EP4073151A1 - Films having special properties - Google Patents

Films having special properties

Info

Publication number
EP4073151A1
EP4073151A1 EP20820445.3A EP20820445A EP4073151A1 EP 4073151 A1 EP4073151 A1 EP 4073151A1 EP 20820445 A EP20820445 A EP 20820445A EP 4073151 A1 EP4073151 A1 EP 4073151A1
Authority
EP
European Patent Office
Prior art keywords
film
carbonate
range
phenyl
polycarbonate
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Withdrawn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
EP20820445.3A
Other languages
German (de)
French (fr)
Inventor
Heinz Pudleiner
Georgios Tziovaras
Kira PLANKEN
Stefan Janke
Christoph Koehler
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 Intellectual Property GmbH and Co KG
Original Assignee
Covestro Intellectual Property GmbH and Co KG
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 Covestro Intellectual Property GmbH and Co KG filed Critical Covestro Intellectual Property GmbH and Co KG
Publication of EP4073151A1 publication Critical patent/EP4073151A1/en
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04—Aromatic polycarbonates
    • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/22—General preparatory processes using carbonyl halides
    • C08G64/24—General preparatory processes using carbonyl halides and phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0075—Antistatics
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/244—All polymers belonging to those covered by group B32B27/36
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • B32B2264/1022—Titania
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • B32B2264/1024—Zirconia
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/104—Oxysalt, e.g. carbonate, sulfate, phosphate or nitrate particles
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/402—Coloured
    • B32B2307/4023—Coloured on the layer surface, e.g. ink
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/402—Coloured
    • B32B2307/4026—Coloured within the layer by addition of a colorant, e.g. pigments, dyes
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/406—Bright, glossy, shiny surface
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/538—Roughness
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/584—Scratch resistance
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/19—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2469/00—Presence of polycarbonate
    • C09J2469/006—Presence of polycarbonate in the substrate

Definitions

  • the invention relates to a film containing i) a Po ly carbonate or copoly carbonate of the formula (1-1), (1-2), (1-3) or (1-4), ii) 0.1 to 5 wt. -% of a first additive; iii) optionally 0.1 to 15% by weight of a second additive that is different from the first additive, the first additive ii) containing or being an antistatic compound, as well as the use of the film according to the invention in a security document and the use of component i) for the production of a laser-engravable foil.
  • the invention also relates to a layer structure comprising the film according to the invention.
  • security documents for the area of security documents, in particular identification documents, the embedding of several security features is absolutely necessary, in particular to ensure the originality of these security documents.
  • security documents in particular identification documents, increasingly include polycarbonate.
  • Documents based on polycarbonate are particularly durable and have a high level of security against forgery.
  • Popular security features are transparent areas in, for example, identification cards or in the data pages of passports. These transparent areas are also called “windows". Holograms, security prints and other elements can be introduced into these windows, which can be recognized as originals or falsifications by looking at them.
  • the function of the security feature is based on the high transparency of polycarbonate. If the transparency of the document in the window is impaired, then it could be a forgery.
  • a problem in the production of the security documents can be the deformation of the film during production, but also the inclusion of air bubbles. Waves often arise in the individual layers, which on the one hand are unsightly, but on the other hand can also lead to the data in the security element not always being correctly recognizable or readable.
  • this invention is concerned with reducing at least one of these problems.
  • Another object of the invention is to provide smooth films for use in security documents.
  • materials for use in security documents which enable the security documents formed therefrom to be deformed to a small extent.
  • Another object is to provide a layer structure that is as smooth as possible and is suitable for the production of security documents.
  • a first subject of the invention relates to a film comprising i) 85 to 95% by weight of a polycarbonate or copolycarbonate of the formula (Ia), (1-2), (1-3) or (I- 4)
  • R 1 and R 2 independently of one another are hydrogen, halogen, preferably chlorine or bromine,
  • 10 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-
  • X is carbon, with the proviso that on at least one atom X, R 3 and R 4 are simultaneously alkyl, or 1 3
  • R 5 represents a C 1 to C 4 alkyl radical, aralkyl radical or aryl radical, preferably a methyl radical or phenyl radical, very particularly preferably a methyl radical; ii) 0.1 to 5% by weight of a first additive; iii) optionally 0.1 to 15% by weight of a second additive which is different from the first additive, the first additive ii) containing or being an antistatic compound.
  • a very particularly preferred dihydroxydiphenylcycloalkane of the formula (Ia) is 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (formula (Ia-1) where R 1 and R 2 are H).
  • Such polycarbonates can be prepared according to EP-A 359953 from dihydroxydiphenylcycloalkanes of the formula (Ia).
  • dihydroxyaryl compounds are resorcinol, 4,4'-dihydroxydiphenyl, bis- (4-hydroxyphenyl) -diphenyl-methane, l, l-bis- (4-hydroxyphenyl) -l-phenyl-ethane, bis- (4-hydroxyphenyl) - l- (l-naphthyl) -ethane, bis- (4-hydroxyphenyl) -l- (2-naphthyl) -ethane, 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis (3 , 5-dimethyl-4-hydroxyphenyl) propane, l, l-bis- (4-hydroxyphenyl) -cyclohexane, 1,1-bis- (3,5-dimethyl-4-hydroxyphenyl) -cyclohexane, l, l- Bis- (4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane,
  • dihydroxyaryl compounds are 4,4'-dihydroxydiphenyl and 2,2-bis (4-hydroxyphenyl) propane.
  • Both a dihydroxyaryl compound to form homopolycarbonates and various dihydroxyaryl compounds to form copolycarbonates can be used. It is possible to use both one dihydroxyaryl compound of the formula (I) or (Ia) with the formation of homopolycarbonates and also several dihydroxyaryl compounds of the formula (I) and / or (Ia) with the formation of copolycarbonates.
  • the various dihydroxyaryl compounds can be linked to one another either randomly or in blocks.
  • the molar ratio of dihydroxyaryl compounds of the formula (Ia) to the other dihydroxyaryl compounds of the formula (I) which may also be used is preferably between 99 mol% (Ia) to 1 mol -% (I) and 2 mol% (Ia) to 98 mol% (I), preferably between 99 mol% (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 very particularly preferred copolycarbonate can be obtained using 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane and 2,2-bis- (4-hydroxyphenyl) propane 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 independently of one another, identically or differently, represent hydrogen, linear or branched C1-C34-alkyl, C7-C34-alkylaryl or C6-C34-aryl, R can also mean -COO-R'", where R '"represents hydrogen, linear or branched Ci-C34-alkyl, C7-C34-alkylaryl or C6-C34-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-iso-propylphenyl-phenyl-carbonate, di- (4-iso-propylphenyl) -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-Pentyl
  • Biphenyl-4-yl-phenyl-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, ethy
  • diaryl compounds are diphenyl carbonate, 4-tert-butylphenyl-phenyl-carbonate, di- (4-tert-butyl-phenyl) -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.
  • one or more monohydroxyaryl compound (s), for example, can additionally be used as chain terminators which were not used to prepare the diaryl carbonate (s) used.
  • chain terminators which were not used to prepare the diaryl carbonate (s) used.
  • These can be those of the general formula (III), in which
  • R A stands for linear or branched C1-C34- alkyl, C 7 -C 34 - alkylaryl, C 6 -C 34 aryl or for -COO-R D , where R D stands for 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, identically or differently, represent hydrogen, linear or branched C1-C34-alkyl, C7-C34-alkylaryl or C6-C34-aryl.
  • Such monohydroxyaryl compounds are, for example, 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- (l-naphthyl) -phenol, 4- (2-naphthyl) -phenol, 4-tritylphenol, methyl salicylate, ethyl salicylate, n-propyl salicylate, iso-propyl salicylate, n-butyl salicylate, iso-
  • Suitable branching agents can be compounds with three or more functional groups, preferably those with three or more hydroxyl groups.
  • Suitable compounds with 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, l-tri- (4-hydroxyphenyl) -ethane, tri- (4-hydroxyphenyl) -phenylmethane, 2,2-bis- (4,4-bis- (4-hydroxyphenyl) -cyclohexyl] -propane, 2,4-bis- (4-hydroxyphenyl-isopropyl) -phenol and tetra- (4-hydroxyphenyl) -methane.
  • suitable compounds with three or more functional groups are, for example, 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.
  • phosgene can also be used in the liquid phase condensation (LPC) process.
  • LPC liquid phase condensation
  • the first additive ii), in particular the antistatic compound is selected from the group consisting of quaternary ammonium or phosphonium salts of a partially or perfluorinated organic acid or quaternary ammonium or phosphonium hexafluorophosphates or mixtures of at least two thereof.
  • anions of such salts suitable as additives according to the invention are, for example, preferably partially or perfluorinated alkyl sulfonates, cyanoperfluoroalkanesulfonylamides, bis (cyano) perfluoroalkylsulfonyl methides, bis (perfluoroalkylsulfonyl) imides, bis (perfluoroalkylsulfonyl) methides,
  • Tris (perfluoroalkylsulfonyl) methides or hexafluorophosphates are possible. Partially fluorinated or perfluorinated alkyl sulfonates are particularly preferred, and perfluoroalkyl sulfonates are very particularly preferred.
  • the cations of such salts suitable as additives according to the invention are, for example, preferably acylic or cyclic tertiary or quaternary ammonium or phosphonium cations.
  • Suitable cyclic cations are, for example, pyridinium, pyridazidinium, pyrimidiunium, pyrazinium, imidazolium, pyrazolium, thiazolium, oxazolime or thiazolium cations.
  • Suitable acyclic cations are, for example, those integrated into the following formula (IV).
  • Particularly preferred suitable quaternary ammonium or phosphonium salts of a perfluoroalkyl sulfonic acid are, for example, those of the general formula (IV)
  • X is N or P, preferably N,
  • R 1 partially or perfluorinated cyclic or linear, branched or unbranched carbon chains with 1 to 30 carbon atoms, preferably 4 to 8 carbon atoms, in the case of the cyclic radicals preferably those with 5 to 7 carbon atoms,
  • R 2 unsubstituted or substituted by halogen, hydroxy, cycloalkyl or alkyl, in particular by Ci to C3-alkyl or C5 to CV cycloalkyl, substituted, cyclic or linear, branched or unbranched carbon chains with 1 to 30 carbon atoms, preferably 3 to 10 Carbon atoms, in the case of cyclic radicals preferably those with 5 to 7 carbon atoms, particularly preferably propyl, 1-butyl, 1-pentyl, hexyl, isopropyl, isobutyl, tert-butyl, neopentyl, 2-pentyl, iso-pentyl, iso-hexyl, Cyclohexyl, cyclohexylmethyl and cyclopentyl,
  • R 3 , R 4 , R 5 each independently of one another unsubstituted or substituted, cyclic or linear, branched or unbranched carbon chains with 1 to 30 by halogen, hydroxy, cycloalkyl or alkyl, in particular by Ci to C3 alkyl or Cs to Cv cycloalkyl Carbon atoms, preferably 1 to 10 carbon atoms, in the case of cyclic radicals preferably those with 5 to 7 carbon atoms, particularly preferably methyl, ethyl, propyl, 1-butyl, 1-pentyl, hexyl, 1-isopropyl, isobutyl, tert-butyl, neopentyl, 2-pentyl, iso-pentyl, iso-hexyl, cyclohexyl, cyclohexylmethyl and cyclopentyl mean.
  • a preferred selection are the ammonium or phosphonium salts in which
  • X is N or P, preferably N,
  • R 1 perfluorinated linear or branched carbon chains with 1 to 30 carbon atoms, preferably 4 to 8 carbon atoms,
  • R 2 each independently halogenated or non-halogenated linear or branched carbon chains with 1 to 30 carbon atoms, preferably 3 to 10 carbon atoms, particularly preferably propyl, 1-butyl, 1-pentyl, hexyl, isopropyl, isobutyl, tert-butyl, neopentyl, 2-pentyl , Iso-pentyl, iso-hexyl,
  • R 3 , R 4 , R 5 each independently of one another halogenated or non-halogenated linear or branched carbon chains having 1 to 30 carbon atoms, preferably 1 to 10 carbon atoms; particularly preferably methyl, ethyl, propyl, 1-butyl, 1-pentyl, hexyl, isopropyl, isobutyl, tert-butyl, neopentyl, 2-pentyl, iso-pentyl, iso-hexyl.
  • Preferred suitable quaternary ammonium or phosphonium salts are:
  • Perfluorobutanesulfonic acid tetrapentylammonium salt Perfluoroctansulfonklatrahexylammoniumsalz, Perfluorbutansulfonklatrahexylammoniumsalz, PerfluorbutansulfonTalkretrimethylneopentylammoniumsalz, PerfluoroctansulfonTalkretrimethylneopentylammoniumsalz, Perfluorbutansulfonklaredimethyldineopentylammoniumsalz, Perfluoroctansulfonklaredimethyldineopentylammoniumsalz, N-methyl perfluorobutyl sulfonate, N-ethyl perfluorobutyl sulfonate, Tetrapropylammoniumperfluorbutylsulfonat, Diisopropyldimethylammoniumperfluorbutylsulfonat, Diisopropyl
  • One or more of the abovementioned quaternary ammonium or phosphonium salts, ie also mixtures, can preferably also be used.
  • the phosphonium sulfonate is preferably a fluorinated phosphonium sulfonate and is composed of a fluorocarbon which contains an organic sulfonate anion and an organic phosphonium cation.
  • organic sulfonate anions include perfluoromethanesulfonate, perfluorobutanesulfonate, perfluorohexanesulfonate, perfluoroheptanesulfonate and perfluorooctanesulfonate.
  • Examples of the aforementioned phosphonium cations include aliphatic phosphonium such as tetramethyl phosphonium, tetraethylphosphonium, tetra- butylphosphonium, Triethylmethylphosphonium, Tributylmethylphosphonium, Tributylethyl- phosphonium, Trioctylmethylphosphonium, Trimethylbutylphosphonium, Trimethyloctylphospho- nium, Trimethyllaurylphosphonium, Trimethylstearylphosphonium, Triethyloctylphosphonium, and aromatic phosphoniums such as tetraphenyl phosphonium, triphenylmethyl - phosphonium, triphenylbenzylphosphonium, tributylbenzylphosphonium.
  • aliphatic phosphonium such as tetramethyl phosphonium, tetraethylphosphonium, tetra- butylphosphonium
  • phosphonium salts preference is given to using tetrabutylphosphonium nonafluorobutylsulfonate.
  • the antistatic compound is selected from the group consisting of quaternary ammonium salts of a partially or perfluorinated organic acid or quaternary ammonium hexafluorophosphates or mixtures of at least two thereof.
  • the perfluorobutanesulphonic acid dimethyldiisopropylammonium salt (diisopropyldimethylammonium perfluorobutylsulphonate) is used.
  • 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 narrowing the solution.
  • Other manufacturing processes are described, for example, in DE-A 1 966931 and NL-A 7 802 830.
  • the salts mentioned are preferably added in amounts of 0.001 to 2% by weight, preferably 0.1 to 1% by weight, based on the total mass of the film before it is shaped, which can be done, for example, by extrusion or coextrusion.
  • the film described above is preferably part of a layer structure, the layer structure furthermore having at least one further layer of a thermoplastic material selected from polymers of ethylenically unsaturated monomers and / or polycondensates of bifunctional reactive compounds, preferably one or more polycarbonate (s) or copolycarbonate (e) based on diphenols, poly- or copolyacrylate (s) and poly- or copolymethacrylate (s), poly- or copolymer (s) with styrene, thermoplastic polyurethane (s), as well as polyolefin (s), poly- or copolycondensate (e) terephthalic acid with a proportion of 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol and / or 2,2,4,4-tetramethyl-1,3-butanediol, preferably 1,4-cyclohexanedimethanol and / or 1, 3-Cyclohexane
  • thermoplastics are polycarbonates or copolycarbonates based on diphenols, poly- or copolyacrylates and poly- or copolymethacrylates such as, for example and preferably, polymethyl methacrylate (PMMA), poly or copolymers with styrene such as, for example and preferably, polystyrene (PS) or polystyrene acrylonitrile (SAN) , thermoplastic polyurethanes, and polyolefins, such as, for example and preferably, polypropylene types or polyolefins based on cyclic olefins (eg TOPASTM), polycondensates or copolycondensates of an aromatic dicarboxylic acid and aliphatic, cycloalophatic and / or araliphatic diols with 2 to 16 carbon atoms, such as, for example and preferably, poly- or copolycondensates of terephthalic acid, particularly preferably poly- or copoly
  • Polyvinyl halides such as, for example and preferably, polyvinyl chloride (PVC), or mixtures of the aforementioned.
  • thermoplastics are one or more polycarbonate (s) or copolycarbonate (s) based on diphenols or blends containing at least one polycarbonate or copolycarbonate.
  • Blends containing at least one polycarbonate or copolycarbonate and at least one polycondensate or copolycondensate of terephthalic acid, naphthalenedicarboxylic acid or a cycloalkyldicarboxylic acid, preferably cyclohexanedicarboxylic acid are very particularly preferred.
  • Blends containing a polycarbonate or copolycarbonate and at least one cyclohexanedicarboxylic acid copolyester, such as Xylex TM from Sabic are also preferred.
  • Polycarbonates or copolycarbonates, in particular with average molecular weights Mw of 500 to 100,000, preferably from 10,000 to 80,000, particularly preferably from 15,000 to 40,000, or their blends with at least one poly- or copolycondensate of terephthalic acid with average molecular weight are very particularly preferred weight Mw from 10,000 to 200,000, preferably from 21,000 to 120,000.
  • polyalkylene terephthalates are suitable as poly- or copolycondensates of terephthalic acid.
  • Suitable polyalkylene terephthalates are, for example, reaction products of aromatic dicarboxylic acids or their reactive derivatives (e.g. 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 with 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% ethylene glycol and / or 1,4-butanediol and / or 1, 4- Cyclohexanedimethanol residues, based on the diol component.
  • the preferred polyalkylene terephthalates can contain up to 20 mol% residues of other aromatic dicarboxylic acids with 8 to 14 carbon atoms or aliphatic dicarboxylic acids with 4 to 12 carbon atoms, such as residues of phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid , 4,4'-diphenyldicarboxylic acid, succinic, adipic, sebacic acid, azelaic acid, cyclohexanediacetic acid.
  • the preferred polyalkylene terephthalates can contain ethylene or butanediol-1,4-glycol residues up to 80 mol% of other aliphatic diols with 3 to 12 carbon atoms or cycloaliphatic diols with 6 to 21 carbon atoms, z. B.
  • the polyalkylene terephthalates can be obtained by incorporating relatively small amounts of 3- or 4-valent alcohols or 3- or 4-basic carboxylic acids, as they are, for. B. in DE-OS 1900270 and US-PS 3692744 are described, are branched. Examples of preferred branching agents are trimesic acid, trimellitic acid, trimethylol ethane and propane and pentaerythritol.
  • branching agent based on the acid component.
  • polyalkylene terephthalates which have been produced solely from terephthalic acid and its reactive derivatives (e.g. its 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 made from at least two of the abovementioned acid components and / or from at least two of the abovementioned alcohol components; particularly preferred copolyesters are poly (ethylene glycol / 1,4-butanediol) terephthalates.
  • the polyalkylene terephthalates preferably used as a component preferably have an intrinsic viscosity of approx. 0.4 to 1.5 dl / g, preferably 0.5 to 1.3 dl / g, each measured in phenol / o-dichlorobenzene (1: 1 wt Parts) at 25 ° C.
  • Such a blend of polycarbonate or copolycarbonate with poly- or copolybutylene terephthalate or glycol-modified poly or copolycyclohexanedimethylene terephthalate can preferably be one with 1 to 90% by weight of polycarbonate or copolycarbonate and 99 to 10% by weight of poly- or copolybutylene terephthalate or glycol-modified poly- or copolycyclohexanedimethylene terephthalate, preferably with 1 to 90% by weight of polycarbonate and 99 to 10% by weight of polybutylene terephthalate or glycol-modified polycyclohexanedimethylene terephthalate, the proportions adding up to 100% by weight.
  • Copolycyclohexanedimethylene terephthalate to one with 20 to 85 wt .-% polycarbonate or copolycarbonate and 80 to 15 wt .-% poly or copolybutylene terephthalate or glycol-modified poly or copolycyclohexanedimethylene terephthalate, preferably with 20 to 85 wt .-% polycarbonate and 80 to 15 Wt% polybutylene terephthalate or glycol modified
  • Copolycyclohexanedimethylene terephthalate to one with 35 to 80 wt .-% polycarbonate or copolycarbonate and 65 to 20 wt .-% poly or copolybutylene terephthalate or glycol-modified poly or copolycyclohexanedimethylene terephthalate, preferably with 35 to 80 wt .-% polycarbonate and 65 to 20 Wt% polybutylene terephthalate or glycol modified
  • Acting polycyclohexanedimethylene terephthalate the proportions adding up to 100% by weight.
  • they can be blends of polycarbonate and glycol-modified polycyclohexanedimethylene terephthalate in the compositions mentioned above.
  • particularly suitable polycarbonates or copolycarbonates are aromatic polycarbonates or copolycarbonates.
  • the polycarbonates or copolycarbonates can be linear or branched in a known manner.
  • polycarbonates can be produced 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. For example, see Schnell, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Volume 9, Interscience Publishers, New York, London, Sydney 1964, to 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 on Drs. U. Grigo, K. Kirchner and PR Müller “Polycarbonate” in Becker / Braun, Kunststoff-Handbuch, Volume 3/1, Polycarbonate, Polyacetale, Polyester, cellulose ester, Carl Hanser Verlag Kunststoff, Vienna 1992, pages 117-299.
  • Suitable diphenols can 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 (hydroxyphenyl) ethers, bis (hydroxyphenyl) ketones, Bis (hydroxyphenyl) sulfides, bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) sulfoxides, l, l'-bis (hydroxyphenyl) diisopropylbenzenes, and their core alkylated and ring halogenated compounds.
  • Preferred dihydroxyaryl compounds are, for example, resorcinol, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis (3,5-dimethyl-4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) diphenyl methane , 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- (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) -l -phenyl-prop
  • R1 and R2 independently of one another are hydrogen, halogen, preferably chlorine or bromine, C1-C8-alkyl, C5-C6-cycloalkyl, C6-C10-aryl, preferably phenyl, and C7-C12-aralkyl, preferably phenyl-C1-C4-alkyl , in particular benzyl, m is an integer from 4 to 7, preferably 4 or 5,
  • R3 and R4 can be selected individually for each X, independently of one another hydrogen or C1-C6-alkyl and
  • X is carbon, with the proviso that X, R3 and R4 on at least one atom are simultaneously alkyl.
  • preference is given to alkyl on one or two atom (s) X, in particular on only one atom X, R3 and R4.
  • the preferred alkyl radical for the radicals R3 and R4 in formula (Ia) is methyl.
  • the X atoms in the alpha position to the diphenyl-substituted C atom (Cl) are preferably not dialkyl-substituted, while alkyl disubstitution in the beta position to Cl is preferred.
  • a very particularly preferred dihydroxydiphenylcycloalkane of the form (Ia) is 1,1-bis (4-hydroxyphcny I) -3, 3, 5-1 rimcthy I - cyc I ohcxan (formula (Ib) with RI and R2 being H).
  • Such polycarbonates can be prepared according to EP-A 359953 from dihydroxydiphenylcycloalkanes of the formula (Ia).
  • dihydroxyaryl compounds are resorcinol, 4,4'-dihydroxydiphenyl, bis- (4-hydroxyphenyl) -diphenyl-methane, l, l-bis- (4-hydroxyphenyl) -l-phenyl-ethane, bis- (4-hydroxyphenyl) - l- (l-naphthyl) -ethane, bis- (4-hydroxyphenyl) -l- (2-naphthyl) -ethane, 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis (3 , 5-dimethyl-4-hydroxyphenyl) propane, l, l-bis- (4-hydroxyphenyl) -cyclohexane, 1,1-bis- (3,5-dimethyl-4-hydroxyphenyl) -cyclohexane, l, l- Bis- (4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane,
  • dihydroxyaryl compounds are 4,4'-dihydroxydiphenyl and 2,2-bis (4-hydroxyphenyl) propane.
  • Both a dihydroxyaryl compound to form homopolycarbonates and various dihydroxyaryl compounds to form copolycarbonates can be used. It is possible to use both one dihydroxyaryl compound of the formula (I) or (Ia) with the formation of homopolycarbonates and also several dihydroxyaryl compounds of the formula (I) and / or (Ia) with the formation of copolycarbonates.
  • the various Dihydroxyaryl compounds be linked to one another both randomly and in blocks.
  • the molar ratio of dihydroxyaryl compounds of the formula (Ia) to the other dihydroxyaryl compounds of the formula (I) which may also be used is preferably between 99 mol% (Ia) to 1 mol -% (I) and 2 mol% (Ia) to 98 mol% (I), preferably between 99 mol% (Ia) to 1 mol% (I) and 10
  • a very particularly preferred copolycarbonate can be obtained using 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane and 2,2-bis- (4-hydroxyphenyl) propane dihydroxyaryl compounds of the formula ( Ia) and (I) are produced.
  • Suitable carbonic acid derivatives can be, for example, those mentioned under formula (II).
  • the polycarbonate or the copolycarbonate has an average molecular weight Mw in a range from 10,000 to 500,000 g / mol, preferably from 15,000 to 400,000 g / mol, particularly preferably from 20,000 to 300,000 g / mol.
  • the polycarbonate or the copolycarbonate is partially produced from the starting products selected from the group consisting of:
  • a very particularly preferred dihydroxydiphenylcycloalkane of the form (Ia) is 1,1-bis (4-hydroxyphcny I) -3, 3, 5-1 rimcthy I - cyc I ohcxan (formula (Ib) with R 1 and R 2 equal to H. ).
  • Such polycarbonates can be prepared according to EP-A 359953 from dihydroxydiphenylcycloalkanes of the formula (Ia).
  • dihydroxyaryl compounds are resorcinol, 4,4'-dihydroxydiphenyl, bis- (4-hydroxyphenyl) -diphenyl-methane, l, l-bis- (4-hydroxyphenyl) -l-phenyl-ethane, bis- (4-hydroxyphenyl) - l- (l-naphthyl) -ethane, bis- (4-hydroxyphenyl) -l- (2-naphthyl) -ethane, 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis (3 , 5-dimethyl-4-hydroxyphenyl) propane, l, l-bis- (4-hydroxyphenyl) -cyclohexane, 1,1-bis- (3,5-dimethyl-4-hydroxyphenyl) -cyclohexane, l, l- Bis- (4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane,
  • dihydroxyaryl compounds are 4,4'-dihydroxydiphenyl and 2,2-bis (4-hydroxyphenyl) propane.
  • Both a dihydroxyaryl compound to form homopolycarbonates and various dihydroxyaryl compounds to form copolycarbonates can be used. It is possible to use both one dihydroxyaryl compound of the formula (I) or (Ia) with the formation of homopolycarbonates and also several dihydroxyaryl compounds of the formula (I) and / or (Ia) with the formation of copolycarbonates.
  • the various dihydroxyaryl compounds can be linked to one another either randomly or in blocks.
  • the molar ratio of dihydroxyaryl compounds of the formula (Ia) to the other dihydroxyaryl compounds of the formula (I) which may also be used is preferably between 99 mol% (Ia) to 1 mol -% (I) and 2 mol% (Ia) to 98 mol% (I), preferably between 99 mol% (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 very particularly preferred copolycarbonate can be made using 1,1-bis (4-hydroxyphenyl) -3, 3, 5 - 1 rimcthy I - cyc I ohcxan and 2,2-bis (4-hydroxyphenyl) propane- compounds of the formula (Ia) and (I) are produced.
  • Suitable carbonic acid derivatives can be, for example, those mentioned under formula (II).
  • 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-iso-propylphenyl-phenyl-carbonate, di- (4-iso-propylphenyl) -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-Pentyl
  • Biphenyl-4-yl-phenyl-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, ethy
  • diaryl compounds are diphenyl carbonate, 4-tert-butylphenyl-phenyl-carbonate, di- (4-tert-butyl-phenyl) -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.
  • one or more monohydroxyaryl compound (s), for example, can additionally be used as chain terminators which were not used to prepare the diaryl carbonate (s) used.
  • chain terminators 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 C1-C34- alkyl, C7-C 34 - represents alkylaryl, C6-C 34 -aryl or -COO-R D 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, identically or differently, represent hydrogen, linear or branched C1-C34-alkyl, C7-C34-alkylaryl or C6-C34-aryl.
  • Such monohydroxyaryl compounds are, for example, 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- (l-naphthyl) -phenol, 4- (2-naphthyl) -phenol, 4-tritylphenol, methyl salicylate, ethyl salicylate, n-propyl salicylate, iso-propyl salicylate, n-butyl salicylate, iso-
  • Suitable branching agents can be compounds with three or more functional groups, preferably those with three or more hydroxyl groups.
  • Suitable compounds with 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, l-tri- (4-hydroxyphenyl) -ethane, tri- (4-hydroxyphenyl) -phenylmethane, 2,2-bis- (4,4-bis- (4-hydroxyphenyl) -cyclohexyl] -propane, 2,4-bis- (4-hydroxyphenyl-isopropyl) -phenol and tetra- (4-hydroxyphenyl) -methane.
  • Suitable compounds with three or more functional groups are, for example, 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.
  • the polycarbonate or the copolycarbonate contains the starting compound (Ib) in a range from 10% by weight to 90% by weight, particularly preferably in a range from 20% by weight to 80% by weight, based on the total mass of the polycarbonate or the copolycarbonate, or the polycarbonate or the copolycarbonate has a molar ratio of (Ib) to other bisphenol A derivatives in a range of 1: 10 to 10: 1, preferably in a range from 1: 5 to 5: 1.
  • the film has at least one, preferably at least two, particularly preferably all of the following properties:
  • (A) a roughness based on ISO 4288: 1996 in a range from 2 pm to 30 pm, preferably in a range from 3 pm to 25 pm, particularly preferably in a range from 5 pm to 20 pm;
  • (C) a gloss in a range from 10 to 110 according to ISO 2813, 2015-02, preferably in a range from 50 to 110, particularly preferably in a range from 60 to 100, or preferably in a range from 10 to 40, especially preferably in a range from 10 to 30;
  • the film preferably has one of the following combinations of features: (A) and (B); (A) and (C);
  • the transparency under (B) depends on the other additives that are added during the production of the film.
  • the film without further additives that is to say only with components i), ii) and iii), preferably has a transparency in a range from 50 to 92%, more preferably in a range from 70 to 92%.
  • the gloss under (C) varies in particular between the extremes in a range from 10 to 30 according to ISO 2813, 2015-02, if both sides of the film have a matt surface and the other extreme in a range from 70 to 110 according to ISO 2813, 2015-02 if both sides of the film have a smooth surface.
  • the further additive is selected from the group consisting of a dye, a pigment or a combination of these.
  • the pigment is preferably selected from the group consisting of a white pigment, a black pigment or a colored pigment, in particular a white pigment.
  • the pigment is selected from the group consisting of titanium dioxide, zirconium dioxide, alkaline earth carbonate such as calcium carbonate and alkaline earth sulfate such as barium sulfate or a mixture of at least two of these.
  • the film contains the fillers mentioned, such as dye or pigment, in each case preferably in a range from 2 to 20% by weight, particularly preferably from 5 to 10% by weight, based on the total weight of the film.
  • the fillers are preferably added in the stated amounts by, for example, extrusion or coextrusion during film production.
  • the fillers mentioned are preferably used in total in an amount in a range from 2 to 50% by weight, particularly preferably from 5 to 40% by weight, based on the total weight of the film.
  • the further additive is introduced into the film by a method with at least the following steps:
  • the coating in step Dl can be carried out by any coating method that a person skilled in the art would select for this.
  • the coating is preferably selected from the group consisting of dipping, printing or a combination thereof.
  • the film is preferably immersed in a dye bath in order to wet the film and produce a layer in the form of a colored layer on the film.
  • the dye bath can be heated to a temperature of up to 99 ° C. In this way, the intensity of the partial coloring can be improved in the plastic part, depending on the polymer used.
  • the dye bath can also be heated to 150 ° C if the heat resistance of the plastic parts allows.
  • the temperature of the dye bath is ⁇ 70 ° C, preferably> 10 ° C to ⁇ 60 ° C, particularly preferably> 15 ° C to ⁇ 50 ° C.
  • the dye bath can comprise at least one colorant, preferably at least one dye, particularly preferably at least one dye from the group of Solvent Dyes and / or Dispers Dyes according to the classification of the Color Index or mixtures of these dyes.
  • Dyes from the group of solvent dyes according to the classification of the Color Index can be, for example, the so-called Macrolex® dyes from Lanxess AG, Germany.
  • Macrolex® dyes from Lanxess AG, Germany.
  • Examples include Macrolex® Blue 3R, Macrolex® Red H, Macrolex® Yellow 6G (Solvent Yellow 179 according to CI), Macrolex® Violet Red R (Dispers Violet 31 according to CI), Macrolex® orange R (Solvent Orange 107 according to CI) or Mixtures of these dyes.
  • Dyes of the group of dispers dyes according to the classification of the Color Index can be, for example, diazo, diphenylamine and anthraquinone compounds, acetate dyes, disperse dyes and / or disperse dyes and include disperse blue # 3, disperse blue # 14, disperse yellow # 3, disperse -Rot # 134 and Dispers-Red # 7.
  • the classification and designation of the dyes cited above are consistent with The Color Index, 3rd Edition, jointly published by the Society of Dyes and Colors and the American Association of Textile Chemists and Colorists (1971).
  • the dyes can generally be used either as a single dye ingredient or as a component of a mixture, depending on the color desired. Thus, the term dye used here also includes the dye mixture.
  • Suitable dyes include water-insoluble diazo-diphenylamine and anthraquinone compounds.
  • the preferred dispersed dyes include Dy star's Palanil Blue E-R150 (Anthraquinone / Disperse Blue), DIANIX Orange E-3RN (Azo Dye / CI Disperse Orange 25) and the aforementioned Macrolex® dyes as solvent dyes.
  • the dye bath preferably comprises: a) solvent and / or dispersant, preferably water and / or organic solvent, particularly preferably water b) colorant, preferably a dye, particularly preferably a dye of the solvent dyes and / or dispersion dyes according to the classification of the color index.
  • a dye particularly preferably a dye of the solvent dyes and / or dispersion dyes according to the classification of the color index.
  • Those dye baths which are suitable for uniformly dyeing polycarbonate plastic parts at temperatures> 80 ° C. have proven to be advantageous. These are described, for example, in WO-A 03/040461, EP-A 2050866, WO-A 03/083207. Under the conditions of the method according to the invention, there is essentially a partial coloring of the film in the irradiated areas, so that an intensive engraving in the form of the layer is visible precisely at these points.
  • the layer containing the dye or the pigment contains the dye or the pigment preferably in an amount in a range from 1 ppm to 180 ppm, particularly preferably in a range from 10 ppm to 160 ppm, very particularly preferably in a range of 15 ppm to 100 ppm.
  • the layer preferably has a thickness in a range from 10 ⁇ m to 500 ⁇ m, particularly preferably in a range from 20 ⁇ m to 400 ⁇ m, very particularly preferably in a range from 50 ⁇ m to 200 ⁇ m.
  • the irradiation in step D2. can be done in any way the skilled person would choose to do this.
  • the irradiation in step D2. preferably takes place with focused non-ionizing electromagnetic radiation, preferably focused non-ionizing electromagnetic radiation with a wavelength in the range from> 0.1 ⁇ m to 1 mm, particularly preferably in the range from 0.15 ⁇ m to ganz 20 ⁇ m, very particularly preferably with fiber radiation of a wavelength in the range from> 0.15 pm to ⁇ 20 pm. Colored is also understood to mean black or white.
  • step D2 In the context of this invention, “essentially” is understood to mean that only those in step D2. Irradiated areas create a colored element that is clearly visible to the eye as a visible colored element. It cannot be ruled out that the plastic part may be slightly colored in the areas that have not been irradiated.
  • the method according to the invention is characterized in that a partial coloring of the film, which in particular contains thermoplastic plastic, is essentially based on the in step D2. irradiated areas.
  • the rest of the film has no or only a very weak coloring in the non-irradiated areas. It is thus possible to color areas of the film in a targeted manner in order, for example, to apply an image, personalization, logo, symbol or lettering to the film using the method according to the invention. These cannot be easily removed from the film surface.
  • the method according to the invention is therefore particularly suitable for the area of producing security and identification documents.
  • Another object of the invention relates to the use of a film according to the invention containing security-relevant data in a security document.
  • Security documents are understood to mean, in particular, documents with security-relevant information, such as identity cards, passports, driver's licenses and the like.
  • the invention also relates to the use of a polycarbonate or a copolycarbonate of the formulas (Ia), (1-2), (1-3) or (1-4) wherein
  • R 1 and R 2 are independently hydrogen, halogen, preferably chlorine or bromine, Ci-C 8 alkyl, Cs-C ö cycloalkyl, C 6 -Cio-aryl, preferably phenyl, and C7-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- C ⁇ - alkyl and
  • X is carbon, with the proviso that on at least one atom X, R 3 and R 4 are simultaneously alkyl, or where R 5 is a C1 to C 4 alkyl radical, aralkyl radical or aryl radical, preferably a methyl radical or phenyl radical, very particularly preferably a methyl radical for the production of a laser-engravable foil.
  • Another object of the invention relates to a layer structure containing at least the following layers:
  • the film according to the invention has been described above. All information on the film, such as raw materials, quantities, shapes and thicknesses can also be used for the films in the layer structure.
  • the further film can be any film that a person skilled in the art would use for this purpose.
  • the further film is preferably selected from the group consisting of a polyurethane film, a polyester film, a polyacrylate film, a polycarbonate film, a silicone film or a combination of at least two of these.
  • the layer structure has a further film S2. on, with the further slide S2.
  • a thermoplastic material selected from polymers of ethylenically unsaturated monomers and / or polycondensates of bifunctional reactive compounds, preferably one or more polycarbonate (s) or copolycarbonate (s) based on diphenols, poly- or copolyacrylate (s) and poly- or copolymethacrylate (s), poly- or copolymer (s) with styrene, thermoplastic polyurethane (s), as well as polyolefin (s), poly- or copolycondensate (s) of terephthalic acid with a proportion of 1,4-cyclohexanedimethanol, 1,3 -Cyclohexanedimethanol and / or 2,2,4,4-tetramethyl-1,3-butanediol, preferably 1,4-cyclohexanedimethanol and / or 1,3-
  • the paper or cardboard layer S4. can be any paper or cardboard layer that one skilled in the art would use for this purpose.
  • the layer structure comprises a further layer containing at least one thermoplastic material and at least one laser-sensitive additive.
  • the additive is preferably a black pigment, particularly preferably carbon black, or a colored pigment as described above in connection with the coloring of the film according to the invention. All information on black pigments and color pigments can also be used for the layer structure.
  • the films according to the invention are distinguished by a higher optical density compared to the comparison films not according to the invention, as can be seen from FIGS. 1 and 2.
  • the optical density was determined with the DENS color densitometer from Techkon in accordance with the recommendations of DIN 5033 Parts 1 -9: Color measurement and the calculations in accordance with ISO 5-3: 2009 (E): Photography - Measuring the optical density - Part 3
  • the glass transition temperature of the polymer was determined to be 157 ° C. (DSC).
  • Example 2 As in Example 1, a mixture of 127.1 g (0.56 mol) of bisphenol A and 137.7 g (0.44 mol) of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane was obtained converted to polycarbonate.
  • the polycarbonate showed a relative solution viscosity of 1.263.
  • the glass transition temperature of the polymer was determined to be 167 ° C. (DSC).
  • Example 2 As in Example 1, a mixture of 149.0 g (0.65 mol) of bisphenol A and 107.9 g (0.35 mol) of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane was obtained converted to polycarbonate.
  • the polycarbonate showed a relative solution viscosity of 1.263.
  • the glass transition temperature of the polymer was determined to be 183 ° C. (DSC).
  • Example 2 As in Example 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 was obtained converted to polycarbonate.
  • the polycarbonate showed a relative solution viscosity of 1.251.
  • the glass transition temperature of the polymer was determined to be 204 ° C. (DSC).
  • Example 2 As in Example 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 was obtained converted to polycarbonate.
  • the polycarbonate showed a relative solution viscosity of 1.248.
  • the glass transition temperature of the polymer was determined to be 216 ° C. (DSC).
  • Example 6 Compounding of a masterbatch for the production of the layer containing a thermoplastic and an antistatic additive
  • the antistatic additive compound was produced using conventional twin-screw compounding extruders (eg ZSK 32) at processing temperatures of 250 to 330 ° C. that are customary for polycarbonate.
  • a master batch was compounded with the following composition and then granulated:
  • Example 3 The plastic from Example 3 was used to extrude the films in a width of 450 mm.
  • an extruder with a screw of 75 mm diameter (D) and a length of 33xD.
  • the screw has a degassing zone;
  • the respective granulate was fed to the feed hopper of the extruder.
  • the material was melted and conveyed in the cylinder / screw plasticizing system of the extruder.
  • the material melt was fed to the smoothing calender, the rolls of which, or the cooling liquid fed in and removed for cooling the rolls, had the temperature specified in Table 1.
  • the final shaping and cooling of the film took place on the smoothing calender (consisting of three rollers).
  • a rubber roller (4 or surface), polished chrome roller (1 surface) or structured steel roller (2 or 6 surface) was used to structure the film surfaces.
  • the rubber roller used for structuring the film surface is disclosed in US Pat. No. 4,368,240 from Nauta Roll Corporation.
  • the film was then transported through a take-off.
  • a protective film made of PE can then be applied to both sides and the film can be rolled up.
  • Table 1 Running speed and temperature profile of the rollers
  • Table 2 Surface textures of the example foils 7 to 10
  • Examples 11 to 16 Toner printing A DIN A4 film sample from Examples 7 to 10 film was printed with a color laser printer from HP (printer model: Ricoh MP C 3003). The film was printed on the side with the respective named side.
  • Print sample Full-surface black print. Resolution of the print sample: 600 dpi.
  • the films according to the invention could be perfectly printed and showed a faultless print image in contrast to the films not according to the invention, which warped during the printing process and showed warpage in the film.
  • the printed films of Examples 11 to 16 "" was placed between two films based on polycarbonate Makrolon ® 3108 Covestro the AG.
  • the stack of foils was placed in a lamination press from Bürkle and laminated under pressure and temperature. Laminating was carried out with the following parameters:
  • the press was then cooled down. Cooling was carried out with continued pressurization. When a temperature of 38 ° C. was reached, the press was opened.

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Abstract

The invention relates to a film containing a special polycarbonate or copolycarbonate of the formula (Ia), (I-2), (I-3) or (I-4) and to the use of the film in a security document and in a layer structure.

Description

Folien mit besonderen Eigenschaften Films with special properties
Die Erfindung betrifft eine Folie enthaltend i) ein Po ly carbonat oder Copoly carbonat der Formel (1-1), (1-2), (1-3) oder (1-4), ii) 0,1 bis 5 Gew.-% eines ersten Zusatzstoffes; iii) optional 0,1 bis 15 Gew.% eines zweiten Zusatzstoffes, der verschieden ist vom ersten Zusatzstoff, wobei der erste Zusatzstoff ii) eine Antistatikverbindung enthält oder ist, sowie die Verwendung der erfindungsgemäßen Folie in einem Sicherheitsdokument und die Verwendung der Komponente i) zur Herstellung einer lasergravierbaren Folie. Weiterhin betrifft die Erfindung einen Schichtaufbau beinhaltend die erfindungsgemäße Folie. The invention relates to a film containing i) a Po ly carbonate or copoly carbonate of the formula (1-1), (1-2), (1-3) or (1-4), ii) 0.1 to 5 wt. -% of a first additive; iii) optionally 0.1 to 15% by weight of a second additive that is different from the first additive, the first additive ii) containing or being an antistatic compound, as well as the use of the film according to the invention in a security document and the use of component i) for the production of a laser-engravable foil. The invention also relates to a layer structure comprising the film according to the invention.
Für den Bereich der Sicherheitsdokumente, insbesondere Identifikationsdokumente ist die Einbettung von mehreren Sicherheitsmerkmalen zwingend erforderlich, insbesondere zur Sicherstellung der Originalität dieser Sicherheitsdokumente. Zunehmend umfassen solche Sicherheitsdokumente, insbesondere Identifikationsdokumente, Polycarbonat. Dokumente basierend auf Polycarbonat sind besonders langlebig und weisen eine hohe Sicherheit gegen Fälschungen auf. Beliebte Sicherheitsmerkmale sind transparente Bereiche in beispielsweise Identifikationskarten oder in Datenseiten von Reisepässen. Diese transparenten Bereiche werden auch „Fenster“ genannt. In diese Fenster können Hologramme, Sicherheitsdrucke und andere Elemente eingebracht werden, welche durch Betrachtung als Original oder Fälschung erkannt werden können. Die Funktion des Sicherheitsmerkmals basiert auf der hohen Transparenz von Polycarbonat. Ist die Transparenz des Dokuments im Fenster beeinträchtigt, dann kann es sich um eine Fälschung handeln. Der Grund dafür: Beim Überkleben des Dokuments mit einer weiteren transparenten Folie, welche z.B. falsche Personalien enthält, erscheint die Veränderung im Fenster deutlich. Das Fenster erscheint bei Durchsicht weniger klar. Ebenfalls ist die Klarheit des Fensters gestört, beim Versuch das Dokument zu öffnen und wieder zu verkleben. For the area of security documents, in particular identification documents, the embedding of several security features is absolutely necessary, in particular to ensure the originality of these security documents. Such security documents, in particular identification documents, increasingly include polycarbonate. Documents based on polycarbonate are particularly durable and have a high level of security against forgery. Popular security features are transparent areas in, for example, identification cards or in the data pages of passports. These transparent areas are also called "windows". Holograms, security prints and other elements can be introduced into these windows, which can be recognized as originals or falsifications by looking at them. The function of the security feature is based on the high transparency of polycarbonate. If the transparency of the document in the window is impaired, then it could be a forgery. The reason for this: When the document is covered with another transparent film, which e.g. contains incorrect personal details, the change in the window clearly appears. The window appears less clear when looking through it. The clarity of the window is also disturbed when trying to open the document and glue it back on.
Ein Problem bei der Fertigung der Sicherheitsdokumente kann einerseits die Verformung der Folie bei der Herstellung sein, aber auch der Einschluss von Fuftblasen. Häufig entstehen Wellen in den einzelnen Schichten, die zum einen unansehnlich sind, aber zum anderen auch dazu führen können, dass die Daten in dem Sicherheitselemente nicht immer richtig erkennbar oder auslesbar sind. A problem in the production of the security documents can be the deformation of the film during production, but also the inclusion of air bubbles. Waves often arise in the individual layers, which on the one hand are unsightly, but on the other hand can also lead to the data in the security element not always being correctly recognizable or readable.
Daher beschäftigt sich diese Erfindung mit der Reduktion mindestens eines dieser Probleme. Insbesondere ist es eine Aufgabe der Erfindung möglichst glatte Folien für Sicherheitsdokumente bereitzustellen, wobei die gedruckten Daten eine möglichst große Schärfe aufweisen sollen. Weiterhin ist es eine Aufgabe der Erfindung glatte Folien für die Verwendung in Sicherheitsdokumenten bereitzustellen. Des Weiteren ist es eine Aufgabe der Erfindung Materialien für die Verwendung in Sicherheitsdokumenten bereitzustellen, die ein geringes Verformen der daraus geformten Sicherheitsdokumente ermöglicht. Eine weitere Aufgabe ist es einen Schichtaufbau bereitzustellen, der möglichst glatt ist und sich zur Herstellung von Sicherheitsdokumenten eignet. Ein erster Gegenstand der Erfindung betrifft eine Folie enthaltend i) 85 bis 95 Gew.-% ein Polycarbonat oder Copolycarbonat der Formel (Ia), (1-2), (1-3) oder (I- 4) Therefore, this invention is concerned with reducing at least one of these problems. In particular, it is an object of the invention to provide films for security documents that are as smooth as possible, the printed data being intended to be as sharp as possible. Another object of the invention is to provide smooth films for use in security documents. Furthermore, it is an object of the invention to provide materials for use in security documents which enable the security documents formed therefrom to be deformed to a small extent. Another object is to provide a layer structure that is as smooth as possible and is suitable for the production of security documents. A first subject of the invention relates to a film comprising i) 85 to 95% by weight of a polycarbonate or copolycarbonate of the formula (Ia), (1-2), (1-3) or (I- 4)
5 worin 5 wherein
R1 und R2 unabhängig voneinander Wasserstoff, Halogen, bevorzugt Chlor oder Brom,R 1 and R 2 independently of one another are hydrogen, halogen, preferably chlorine or bromine,
Ci-Cs-Alkyl, Cs-Cö-Cycloalkyl, Cö-Cio-Aryl, bevorzugt Phenyl, und C7-Ci2-Aralkyl, bevorzugt Phenyl-Ci-C4- Alkyl, insbesondere Benzyl, Ci-Cs-alkyl, Cs-C ö -cycloalkyl, C ö -Cio-aryl, preferably phenyl, and C7-Ci2-aralkyl, preferably phenyl-Ci-C4-alkyl, especially benzyl,
10 m eine ganze Zahl von 4 bis 7, bevorzugt 4 oder 5, 10 m is an integer from 4 to 7, preferably 4 or 5,
R3 und R4 für jedes X individuell wählbar, unabhängig voneinander Wasserstoff oder Ci-R 3 and R 4 can be selected individually for each X, independently of one another hydrogen or Ci-
CÖ- Alkyl und C Ö - alkyl and
X Kohlenstoff bedeuten, mit der Maßgabe, dass an mindestens einem Atom X, R3 und R4 gleichzeitig Alkyl bedeuten, oder 1 3X is carbon, with the proviso that on at least one atom X, R 3 and R 4 are simultaneously alkyl, or 1 3
15 1 4 worin R5 für einen Ci - bis C4- Alkylrest, Aralkylrest oder Arylrest, bevorzugt für einen Methylrest oder Phenylrest, ganz besonders bevorzugt für einen Methylrest, steht; ii) 0,1 bis 5 Gew.-% eines ersten Zusatzstoffes; iii) optional 0,1 bis 15 Gew.% eines zweiten Zusatzstoffes, der verschieden ist vom ersten Zusatzstoff wobei der erste Zusatzstoff ii) eine Antistatikverbindung enthält oder ist. 15 1 4 wherein R 5 represents a C 1 to C 4 alkyl radical, aralkyl radical or aryl radical, preferably a methyl radical or phenyl radical, very particularly preferably a methyl radical; ii) 0.1 to 5% by weight of a first additive; iii) optionally 0.1 to 15% by weight of a second additive which is different from the first additive, the first additive ii) containing or being an antistatic compound.
Ein ganz besonders bevorzugtes Dihydroxydiphenylcycloalkan der Formel (Ia) ist l,l-Bis-(4- hydroxyphenyl)-3,3,5-trimethyl-cyclohexan (Formel (Ia-1) mit R1 und R2 gleich H). A very particularly preferred dihydroxydiphenylcycloalkane of the formula (Ia) is 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (formula (Ia-1) where R 1 and R 2 are H).
Solche Polycarbonate können gemäß der EP-A 359953 aus Dihydroxydiphenylcycloalkanen der Formel (Ia) hergestellt werden. Such polycarbonates can be prepared according to EP-A 359953 from dihydroxydiphenylcycloalkanes of the formula (Ia).
Besonders bevorzugte Dihydroxyarylverbindungen sind Resorcin, 4,4'-Dihydroxydiphenyl, Bis-(4- hydroxyphenyl)-diphenyl-methan, l,l-Bis-(4-hydroxyphenyl)-l-phenyl-ethan, Bis-(4-hydroxyphenyl)- l-(l-naphthyl)-ethan, Bis-(4-hydroxyphenyl)-l-(2-naphthyl)-ethan, 2,2-Bis-(4-hydroxyphenyl)- propan, 2,2-Bis(3,5-dimethyl-4-hydroxyphenyl)-propan, l,l-Bis-(4-hydroxyphenyl)-cyclohexan, 1,1- Bis-(3,5-dimethyl-4-hydroxyphenyl)-cyclohexan, l,l-Bis-(4-hydroxyphenyl)-3,3,5-trimethyl- cyclohexan, l,l'-Bis-(4-hydroxyphenyl)-3-diisopropyl-benzol und 1,1'- Bis-(4-hydroxyphenyl)-4- diisopropyl-benzol. Particularly preferred dihydroxyaryl compounds are resorcinol, 4,4'-dihydroxydiphenyl, bis- (4-hydroxyphenyl) -diphenyl-methane, l, l-bis- (4-hydroxyphenyl) -l-phenyl-ethane, bis- (4-hydroxyphenyl) - l- (l-naphthyl) -ethane, bis- (4-hydroxyphenyl) -l- (2-naphthyl) -ethane, 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis (3 , 5-dimethyl-4-hydroxyphenyl) propane, l, l-bis- (4-hydroxyphenyl) -cyclohexane, 1,1-bis- (3,5-dimethyl-4-hydroxyphenyl) -cyclohexane, l, l- Bis- (4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane, l, l'-bis- (4-hydroxyphenyl) -3-diisopropyl-benzene and 1,1'-bis- (4-hydroxyphenyl) - 4-diisopropyl benzene.
Ganz besonders bevorzugte Dihydroxyarylverbindungen sind 4,4'-Dihydroxydiphenyl und 2,2-Bis-(4- hydroxyphenyl)-propan. Very particularly preferred dihydroxyaryl compounds are 4,4'-dihydroxydiphenyl and 2,2-bis (4-hydroxyphenyl) propane.
Es können sowohl eine Dihydroxyarylverbindung unter Bildung von Homopolycarbonaten als auch verschiedene Dihydroxyarylverbindungen unter Bildung von Copolycarbonaten verwendet werden. Es können sowohl eine Dihydroxyarylverbindung der Formel (I) oder (Ia) unter Bildung von Homopolycarbonaten als auch mehrere eine Dihydroxyarylverbindungen der Formel (I) und/oder (Ia) unter Bildung von Copolycarbonaten verwendet werden. Dabei können die verschiedenen Dihydroxyarylverbindungen sowohl statistisch als auch blockweise miteinander verknüpft sein. Im Falle von Copolycarbonaten aus Dihydroxyarylverbindungen der Formel (I) und (Ia), beträgt das molare Verhältnis von Dihydroxyarylverbindungen der Formel (Ia) zu den gegebenenfalls mitzuverwendenden anderen Dihydroxyarylverbindungen der Formel (I) vorzugsweise zwischen 99 Mol-% (Ia) zu 1 Mol-% (I) und 2 Mol-% (Ia) zu 98 Mol-% (I), vorzugsweise zwischen 99 Mol-% (Ia) zu 1 Mol-% (I) und 10 Mol-% (Ia) zu 90 Mol-% (I) und insbesondere zwischen 99 Mol-% (Ia) zu 1 Mol-% (I) und 30 Mol-% (Ia) zu 70 Mol-% (I). Both a dihydroxyaryl compound to form homopolycarbonates and various dihydroxyaryl compounds to form copolycarbonates can be used. It is possible to use both one dihydroxyaryl compound of the formula (I) or (Ia) with the formation of homopolycarbonates and also several dihydroxyaryl compounds of the formula (I) and / or (Ia) with the formation of copolycarbonates. The various dihydroxyaryl compounds can be linked to one another either randomly or in blocks. In the case of copolycarbonates made from 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) which may also be used is preferably between 99 mol% (Ia) to 1 mol -% (I) and 2 mol% (Ia) to 98 mol% (I), preferably between 99 mol% (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).
Ein ganz besonders bevorzugtes Copolycarbonat kann unter Verwendung von 1,1 -Bis-(4- hydroxyphenyl)-3,3,5-trimethyl-cyclohexan und 2,2-Bis-(4-hydroxyphenyl)-propan Dihydroxyaryl verbindungen der Formel (Ia) und (I) hergestellt werden. A very particularly preferred copolycarbonate can be obtained using 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane and 2,2-bis- (4-hydroxyphenyl) propane dihydroxyaryl compounds of the formula (Ia ) and (I).
Geeignete Kohlensäurederivate können beispielsweise Diarylcarbonate der allgemeinen Formel (II) sein, worin Suitable carbonic acid derivatives can be, for example, diaryl carbonates of the general formula (II), wherein
R, R' und R" unabhängig voneinander gleich oder verschieden für Wasserstoff, lineares oder verzweigtes C1-C34- Alkyl, C7-C34-Alkylaryl oder C6-C34-Aryl stehen, R weiterhin auch -COO-R'" bedeuten kann, wobei R'" für Wasserstoff, lineares oder verzweigtes Ci-C34-Alkyl, C7-C34-Alkylaryl oder C6-C34-Aryl steht. R, R 'and R "independently of one another, identically or differently, represent hydrogen, linear or branched C1-C34-alkyl, C7-C34-alkylaryl or C6-C34-aryl, R can also mean -COO-R'", where R '"represents hydrogen, linear or branched Ci-C34-alkyl, C7-C34-alkylaryl or C6-C34-aryl.
Bevorzugte Diarylcarbonate sind beispielsweise Diphenylcarbonat, Methylphenyl-phenyl-carbonate und Di-(methylphenyl)-carbonate, 4-Ethylphenyl-phenyl-carbonat, Di-(4-ethylphenyl)-carbonat, 4-n- Propylphenyl-phenyl-carbonat, Di-(4-n-propylphenyl)-carbonat, 4-iso-Propylphenyl -phenyl-carbonat, Di-(4-iso-propylphenyl)-carbonat, 4-n-Butylphenyl-phenyl-carbonat, Di-(4-n-butylphenyl)-carbonat, 4-iso-Butylphenyl-phenyl-carbonat, Di-(4-iso-butylphenyl)-carbonat, 4-tert-Butylphenyl-phenyl- carbonat, Di-(4-tert-butylphenyl)-carbonat, 4-n-Pentylphenyl-phenyl-carbonat, Di-(4-n-pentylphenyl)- carbonat, 4-n-Hexylphenyl-phenyl-carbonat, Di-(4-n-hexylphenyl)-carbonat, 4-iso-Octylphenyl- phenyl-carbonat, Di-(4-iso-octylphenyl)-carbonat, 4-n-Nonylphenyl-phenyl-carbonat, Di-(4-n- nonylphenyl) -carbonat, 4-Cyclohexylphenyl -phenyl-carbonat, Di-(4-cyclohexylphenyl)-carbonat, 4-(l- Methyl- 1 -phenylethyl)-phenyl-phenyl-carbonat, Di- [4-( 1 -methyl- 1 -phenylethyl) -phenyl] -carbonat,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-iso-propylphenyl-phenyl-carbonate, di- (4-iso-propylphenyl) -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-nonylphenylphenyl carbonate, di (4-n-nonylphenyl) carbonate, 4-cyclohexylphenylphenyl carbonate, di- (4-cyclohexylphenyl) ) carbonate, 4- (l-methyl-1-phenylethyl) -phenyl-phenyl-carbonate, di- [4- (1 -methyl-1-phenylethyl) -phenyl] -carbonate,
Biphenyl-4-yl -phenyl-carbonat, Di-(biphenyl-4-yl)-carbonat, 4-( 1 -Naphthyl)-phenyl-phenyl-carbonat, 4-(2-Naphthyl)-phenyl-phenyl-carbonat, Di-[4-(l-naphthyl)-phenyl]-carbonat, Di-[4-(2- naphthyl)phenyl] -carbonat, 4-Phenoxyphenyl-phenyl-carbonat, Di-(4-phenoxyphenyl)-carbonat, 3- Pentadecylphenyl-phenyl-carbonat, Di-(3-pentadecylphenyl)-carbonat, 4-Tritylphenyl-phenyl- carbonat, Di-(4-tritylphenyl)-carbonat, Methylsalicylat-phenyl-carbonat, Di-(methylsalicylat)-carbonat, Ethylsalicylat-phenyl-carbonat, Di-(ethylsalicylat)-carbonat, n-Propylsalicylat-phenyl-carbonat, Di-(n- propylsalicylat)-carbonat, iso-Propylsalicylat-phenyl-carbonat, Di-(iso-propylsalicylat)-carbonat, n- Butylsalicylat-phenyl-carbonat, Di-(n-butylsalicylat)-carbonat, iso-Butylsalicylat-phenyl-carbonat, Di- (iso-butylsalicylat)-carbonat, tert-Butylsalicylat-phenyl-carbonat, Di-(tert-butylsalicylat)-carbonat, Di- (phenylsalicylat)-carbonat und Di-(benzylsalicylat)-carbonat. Biphenyl-4-yl-phenyl-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.
Besonders bevorzugte Diarylverbindungen sind Diphenylcarbonat, 4-tert-Butylphenyl-phenyl-carbonat, Di-(4-tert-butylphenyl)-carbonat, Biphenyl-4-yl-phenyl-carbonat, Di-(biphenyl-4-yl)-carbonat, 4-( 1 - Methyl- 1 -phenylethyl)-phenyl-phenyl-carbonat, Di- [4-( 1 -methyl- 1 -phenylethyl) -phenyl] -carbonat und Di-(methylsalicylat)-carbonat. Ganz besonders bevorzugt ist Diphenylcarbonat. Particularly preferred diaryl compounds are diphenyl carbonate, 4-tert-butylphenyl-phenyl-carbonate, di- (4-tert-butyl-phenyl) -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.
Es können sowohl ein Diarylcarbonat als auch verschiedene Diarylcarbonate verwendet werden. Zur Steuerung bzw. Veränderung der Endgruppen können zusätzlich beispielsweise eine oder mehrere Monohydroxyarylverbindung(en) als Kettenabbrecher eingesetzt werden, die nicht zur Herstellung des oder der verwendeten Diarylcarbonat(e) verwendet wurde(n). Dabei kann es sich um solche der allgemeinen Formel (III) handeln, wobei Both a diaryl carbonate and various diaryl carbonates can be used. To control or change the end groups, one or more monohydroxyaryl compound (s), for example, can additionally be used as chain terminators which were not used to prepare the diaryl carbonate (s) used. These can be those of the general formula (III), in which
RA für lineares oder verzweigtes C1-C34- Alkyl, C7-C34- Alkylaryl, C6-C34-Aryl oder für -COO-RD steht, wobei RD für Wasserstoff, lineares oder verzweigtes Ci-C34-Alkyl, C7-C34- Alkylaryl oder C6-C34- Aryl steht, und R A stands for linear or branched C1-C34- alkyl, C 7 -C 34 - alkylaryl, C 6 -C 34 aryl or for -COO-R D , where R D stands for hydrogen, linear or branched Ci-C 34 - Alkyl, C 7 -C 34 - alkylaryl or C 6 -C 34 - aryl, and
RB, Rc unabhängig voneinander gleich oder verschieden für Wasserstoff, lineares oder verzweigtes Ci- C34- Alkyl, C7-C34- Alkylaryl oder C6-C34-Aryl stehen. R B , R c independently of one another, identically or differently, represent hydrogen, linear or branched C1-C34-alkyl, C7-C34-alkylaryl or C6-C34-aryl.
Solche Monohydroxyarylverbindungen sind beispielsweise 1-, 2- oder 3-Methylphenol, 2,4- Dimethylphenol 4-Ethylphenol, 4-n-Propylphenol, 4-iso-Propylphenol, 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-(l -Methyl- l-phenylethyl)-phenol, 4- Phenylphenol, 4-Phenoxyphenol, 4-(l-Naphthyl)-phenol, 4-(2-Naphthyl)-phenol, 4-Tritylphenol, Methylsalicylat, Ethylsalicylat, n-Propylsalicylat, iso-Propylsalicylat, n-Butylsalicylat, iso-Such monohydroxyaryl compounds are, for example, 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- (l-naphthyl) -phenol, 4- (2-naphthyl) -phenol, 4-tritylphenol, methyl salicylate, ethyl salicylate, n-propyl salicylate, iso-propyl salicylate, n-butyl salicylate, iso-
Butylsalicylat, tert-Butylsalicylat, Phenylsalicylat und Benzylsalicylat. Butyl salicylate, tert-butyl salicylate, phenyl salicylate and benzyl salicylate.
Bevorzugt sind 4-tert-Butylphenol, 4-iso-Octylphenol und 3-Pentadecylphenol. 4-tert-butylphenol, 4-iso-octylphenol and 3-pentadecylphenol are preferred.
Geeignete Verzweiger können Verbindungen mit drei und mehr funktionellen Gruppen, vorzugsweise solche mit drei oder mehr Hydroxylgruppen. Suitable branching agents can be compounds with three or more functional groups, preferably those with three or more hydroxyl groups.
Geeignete Verbindungen mit drei oder mehr phenolischen Hydroxylgruppen sind beispielsweise Phloroglucin, 4,6-Dimethyl-2,4,6-tri-(4-hydroxyphenyl)-hepten-2, 4,6-Dimethyl-2,4,6-tri-(4- hydroxyphenyl)-heptan, 1 ,3,5-Tri-(4-hydroxyphenyl)-benzol, 1 , 1 , l-Tri-(4-hydroxyphenyl)-ethan, Tri- (4-hydroxyphenyl)-phenylmethan, 2,2-Bis-(4,4-bis-(4-hydroxyphenyl)-cyclohexyl]-propan, 2,4-Bis-(4- hydroxyphenyl-isopropyl)-phenol und Tetra-(4-hydroxyphenyl)-methan. Suitable compounds with 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, l-tri- (4-hydroxyphenyl) -ethane, tri- (4-hydroxyphenyl) -phenylmethane, 2,2-bis- (4,4-bis- (4-hydroxyphenyl) -cyclohexyl] -propane, 2,4-bis- (4-hydroxyphenyl-isopropyl) -phenol and tetra- (4-hydroxyphenyl) -methane.
Sonstige geeignete Verbindungen mit drei und mehr funktionellen Gruppen sind beispielsweise 2,4- Dihydroxybenzoesäure, Trimesinsäure(trichlorid), Cyanursäuretrichlorid und 3,3-Bis-(3-methyl-4- hydroxyphenyl)-2-oxo-2,3-dihydroindol. Bevorzugte Verzweiger sind 3,3-Bis-(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindol und 1,1,1- Tri- (4 -hydroxy phenyl) -ethan. Other suitable compounds with three or more functional groups are, for example, 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.
Neben den Diarylcarbonaten kann im Phasengrenzflächen- („liquid phase condensation“, LPC)- Verfahren auch Phosgen eingesetzt werden. In addition to the diaryl carbonates, phosgene can also be used in the liquid phase condensation (LPC) process.
In einer bevorzugten Ausgestaltung der Folie ist der erste Zusatzstoff ii), insbesondere die Antistatikverbindung, ausgewählt aus der Gruppe bestehend aus quaternären Ammonium- oder Phosphoniumsalzen einer teil- oder perfluorierten organischen Säure oder quaternären Ammonium oder Phosphoniumhexafluorophosphaten oder Mischungen aus mindestens zwei hiervon. In a preferred embodiment of the film, the first additive ii), in particular the antistatic compound, is selected from the group consisting of quaternary ammonium or phosphonium salts of a partially or perfluorinated organic acid or quaternary ammonium or phosphonium hexafluorophosphates or mixtures of at least two thereof.
Solche Additive und deren Verwendung als Antistatika sind in der Literatur beschrieben (vgl. DE-A 25 06 726, EP-A 1 290 106, EP 897 950 A2 oder US 6,372,829). Such additives and their use as antistatic agents are described in the literature (cf. DE-A 25 06 726, EP-A 1 290 106, EP 897 950 A2 or US Pat. No. 6,372,829).
Als Anionen solcher erfindungsgemäß als Additive geeigneten Salze kommen beispielsweise bevorzugt teil- oder perfluorierte Alkylsulfonate, Cyanoperfluoralkansulfonylamide, Bis(cyano)perfluoralkyl- sulfonylmethide, Bis(perfluoralkylsulfonyl)imide, Bis(perfluoralkylsulfonyl)methide,The anions of such salts suitable as additives according to the invention are, for example, preferably partially or perfluorinated alkyl sulfonates, cyanoperfluoroalkanesulfonylamides, bis (cyano) perfluoroalkylsulfonyl methides, bis (perfluoroalkylsulfonyl) imides, bis (perfluoroalkylsulfonyl) methides,
Tris(perfluoralkylsulfonyl)methide oder Hexafluorophosphate in Frage. Besonders bevorzugt sind teil- oder perfluorierte Alkylsulfonate, ganz besonders bevorzugt Perfluoralkylsulfonate. Als Kationen solcher erfindungsgemäß als Additive geeigneten Salze kommen beispielsweise bevorzugt acylische oder cyclische tertiäre oder quaternäre Ammonium- oder Phosphoniumkationen. Als geeignete cyclische Kationen kommen beispielsweise Pyridinium, Pyridazidinium, Pyrimidiunium, Pyrazinium, Imidazolium, Pyrazolium, Thiazolium Oxazolim oder Thiazolium-Kationen in Frage. Als geeignete acyclischen Kationen kommen beispielsweise die in die folgende Formel (IV) integrierten in Frage.Tris (perfluoroalkylsulfonyl) methides or hexafluorophosphates are possible. Partially fluorinated or perfluorinated alkyl sulfonates are particularly preferred, and perfluoroalkyl sulfonates are very particularly preferred. The cations of such salts suitable as additives according to the invention are, for example, preferably acylic or cyclic tertiary or quaternary ammonium or phosphonium cations. Suitable cyclic cations are, for example, pyridinium, pyridazidinium, pyrimidiunium, pyrazinium, imidazolium, pyrazolium, thiazolium, oxazolime or thiazolium cations. Suitable acyclic cations are, for example, those integrated into the following formula (IV).
Besonders bevorzugt geeignete quarternäre Ammonium- oder Phosphoniumsalze einer Perfluoralkyl sulfonsäure sind beispielsweise solche der allgemeinen Formel (IV) Particularly preferred suitable quaternary ammonium or phosphonium salts of a perfluoroalkyl sulfonic acid are, for example, those of the general formula (IV)
R'-SOs XR2R3R4R5 (IV) in welcher R'-SOs XR 2 R 3 R 4 R 5 (IV) in which
X N oder P, bevorzugt N bedeuten, X is N or P, preferably N,
R1 teil- oder perfluorierte cyclische oder lineare, verzweigte oder unverzweigte Kohlenstoffketten mit 1 bis 30 Kohlenstoffatomen, bevorzugt 4 bis 8 Kohlenstoffatomen, im Falle der cyclischen Reste bevorzugt solche mit 5 bis 7 Kohlenstoffatomen, R 1 partially or perfluorinated cyclic or linear, branched or unbranched carbon chains with 1 to 30 carbon atoms, preferably 4 to 8 carbon atoms, in the case of the cyclic radicals preferably those with 5 to 7 carbon atoms,
R2 unsubstituierte oder durch Halogen, Hydroxy, Cycloalkyl oder Alkyl, insbesondere durch Ci bis C3-Alkyl bzw.C5 bis CVCycloalkyl, substituierte, cyclische oder lineare, verzweigte oder unverzweigte Kohlenstoffketten mit 1 bis 30 Kohlenstoffatomen, bevorzugt 3 bis 10 Kohlenstoffatomen, im Falle cyclischer Reste bevorzugt solche mit 5 bis 7 Kohlenstoffatomen, besonders bevorzugt Propyl, 1 -Butyl, 1-Pentyl, Hexyl, Isopropyl, Isobutyl, tert-Butyl, Neopentyl, 2-Pentyl, Iso-Pentyl, Iso-Hexyl, Cyclohexyl, Cyclohexylmethyl und Cyclopentyl,R 2 unsubstituted or substituted by halogen, hydroxy, cycloalkyl or alkyl, in particular by Ci to C3-alkyl or C5 to CV cycloalkyl, substituted, cyclic or linear, branched or unbranched carbon chains with 1 to 30 carbon atoms, preferably 3 to 10 Carbon atoms, in the case of cyclic radicals preferably those with 5 to 7 carbon atoms, particularly preferably propyl, 1-butyl, 1-pentyl, hexyl, isopropyl, isobutyl, tert-butyl, neopentyl, 2-pentyl, iso-pentyl, iso-hexyl, Cyclohexyl, cyclohexylmethyl and cyclopentyl,
R3, R4, R5 jeweils unabhängig voneinander unsubstituierte oder durch Halogen, Hydroxy, Cycloalkyl oder Alkyl, insbesondere durch Ci bis C3- Alkyl, bzw.Cs bis CvCycloalkyl, substituierte, cyclische oder lineare, verzweigte oder unverzweigte Kohlenstoffketten mit 1 bis 30 Kohlenstoffatomen, bevorzugt 1 bis 10 Kohlenstoffatomen, im Falle cyclischer Reste bevorzugt solche mit 5 bis 7 Kohlenstoffatomen, besonders bevorzugt Methyl, Ethyl, Propyl, 1 -Butyl, 1- Pentyl, Hexyl, 1 -Isopropyl, Isobutyl, tert-Butyl, Neopentyl, 2-Pentyl, Iso-Pentyl, Iso-Hexyl, Cyclohexyl, Cyclohexylmethyl und Cyclopentyl bedeuten. R 3 , R 4 , R 5 each independently of one another unsubstituted or substituted, cyclic or linear, branched or unbranched carbon chains with 1 to 30 by halogen, hydroxy, cycloalkyl or alkyl, in particular by Ci to C3 alkyl or Cs to Cv cycloalkyl Carbon atoms, preferably 1 to 10 carbon atoms, in the case of cyclic radicals preferably those with 5 to 7 carbon atoms, particularly preferably methyl, ethyl, propyl, 1-butyl, 1-pentyl, hexyl, 1-isopropyl, isobutyl, tert-butyl, neopentyl, 2-pentyl, iso-pentyl, iso-hexyl, cyclohexyl, cyclohexylmethyl and cyclopentyl mean.
Eine bevorzugte Auswahl stellen dabei die Ammonium- oder Phosphoniumsalze dar in welchenA preferred selection are the ammonium or phosphonium salts in which
X N oder P, bevorzugt N bedeuten, X is N or P, preferably N,
R1 perfluorierte lineare oder verzweigte Kohlenstoffketten mit 1 bis 30 Kohlenstoffatomen, bevorzugt 4 bis 8 Kohlenstoffatomen, R 1 perfluorinated linear or branched carbon chains with 1 to 30 carbon atoms, preferably 4 to 8 carbon atoms,
R2 jeweils unabhängig voneinander halogenierte oder nichthalogenierte lineare oder verzweigte Kohlenstoffketten mit 1 bis 30 Kohlenstoffatomen, bevorzugt 3 bis 10 Kohlenstoffatomen besonders bevorzugt Propyl, I-Butyl, I-Pentyl, Hexyl, Isopropyl, Isobutyl, tert-Butyl, Neopentyl, 2-Pentyl, Iso-Pentyl, Iso-Hexyl, R 2 each independently halogenated or non-halogenated linear or branched carbon chains with 1 to 30 carbon atoms, preferably 3 to 10 carbon atoms, particularly preferably propyl, 1-butyl, 1-pentyl, hexyl, isopropyl, isobutyl, tert-butyl, neopentyl, 2-pentyl , Iso-pentyl, iso-hexyl,
R3, R4, R5 jeweils unabhängig voneinander halogenierte oder nichthalogenierte lineare oder verzweigte Kohlenstoffketten mit 1 bis 30 Kohlenstoffatomen, bevorzugt 1 bis 10 Kohlenstoffatomen steht; besonders bevorzugt Methyl, Ethyl, Propyl, I-Butyl, I-Pentyl, Hexyl, Isopropyl, Isobutyl, tert- Butyl, Neopentyl, 2-Pentyl, Iso-Pentyl, Iso-Hexyl bedeuten. R 3 , R 4 , R 5 each independently of one another halogenated or non-halogenated linear or branched carbon chains having 1 to 30 carbon atoms, preferably 1 to 10 carbon atoms; particularly preferably methyl, ethyl, propyl, 1-butyl, 1-pentyl, hexyl, isopropyl, isobutyl, tert-butyl, neopentyl, 2-pentyl, iso-pentyl, iso-hexyl.
Bevorzugt geeignete quarternäre Ammonium- oder Phosphoniumsalze sind: Preferred suitable quaternary ammonium or phosphonium salts are:
Perfluoroctansulfonsäuretetrapropylammoniumsalz,Perfluorooctanesulfonic acid tetrapropylammonium salt,
Perfluorbutansulfonsäuretetrapropylammoniumsalz,Perfluorobutanesulfonic acid tetrapropylammonium salt,
Perfluoroctansulfonsäuretetrabutylammoniumsalz,Perfluorooctanesulfonic acid tetrabutylammonium salt,
Perfluorbutansulfonsäuretetrabutylammoniumsalz,Perfluorobutanesulfonic acid tetrabutylammonium salt,
Perfluoroctansulfonsäuretetrapentylammoniumsalz, Perfluorooctanesulfonic acid tetrapentylammonium salt,
Perfluorbutansulfonsäuretetrapentylammoniumsalz, Perfluoroctansulfonsäuretetrahexylammoniumsalz, Perfluorbutansulfonsäuretetrahexylammoniumsalz, Perfluorbutansulfonsäuretrimethylneopentylammoniumsalz, Perfluoroctansulfonsäuretrimethylneopentylammoniumsalz, Perfluorbutansulfonsäuredimethyldineopentylammoniumsalz, Perfluoroctansulfonsäuredimethyldineopentylammoniumsalz, N-Methyl-tripropylammoniumperfluorbutylsulfonat, N-Ethyl-tripropylammoniumperfluorbutylsulfonat, Tetrapropylammoniumperfluorbutylsulfonat, Diisopropyldimethylammoniumperfluorbutylsulfonat, Diisopropyldimethylammoniumperfluoroctylsulfonat, N-Methyl-tributylammoniumperfluoroctylsulfonat Cyclohexyldiethylmethylammoniumperfluoroctylsulfonat, Cyclohexyltrimethylammoniumperfluoroctylsulfonat, sowie die entsprechenden Phosphoniumsalze. Bevorzugt sind die Ammoniumsalze. Perfluorobutanesulfonic acid tetrapentylammonium salt, Perfluoroctansulfonsäuretetrahexylammoniumsalz, Perfluorbutansulfonsäuretetrahexylammoniumsalz, Perfluorbutansulfonsäuretrimethylneopentylammoniumsalz, Perfluoroctansulfonsäuretrimethylneopentylammoniumsalz, Perfluorbutansulfonsäuredimethyldineopentylammoniumsalz, Perfluoroctansulfonsäuredimethyldineopentylammoniumsalz, N-methyl perfluorobutyl sulfonate, N-ethyl perfluorobutyl sulfonate, Tetrapropylammoniumperfluorbutylsulfonat, Diisopropyldimethylammoniumperfluorbutylsulfonat, Diisopropyldimethylammoniumperfluoroctylsulfonat, N-methyl-tributylammoniumperfluoroctylsulfonat Cyclohexyldiethylmethylammoniumperfluoroctylsulfonat, Cyclohexyltrimethylammoniumperfluoroctylsulfonat, and the corresponding phosphonium salts. The ammonium salts are preferred.
Bevorzugt können auch ein oder mehrere der vorstehend genannten quartären Ammonium- oder Phosphoniumsalze, also auch Mischungen eingesetzt werden. One or more of the abovementioned quaternary ammonium or phosphonium salts, ie also mixtures, can preferably also be used.
Das Phosphoniumsulfonat ist vorzugsweise ein fluoriertes Phosphoniumsulfonat und setzt sich aus einem Fluorkohlenstoff zusammen, welcher ein organisches Sulfonatanion und ein organisches Phosphoniumkation enthält. Beispiele derartiger organischer Sulfonatanionen beinhalten Perfluoromethansulfonat, Perfluorobutansulfonat, Perfluorohexansulfonat, Perfluoroheptansulfonat und Perfluorooktansulfonat. Beispiele der zuvor genannten Phosphoniumkationen beinhalten aliphatisches Phosphonium, wie beispielsweise Tetramethylphosphonium, Tetraethylphosphonium, Tetra- butylphosphonium, Triethylmethylphosphonium, Tributylmethylphosphonium, Tributylethyl- phosphonium, Trioctylmethylphosphonium, Trimethylbutylphosphonium, Trimethyloctylphospho- nium, Trimethyllaurylphosphonium, Trimethylstearylphosphonium, Triethyloctylphosphonium, und aromatische Phosphoniums, wie beispielsweise Tetraphenylphosphonium, Triphenylmethyl- phosphonium, Triphenylbenzylphosphonium, Tributylbenzylphosphonium. The phosphonium sulfonate is preferably a fluorinated phosphonium sulfonate and is composed of a fluorocarbon which contains an organic sulfonate anion and an organic phosphonium cation. Examples of such organic sulfonate anions include perfluoromethanesulfonate, perfluorobutanesulfonate, perfluorohexanesulfonate, perfluoroheptanesulfonate and perfluorooctanesulfonate. Examples of the aforementioned phosphonium cations include aliphatic phosphonium such as tetramethyl phosphonium, tetraethylphosphonium, tetra- butylphosphonium, Triethylmethylphosphonium, Tributylmethylphosphonium, Tributylethyl- phosphonium, Trioctylmethylphosphonium, Trimethylbutylphosphonium, Trimethyloctylphospho- nium, Trimethyllaurylphosphonium, Trimethylstearylphosphonium, Triethyloctylphosphonium, and aromatic phosphoniums such as tetraphenyl phosphonium, triphenylmethyl - phosphonium, triphenylbenzylphosphonium, tributylbenzylphosphonium.
Von den Phosphonium-Salzen wird bevorzugt Tetrabutylphosphonium-nonafluorbutylsulfonat eingesetzt. Of the phosphonium salts, preference is given to using tetrabutylphosphonium nonafluorobutylsulfonate.
In einer bevorzugten Ausgestaltung der Folie ist die Antistatikverbindung ausgewählt aus der Gruppe bestehend aus quaternären Ammoniumsalzen einer teil- oder perfluorierten organischen Säure oder quaternären Ammoniumhexafluorophosphaten oder Mischungen aus mindestens zwei hiervon. Ganz besonders geeignet ist das Perfluoroctansulfonsäuretetrapropylammoniumsalz, das Perfluor- octansulfonsäuretetrabutylammoniumsalz, das Perfluoroctansulfonsäuretetrapentylammoniumsalz, das Perfluoroctansulfonsäuretetrahexylammoniumsalz und das Perfluoroctansulfonsäuredimethyldiiso- propylammoniumsalz sowie die entsprechenden Perfluorbutansulfonsäuresalze. In a preferred embodiment of the film, the antistatic compound is selected from the group consisting of quaternary ammonium salts of a partially or perfluorinated organic acid or quaternary ammonium hexafluorophosphates or mixtures of at least two thereof. The perfluorooctanesulphonic acid tetrapropylammonium salt, the perfluorooctanesulphonic acid tetrabutylammonium salt, the perfluorooctanesulphonic acid tetrapentylammonium salt, the perfluorooctanesulphonic acid tetrahexylammonium salt and the perfluorooctanesulphonatesulfonic acid dimethyldiisobutylammonium sulfonic acid as well as the corresponding perfluorooctanesulfonic acid dimethyldiisobutylammonium salt are particularly suitable.
In einer ganz besonders bevorzugten Ausführungsform der Erfindung wird das Perfluorbutansulfonsäuredimethyldiisopropylammoniumsalz (Diisopropyldimethylammonium- perfluorbutylsulfonat) verwendet. In a very particularly preferred embodiment of the invention, the perfluorobutanesulphonic acid dimethyldiisopropylammonium salt (diisopropyldimethylammonium perfluorobutylsulphonate) is used.
Die genannten Salze sind bekannt oder können nach bekannten Methoden hergestellt werden. Die Salze der Sulfonsäuren lassen sich beispielsweise durch Zusammengehen äquimolarer Mengen der freien Sulfonsäure mit der Hydroxyform des entsprechenden Kations in Wasser bei Raumtemperatur und Ein engen der Lösung darstellen. Andere Herstellungsverfahren sind beschrieben z.B. in DE-A 1 966931 und NL-A 7 802 830. 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 narrowing the solution. Other manufacturing processes are described, for example, in DE-A 1 966931 and NL-A 7 802 830.
Die genannten Salze werden vorzugsweise in Mengen von 0.001 bis 2 Gew.%, bevorzugt von 0.1 bis 1 Gew.%, bezogen auf die Gesamtmasse der Folie vor ihrer Formgebung, welche zum Beispiel durch Extrusion oder Coextrusion erfolgen kann, zugegeben. The salts mentioned are preferably added in amounts of 0.001 to 2% by weight, preferably 0.1 to 1% by weight, based on the total mass of the film before it is shaped, which can be done, for example, by extrusion or coextrusion.
Bevorzugt ist die zuvor beschriebene Folie Bestandteil eines Schichtaufbaus, wobei der Schichtaufbau weiterhin wenigstens eine weitere Schicht eines thermoplastischen Kunststoffes aufweist, ausgewählt aus Polymerisaten von ethylenisch ungesättigten Monomeren und/oder Polykondensaten von bifunktionellen reaktiven Verbindungen, bevorzugt um ein oder mehrere Polycarbonat(e) oder Copolycarbonat(e) auf Basis von Diphenolen, Poly- oder Copolyacrylat(e) und Poly- oder Copolymethacrylat(e), Poly- oder Copolymer(e) mit Styrol, thermoplastische Polyurethan(e), sowie Polyolefin(e), Poly- oder Copolykondensat(e) der Terephthalsäure mit einem Anteil an 1,4- Cyclohexandimethanol, 1,3-Cyclohexandimethanol und/oder 2,2,4,4-Tetramethyl-l,3-butandiol, vorzugsweise 1,4-Cyclohexandimethanol und/oder 1,3-Cyclohexandimethanol, Poly- oder Copolykondensate der Naphthalindicarbonsäure, Poly- oder Copolykondensat(e) wenigstens einer Cycloalkyldicarbonsäure, Mischungen aus diesen oder deren Blends, besonders bevorzugt um ein oder mehrere Polycarbonat(e) oder Copolycarbonat(e) auf Basis von Diphenolen oder Blends enthaltend wenigstens ein Polycarbonat oder Copolycarbonat. The film described above is preferably part of a layer structure, the layer structure furthermore having at least one further layer of a thermoplastic material selected from polymers of ethylenically unsaturated monomers and / or polycondensates of bifunctional reactive compounds, preferably one or more polycarbonate (s) or copolycarbonate (e) based on diphenols, poly- or copolyacrylate (s) and poly- or copolymethacrylate (s), poly- or copolymer (s) with styrene, thermoplastic polyurethane (s), as well as polyolefin (s), poly- or copolycondensate (e) terephthalic acid with a proportion of 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol and / or 2,2,4,4-tetramethyl-1,3-butanediol, preferably 1,4-cyclohexanedimethanol and / or 1, 3-Cyclohexanedimethanol, polycondensates or copolycondensates of naphthalenedicarboxylic acid, polycondensate (s) of at least one cycloalkyldicarboxylic acid, mixtures of these or their blends, especially bev Preferably one or more polycarbonate (s) or copolycarbonate (s) based on diphenols or blends containing at least one polycarbonate or copolycarbonate.
Besonders geeignete thermoplastische Kunststoffe sind Polycarbonate oder Copolycarbonate auf Basis von Diphenolen, Poly- oder Copolyacrylate und Poly- oder Copolymethacrylate wie beispielhaft und vorzugsweise Polymethylmethacrylat (PMMA), Poly- oder Copolymere mit Styrol wie beispielhaft und vorzugsweise Polystyrol (PS) oder Polystyrolacrylnitril (SAN), thermoplastische Polyurethane, sowie Polyolefine, wie beispielhaft und vorzugsweise Polypropylentypen oder Polyolefine auf der Basis von cyclischen Olefinen (z.B. TOPASTM), Poly- oder Copolykondensate einer aromatischen Dicarbonsäure und aliphatischen, cycloalophatischen und/oder araliphatischen Diolen mit 2 bis 16 Kohlenstoffatomen, wie beispielhaft und vorzugsweise Poly- oder Copolykondensate der Terephthalsäure, besonders bevorzugt Poly- oder Copolyethylenterephthalat (PET oder CoPET), glycol-modifiziertes PET (PETG), glycol-modifiziertes Poly- oder Copolycyclohexandimethylenterephthalat (PCTG) oder Poly- oder Copolybutylenterephthalat (PBT oder CoPBT), vorzugsweise Poly- oder Copolykondensate der Naphthalindicarbonsäure, besonders bevorzugt Polyethylenglykolnaphthalat (PEN), Poly- oder Copolykondensat(e) wenigstens einer Cycloalkyldicarbonsäure, wie beispielhaft und vorzugsweise Polycyclohexandimethanolcyclohexandicarbonsäure (PCCD), Polysulfone (PSU),Particularly suitable thermoplastics are polycarbonates or copolycarbonates based on diphenols, poly- or copolyacrylates and poly- or copolymethacrylates such as, for example and preferably, polymethyl methacrylate (PMMA), poly or copolymers with styrene such as, for example and preferably, polystyrene (PS) or polystyrene acrylonitrile (SAN) , thermoplastic polyurethanes, and polyolefins, such as, for example and preferably, polypropylene types or polyolefins based on cyclic olefins (eg TOPASTM), polycondensates or copolycondensates of an aromatic dicarboxylic acid and aliphatic, cycloalophatic and / or araliphatic diols with 2 to 16 carbon atoms, such as, for example and preferably, poly- or copolycondensates of terephthalic acid, particularly preferably poly- or copolyethylene terephthalate (PET or CoPET), glycol-modified PET (PETG), glycol-modified poly - or copolycyclohexanedimethylene terephthalate (PCTG) or poly- or copolybutylene terephthalate (PBT or CoPBT), preferably polycondensates or copolycondensates of naphthalenedicarboxylic acid, particularly preferably polyethylene glycol naphthalate (PEN), poly- or copolybutylene-cycloacid (e.g. ), Polysulfones (PSU),
Polyvinylhalogenide, wie beispielhaft und vorzusgweise Polyvinylchlorid (PVC), oder Mischungen aus den vorangehend genannten. Polyvinyl halides, such as, for example and preferably, polyvinyl chloride (PVC), or mixtures of the aforementioned.
Besonders bevorzugte thermoplastische Kunststoffe sind ein oder mehrere Polycarbonat(e) oder Copolycarbonat(e) auf Basis von Diphenolen oder Blends enthaltend wenigstens ein Polycarbonat oder Copolycarbonat. Ganz besonders bevorzugt sind Blends enthaltend wenigstens ein Polycarbonat oder Copolycarbonat und wenigstens ein Poly- oder Copolykondensat der Terephthalsäure, der Naphthalindicarbonsäure oder einer Cycloalkyldicarbonsäure, bevorzugt der Cyclohexandicarbonsäure. Weiterhin bevorzugt sind Blends enthaltend ein Polycarbonat oder Copolycarbonat und wenigstens ein Cyclohexandicarbonsäure-Copolyester, wie Xylex™ von Sabic. Ganz besonders bevorzugt sind Polycarbonate oder Copolycarbonate, insbesondere mit mittleren Molekulargewichten Mw von 500 bis 100 000, bevorzugt von 10 000 bis 80 000, besonders bevorzugt von 15 000 bis 40 000 oder deren Blends mit wenigstens einem Poly- oder Copolykondensat der Terephthalsäure mit mittleren Molekular gewichten Mw von 10.000 bis 200.000, bevorzugt von 21.000 bis 120.000. Particularly preferred thermoplastics are one or more polycarbonate (s) or copolycarbonate (s) based on diphenols or blends containing at least one polycarbonate or copolycarbonate. Blends containing at least one polycarbonate or copolycarbonate and at least one polycondensate or copolycondensate of terephthalic acid, naphthalenedicarboxylic acid or a cycloalkyldicarboxylic acid, preferably cyclohexanedicarboxylic acid, are very particularly preferred. Blends containing a polycarbonate or copolycarbonate and at least one cyclohexanedicarboxylic acid copolyester, such as Xylex ™ from Sabic, are also preferred. Polycarbonates or copolycarbonates, in particular with average molecular weights Mw of 500 to 100,000, preferably from 10,000 to 80,000, particularly preferably from 15,000 to 40,000, or their blends with at least one poly- or copolycondensate of terephthalic acid with average molecular weight are very particularly preferred weight Mw from 10,000 to 200,000, preferably from 21,000 to 120,000.
Als Poly- oder Copolykondensate der Terephthalsäure eignen sich in bevorzugten Ausführungsformen der Erfindung Polyalkylenterephthalate. Geeignete Polyalkylenterephthalate sind beispielsweise Reaktionsprodukte aus aromatischen Dicarbonsäuren oder ihren reaktionsfähigen Derivaten (z. B. Dimethylestern oder Anhydriden) und aliphatischen, cylcoaliphatischen oder araliphatischen Diolen und Mischungen dieser Reaktionsprodukte. In preferred embodiments of the invention, polyalkylene terephthalates are suitable as poly- or copolycondensates of terephthalic acid. Suitable polyalkylene terephthalates are, for example, reaction products of aromatic dicarboxylic acids or their reactive derivatives (e.g. dimethyl esters or anhydrides) and aliphatic, cycloaliphatic or araliphatic diols and mixtures of these reaction products.
Bevorzugte Polyalkylenterephthalate lassen sich aus Terephthalsäure (oder ihren reaktionsfähigen Derivaten) und aliphatischen oder cycloaliphatischen Diolen mit 2 bis 10 C-Atomen nach bekannten Methoden herstellen (Kunststoff-Handbuch, Bd. VIII, S. 695 ff, Karl-Hanser-Verlag, München 1973).Preferred polyalkylene terephthalates can be prepared from terephthalic acid (or its reactive derivatives) and aliphatic or cycloaliphatic diols with 2 to 10 carbon atoms by known methods (Kunststoff-Handbuch, Vol. VIII, p. 695 ff, Karl-Hanser-Verlag, Munich 1973 ).
Bevorzugte Polyalkylenterephthalate enthalten mindestens 80 Mol-%, vorzugsweise 90 Mol-% Terephthalsäurereste, bezogen auf die Dicarbonsäurekomponente, und mindestens 80 Mol-%, vorzugsweise mindestens 90 Mol-% Ethylenglykol- und/oder Butandiol-1,4- und/oder 1,4- Cyclohexandimethanol-Reste, bezogen auf die Diolkomponente. Die bevorzugten Polyalkylenterephthalate können neben Terephthalsäureresten bis zu 20 Mol-% Reste anderer aromatischer Dicarbonsäuren mit 8 bis 14 C- Atomen oder aliphatischer Dicarbonsäuren mit 4 bis 12 C-Atomen enthalten, wie beispielsweise Reste von Phthalsäure, Isophthalsäure, Naphthalin-2,6- dicarbonsäure, 4,4'-Diphenyldicarbonsäure, Bernstein-, Adipin-, Sebacinsäure, Azelainsäure, Cyclohexandiessigsäure. 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% ethylene glycol and / or 1,4-butanediol and / or 1, 4- Cyclohexanedimethanol residues, based on the diol component. In addition to terephthalic acid residues, the preferred polyalkylene terephthalates can contain up to 20 mol% residues of other aromatic dicarboxylic acids with 8 to 14 carbon atoms or aliphatic dicarboxylic acids with 4 to 12 carbon atoms, such as residues of phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid , 4,4'-diphenyldicarboxylic acid, succinic, adipic, sebacic acid, azelaic acid, cyclohexanediacetic acid.
Die bevorzugten Polyalkylenterephthalate können neben Ethylen- bzw. Butandiol-l,4-glykol-Resten bis zu 80 Mol-% anderer aliphatischer Diole mit 3 bis 12 C-Atomen oder cycloaliphatischer Diole mit 6 bis 21 C-Atomen enthalten, z. B. Reste von Propandiol-1,3, 2-Ethylpropandiol-l,3, Neopentylglykol, Pentan-diol-1,5, Hexandiol-1,6, Cyclohexan-dimethanol-1,4, 3-Methylpentandiol-2,4, 2- Methylpentandiol-2,4, 2,2,4-Trimethylpentandiol-l,3 und 2-Ethylhexandiol-l,6, 2,2- Diethylpropandiol-1,3, Hexandiol-2,5, l,4-Di-([beta]-hydroxyethoxy)-benzol, 2,2-Bis-(4- hydroxycyclohexyl) -propan, 2,4-Dihydroxy-l,l,3,3-tetramethyl-cyclobutan, 2,2-Bis-(3-[beta]- hydroxyethoxyphenyl)-propan und 2,2-Bis-(4-hydroxypropoxyphenyl)-propan (vgl. DE-OS 2407674, 2407776, 27 15932). The preferred polyalkylene terephthalates can contain ethylene or butanediol-1,4-glycol residues up to 80 mol% of other aliphatic diols with 3 to 12 carbon atoms or cycloaliphatic diols with 6 to 21 carbon atoms, z. B. residues of 1,3-propanediol, 2-ethylpropanediol-1,3, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 3-methylpentanediol-2,4, 2- methylpentanediol-2,4, 2,2,4-trimethylpentanediol-1,3 and 2-ethylhexanediol-1,6, 2,2-diethylpropanediol-1,3, hexanediol-2,5, 1,4-di- ([beta] -hydroxyethoxy) -benzene, 2,2-bis- (4-hydroxycyclohexyl) -propane, 2,4-dihydroxy-1,1,3,3-tetramethyl-cyclobutane, 2,2-bis- (3 - [beta] - hydroxyethoxyphenyl) propane and 2,2-bis (4-hydroxypropoxyphenyl) propane (cf. DE-OS 2407674, 2407776, 27 15932).
Die Polyalkylenterephthalate können durch Einbau relativ kleiner Mengen 3- oder 4-wertiger Alkohole oder 3- oder 4-basischer Carbonsäuren, wie sie z. B. in der DE-OS 1900270 und der US-PS 3692744 beschrieben sind, verzweigt werden. Beispiele bevorzugter Verzweigungsmittel sind Trimesinsäure, Trimellitsäure, Trimethylolethan und -propan und Pentaerythrit. The polyalkylene terephthalates can be obtained by incorporating relatively small amounts of 3- or 4-valent alcohols or 3- or 4-basic carboxylic acids, as they are, for. B. in DE-OS 1900270 and US-PS 3692744 are described, are branched. Examples of preferred branching agents are trimesic acid, trimellitic acid, trimethylol ethane and propane and pentaerythritol.
Vorzugsweise wird nicht mehr als 1 Mol-% des Verzweigungsmittels, bezogen auf die Säurekomponente, verwendet. Preferably no more than 1 mol% of the branching agent, based on the acid component, is used.
Besonders bevorzugt sind Polyalkylenterephthalate, die allein aus Terephthalsäure und deren reaktionsfähigen Derivaten (z. B. deren Dialkylestern) und Ethylenglykol und/oder Butandiol-1,4 und/oder 1,4-Cyclohexandimethanol-Reste hergesteht worden sind, und Mischungen dieser Polyalkylenterephthalate. Particularly preferred are polyalkylene terephthalates which have been produced solely from terephthalic acid and its reactive derivatives (e.g. its dialkyl esters) and ethylene glycol and / or 1,4-butanediol and / or 1,4-cyclohexanedimethanol radicals, and mixtures of these polyalkylene terephthalates.
Bevorzugte Polyalkylenterephthalate sind auch Copolyester, die aus mindestens zwei der obengenannten Säurekomponenten und/oder aus mindestens zwei der obengenannten Alkoholkomponenten hergesteht sind, besonders bevorzugte Copolyester sind Poly- (ethylenglykol/butandiol- 1 ,4)-terephthalate. Preferred polyalkylene terephthalates are also copolyesters made from at least two of the abovementioned acid components and / or from at least two of the abovementioned alcohol components; particularly preferred copolyesters are poly (ethylene glycol / 1,4-butanediol) terephthalates.
Die als Komponente vorzugsweise verwendeten Polyalkylenterephthalate besitzen bevorzugt eine intrinsische Viskosität von ca. 0,4 bis 1,5 dl/g, vorzugsweise 0,5 bis 1,3 dl/g, jeweils gemessen in Phenol/o-Dichlorbenzol (1:1 Gew. -Teile) bei 25°C. The polyalkylene terephthalates preferably used as a component preferably have an intrinsic viscosity of approx. 0.4 to 1.5 dl / g, preferably 0.5 to 1.3 dl / g, each measured in phenol / o-dichlorobenzene (1: 1 wt Parts) at 25 ° C.
In besonders bevorzugten Ausführungsformen der Erfindung handelt es sich bei dem Blend von wenigstens einem Polycarbonat oder Copolycarbonat mit wenigstens einem Poly- oder Copolykondensat der Tereph thalsäure um einen Blend aus wenigstens einem Poly carbonat oder Copolycarbonat mit Poly- oder Copolybutylenterephthalat oder glycol-modifiziertem Poly- oder Copolycyclohexandimethylenterephthalat. Bei einem solchen Blend aus Polycarbonat oder Copolycarbonat mit Poly- oder Copolybutylenterephthalat oder glycol-modifiziertem Poly- oder Copolycyclohexandimethylenterephthalat kann es sich bevorzugt um einen solchen mit 1 bis 90 Gew.-% Poly carbonat oder Copolycarbonat und 99 bis 10 Gew.-% Poly- oder Copolybutylenterephthalat oder glycol-modifiziertem Poly- oder Copolycyclohexandimethylenterephthalat, vorzugsweise mit 1 bis 90 Gew.-% Polycarbonat und 99 bis 10 Gew.-% Polybutylenterephthalat oder glycol-modifiziertem Polycyclohexandimethylenterephthalat handeln, wobei sich die Anteile zu 100 Gew.-% addieren. Besonders bevorzugt kann es sich bei einem solchen Blend aus Polycarbonat oder Copolycarbonat mit Poly- oder Copolybutylenterephthalat oder glycol-modifiziertes Poly- oderIn particularly preferred embodiments of the invention, the blend of at least one polycarbonate or copolycarbonate with at least one poly- or Copolycondensate of terephthalic acid around a blend of at least one polycarbonate or copolycarbonate with poly- or copolybutylene terephthalate or glycol-modified poly- or copolycyclohexanedimethylene terephthalate. Such a blend of polycarbonate or copolycarbonate with poly- or copolybutylene terephthalate or glycol-modified poly or copolycyclohexanedimethylene terephthalate can preferably be one with 1 to 90% by weight of polycarbonate or copolycarbonate and 99 to 10% by weight of poly- or copolybutylene terephthalate or glycol-modified poly- or copolycyclohexanedimethylene terephthalate, preferably with 1 to 90% by weight of polycarbonate and 99 to 10% by weight of polybutylene terephthalate or glycol-modified polycyclohexanedimethylene terephthalate, the proportions adding up to 100% by weight. In the case of such a blend of polycarbonate or copolycarbonate with poly- or copolybutylene terephthalate or glycol-modified poly- or polybutylene terephthalate, it can be particularly preferred
Copolycyclohexandimethylenterephthalat um einen solchen mit 20 bis 85 Gew.-% Polycarbonat oder Copolycarbonat und 80 bis 15 Gew.-% Poly- oder Copolybutylenterephthalat oder glycol-modifiziertem Poly- oder Copolycyclohexandimethylenterephthalat, vorzugsweise mit 20 bis 85 Gew.-% Polycarbonat und 80 bis 15 Gew.-% Polybutylenterephthalat oder glycol-modifiziertemCopolycyclohexanedimethylene terephthalate to one with 20 to 85 wt .-% polycarbonate or copolycarbonate and 80 to 15 wt .-% poly or copolybutylene terephthalate or glycol-modified poly or copolycyclohexanedimethylene terephthalate, preferably with 20 to 85 wt .-% polycarbonate and 80 to 15 Wt% polybutylene terephthalate or glycol modified
Polycyclohexandimethylenterephthalat handeln, wobei sich die Anteile zu 100 Gew.-% addieren. Ganz besonders bevorzugt kann es sich bei einem solchen Blend aus Polycarbonat oder Copolycarbonat mit Poly- oder Copolybutylenterephthalat oder glycol-modifiziertem Poly- oderActing polycyclohexanedimethylene terephthalate, the proportions adding up to 100% by weight. In such a blend of polycarbonate or copolycarbonate with poly- or copolybutylene terephthalate or glycol-modified poly- or poly- or glycol-modified poly- or
Copolycyclohexandimethylenterephthalat um einen solchen mit 35 bis 80 Gew.-% Polycarbonat oder Copolycarbonat und 65 bis 20 Gew.-% Poly- oder Copolybutylenterephthalat oder glycol-modifiziertem Poly- oder Copolycyclohexandimethylenterephthalat, vorzugsweise mit 35 bis 80 Gew.-% Polycarbonat und 65 bis 20 Gew.-% Polybutylenterephthalat oder glycol-modifiziertemCopolycyclohexanedimethylene terephthalate to one with 35 to 80 wt .-% polycarbonate or copolycarbonate and 65 to 20 wt .-% poly or copolybutylene terephthalate or glycol-modified poly or copolycyclohexanedimethylene terephthalate, preferably with 35 to 80 wt .-% polycarbonate and 65 to 20 Wt% polybutylene terephthalate or glycol modified
Polycyclohexandimethylenterephthalat handeln, wobei sich die Anteile zu 100 Gew.-% addieren. In ganz besonders bevorzugten Ausführungsformen kann es sich um Blends aus Polycarbonat und glycol- modifiziertem Polycyclohexandimethylenterephthalat in den vorangehend genannten Zusammensetzungen handeln. Acting polycyclohexanedimethylene terephthalate, the proportions adding up to 100% by weight. In very particularly preferred embodiments, they can be blends of polycarbonate and glycol-modified polycyclohexanedimethylene terephthalate in the compositions mentioned above.
Als Polycarbonate oder Copolycarbonate eignen sich in bevorzugten Ausführungsformen besonders aromatische Polycarbonate oder Copolycarbonate. In preferred embodiments, particularly suitable polycarbonates or copolycarbonates are aromatic polycarbonates or copolycarbonates.
Die Polycarbonate oder Copolycarbonate können in bekannter Weise linear oder verzweigt sein.The polycarbonates or copolycarbonates can be linear or branched in a known manner.
Die Herstellung dieser Polycarbonate kann in bekannter Weise aus Diphenolen, Kohlensäurederivaten, gegebenenfalls Kettenabbrechern und gegebenenfalls Verzweigern erfolgen. Einzelheiten der Herstellung von Polycarbonaten sind in vielen Patentschriften seit etwa 40 Jahren niedergelegt. Beispielhaft sei hier nur auf Schnell, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Volume 9, Interscience Publishers, New York, London, Sydney 1964, auf D. Freitag, U. Grigo, P. R. Müller, H. Nouvertne', BAYER AG, "Polycarbonates" in Encyclopedia of Polymer Science and Engineering, Volume 11, Second Edition, 1988, Seiten 648-718 und schließlich auf Dres. U. Grigo, K. Kirchner und P. R. Müller "Polycarbonate" in Becker/Braun, Kunststoff-Handbuch, Band 3/1, Polycarbonate, Polyacetale, Polyester, Celluloseester, Carl Hanser Verlag München, Wien 1992, Seiten 117-299 verwiesen. These polycarbonates can be produced 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. For example, see Schnell, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Volume 9, Interscience Publishers, New York, London, Sydney 1964, to 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 on Drs. U. Grigo, K. Kirchner and PR Müller "Polycarbonate" in Becker / Braun, Kunststoff-Handbuch, Volume 3/1, Polycarbonate, Polyacetale, Polyester, cellulose ester, Carl Hanser Verlag Munich, Vienna 1992, pages 117-299.
Geeignete Diphenole können beispielsweise Dihydroxyarylverbindungen der allgemeinen Formel (I) sein, Suitable diphenols can be, for example, dihydroxyaryl compounds of the general formula (I),
HO-Z-OH (I) worin Z ein aromatischer Rest mit 6 bis 34 C- Atomen ist, der einen oder mehrere gegebenenfalls substituierte aromatische Kerne und aliphatische oder cycloaliphatische Reste bzw. Alkylaryle oder Heteroatome als Brückenglieder enthalten kann. HO-Z-OH (I) where Z is an aromatic radical with 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.
Beispiele für geeignete Dihydroxyarylverbindungen sind: Dihydroxybenzole, Dihydroxydiphenyle, Bis-(hydroxyphenyl)-alkane, Bis-(hydroxyphenyl)-cycloalkane, Bis-(hydroxyphenyl)-aryle, Bis- (hydroxyphenyl)-ether, Bis-(hydroxyphenyl)-ketone, Bis-(hydroxyphenyl)-sulfide, Bis- (hydroxyphenyl)-sulfone, Bis-(hydroxyphenyl)-sulfoxide, l,l'-Bis-(hydroxyphenyl)- diisopropylbenzole, sowie deren kemalkylierte und kernhalogenierte Verbindungen. Examples of suitable dihydroxyaryl compounds are: dihydroxybenzenes, dihydroxydiphenyls, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) cycloalkanes, bis (hydroxyphenyl) aryls, bis (hydroxyphenyl) ethers, bis (hydroxyphenyl) ketones, Bis (hydroxyphenyl) sulfides, bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) sulfoxides, l, l'-bis (hydroxyphenyl) diisopropylbenzenes, and their core alkylated and ring halogenated compounds.
Diese und weitere geeignete andere Dihydroxyarylverbindungen sind z.B. in DE-A 3 832396, FR-A 1 561 518, in H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964, S. 28 ff.; S.102 ff. und in D.G. Legrand, J.T. Bendler, Handbook of Polycarbonate Science and Technology, Marcel Dekker New York 2000, S. 72 ff. beschrieben. These and other suitable other dihydroxyaryl compounds are described, for example, in DE-A 3 832396, FR-A 1 561 518, in H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964, p. 28 ff .; P.102 ff. And in D.G. Legrand, J.T. Bendler, Handbook of Polycarbonate Science and Technology, Marcel Dekker New York 2000, p. 72 ff.
Bevorzugte Dihydroxyarylverbindungen sind beispielsweise Resorcin, 4,4'-Dihydroxydiphenyl, Bis-(4- hydroxyphenyl)-methan, Bis-(3,5-dimethyl-4-hydroxyphenyl)-methan, Bis-(4-hydroxyphenyl)- diphenyl-methan, 1 , 1 -Bis-(4-hydroxyphenyl)- 1 -phenyl-ethan, 1 , 1 -Bis-(4-hydroxyphenyl)- 1 -( 1 - naphthyl)-ethan, l,l-Bis-(4-hydroxyphenyl)-l-(2-naphthyl)-ethan, 2,2-Bis-(4-hydroxyphenyl)-propan, 2,2-Bis-(3-methyl-4-hydroxyphenyl)-propan, 2,2-Bis-(3,5-dimethyl-4-hydroxyphenyl)-propan, 2,2- Bis-(4-hydroxyphenyl)-l -phenyl-propan, 2,2-Bis-(4-hydroxyphenyl)-hexafluor-propan, 2,4-Bis-(4- hydroxyphenyl)-2-methyl-butan, 2,4-Bis-(3,5-dimethyl-4-hydroxyphenyl)-2-methylbutan, 1,1 -Bis-(4- hydroxyphenyl)-cyclohexan, 1 , 1 -Bis-(3,5-dimethyl-4-hydroxyphenyl)-cyclohexan, 1,1 -Bis-(4- hydroxyphenyl)-4-methyl-cylohexan, l,3-Bis-[2-(4-hydroxyphenyl)-2-propyl]-benzol, 1,1'- Bis-(4- hydroxyphenyl)-3-diisopropyl-benzol, l,l'-Bis-(4-hydroxyphenyl)-4-diisopropyl-benzol, l,3-Bis-[2- (3,5-dimethyl-4-hydroxyphenyl)-2-propyl]-benzol, Bis-(4-hydroxyphenyl)-ether, Bis-(4- hydroxyphenyl)-sulfid, Bis-(4-hydroxyphenyl)-sulfon, Bis-(3,5-dimethyl-4-hydroxyphenyl)-sulfon und 2,2',3,3,-Tetrahydro-3,3,3,,3,-tetramethyl-l,r-spirobi-[lH-inden]-5,5'-diol oderPreferred dihydroxyaryl compounds are, for example, resorcinol, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis (3,5-dimethyl-4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) diphenyl methane , 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- (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) -l -phenyl-propane, 2,2-bis- (4-hydroxyphenyl) -hexafluoropropane, 2 , 4-bis- (4-hydroxyphenyl) -2-methyl-butane, 2,4-bis- (3,5-dimethyl-4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4-hydroxyphenyl) -cyclohexane, 1,1-bis- (3,5-dimethyl-4-hydroxyphenyl) -cyclohexane, 1,1-bis- (4-hydroxyphenyl) -4-methyl-cyclohexane, 1,3-bis- [2- (4-hydroxyphenyl) -2-propyl] -benzene, 1,1'-bis- (4-hydroxyphenyl) -3-diisopropyl-benzene, 1,1'-bis- (4-hydroxyphenyl) -4-diisopropyl-benzene , 1,3-bis [2- (3,5-dimethyl-4-hydroxyphenyl) -2- propyl] benzene, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone and 2,2 ', 3,3-tetrahydro-3,3,3, 3-tetramethyl-l, r-spirobi- [lH-indene] -5,5'-diol or
Dihydroxydiphenylcycloalkane der Formel (Ia) worin Dihydroxydiphenylcycloalkanes of the formula (Ia) wherein
RI und R2 unabhängig voneinander Wasserstoff, Halogen, bevorzugt Chlor oder Brom, C1-C8- Alkyl, C5-C6-Cycloalkyl, C6-C10-Aryl, bevorzugt Phenyl, und C7-C12-Aralkyl, bevorzugt Phenyl-Cl- C4- Alkyl, insbesondere Benzyl, m eine ganze Zahl von 4 bis 7, bevorzugt 4 oder 5, R1 and R2 independently of one another are hydrogen, halogen, preferably chlorine or bromine, C1-C8-alkyl, C5-C6-cycloalkyl, C6-C10-aryl, preferably phenyl, and C7-C12-aralkyl, preferably phenyl-C1-C4-alkyl , in particular benzyl, m is an integer from 4 to 7, preferably 4 or 5,
R3 und R4 für jedes X individuell wählbar, unabhängig voneinander Wasserstoff oder C1-C6- Alkyl und R3 and R4 can be selected individually for each X, independently of one another hydrogen or C1-C6-alkyl and
X Kohlenstoff bedeuten, mit der Maßgabe, dass an mindestens einem Atom X, R3 und R4 gleichzeitig Alkyl bedeuten. Bevorzugt sind in der Formel (Ia) an einem oder zwei Atom(en) X, insbesondere nur an einem Atom X R3 und R4 gleichzeitig Alkyl. X is carbon, with the proviso that X, R3 and R4 on at least one atom are simultaneously alkyl. In the formula (Ia), preference is given to alkyl on one or two atom (s) X, in particular on only one atom X, R3 and R4.
Bevorzugter Alkylrest für die Reste R3 und R4 in Formel (Ia) ist Methyl. Die X- Atome in alpha-Stellung zu dem Diphenylsubstituierten C-Atom (C-l) sind bevorzugt nicht dialkylsubstituiert, dagegen ist die Alkyldisubstitution in beta-Stellung zu C-l bevorzugt. Besonders bevorzugte Dihydroxydiphenylcycloalkane der Formenl (Ia) sind solche mit 5 und 6 Ring-C-Atomen X im cycloaliphatischen Rest (m = 4 oder 5 in Formel (Ia)), beispielsweise die Diphenole der Formeln (Ib), (Ic) oder (Id). Ein ganz besonders bevorzugtes Dihydroxydiphenylcycloalkane der Formenl (Ia) ist l,l-Bis-(4- h y d r o x y p h c n y I ) - 3 , 3 , 5 - 1 r i m c t h y I - c y c I o h c x a n (Formel (Ib) mit RI und R2 gleich H). Solche Polycarbonate können gemäß der EP-A 359953 aus Dihydroxydiphenylcycloalkanen der Formel (Ia) hergestellt werden. The preferred alkyl radical for the radicals R3 and R4 in formula (Ia) is methyl. The X atoms in the alpha position to the diphenyl-substituted C atom (Cl) are preferably not dialkyl-substituted, while alkyl disubstitution in the beta position to Cl is preferred. Particularly preferred dihydroxydiphenylcycloalkanes of the formulas (Ia) are those with 5 and 6 ring carbon atoms X in the cycloaliphatic radical (m = 4 or 5 in formula (Ia)), for example the diphenols of the formulas (Ib), (Ic) or ( Id). A very particularly preferred dihydroxydiphenylcycloalkane of the form (Ia) is 1,1-bis (4-hydroxyphcny I) -3, 3, 5-1 rimcthy I - cyc I ohcxan (formula (Ib) with RI and R2 being H). Such polycarbonates can be prepared according to EP-A 359953 from dihydroxydiphenylcycloalkanes of the formula (Ia).
Besonders bevorzugte Dihydroxyarylverbindungen sind Resorcin, 4,4'-Dihydroxydiphenyl, Bis-(4- hydroxyphenyl)-diphenyl-methan, l,l-Bis-(4-hydroxyphenyl)-l-phenyl-ethan, Bis-(4-hydroxyphenyl)- l-(l-naphthyl)-ethan, Bis-(4-hydroxyphenyl)-l-(2-naphthyl)-ethan, 2,2-Bis-(4-hydroxyphenyl)- propan, 2,2-Bis(3,5-dimethyl-4-hydroxyphenyl)-propan, l,l-Bis-(4-hydroxyphenyl)-cyclohexan, 1,1- Bis-(3,5-dimethyl-4-hydroxyphenyl)-cyclohexan, l,l-Bis-(4-hydroxyphenyl)-3,3,5-trimethyl- cyclohexan, l,l'-Bis-(4-hydroxyphenyl)-3-diisopropyl-benzol und 1,1'- Bis-(4-hydroxyphenyl)-4- diisopropyl-benzol. Particularly preferred dihydroxyaryl compounds are resorcinol, 4,4'-dihydroxydiphenyl, bis- (4-hydroxyphenyl) -diphenyl-methane, l, l-bis- (4-hydroxyphenyl) -l-phenyl-ethane, bis- (4-hydroxyphenyl) - l- (l-naphthyl) -ethane, bis- (4-hydroxyphenyl) -l- (2-naphthyl) -ethane, 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis (3 , 5-dimethyl-4-hydroxyphenyl) propane, l, l-bis- (4-hydroxyphenyl) -cyclohexane, 1,1-bis- (3,5-dimethyl-4-hydroxyphenyl) -cyclohexane, l, l- Bis- (4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane, l, l'-bis- (4-hydroxyphenyl) -3-diisopropyl-benzene and 1,1'-bis- (4-hydroxyphenyl) - 4-diisopropyl benzene.
Ganz besonders bevorzugte Dihydroxyarylverbindungen sind 4,4'-Dihydroxydiphenyl und 2,2-Bis-(4- hydroxyphenyl)-propan. Very particularly preferred dihydroxyaryl compounds are 4,4'-dihydroxydiphenyl and 2,2-bis (4-hydroxyphenyl) propane.
Es können sowohl eine Dihydroxyarylverbindung unter Bildung von Homopolycarbonaten als auch verschiedene Dihydroxyarylverbindungen unter Bildung von Copolycarbonaten verwendet werden. Es können sowohl eine Dihydroxyarylverbindung der Formel (I) oder (Ia) unter Bildung von Homopolycarbonaten als auch mehrere eine Dihydroxyarylverbindungen der Formel (I) und/oder (Ia) unter Bildung von Copolycarbonaten verwendet werden. Dabei können die verschiedenen Dihydroxyarylverbindungen sowohl statistisch als auch blockweise miteinander verknüpft sein. Im Falle von Copolycarbonaten aus Dihydroxyarylverbindungen der Formel (I) und (Ia), beträgt das molare Verhältnis von Dihydroxyarylverbindungen der Formel (Ia) zu den gegebenenfalls mitzuverwendenden anderen Dihydroxyarylverbindungen der Formel (I) vorzugsweise zwischen 99 Mol-% (Ia) zu 1 Mol-% (I) und 2 Mol-% (Ia) zu 98 Mol-% (I), vorzugsweise zwischen 99 Mol-% (Ia) zu 1 Mol-% (I) und 10Both a dihydroxyaryl compound to form homopolycarbonates and various dihydroxyaryl compounds to form copolycarbonates can be used. It is possible to use both one dihydroxyaryl compound of the formula (I) or (Ia) with the formation of homopolycarbonates and also several dihydroxyaryl compounds of the formula (I) and / or (Ia) with the formation of copolycarbonates. The various Dihydroxyaryl compounds be linked to one another both randomly and in blocks. In the case of copolycarbonates made from 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) which may also be used is preferably between 99 mol% (Ia) to 1 mol -% (I) and 2 mol% (Ia) to 98 mol% (I), preferably between 99 mol% (Ia) to 1 mol% (I) and 10
Mol-% (Ia) zu 90 Mol-% (I) und insbesondere zwischen 99 Mol-% (Ia) zu 1 Mol-% (I) und 30 Mol-% (Ia) zu 70 Mol-% (I). 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).
Ein ganz besonders bevorzugtes Copolycarbonat kann unter Verwendung von 1,1 -Bis-(4- hydroxyphenyl)-3,3,5-trimethyl-cyclohexan und 2,2-Bis-(4-hydroxyphenyl)-propan Dihydroxyaryl- Verbindungen der Formel (Ia) und (I) hergestellt werden. A very particularly preferred copolycarbonate can be obtained using 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane and 2,2-bis- (4-hydroxyphenyl) propane dihydroxyaryl compounds of the formula ( Ia) and (I) are produced.
Geeignete Kohlensäurederivate können beispielsweise die unter Formel (II) genannten sein. Suitable carbonic acid derivatives can be, for example, those mentioned under formula (II).
In einer bevorzugten Ausgestaltung der Folie weist das Polycarbonat oder das Copolycarbonat ein mittleres Molekulargewicht Mw in einem Bereich von 10000 bis 500000 g/mol, bevorzugt von 15000 bis 400000 g/mol, besonders bevorzugt von 20000 bis 300000 g/mol auf. In einer bevorzugten Ausgestaltung der Folie ist das Polycarbonat oder das Copolycarbonat teilweise aus den Ausgangsprodukten hergestellt, ausgewählt aus der Gruppe bestehend aus: In a preferred embodiment of the film, the polycarbonate or the copolycarbonate has an average molecular weight Mw in a range from 10,000 to 500,000 g / mol, preferably from 15,000 to 400,000 g / mol, particularly preferably from 20,000 to 300,000 g / mol. In a preferred embodiment of the film, the polycarbonate or the copolycarbonate is partially produced from the starting products selected from the group consisting of:
(Ic), oder Mischungen aus mindestens zwei hiervon. (Ic), or mixtures of at least two of these.
Ein ganz besonders bevorzugtes Dihydroxydiphenylcycloalkane der Formenl (Ia) ist l,l-Bis-(4- h y d r o x y p h c n y I ) - 3 , 3 , 5 - 1 r i m c t h y I - c y c I o h c x a n (Formel (Ib) mit R1 und R2 gleich H). A very particularly preferred dihydroxydiphenylcycloalkane of the form (Ia) is 1,1-bis (4-hydroxyphcny I) -3, 3, 5-1 rimcthy I - cyc I ohcxan (formula (Ib) with R 1 and R 2 equal to H. ).
Solche Polycarbonate können gemäß der EP-A 359953 aus Dihydroxydiphenylcycloalkanen der Formel (Ia) hergestellt werden. Such polycarbonates can be prepared according to EP-A 359953 from dihydroxydiphenylcycloalkanes of the formula (Ia).
Besonders bevorzugte Dihydroxyarylverbindungen sind Resorcin, 4,4'-Dihydroxydiphenyl, Bis-(4- hydroxyphenyl)-diphenyl-methan, l,l-Bis-(4-hydroxyphenyl)-l-phenyl-ethan, Bis-(4-hydroxyphenyl)- l-(l-naphthyl)-ethan, Bis-(4-hydroxyphenyl)-l-(2-naphthyl)-ethan, 2,2-Bis-(4-hydroxyphenyl)- propan, 2,2-Bis(3,5-dimethyl-4-hydroxyphenyl)-propan, l,l-Bis-(4-hydroxyphenyl)-cyclohexan, 1,1- Bis-(3,5-dimethyl-4-hydroxyphenyl)-cyclohexan, l,l-Bis-(4-hydroxyphenyl)-3,3,5-trimethyl- cyclohexan, l,l'-Bis-(4-hydroxyphenyl)-3-diisopropyl-benzol und 1,1'- Bis-(4-hydroxyphenyl)-4- diisopropyl-benzol. Particularly preferred dihydroxyaryl compounds are resorcinol, 4,4'-dihydroxydiphenyl, bis- (4-hydroxyphenyl) -diphenyl-methane, l, l-bis- (4-hydroxyphenyl) -l-phenyl-ethane, bis- (4-hydroxyphenyl) - l- (l-naphthyl) -ethane, bis- (4-hydroxyphenyl) -l- (2-naphthyl) -ethane, 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis (3 , 5-dimethyl-4-hydroxyphenyl) propane, l, l-bis- (4-hydroxyphenyl) -cyclohexane, 1,1-bis- (3,5-dimethyl-4-hydroxyphenyl) -cyclohexane, l, l- Bis- (4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane, l, l'-bis- (4-hydroxyphenyl) -3-diisopropyl-benzene and 1,1'-bis- (4-hydroxyphenyl) - 4-diisopropyl benzene.
Ganz besonders bevorzugte Dihydroxyarylverbindungen sind 4,4'-Dihydroxydiphenyl und 2,2-Bis-(4- hydroxyphenyl)-propan. Very particularly preferred dihydroxyaryl compounds are 4,4'-dihydroxydiphenyl and 2,2-bis (4-hydroxyphenyl) propane.
Es können sowohl eine Dihydroxyarylverbindung unter Bildung von Homopolycarbonaten als auch verschiedene Dihydroxyarylverbindungen unter Bildung von Copolycarbonaten verwendet werden. Es können sowohl eine Dihydroxyarylverbindung der Formel (I) oder (Ia) unter Bildung von Homopolycarbonaten als auch mehrere eine Dihydroxyarylverbindungen der Formel (I) und/oder (Ia) unter Bildung von Copolycarbonaten verwendet werden. Dabei können die verschiedenen Dihydroxyarylverbindungen sowohl statistisch als auch blockweise miteinander verknüpft sein. Im Falle von Copolycarbonaten aus Dihydroxyarylverbindungen der Formel (I) und (Ia), beträgt das molare Verhältnis von Dihydroxyarylverbindungen der Formel (Ia) zu den gegebenenfalls mitzuverwendenden anderen Dihydroxyarylverbindungen der Formel (I) vorzugsweise zwischen 99 Mol-% (Ia) zu 1 Mol-% (I) und 2 Mol-% (Ia) zu 98 Mol-% (I), vorzugsweise zwischen 99 Mol-% (Ia) zu 1 Mol-% (I) und 10 Mol-% (Ia) zu 90 Mol-% (I) und insbesondere zwischen 99 Mol-% (Ia) zu 1 Mol-% (I) und 30 Mol-% (Ia) zu 70 Mol-% (I). Ein ganz besonders bevorzugtes Copolycarbonat kann unter Verwendung von 1,1 -Bis-(4- h y d r o x y p h c n y I ) - 3 , 3 , 5 - 1 r i m c t h y I - c y c I o h c x a n und 2,2-Bis-(4-hydroxyphenyl)-propan-verbindungen der Formel (Ia) und (I) hergestellt werden. Both a dihydroxyaryl compound to form homopolycarbonates and various dihydroxyaryl compounds to form copolycarbonates can be used. It is possible to use both one dihydroxyaryl compound of the formula (I) or (Ia) with the formation of homopolycarbonates and also several dihydroxyaryl compounds of the formula (I) and / or (Ia) with the formation of copolycarbonates. The various dihydroxyaryl compounds can be linked to one another either randomly or in blocks. In the case of copolycarbonates made from 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) which may also be used is preferably between 99 mol% (Ia) to 1 mol -% (I) and 2 mol% (Ia) to 98 mol% (I), preferably between 99 mol% (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 very particularly preferred copolycarbonate can be made using 1,1-bis (4-hydroxyphenyl) -3, 3, 5 - 1 rimcthy I - cyc I ohcxan and 2,2-bis (4-hydroxyphenyl) propane- compounds of the formula (Ia) and (I) are produced.
Geeignete Kohlensäurederivate können beispielsweise die unter Formel (II) genannten sein. Suitable carbonic acid derivatives can be, for example, those mentioned under formula (II).
Bevorzugte Diarylcarbonate sind beispielsweise Diphenylcarbonat, Methylphenyl-phenyl-carbonate und Di-(methylphenyl)-carbonate, 4-Ethylphenyl-phenyl-carbonat, Di-(4-ethylphenyl)-carbonat, 4-n- Propylphenyl-phenyl-carbonat, Di-(4-n-propylphenyl)-carbonat, 4-iso-Propylphenyl -phenyl-carbonat, Di-(4-iso-propylphenyl)-carbonat, 4-n-Butylphenyl-phenyl-carbonat, Di-(4-n-butylphenyl)-carbonat, 4-iso-Butylphenyl-phenyl-carbonat, Di-(4-iso-butylphenyl)-carbonat, 4-tert-Butylphenyl-phenyl- carbonat, Di-(4-tert-butylphenyl)-carbonat, 4-n-Pentylphenyl-phenyl-carbonat, Di-(4-n-pentylphenyl)- carbonat, 4-n-Hexylphenyl-phenyl-carbonat, Di-(4-n-hexylphenyl)-carbonat, 4-iso-Octylphenyl- phenyl-carbonat, Di-(4-iso-octylphenyl)-carbonat, 4-n-Nonylphenyl-phenyl-carbonat, Di-(4-n- nonylphenyl) -carbonat, 4-Cyclohexylphenyl -phenyl-carbonat, Di-(4-cyclohexylphenyl)-carbonat, 4-(l- Methyl- 1 -phenylethyl)-phenyl-phenyl-carbonat, Di- [4-( 1 -methyl- 1 -phenylethyl) -phenyl] -carbonat,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-iso-propylphenyl-phenyl-carbonate, di- (4-iso-propylphenyl) -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-nonylphenylphenyl carbonate, di (4-n-nonylphenyl) carbonate, 4-cyclohexylphenylphenyl carbonate, di- (4-cyclohexylphenyl) ) carbonate, 4- (l-methyl-1-phenylethyl) -phenyl-phenyl-carbonate, di- [4- (1 -methyl-1-phenylethyl) -phenyl] -carbonate,
Biphenyl-4-yl -phenyl-carbonat, Di-(biphenyl-4-yl)-carbonat, 4-( 1 -Naphthyl)-phenyl-phenyl-carbonat, 4-(2-Naphthyl)-phenyl-phenyl-carbonat, Di-[4-(l-naphthyl)-phenyl]-carbonat, Di-[4-(2- naphthyl)phenyl] -carbonat, 4-Phenoxyphenyl-phenyl-carbonat, Di-(4-phenoxyphenyl)-carbonat, 3- Pentadecylphenyl-phenyl-carbonat, Di-(3-pentadecylphenyl)-carbonat, 4-Tritylphenyl-phenyl- carbonat, Di-(4-tritylphenyl)-carbonat, Methylsalicylat-phenyl-carbonat, Di-(methylsalicylat)-carbonat, Ethylsalicylat-phenyl-carbonat, Di-(ethylsalicylat)-carbonat, n-Propylsalicylat-phenyl-carbonat, Di-(n- propylsalicylat)-carbonat, iso-Propylsalicylat-phenyl-carbonat, Di-(iso-propylsalicylat)-carbonat, n- Butylsalicylat-phenyl-carbonat, Di-(n-butylsalicylat)-carbonat, iso-Butylsalicylat-phenyl-carbonat, Di- (iso-butylsalicylat)-carbonat, tert-Butylsalicylat-phenyl-carbonat, Di-(tert-butylsalicylat)-carbonat, Di- (phenylsalicylat)-carbonat und Di-(benzylsalicylat)-carbonat. Biphenyl-4-yl-phenyl-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.
Besonders bevorzugte Diarylverbindungen sind Diphenylcarbonat, 4-tert-Butylphenyl-phenyl-carbonat, Di-(4-tert-butylphenyl)-carbonat, Biphenyl-4-yl-phenyl-carbonat, Di-(biphenyl-4-yl)-carbonat, 4-( 1 - Methyl- 1 -phenylethyl)-phenyl-phenyl-carbonat, Di- [4-( 1 -methyl- 1 -phenylethyl) -phenyl] -carbonat und Di-(methylsalicylat)-carbonat. Ganz besonders bevorzugt ist Diphenylcarbonat. Particularly preferred diaryl compounds are diphenyl carbonate, 4-tert-butylphenyl-phenyl-carbonate, di- (4-tert-butyl-phenyl) -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.
Es können sowohl ein Diarylcarbonat als auch verschiedene Diarylcarbonate verwendet werden.Both a diaryl carbonate and various diaryl carbonates can be used.
Zur Steuerung bzw. Veränderung der Endgruppen können zusätzlich beispielsweise eine oder mehrere Monohydroxyarylverbindung(en) als Kettenabbrecher eingesetzt werden, die nicht zur Herstellung des oder der verwendeten Diarylcarbonat(e) verwendet wurde(n). Dabei kann es sich um solche der allgemeinen Formel (III) handeln, wobei To control or change the end groups, one or more monohydroxyaryl compound (s), for example, can additionally be used as chain terminators which were not used to prepare the diaryl carbonate (s) used. These can be those of the general formula (III), in which
RA für lineares oder verzweigtes C1-C34- Alkyl, C7-C34- Alkylaryl, C6-C34-Aryl oder für -COO-RD steht, wobei RD für Wasserstoff, lineares oder verzweigtes Ci-C34-Alkyl, C7-C34- Alkylaryl oder C6-C34- Aryl steht, und R A is linear or branched C1-C34- alkyl, C7-C 34 - represents alkylaryl, C6-C 34 -aryl or -COO-R D wherein R D is hydrogen, linear or branched Ci-C 34 alkyl, C 7 -C 34 - alkylaryl or C 6 -C 34 - aryl, and
RB, Rc unabhängig voneinander gleich oder verschieden für Wasserstoff, lineares oder verzweigtes Ci- C34- Alkyl, C7-C34- Alkylaryl oder C6-C34-Aryl stehen. R B , R c independently of one another, identically or differently, represent hydrogen, linear or branched C1-C34-alkyl, C7-C34-alkylaryl or C6-C34-aryl.
Solche Monohydroxyarylverbindungen sind beispielsweise 1-, 2- oder 3-Methylphenol, 2,4- Dimethylphenol 4-Ethylphenol, 4-n-Propylphenol, 4-iso-Propylphenol, 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-(l -Methyl- l-phenylethyl)-phenol, 4- Phenylphenol, 4-Phenoxyphenol, 4-(l-Naphthyl)-phenol, 4-(2-Naphthyl)-phenol, 4-Tritylphenol, Methylsalicylat, Ethylsalicylat, n-Propylsalicylat, iso-Propylsalicylat, n-Butylsalicylat, iso-Such monohydroxyaryl compounds are, for example, 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- (l-naphthyl) -phenol, 4- (2-naphthyl) -phenol, 4-tritylphenol, methyl salicylate, ethyl salicylate, n-propyl salicylate, iso-propyl salicylate, n-butyl salicylate, iso-
Butylsalicylat, tert-Butylsalicylat, Phenylsalicylat und Benzylsalicylat. Butyl salicylate, tert-butyl salicylate, phenyl salicylate and benzyl salicylate.
Bevorzugt sind 4-tert-Butylphenol, 4-iso-Octylphenol und 3-Pentadecylphenol. 4-tert-butylphenol, 4-iso-octylphenol and 3-pentadecylphenol are preferred.
Geeignete Verzweiger können Verbindungen mit drei und mehr funktionellen Gruppen, vorzugsweise solche mit drei oder mehr Hydroxylgruppen. Suitable branching agents can be compounds with three or more functional groups, preferably those with three or more hydroxyl groups.
Geeignete Verbindungen mit drei oder mehr phenolischen Hydroxylgruppen sind beispielsweise Phloroglucin, 4,6-Dimethyl-2,4,6-tri-(4-hydroxyphenyl)-hepten-2, 4,6-Dimethyl-2,4,6-tri-(4- hydroxyphenyl)-heptan, 1 ,3,5-Tri-(4-hydroxyphenyl)-benzol, 1 , 1 , l-Tri-(4-hydroxyphenyl)-ethan, Tri- (4-hydroxyphenyl)-phenylmethan, 2,2-Bis-(4,4-bis-(4-hydroxyphenyl)-cyclohexyl]-propan, 2,4-Bis-(4- hydroxyphenyl-isopropyl)-phenol und Tetra-(4-hydroxyphenyl)-methan. Suitable compounds with 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, l-tri- (4-hydroxyphenyl) -ethane, tri- (4-hydroxyphenyl) -phenylmethane, 2,2-bis- (4,4-bis- (4-hydroxyphenyl) -cyclohexyl] -propane, 2,4-bis- (4-hydroxyphenyl-isopropyl) -phenol and tetra- (4-hydroxyphenyl) -methane.
Sonstige geeignete Verbindungen mit drei und mehr funktionellen Gruppen sind beispielsweise 2,4- Dihydroxybenzoesäure, Trimesinsäure(trichlorid), Cyanursäuretrichlorid und 3,3-Bis-(3-methyl-4- hydroxyphenyl)-2-oxo-2,3-dihydroindol. Other suitable compounds with three or more functional groups are, for example, 2,4-dihydroxybenzoic acid, trimesic acid (trichloride), cyanuric acid trichloride and 3,3-bis- (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole.
Bevorzugte Verzweiger sind 3,3-Bis-(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindol und 1,1,1- Tri- (4 -hydroxy phenyl) -ethan. Preferred branching agents are 3,3-bis- (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole and 1,1,1-tri- (4-hydroxyphenyl) ethane.
In einer bevorzugten Ausgestaltung der Folie beinhaltet das Polycarbonat oder das Copolycarbonat die Ausgangsverbindung (Ib) in einem Bereich von 10 Gew.-% bis 90 Gew.-%, besonders bevorzugt in einem Bereich von 20 Gew.-% bis 80 Gew.-%, bezogen auf die Gesamtmasse des Polycarbonats oder des Copolycarbonats, oder das Polycarbonat oder das Copolycarbonat weist ein molares Verhältnis von (Ib) zu anderen Bisphenol A Abkömmlingen in einem Bereich von 1:10 bis 10:1, bevorzugt in einem Bereich von 1:5 bis 5:1 auf. In a preferred embodiment of the film, the polycarbonate or the copolycarbonate contains the starting compound (Ib) in a range from 10% by weight to 90% by weight, particularly preferably in a range from 20% by weight to 80% by weight, based on the total mass of the polycarbonate or the copolycarbonate, or the polycarbonate or the copolycarbonate has a molar ratio of (Ib) to other bisphenol A derivatives in a range of 1: 10 to 10: 1, preferably in a range from 1: 5 to 5: 1.
In einer bevorzugten Ausgestaltung der Folie weist die Folie mindestens eine, bevorzugt mindestens zwei, besonders bevorzugt alle der folgenden Eigenschaften auf: In a preferred embodiment of the film, the film has at least one, preferably at least two, particularly preferably all of the following properties:
(A) eine Rauigkeit in Anlehnung an ISO 4288:1996 in einem Bereich von 2 pm bis 30 pm, bevorzugt in einem Bereich von 3 pm bis 25 pm, besonders bevorzugt in einem Bereich von 5 pm bis 20 pm; (A) a roughness based on ISO 4288: 1996 in a range from 2 pm to 30 pm, preferably in a range from 3 pm to 25 pm, particularly preferably in a range from 5 pm to 20 pm;
(B) eine Transparenz in einem Bereich von 2% bis 92%, gemessen gemäß ISO 13468-2:2006-07;(B) a transparency in a range of 2% to 92%, measured according to ISO 13468-2: 2006-07;
(C) einen Glanz in einem Bereich von 10 bis 110 nach ISO 2813, 2015-02, bevorzugt in einem Bereich von 50 bis 110, besonders bevorzugt in einem Bereich von 60 bis 100, oder bevorzugt in einem Bereich von 10 bis 40, besonders bevorzugt in einem Bereich von 10 bis 30; (C) a gloss in a range from 10 to 110 according to ISO 2813, 2015-02, preferably in a range from 50 to 110, particularly preferably in a range from 60 to 100, or preferably in a range from 10 to 40, especially preferably in a range from 10 to 30;
(D) eine Kratzfestigkeit in einem Bereich von 4B bis 3H, bevorzugt von 2B bis 2H, besonders bevorzugt von 1B bis 1H, gemessen gemäß DIN EN ISO 15184-2011-05; (D) a scratch resistance in a range from 4B to 3H, preferably from 2B to 2H, particularly preferably from 1B to 1H, measured in accordance with DIN EN ISO 15184-2011-05;
(E) eine Vicat-Erweichungstemperatur in einem Bereich von 160 °C bis 230 °C, bevorzugt in einem Bereich von 170 °C bis 220 °C, gemäß ISO 306:2004 (Methode B12050N; 120°C/h); (E) a Vicat softening temperature in a range from 160 ° C. to 230 ° C., preferably in a range from 170 ° C. to 220 ° C., according to ISO 306: 2004 (method B12050N; 120 ° C./h);
(F) einen Oberflächenwiderstand < 1014 W, bevorzugt < 5*1013 W, gemäß DINIEC 93:1980 (Firma Fischer). (F) a surface resistance <10 14 W, preferably <5 * 10 13 W, according to DINIEC 93: 1980 (Fischer company).
Bevorzugt weist die Folie eine der folgenden Merkmalskombinationen auf: (A) und (B); (A) und (C);The film preferably has one of the following combinations of features: (A) and (B); (A) and (C);
(A) und (D); (A) und (E); (A) und (F); (B) und (C); (B) und (D); (B) und (E); (B) und (F); (C) und (D);(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) und (E); (C) und (F); (D) und (E); (D) und (F); (E) und (F); (A), (B) und (C); (A), (B) und (D); (A),(C) and (E); (C) and (F); (D) and (E); (D) and (F); (E) and (F); (A), (B) and (C); (A), (B) and (D); (A),
(B) und (E); (A), (B) und (F); (B), (C) und (D); (B), (C) und (E); (B), (C) und (F); (C), (D) und (E); (C),(B) and (E); (A), (B) and (F); (B), (C) and (D); (B), (C) and (E); (B), (C) and (F); (C), (D) and (E); (C),
(D) und (F); (D), (E) und (F); (A), (B), (C) und (D); (A), (B), (C) und (E); (A), (B), (C) und (F); (B),(D) and (F); (D), (E) and (F); (A), (B), (C) and (D); (A), (B), (C) and (E); (A), (B), (C) and (F); (B),
(C), (D) und (E); (B), (C), (D) und (F); (C), (D), (E), und (F); (A), (B), (C), (D) und (E); (A), (B), (C),(C), (D) and (E); (B), (C), (D) and (F); (C), (D), (E), and (F); (A), (B), (C), (D) and (E); (A), (B), (C),
(D) und (F); (B), (C), (D), (E) und (F); (A), (B), (C), (D), (E) und (F). (D) and (F); (B), (C), (D), (E) and (F); (A), (B), (C), (D), (E) and (F).
Die Transparenz unter (B) ist abhängig von den weiteren Zusatzstoffen, die bei der Herstellung der Folie hinzugegeben werden. Die Folie ohne weitere Zusatzstoffe, also nur mit den Komponenten i), ii) und iii) weist bevorzugt eine Transparenz in einem Bereich von 50 bis 92 %, weiter bevorzugt in einem Bereich von 70 bis 92 % auf. The transparency under (B) depends on the other additives that are added during the production of the film. The film without further additives, that is to say only with components i), ii) and iii), preferably has a transparency in a range from 50 to 92%, more preferably in a range from 70 to 92%.
Der Glanz unter (C) variiert insbesondere zwischen den Extremen in einem Bereich von 10 bis 30 nach ISO 2813, 2015-02, wenn beide Seiten der Folie eine mattierte Oberfläche aufweisen und dem anderen Extrem in einem Bereich von 70 bis 110 nach ISO 2813, 2015-02, wenn beide Seiten der Folie eine glatte Oberfläche aufweisen. In einer bevorzugten Ausgestaltung der Folie ist der weitere Zusatzstoff ausgewählt aus der Gruppe bestehend aus einem Farbstoff, einem Pigment oder einer Kombination aus diesen. Bevorzugt ist das Pigment ausgewählt aus der Gruppe bestehend aus einem Weißpigment, einem Schwarzpigment oder einem Buntpigment, insbesondere einem Weißpigment. The gloss under (C) varies in particular between the extremes in a range from 10 to 30 according to ISO 2813, 2015-02, if both sides of the film have a matt surface and the other extreme in a range from 70 to 110 according to ISO 2813, 2015-02 if both sides of the film have a smooth surface. In a preferred embodiment of the film, the further additive is selected from the group consisting of a dye, a pigment or a combination of these. The pigment is preferably selected from the group consisting of a white pigment, a black pigment or a colored pigment, in particular a white pigment.
In einer bevorzugten Ausgestaltung der Folie ist das Pigment ausgewählt aus der Gruppe bestehend aus Titandioxid, Zirkoniumdioxid, Erdalkalicarbonat, wie Calciumcarbonat und Erdalkalisulfat, wie Bariumsulfat oder einer Mischung aus mindestens zwei hiervon. Die Folie enthält die genannten Füllstoffe, wie Farbstoff oder Pigment, jeweils bevorzugt in einem Bereich von 2 bis 20 Gew.-%, besonders bevorzugt von 5 bis 10 Gew.-%, bezogen auf das Gesamtgewicht der Folie. Die Füllstoffe werden vorzugsweise in den genannten Mengen durch zum Beispiel Extrusion oder Coextrusion bei der Folienherstellung zugegeben. Die genannten Füllstoffe werden vorzugsweise insgesamt in einer Menge in einem Bereich von 2 bis 50 Gew.-%, besonders bevorzugt von 5 bis 40 Gew.-%, bezogen auf das Gesamtgewicht der Folie eingesetzt. In a preferred embodiment of the film, the pigment is selected from the group consisting of titanium dioxide, zirconium dioxide, alkaline earth carbonate such as calcium carbonate and alkaline earth sulfate such as barium sulfate or a mixture of at least two of these. The film contains the fillers mentioned, such as dye or pigment, in each case preferably in a range from 2 to 20% by weight, particularly preferably from 5 to 10% by weight, based on the total weight of the film. The fillers are preferably added in the stated amounts by, for example, extrusion or coextrusion during film production. The fillers mentioned are preferably used in total in an amount in a range from 2 to 50% by weight, particularly preferably from 5 to 40% by weight, based on the total weight of the film.
In einer bevorzugten Ausgestaltung der Folie wird der weitere Zusatzstoff durch ein Verfahren in die Folie eingebracht mit mindestens den Schritten: In a preferred embodiment of the film, the further additive is introduced into the film by a method with at least the following steps:
Dl. mindestens teilweises Beschichten der Folie mit einer Schicht, enthaltend einen Farbstoff oder ein Pigment, D. At least partial coating of the film with a layer containing a dye or a pigment,
D2. mindestens teilweises Bestrahlen der Folie aus Dl. mit fokussierter nicht-ionisierender elektromagnetischer Strahlung, wobei eine partielle Einfärbung der Folie nur an den in Schritt D2. bestrahlten Stellen erfolgt.D2. at least partial irradiation of the film from DI. with focused non-ionizing electromagnetic radiation, partial coloring of the film only on the in step D2. irradiated areas.
Das Beschichten in Schritt Dl. Kann durch jede Beschichtungsmethode erfolgen, die ein Fachmann hierfür auswählen würde. Das Beschichten ist bevorzugt ausgewählt aus der Gruppe bestehend aus Tauchen, Drucken oder einer Kombination hieraus. The coating in step Dl. Can be carried out by any coating method that a person skilled in the art would select for this. The coating is preferably selected from the group consisting of dipping, printing or a combination thereof.
Bevorzugt wird die Folie in ein Färbungsbad getaucht, um die Folie zu benetzen und eine Schicht in Form einer Farbschicht auf die Folie zu erzeugen. Das Färbungsbad kann auf eine Temperatur bis 99 °C erwärmt werden. Hierdurch kann die Intensität der partiellen Einfärbung je nach verwendetem Polymer im Kunststoffteil verbessert werden. Bei Bestrahlung der Kunststoffteile in einem Autoklaven kann das Färbungsbad auch auf 150°C erwärmt werden, wenn das die Wärmeformbeständigkeit der Kunststoffteile zulässt In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens beträgt die Temperatur des Färbungsbads < 70 °C, bevorzugt > 10 °C bis < 60 °C, besonders bevorzugt > 15°C bis < 50°C. Das Färbungsbad kann mindestens ein Farbmittel, vorzugsweise mindestens einen Farbstoff, besonders bevorzugt mindestens einen Farbstoff der Gruppe Solvent Dyes und/oder Dispers Dyes gemäß Klassifizierung des Colour Index oder Mischungen aus diesen Farbstoffen umfassen. The film is preferably immersed in a dye bath in order to wet the film and produce a layer in the form of a colored layer on the film. The dye bath can be heated to a temperature of up to 99 ° C. In this way, the intensity of the partial coloring can be improved in the plastic part, depending on the polymer used. When the plastic parts are irradiated in an autoclave, the dye bath can also be heated to 150 ° C if the heat resistance of the plastic parts allows. In a preferred embodiment of the method according to the invention, the temperature of the dye bath is <70 ° C, preferably> 10 ° C to <60 ° C, particularly preferably> 15 ° C to <50 ° C. The dye bath can comprise at least one colorant, preferably at least one dye, particularly preferably at least one dye from the group of Solvent Dyes and / or Dispers Dyes according to the classification of the Color Index or mixtures of these dyes.
Der Colour Index (CI) der Society of Dyers and Colourists und der American Association of Textile Chemists and Colorists charakterisiert alle Farbmittel eindeutig durch den Gruppennamen und den Zahlen für die chemische Zusammensetzung bzw. chemische Struktur. The Color Index (CI) of the Society of Dyers and Colourists and the American Association of Textile Chemists and Colorists uniquely characterizes all colorants by the group name and the numbers for the chemical composition or chemical structure.
Farbstoffe der Gruppe der Solvent Dyes gemäß Klassifizierung des Colour Index können beispielsweise die sogenannten Macrolex® Farbstoffe der Firma Lanxess AG, Deutschland sein. Beispielhaft genannt sind Macrolex® Blau 3R, Macrolex® Rot H, Macrolex® Gelb 6G (Solvent Yellow 179 gemäß CI), Macrolex® Violet Rot R (Dispers Violet 31 gemäß CI), Macrolex® orange R (Solvent Orange 107 gemäß CI) oder Mischungen aus diesen Farbstoffe. Dyes from the group of solvent dyes according to the classification of the Color Index can be, for example, the so-called Macrolex® dyes from Lanxess AG, Germany. Examples include Macrolex® Blue 3R, Macrolex® Red H, Macrolex® Yellow 6G (Solvent Yellow 179 according to CI), Macrolex® Violet Red R (Dispers Violet 31 according to CI), Macrolex® orange R (Solvent Orange 107 according to CI) or Mixtures of these dyes.
Farbstoffe der Gruppe der Dispers Dyes gemäß Klassifizierung des Colour Index können beispielsweise Diazo-, Diphenylamin- und Anthrachinonverbindungen, Acetatfarbstoffe, Dispersionsfarbstoffe und/oder Dispersolfarbstoffe sein und schließen Dispers-Blau #3, Dispers-Blau #14, Dispers-Gelb #3, Dispers-Rot #134 und Dispers-Rot#7 ein. Die Klassifikation und Bezeichnung der vorstehend zitierten Farbstoffe stimmen mit „The Colour Index“, 3. Ausgabe, gemeinsam veröffentlicht von the Society of Dyes and Colors und the American Association of Textile Chemists and Colorists (1971) überein. Die Farbstoffe können ganz allgemein entweder als einziger Farbstoffbestandteil oder als Komponente einer Mischung in Abhängigkeit von der gewünschten Farbe angewandt werden. Somit schließt der hier verwendete Begriff des Farbstoffs auch die Farbstoffmischung ein. Dyes of the group of dispers dyes according to the classification of the Color Index can be, for example, diazo, diphenylamine and anthraquinone compounds, acetate dyes, disperse dyes and / or disperse dyes and include disperse blue # 3, disperse blue # 14, disperse yellow # 3, disperse -Rot # 134 and Dispers-Red # 7. The classification and designation of the dyes cited above are consistent with The Color Index, 3rd Edition, jointly published by the Society of Dyes and Colors and the American Association of Textile Chemists and Colorists (1971). The dyes can generally be used either as a single dye ingredient or as a component of a mixture, depending on the color desired. Thus, the term dye used here also includes the dye mixture.
Unter den geeigneten Farbstoffen sind wasserunlösliche Diazo-Diphenylamin- und Anthrachinonverbindungen zu nennen. Besonders geeignet sind Acetat-Farbstoffe, dispergierte Acetat- Farbstoffe, Dispersionsfarbstoffe und Dispersol-Farbstoffe, wie sie im Colour Index 3. Auflage, Band 2, The Societey of Dyers and Colourists, 1971. S. 2479 bzw. 2187-2743 offenbart sind. Suitable dyes include water-insoluble diazo-diphenylamine and anthraquinone compounds. Acetate dyes, dispersed acetate dyes, disperse dyes and dispersol dyes, as disclosed in the Color Index 3rd Edition, Volume 2, The Society of Dyers and Colourists, 1971, pp. 2479 and 2187-2743, are particularly suitable.
Die bevorzugten dispergierten Farbstoffe schließen Dy star 's Palanil Blau E-R150 (Anthrachinon/Dispers-Blau), DIANIX Orange E-3RN (Azofarbstoff/Cl Dispers-Orange 25) und die vorstehend genannten Macrolex® Farbstoffe als Solvent Dyes ein. The preferred dispersed dyes include Dy star's Palanil Blue E-R150 (Anthraquinone / Disperse Blue), DIANIX Orange E-3RN (Azo Dye / CI Disperse Orange 25) and the aforementioned Macrolex® dyes as solvent dyes.
Bevorzugt umfasst das Färbungsbad: a) Lösungsmittel und/oder Dispergiermittel, vorzugsweise Wasser und/oder organisches Lösungsmittel, besonders bevorzugt Wasser b) Farbmittel, vorzugsweise einen Farbstoff, besonders bevorzugt einen Farbstoff der Solvent Dyes und/oder Dispers Dyes gemäß Klassifizierung des Colour Index. Vorteilhaft haben sich solche Färbungsbäder erwiesen, die zum gleichmäßigen Einfärben von Polycarbonat-Kunststoffteilen bei Temperaturen > 80 °C geeignet sind. Diese werden beispielsweise beschrieben in WO-A 03/ 040461, EP-A 2050866, WO-A 03/083207. Unter den Bedingungen des erfindungsgemäßen Verfahrens erfolgt im Wesentlichen eine partielle Einfärbung der Folie an den bestrahlten Bereichen, so dass genau an diesen Stellen eine intensive Gravur in Form der Schicht sichtbar wird. The dye bath preferably comprises: a) solvent and / or dispersant, preferably water and / or organic solvent, particularly preferably water b) colorant, preferably a dye, particularly preferably a dye of the solvent dyes and / or dispersion dyes according to the classification of the color index. Those dye baths which are suitable for uniformly dyeing polycarbonate plastic parts at temperatures> 80 ° C. have proven to be advantageous. These are described, for example, in WO-A 03/040461, EP-A 2050866, WO-A 03/083207. Under the conditions of the method according to the invention, there is essentially a partial coloring of the film in the irradiated areas, so that an intensive engraving in the form of the layer is visible precisely at these points.
Die Schicht, enthaltend den Farbstoff oder das Pigment, enthält den Farbstoff oder das Pigment bevorzugt in einer Menge in einem Bereich von 1 ppm bis 180 ppm, besonders bevorzugt in einem Bereich von 10 ppm bis 160 ppm, ganz besonders bevorzugt in einem Bereich von 15 ppm bis 100 ppm.The layer containing the dye or the pigment contains the dye or the pigment preferably in an amount in a range from 1 ppm to 180 ppm, particularly preferably in a range from 10 ppm to 160 ppm, very particularly preferably in a range of 15 ppm to 100 ppm.
Die Schicht weist bevorzugt eine Dicke in einem Bereich von 10 pm bis 500 pm, besonders bevorzugt in einem Bereich von 20 pm bis 400 pm, ganz besonders bevorzugt in einem Bereich von 50 pm bis 200 pm auf. The layer preferably has a thickness in a range from 10 μm to 500 μm, particularly preferably in a range from 20 μm to 400 μm, very particularly preferably in a range from 50 μm to 200 μm.
Das Bestrahlen in Schritt D2. kann auf jede Art erfolgen, die der Fachmann hierfür auswählen würde. Das Bestrahlen in Schritt D2. erfolgt bevorzugt mit fokussierter nicht-ionisierender elektromagnetischer Strahlung, vorzugsweise fokussierter nicht-ionisierender elektromagnetischer Strahlung mit einer Wellenlänge im Bereich von > 0,1 pm bis < 1 mm, besonders bevorzugt im Bereich von > 0,15 pm bis < 20 pm, ganz besonders bevorzugt mit Faserstrahlung einer Wellenlänge im Bereich von > 0,15 pm bis < 20 pm. Unter farbig wird auch schwarz oder weiß verstanden. The irradiation in step D2. can be done in any way the skilled person would choose to do this. The irradiation in step D2. preferably takes place with focused non-ionizing electromagnetic radiation, preferably focused non-ionizing electromagnetic radiation with a wavelength in the range from> 0.1 μm to 1 mm, particularly preferably in the range from 0.15 μm to ganz 20 μm, very particularly preferably with fiber radiation of a wavelength in the range from> 0.15 pm to <20 pm. Colored is also understood to mean black or white.
Eine Möglichkeit durch Tauchen und anschließendem Bestrahlen eine Farbschicht zumindest teilweise auf die Folie aufzubringen, wird in der US 2019/0106837 Al beschrieben One possibility of at least partially applying a layer of paint to the film by dipping and subsequent irradiation is described in US 2019/0106837 A1
Im Rahmen dieser Erfindung wird unter „im Wesentlichen“ verstanden, dass lediglich an den in Schritt D2. bestrahlten Stellen ein farbiges Element entsteht, welches mit dem Auge als sichtbares farbiges Element eindeutig zu erkennen ist. Es ist hierbei nicht ausgeschlossen, dass eine leichte Einfärbung des Kunststoffteils, an den nicht bestrahlten Stellen erfolgen kann. In the context of this invention, “essentially” is understood to mean that only those in step D2. Irradiated areas create a colored element that is clearly visible to the eye as a visible colored element. It cannot be ruled out that the plastic part may be slightly colored in the areas that have not been irradiated.
Das erfindungsgemäße Verfahren zeichnet sich dadurch aus, dass eine partielle Einfärbung der Folie, die insbesondere thermoplastisches Kunststoff enthält, im Wesentlichen an den in Schritt D2. bestrahlten Stellen erfolgt. Die restliche Folie weist keine bzw. nur eine sehr schwache Einfärbung an den nicht bestrahlten Bereichen auf. Somit ist es möglich, gezielt Bereiche der Folie einzufärben, um beispielsweise Bild, Personalisierung, Logo, Symbol oder Schriftzug auf die Folie durch das erfindungsgemäße Verfahren aufzubringen. Diese lassen sich nicht ohne weiteres von der Folienoberfläche entfernen. Somit eignet sich das erfindungsgemäße Verfahren insbesondere für den Bereich der Herstellung von Sicherheits- und Identifikationsdokumente. Ein weiterer Gegenstand der Erfindung betrifft die Verwendung einer erfindungsgemäßen Folie beinhaltend sicherheitsrelevante Daten in einem Sicherheitsdokument. Unter Sicherheitsdokumenten werden insbesondere Dokumente mit sicherheitsrelevanten Angaben verstanden, wie Personalausweise, Pässe, Führerscheine und ähnliche. Ein weiterer Gegenstand der Erfindung betrifft die Verwendung eines Poly carbonats oder eines Copolycarbonats der Formeln (Ia), (1-2), (1-3) oder (1-4) worin The method according to the invention is characterized in that a partial coloring of the film, which in particular contains thermoplastic plastic, is essentially based on the in step D2. irradiated areas. The rest of the film has no or only a very weak coloring in the non-irradiated areas. It is thus possible to color areas of the film in a targeted manner in order, for example, to apply an image, personalization, logo, symbol or lettering to the film using the method according to the invention. These cannot be easily removed from the film surface. The method according to the invention is therefore particularly suitable for the area of producing security and identification documents. Another object of the invention relates to the use of a film according to the invention containing security-relevant data in a security document. Security documents are understood to mean, in particular, documents with security-relevant information, such as identity cards, passports, driver's licenses and the like. The invention also relates to the use of a polycarbonate or a copolycarbonate of the formulas (Ia), (1-2), (1-3) or (1-4) wherein
R1 und R2 unabhängig voneinander Wasserstoff, Halogen, bevorzugt Chlor oder Brom, Ci-C8-Alkyl, Cs-Cö-Cycloalkyl, C6-Cio-Aryl, bevorzugt Phenyl, und C7-Ci2-Aralkyl, bevorzugt Phenyl-Ci-C4-Alkyl, insbesondere Benzyl, m eine ganze Zahl von 4 bis 7, bevorzugt 4 oder 5, R 1 and R 2 are independently hydrogen, halogen, preferably chlorine or bromine, Ci-C 8 alkyl, Cs-C ö cycloalkyl, C 6 -Cio-aryl, preferably phenyl, and C7-Ci2 aralkyl, preferably phenyl Ci-C4-alkyl, in particular benzyl, m is an integer from 4 to 7, preferably 4 or 5,
R3 und R4 für jedes X individuell wählbar, unabhängig voneinander Wasserstoff oder Ci- CÖ- Alkyl und R 3 and R 4 can be selected individually for each X, independently of one another hydrogen or Ci- C Ö - alkyl and
X Kohlenstoff bedeuten, mit der Maßgabe, dass an mindestens einem Atom X, R3 und R4 gleichzeitig Alkyl bedeuten, oder worin R5 für einen Ci- bis C4- Alkylrest, Aralkylrest oder Arylrest, bevorzugt für einen Methylrest oder Phenylrest, ganz besonders bevorzugt für einen Methylrest, steht zur Herstellung einer lasergravierbaren Folie. X is carbon, with the proviso that on at least one atom X, R 3 and R 4 are simultaneously alkyl, or where R 5 is a C1 to C 4 alkyl radical, aralkyl radical or aryl radical, preferably a methyl radical or phenyl radical, very particularly preferably a methyl radical for the production of a laser-engravable foil.
Alle Angaben zu den Polycarbonaten oder den Copolycarbonaten der Formeln (Ia), (1-2), (1-3) oder (I- 4) sind entsprechend denen, der im Zusammenhang mit der erfindungsgemäßen Folie beschriebenen zu entnehmen. Alle Angaben zu dem Verfahren des Lasergravierens zum Einfärben der Folie wurde zuvor beschrieben und ist ebenfalls für die Verwendung anwendbar. All information on the polycarbonates or the copolycarbonates of the formulas (Ia), (1-2), (1-3) or (I- 4) can be found in the same way as those described in connection with the film according to the invention. All information on the method of laser engraving for coloring the film has been described above and is also applicable to the use.
Ein weiterer Gegenstand der Erfindung betrifft einen Schichtaufbau, enthaltend mindestens folgende Schichten: Another object of the invention relates to a layer structure containing at least the following layers:
Sl. eine erfindungsgemäße Folie, Sl. a film according to the invention,
52. ggf. eine weitere Folie, 52. possibly another slide,
53. ggf. eine weitere erfindungsgemäße Folie, 53. possibly another film according to the invention,
54. ggf. eine Papier- oder Kartonschicht. 54. if necessary a layer of paper or cardboard.
Die erfindungsgemäße Folie wurde zuvor beschrieben. Sämtliche Angaben zu der Folie, wie Einsatzstoffe, Mengenangaben, Formen und Dicken sind ebenfalls für die Folien in dem Schichtaufbau anwendbar. The film according to the invention has been described above. All information on the film, such as raw materials, quantities, shapes and thicknesses can also be used for the films in the layer structure.
Die weitere Folie kann jede Folie sein, die der Fachmann hierfür einsetzen würde. Bevorzugt ist die weitere Folie ausgewählt aus der Gruppe bestehend aus einer Polyurethanfolie, einer Polyesterfolie, einer Polyacrylatfolie, einer Polycarbonatfolie, einer Siliconfolie oder einer Kombination aus mindestens zwei hiervon. The further film can be any film that a person skilled in the art would use for this purpose. The further film is preferably selected from the group consisting of a polyurethane film, a polyester film, a polyacrylate film, a polycarbonate film, a silicone film or a combination of at least two of these.
In einer bevorzugten Ausgestaltung des Schichtaufbaus, weist der Schichtaufbau eine weitere Folie S2. auf, wobei die weitere Folie S2. einen thermoplastischen Kunststoff beinhaltet, ausgewählt aus Polymerisaten von ethylenisch ungesättigten Monomeren und/oder Polykondensaten von bifunktionellen reaktiven Verbindungen, bevorzugt um ein oder mehrere Polycarbonat(e) oder Copolycarbonat(e) auf Basis von Diphenolen, Poly- oder Copolyacrylat(e) und Poly- oder Copolymethacrylat(e), Poly- oder Copolymer(e) mit Styrol, thermoplastische Polyurethan(e), sowie Polyolefin(e), Poly- oder Copolykondensat(e) der Terephthalsäure mit einem Anteil an 1,4- Cyclohexandimethanol, 1,3-Cyclohexandimethanol und/oder 2,2,4,4-Tetramethyl-l,3-butandiol, vorzugsweise 1,4-Cyclohexandimethanol und/oder 1,3-Cyclohexandimethanol, Poly- oder Copolykondensate der Naphthalindicarbonsäure, Poly- oder Copolykondensat(e) wenigstens einer Cycloalkyldicarbonsäure, Mischungen aus diesen oder deren Blends, besonders bevorzugt um ein oder mehrere Polycarbonat(e) oder Copolycarbonat(e) auf Basis von Diphenolen oder Blends enthaltend wenigstens ein Polycarbonat oder Copolycarbonat Bevorzugt entspricht die weitere Folie dem Aufbau und den Eigenschaften wie für die weitere Folie im Zusammenhang mit der erfindungsgemäßen Folie zuvor beschrieben. In a preferred embodiment of the layer structure, the layer structure has a further film S2. on, with the further slide S2. Contains a thermoplastic material selected from polymers of ethylenically unsaturated monomers and / or polycondensates of bifunctional reactive compounds, preferably one or more polycarbonate (s) or copolycarbonate (s) based on diphenols, poly- or copolyacrylate (s) and poly- or copolymethacrylate (s), poly- or copolymer (s) with styrene, thermoplastic polyurethane (s), as well as polyolefin (s), poly- or copolycondensate (s) of terephthalic acid with a proportion of 1,4-cyclohexanedimethanol, 1,3 -Cyclohexanedimethanol and / or 2,2,4,4-tetramethyl-1,3-butanediol, preferably 1,4-cyclohexanedimethanol and / or 1,3-cyclohexanedimethanol, polycondensates or copolycondensates of naphthalenedicarboxylic acid, poly- or copolycondensate (s) at least one cycloalkyldicarboxylic acid, mixtures of these or their blends, particularly preferably one or more polycarbonate (s) or copolycarbonate (s) based on diphenols or blends containing at least one polycarbonate or the like the copolycarbonate The further film preferably corresponds to the structure and properties as described above for the further film in connection with the film according to the invention.
Die Papier- oder Kartonschicht S4. kann jede Papier- oder Kartonschicht sein, die der Fachmann für diesen Zweck einsetzen würde. The paper or cardboard layer S4. can be any paper or cardboard layer that one skilled in the art would use for this purpose.
In einer bevorzugten Ausführungsform des Schichtaufbaus, umfasst der Schichtaufbau eine weitere Schicht enthaltend wenigstens einen thermoplastischen Kunststoff und wenigstens ein lasersensibles Additiv umfasst. Bevorzugt handelt es sich bei dem Additiv um ein Schwarzpigment, besonders bevorzugt Ruß, oder ein Farbpigment, wie sie zuvor im Zusammenhang mit dem Einfärben der erfindungsgemäßen Folie beschrieben wurden. Alle Angaben zu den Schwarzpigmenten und Farbpigmenten sind ebenfalls für den Schichtaufbau anwendbar. In a preferred embodiment of the layer structure, the layer structure comprises a further layer containing at least one thermoplastic material and at least one laser-sensitive additive. The additive is preferably a black pigment, particularly preferably carbon black, or a colored pigment as described above in connection with the coloring of the film according to the invention. All information on black pigments and color pigments can also be used for the layer structure.
In den Figuren In the figures
Fig. 1 Darstellung der Gegenüberstellung der Rauhigkeit und optischen Dichte von erfindungsgemäßen und nicht erfindungsgemäßen Folien 1 shows the comparison of the roughness and optical density of films according to the invention and not according to the invention
Fig. 2 Darstellung der Gegenüberstellung des Glanzes und der optischen Dichte von erfindungsgemäßen und nicht erfindungsgemäßen Folien 2 shows the comparison of the gloss and the optical density of films according to the invention and not according to the invention
Die erfindungsgemäßen Folien zeichnen sich durch höhere optische Dichte im Vergleich zu den nicht erfindungsgemäßen Vergleichsfolien aus, wie dies aus den Figuren 1 und 2 abzulesen ist. Die optische Dichte wurde ermittelt mit dem Farbdensitometer DENS der Fa. Techkon gemäß den Empfehlungen der DIN 5033 Teile 1 -9: Farbmessung und den Berechnungen gemäß ISO 5-3:2009 (E): Fotographie - Messen der optischen Dichte - Teil 3 The films according to the invention are distinguished by a higher optical density compared to the comparison films not according to the invention, as can be seen from FIGS. 1 and 2. The optical density was determined with the DENS color densitometer from Techkon in accordance with the recommendations of DIN 5033 Parts 1 -9: Color measurement and the calculations in accordance with ISO 5-3: 2009 (E): Photography - Measuring the optical density - Part 3
Beispiele Beispiel 1 Examples Example 1
183,3 g (0,80 Mol) Bisphenol A (2,2-Bis-(4-hydroxyphenyl)-propan, 61,1 g (0,20 Mol) l,l-Bis-(4- hydroxyphenyl)-3,3,5-trimethylcyclohexan, 336,6 g (6 Mol KOH und 2700 g Wasser wurden in einer Inertgas-Atmosphäre unter Rühren gelöst. Dann wurd eine Fösung von 1,88 g Phenol in 2500 ml Methylenchlorid zugefügt. In die gut gerührte Lösung wurden bei pH 13 bis 14 und 21 bis 25°C 198 g (2 Mol) Phosgen eingeleitet. Danach wurde 1 ml Ethylpiperidin zugegeben und noch 45 Min. gerührt. Die bisphenolatfreie wässrige Phase wurde abgetrennt, die organische Phase nach Ansäuern mit Phosphorsäure mit Wasser neutral gewaschen und vom Lösungsmittel befreit. Das Polycarbonat zeigte eine relative Lösungsviskosität von 1,255. 183.3 g (0.80 moles) bisphenol A (2,2-bis (4-hydroxyphenyl) propane, 61.1 g (0.20 moles) 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 Methylene chloride added. 198 g (2 mol) of phosgene were passed into the well-stirred solution at pH 13 to 14 and 21 to 25 ° C. Then 1 ml of ethyl piperidine was added and the mixture was stirred for a further 45 minutes. The bisphenolate-free aqueous phase was separated off, the organic phase, after acidification with phosphoric acid, washed neutral with water and freed from the solvent. The polycarbonate showed a relative solution viscosity of 1.255.
Die Glastemperatur des Polymers wurde zu 157°C bestimmt (DSC). The glass transition temperature of the polymer was determined to be 157 ° C. (DSC).
Beispiel 2 Example 2
Wie in Beispiel 1 wurde eine Mischung aus 127,1 g (0,56 Mol) Bisphenol A und 137,7 g (0,44 Mol) l,l-Bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexan zum Polycarbonat umgesetzt. As in Example 1, a mixture of 127.1 g (0.56 mol) of bisphenol A and 137.7 g (0.44 mol) of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane was obtained converted to polycarbonate.
Das Polycarbonat zeigte eine relative Lösungsviskosität von 1,263. The polycarbonate showed a relative solution viscosity of 1.263.
Die Glastemperatur des Polymers wurde zu 167°C bestimmt (DSC). The glass transition temperature of the polymer was determined to be 167 ° C. (DSC).
Beispiel 3 Example 3
Wie in Beispiel 1 wurde eine Mischung aus 149,0 g (0,65 Mol) Bisphenol A und 107,9 g (0,35 Mol) l,l-Bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexan zum Polycarbonat umgesetzt. As in Example 1, a mixture of 149.0 g (0.65 mol) of bisphenol A and 107.9 g (0.35 mol) of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane was obtained converted to polycarbonate.
Das Polycarbonat zeigte eine relative Lösungsviskosität von 1,263. The polycarbonate showed a relative solution viscosity of 1.263.
Die Glastemperatur des Polymers wurde zu 183°C bestimmt (DSC). The glass transition temperature of the polymer was determined to be 183 ° C. (DSC).
Beispiel 4 Example 4
Wie in Beispiel 1 wurde eine Mischung aus 91,6 g (0,40 Mol) Bisphenol A und 185,9 g (0,60 Mol) 1,1- Bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexan zum Polycarbonat umgesetzt. As in Example 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 was obtained converted to polycarbonate.
Das Polycarbonat zeigte eine relative Lösungsviskosität von 1,251. The polycarbonate showed a relative solution viscosity of 1.251.
Die Glastemperatur des Polymers wurde zu 204°C bestimmt (DSC). The glass transition temperature of the polymer was determined to be 204 ° C. (DSC).
Beispiel 5 Example 5
Wie in Beispiel 1 wurde eine Mischung aus 44,2 g (0,19 Mol) Bisphenol A und 250,4 g (0,81 Mol) 1,1- Bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexan zum Polycarbonat umgesetzt. As in Example 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 was obtained converted to polycarbonate.
Das Polycarbonat zeigte eine relative Lösungsviskosität von 1,248. The polycarbonate showed a relative solution viscosity of 1.248.
Die Glastemperatur des Polymers wurde zu 216°C bestimmt (DSC). The glass transition temperature of the polymer was determined to be 216 ° C. (DSC).
Beispiel 6: Compoundierung eines Masterbatches für die Herstellung der Schicht enthaltend einen thermoplastischen Kunststoff und ein Antistat-Additiv Herstellung des Antistat-Additiv-Compounds wurde mit herkömmlichen Zweischnecken Compoundierextrudern (z.B. ZSK 32) bei für Polycarbonat üblichen Verarbeitungstemperaturen von 250 bis 330°C durchgeführt. Example 6: Compounding of a masterbatch for the production of the layer containing a thermoplastic and an antistatic additive The antistatic additive compound was produced using conventional twin-screw compounding extruders (eg ZSK 32) at processing temperatures of 250 to 330 ° C. that are customary for polycarbonate.
Es wurde ein Master-Batch mit folgender Zusammensetzung compoundiert und anschließend granuliert: A master batch was compounded with the following composition and then granulated:
• 90 Gew.-% Polycarbonat aus Beispiel 3 • 90% by weight of polycarbonate from Example 3
• 10 Gew.-% N,N,N,N-Dimethyldiisoproylammoniumperfluorbutansulfonat. • 10% by weight of N, N, N, N-dimethyldiisopropylammonium perfluorobutanesulfonate.
Beispiele 7 bis 10 für Folien-Extrusion Examples 7 to 10 for film extrusion
Zur Extrusion der Folien in einer Breite von 450 mm wurde der Kunststoff aus Beispiel 3 eingesetzt. Die verwendete Anlage bestand aus The plastic from Example 3 was used to extrude the films in a width of 450 mm. The system used consisted of
- einem Extruder mit einer Schnecke von 75 mm Durchmesser (D) und einer Länge von 33xD. Die Schnecke weist eine Entgasungszone auf; - an extruder with a screw of 75 mm diameter (D) and a length of 33xD. The screw has a degassing zone;
- einer Schmelzepumpe; - a melt pump;
- einem Umlenkkopf; - a deflection head;
- einer Breitschlitzdüse mit 450 mm Breite; - a slot nozzle with a width of 450 mm;
- einem Dreiwalzen-Glättkalander mit horizontaler W alzenanordnung, wobei die dritte W alze um +/- 45° gegenüber der Horizontalen schwenkbar ist; - A three-roll smoothing calender with a horizontal roll arrangement, the third roll being pivotable by +/- 45 ° relative to the horizontal;
- einer Rollenbahn; - a roller conveyor;
- Dickenmessung - Thickness measurement
- einer Einrichtung zum beidseitigen Aufbringen von Schutzfolie; - A device for applying protective film on both sides;
- einer Abzugseinrichtung; - a trigger device;
- Aufwickelstation. - rewinding station.
Das jeweilige Granulat wurde dem Fülltrichter des Extruders zugeführt. Im Plastifiziersystem Zylinder/Schnecke des Extruders erfolgte das Aufschmelzen und Fördern des Materials. Die Materialschmelze wurde dem Glättkalander zugeführt, dessen Walzen, bzw. die zur Kühlung der Walzen zu- und abgeführte Kühlflüssigkeit, die in der Tabelle 1 genannte Temperatur aufwiesen. Auf dem Glättkalander (bestehend aus drei Walzen) erfolgte die endgültige Formgebung und Abkühlung der Folie. Zur Strukturierung der Folienoberflächen wurden dabei wahlweise eine Gummi-Walze (4-er oder Oberfläche), polierte Chrom-Walze (1-er Oberfläche) oder strukturierte Stahlwalze (2-er und 6-er Oberfläche) eingesetzt. Die für die Strukturierung der Folienoberfläche verwendete Gummi-Walze ist in US- 4 368 240 der Fa. Nauta Roll Corporation offenbart. Anschließend wurde die Folie durch einen Abzug transportiert. Danach kann ggf. eine Schutzfolie aus PE beidseitig aufgebracht werden und eine Aufwicklung der Folie erfolgen. The respective granulate was fed to the feed hopper of the extruder. The material was melted and conveyed in the cylinder / screw plasticizing system of the extruder. The material melt was fed to the smoothing calender, the rolls of which, or the cooling liquid fed in and removed for cooling the rolls, had the temperature specified in Table 1. The final shaping and cooling of the film took place on the smoothing calender (consisting of three rollers). A rubber roller (4 or surface), polished chrome roller (1 surface) or structured steel roller (2 or 6 surface) was used to structure the film surfaces. The rubber roller used for structuring the film surface is disclosed in US Pat. No. 4,368,240 from Nauta Roll Corporation. The film was then transported through a take-off. A protective film made of PE can then be applied to both sides and the film can be rolled up.
Tabelle 0: Temperaturverlauf des Extruders und der Düse Table 0: Temperature profile of the extruder and the nozzle
Tabelle 1: Laufgeschwindigkeit und Temperaturprofil der Walzen Tabelle 2: Oberflächentexturen der Beispielfolien 7 bis 10 Table 1: Running speed and temperature profile of the rollers Table 2: Surface textures of the example foils 7 to 10
Es wurden 100 mih dicke Folien extrudiert. Sheets 100 milliliters thick were extruded.
Beispiele 11 bis 16: Toner-Druck Ein DIN-A 4 Folienmuster der Beispiele 7 bis 10 Folie wurde mit einem Farblaserdrucker der Firma HP bedruckt (Model des Druckers: Ricoh MP C 3003). Die Folie wurde auf der Seite mit der jeweilig benannten Seite bedruckt. Examples 11 to 16: Toner printing A DIN A4 film sample from Examples 7 to 10 film was printed with a color laser printer from HP (printer model: Ricoh MP C 3003). The film was printed on the side with the respective named side.
Druckmuster: Vollflächiger Schwarz-Druck Auflösung des Druckmusters: 600 dpi. Die erfindungsgemäßen Folien ließen sich einwandfrei bedrucken und zeigten ein fehlerfreies Druckbild im Gegensatz zu den nicht erfindungsgemäßen Folien, die sich beim Druckvorgang verzogen und Verwerfungen in der Folie aufwiesen. Print sample: Full-surface black print. Resolution of the print sample: 600 dpi. The films according to the invention could be perfectly printed and showed a faultless print image in contrast to the films not according to the invention, which warped during the printing process and showed warpage in the film.
Tabelle 3: Oberflächentexturen der Beispielfolien 11 bis 16" Table 3: Surface textures of the example foils 11 to 16 "
Beispiel 17 bis 24: Kartenlamination Example 17 to 24: Card lamination
Die bedruckte Folien der Beispiele 11 bis 16"" wurde zwischen zwei weitere Folien auf Basis von Polycarbonat Makroion 3108® der Covestro AG, gelegt. Der Folienstapel wurde in eine Laminierpresse der Firma Bürkle gelegt und unter Druck und Temperatur laminiert. Laminiert wurde mit folgenden Parametern: The printed films of Examples 11 to 16 "" was placed between two films based on polycarbonate Makrolon ® 3108 Covestro the AG. The stack of foils was placed in a lamination press from Bürkle and laminated under pressure and temperature. Laminating was carried out with the following parameters:
Temperatur: 195°C Temperature: 195 ° C
Niedriger Vordruck während der Aufwärmzeit: 15 N/cm2 Aufwärmdauer: 8 Minuten. Hoher Druck während der Laminierung: 300 N/cm2 Laminierdauer: 2 Minuten. Low pre-pressure during the warm-up time: 15 N / cm 2 Warm-up time: 8 minutes. High pressure during lamination: 300 N / cm 2 lamination time: 2 minutes.
Anschließend wurde Abkühlung der Presse eingeleitet. Abgekühlt wurde unter anhaltender Druckbeaufschlagung. Bei Erreichen einer Temperatur von 38°C wurde die Presse geöffnet. The press was then cooled down. Cooling was carried out with continued pressurization. When a temperature of 38 ° C. was reached, the press was opened.
Auswertung der optischen Dichte Evaluation of the optical density
Tabelle 4: Auswertung der optischen Dichte und Glanz der Beispiele 17 bis 24 Table 4: Evaluation of the optical density and gloss of Examples 17 to 24
Wie aus der Tabelle 4 abzulesen ist, ist sowohl eine Erhöhung bzw. näherungsweise Angleichung der optischen Dichte bei meist gleichbleibenden Glanzwerten als auch eine Erhöhung der optischen Dichte bei gleichbleibender Rauigkeit nach dem Bedrucken der erfindungsgemäßen Folien aus Beispielen 20 bis 22 und 24 gegenüber den nicht erfindungsgemäßen Beispielen 17 bis 19 und 23, jeweils auf die entsprechende Zusammensetzung bezogen, zu erkennen. Optisch wurden die Ergebnisse für die Darstellung der optischen Dichte bei verschiedenen Rauigkeiten in Figur 1 und bei unterschiedlichen Glanzgraden in Figur 2 für die Beispiele 17 bis 24 dargesteht. Das entscheidende Merkmal bei zu bedruckenden Folien ist jedoch die Schärfe des Drucks. Hier ist festzustellen, dass es Bereiche des Glanzes und der Rauigkeit gibt, die ein schlechtes Druckbild erzeugen, während die erfindungsgemäßen Folien alle ein gutes bis sehr gutes Druckbild erkennen lassen, wie in der Tabelle 5 abzulesen ist: Auswertung des Druckbildes As can be seen from Table 4, there is both an increase or approximation of the optical density with mostly constant gloss values and an increase in the optical density with constant roughness after printing the films according to the invention from Examples 20 to 22 and 24 compared to those not according to the invention Examples 17 to 19 and 23, each based on the corresponding composition, can be seen. The results for the representation of the optical density at different roughness levels were shown optically in FIG. 1 and at different degrees of gloss in FIG. 2 for Examples 17 to 24. The decisive feature of foils to be printed, however, is the sharpness of the print. It should be noted here that there are areas of gloss and roughness that produce a poor print image, while the foils according to the invention all show a good to very good print image, as in Table 5 shows: Evaluation of the print image
Tabelle 5: Auswertung des Druckbildes der Beispiele 17 bis 24 Table 5: Evaluation of the print image of Examples 17 to 24

Claims

Patentansprüche Claims
Eine Folie enthaltend i) 85 bis 95 Gew.-% eines Polycarbonat oder Copolycarbonat der Formel (Ia), (1-2), (1-3) oder (1-4), wobei (Ia) worin A film containing i) 85 to 95% by weight of a polycarbonate or copolycarbonate of the formula (Ia), (1-2), (1-3) or (1-4), where (Ia) wherein
R1 und R2 unabhängig voneinander Wasserstoff, Halogen, bevorzugt Chlor oder Brom, Ci-Cs-Alkyl, Cs-Cö-Cycloalkyl, Cö-Cio-Aryl, bevorzugt Phenyl, und CVCn-Aralkyl, bevorzugt Phenyl-Ci-C4-Alkyl, insbesondere Benzyl, m eine ganze Zahl von 4 bis 7, bevorzugt 4 oder 5, R 1 and R 2 are independently hydrogen, halogen, preferably chlorine or bromine, Ci-Cs-alkyl, Cs-C ö cycloalkyl, C ö -Cio-aryl, preferably phenyl, and CVCn-aralkyl, preferably phenyl-Ci-C4 -Alkyl, in particular benzyl, m is an integer from 4 to 7, preferably 4 or 5,
R3 und R4 für jedes X individuell wählbar, unabhängig voneinander Wasserstoff oder Ci- CV Alkyl und X Kohlenstoff bedeuten, mit der Maßgabe, dass an mindestens einem Atom X, R3 und R4 gleichzeitig Alkyl bedeuten, oder wobei R 3 and R 4 can be selected individually for each X, independently of one another, are hydrogen or Ci- CV alkyl and X is carbon, with the proviso that on at least one atom X, R 3 and R 4 are simultaneously alkyl, or where
(1-3) (1-4) worin R5 für einen Ci- bis C4- Alkylrest, Aralkylrest oder Arylrest, bevorzugt für einen Methylrest oder Phenylrest, ganz besonders bevorzugt für einen Methylrest, steht; ii) 0,1 bis 5 Gew.-% eines ersten Zusatzstoffes; iii) optional 0,1 bis 15 Gew.% eines zweiten Zusatzstoffes, der verschieden ist vom ersten Zusatzstoff; wobei der erste Zusatzstoff ii) eine Antistatikverbindung enthält oder ist. (1-3) (1-4) wherein R 5 represents a C1 to C4 alkyl radical, aralkyl radical or aryl radical, preferably a methyl radical or phenyl radical, very particularly preferably a methyl radical; ii) 0.1 to 5% by weight of a first additive; iii) optionally 0.1 to 15% by weight of a second additive that is different from the first additive; wherein the first additive ii) contains or is an antistatic compound.
2. Die Folie gemäß Anspruch 1, wobei der erste Zusatzstoff ii), insbesondere die Antistatikverbin dung, ausgewählt ist aus der Gruppe bestehend aus quaternären Ammonium- oder Phosphonium- salzen einer teil- oder perfluorierten organischen Säure oder quaternären Ammonium- oder Phosphoniumhexafluorophosphaten oder Mischungen aus mindestens zwei hiervon. 2. The film according to claim 1, wherein the first additive ii), in particular the antistatic compound, is selected from the group consisting of quaternary ammonium or phosphonium salts of a partially or perfluorinated organic acid or quaternary ammonium or phosphonium hexafluorophosphates or mixtures of at least two of these.
3. Die Folie gemäß einem der vorhergehenden Ansprüche, wobei die Antistatikverbindung ausgewählt ist aus der Gruppe bestehend aus quaternären Ammoniumsalzen einer teil- oder perfluorierten organischen Säure oder quaternären Ammoniumhexafluorophosphaten oder Mischungen aus mindestens zwei hiervon. 4. Die Folie gemäß einem der vorhergehenden Ansprüche, wobei das Polycarbonat oder das3. The film according to one of the preceding claims, wherein the antistatic compound is selected from the group consisting of quaternary ammonium salts of a partially or perfluorinated organic acid or quaternary ammonium hexafluorophosphates or mixtures of at least two thereof. 4. The film according to one of the preceding claims, wherein the polycarbonate or the
Copolycarbonat ein mittleres Molekulargewicht Mw in einem Bereich von 10 000 bis 500 000 g/mol, bevorzugt von 15000 bis 400000 g/mol, besonders bevorzugt von 20000 bis 300000 g/mol aufweist. Copolycarbonate has an average molecular weight Mw in a range from 10,000 to 500,000 g / mol, preferably from 15,000 to 400,000 g / mol, particularly preferably from 20,000 to 300,000 g / mol.
5. Die Folie gemäß einem der vorhergehenden Ansprüche, wobei das Polycarbonat oder das Copolycarbonat teilweise aus den Ausgangsprodukten hergestellt ist, ausgewählt aus der Gruppe bestehend aus: (Ib), oder Mischungen aus mindestens zwei hiervon. 5. The film according to one of the preceding claims, wherein the polycarbonate or the copolycarbonate is partially produced from the starting products selected from the group consisting of: (Ib), or mixtures of at least two of these.
6. Die Folie gemäß einem der vorhergehenden Ansprüche, wobei das Poly carbonat oder das Copolycarbonat die Ausgangsverbindung (Ib) in einem Bereich von 10 Gew.-% bis 90 Gew.-%, bezogen auf die Gesamtmasse des Polycarbonats oder des Copolycarbonats beinhaltet oder das Polycarbonat oder das Copolycarbonat ein molares Verhältnis von (Ib) zu anderen Bisphenol A6. The film according to one of the preceding claims, wherein the poly carbonate or the copolycarbonate contains the starting compound (Ib) in a range of 10 wt .-% to 90 wt .-%, based on the total mass of the polycarbonate or the copolycarbonate or the Polycarbonate or the copolycarbonate has a molar ratio of (Ib) to other bisphenol A.
Abkömmlingen in einem Bereich von 1:10 bis 10:1, bevorzugt in einem Bereich von 1:5 bis 5:1 aufweist. Has descendants in a range from 1:10 to 10: 1, preferably in a range from 1: 5 to 5: 1.
7. Die Folie gemäß einem der vorhergehenden Ansprüche, wobei die Folie mindestens eine, bevorzugt mindestens zwei, besonders bevorzugt alle der folgenden Eigenschaften aufweist: (A) eine Rauigkeit in Anlehnung an ISO 4288: 1996 in einem Bereich von 2 pm bis 30 pm, bevorzugt in einem Bereich von 3 pm bis 25 pm, besonders bevorzugt in einem Bereich von 5 pm bis 20 pm; 7. The film according to one of the preceding claims, wherein the film has at least one, preferably at least two, particularly preferably all of the following properties: (A) a roughness based on ISO 4288: 1996 in a range from 2 pm to 30 pm, preferably in a range from 3 pm to 25 pm, particularly preferably in a range from 5 pm to 20 pm;
(B) eine Transparenz in einem Bereich von 2% bis 92%, gemessen gemäß ISO 13468- 2:2006-07; (C) einen Glanz in einem Bereich von 10 bis 110 nach ISO 2813, 2015-02, bevorzugt in einem Bereich von 50 bis 110, besonders bevorzugt in einem Bereich von 60 bis 100, oder bevorzugt in einem Bereich von 10 bis 40, besonders bevorzugt in einem Bereich von 10 bis 30; (D) eine Kratzfestigkeit in einem Bereich von 4B bis 3H, bevorzugt von 2B bis 2H, besonders bevorzugt von B bis 1H, gemessen gemäß DIN EN ISO 15184-2011-05;(B) a transparency in a range from 2% to 92%, measured according to ISO 13468-2: 2006-07; (C) a gloss in a range from 10 to 110 according to ISO 2813, 2015-02, preferably in a range from 50 to 110, particularly preferably in a range from 60 to 100, or preferably in a range from 10 to 40, especially preferably in a range from 10 to 30; (D) a scratch resistance in a range from 4B to 3H, preferably from 2B to 2H, particularly preferably from B to 1H, measured in accordance with DIN EN ISO 15184-2011-05;
(E) eine Vicat-Erweichungstemperatur in einem Bereich von 160 °C bis 230 °C, bevorzugt in einem Bereich von 170 °C bis 220 °C, gemäß ISO 306:2004 (Methode B120 50N; 120°C/h); (E) a Vicat softening temperature in a range from 160 ° C. to 230 ° C., preferably in a range from 170 ° C. to 220 ° C., according to ISO 306: 2004 (method B120 50N; 120 ° C./h);
(F) einen Oberflächenwiderstand < 1014 W, bevorzugt < 5*1013 W, gemäß DIN IEC 93: 1980 (Firma Fischer). (F) a surface resistance <10 14 W, preferably <5 * 10 13 W, according to DIN IEC 93: 1980 (Fischer).
8. Die Folie gemäß einem der vorhergehenden Ansprüche, wobei der weitere Zusatzstoff ausgewählt ist aus der Gruppe bestehend aus einem Farbstoff, einem Pigment oder einer Kombination aus diesen. 8. The film according to one of the preceding claims, wherein the further additive is selected from the group consisting of a dye, a pigment or a combination of these.
9. Die Folie gemäß einem der vorhergehenden Ansprüche, wobei das Pigment ausgewählt ist aus der Gruppe bestehend aus Titandioxid, Zirkoniumdioxid, Calciumcarbonat und Bariumsulfat oder einer Mischung aus mindestens zwei hiervon. 9. The film according to one of the preceding claims, wherein the pigment is selected from the group consisting of titanium dioxide, zirconium dioxide, calcium carbonate and barium sulfate or a mixture of at least two thereof.
10. Die Folie gemäß einem der vorhergehenden Ansprüche, wobei der weitere Zusatzstoff durch ein Verfahren in die Folie eingebracht wird mit mindestens den Schritten: 10. The film according to one of the preceding claims, wherein the further additive is introduced into the film by a method with at least the following steps:
Dl. mindestens teilweises Beschichten der Folie mit einer Schicht, enthaltend einen Farbstoff oder ein Pigment, D. At least partial coating of the film with a layer containing a dye or a pigment,
D2. mindestens teilweises Bestrahlen der Folie aus Dl. mit fokussierter nicht-ionisierender elektromagnetischer Strahlung, wobei eine partielle Einfärbung der Folie nur an den in Schritt D2. bestrahlten Stellen erfolgt.D2. at least partial irradiation of the film from DI. with focused non-ionizing electromagnetic radiation, partial coloring of the film only on the in step D2. irradiated areas.
11. Verwendung einer Folie gemäß einem der Ansprüche 1 bis 11 beinhaltend sicherheitsrelevante Daten in einem Sicherheitsdokument. 11. Use of a film according to one of claims 1 to 11 containing security-relevant data in a security document.
12. Verwendung eines Polycarbonats oder eines Copolycarbonats gemäß der Formel (Ia), (1-2), (1-3) oder (1-4) worin R1 und R2 unabhängig voneinander Wasserstoff, Halogen, bevorzugt Chlor oder Brom, Ci-Cs-Alkyl, Cs-Cö-Cycloalkyl, Cö-Cio-Aryl, bevorzugt Phenyl, und CVCn-Aralkyl, bevorzugt Phenyl-Ci-C4-Alkyl, insbesondere Benzyl, m eine ganze Zahl von 4 bis 7, bevorzugt 4 oder 5, 12. Use of a polycarbonate or a copolycarbonate according to the formula (Ia), (1-2), (1-3) or (1-4) wherein R 1 and R 2 are independently hydrogen, halogen, preferably chlorine or bromine, Ci-Cs-alkyl, Cs-C ö cycloalkyl, C ö -Cio-aryl, preferably phenyl, and CVCn-aralkyl, preferably phenyl-Ci-C4 -Alkyl, in particular benzyl, m is an integer from 4 to 7, preferably 4 or 5,
R3 und R4 für jedes X individuell wählbar, unabhängig voneinander Wasserstoff oder Ci- CÖ- Alkyl und R 3 and R 4 can be selected individually for each X, independently of one another hydrogen or Ci- C Ö - alkyl and
X Kohlenstoff bedeuten, mit der Maßgabe, dass an mindestens einem Atom X, R3 und R4 gleichzeitig Alkyl bedeuten, oder worin R5 für einen Ci- bis C4- Alkylrest, Aralkylrest oder Arylrest, bevorzugt für einen Methylrest oder Phenylrest, ganz besonders bevorzugt für einen Methylrest, steht zur Herstellung einer lasergravierbaren Folie. X is carbon, with the proviso that on at least one atom X, R 3 and R 4 are simultaneously alkyl, or where R 5 represents a C1 to C4 alkyl radical, aralkyl radical or aryl radical, preferably a methyl radical or phenyl radical, very particularly preferably a methyl radical, for the production of a laser-engravable film.
13. Ein Schichtaufbau, enthaltend folgende Schichten: 13. A layer structure containing the following layers:
51. eine Folie gemäß einem der Ansprüche 1 bis 10, 51. a film according to one of claims 1 to 10,
52. ggf. eine weitere Schicht oder Folie, 52. possibly another layer or foil,
53. ggf. eine weitere Folie gemäß einem der Ansprüche 1 bis 10, 53. if necessary, a further film according to one of claims 1 to 10,
54. ggf. eine Papier- oder Kartonschicht. 54. if necessary a layer of paper or cardboard.
14. Der Schichtaufbau gemäß Anspruch 13, enthaltend wenigstens eine weiter Folie S2., wobei die weitere Folie S2. einen thermoplastischen Kunststoff beinhaltet, ausgewählt aus Polymerisaten von ethylenisch ungesättigten Monomeren und/oder Polykondensaten von bifunktionellen reaktiven Verbindungen, bevorzugt um ein oder mehrere Polycarbonat(e) oder Copolycarbonat(e) auf Basis von Diphenolen, Poly- oder Copolyacrylat(e) und Poly- oder Copolymethacrylat(e), Poly- oder Copolymer(e) mit Styrol, thermoplastische Polyurethan(e), sowie Polyolefin(e), Poly- oder Copolykondensat(e) der Terephthalsäure mit einem Anteil an 1,4-Cyclohexandimethanol, 1,3- Cyclohexandimethanol und/oder 2,2,4,4-Tetramethyl-l,3-butandiol, vorzugsweise 1,4- Cyclohexandimethanol und/oder 1,3-Cyclohexandimethanol, Poly- oder Copolykondensate der Naphthalindicarbonsäure, Poly- oder Copolykondensat(e) wenigstens einer Cycloalkyldicarbonsäure, Mischungen aus diesen oder deren Blends, besonders bevorzugt um ein oder mehrere Polycarbonat(e) oder Copolycarbonat(e) auf Basis von Diphenolen oder Blends enthaltend wenigstens ein Polycarbonat oder Copolycarbonat. 14. The layer structure according to claim 13, containing at least one further film S2., Wherein the further film S2. Contains a thermoplastic material selected from polymers of ethylenically unsaturated monomers and / or polycondensates of bifunctional reactive compounds, preferably one or more polycarbonate (s) or copolycarbonate (s) based on diphenols, poly- or copolyacrylate (s) and poly- or copolymethacrylate (s), poly- or copolymer (s) with styrene, thermoplastic polyurethane (s), as well as polyolefin (s), poly- or copolycondensate (s) of terephthalic acid with a proportion of 1,4-cyclohexanedimethanol, 1,3 - Cyclohexanedimethanol and / or 2,2,4,4-tetramethyl-1,3-butanediol, preferably 1,4-cyclohexanedimethanol and / or 1,3-cyclohexanedimethanol, polycondensates or copolycondensates of naphthalenedicarboxylic acid, poly- or copolycondensate (s) at least a cycloalkyldicarboxylic acid, mixtures of these or their blends, particularly preferably one or more polycarbonate (s) or copolycarbonate (s) based on diphenols or blends containing at least one polycarbonate or copolycarbonate.
15. Der Schichtaufbau gemäß Anspruch 14, dadurch gekennzeichnet, dass der Schichtaufbau eine weitere Schicht enthaltend wenigstens einen thermoplastischen Kunststoff und wenigstens ein lasersensibles Additiv umfasst. 15. The layer structure according to claim 14, characterized in that the layer structure comprises a further layer containing at least one thermoplastic and at least one laser-sensitive additive.
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