EP4351873A1 - Ultrathin layered structure with specific properties - Google Patents
Ultrathin layered structure with specific propertiesInfo
- Publication number
- EP4351873A1 EP4351873A1 EP22732123.9A EP22732123A EP4351873A1 EP 4351873 A1 EP4351873 A1 EP 4351873A1 EP 22732123 A EP22732123 A EP 22732123A EP 4351873 A1 EP4351873 A1 EP 4351873A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- range
- layer
- polymer
- layered structure
- din
- 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.)
- Pending
Links
- 229920000642 polymer Polymers 0.000 claims abstract description 113
- 238000000034 method Methods 0.000 claims abstract description 36
- 238000000113 differential scanning calorimetry Methods 0.000 claims abstract description 13
- 239000000654 additive Substances 0.000 claims abstract description 7
- 230000009477 glass transition Effects 0.000 claims abstract description 7
- 238000002844 melting Methods 0.000 claims abstract description 5
- 230000008018 melting Effects 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 45
- 239000004417 polycarbonate Substances 0.000 claims description 45
- 229920000515 polycarbonate Polymers 0.000 claims description 44
- 239000008187 granular material Substances 0.000 claims description 27
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 24
- -1 polyethylene Polymers 0.000 claims description 17
- 239000004952 Polyamide Substances 0.000 claims description 15
- 229920002647 polyamide Polymers 0.000 claims description 15
- 239000000155 melt Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000004698 Polyethylene Substances 0.000 claims description 10
- 150000001925 cycloalkenes Chemical class 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229920000573 polyethylene Polymers 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 8
- 238000012805 post-processing Methods 0.000 claims description 8
- 239000011888 foil Substances 0.000 claims description 5
- 238000005096 rolling process Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000010330 laser marking Methods 0.000 claims description 3
- 238000007639 printing Methods 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 230000010287 polarization Effects 0.000 claims description 2
- 230000003746 surface roughness Effects 0.000 claims description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 15
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 12
- 229920001283 Polyalkylene terephthalate Polymers 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- WKBPZYKAUNRMKP-UHFFFAOYSA-N 1-[2-(2,4-dichlorophenyl)pentyl]1,2,4-triazole Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(CCC)CN1C=NC=N1 WKBPZYKAUNRMKP-UHFFFAOYSA-N 0.000 description 5
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 3
- 230000032798 delamination Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000009499 grossing Methods 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 3
- 239000004425 Makrolon Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- YQPCHPBGAALCRT-UHFFFAOYSA-N 2-[1-(carboxymethyl)cyclohexyl]acetic acid Chemical compound OC(=O)CC1(CC(O)=O)CCCCC1 YQPCHPBGAALCRT-UHFFFAOYSA-N 0.000 description 1
- AJKXDPSHWRTFOZ-UHFFFAOYSA-N 2-ethylhexane-1,6-diol Chemical compound CCC(CO)CCCCO AJKXDPSHWRTFOZ-UHFFFAOYSA-N 0.000 description 1
- CPHURRLSZSRQFS-UHFFFAOYSA-N 3-[4-[2-[4-(3-hydroxypropoxy)phenyl]propan-2-yl]phenoxy]propan-1-ol Chemical compound C=1C=C(OCCCO)C=CC=1C(C)(C)C1=CC=C(OCCCO)C=C1 CPHURRLSZSRQFS-UHFFFAOYSA-N 0.000 description 1
- RBQLGIKHSXQZTB-UHFFFAOYSA-N 3-methylpentane-2,4-diol Chemical compound CC(O)C(C)C(C)O RBQLGIKHSXQZTB-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- CDBAMNGURPMUTG-UHFFFAOYSA-N 4-[2-(4-hydroxycyclohexyl)propan-2-yl]cyclohexan-1-ol Chemical compound C1CC(O)CCC1C(C)(C)C1CCC(O)CC1 CDBAMNGURPMUTG-UHFFFAOYSA-N 0.000 description 1
- 101100087530 Caenorhabditis elegans rom-1 gene Proteins 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 101100305983 Mus musculus Rom1 gene Proteins 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000006085 branching agent Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- OHMBHFSEKCCCBW-UHFFFAOYSA-N hexane-2,5-diol Chemical compound CC(O)CCC(C)O OHMBHFSEKCCCBW-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 125000005487 naphthalate group Chemical group 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- XRVCFZPJAHWYTB-UHFFFAOYSA-N prenderol Chemical compound CCC(CC)(CO)CO XRVCFZPJAHWYTB-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/06—Interconnection of layers permitting easy separation
-
- 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
- B32B27/18—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
- B32B27/32—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
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
- B32B27/325—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polycycloolefins
-
- 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
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- 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
-
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- 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
- B32B2250/40—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
- 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
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/42—Polarizing, birefringent, filtering
-
- 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
- B32B2307/51—Elastic
-
- 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
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- 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
- B32B2307/54—Yield strength; Tensile strength
-
- 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
- B32B2307/70—Other properties
- B32B2307/72—Density
-
- 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
- B32B2307/70—Other properties
- B32B2307/73—Hydrophobic
-
- 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
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
-
- 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
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
-
- 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
- B32B2605/00—Vehicles
- B32B2605/003—Interior finishings
Definitions
- the invention is related to a layered structure S. comprising at least two layers, at least one layer A. and at least one layer B. and a process for its production as well as the use as coating for interior and exterior applications.
- a first aspect of the invention refers to a layered structure S., comprising:
- A. at least one first layer A., with a first outer surface A1 and a second surface A2, comprising at least polymer (A), wherein the first layer A. has a thickness in the region of 10 to 50 pm, preferably in the range of 10 to 30 pm, and
- layer B at least one further layer B. comprising at least polymer (B), wherein layer A. of the layered structure S. provides at least one, preferably two, more preferably three, most preferably all of the following properties:
- a glass-transition temperature Tg of > 70°C preferably in a range of from 80 to 250 °C, more preferably in a range of from 80 to 240 °C; most preferably in a range of from 80 to 200 °C, determined via differential scanning calorimetry (DSC) according to standard DIN EN 61006:2004 at a heating -rate of 20 K/min with definition of T g as the midpoint temperature (tangent method) or a vicat softening temperature B/50 determined according to ISO 306-2014-03 (50N; 50°/h) of > 70°C; preferably in a range of from 75 to 230 °C, more preferably in a range of from 80 to 230 °C; most preferably in a range of from 85 to 225 °C;
- Melt volume rate (MVR; measured according to DIN ISOl 133-1-2012-03; 300°C, 2.16 kg) of > 3 cm 3 / 10 min, more preferably of > 3.5 cm 3 / 10 min, even more preferably of > 4 cm 3 / 10 min;
- additives in a range of from 0.01 to 0.5 wt.-%, preferably in a range of from 0.02 to 0.3 wt- %, more preferably in a range of from 0.05 to 0.1 wt.-%.
- the layered structure S. provides one property or one property combination selected from the group consisting of SI.; S2.; S3.; S4.; S5.; S6.; SI. and S2.; SI. and S3.; SI. and S4.; SI. and S5.; SI. and S6.; S2. and S3.; S2. and S4.; S2. and S5.; S2. and S6.; S3, and S4.; S3, and S5.; S3, and S6.; S4. and S5.; S4. and S6.; S5. and S6.; SI. and S2. and S3.; SI. and S2. and S4.; SI. and S2. and S5.; SI. and S2. and S3, and S4.; SI. and S3, and S5.; SI. and S3, and S6.; SI. and S4. and S5.; SI. and S2. and S6.; SI. and S3, and S4.; SI. and S3, and S5.; SI. and S3, and S6.; SI. and S4. and S5.; SI. and S4. and
- S4. and S6. SI. and S5. and S6.; S2. and S3, and S4.; S2. and S3, and S5.; S2. and S3, and S6.; S2. and
- SI. S2. and S3, and S4. SI. and S2. and S3, and S5.; SI. and S2. and S3, and S6.; SI. and S2. and S4. and S5.; SI. and S2. and S4. and S6.; SI. and S2. and S4. and S6.; SI. and S2. and S5. and S6.; SI. and S3, and S4. and S5.; SI. and S3, and S4. and S6.; SI. and S3, and S5. and S6.; SI. and S4. and
- SI. and S2. and S4. and S5. and S6. SI. and S3, and S4. and S5. and S6.; S2. and S3, and S4. and S5. and S6.; SI. and S2. and S3, and S4. and S5. and S6..
- the adhesion force between the at least one first layer A. and the at least one further layer B. is in a range of from 0.001 to 0.05 N/cm, preferably in a range of from 0.005 to 0.04 N/cm, more preferably in a range of from 0.01 to 0.02 N/cm, measured according to ASTM D903-1998 at a pulling angle of 180°.
- the layered structure S. preferably layer A. provides at least one, preferably two, more preferably all of the following properties:
- the layered structure S. provides one property or one property combination selected from the group consisting of S7.; S8.; S9.; S10.; S11.; S7. and S8.; S7. and S9.; S7. and S10.; S7. and S11.; S8. and S9.; S8. and S10.; S8. and S11.; S9. and S10.; S9. and S11.; S10. and S11.; S7. and S8. and S9.; S7.
- the layered structure S. provides in addition to any of properties S1.
- the adhesion is selected in a range where the two layers A. and B. could be separated easily by manual force but do not fall apart on their own without input of any force.
- the adhesion between the layers A. and B. allow a transportation of the layered structure S. without the risk of cracks in the thin layer A., but make it easy to provide layer A. for further processing by just separating layer B. by hand or a machine using small forces.
- the separation of layer A. from layer B. is preferably provided without any detectable residues of polymer (B) on layer A.
- the adjustment of the adhesion between layer A. and layer B. is not supported by any additives in layer A.
- additive means molecules which have a molecular mass of ⁇ 1000 g/mol, more preferably of ⁇ 500 g/mol, even more preferably of ⁇ 300 g/mol.
- layer A. provides at least one, preferably at least two, more preferably all of the following properties: a1. a gloss at 60° angle in a range of 10 to 110, measured according to DIN EN ISO 2813-2015-02; a2.
- the first layer A. of the layered structure S. provides a property or a property combination selected from the group consisting of a1.; a2.; a3.; a4.; a5.; a6.; a7.; a8.; a9.; a1. and a2.; a1. and a3.; a1. and a4.; a1. and a5.; a1. and a6.; a1. and a7.; a1.1.
- layer A. differs from layer B. in at least one, preferably in at least two and even more preferably in all of the following properties:
- Prl. a difference of the thickness in a range of from 0.01 to 50 pm, preferably of from 0.02 to 30 pm, more preferably of from 0.03 to 10 pm, most preferably of from 0.05 to 1 pm;
- Pr2. a difference of tensile strength in a range of from 50 to 500 kPa, preferably of from 60 to 400 kPa, measured according to DIN EN ISO 527-1:2012-06;
- n a difference of refractive index n of ⁇ 0.5, preferably ⁇ 0.3, more preferably ⁇ 0.1;
- Pr5. a difference of birefringence of ⁇ 10 nm, preferably ⁇ 5, more preferably ⁇ 2.
- Polymer (A) can be any polymer the person skilled in the art would select for the establishment of layer A. in a layered structure S..
- the polymer (A) provides a Tg in a range of from 100 to 180 °C, more preferably in a range of from 120 to 160 °C, most preferably of from 130 to 150 °C, determined via differential scanning calorimetry (DSC) according to standard DIN EN 61006:2004 at a heating-rate of 20 K/min with definition of Tg as the midpoint temperature (tangent method).
- DSC differential scanning calorimetry
- Polymer (B) can be any polymer the person skilled in the art would select for the establishment of layer B. in a layered structure S..
- the polymer (B) provides a Tg in a range of from 10 to 80 °C, more preferably in a range of from 20 to 60 °C, most preferably of from 30 to 50 °C, determined via differential scanning calorimetry (DSC) according to standard DIN EN 61006:2004 at a heating-rate of 20 K/min with definition of Tg as the midpoint temperature (tangent method).
- DSC differential scanning calorimetry
- Particularly suitable polymers (A) or (B) are one or more polycarbonate(s) or copolycarbonate (s) based on diphenols, poly- or copolyacrylate(s) and poly- or copolymethacrylate(s) such as, by way of example and preferably, polymethylmethacrylate or poly(meth)acrylate (PMMA), polymer(s) or copolymer(s) with styrene such as, by way of example and preferably, polystyrene (PS), acrylonitrile-butadiene- styrene (ABS), or polystyrene-acrylonitrile (SAN), thermoplastic polyurethane(s) and also polyolefin(s) such as, by way of example and preferably, polypropylene types or polyolefins based on cyclic olefins (COC) e.g.
- COC cyclic olefins
- TOPAS ® of Hoechst now TOPAS Advanced Polymers
- poly- or copolycondensate(s) of terephthalic acid such as, by way of example and 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), polyamide (PA), poly- or copolycondensate(s) of naphthalenedicarboxylic acid such as, by way of example and preferably, polyethylene glycol naphthalate (PEN), poly- or copolycondensate(s) of at least one cycloalkyldicarboxylic acid such as, by way of example and preferably, polycyclohexanedimethanolcyclohexanedicarboxylic acid (PCCD), polysulfone
- Particularly preferred polymers (A) or (B) are one or more polycarbonate (s) or copolycarbonate (s) based on diphenols or blends comprising at least one polycarbonate or copolycarbonate. Very particular preference is given to blends containing at least one polycarbonate or copolycarbonate and at least one poly- or copolycondensate of terephthalic acid, of naphthalenedicarboxylic acid or of a cycloalkyldicarboxylic acid, preferably of cyclohexanedicarboxylic acid.
- polycarbonates or copolycarbonates especially having average molecular weights Mw of 500 to 100000, preferably of 10 000 to 80 000, particularly preferably of 15 000 to 40 000, or blends thereof with at least one poly- or copolycondensate of terephthalic acid having average molecular weights Mw of 10 000 to 200 000, preferably of 21 000 to 120 000.
- Suitable poly- or copolycondensates of terephthalic acid in preferred embodiments of the invention are polyalkylene terephthalate s.
- Suitable polyalkylene terephthalates are for example reaction products of aromatic dicarboxylic acids or their reactive derivatives (for example dimethyl esters or anhydrides) and aliphatic, cycloaliphatic or araliphatic diols and mixtures of these reaction products.
- Preferred polyalkylene terephthalates may be prepared from terephthalic acid (or reactive derivatives thereof) and aliphatic or cycloaliphatic diols having 2 to IO C 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%, of terephthalic acid radicals, based on the dicarboxylic acid component, and at least 80 mol%, preferably at least 90 mol%, of ethylene glycol and/or butane- 1,4-diol and/or cyclohexane- 1,4-dimethanol radicals based on the diol component.
- the preferred polyalkylene terephthalates may contain, in addition to terephthalic acid radicals, up to 20 mol% of radicals of other aromatic dicarboxylic acids having 8 to 14 carbon atoms or of aliphatic dicarboxylic acids having 4 to 12 carbon atoms, such as for example radicals of phthalic acid, isophthalic acid, naphthalene-2, 6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexanediacetic acid.
- radicals of phthalic acid isophthalic acid, naphthalene-2, 6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexanediacetic acid.
- the preferred polyalkylene terephthalates may contain, in addition to ethylene and/or butane- 1,4-diol glycol radicals, up to 80 mol% of other aliphatic diols having 3 to 12 carbon atoms or of cycloaliphatic diols having 6 to 21 carbon atoms, for example radicals of propane-1, 3-diol, 2-ethylpropane-l,3-diol, neopentyl glycol, pentane-1, 5-diol, hexane- 1,6-diol, cyclohexane- 1,4-dimethanol, 3-methylpentane- 2,4-diol, 2-methylpentane-2,4-diol, 2,2,4-trimethylpentane-l,3-diol and 2-ethylhexane- 1,6-diol, 2,2- diethylpropane-1, 3-diol, hex
- the polyalkylene terephthalates may be branched by incorporation of relatively small amounts of tri- or tetrahydric alcohols or tri- or tetrabasic carboxylic acids, as described for example in DE-OS 19 00 270 and US-PS 3 692 744.
- preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and trimethylolpropane and pentaerythritol.
- polymer (A) and/or polymer (B) are independently selected from the group consisting of a polycarbonate, a co-polycarbonate, a blend of polycarbonates, a blend of co-polycarbonates, polyamide, cyclo olefin copolymer (COC), a polyethylene or a mixture or blend of at least two thereof.
- polymer (A) is selected from the group consisting of a polycarbonate or poly-carbonate, a polyamide, a PET or a mixture or blend of at least two thereof, especially those as described above.
- polymer (B) is selected from the group consisting of a cyclo olefin copolymer (COC) and a polyamide, a polyethylene or a mixture thereof.
- COC cyclo olefin copolymer
- polymer (A) is selected from the group consisting of a polycarbonate or poly-carbonate, a polyamide, a PET or a mixture or blend of at least two thereof, especially those as described above and polymer (B) is selected from the group consisting of a cyclo olefin copolymer (COC) and a polyamide, a polyethylene or a mixture thereof.
- COC cyclo olefin copolymer
- layer A. comprises 80 to 100 wt.-%, based on the total weight of layer b. of a polymer (A) which is selected from the group consisting of a polycarbonate or poly-carbonate, a polyamide, a PET or a mixture or blend of at least two thereof, especially those as described above.
- a polymer (A) which is selected from the group consisting of a polycarbonate or poly-carbonate, a polyamide, a PET or a mixture or blend of at least two thereof, especially those as described above.
- layer B. comprises 80 to 100 wt.-%, based on the total weight of layer b. of a polymer (B) which is selected from the group consisting of a cyclo olefin copolymer (COC) and a polyamide, a polyethylene or a mixture thereof
- a polymer (B) which is selected from the group consisting of a cyclo olefin copolymer (COC) and a polyamide, a polyethylene or a mixture thereof
- layer A. comprises polymer (A) in an amount in a range of from 50 to 100 wt.-%; preferably in a range of from 70 to 99 wt.-%, more preferably in a range of from 80 to 97 wt.-%, most preferably in a range of from 90 to 95 wt.-%.
- Layer A. may comprise at least one further additive.
- the additive is preferably selected from the group consisting of pigments, dyes, surfactants, a UV absorber and a colorant or mixtures of at least two thereof.
- layer A is preferably selected from the group consisting of pigments, dyes, surfactants, a UV absorber and a colorant or mixtures of at least two thereof.
- layer B. comprises polymer (B) in an amount in a range of from 50 to 100 wt.-%, preferably in a range of from 70 to 99 wt.-%, more preferably in a range of from 80 to 97 wt.-%, most preferably in a range of from 90 to 95 wt.-%.
- Layer B. may comprise at least one further additive.
- the additive is preferably selected from the group consisting of pigments, dyes, surfactants, a UV absorber and a colorant or mixtures of at least two thereof.
- the first layer A comprises the polymer (A) or a polymer combination comprising polymer (A), wherein the polymer (A) or the polymer combination comprising polymer (A) provides a Tg in a range of from 100 to 180 °C, more preferably in a range of from 120 to 160 °C, most preferably of from 130 to 150 °C determined via differential scanning calorimetry (DSC) according to standard DIN EN 61006:2004 at a heating -rate of 20 K/min with definition of Tg as the midpoint temperature (tangent method.
- DSC differential scanning calorimetry
- the second layer B comprises the polymer (B) or a polymer combination comprising polymer (B), wherein the polymer (B) or the polymer combination comprising polymer (B) provides a Tg in a range of from 10 to 80 °C, more preferably in a range of from 20 to 60 °C, most preferably of from 30 to 50 °C, determined via differential scanning calorimetry (DSC) according to standard DIN EN 61006:2004 at a heating-rate of 20 K/min with definition of Tg as the midpoint temperature (tangent method).
- DSC differential scanning calorimetry
- the layered structure S. comprises a first layer A. and a second layer B.
- the first layer A. of the layered structure S. comprises at least one polymer (A) providing a Tg in a range of from 100 to 180 °C, more preferably in a range of from 120 to 160 °C, most preferably of from 130 to 150 °C, and the second layer B.
- Tg in a range of from 10 to 80 °C, more preferably in a range of from 20 to 60 °C, most preferably of from 30 to 50 °C, determined via differential scanning calorimetry (DSC) according to standard DIN EN 61006:2004 at a heating-rate of 20 K/min with definition of Tg as the midpoint temperature (tangent method)
- the first layer A. comprises at least one polymer (A) in an amount in a range of 80 to 100 wt.-%, wherein the at least one polymer (A) provides a Tg in a range of from 100 to 180 °C, more preferably in a range of from 120 to 160 °C, most preferably of from 130 to 150 °C, and the second layer B.
- the polymer (B) comprises the polymer (B) in an amount in a range of 80 to 100 wt.-%, wherein the polymer (B) provides a Tg in a range of from 10 to 80 °C, more preferably in a range of from 20 to 60 °C, most preferably of from 30 to 50 °C, determined via differential scanning calorimetry (DSC) according to standard DIN EN 61006:2004 at a heating-rate of 20 K/min with definition of Tg as the midpoint temperature (tangent method).
- DSC differential scanning calorimetry
- the layered structure S. further comprises at least one layer C., comprising a polymer (C).
- Polymer (C) can be any polymer the person skilled in the art would select for the establishment of layer C. in a layered structure S..
- the polymer (C) is different from the polymer (A) and/or polymer (B).
- polymer (C) is different from polymer (A) and polymer (B).
- polymer (C) is selected from the group consisting of a polycarbonate, a co-polycarbonate, a blend of polycarbonates, a blend of co-polycarbonates, polyamide, cyclo olefin copolymer (COC), a polyethylene or a mixture or blend of at least two thereof. Examples of preferred polycarbonates are mentioned above with respect to the polymer (A) which are also preferred for polymer (C).
- polymer (C) is a polyethylene.
- Layer C. may comprise at least one further additive.
- the additive is preferably selected from the group consisting of pigments, dyes, surfactants, deformers, plasticizers, a UV absorber and a colorant or mixtures of at least two thereof.
- layer C. comprises the additive or the additives in a total amount in a range of from 0.01 to 0.5 wt.-%, more preferably in an range of from 0.05 to 0.4 wt.-% , most preferably in an range of from 0.1 to 0.3 wt.-%, based on the total weight of layer C..
- the at least further layer B. is positioned between two layers A..
- at least one layer C. is positioned on top of each layer A..
- the at least one layer A. is positioned between at least one further layer B. and at least one layer C..
- the layered structure S. is assembled in a layer combination selected from the group consisting of : layer A. and layer B.; layer A., layer B., layer A; layer C., layer A. and layer B; layer C., layer A., layer B., layer A., layer C., layer A., layer B., layer A., layer C., layer A., layer B., layer A., layer C.
- a further aspect of the invention relates to a process for the manufacturing of a layered structure S., wherein the layered structure S. comprises at least one first layer A. having a thickness in a range of from 10 to 50 pm, preferably 10 to 30 pm, comprising at least the following steps
- P 1 providing a granulate A. comprising a polymer (A);
- P2. providing a granulate B. comprising a polymer (B);
- P5. combining the melts of at least melt (A) and melt (B) and optionally melt (C) to receive a co-extrudate of at least one layer A. from melt (A) with a thickness in a range of from 10 to 50 ⁇ m and a layer B. from melt (B) and optionally at least one layer C. from melt (C) to receive the layered structure S.; P6. cooling down the layered structure S. to a temperature in a range of from 20 to 40 °C; P7. optionally rolling up the layered structure S. onto a roll; P8.
- optionally post processing the layered structure S. whereby the post processing is preferably selected from the group consisting of printing onto at least one surface, forming, laser marking or a combination of at least two thereof; P9. optionally delaminating layers A., B. and optionally C. through an unwinding and rewinding process.
- Providing in step P1. of granulate A. comprising a polymer (A) can be established by any means the person skilled in the art would select for the process.
- Providing in step P2. of granulate B. comprising a polymer (B) can be established by any means the person skilled in the art would select for the process.
- step P1. or step P2. or step P3. are established by using an extruder.
- the heating of granulate A. and granulate B. and optionally granulate C. in step P4. to a temperature T which is at least 10 °C higher than the softening point or the glass transition temperature of the respective polymer (A), (B) and optionally (C) to receive the melts (A), (B) and optionally (C) could be established by any means selected by the person skilled in the art.
- the extruder includes means for heating.
- the melts of at least melt (A) and melt (B) and optionally melt (C) in step P5. to receive at least one layer A. from melt (A) with a thickness in a range of from 10 to 50 ⁇ m and a layer B. from melt (B) and optionally at least one layer C. from melt (C) to receive the layered structure S.
- the melts (A) and (B) and optionally (C) are combined in or in front of a slot die and a co-extrudate is received.
- the layered structure S. comprises a layer sequence selected from the group consisting of layer A. – B-; A. – B.
- Cooling down the layered structure S. in step P6. to a temperature in a range of from 20 to 40 °C could be established by any means the person skilled in the art would select for cooling layers.
- cooling is established by storing the layered structure S. at room temperature, preferably in a temperature range of 20 to 30 °C, more preferably in a range of 22 to 27 °C.
- a cooling medium like a cool fluid in form of cool air or cool water may be directed onto the layer.
- the cool fluid in form of air or water preferably has a temperature in a range of rom 1°C to 20°C.
- Rolling up the layered structure S. onto a roll in step P7. may be established by any means the person skilled in the art would select for rolling layers.
- the rolling up is established by a conventional roll winder.
- Post processing the layered structure S. in step P8. may be selected from any processing the person skilled in the art would select for a post processing of layers.
- the post processing is preferably selected from the group consisting of printing onto at least one surface, forming, laser marking or a combination of at least two thereof.
- Delaminating layers A., B. and optionally C. may optionally performed in step P9. through an unwinding and rewinding process. Delamination may be established by a process selected from any processing the person skilled in the art would select for a post processing of layers. If delamination is not performed by hand a conventional delamination machine could be used.
- the polymer (A), the polymer (B) and/or the polymer (C) are independently selected from the group consisting of a polycarbonate, a co-polycarbonate, a blend of polycarbonates, a blend of co-polycarbonates, polyamide, cyclo olefin copolymer (COC), polyethylene or a mixture or blend of at least two thereof.
- the polymer (C) is a polyethylene.
- the polymer (B) is a COC.
- polymer (A) is selected from the group consisting of a polycarbonate, a co-polycarbonate, a blend of polycarbonates, a blend of co-polycarbonates, polyamide, cyclo olefin copolymer (COC), or a mixture or blend of at least two thereof, but different from polymer (B) and preferably different from polymer (C).
- polymer (A) is a polycarbonate or a co polycarbonate.
- a further aspect of the invention relates to a foil with a thickness in a range of from 10 bis 100 pm, preferably in a range of from 20 to 80 pm produced by the process according to the invention.
- a further aspect of the invention relates to a use of the layered structure S. according to the invention or produced by a process according to the invention or a foil according to the invention as cover for surfaces.
- the use of the layered structure S. incorporates a method to use the layered structure S. or the foil as cover for surfaces.
- the surface could be any surface the person skilled in the art would choose to cover.
- the surface is preferably selected from the group consisting of a display, a screen, glasses, surfaces of the interior of an automotive.
- the cover is preferably a protective cover for the surface.
- Figure 1 a schematic illustration of a layered structure S. according to the invention with layer A. and layer B..
- Figure 2 a schematic illustration of a layered structure S. according to the invention with layer A. and layer B. and layer C..
- Figure 3 A schematic illustration of a process according to the invention
- the layered structure S. 50 comprises a first layer A. 10 comprising polymer (A) and a second layer B. 20 comprising polymer (B).
- Polymer (A) is a COC, preferably a TOPAS from Hoechst (now TOPAS Advanced Polymers), polymer (B) is Makrolon ® 3108 of Covestro AG.
- the thickness of layer A. is about 30 pm and the thickness of layer B. is about 100 pm.
- further layers may be positioned on the side of second layer B. opposite to the side where layer A. is positioned or on layer A. on the side of layer A. opposite to the side where layer B. is positioned.
- two layers of layer A. are positioned on both sides of layer B., which form a part of the layered structure S. in figure 2.
- FIG 2 a schematic illustration of a layered structure S. 50 according to the invention is shown comprising 5 layers, two first layers A. 10 comprising polymer (A), a second layer B. 20 comprising polymer (B) and two third layers C. 30 comprising polymer (C).
- the materials of layer A. and B. are the same as described for the layered structure S. 50 of figure 1.
- Polymer (C) is a polyethylene.
- further layers may be positioned on both sides of the layered structure S. 50.
- step PI. 100 providing of granulate A. comprising polymer (A) as described in figure 1 is established by pouring granulate A. into an extruder.
- step P2. providing of granulate B. comprising polymer (B) as described in figure 1 is established by pouring granulate B. into a second extruder.
- step P3. providing of granulate C. comprising polymer (C) as described in figure 1 is established by pouring the granulate C. into a third extruder.
- step P4. 400 heating of the granulates (A), (B) and optionally (C) is established inside the extruders.
- the extruder can be any commercially available extruders which are able to extrude polymers as mentioned for the layers A., B. and C..
- the extruder heats the respective granulates to a temperature T which is at least 80 °C, preferably at least 100 °C higher than the softening point or the glass transition temperature of the respective polymer (A), (B) and optionally (C) to receive the melts (A), (B) and optionally (C).
- T which is at least 80 °C, preferably at least 100 °C higher than the softening point or the glass transition temperature of the respective polymer (A), (B) and optionally (C) to receive the melts (A), (B) and optionally (C).
- step P5. 500 the melts of at least melt (A) and melt (B) and optionally melt (C) are combined to receive one or two layers A. from melt (A) with a thickness of about 10 to 30 pm on one or both sides of one layer B.
- the layered structure S. 50 is cooled in step P6. 600 at room temperature for several hours. This cooling process might be accelerated by providing cooling media like cool air or water with a temperature in a range of 1 to 20°C.
- the layered structure S. 50 is rolled up onto a roll by a winder in an optional step P7 700.
- the layered structure S. 50 might be post treated in step P8. 800.
- step P9. 900 the layered structure S. 50 is delaminated between layer A. and layer B. to receive one or two thin layer A..
- the production of the masterbatch for the production of layer A. of the co-extruded fdm was carried out with a conventional twin-screw compounding extruder (ZSK 32) at processing temperatures customary for polycarbonate of 250°C to 330°C.
- Master batch 1 100 wt.-% Makrolon ® 3108, or
- Master batch 2 100 wt.-% DurabioTM 7340, Mitsubishi Chemical Performance Polymers, Japan Masterbatch for layer B. :
- the production of the masterbatch for the production of layer B. of the co-extruded fdm was carried out with a conventional twin-screw compounding extruder (ZSK 32) at processing temperatures customary for COCs of 210°C to 240°C.
- Master batch 3 100 wt.-% TOPAS ® (Mitsui, Japan), or
- Master batch 7 Desmopan® 786E (polycarbonate type TPU) (Covestro Deutschland AG, Germany); or
- Master batch 8 TPU Desmopan® 3660D (Covestro Deutschland AG, Germany).
- the employed apparatus for producing the co-extruded fdm comprises: an extruder for melting polymer (A) and extrusion of melt (A) to form layer A. containing at least one polycarbonate with a screw of 60 mm in diameter (D) and a length of 33 D.
- the screw has a degassing zone; an extruder for extrusion melting polymer (B) and extrusion of melt (B) to form layer B.
- a melt pump ; a crosshead; a slot die of 450 mm in width; a three-roller smoothing calendar with horizontal roller orientation, wherein the third roller can swivel by +/- 45° relative to the horizontal; ⁇ a roller conveyor; thickness measuring means; means for double-sided application of protective fdm; a haul-off; a winding station.
- the granulate(s) of the masterbatch was/were conveyed from the dryer into the fdling hopper of the extruder.
- the material was melted and conveyed in the barrel/screw plasticizing system of the extruder.
- the melt passed from the slot die onto the smoothing calendar.
- the final shaping and cooling of the film was carried out on the smoothing calendar (consisting of three rollers).
- the surfaces were embossed using a textured steel roller (no. 6 side) and a textured silicone rubber roller (no. 2 side).
- the rubber roller used for texturing the film surface is disclosed in US-4 368 240 from Nauta Roll Corporation. The film was subsequently transported through a haul -off and then the film was wound up.
- inventive examples of layered structures S. are listed together with adhesion forces between different materials for layer A. and layer B..
- the cited materials are formed from the master batches as mentioned above.
- the layer A. could be delaminated from layer B. by hand without deforming one of the layers A. and B. and without any residues on the layers A. and B. of material of the respective other layer or polymer of that other layer.
- Table 1 Values of adhesion forces between different materials for layer A. and layer B. * measured by de lamination according to ASTM D903-1998 at a pulling angle of 180°
- Table 2 comparative examples of adhesion forces between different layered structures comprising two layers (layer A. and layer B.) are listed. The two layers A. and B. could not be delaminated from each other by hand. If higher forces are applied to delaminate the layers A. and B. the layers are destroyed or at least tears can be seen in at least one of the layers A. and/or B..
- Table 2 Values of adhesion forces between different materials for layer A. and layer B. of a comparative layered structure
Abstract
The invention relates to a layered structure S. comprising: A. at least one first layer A., with a first outer surface A1 and a second surface A2, comprising at least polymer (A), wherein the layer A. has a thickness in the region of 10 to 50 µm, preferably in the range of 10 to 30 µm, and B. at least one further layer B. comprising at least polymer (B), wherein the layer A. of layered structure S. provides at least one, preferably two, more preferably all of the following properties: S1. an adhesion force between the at least one first layer A. and the at least one further layer B. in a range of from 0.001 to 0.05 N/cm, measured according to ASTM D903-1998 at a pulling angle of 180°; S2. a hardness of ≥ 85 D, preferably of ≥ 87 D, more preferably of ≥ 90 D, according to DIN EN ISO 868-2003-10;S3. a melting temperature ≥ 200°C; preferably in a range of from 210 to 350 °C, more preferably in a range of from 230 to 330 °C; most preferably in a range of from 250 to 320 °C, determined via differential scanning calorimetry (DSC) according to standard DIN EN 61006:2004 at a heating-rate of 20 K/min with definition of Tg as the midpoint temperature (tangent method); S4. a glass-transition temperature Tg of ≥ 70°C; preferably in a range of from 80 to 250 °C, more preferably in a range of from 80 to 240 °C; most preferably in a range of from 80 to 200 °C, determined via differential scanning calorimetry (DSC) according to standard DIN EN 61006:2004 at a heating-rate of 20 K/min with definition of Tg as the midpoint temperature (tangent method S5. Melt volume rate (MVR; measured according to DIN ISO1133-1-2012-03; 300°C, 2.16 kg) of ≥ 3 cm³/10 min, more preferably of ≥ 3.5 cm³/10 min, even more preferably of ≥ 4 cm³/10 min; S6. additives in a range of from 0.01 to 0.5 wt.-%,.
Description
Ultrathin layered structure with specific properties
The invention is related to a layered structure S. comprising at least two layers, at least one layer A. and at least one layer B. and a process for its production as well as the use as coating for interior and exterior applications.
The production of very thin layers has limits because a lot of parameters have to be controlled during production, transportation and use of the thin layer. So far it is not easy to produce thin fdms with continuous good quality in a broad manner for various applications.
Therefore, it exists a need to develop a layered structure that incorporates at least one thin layer which can easily be separated to provide a thin fdm. Further, it exists a need to develop a layered structure that incorporates at least one thin layer with a high quality standard especially with respect to a constant thickness which can be used for different applications like interior as well as exterior applications.
A solution for such a layered structure is described in claim 1 and its dependent claims in correlation to a layered structure S..
A first aspect of the invention refers to a layered structure S., comprising:
A. at least one first layer A., with a first outer surface A1 and a second surface A2, comprising at least polymer (A), wherein the first layer A. has a thickness in the region of 10 to 50 pm, preferably in the range of 10 to 30 pm, and
B. at least one further layer B. comprising at least polymer (B), wherein layer A. of the layered structure S. provides at least one, preferably two, more preferably three, most preferably all of the following properties:
51. an adhesion force between the at least one first layer A. and the at least one further layer B. in a range of from 0.001 to 0.05 N/cm, preferably in a range of from 0.005 to 0.04 N/cm, more preferably in a range of from 0.01 to 0.02 N/cm, measured according to ASTM D903- 1998 at a pulling angle of 180°;
52. a hardness of > 85 D, preferably of > 87 D, more preferably of > 90 D, according to DIN EN ISO 868-2003-10;
53. a melting temperature > 200°C; preferably in a range of from 210 to 350 °C, more preferably in a range of from 230 to 330 °C; most preferably in a range of from 250 to 320 °C, determined via differential scanning calorimetry (DSC) according to standard DIN EN 61006:2004 at a heating -rate of 20 K/min with definition of Tg as the midpoint temperature (tangent method);
54. a glass-transition temperature Tg of > 70°C; preferably in a range of from 80 to 250 °C, more preferably in a range of from 80 to 240 °C; most preferably in a range of from 80 to 200 °C,
determined via differential scanning calorimetry (DSC) according to standard DIN EN 61006:2004 at a heating -rate of 20 K/min with definition of Tg as the midpoint temperature (tangent method) or a vicat softening temperature B/50 determined according to ISO 306-2014-03 (50N; 50°/h) of > 70°C; preferably in a range of from 75 to 230 °C, more preferably in a range of from 80 to 230 °C; most preferably in a range of from 85 to 225 °C;
55. Melt volume rate (MVR; measured according to DIN ISOl 133-1-2012-03; 300°C, 2.16 kg) of > 3 cm3/ 10 min, more preferably of > 3.5 cm3/ 10 min, even more preferably of > 4 cm3/ 10 min;
56. additives in a range of from 0.01 to 0.5 wt.-%, preferably in a range of from 0.02 to 0.3 wt- %, more preferably in a range of from 0.05 to 0.1 wt.-%.
Preferably, the layered structure S. provides one property or one property combination selected from the group consisting of SI.; S2.; S3.; S4.; S5.; S6.; SI. and S2.; SI. and S3.; SI. and S4.; SI. and S5.; SI. and S6.; S2. and S3.; S2. and S4.; S2. and S5.; S2. and S6.; S3, and S4.; S3, and S5.; S3, and S6.; S4. and S5.; S4. and S6.; S5. and S6.; SI. and S2. and S3.; SI. and S2. and S4.; SI. and S2. and S5.; SI. and S2. and S6.; SI. and S3, and S4.; SI. and S3, and S5.; SI. and S3, and S6.; SI. and S4. and S5.; SI. and
S4. and S6.; SI. and S5. and S6.; S2. and S3, and S4.; S2. and S3, and S5.; S2. and S3, and S6.; S2. and
54. and S5.; S2. and S4. and S6.; S2. and S5. and S6.; S3, and S4. and S5.; S3, and S4. and S6.; S3, and
55. and S6.; S4. and S5. and S6.; SI. and S2. and S3, and S4.; SI. and S2. and S3, and S5.; SI. and S2. and S3, and S6.; SI. and S2. and S4. and S5.; SI. and S2. and S4. and S6.; SI. and S2. and S5. and S6.; SI. and S3, and S4. and S5.; SI. and S3, and S4. and S6.; SI. and S3, and S5. and S6.; SI. and S4. and
55. and S6.; S2. and S3, and S4. and S5.; S2. and S3, and S4. and S6.; S2. and S3, and S5. and S6.; SI. and S2. and S3, and S4. and S5.; SI. and S2. and S3, and S4. and S6.; SI. and S2. and S3, and S5. and
56.; SI. and S2. and S4. and S5. and S6.; SI. and S3, and S4. and S5. and S6.; S2. and S3, and S4. and S5. and S6.; SI. and S2. and S3, and S4. and S5. and S6..
It is preferred that the adhesion force between the at least one first layer A. and the at least one further layer B. is in a range of from 0.001 to 0.05 N/cm, preferably in a range of from 0.005 to 0.04 N/cm, more preferably in a range of from 0.01 to 0.02 N/cm, measured according to ASTM D903-1998 at a pulling angle of 180°.
In a preferred embodiment of the layered structure S. the layered structure S., preferably layer A. provides at least one, preferably two, more preferably all of the following properties:
57. a thickness in a range of from 15 to 250 pm, preferable in a range of from 20 to 200 pm, and most preferably in a range of from 30 to 100 pm;
58. a deviation of the thickness across an area of 20 * 20 cm, preferably of 50 * 50 cm, more preferably of 100* 100 cm in a range of from 0.01 to 5 pm, preferably of from
0.02 to 2 µm, more preferably of from 0.03 to 1 µm, most preferably of from 0.05 to 0.5 µm; S9. a tensile strength in a range of from 10 to 150 MPa, preferably of from 20 to 100 MPa, measured according to DIN EN ISO 527-1:2012-06; S10. an elongation at break in a range of from 20 bis 500 %, preferably of from 50 to 400 %, measured according to DIN N ISO 527-1:2012-06; S11. water absorption (ISO 62:2008);) at 23°C for 24 h) in a range of from 0.01 to 0.5 wt.- %, more preferably) in a range of from 0.05 to 0.4 wt.-% (saturation value). Preferably, the layered structure S. provides one property or one property combination selected from the group consisting of S7.; S8.; S9.; S10.; S11.; S7. and S8.; S7. and S9.; S7. and S10.; S7. and S11.; S8. and S9.; S8. and S10.; S8. and S11.; S9. and S10.; S9. and S11.; S10. and S11.; S7. and S8. and S9.; S7. and S8. and S10.; S7. and S8. and S11.; S7. and S9. and S10.; S7. and S9. and S11.; S8. and S9. and S10.; S8. and S9. and S11.; S8. and S10. and S11.; S9. and S10. and S11.; S7. and S8. and S9. and S10.; S7. and S8. and S9. and S11.; S7. and S8. and S10. and S11.; S7. and S9. and S10. and S11.; S8. and S9. and S10. and S11.; S7. and S8. and S9. and S10. and S11.. Preferably, the layered structure S. provides in addition to any of properties S1. to S6 and their mentioned combinations any combination of properties listed for S7. to S11. above. Preferably, the adhesion is selected in a range where the two layers A. and B. could be separated easily by manual force but do not fall apart on their own without input of any force. The adhesion between the layers A. and B. allow a transportation of the layered structure S. without the risk of cracks in the thin layer A., but make it easy to provide layer A. for further processing by just separating layer B. by hand or a machine using small forces. The separation of layer A. from layer B. is preferably provided without any detectable residues of polymer (B) on layer A. Preferably, the adjustment of the adhesion between layer A. and layer B. is not supported by any additives in layer A. or layer B.. As the layered structure S. may be used in specific applications where no additives are desired, the content of additives like plasticizers, deformers, pigments and any other organic or inorganic components are preferably low. According to the invention additive means molecules which have a molecular mass of ≤ 1000 g/mol, more preferably of ≤ 500 g/mol, even more preferably of ≤ 300 g/mol. In a preferred embodiment of the layered structure S. layer A. provides at least one, preferably at least two, more preferably all of the following properties: a1. a gloss at 60° angle in a range of 10 to 110, measured according to DIN EN ISO 2813-2015-02;
a2. a surface roughness of at least the first surface A1 in a range of 0.1 to 5.50 µm, measured according to DIN EN ISO 4287:2010-07/DIN EN ISO 4288:1998-04; a3. a birefringence in a range of from 1 to 100 nm, measured by a polarization microscope; a4. a transparency in a range of from 5 to 95 %, measured according to ASTM D1003-13; a5. a density in a range of from 1 to 1.35 g/l, measured according to DIN EN ISO 1183-1:2019-09; a6. a tensile strength in a range of from 10 to 150 MPa, preferably of from 20 to 100 MPa, measured according to DIN EN ISO 527-1:2012-06; a7. an elongation at break in a range of from 20 bis 500 %, preferably of from 50 to 400 %, measured according to DIN N ISO 527-1:2012-06;; a8. a thickness in a range of from 5 to 50 µm, preferable in a range of from 10 to 25 µm, and most preferably in a range of from 10 to 20 µm; a9. a deviation of the thickness in a range of from 0.001 to 0.1 µm, preferably of from 0.002 to 0.05 µm, more preferably of from 0.003 to 0.03 µm, most preferably of from 0.005 to 0.01 µm. Preferably, the first layer A. of the layered structure S. provides a property or a property combination selected from the group consisting of a1.; a2.; a3.; a4.; a5.; a6.; a7.; a8.; a9.; a1. and a2.; a1. and a3.; a1. and a4.; a1. and a5.; a1. and a6.; a1. and a7.; a1. and a8.; a1. and a9.; a2. and a3.; a2. and a4.; a2. and a5.; a2. and a6.; a2. and a7.; a2. and a8.; a2. and a9.; a3. and a4.; a3. and a5.; a3. and a6.; a3. and a7.; a3. and a8.; a3. and a9.; a4. and a5.; a4. and a6.; a4. and a7.; a4. and a8.; a4. and a9.; a5. and a6.; a5. and a7.; a5. and a8.; a5. and a9.; a6. and a7.; a6. and a8.; a6. and a9.; a7. and a8.; a7. and a9.; a8. and a9.; a1. and a2. and a3.; a1. and a2. and a4.; a1. and a2. and a5.; a1. and a2. and a6.; a1. and a2. and a7.; a1. and a2. and a8.; a1. and a2. and a9.; a1. and a3. and a4.; a1. and a3. and a5.; a1. and a3. and a6.; a1. and a3. and a7.; a1. and a3. and a8.; a1. and a3. and a9.; a1. and a4. and a5.; a1. and a4. and a6.; a1. and a4. and a7.; a1. and a4. and a8.; a1. and a4. and a9.; a1. and a5. and a6.; a1. and a5. and a7.; a1. and a5. and a8.; a1. and a5. and a9.; a1. and a6. and a7.; a1. and a6. and a8.; a1. and a6. and a9.; a1. and a7. and a8.; a1. and a7. and a9.; a1. and a8. and a9.; a2. and a3. and a4.; a2. and a3. and a5.; a2. and a3. and a6.; a2. and a3. and a7.; a2. and a3. and a8.; a2. and a3. and a9.; a2. and a4. and a5.; a2. and a4. and a6.; a2. and a4. and a7.; a2. and a4. and a8.; a2. and a4. and a9.; a2. and a5. and a6.; a2. and a5. and a7.; a2. and a5. and a8.; a2. and a5. and a9.; a2. and a6. and a7.; a2. and a6. and a8.; a2. and a6. and a9.; a2. and a7. and a8.; a2. and a7. and a9.; a2. and a8. and a9.; a3. and a4. and a5.; a3. and a4. and a6.; a3. and a4. and a7.; a3. and a4. and a8.; a3. and a4. and a9.; a3. and a5. and a6.; a3. and a5. and a7.; a3. and a5. and a8.; a3. and a5. and a9.; a3. and a6. and a7.; a3. and a6. and a8.; a3. and a6. and a9.; a3. and a7. and a8.; a3. and a7. and a9.; a3. and a8. and a9.; a4. and a5. and a6.; a4. and a5. and a7.; a4. and a5. and a8.; a4. and a5. and a9.; a4. and a6. and a7.; a4. and a6. and a8.; a4. and a6. and a9.; a4. and a7. and a8.; a4. and a7. and a9.; a4. and a8. and a9.; a5. and a6. and a7.; a5. and a6. and a8.; a5. and a6. and a9.; a5. and a7. and a8.; a5. and a7. and a9.; a5. and a8. and a9.; a6. and a7. and a8.; a6. and a7. and a9.; a6. and a8. and a9.; a7. and a8. and a9.; a1. and a2. and a3. and a4.; a1. and a2. and a3. and a5.; a1. and a2. and a3. and a6.; a1.
and a2. and a3. and a7.; al. and a2. and a3. and a8.; al. and a2. and a3. and a9.; al. and a2. and a4. and a5.; al. and a2. and a4. and a6.; al. and a2. and a4. and a7.; al. and a2. and a4. and a8.; al. and a2. and a4. and a9.; al. and a2. and a5. and a6.; al. and a2. and a5. and a7.; al. and a2. and a5. and a8.; al. and a2. and a5. and a9.; al. and a2. and a6. and a7.; al. and a2. and a6. and a8.; al. and a2. and a6. and a9.; al. and a2. and a7. and a8.; al. and a2. and a7. and a9.; al. and a2. and a8. and a9.; al. and a3. and a4. and a5.; al. and a3. and a4. and a6.; al. and a3. and a4. and a7.; al. and a3. and a4. and a8.; al. and a3. and a4. and a9.; al. and a3. and a5. and a6.; al. and a3. and a5. and a7.; al. and a3. and a5. and a8.; al. and a3. and a5. and a9.; al. and a3. and a6. and a7.; al. and a3. and a6. and a8.; al. and a3. and a6. and a9.; al. and a3. and a7. and a8.; al. and a3. and a7. and a9.; al. and a3. and a8. and a9.; al. and a4. and a5. and a6.; al. and a4. and a5. and a7.; al. and a4. and a5. and a8.; al. and a4. and a5. and a9.; al. and a4. and a6. and a7.; al. and a4. and a6. and a8.; al. and a4. and a6. and a9.; al. and a4. and a7. and a8.; al. and a4. and a7. and a9.; al. and a4. and a8. and a9.; al. and a5. and a6. and a7.; al. and a5. and a6. and a8.; al. and a5. and a6. and a9.; al. and a5. and a7. and a8.; al. and a5. and a7. and a9.; al. and a5. and a8. and a9.; al. and a6. and a7. and a8.; al. and a6. and a7. and a9.; al. and a6. and a8. and a9.; al. and a7. and a8. and a9.; a2. and a3. and a4. and a5.; a2. and a3. and a4. and a6.; a2. and a3. and a4. and a7.; a2. and a3. and a4. and a8.; a2. and a3. and a4. and a9.; a2. and a3. and a5. and a6.; a2. and a3. and a5. and a7.; a2. and a3. and a5. and a8.; a2. and a3. and a5. and a9.; a2. and a3. and a6. and a7.; a2. and a3. and a6. and a8.; a2. and a3. and a6. and a9.; a2. and a3. and a7. and a8.; a2. and a3. and a7. and a9.; a2. and a3. and a8. and a9.; a2. and a4. and a5. and a6.; a2. and a4. and a5. and a7.; a2. and a4. and a5. and a8.; a2. and a4. and a5. and a9.; a2. and a4. and a6. and a7.; a2. and a4. and a6. and a8.; a2. and a4. and a6. and a9.; a2. and a4. and a7. and a8.; a2. and a4. and a7. and a9.; a2. and a4. and a8. and a9.; a2. and a5. and a6. and a7.; a2. and a5. and a6. and a8.; a2. and a5. and a6. and a9.; a2. and a5. and a7. and a8.; a2. and a5. and a7. and a9.; a2. and a5. and a8. and a9.; a2. and a6. and a7. and a8.; a2. and a6. and a7. and a9.; a2. and a6. and a8. and a9.; a2. and a7. and a8. and a9.; a3. and a4. and a5. and a6.; a3. and a4. and a5. and a7.; a3. and a4. and a5. and a8.; a3. and a4. and a5. and a9.; a3. and a4. and a6. and a7.; a3. and a4. and a6. and a8.; a3. and a4. and a6. and a9.; a3. and a4. and a7. and a8.; a3. and a4. and a7. and a9.; a3. and a4. and a8. and a9.; a3. and a5. and a6. and a7.; a3. and a5. and a6. and a8.; a3. and a5. and a6. and a9.; a3. and a5. and a7. and a8.; a3. and a5. and a7. and a9.; a3. and a5. and a8. and a9.; a3. and a6. and a7. and a8.; a3. and a6. and a7. and a9.; a3. and a6. and a8. and a9.; a3. and a7. and a8. and a9.; a4. and a5. and a6. and a7.; a4. and a5. and a6. and a8.; a4. and a5. and a6. and a9.; a4. and a5. and a7. and a8.; a4. and a5. and a7. and a9.; a4. and a5. and a8. and a9.; a5. and a6. and a7. and a8.; a5. and a6. and a7. and a9.; a5. and a6. and a8. and a9.; a6. and a7. and a8. and a9.; al. and a2. and a3. and a4. and a5.; al. and a2. and a3. and a4. and a6.; al. and a2. and a3. and a4. and a7.; al. and a2. and a3. and a4. and a8.; al. and a2. and a3. and a4. and a9.; al. and a2. and a4. and a5. and a6.; al. and a2. and a4. and a5. and a7.; al. and a2. and a4. and a5. and a8.; al. and a2. and a4. and a5. and a9.; al. and a2. and a4. and a6. and a7.; al. and a2. and a4. and a6. and a8.; al. and a2. and a4. and a6. and a9.; al. and a2. and a4. and a7. and a8.; al. and a2. and a4. and a7. and a9.; al. and a2. and a4. and a8. and a9.; al. and
a2. and a5. and a6. and a7.; al. and a2. and a5. and a6. and a8.; al. and a2. and a5. and a6. and a9.; al. and a2. and a5. and a7. and a8.; al. and a2. and a5. and a7. and a9.; al. and a2. and a5. and a8. and a9.; al. and a2. and a6. and a7. and a8.; al. and a2. and a6. and a7. and a9.; al. and a2. and a6. and a8. and a9.; al. and a2. and a7. and a8. and a9.; al. and a3. and a4. and a5. and a6.; al. and a3. and a4. and a5. and a7.; al. and a3. and a4. and a5. and a8.; al. and a3. and a4. and a5. and a9.; al. and a3. and a4. and a6. and a7.; al. and a3. and a4. and a6. and a8.; al. and a3. and a4. and a6. and a9.; al. and a3. and a4. and a7. and a8.; al. and a3. and a4. and a7. and a9.; al. and a3. and a4. and a8. and a9.; al. and a3. and a5. and a6. and a7.; al. and a3. and a5. and a6. and a8.; al. and a3. and a5. and a6. and a9.; al. and a3. and a5. and a7. and a8.; al. and a3. and a5. and a7. and a9.; al. and a3. and a5. and a8. and a9.; al. and a3. and a6. and a7. and a8.; al. and a3. and a6. and a7. and a9.; al. and a3. and a6. and a8. and a9.; al. and a3. and a7. and a8. and a9.; al. and a4. and a5. and a6. and a7.; al. and a4. and a5. and a6. and a8.; al. and a4. and a5. and a6. and a9.; al. and a4. and a5. and a7. and a8.; al. and a4. and a5. and a7. and a9.; al. and a4. and a5. and a8. and a9.; al. and a4. and a6. and a7. and a8.; al. and a4. and a6. and a7. and a9.; al. and a4. and a6. and a8. and a9.; al. and a4. and a7. and a8. and a9.; al. and a5. and a6. and a7. and a8.; al. and a5. and a6. and a7. and a9.; al. and a5. and a6. and a8. and a9.; al. and a5. and a7. and a8. and a9.; al. and a6. and a7. and a8. and a9.; a2. and a3. and a4. and a5. and a6.; a2. and a3. and a4. and a5. and a7.; a2. and a3. and a4. and a5. and a8.; a2. and a3. and a4. and a5. and a9.; a2. and a3. and a4. and a6. and a7.; a2. and a3. and a4. and a6. and a8.; a2. and a3. and a4. and a6. and a9.; a2. and a3. and a4. and a7. and a8.; a2. and a3. and a4. and a7. and a9.; a2. and a3. and a4. and a8. and a9.; a2. and a3. and a5. and a6. and a7.; a2. and a3. and a5. and a6. and a8.; a2. and a3. and a5. and a6. and a9.; a2. and a3. and a5. and a7. and a8.; a2. and a3. and a5. and a7. and a9.; a2. and a3. and a5. and a8. and a9.; a2. and a3. and a6. and a7. and a8.; a2. and a3. and a6. and a7. and a9.; a2. and a3. and a6. and a8. and a9.; a2. and a3. and a7. and a8. and a9.; a2. and a4. and a5. and a6. and a7.; a2. and a4. and a5. and a6. and a8.; a2. and a4. and a5. and a6. and a9.; a2. and a4. and a5. and a7. and a8.; a2. and a4. and a5. and a7. and a9.; a2. and a4. and a5. and a8. and a9.; a2. and a4. and a6. and a7. and a8.; a2. and a4. and a6. and a7. and a9.; a2. and a4. and a6. and a8. and a9.; a2. and a4. and a7. and a8. and a9.; a2. and a5. and a6. and a7. and a8.; a2. and a5. and a6. and a7. and a9.; a2. and a5. and a6. and a8. and a9.; a2. and a5. and a7. and a8. and a9.; a2. and a6. and a7. and a8. and a9.; a3. and a4. and a5. and a6. and a7.; a3. and a4. and a5. and a6. and a8.; a3. and a4. and a5. and a6. and a9.; a3. and a4. and a5. and a7. and a8.; a3. and a4. and a5. and a7. and a9.; a3. and a4. and a5. and a8. and a9.; a3. and a4. and a6. and a7. and a8.; a3. and a4. and a6. and a7. and a9.; a3. and a4. and a6. and a8. and a9.; a3. and a4. and a7. and a8. and a9.; a3. and a5. and a6. and a7. and a8.; a3. and a5. and a6. and a7. and a9.; a3. and a5. and a6. and a8. and a9.; a3. and a5. and a7. and a8. and a9.; a3. and a6. and a7. and a8. and a9.; a4. and a5. and a6. and a7. and a8.; a4. and a5. and a6. and a7. and a9.; a4. and a5. and a6. and a8. and a9.; a4. and a5. and a7. and a8. and a9.; a4. and a6. and a7. and a8. and a9.; a5. and a6. and a7. and a8. and a9.; al. and a2. and a3. and a4. and a5. and a6.; al. and a2. and a3. and a4. and a5. and a7.; al. and a2. and a3. and a4. and a5. and a8.; al. and a2. and a3. and a4. and a5. and a9.; al. and a2. and a3. and a4. and a6. and a7.;
a1. and a2. and a3. and a4. and a6. and a8.; a1. and a2. and a3. and a4. and a6. and a9.; a1. and a2. and a3. and a4. and a7. and a8.; a1. and a2. and a3. and a4. and a7. and a9.; a1. and a2. and a3. and a4. and a8. and a9.; a1. and a2. and a3. and a5. and a6. and a7.; a1. and a2. and a3. and a5. and a6. and a8.; a1. and a2. and a3. and a5. and a6. and a9.; a1. and a2. and a3. and a5. and a7. and a8.; a1. and a2. and a3. and a5. and a7. and a9.; a1. and a2. and a3. and a5. and a8. and a9.; a1. and a2. and a3. and a6. and a7. and a8.; a1. and a2. and a3. and a6. and a7. and a9.; a1. and a2. and a3. and a6. and a8. and a9.; a1. and a2. and a3. and a7. and a8. and a9.; a1. and a2. and a4. and a5. and a6. and a7.; a1. and a2. and a4. and a5. and a6. and a8.; a1. and a2. and a4. and a5. and a6. and a9.; a1. and a2. and a4. and a5. and a7. and a8.; a1. and a2. and a4. and a5. and a7. and a9.; a1. and a2. and a4. and a5. and a8. and a9.; a1. and a2. and a4. and a6. and a7. and a8.; a1. and a2. and a4. and a6. and a7. and a9.; a1. and a2. and a4. and a6. and a8. and a9.; a1. and a2. and a4. and a7. and a8. and a9.; a1. and a2. and a5. and a6. and a7. and a8.; a1. and a2. and a5. and a6. and a7. and a9.; a1. and a2. and a5. and a6. and a8. and a9.; a1. and a2. and a5. and a7. and a8. and a9.; a1. and a2. and a6. and a7. and a8. and a9.; a1. and a3. and a4. and a5. and a6. and a7.; a1. and a3. and a4. and a5. and a6. and a8.; a1. and a3. and a4. and a5. and a6. and a9.; a1. and a3. and a4. and a5. and a7. and a8.; a1. and a3. and a4. and a5. and a7. and a9.; a1. and a3. and a4. and a5. and a8. and a9.; a1. and a3. and a4. and a6. and a7. and a8.; a1. and a3. and a4. and a6. and a7. and a9.; a1. and a3. and a4. and a6. and a8. and a9.; a1. and a3. and a4. and a7. and a8. and a9.; a1. and a3. and a5. and a6. and a7. and a8.; a1. and a3. and a5. and a6. and a7. and a9.; a1. and a3. and a5. and a6. and a8. and a9.; a1. and a3. and a5. and a7. and a8. and a9.; a1. and a3. and a6. and a7. and a8. and a9.; a1. and a4. and a5. and a6. and a7. and a8.; a1. and a4. and a5. and a6. and a7. and a9.; a1. and a4. and a5. and a6. and a8. and a9.; a1. and a4. and a5. and a7. and a8. and a9.; a1. and a4. and a6. and a7. and a8. and a9.; a1. and a5. and a6. and a7. and a8. and a9.; a2. and a3. and a4. and a5. and a6. and a7.; a2. and a3. and a4. and a5. and a6. and a8.; a2. and a3. and a4. and a5. and a6. and a9.; a2. and a3. and a4. and a5. and a7. and a8.; a2. and a3. and a4. and a5. and a7. and a9.; a2. and a3. and a4. and a5. and a8. and a9.; a2. and a3. and a4. and a6. and a7. and a8.; a2. and a3. and a4. and a6. and a7. and a9.; a2. and a3. and a4. and a6. and a8. and a9.; a2. and a3. and a4. and a7. and a8. and a9.; a2. and a3. and a5. and a6. and a7. and a8.; a2. and a3. and a5. and a6. and a7. and a9.; a2. and a3. and a5. and a6. and a8. and a9.; a2. and a3. and a5. and a7. and a8. and a9.; a2. and a3. and a6. and a7. and a8. and a9.; a2. and a4. and a5. and a6. and a7. and a8.; a2. and a4. and a5. and a6. and a7. and a9.; a2. and a4. and a5. and a6. and a8. and a9.; a2. and a4. and a5. and a7. and a8. and a9.; a2. and a4. and a6. and a7. and a8. and a9.; a2. and a5. and a6. and a7. and a8. and a9.; a3. and a4. and a5. and a6. and a7. and a8.; a3. and a4. and a5. and a6. and a7. and a9.; a3. and a4. and a5. and a6. and a8. and a9.; a3. and a4. and a5. and a7. and a8. and a9.; a3. and a4. and a6. and a7. and a8. and a9.; a3. and a5. and a6. and a7. and a8. and a9.; a4. and a5. and a6. and a7. and a8. and a9.; a1. and a2. and a3. and a4. and a5. and a6. and a7.; a1. and a2. and a3. and a4. and a5. and a6. and a8.; a1. and a2. and a3. and a4. and a5. and a6. and a9.; a1. and a2. and a3. and a4. and a5. and a7. and a8.; a1. and a2. and a3. and a4. and a5. and a7. and a9.; a1. and a2. and a3. and a4. and a5. and a8. and a9.; a1. and a2. and a3. and a4. and a6. and a7. and a8.; a1. and
a2. and a3. and a4. and a6. and a7. and a9.; al. and a2. and a3. and a4. and a6. and a8. and a9.; al. and a2. and a3. and a4. and a7. and a8. and a9.; al. and a2. and a3. and a5. and a6. and a7. and a8.; al. and a2. and a3. and a5. and a6. and a7. and a9.; al. and a2. and a3. and a5. and a6. and a8. and a9.; al. and a2. and a3. and a5. and a7. and a8. and a9.; al. and a2. and a3. and a6. and a7. and a8. and a9.; al. and a2. and a4. and a5. and a6. and a7. and a8.; al. and a2. and a4. and a5. and a6. and a7. and a9.; al. and a2. and a4. and a5. and a6. and a8. and a9.; al. and a2. and a4. and a5. and a7. and a8. and a9.; al. and a2. and a4. and a6. and a7. and a8. and a9.; al. and a2. and a5. and a6. and a7. and a8. and a9.; al. and a3. and a4. and a5. and a6. and a7. and a8.; al. and a3. and a4. and a5. and a6. and a7. and a9.; al. and a3. and a4. and a5. and a6. and a8. and a9.; al. and a3. and a4. and a5. and a7. and a8. and a9.; al. and a3. and a4. and a6. and a7. and a8. and a9.; al. and a3. and a5. and a6. and a7. and a8. and a9.; al. and a4. and a5. and a6. and a7. and a8. and a9.; a2. and a3. and a4. and a5. and a6. and a7. and a8.; a2. and a3. and a4. and a5. and a6. and a7. and a9.; a2. and a3. and a4. and a5. and a6. and a8. and a9.; a2. and a3. and a4. and a5. and a7. and a8. and a9.; a2. and a3. and a4. and a6. and a7. and a8. and a9.; a2. and a3. and a5. and a6. and a7. and a8. and a9.; a2. and a4. and a5. and a6. and a7. and a8. and a9.; a3. and a4. and a5. and a6. and a7. and a8. and a9.; al. and a2. and a3. and a4. and a5. and a6. and a7. and a8.; al. and a2. and a3. and a4. and a5. and a6. and a7. and a9.; al. and a2. and a3. and a4. and a5. and a6. and a8. and a9.; al. and a2. and a3. and a4. and a5. and a7. and a8. and a9.; al. and a2. and a3. and a4. and a6. and a7. and a8. and a9.; al. and a2. and a3. and a5. and a6. and a7. and a8. and a9.; al. and a2. and a4. and a5. and a6. and a7. and a8. and a9.; al. and a3. and a4. and a5. and a6. and a7. and a8. and a9.; a2. and a3. and a4. and a5. and a6. and a7. and a8. and a9.; al. and a2. and a3. and a4. and a5. and a6. and a7. and a8. and a9..
Preferably layer A. differs from layer B. in at least one, preferably in at least two and even more preferably in all of the following properties:
Prl. a difference of the thickness in a range of from 0.01 to 50 pm, preferably of from 0.02 to 30 pm, more preferably of from 0.03 to 10 pm, most preferably of from 0.05 to 1 pm;
Pr2. a difference of tensile strength in a range of from 50 to 500 kPa, preferably of from 60 to 400 kPa, measured according to DIN EN ISO 527-1:2012-06;
Pr3. a difference of elongation at break in a range of from 10 bis 100 %, preferably of from 20 to 80 %, measured according to DIN N ISO 527-1:2012-06;
Pr4. a difference of refractive index n of < 0.5, preferably < 0.3, more preferably < 0.1;
Pr5. a difference of birefringence of < 10 nm, preferably < 5, more preferably < 2.
Polymer (A) can be any polymer the person skilled in the art would select for the establishment of layer A. in a layered structure S.. Preferably, the polymer (A) provides a Tg in a range of from 100 to 180 °C, more preferably in a range of from 120 to 160 °C, most preferably of from 130 to 150 °C, determined
via differential scanning calorimetry (DSC) according to standard DIN EN 61006:2004 at a heating-rate of 20 K/min with definition of Tg as the midpoint temperature (tangent method).
Polymer (B) can be any polymer the person skilled in the art would select for the establishment of layer B. in a layered structure S.. Preferably, the polymer (B) provides a Tg in a range of from 10 to 80 °C, more preferably in a range of from 20 to 60 °C, most preferably of from 30 to 50 °C, determined via differential scanning calorimetry (DSC) according to standard DIN EN 61006:2004 at a heating-rate of 20 K/min with definition of Tg as the midpoint temperature (tangent method).
Particularly suitable polymers (A) or (B) are one or more polycarbonate(s) or copolycarbonate (s) based on diphenols, poly- or copolyacrylate(s) and poly- or copolymethacrylate(s) such as, by way of example and preferably, polymethylmethacrylate or poly(meth)acrylate (PMMA), polymer(s) or copolymer(s) with styrene such as, by way of example and preferably, polystyrene (PS), acrylonitrile-butadiene- styrene (ABS), or polystyrene-acrylonitrile (SAN), thermoplastic polyurethane(s) and also polyolefin(s) such as, by way of example and preferably, polypropylene types or polyolefins based on cyclic olefins (COC) e.g. TOPAS® of Hoechst (now TOPAS Advanced Polymers), poly- or copolycondensate(s) of terephthalic acid such as, by way of example and 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), polyamide (PA), poly- or copolycondensate(s) of naphthalenedicarboxylic acid such as, by way of example and preferably, polyethylene glycol naphthalate (PEN), poly- or copolycondensate(s) of at least one cycloalkyldicarboxylic acid such as, by way of example and preferably, polycyclohexanedimethanolcyclohexanedicarboxylic acid (PCCD), polysulfones (PSU), mixtures of at least two of the aforementioned or blends thereof.
Particularly preferred polymers (A) or (B) are one or more polycarbonate (s) or copolycarbonate (s) based on diphenols or blends comprising at least one polycarbonate or copolycarbonate. Very particular preference is given to blends containing at least one polycarbonate or copolycarbonate and at least one poly- or copolycondensate of terephthalic acid, of naphthalenedicarboxylic acid or of a cycloalkyldicarboxylic acid, preferably of cyclohexanedicarboxylic acid. Very particular preference is given to polycarbonates or copolycarbonates, especially having average molecular weights Mw of 500 to 100000, preferably of 10 000 to 80 000, particularly preferably of 15 000 to 40 000, or blends thereof with at least one poly- or copolycondensate of terephthalic acid having average molecular weights Mw of 10 000 to 200 000, preferably of 21 000 to 120 000.
Suitable poly- or copolycondensates of terephthalic acid in preferred embodiments of the invention are polyalkylene terephthalate s. Suitable polyalkylene terephthalates are for example reaction products of
aromatic dicarboxylic acids or their reactive derivatives (for example dimethyl esters or anhydrides) and aliphatic, cycloaliphatic or araliphatic diols and mixtures of these reaction products.
Preferred polyalkylene terephthalates may be prepared from terephthalic acid (or reactive derivatives thereof) and aliphatic or cycloaliphatic diols having 2 to IO C atoms by known methods (Kunststoff- Handbuch, vol. VIII, p. 695 ff, Karl-Hanser-Verlag, Munich 1973).
Preferred polyalkylene terephthalates contain at least 80 mol%, preferably 90 mol%, of terephthalic acid radicals, based on the dicarboxylic acid component, and at least 80 mol%, preferably at least 90 mol%, of ethylene glycol and/or butane- 1,4-diol and/or cyclohexane- 1,4-dimethanol radicals based on the diol component.
The preferred polyalkylene terephthalates may contain, in addition to terephthalic acid radicals, up to 20 mol% of radicals of other aromatic dicarboxylic acids having 8 to 14 carbon atoms or of aliphatic dicarboxylic acids having 4 to 12 carbon atoms, such as for example radicals of phthalic acid, isophthalic acid, naphthalene-2, 6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexanediacetic acid.
The preferred polyalkylene terephthalates may contain, in addition to ethylene and/or butane- 1,4-diol glycol radicals, up to 80 mol% of other aliphatic diols having 3 to 12 carbon atoms or of cycloaliphatic diols having 6 to 21 carbon atoms, for example radicals of propane-1, 3-diol, 2-ethylpropane-l,3-diol, neopentyl glycol, pentane-1, 5-diol, hexane- 1,6-diol, cyclohexane- 1,4-dimethanol, 3-methylpentane- 2,4-diol, 2-methylpentane-2,4-diol, 2,2,4-trimethylpentane-l,3-diol and 2-ethylhexane- 1,6-diol, 2,2- diethylpropane-1, 3-diol, hexane-2, 5-diol, l,4-di([beta]-hydroxyethoxy)benzene, 2,2-bis(4- hydroxycyclohexyl)propane, 2,4-dihydroxy-l,l,3,3-tetramethylcyclobutane, 2,2-bis(3-[beta]- hydroxyethoxyphenyl)propane and 2,2-bis(4-hydroxypropoxyphenyl)propane (cf. DE-OS 24 07 674, 24 07 776, 27 15 932).
The polyalkylene terephthalates may be branched by incorporation of relatively small amounts of tri- or tetrahydric alcohols or tri- or tetrabasic carboxylic acids, as described for example in DE-OS 19 00 270 and US-PS 3 692 744. Examples of preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and trimethylolpropane and pentaerythritol.
In a preferred embodiment of the layered structure S. polymer (A) and/or polymer (B) are independently selected from the group consisting of a polycarbonate, a co-polycarbonate, a blend of polycarbonates, a blend of co-polycarbonates, polyamide, cyclo olefin copolymer (COC), a polyethylene or a mixture or blend of at least two thereof.
Preferably, polymer (A) is selected from the group consisting of a polycarbonate or poly-carbonate, a polyamide, a PET or a mixture or blend of at least two thereof, especially those as described above.
Preferably, polymer (B) is selected from the group consisting of a cyclo olefin copolymer (COC) and a polyamide, a polyethylene or a mixture thereof.
Preferably, polymer (A) is selected from the group consisting of a polycarbonate or poly-carbonate, a polyamide, a PET or a mixture or blend of at least two thereof, especially those as described above and polymer (B) is selected from the group consisting of a cyclo olefin copolymer (COC) and a polyamide, a polyethylene or a mixture thereof.
Preferably, layer A. comprises 80 to 100 wt.-%, based on the total weight of layer b. of a polymer (A) which is selected from the group consisting of a polycarbonate or poly-carbonate, a polyamide, a PET or a mixture or blend of at least two thereof, especially those as described above.
Preferably, layer B. comprises 80 to 100 wt.-%, based on the total weight of layer b. of a polymer (B) which is selected from the group consisting of a cyclo olefin copolymer (COC) and a polyamide, a polyethylene or a mixture thereof
In a preferred embodiment of the layered structure S. layer A. comprises polymer (A) in an amount in a range of from 50 to 100 wt.-%; preferably in a range of from 70 to 99 wt.-%, more preferably in a range of from 80 to 97 wt.-%, most preferably in a range of from 90 to 95 wt.-%. Layer A. may comprise at least one further additive. The additive is preferably selected from the group consisting of pigments, dyes, surfactants, a UV absorber and a colorant or mixtures of at least two thereof. Preferably, layer A. comprises the additive or the sum of all additives in an amount in a range of from 0.1 to 10 wt.-%, more preferably in an range of from 0.2 to 7 wt.-% , most preferably in an range of from 0.5 to 5 wt.-%, based on the total weight of layer A..
In a preferred embodiment of the layered structure S. layer B. comprises polymer (B) in an amount in a range of from 50 to 100 wt.-%, preferably in a range of from 70 to 99 wt.-%, more preferably in a range of from 80 to 97 wt.-%, most preferably in a range of from 90 to 95 wt.-%. Layer B. may comprise at least one further additive. The additive is preferably selected from the group consisting of pigments, dyes, surfactants, a UV absorber and a colorant or mixtures of at least two thereof. Preferably, layer B. comprises the additive or the sum of all additives in an amount in a range of from 0.1 to 10 wt.-%, more preferably in an range of from 0.2 to 7 wt.-% , most preferably in an range of from 0.5 to 5 wt.-%, based on the total weight of layer B..
Preferably, the first layer A. comprises the polymer (A) or a polymer combination comprising polymer (A), wherein the polymer (A) or the polymer combination comprising polymer (A) provides a Tg in a
range of from 100 to 180 °C, more preferably in a range of from 120 to 160 °C, most preferably of from 130 to 150 °C determined via differential scanning calorimetry (DSC) according to standard DIN EN 61006:2004 at a heating -rate of 20 K/min with definition of Tg as the midpoint temperature (tangent method.
Preferably, the second layer B. comprises the polymer (B) or a polymer combination comprising polymer (B), wherein the polymer (B) or the polymer combination comprising polymer (B) provides a Tg in a range of from 10 to 80 °C, more preferably in a range of from 20 to 60 °C, most preferably of from 30 to 50 °C, determined via differential scanning calorimetry (DSC) according to standard DIN EN 61006:2004 at a heating-rate of 20 K/min with definition of Tg as the midpoint temperature (tangent method).
Preferably, the layered structure S. comprises a first layer A. and a second layer B. wherein the first layer A. of the layered structure S. comprises at least one polymer (A) providing a Tg in a range of from 100 to 180 °C, more preferably in a range of from 120 to 160 °C, most preferably of from 130 to 150 °C, and the second layer B. comprises at least one polymer (B) providing a Tg in a range of from 10 to 80 °C, more preferably in a range of from 20 to 60 °C, most preferably of from 30 to 50 °C, determined via differential scanning calorimetry (DSC) according to standard DIN EN 61006:2004 at a heating-rate of 20 K/min with definition of Tg as the midpoint temperature (tangent method)
In a preferred embodiment of the layered structure S., the first layer A. comprises at least one polymer (A) in an amount in a range of 80 to 100 wt.-%, wherein the at least one polymer (A) provides a Tg in a range of from 100 to 180 °C, more preferably in a range of from 120 to 160 °C, most preferably of from 130 to 150 °C, and the second layer B. comprises the polymer (B) in an amount in a range of 80 to 100 wt.-%, wherein the polymer (B) provides a Tg in a range of from 10 to 80 °C, more preferably in a range of from 20 to 60 °C, most preferably of from 30 to 50 °C, determined via differential scanning calorimetry (DSC) according to standard DIN EN 61006:2004 at a heating-rate of 20 K/min with definition of Tg as the midpoint temperature (tangent method).
In a preferred embodiment of the layered structure S., the layered structure S. further comprises at least one layer C., comprising a polymer (C). Polymer (C) can be any polymer the person skilled in the art would select for the establishment of layer C. in a layered structure S..
In a preferred embodiment of the layered structure S. the polymer (C) is different from the polymer (A) and/or polymer (B).. Preferably, polymer (C) is different from polymer (A) and polymer (B). Preferably, polymer (C) is selected from the group consisting of a polycarbonate, a co-polycarbonate, a blend of polycarbonates, a blend of co-polycarbonates, polyamide, cyclo olefin copolymer (COC), a polyethylene or a mixture or blend of at least two thereof. Examples of preferred polycarbonates are
mentioned above with respect to the polymer (A) which are also preferred for polymer (C). Preferably, polymer (C) is a polyethylene.
Layer C. may comprise at least one further additive. The additive is preferably selected from the group consisting of pigments, dyes, surfactants, deformers, plasticizers, a UV absorber and a colorant or mixtures of at least two thereof. Preferably, layer C. comprises the additive or the additives in a total amount in a range of from 0.01 to 0.5 wt.-%, more preferably in an range of from 0.05 to 0.4 wt.-% , most preferably in an range of from 0.1 to 0.3 wt.-%, based on the total weight of layer C..
In a preferred embodiment of the layered structure S. the at least further layer B. is positioned between two layers A.. Preferably at least one layer C. is positioned on top of each layer A.. In an alternative embodiment of the layered structure S. the at least one layer A. is positioned between at least one further layer B. and at least one layer C..
Preferably, the layered structure S. is assembled in a layer combination selected from the group consisting of : layer A. and layer B.; layer A., layer B., layer A; layer C., layer A. and layer B; layer C., layer A., layer B., layer A., layer C., layer A., layer B., layer A., layer C.
A further aspect of the invention relates to a process for the manufacturing of a layered structure S., wherein the layered structure S. comprises at least one first layer A. having a thickness in a range of from 10 to 50 pm, preferably 10 to 30 pm, comprising at least the following steps
P 1. providing a granulate A. comprising a polymer (A);
P2. providing a granulate B. comprising a polymer (B);
P3. optionally, providing a granulate C. comprising a polymer (C);
P4. heating granulate A. and granulate B. and optionally granulate C. to a temperature T which is at least 80 °C, preferably at least 100°C higher than the softening point or the glass transition temperature of the respective polymer (A), (B) and optionally (C) to receive the melts (A), (B) and optionally (C);
P5. combining the melts of at least melt (A) and melt (B) and optionally melt (C) to receive a co-extrudate of at least one layer A. from melt (A) with a thickness in a range of from
10 to 50 µm and a layer B. from melt (B) and optionally at least one layer C. from melt (C) to receive the layered structure S.; P6. cooling down the layered structure S. to a temperature in a range of from 20 to 40 °C; P7. optionally rolling up the layered structure S. onto a roll; P8. optionally post processing the layered structure S., whereby the post processing is preferably selected from the group consisting of printing onto at least one surface, forming, laser marking or a combination of at least two thereof; P9. optionally delaminating layers A., B. and optionally C. through an unwinding and rewinding process. Providing in step P1. of granulate A. comprising a polymer (A) can be established by any means the person skilled in the art would select for the process. Providing in step P2. of granulate B. comprising a polymer (B) can be established by any means the person skilled in the art would select for the process. Providing in step P2. of granulate C. comprising a polymer (C) can be established by any means the person skilled in the art would select for the process. Preferably, providing in step P1. or step P2. or step P3. are established by using an extruder. The heating of granulate A. and granulate B. and optionally granulate C. in step P4. to a temperature T which is at least 10 °C higher than the softening point or the glass transition temperature of the respective polymer (A), (B) and optionally (C) to receive the melts (A), (B) and optionally (C) could be established by any means selected by the person skilled in the art. If an extruder is utilized in steps P1. to P3. the extruder includes means for heating. Combining the melts of at least melt (A) and melt (B) and optionally melt (C) in step P5. to receive at least one layer A. from melt (A) with a thickness in a range of from 10 to 50 µm and a layer B. from melt (B) and optionally at least one layer C. from melt (C) to receive the layered structure S. can be performed by any means the person skilled in the art would select for combining melts. Preferably the melts (A) and (B) and optionally (C) are combined in or in front of a slot die and a co-extrudate is received. Preferably, the layered structure S. comprises a layer sequence selected from the group consisting of layer A. – B-; A. – B. – A.; C.- A. - B.- A. - C. Cooling down the layered structure S. in step P6. to a temperature in a range of from 20 to 40 °C could be established by any means the person skilled in the art would select for cooling layers. Preferably, cooling is established by storing the layered structure S. at room temperature, preferably in a temperature range of 20 to 30 °C, more preferably in a range of 22 to 27 °C. If cooling shall be accelerated, a cooling medium, like a cool fluid in form of cool air or cool water may be directed onto the layer. The cool fluid in form of air or water preferably has a temperature in a range of rom 1°C to 20°C.
Rolling up the layered structure S. onto a roll in step P7. may be established by any means the person skilled in the art would select for rolling layers. Preferably, the rolling up is established by a conventional roll winder.
Post processing the layered structure S. in step P8. may be selected from any processing the person skilled in the art would select for a post processing of layers. The post processing is preferably selected from the group consisting of printing onto at least one surface, forming, laser marking or a combination of at least two thereof.
Delaminating layers A., B. and optionally C. may optionally performed in step P9. through an unwinding and rewinding process. Delamination may be established by a process selected from any processing the person skilled in the art would select for a post processing of layers. If delamination is not performed by hand a conventional delamination machine could be used.
In a preferred embodiment of the process, the polymer (A), the polymer (B) and/or the polymer (C) are independently selected from the group consisting of a polycarbonate, a co-polycarbonate, a blend of polycarbonates, a blend of co-polycarbonates, polyamide, cyclo olefin copolymer (COC), polyethylene or a mixture or blend of at least two thereof. Preferably, the polymer (C) is a polyethylene. Preferably, the polymer (B) is a COC.
In a preferred embodiment of the process polymer (A) is selected from the group consisting of a polycarbonate, a co-polycarbonate, a blend of polycarbonates, a blend of co-polycarbonates, polyamide, cyclo olefin copolymer (COC), or a mixture or blend of at least two thereof, but different from polymer (B) and preferably different from polymer (C). Preferably, polymer (A) is a polycarbonate or a co polycarbonate.
A further aspect of the invention relates to a foil with a thickness in a range of from 10 bis 100 pm, preferably in a range of from 20 to 80 pm produced by the process according to the invention.
A further aspect of the invention relates to a use of the layered structure S. according to the invention or produced by a process according to the invention or a foil according to the invention as cover for surfaces. The use of the layered structure S. incorporates a method to use the layered structure S. or the foil as cover for surfaces. The surface could be any surface the person skilled in the art would choose to cover. The surface is preferably selected from the group consisting of a display, a screen, glasses, surfaces of the interior of an automotive. The cover is preferably a protective cover for the surface.
Figures
Examples of a layered structure S. are shown in
Figure 1: a schematic illustration of a layered structure S. according to the invention with layer A. and layer B..
Figure 2: a schematic illustration of a layered structure S. according to the invention with layer A. and layer B. and layer C..
Figure 3: A schematic illustration of a process according to the invention
In figure 1 a schematic illustration of a layered structure S. 50 according to the invention is shown. The layered structure S. 50 comprises a first layer A. 10 comprising polymer (A) and a second layer B. 20 comprising polymer (B). Polymer (A) is a COC, preferably a TOPAS from Hoechst (now TOPAS Advanced Polymers), polymer (B) is Makrolon® 3108 of Covestro AG. The thickness of layer A. is about 30 pm and the thickness of layer B. is about 100 pm. Optionally, further layers may be positioned on the side of second layer B. opposite to the side where layer A. is positioned or on layer A. on the side of layer A. opposite to the side where layer B. is positioned. Preferably, two layers of layer A. are positioned on both sides of layer B., which form a part of the layered structure S. in figure 2.
In figure 2 a schematic illustration of a layered structure S. 50 according to the invention is shown comprising 5 layers, two first layers A. 10 comprising polymer (A), a second layer B. 20 comprising polymer (B) and two third layers C. 30 comprising polymer (C). The materials of layer A. and B. are the same as described for the layered structure S. 50 of figure 1. Polymer (C) is a polyethylene. Optionally, further layers may be positioned on both sides of the layered structure S. 50.
In figure 3 the main steps of the process for manufacturing structure S. 50 according to the invention is illustrated. In step PI. 100, providing of granulate A. comprising polymer (A) as described in figure 1 is established by pouring granulate A. into an extruder. In step P2. 200, providing of granulate B. comprising polymer (B) as described in figure 1 is established by pouring granulate B. into a second extruder. In an optional step P3. 300, providing of granulate C. comprising polymer (C) as described in figure 1 is established by pouring the granulate C. into a third extruder. In step P4. 400 heating of the granulates (A), (B) and optionally (C) is established inside the extruders. The extruder can be any commercially available extruders which are able to extrude polymers as mentioned for the layers A., B. and C.. The extruder heats the respective granulates to a temperature T which is at least 80 °C, preferably at least 100 °C higher than the softening point or the glass transition temperature of the respective polymer (A), (B) and optionally (C) to receive the melts (A), (B) and optionally (C). In step P5. 500 the melts of at least melt (A) and melt (B) and optionally melt (C) are combined to receive one or two layers A. from melt (A) with a thickness of about 10 to 30 pm on one or both sides of one layer B. from melt (B) and optionally at least one layer C from melt (C) on top of one of the layers A. to receive the layered structure S. 50 as shown in figure 2. The layered structure S. 50 is cooled in step P6. 600 at room temperature for several hours. This cooling process might be accelerated by providing cooling media
like cool air or water with a temperature in a range of 1 to 20°C. After the layered structure S. 50 has been cooled down to room temperature around 23 °C, the layered structure S. 50 is rolled up onto a roll by a winder in an optional step P7 700. The layered structure S. 50 might be post treated in step P8. 800. In step P9. 900 the layered structure S. 50 is delaminated between layer A. and layer B. to receive one or two thin layer A..
Experimental part:
Masterbatch for layer A. :
The production of the masterbatch for the production of layer A. of the co-extruded fdm was carried out with a conventional twin-screw compounding extruder (ZSK 32) at processing temperatures customary for polycarbonate of 250°C to 330°C.
A master batch having the following composition was compounded and subsequently granulated: Master batch 1 : 100 wt.-% Makrolon® 3108, or
Master batch 2: 100 wt.-% Durabio™ 7340, Mitsubishi Chemical Performance Polymers, Japan Masterbatch for layer B. :
The production of the masterbatch for the production of layer B. of the co-extruded fdm was carried out with a conventional twin-screw compounding extruder (ZSK 32) at processing temperatures customary for COCs of 210°C to 240°C.
A master batch having the following composition was compounded and subsequently granulated: Master batch 3: 100 wt.-% TOPAS® (Mitsui, Japan), or
Master batch 4: 100 wt.-% Grilamid® TR90 (EMS Chemie, Switzerland), or
Master batch 5: TPU Desmopan® 9365D (Covestro Deutschland AG, Germany), or
Master batch 6: TPU Desmopan® 9385D (Covestro Deutschland AG, Germany); or
Master batch 7: Desmopan® 786E (polycarbonate type TPU) (Covestro Deutschland AG, Germany); or
Master batch 8: TPU Desmopan® 3660D (Covestro Deutschland AG, Germany).
Production of co-extruded film comprising layer A. and layer B.
The employed apparatus for producing the co-extruded fdm comprises: an extruder for melting polymer (A) and extrusion of melt (A) to form layer A. containing at least one polycarbonate with a screw of 60 mm in diameter (D) and a length of 33 D. The screw has a degassing zone; an extruder for extrusion melting polymer (B) and extrusion of melt (B) to form layer B. a melt pump;
a crosshead; a slot die of 450 mm in width; a three-roller smoothing calendar with horizontal roller orientation, wherein the third roller can swivel by +/- 45° relative to the horizontal; · a roller conveyor; thickness measuring means; means for double-sided application of protective fdm; a haul-off; a winding station. The granulate(s) of the masterbatch was/were conveyed from the dryer into the fdling hopper of the extruder. The material was melted and conveyed in the barrel/screw plasticizing system of the extruder. The melt passed from the slot die onto the smoothing calendar. The final shaping and cooling of the film was carried out on the smoothing calendar (consisting of three rollers). The surfaces were embossed using a textured steel roller (no. 6 side) and a textured silicone rubber roller (no. 2 side). The rubber roller used for texturing the film surface is disclosed in US-4 368 240 from Nauta Roll Corporation. The film was subsequently transported through a haul -off and then the film was wound up.
In Table 1 inventive examples of layered structures S. are listed together with adhesion forces between different materials for layer A. and layer B.. The cited materials are formed from the master batches as mentioned above. The layer A. could be delaminated from layer B. by hand without deforming one of the layers A. and B. and without any residues on the layers A. and B. of material of the respective other layer or polymer of that other layer.
Table 1: Values of adhesion forces between different materials for layer A. and layer B.
* measured by de lamination according to ASTM D903-1998 at a pulling angle of 180°
In Table 2 comparative examples of adhesion forces between different layered structures comprising two layers (layer A. and layer B.) are listed. The two layers A. and B. could not be delaminated from each other by hand. If higher forces are applied to delaminate the layers A. and B. the layers are destroyed or at least tears can be seen in at least one of the layers A. and/or B..
Table 2: Values of adhesion forces between different materials for layer A. and layer B. of a comparative layered structure
* measured by de lamination according to ASTM D903-1998 at a pulling angle of 180°
Claims
Patent Claims:
1. A layered structure S., comprising:
A. at least one first layer A., with a first outer surface A1 and a second surface A2, comprising at least polymer (A), wherein the first layer A. has a thickness in the region of 10 to 50 pm, preferably in the range of 10 to 30 pm, and
B. at least one further layer B. comprising at least polymer (B), wherein layer A. of the layered structure S. provides at least one, preferably two, more preferably all of the following properties:
51. an adhesion force between the at least one first layer A. and the at least one further layer B. in a range of from 0.001 to 0.05 N/cm, measured according to ASTM D903-1998 at a pulling angle of 180°;
52. a hardness > 85 D, measured according to DIN EN ISO 868-2003-10;
53. a melting temperature > 200°C; preferably in a range of from 210 to 350 °C, more preferably in a range of from 230 to 330 °C; most preferably in a range of from 250 to 320 °C, determined via differential scanning calorimetry (DSC) according to standard DIN EN 61006:2004 at a heating -rate of 20 K/min with definition of Tg as the midpoint temperature (tangent method)
54. a glass-transition temperature Tg of > 70°C; preferably in a range of from 80 to 250 °C, more preferably in a range of from 80 to 240 °C; most preferably in a range of from 80 to 200 °C, determined via differential scanning calorimetry (DSC) according to standard DIN EN 61006:2004 at a heating -rate of 20 K/min with definition of Tg as the midpoint temperature (tangent method) or a vicat softening temperature B/50 determined according to ISO 306-2014-03 (50N; 50°/h) of > 70°C; preferably in a range of from 75 to 230 °C, more preferably in a range of from 80 to 230 °C; most preferably in a range of from 85 to 225 °C;
55. Melt volume rate (MVR; measured according to DIN ISO 1133-1-2012-03; 300°C, 2.16 kg) of > 3 cm3/10 min, more preferably of > 3.5 cmVlO min, even more preferably of > 4 cm3/ 10 min;
56. additives in a range of from 0.01 to 0.5 wt.-%.
2. The layered structure S. according to claim 1, preferably layer A., wherein the layered structure S. and preferably layer A. provides at least one, preferably two, more preferably all of the following properties:
57. a thickness in a range of from 15 to 250 mih, preferable in a range of from 20 to 200 pm, and most preferably in a range of from 30 to 100 pm;
58. a deviation of the thickness across an area of 20 * 20 cm in a range of from 0.01 to 1 pm, preferably of from 0.02 to 0.5 pm, more preferably of from 0.03 to 0.3 pm, most preferably of from 0.05 to 0.1 pm;
59. a tensile strength in a range of from 10 to 150 MPa, preferably of from 20 to 100 MPa, measured according to DIN EN ISO 527-1:2012-06;;
S 10. an elongation at break in a range of from 20 bis 500 %, preferably of from 50 to 400 %, measured according to DIN N ISO 527-1:2012-06;
SI 1. water absorption (ISO 62:2008);) at 23°C for 24 h) in a range of from 0.01 to 0.5 wt.- %, more preferably) in a range of from 0.05 to 0.4 wt.-% (saturation value).
3. The layered structure S. according to any of the preceding claims, wherein layer A. provides at least one, preferably at least two, more preferably all of the following properties: al . a gloss at 60° angle in a range of 10 to 110, measured according to DIN EN ISO 2813- 2015-02; a2. a surface roughness of at least the first surface Al in a range of 0.1 to 5.50 pm, measured according to DIN EN ISO 4287:2010-07/DIN EN ISO 4288: 1998-04; a3. a birefringence in a range of from 1 to 100 nm, measured by a polarization microscope; a4. a transparency in a range of from 5 to 95 %, measured according to ASTM D 1003-13; a5. a density in a range of from 1 to 1.35 g/1, measured according to ISO 1183-1:2019-09; a6. a tensile strength in a range of from 10 to 150 MPa, preferably of from 20 to 100 MPa, measured according to DIN EN ISO 527-1:2012-06;; a7. an elongation at break in a range of from 20 bis 500 %, preferably of from 50 to 400 %, measured according to DIN N ISO 527-1:2012-06;; a8. a thickness in a range of from 5 to 50 pm, preferable in a range of from 10 to 25 pm, and most preferably in a range of from 10 to 20 pm; a9. a deviation of the thickness in a range of from 0.01 to 1 pm, preferably of from 0.02 to 0.5 pm, more preferably of from 0.03 to 0.3 pm, most preferably of from 0.05 to 0.1 pm.
4. The layered structure S. according to any of the preceding claims, wherein polymer (A) and/or polymer (B), are independently selected from the group consisting of a polycarbonate, a co polycarbonate, a blend of polycarbonates, a blend of co-polycarbonates, polyamide, cyclo olefin copolymer (COC), a polyethylene or a mixture or blend of at least two thereof.
5. The layered structure S. according to any of the preceding claims, wherein layer A. comprises the polymer (A) in an amount in a range of from 50 to 100 wt.-%; preferably in a range of from 70 to
99 wt.-%, more preferably in a range of from 80 to 97 wt.-%, most preferably in a range of from 90 to 95 wt.-%.
6. The layered structure S. according to any of the preceding claims, wherein layer B. comprises the polymer (B) in an amount in a range of from 50 to 100 wt.-%, preferably in a range of from 70 to 99 wt.-%, more preferably in a range of from 80 to 97 wt.-%, most preferably in a range of from 90 to 95 wt.-%.
7. The layered structure S. according to any of the preceding claims, wherein the first layer A. of the layered structure S. comprises at least one polymer (A) in an amount in a range of 80 to 100 wt.-%, wherein the at least one polymer (A) provides a Tg in a range of from 100 to 180 °C, more preferably in a range of from 120 to 160 °C, most preferably of from 130 to 150 °C, and the second layer B. comprises at least one polymer (B) in an amount in a range of 80 to 100 wt.-%, wherein the at least one polymer (B) provides a Tg in a range of from 10 to 80 °C, more preferably in a range of from 20 to 60 °C, most preferably of from 30 to 50 °C, determined via differential scanning calorimetry (DSC) according to standard DIN EN 61006:2004 at a heating-rate of 20 K/min with definition of Tg as the midpoint temperature (tangent method).
8. The layered structure S. according to any of the preceding claims, wherein the layered structure S. further comprises at least one layer C., comprising a polymer (C).
9. The layered structure S. according to any of the preceding claims, wherein the polymer (C) is different from the polymer (A) and/or polymer (B).
10. The layered structure S. according to the preceding claim, wherein the at least further layer B. is positioned between two layers A..
11. A process for the manufacture of a layered structure S., wherein the layered structure S. comprises at least one first layer A. having a thickness in a range of from 10 to 50 pm, preferably 10 to 30 pm, comprising at least the following steps
PI. Providing a granulate A. comprising a polymer (A),
P2. Providing a granulate B. comprising a polymer (B),
P3. Optionally, providing a granulate C. comprising a polymer (C),
P4. heating granulate A. and granulate B. and optionally granulate C. to a temperature T which is at least 80 °C, preferably at least 100°C higher than the softening point or the
glass transition temperature of the respective polymer (A), (B) and optionally (C) to receive the melts (A), (B) and optionally (C);
P5. combining the melts of at least melt (A) and melt (B) and optionally melt (C) to receive a co-extrudate of at least one layer A. from melt (A) with a thickness in a range of from 10 to 50 pm and a layer B. from melt (B) and optionally at least one layer C. from melt
(C) to receive the layered structure S.;
P6. cooling down the layered structure S. to a temperature in a range of from 20 to 40 °C;
P7. optionally rolling up the layered structure S. onto a roll;
P8. optionally post processing the layered structure S., whereby the post processing is preferably selected from the group consisting of printing onto at least one surface, forming, laser marking or a combination of at least two thereof;
P9. optionally delaminating layers A., B. and optionally C. through an unwinding and rewinding process.
12. The process according to claim 11, wherein the polymer (A), the polymer (B) and/or the polymer (C) are independently selected from the group consisting of a polycarbonate, a co-polycarbonate, a blend of polycarbonates, a blend of co-polycarbonates, polyamide, cyclo olefin copolymer (COC), or a mixture or blend of at least two thereof.
13. The process according to any of claims 11 or 12, wherein polymer (A) is selected from the group consisting of a polycarbonate, a co-polycarbonate, a blend of polycarbonates, a blend of co- polycarbonates, polyamide, cyclo olefin copolymer (COC), or a mixture or blend of at least two thereof, but different from polymer (B).
14. A foil with a thickness in a range of from 10 bis 100 pm produced by the process according to any of claims 11 to 13.
15. A use of the layered structure S. according to any of claims 1 to 10 or produced by a process according to any of claims 11 to 13 or of the foil according to claim 14 as cover for surfaces.
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PCT/EP2022/065157 WO2022258506A1 (en) | 2021-06-07 | 2022-06-03 | Ultrathin layered structure with specific properties |
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FR1580834A (en) | 1968-01-04 | 1969-09-12 | ||
US4368240A (en) | 1981-07-27 | 1983-01-11 | Nauta Roll Corporation | High gloss rubber roll |
JP2002103410A (en) * | 2000-09-29 | 2002-04-09 | Toray Ind Inc | Method for manufacturing polymeric sheet, and polymeric sheet |
US20060159888A1 (en) * | 2004-10-29 | 2006-07-20 | Hebrink Timothy J | Optical films incorporating cyclic olefin copolymers |
US11344386B2 (en) * | 2019-01-30 | 2022-05-31 | Usi Corporation | Multilayer sheet structure for dental appliance |
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