Laminated multilayer polymer containing film comprising a copolyamide of a diamine, a dimer acid and a lactam

Abstract

A laminated multilayer polymer containing film (P) comprises at least one layer comprising at least one copolyamide wherein the copolyamide is prepared by polymerizing the following components: (A) 15% to 84% by weight of at least one lactam, (B) 16% to 85% by weight of a monomer mixture (M) comprising the following components: (B1) at least one C32-C40 dimer acid and (B2) at least one C4-C12 diamine, where the percentages by weight of components (A) and (B) are each based on the sum total of the percentages by weight of components (A) and (B) and wherein the laminated multilayer polymer containing film (P) comprises at least one further layer, where the at least one further layer is selected from the group consisting of (i) at least one further polymer (FP) selected from the group consisting of polyolefins, poly(ethylene-vinyl alcohols), poly(ethylene-vinyl acetates), polyethylene terephthalates, polyvinylidene chlorides, maleic anhydride-grafted polyolefins, polyesters and ionomers and (ii) aluminum metal and/or tin metal.

Claims

1. A laminated multilayer polymer containing film (P) comprising at least one layer, the at least one layer consisting of at least one copolyamide, wherein the at least one copolyamide is prepared by polymerizing the following components: (A) 15% to 84% by weight of at least one lactam, and (B) 16% to 85% by weight of a monomer mixture (M) comprising the following components: (B1) at least one C.sub.32-C.sub.40 dimer acid, and (B2) at least one C.sub.4-C.sub.12 diamine, where the percentages by weight of components (A) and (B) are each based on the sum total weight of components (A) and (B), and wherein the laminated multilayer polymer containing film (P) further comprises at least one further layer, wherein the at least one further layer is at least one selected from the group consisting of (i) at least one further polymer (FP) selected from the group consisting of polyolefins, poly(ethylene-vinyl alcohols), poly(ethylene-vinyl acetates), polyethylene terephthalates, polyvinylidene chlorides, maleic anhydride-grafted polyolefins, polyesters, and ionomers, and (ii) aluminum metal and/or tin metal.

2. The laminated multilayer polymer containing film (P) according to claim 1, wherein component (A) is at least one selected from the group consisting of 3-aminopropanolactam, 4-aminobutanolactam, 5-aminopentanolactam, 6-aminohexanolactam, 7-aminoheptanolactam, 8-aminooctanolactam, 9-aminononanolactam, 10-aminodecanolactam, 11-aminoundecanolactam, and 12-aminododecanolactam.

3. The laminated multilayer polymer containing film (P) according to claim 1, wherein component (B) comprises in the range from 45 to 55 mol % of component (B1) and in the range from 45 to 55 mol % of component (B2), based in each case on the total molar amount of component (B).

4. The laminated multilayer polymer containing film (P) according to claim 1, wherein component (B2) is at least one selected from the group consisting of tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, decamethylenediamine, and dodecamethylenediamine.

5. The laminated multilayer polymer containing film (P) according to claim 1, wherein component (B1) is prepared from at least one unsaturated fatty acid selected from the group consisting of an unsaturated C16 fatty acid, an unsaturated C.sub.18 fatty acid, and an unsaturated C.sub.20 fatty acid.

6. The laminated multilayer polymer containing film (P) according to claim 1, wherein the at least one copolyamide has a viscosity number (VN.sub.(C)) in the range from 150 to 300 ml/g, determined in a 0.5% by weight solution of the at least one copolyamide in a mixture of phenol/o-dichlorobenzene having a weight ratio of 1:1.

7. The laminated multilayer polymer containing film (P) according to claim 1, wherein the at least one copolyamide has a glass transition temperature (T.sub.M(C)), in the range from 20 to 50° C.

8. The laminated multilayer polymer containing film (P) according to claim 1, wherein the at least one copolyamide has a melting temperature (T.sub.M(C)), in the range from 150 to 210° C.

9. The laminated multilayer polymer containing film (P) according to claim 1, wherein the at least one further polymer (FP) is selected from the group consisting of polyolefins, poly(ethylene-vinyl acetates), and polyethylene terephthalates.

10. The laminated multilayer polymer containing film (P) according to claim 1, wherein the least one further layer, comprises (i) the at least one further polymer (FP) selected from the group consisting of polyolefins, poly(ethylene-vinyl acetates), and polyethylene terephthalates, and (ii) aluminum and/or tin metal.

11. The laminated multilayer polymer containing film (P) according to claim 1, comprising at least one outer layer comprising a polyolefin and at least one layer comprising aluminum and/or tin metal.

12. The laminated multilayer polymer containing film (P) according to claim 1, comprising: one outer layer consisting essentially of polypropylene, an adjacent next layer or layers comprising the at least one copolyamide, a further layer of aluminum adjacent to the adjacent next layer or layers, and finally adjacent to the further layer of aluminum, a layer of polyethylene terephthalate.

13. The laminated multilayer polymer containing film (P) according to claim 1, wherein the laminated multilayer polymer containing film (P) is produced by a lamination process of polymer layers which are obtained by at least one process selected from the group consisting of a casting process, a blowing process, and a biaxially orientation process.

14. The laminated multilayer polymer containing film (P) according to claim 1, wherein the laminated multilayer polymer containing film (P) has a thickness in the range from 0.1 μm to 1 mm.

15. The laminated multilayer polymer containing film (P) according to claim 1, wherein the at least one copolyamide is a random copolymer.

16. A process for producing a the laminated multilayer polymer containing film (P) according to claim 1, comprising the steps of i) preparing at least two films, and ii) laminating the at least two films, wherein at least one film in step i) is obtained from a the at least one copolyamide as and the other film or films in step i) is/are obtained from a at least one component selected from the group consisting of a) at least one further polymer (FP) selected from the group consisting of polyolefins, poly(ethylene-vinyl alcohols), poly(ethylene-vinyl acetates), polyethylene terephthalates, polyvinylidene chlorides, maleic anhydride-grafted polyolefins, polyesters, and ionomers, and b) aluminum metal and/or tin metal.

17. A packaging film, comprising the laminated multilayer polymer containing film (P) according to claim 1.

18. A retortable packaging film, comprising the laminated multilayer polymer containing film (P) according to claim 1, wherein the laminated multilayer polymer containing film (P) comprises aluminum.

19. A laminated multilayer polymer containing film (P) consisting of: (I) at least one layer consisting of at least one copolyamide, wherein the at least one copolyamide is prepared by polymerizing the following components: (A) 15% to 84% by weight of at least one lactam, and (B) 16% to 85% by weight of a monomer mixture (M) comprising the following components: (B1) at least one C.sub.32-C.sub.40 dimer acid, and (B2) at least one C.sub.4-C.sub.12 diamine, where the percentages by weight of components (A) and (B) are each based on the sum total weight of components (A) and (B), and (II) at least one further layer, wherein the at least one further layer is at least one selected from the group consisting of (i) at least one further polymer (FP) selected from the group consisting of polyolefins, poly(ethylene-vinyl alcohols), poly(ethylene-vinyl acetates), polyethylene terephthalates, polyvinylidene chlorides, maleic anhydride-grafted polyolefins, polyesters, and ionomers, and (ii) aluminum metal and/or tin metal; and (III) optionally one or more additives selected from the group consisting of stabilizers, dyes, antistats, tackifiers, anti-blockers, processing auxiliaries, antioxidants, light stabilizers, UV absorbers, lubricants, nucleating aids, and combinations thereof.

20. The laminated multilayer polymer containing film (P) according to claim 19, wherein the at least one further layer is selected from the group consisting of (i) at least one further polymer (FP) selected from the group consisting of poly(ethylene-vinyl alcohols), poly(ethylene-vinyl acetates), polyethylene terephthalates, polyvinylidene chlorides, maleic anhydride-grafted polyolefins, polyesters, and ionomers, and (ii) aluminum metal and/or tin metal.

Description

EXAMPLES

(1) The properties of the polymer films (P) were determined as follows:

(2) The viscosity number of copolyamides comprising units derived from a C.sub.32-C.sub.40 dimer acid was determined in a 0.5% by weight solution of phenol/o-dichlorobenzene in a weight ratio of 1:1 at 25° C.

(3) The viscosity number of polyamides that do not comprise any units derived from a C.sub.32-C.sub.40 dimer acid was determined in a 0.5% by weight solution in 96% by weight sulfuric acid at 25° C. according to EN ISO 307: 2007+Amd 1: 2013.

(4) The glass transition temperatures and melting temperatures were determined according to ISO 11357-1: 2009, ISO 11357-2: 2013 and ISO 11357-3: 2011. For this purpose, two heating runs were conducted and the glass transition and melting temperatures were ascertained from the second heating run.

(5) The densities of the polyamides were determined by the gas pycnometer method according to EN ISO 1183-3: 1999.

(6) For determination of the proportion of polyamide 6.36 in the copolyamide, the copolyamide was hydrolyzed in dilute hydrochloric acid (20%). This protonates the units derived from hexamethylenediamine, with the chloride ion from the hydrochloric acid forming the counterion. By means of ion exchanger, this chloride ion was then exchanged for a hydroxide ion with release of hexamethylenediamine. By titration with 0.1 molar hydrochloric acid, the hexamethylenediamine concentration is then determined, from which the proportion of polyamide 6.36 in the copolyamide can be calculated.

(7) Tear propagation resistance is determined according to Elmendorf, DIN ISO 6383-2: 2004 in extrusion direction (MD) and at right angles thereto (TD). The films were conditioned under standard climatic conditions for non-tropical countries according to DIN EN ISO 291: 2008.

(8) Modulus of elasticity is determined according to ISO 527-3: 1995.

(9) The impact resistance of the polymer film (P) was determined according to DIN ISO 7765-2: 1994 with 5 specimens at a relative air humidity of 50%, with reporting of the puncture energy in the present context.

Preparation of Films

(10) For the preparation of certain films, the following polymers and metal components were used:

Polyamides

(11) A-1 nylon-6 from BASF SE, sold under the Ultramid® B36L brand name, with a viscosity number of 218 mL/g, a glass transition temperature of 57° C., a melting temperature of 220° C. and a density of 1.153 g/mL.

(12) Copolyamides with Dimer Acid:

(13) C-1 A copolyamide of nylon-6 and polyamide 6.36, prepared by the following method:

(14) 932 kg of caprolactam (component (A)), 323.2 kg of Pripol® 1009 from Croda (C36 dimer acid, hydrogenated, component (B1)), 77.84 kg of 85% by weight hexamethylenediamine solution (component (B2)) in water and 153 kg of water were mixed in a 1930 L tank and blanketed with nitrogen. The outside temperature of the tank was heated to 290° C. and the mixture was stirred at this temperature for 11 hours. In the first 7 h the mixture was stirred at elevated pressure, in the next 4 hours under reduced pressure, during which water formed was distilled off. The copolyamide obtained was discharged from the tank, extruded and pelletized. The pellets of the copolyamide obtained were extracted with water at 95° C. for 4×6 hours and then dried at 90° C. to 140° C. in a nitrogen stream for 10 hours. The copolyamide obtained had a viscosity number of 259 mL/g, a glass transition temperature of 38° C. and a melting temperature of 188° C. The proportion of polyamide 6.36 in the copolyamide, based on the total weight of the copolyamide, was 30.3% by weight; the density was 1.076 g/mL.

(15) Production of Monofilms by a Casting Process:

(16) The monofilms LA-1, LA-2, LC-1 and LC-2, having the thicknesses as described below were prepared by extrusion of the respective polymers as described below on a Battenfeld cast extrusion line with an extruder of 45 mm in diameter and a throughput of 10 kg/h. The chill roll was cooled to 20° C. The films had a width of 250 mm.

(17) LA-1: Nylon-6 film produced from polyamide A-1 in a thickness of 25 μm.

(18) LA-2: Nylon-6 film produced from polyamide A-1 in a thickness of 95 μm.

(19) LC-1: Copolyamide film produced from copolyamide C-1 in a thickness of 25 μm.

(20) LC-2: Copolyamide film produced from copolyamide C-1 in a thickness of 95 μm.

(21) Further Films were Commercially Obtained as Follows:

(22) FPL-1: Aluminum film in 9 μm thickness and 250 mm width from Amcor Flexibles® Italia S.R.L.

(23) FPL-2: Polyethylene terephthalate (PET) film in 12 μm thickness and 250 mm width from Mitsubishi® sold under the name Hostaphan® RNK.

(24) FPL-3: Cast Polypropylene film in 60 μm thickness and 250 mm width from Mitsui Chemicals sold under the name RXC-22.

Preparation of Laminated Films (P)

(25) The respective selection of above described films LA-1, LA-2, LC-1, LC-2, FPL-1, FPL-2 and FPL-3 as shown in the tables below, were sequentially laminated on a DRYTEC laboratory dryer in a film width of 250 mm and an oven length of 4 m with 4 g/m.sup.2 glue (described below). The temperature of the first dryer was 80° C., the temperature of the second dryer was 60° C. The laminating speed was 20 m/min, and the lamination itself were run at 50° C. and a pressure of 5 bar with the glue Epotal® CF 605 containing 4.75% Basonat® LR 9056, both commercially available from BASF SE. After lamination, the film was run over a chill roll of 20° C.

(26) The properties of the laminated films (P) are shown in Tables 1 to 3.

(27) TABLE-US-00001 TABLE 1 V1 B2 Film Structure FLP-2/LA-2 FLP-2/LC-2 Modulus of elasticity (MD) [MPa]  988 790 Modulus of elasticity (TD) [MPa] 1010 840 Tear propagation [mN] 2980 (8N 3377 (8N resistance (MD) pendulum) pendulum) Tear propagation [mN] 1987 (8N 2754 (8N resistance (TD) pendulum) pendulum)

(28) TABLE-US-00002 TABLE 2 V3 B4 Film Structure FLP-2/LA-1/ FLP-2/LC-1/ FLP-3 FLP-3 Modulus of elasticity (MD) [MPa] 1160 1050 Modulus of elasticity (TD) [MPa] 1080 1040 Tear propagation [mN] 2394 (8N 10656 (32N resistance (MD) pendulum) pendulum) Tear propagation [mN] 1527 (8N 2061 (8N resistance (TD) pendulum) pendulum) Puncture energy [N]  244  246

(29) TABLE-US-00003 TABLE 3 V5 B6 Film Structure FLP-2/FLP-1/ FLP-2/FLP-1/ LA-1/FLP-3 LC-1/FLP-3 Modulus of elasticity (MD) [MPa] 1060 991 Modulus of elasticity (TD) [MPa] 1010 964 Tear propagation [mN] 1563 (8N 5593 (8N resistance (MD) pendulum) pendulum) Tear propagation [mN] 2593 (8N 3923 (8N resistance (TD) pendulum) pendulum) Puncture energy [N]  230 258

(30) As can be seen from the above Tables 1 to 3, at least the tear propagation resistances (MD, TD) of laminated films (P) containing LC-1, respectively LC-2, are significantly higher.