preferably using Temperatures in a range from 180°C to 230°C, particularly preferably from 190°C to 210°C. At the same time as the elevated temperature, preference is given to a pressure in a range from 10 N/cm ² to 400 N/cm ² , preferably from 30 N/cm ² to 300 N/cm ² , particularly preferably from 40 N/cm ² to 250 N / cm ² applied. Preference is given to using the multilayer structure (MA) according to the invention to produce a laminate within 15 seconds, preferably within 10 seconds, particularly preferably within 5 seconds, in particular in a range from 5 to 10 seconds.

Another subject of the invention relates to the use of the multi-layer structure (MA) according to the invention or the multi-layer structure (MA) produced by the process according to the invention for a surface treatment, in particular a lamination, which is carried out at least on one side of the multi-layer structure (MA) to be laminated at a temperature (TI ) in a range from >160°C to <250°C, preferably in a range from >170°C to <240°C; more preferably in a range from >180°C to <230°C, particularly preferably in a range from >185°C to <220°C, very particularly preferably in a range from >190°C to <210°C. At the same time as the elevated temperature, preference is given to a pressure in a range from 10 N/cm ² to 400 N/cm ² , preferably from 30 N/cm ² to 300 N/cm ² , particularly preferably from 40 N/cm ² to 250 N / cm ² applied.

When using the multilayer structure (MA) according to the invention for a surface treatment, in particular for a lamination, the multilayer structure (MA) is first provided and together with a substrate, for example a polymer layer (S4), which preferably includes a polymer (S2), such as as described above, for as short a period of time as possible, preferably for 5 to 30 seconds, preferably 7 to 20 seconds, to the selected temperature (TI) and to an elevated pressure. The pressure is preferably in a range from 10 N/cm ² to 400 N/cm ² , preferably from 30 N/cm ² to 300 N/cm ² , particularly preferably from 40 N/cm ² to 250 N/cm ² . Since both temperature and pressure are preferably transferred to the polymer layers (S1) to (S3) and substrate via a cylinder or roller, the pressure is only applied for the time periods mentioned above for the temperature effect of the selected temperature (TI). The effect of the increased temperature (TI) and the increased pressure can also take place over several rollers, for example 2 to 4 rollers, which together cover the stated period of 5 to 30 seconds, preferably 7 to 20 seconds, in contact with the multilayer structure (MA) plus further layers such as (S4) in order to produce the laminate. After the lamination process, a layer composite is obtained, which holds the layers laminated together in such a way that the layer composite can only be separated into the layers again by destroying the laminate, or that the individual layers can no longer be separated from one another at all.

All properties, compositions, dimensions and configurations of the multilayer structure (MA) according to the invention and its production process can also be used in connection with its use.

In a preferred embodiment of use, the multi-layer structure (MA) according to the invention is used to produce a security document, preferably an identification document, in particular in a structure as previously described for this purpose.

As already mentioned, further security features can be introduced into the security document. The security document created in this way, preferably an identification document and/or bank card, can be produced, for example, in such a way that a stack of layers is put together from the various polymer layers and substrates for the structure of the security document, preferably an identification document and/or bank card, and laminated to form a layered composite and then into the appropriate one Form of security document, preferably identification document and / or bank card is tailored. Optionally, further layers can be subsequently applied to this composite laminate, for example by adhering and/or laminating further films or coating by means of paint compositions.

The following examples serve to illustrate the invention by way of example and are not to be construed as a limitation. In the context of the description of the polymer layers (S1) to (S3) or the multilayer structure, films are also used as a synonym for polymer layers.

examples

Raw materials used:

Eastar™ DN 010 (DN 010): Poly- or copolycondensate of a terephthalic acid from 54.9% by weight terephthalic acid, 9.3% by weight (38 mol% based on the diol component) ethylene glycol and 35.8% by weight % (62 mol % based on the diol component) 1,4-cyclohexanedimethanol, with an inherent viscosity of 0.74 dl/g (measured in a 1:1 mixture of phenol and tetrachloroethane at 25° C.) from Eastman Chemical Company .

Pocan™ B 1600 (PBT 1600): Unmodified polycondensate of terephthalic acid and 1,4-butanediol as the diol component with a melt volume rate (MVR) of 14 g/10 min according to ISO 1133 at 260° C. and 2.16 kg from Fanxess AG.

Makroion™ 3108: high-viscosity, amorphous, thermoplastic bisphenol A polycarbonate from Covestro AG with an MVR of 6.5 g/10min according to ISO 1133-1:2011 at 300°C and 1.2 kg application weight and a Vicat softening point (VST) according to ISO 306:2004 method B120 at 50 N; 120 °C/h of 150 °C and a glass transition temperature T _g according to ISO 11357-1,-2 of 149 °C.

KRONOS™ 2230: Titanium dioxide from Kronos for polycarbonate and other engineering thermoplastics with a T1O2 content > 96%

Example 1: High-temperature polycarbonate PC 1 as polymer (PI) or (P3):

149.0 g (0.65 mol) bisphenol A (2,2-bis(4-hydroxyphenyl)propane, 107.9 g (0.35 mol) 1,1-bis(4-hydroxyphenyl)-3 ,3,5-trimethylcyclohexane, 336.6 g (6 moles of KOH and 2700 g of water were dissolved in an inert gas atmosphere with stirring. Then a solution of 1.88 g of phenol in 2500 ml of methylene chloride was added 198 g (2 mol) phosgene were passed into the solution at pH 13 to 14 and 21 to 25° C. 1 ml ethylpiperidine was then added and the mixture was stirred for a further 45 minutes Washed neutral with water and freed from solvent. The polycarbonate showed a relative solution viscosity of 1.255, determined according to DIN EN ISO 1628-1:2009. The Vicat softening point of the polymer was determined according to ISO 306:2004 method B120 at 50 N; 120 °C/ h determined to be 183°C.

Example 2: High-temperature polycarbonate PC 2 as a polymer (PI) or (P3):

Analogously to PC 1, a mixture of 91.6 g (0.40 mol) of bisphenol A and 185.9 g (0.60 mol) of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane converted to the corresponding polycarbonate 2. The polycarbonate showed a relative solution viscosity of 1.251, determined according to DIN EN ISO 1628-1:2009.

The Vicat softening point of the polymer was determined according to ISO 306:2004 Method B120 at 50 N; 120 °C/h determined to 204 °C.

Example 3: High-temperature polycarbonate PC 3 as a polymer (PI) or (P3):

Analogously to PC 1, a mixture of 44.2 g (0.19 mol) of bisphenol A and 250.4 g (0.81 mol) of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane converted to the corresponding polycarbonate.

The polycarbonate showed a relative solution viscosity of 1.248, determined according to DIN EN ISO 1628-1:2009.

The Vicat softening point of the polymer (PI) was determined according to ISO 306:2004 method B120 at 50 N; 120 °C/h determined to 216 °C.

Example 4: compounding of a batch for the production of a polymer layer (S4) comprising a thermoplastic as polymer (P2) and a white pigment as filler: The batches for producing a white layer were produced using a conventional twin-screw compounding extruder (ZSK 32) at processing temperatures of 250 to 330.degree.

Batches with the compositions according to Table 1 were compounded and then granulated:

Table 1: Composition of compounds for the production of polymer layers (S4) comprising thermoplastics as polymer (P2)

General manufacturing instructions for mono-layer extrusion films

The system used consists of

^■ an extruder with a screw of 105 mm diameter (D) and a length of 41xD. The screw has a degassing zone;

^■ a deflection head;

^■ a slot die with a width of 1500 mm;

^■ a three-roll smoothing calender with a horizontal arrangement of rolls, the third roll being pivotable by +/- 45° with respect to the horizontal;

^■ a roller conveyor;

^■ a device for applying protective film to both sides;

^■ an extraction device;

^■ Rewind station.

The granules of a polymer (P2) were fed into the hopper of the extruder. The respective material was melted and conveyed in the respective cylinder/screw plasticizing system. The material melt was fed to the nozzle. From the die, the melt reached the smoothing calender. The final shaping and cooling of the material into a polymer layer (S4), which can serve as a substrate or intermediate layer, took place on the smoothing calender. A matted steel roller (surface 4) and a matted rubber roller (surface 4) were used to structure the film surfaces. The film or layer (S4) was then transported through a take-off, after which the layer (S4) was wound up. In this way, according to Table 2, the corresponding white opaque extrusion layers were produced.

Table 2: White opaque monolayer extrusion films * not according to the invention

Table 3: Transparent mono-layer extrusion films

* not according to the invention

Example 8 Compounding of a Masterbatch Containing a Laser-Sensitive Additive

The masterbatch used to produce the laserable polymer layer(s) was produced using a conventional twin-screw compounding extruder (ZSK 32) at processing temperatures of 250 to 330.degree.

A master batch with the following composition was compounded and then granulated:

• 99.994% by weight Makroion™ 3108 polycarbonate

• 0.006% by weight (60 ppm) Vulcan XC 72 101 (carbon black from Cabot) with an average particle size of 95 nm.

General manufacturing instructions for extruded and coextruded films

The system used consists of

^■ a co-extruder for applying the top layer with a screw that is 25 D long and has a diameter of 35 mm

^■ a deflection head;

^■ a special coextrusion sheet die with a width of 1500 mm;

^■ a roller conveyor;

^■ a device for applying protective film to both sides;

^■ an extraction device;

^■ Rewind station.

The base material granules were fed to the hopper of the main extruder. In the respective cylinder/screw plasticizing system, the respective material was melted and conveyed in the form of the polymers (PI) or (P2). Both material melts were brought together in the coextrusion die. From the die, the melt reached the smoothing calender. The final shaping and cooling of the material takes place on the smoothing calender. A structured metal roller (6-er surface) and a structured rubber roller (2-layer surface) are used. The film was then transported through a take-off, after which the film was wound up as a multilayer structure (MA) according to the invention.

The compositions of the films of the examples are described in Tables 4 and 5. Table 4: Composition of the two-layer coextrusion films (Examples 9 to 15)

To produce three-layer multilayer structures (MA), the procedure was exactly as described for the two-layer structures, with the difference that the melt of the polymer (PI) was divided into two strands and on both sides of the strand of the polymer (P2) in the Nozzle was guided, so that a multilayer structure (MA) with the layers (Si) - (S2) - (S3) was obtained.

Table 5: Composition of the three-layer (Sl)-(S2)-(S3) coextruded films (Ex. 17 to

19)

Production of identification documents (ID card) by roll lamination (Examples 20 to 31)

The ID documents were laminated according to the layer structure in Tables 6 and 7 as follows:

A stack was formed from the foils in the order mentioned and the lamination was carried out on a roller laminator from Melzer with the following parameters.

Table 6: Laminate layer structure

The roll laminator has 2 upper and 2 lower laminating tapes of the type standard ID 3 format with a width of approx. 120 mm each. Each of the belts has two heating and one cooling area (each heating area with 3 heating elements and a cooling area with 6 cooling elements in between) and can be heated or cooled separately and comes with an outer layer of the multi-layer structure plus a substrate in the form of the polymer layer (S4) in contact. The two upper lamination tapes preferably come into contact with the polymer layer (S1) and the two lower ones with the polymer layer (S4). The lamination tapes each have a heating unit M330 and a cooling unit M220. The top two lamination tapes were heated to the temperature (TI) given in Table 7. The two bottom lamination tapes were heated to a lower temperature than (TI) as also indicated in Table 7. The cooling units are each arranged after a heating unit. The residence times are also listed in Table 7.

When calculating the heat flows and heat inputs into the polymer layers (1) or (2), the throughput times used in experiments 20 to 29 and reference experiments 1 and 2 were 2×8 seconds (examples 20 to 29) and 2×14 seconds, respectively used in reference experiment 1 or 2 from Table 7. The width and length of the heating zones—ie the areas (0.12 m×2 m=0.24 m ² )—are the same in reference experiments 1 and 2 and in experiments 20 to 19 according to the invention.

An average heat flow of 11.47 J/s was used for reference tests 1 and 2 from Table 7. With a contact area of the laminate with the rollers of 0.24 m ² this corresponds to an average heat input on the upper side of the respective reference laminate of 47.8 J/s*m ² (heat flow/area 11.47 J/s: 0.24 ^m2 = 47.8 J/s* ^m2 ).

For tests 20 to 29, the average heat flow was 52.7 J/s and the heat input calculated from heat flow/area was 219.6J/s*m ² ( 52.7 J7s : 0.24 m ² = 219.6 J/s*m ² ).

The mean value was used for the heat input, since, starting from an initial temperature of 25°C, the heat flow is very high at the beginning and decreases more and more as the contact temperatures of 176°C to 209°C are approached. Production of laminates Table 7: Conditions of two reference examples and Examples 20 to 29 according to the invention

Due to the higher temperature (TI), which can be used on the side of the polymer layer (Sl), without melting it to such an extent that it shows morphological changes, in contrast to the conventional polymer layers as shown for the reference experiments, a significantly increased throughput number be reached. The number of pieces per hour could be increased from 2616 per hour with conventional material to 4100 per hour. This could still be increased if the speed of the lamination belts could be further increased. With a temperature (TI) of 200°C, the maximum number of pieces possible on the system of 4100 pieces/hour was reached, with the material not showing any structural changes, for example in the form of bubbles, even at 220°C. All laminates with the multilayer structure (MA) according to the invention could be laminated much more quickly than the reference film without any loss of adhesive force. The lamination time could be halved, so that the productivity of the roll lamination line could be doubled.

In Figure 1, a multi-layer structure (MA) 100 according to the invention is shown schematically, which comprises a first polymer layer (Sl) 10 and a further polymer layer (S2) 20. In addition, the multi-layer structure (MA) 100 shown comprises a polymer layer (S3) 30.

The method is shown schematically in FIG. In step i) 100 was the first polymer layer

(51) provided rolled on a roll so that it could be fed from the roll onto the laminating line of the laminating machine. In step ii) 200 was the further polymer layer

(52) provided rolled up on a roll, so that the further polymer layer (S2) could be guided parallel to the first polymer layer (S1) onto the lamination belt of the lamination machine. Optionally, a third polymer layer (S3) was provided rolled up on a roll, so that the third polymer layer (S3) could be guided parallel to the first polymer layer (S1) and further polymer layer (S2) onto the lamination belt of the lamination machine, so that a layer sequence (S1 ), (S2), optionally (S3). In the laminating machine, a laminate was formed from the layer sequence S1), (S2), optionally (S3) at a temperature of 185 to 220° C., as listed in Table 7, in step iv) 400 . The lamination tape moved at a speed of 0.1 m/s. In an optional step v) 500 the laminate is wound onto a roll.

Claims

patent claims

1 A multi-layer structure (MA), comprising

(53) optionally at least one third polymer layer (S3) which has a Vicat softening point >149°C, preferably >160°C, more preferably >170°C; more preferably >180°C, determined according to ISO 306:2004 (50N; 50°/h).

2 The multilayer structure (MA) according to claim 1, wherein the polymer layer (S2) contains at least one polymer (P2) selected from the group consisting of a polycarbonate, a mixture or a blend of a polycarbonate and a co-polyester or mixtures of at least two of these.

3. The multilayer structure (MA) according to any one of the preceding claims, wherein the polymer layer (S3) contains at least one polymer (P3) selected from the group consisting of a polycarbonate, a co-polycarbonate and mixtures of at least two of these.

4. The multilayer structure (MA) according to any one of the preceding claims, wherein the polymer (PI) or the polymer (P3) is a polycarbonate or co-polycarbonate of the formula (Ia), (1-2), (1-3) or ( 1-4), where (Ia) wherein R ¹ and R ² are independently hydrogen, halogen, preferably chlorine or bromine, Ci-Cs-alkyl, CVCVCycloalkyl. Ce-Cio-Aryl, preferably phenyl, and C ₆ -Ci2-aralkyl, preferably phenyl-Ci-C4-alkyl, in particular benzyl, m is an integer from 4 to 7, preferably 4 or 5,

R ³ and R ⁴ can be selected individually for each X, independently of one another hydrogen or Ci-Ce-alkyl and

X is carbon, with the proviso that on at least one atom X, R ³ and R ⁴ are simultaneously alkyl, or in which R ⁵ is a C 1 -C 10 alkyl radical, aralkyl radical or aryl radical, preferably a methyl radical or phenyl radical, very particularly preferably a methyl radical;

5. The multi-layer structure (MA) according to claim 4, wherein the polycarbonate or the co-polycarbonate is partially produced from the starting products selected from the group consisting of: or mixtures of at least two of these.

6. The multilayer structure (MA) according to any one of the preceding claims, wherein the polycarbonate or the co-polycarbonate, the starting compound (Ib) in a range of 10% by weight to 90% by weight, based on the total weight of the polycarbonate or the co-polycarbonate, or the polycarbonate or the co-polycarbonate contains a molar ratio of (Ib) to other bisphenol A derivatives in a range of 1: 10 to 10:1, preferably in a range of 1:5 to 5:1.

7. The multi-layer structure (MA) according to any one of the preceding claims, wherein the complete multi-layer structure (MA) or one of the polymer layers (S1) or (S3) has at least one, preferably at least two, particularly preferably all of the following properties:

(A) a thickness in a range from 10 to 500 μm, preferably in a range from 20 to 400 μm, particularly preferably in a range from 30 to 200 μm, very particularly preferably in a range from 50 to 100 μm.

(B) a vertical deviation in the thickness of the multilayer structure (MA) in a range from >0.002 to <0.020 mm, more preferably in a range from >0.003 to <0.015 mm, most preferably in a range from >0.005 to <0, 01 mm over the entire surface of the multi-layer structure (MA);

(C) a layer thickness tolerance of 4 to 20%, more preferably 5 to 15%, particularly preferably 6 to 10%, based on the average layer thickness of a 500 mm*600 mm layer structure or polymer layer (S1) or (S3);

(D) heat resistance up to a temperature of 350°C, more preferably up to 380°C;

(E) a transparency in a range from 20 to 98%, preferably from 50 to 95%, particularly preferably from 60 to 90%, measured according to ISO 13468-2:2006-07;

8. A method for producing a multilayer structure (MA) having a first outside (AS1) and a second outside (AS2) lying opposite the outside (AS1), comprising the steps of i) providing at least one first polymer layer (S1); ii) providing at least one further polymer layer (S2); iii) optionally providing at least one third polymer layer (S3); iv) Forming a laminate from a separate polymer layer (S1), (S2) and optionally (S3) at a temperature (TI) of at least 150° C., preferably at least 180° C., more preferably at least 200° C. and at most 300° C; wherein at least one of the outer sides (AS1) or (AS2) is formed by one of the polymer layers (Sl) or (S3), each of which contains or consists of a polymer (PI) or (P2), each of which has a Vicat softening point > 149 °C, preferably >160°C, more preferably >170°C; more preferably >180°C, determined according to ISO 306:2004 (50N; 50°/h).

9. The method according to claim 8, wherein the heat input into the respective polymer layer (S1), (S2) or (S3) in step iv) is >50 J/s*m ² , preferably >60 J/s*m ² , particularly preferably > 80 J/s*m ² .

10. The method according to any one of claims 8 or 9, wherein the input of heat to the respective polymer layer Sl), (S2) or (S3) in step iv) to achieve the temperature (TI) starting from 23 ° C within < 15 seconds, preferably <10 seconds, more preferably <5 seconds.

11. The method according to any one of claims 8 to 10, wherein the polymer layer (Sl) or the polymer layer (S3) at least one polymer (PI) or (P3) selected from the group consisting of a polycarbonate, a co-polycarbonate or a mixture of at least two of these.

12. The method according to any one of claims 8 to 11, wherein the polymer layer (S2) contains at least one polymer (P2) selected from the group consisting of a polycarbonate, a mixture or a blend of a polycarbonate and a co-polyester or a Mixture of at least two of these.

13. A laminate, in particular a security document, containing a multi-layer structure according to any one of claims 1 to 7 or obtainable by the method according to any one of claims 8 to 12

14. A use of a multi-layer structure (MA) according to one of claims 1 to 7 or produced according to one of claims 8 to 12 for a surface treatment, in particular a lamination, which is carried out at least on one side of the multi-layer structure (MA) to be laminated at a temperature (TI ) in a range from >160°C to <250°C, preferably in a range from >170°C to <240°C; more preferably in a range from >180°C to <230°C, particularly preferably in a range from >185°C to <220°C, very particularly preferably in a range from >190°C to <210°C.

15. The use according to claim 14 for the production of a security document, preferably an identification document.