# US 10,864,708 B2 · Multi-layer film with improved modulus properties

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- Number: US 10,864,708 B2
- Document ID: US10864708B2
- Status: Granted
- Kind: B2
- Application number: 16/224,867
- Filed: 2018-12-19
- Published: 2019-05-16
- Granted: 2020-12-15
- Earliest claimed: 2018-12-19
- Assignees: Covestro Deutschland AG
- Applicants: Covestro Deutschland AG
- Inventors: Heinz Pudleiner; Klaus Meyer; Juergen Winkler; Wolfgang Braeuer; Joerg Nickel; Craig Pehlert; Chunhua Li; Yan Chen
- Web page: https://patentgrep.com/patent/US10864708B2

## CPC

- B32B 27/08: of synthetic resin
- A61C 5/007: {Dental splints; teeth or jaw immobilisation devices; stabilizing retainers bonded to teeth after orthodontic treatments}
- A61C 13/0022: {Blanks or green, unfinished dental restoration parts}
- B29C 48/0011: {combined with compression moulding}
- B29C 48/0017: {combined with blow-moulding or thermoforming}
- B29C 48/08: flexible, e.g. films
- B29C 48/21: the layers being joined at their surfaces
- B29C 48/625: characterised by the ratio of the threaded length of the screw to its outside diameter [L/D ratio]
- B29C 48/92: Measuring, controlling or regulating
- B32B 27/36: comprising polyesters
- B32B 27/365: {comprising polycarbonates}
- B32B 27/40: comprising polyurethanes
- C08J 7/042: {with two or more layers, where at least one layer of a composition contains a polymer binder}
- C08L 67/02: Polyesters derived from dicarboxylic acids and dihydroxy compounds (C08L67/06 takes precedence)
- C08L 69/00: Compositions of polycarbonates; Compositions of derivatives of polycarbonates
- C08L 75/08: from polyethers
- B29C 48/30: Extrusion nozzles or dies (extrusion characterised by the shape or cross-section of the extruded article B29C48/03)
- B29C 48/34: Cross-head annular extrusion nozzles, i.e. for simultaneously receiving moulding material and the preform to be coated
- B29C 2948/92609: Dimensions
- B29C 2948/92704: Temperature
- B32B 2250/03: 3 layers
- B32B 2250/24: All layers being polymeric
- B32B 2250/40: Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
- B32B 2307/4026: within the layer by addition of a colorant, e.g. pigments, dyes
- B32B 2307/412: Transparent
- B32B 2307/536: Hardness
- B32B 2307/54: Yield strength; Tensile strength
- B32B 2307/732: Dimensional properties
- B32B 2457/12: Photovoltaic modules
- B32B 2535/00: Medical equipment, e.g. bandage, prostheses or catheter
- C08J 2369/00: Characterised by the use of polycarbonates; Derivatives of polycarbonates
- C08J 2467/02: Polyesters derived from dicarboxylic acids and dihydroxy compounds (C08J2467/06 takes precedence)
- C08J 2475/04: Polyurethanes
- Y10T 428/24967: Absolute thicknesses specified
- Y10T 428/24983: Hardness
- B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- A61C: DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE (non-driven toothbrushes A46B; {tongue scrapers A61B17/24;} preparations for dentistry A61K6/00; preparations for cleaning the teeth or mouth A61K8/00, A61Q11/00)
- B29C: SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING (making preforms B29B11/00; making laminated products by combining previously unconnected layers which become one product whose layers will remain together B32B37/00 - B32B41/00)
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

The invention relates to a multi-layer, preferably co-extruded, plastic film with improved modulus properties, which is suitable, in particular, for producing three-dimensionally shaped articles.

## Claims

### Claim 1

A three-layer plastic film, comprising:
a core layer A comprising at least one polycarbonate or copolycarbonate and/or a polyester or copolyester having a glass transition temperature Tg from 80° C. to 200° C.,
two outer layers B comprising at least one thermoplastic polyurethane exhibiting a hardness from 45 Shore D to 85 Shore D;
wherein the core layer A is located between the two outer layers B.

### Claim 2 (depends on 1)

The three-layer plastic film according to claim 1, wherein the core layer A comprises at least one polyester or copolyester having an inherent viscosity from 0.50 dL/g to 1.20 dL/g and a glass transition temperature Tg from 80° C. to 200° C.

### Claim 3 (depends on 1)

The three-layer plastic film according to claim 1, wherein
the core layer A comprises at least one copolyester that exhibits residues from
(a) a dicarboxylic acid component comprising
i) 70 mole % to 100 mole % terephthalic acid residues,
ii) 0 mole % to 30 mole % aromatic dicarboxylic acid residues with up to 20 carbon atoms, and
iii) 0 mole % to 10 mole % aliphatic dicarboxylic acid residues with up to 16 carbon atoms, and
(b) a diol component comprising
i) 5 mole % to 50 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, and
ii) 50 mole % to 95 mole % 1,4-cyclohexanedimethanol residues,
wherein the sum of the mole % of residues i)-iii) of the dicarboxylic acid component amounts to 100 mole % and the sum of the mole % of residues i) and ii) of the diol component amounts to 100 mole %
and wherein the inherent viscosity of the copolyester is from 0.50 dL/g to 1.20 dL/g and the copolyester has a glass transition temperature Tg from 80° C. to 150° C.,
the two outer layers B comprise at least one thermoplastic polyurethane, the thermoplastic polyurethane exhibiting a hardness from 45 Shore D to 85 Shore D and being obtained from
a) one or more linear polyether diols with mean molecular weights from 500 g/mol to 10,000 g/mol, and, on average, in each instance at least 1.8 and at most 3.0, Tserevitinov-active hydrogen atoms
b) one or more organic diisocyanates,
c) one or more diol chain-extenders with molecular weights from 60 g/mol to 500 g/mol and with, on average, 1.8 to 3.0 Tserevitinov-active hydrogen atoms
in the presence of
d) optionally, one or more catalysts
with addition of
e) optionally, auxiliary substances and additives,
wherein the molar ratio of the NCO groups in b) to the groups in a) and c) that are reactive towards isocyanate amounts to 0.85:1 to 1.2:1.

### Claim 4 (depends on 1)

The three-layer plastic film according to claim 1, wherein the thermoplastic polyurethane exhibits a hardness from 50 Shore D to 80 Shore D.

### Claim 5 (depends on 3)

The three-layer plastic film according to claim 3, wherein the polyether diols a) used for producing the thermoplastic polyurethane are selected from one or more polyether diols of the group based on 1,4-butanediol units and/or 1,3-propylene glycol units.

### Claim 6 (depends on 3)

The three-layer plastic film according to claim 3, wherein the organic diisocyanate b) used for producing the thermoplastic polyurethane is selected from one or more isocyanates of the group containing 4,4′-diphenylmethane diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate or 1,6-hexamethylene diisocyanate.

### Claim 7 (depends on 3)

The three-layer plastic film according to claim 3, wherein the diol chain-extender c) used for producing of the thermoplastic polyurethane is selected from one or more chain-extenders of the group containing 1,4-butanediol, 1,3-propanediol, 1,2-propanediol, 1,2-ethylene glycol, 1,6-hexanediol, 1,4-di(β-hydroxyethyl)hydroquinone or 1,4-di(β-hydroxyethyl)bisphenol A.

### Claim 8 (depends on 3)

The three-layer plastic film according to claim 3, wherein the thermoplastic polyurethane was produced in the prepolymer process.

### Claim 9 (depends on 3)

The three-layer plastic film according to claim 3, wherein the diol component of the copolyester comprises 10 mole % to 35 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 65 mole % to 90 mole % 1,4-cyclohexanedimethanol residues, the sum of the mole % of these two components of the diol component amounting to 100 mole %.

### Claim 10 (depends on 3)

The three-layer plastic film according to claim 3, wherein the residues from the dicarboxylic acid component of the polyester include 95 mole % to 100 mole % terephthalic acid residues.

### Claim 11 (depends on 1)

The three-layer plastic film according to claim 1, wherein the film has been co-extruded.

### Claim 12 (depends on 1)

The three-layer plastic film according to claim 1, wherein the film has a total thickness from 300 μm to 2000 μm.

### Claim 13 (depends on 1)

The three-layer plastic film according to claim 1, wherein the core layer A has a layer thickness from 250 μm to 1600 μm.

### Claim 14 (depends on 1)

The three-layer plastic film according to claim 1, wherein the outer layers B each have a layer thickness from 25 μm to 500 μm.

### Claim 15 (depends on 2)

The three-layer plastic film according to claim 2, wherein the poly or copolyester exhibits an inherent viscosity from 0.50 dL/g to 0.80 dL/g.

### Claim 16 (depends on 1)

The three-layer plastic film according to claim 1, wherein the poly- or copolyester exhibits a glass transition temperature Tg from 85° C. to 130° C.

### Claim 17 (depends on 1)

A three-dimensionally shaped article obtained by three-dimensionally forming the three-layer plastic film according to claim 1.