EP1360241A1

EP1360241A1 - Co-extruded, multi-layered, biaxially-oriented weldable flat film for the production of welded tubular films and use thereof

Info

Publication number: EP1360241A1
Application number: EP01915181A
Authority: EP
Inventors: Hartmut Grund; Horst Lang; Helmut Schauer
Original assignee: Naturin GmbH and Co; Naturin Werk Becker and Co
Current assignee: Naturin GmbH and Co; Naturin Werk Becker and Co
Priority date: 2001-02-01
Filing date: 2001-02-01
Publication date: 2003-11-12
Also published as: NO20024712D0; US6994912B2; BR0109742A; WO2002060991A1; MXPA03006762A; HUP0300964A2; NO20024712L; PL362480A1; CA2434588A1; US20040067381A1; CZ20032128A3

Abstract

The invention relates to a co-extruded, multi-layered, biaxially-oriented and weldable flat film for the production of welded tubular films and use thereof for the wrapping and packaging of foodstuffs. Said weldable flat film comprises two weldable surface layers, made from at least one co-polyamide and at least one amorphous polyamide and/or at least one homo-polyamide and/or at least one modified polyolefin.

Description

Coextruded, multilayer, biaxially stretched, weldable flat film for the production of welded tubular films and their use

The invention relates to a coextruded, multilayer, biaxially stretched, weldable flat film, from which tubular films are produced in a known manner by welding, which are used for packaging and wrapping foodstuffs, in particular pasty foodstuffs.

Multilayer biaxially stretched flat films which are produced either by coextrusion of a tubular film and cutting open the tube or by direct coextrusion of a flat film are known. Such multilayer flat films can be used to produce tubular films by welding for packaging purposes of all kinds, either by bending the flat film together in a known manner to form a tube and by connecting the abutting opposite edges to one another by a sealing strip running in the longitudinal direction. A second possibility is to bend the flat film together to form a tube by letting the opposite edges overlap and by welding the overlapping areas together. The third possibility of forming a tubular film from a flat film is to bend the flat film together to form a tubular film and to weld opposite edge regions to one another along the longitudinal axis, a longitudinal fold being formed in which the same sides of the flat film lie against one another.

In addition to high water vapor and oxygen permeability, such films must meet high requirements with regard to weldability, in particular strength of the weld seam.

The object of the invention is therefore to provide a flat film which fulfills the above-mentioned requirements.

This object is achieved by a multilayer, biaxially stretched flat film, in which the two weldable surface layers consist of at least one copolyamide and at least one amorphous polyamide and / or at least one homopolyamide and / or at least one modified polyolefin, and the at least one between the two weldable surface layers contains another layer. The surface layers are made up of at least one sealable copolyamide. Such known copolyamides are prepared from monomers selected from the group consisting of caprolactam, laurolactam, omegaaminoundecanoic acid, adipic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, terephthalic acid, isophthalic acid, tetramethylenediamine, pentamethylenediamine and octamethylenediamine, hexamethylene diamine, octamethylene diamine, octamethylene diamine, octamethylene diamine, hexamethylene diamine, octamethylene diamine, hexamethylene diamine, octamethylene diamine, and hexamethylene diamine, hexamethylene diamine, octamethylene diamine, hexamethylene diamine, octamethylene diamine, and hexamethylene diamine, hexamethylene diamine, octamethylene diamine, octamethylene diamine, and hexamethylene diamine, hexamethylene diamine, hexamethylene diamine, octamethylene diamine, and hexamethylene diamine, octamethylene diamine, hexamethylene diamine, hexamethylene diamine, hexamethylene diamine, and hexamethylene diamine, and The wall thickness of the respective surface layer is between 5 and 16 μm.

Surprisingly, the addition of an amorphous polyamide and / or a homopolyamide and / or a modified polyolefin to a copolyamide in the surface layer significantly increases the seal seam strength compared to pure copolyamide, or high seal seam strengths are achieved even at lower sealing temperatures. The film according to the invention thus has considerable advantages in terms of application technology.

The amorphous polyamides used for the surface layer are polyamides whose glass transition temperature in the dry state is between 50 and 200 ° C. Examples include polyamide 6I / 6T, polyamide 6-3 -T and polyamide 61.

Polyamides which can be prepared from the same monomers as the copolyamides already described above are used as homopolyamides for the surface layer. The homopolyamides can have both aliphatic and partly aromatic character.

The modified polyolefins are copolymers of ethylene or propylene and optionally further linear alpha olefins having 3 to 8 carbon atoms with alpha-beta unsaturated carboxylic acids, preferably acrylic acid, methacrylic acid and / or their metal salts and / or their alkyl esters or corresponding graft copolymers of the monomers mentioned with polyolefins or partially saponified ethylene / vinyl acetate copolymers which are optionally graft-polymerized with an alpha-beta-unsaturated carboxylic acid and have a low degree of saponification or mixtures thereof. Furthermore, the modified polyolefins can be modified homo- or copolymers of ethylene and / or propylene and, if appropriate, further linear alpha-olefins having 3 to 8 carbon atoms, which are Contain monomers from the group of the alpha-beta-unsaturated dicarboxylic acids, preferably maleic acid, fumaric acid, itaconic acid or their acid anhydrides, grafted esters, acid amides or acid imides.

The main component of the respective surface layer is a sealable copolyamide or a mixture of sealable copolyamides, this main component being present in amounts between 50 and 95% by weight. The other components, amorphous polyamide, homopolyamide and modified polyolefin, can be mixed with the main constituent in amounts of 0 to 30% by weight, based on the entire surface layer.

At least one further layer is located between the two surface layers of the flat film according to the invention. The additional layer or layers arranged between the two surface layers serve to give the flat film, in addition to the weldability, other desired properties such as a high barrier to oxygen and water vapor, high puncture resistance or good mechanical properties.

Materials that can form the layers between the two surface layers are polyamides, polyolefins, modified polyolefins and ethylene vinyl alcohol copolymers. Mixtures of these materials with one another can also be used. Additional layers of adhesion promoters may also be present if adjacent layers do not have sufficient adhesion to one another.

Polyamides as the intermediate layer can be homo- and / or copolyamides which are produced from monomers which are selected from the group caprolactam, laurolactam, omegaaminoundecanoic acid, adipic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, terephthalic acid, isophthalic acid, tetramethylene diamine, tetramethylene diamine Octamethylenediamine and xylylenediamine. Preferred homo- and copolyamides are polyamide 6, polyamide 12, polyamide 66, polyamide 610, polyamide 612, polyamide MXD6, polyamide 6/66, polyamide 6/12 and polyamide 6I / 6T. The wall thickness of the polyamide intermediate layer is between 5 and 30 μm.

Polyolefins as an intermediate layer are homopolymers of ethylene or propylene and / or copolymers of linear alpha olefins with 2 to 8 carbon atoms. Preferably for this Layer of linear low density polyethylene, high density polyethylene, polypropylene homopolymer, polypropylene block and polypropylene random copolymer used. The wall thickness of the polyolefin intermediate layer is between 5 and 30 μm.

The modified polyolefins as the intermediate layer are copolymers of ethylene or propylene and optionally further linear alpha olefins having 3 to 8 carbon atoms with alpha-beta-unsaturated carboxylic acids, preferably acrylic acid, methacrylic acid and / or their metal salts and / or their alkyl esters or Corresponding graft copolymers of the monomers mentioned onto polyolefins or partially saponified ethylene-vinyl acetate copolymers, which are optionally graft-polymerized with an alpha-beta-unsaturated carboxylic acid and have a low degree of saponification or mixtures thereof. Furthermore, the modified polyolefins can be modified homo- or copolymers of ethylene and / or propylene and, if appropriate, further linear alpha-olefins having 3 to 8 carbon atoms, the monomers from the group of the alpha-beta-unsaturated dicarboxylic acids, preferably maleic acid, fumaric acid, itaconic acid or their acid anhydrides , Acid esters, acid amides or acid imides grafted on. The wall thickness of the intermediate layer made of modified polyolefin is between 5 and 30 μm.

The ethylene vinyl alcohol copolymers as an intermediate layer are produced by completely saponifying copolymers of ethylene with vinyl acetate. In general, the ethylene content in the ethylene-vinyl alcohol copolymers is between 27 and 48 mol%. For the intermediate layer, ethylene-vinyl alcohol copolymers are preferred, the ethylene content of which is between 34 and 48 mol%. The wall thickness of the intermediate layer made of ethylene vinyl alcohol copolymer is between 3 and 20 μm.

If adhesion promoters are used in the intermediate layer, these are homopolymers or copolymers of ethylene and / or propylene and, if appropriate, further linear alpha-olefins having 3 to 8 carbon atoms, the monomers from the group of the alpha-beta-unsaturated dicarboxylic acids, preferably maleic acid , Fumaric acid, itaconic acid or their acid anhydrides, acid esters, acid amides or acid imides grafted on. Preferred sequences of the individual layers in the multilayer flat films according to the invention are given below, the letters and numbers having the following meanings:

A: Weldable surface layer

B: polyamide intermediate layer

C: Interlayer polyolefin

D: Modified polyolefin intermediate layer

E: ethylene vinyl alcohol intermediate layer

F: Intermediate layer of adhesion promoter

The number indices 1,2 denote several layers from the same raw material class.

Three-layer structure:

AIBAS; A.DA ₂ ; A _t EA2

Four-layer structure:

A.BDA ₂ ; AιBEA ₂ ; A1DEA2

Five-layer structure:

AιF! CF ₂ A ₂ ; AJFJBFJAZ; AiFiBEAa; A ₁ DBEA ₂ ; AiFiEFzAj;

Six-layer structure:

AiEBFDAj; A1F1EBF2A2; AjDiEBDΣAj; AιFιCF ₂ EA ₂ ; AιBιEDB A2; AιBDιCD ₂ A ₂ ;

Seven-layer structure:

AιD _l BιEB ₂ D ₂ A ₂ ; A ₁ FB ₁ EB ₂ DA ₂ ; A! FιEF ₂ BDA ₂ ; AιF _! EDCF ₂ A ₂ The flat film may also contain customary auxiliaries, for example antiblocking agents, stabilizers, antistatic agents or lubricants. These auxiliaries are usually added in amounts of 0.1 to 5% by weight. Furthermore, the film can be colored by adding pigments or pigment mixtures.

The flat films according to the invention can be produced by two methods known per se. On the one hand, a primary tube with the desired number of layers can be produced by coextrusion, which is then biaxially stretched and heat-set. The tubular film obtained is then cut open on the long side and results in the desired flat film. In the second method, a flat film with the desired number of layers and with a higher wall thickness is produced directly by coextrusion, which is then biaxially stretched and heat-set and directly yields the desired flat film. Both methods make it possible to produce wide flat films that are too wide for use in packaging and wrapping food. In this case, it is possible to cut the wide flat films in the longitudinal direction into narrower panels, which can then be welded to tubular films of the desired dimension.

The tubular films according to the invention have total wall thicknesses of 30 to 100 μm, preferably 40 to 80 μm.

Weld strengths were determined on the tubular films according to the invention and on the comparative example.

To determine the weld seam strength, 50 mm wide strips were taken from the respective flat foils transversely to the running direction. In each case two strips were welded to one another, welding on the one hand overlapping surface layer 1 with surface layer 2 (welding method 1) and welding on the other hand with surface layer 1 lying on top of one another (welding method 2). A SGPE 20 laboratory welding machine from W. Kopp Verpackungsmaschinen served as the welding machine. 25 mm wide strip samples were taken from the welded samples in such a way that the weld seam was transverse to the longitudinal direction of the strip. The strip samples were on a tensile testing machine from Instron with a Pull-off speed of 500 mm / min pulled apart until the weld seam breaks. The maximum force achieved is referred to below as weld strength.

At a sealing temperature of 120 ° C., welded according to welding method 1, the flat films according to the invention show significantly higher weld seam strengths than the comparative example. In test specimens produced according to welding method 2, significantly better weld seam strengths are achieved both at 180 and 200 ° C sealing temperature than in the comparative example.

The invention is illustrated by the following examples:

Example 1 :

Five-layer flat film:

The individual polymers for the different layers were plasticized and homogenized in five extruders on a tubular film coextrusion system. The five melt streams were fed to a five-layer extrusion head in accordance with the desired individual wall thickness ratios and formed into a primary tube, biaxially stretched and heat-set. The primary pipe had a diameter of 67.5 mm and an average total wall thickness of 0.68 mm. It was heated to 122 ° C. with infrared radiation and stretched with an area stretch ratio of 10.4. The biaxially stretched tube was heat set, laid flat and wound up. The mean total wall thickness of the hose was 65 μm. The lying width was 356 mm.

The layers of the finished hose consisted of the following polymers with the specified individual wall thicknesses:

1st layer (outer layer): mixture 90% polyamide 6/12, Grilon CF6S from EMS-

Chemistry and 10% ionomer resin, Surlyn 1652 from Du Pont de Nemours GmbH, 10 μm 2nd layer: adhesion promoter, modified polyethylene, Admer NF 478 E der

Mitsui Chemicals Inc., 15 μm

3rd layer: polyamide 6, Durethan B 40 F from Bayer AG, 14 μm

4th layer: adhesion promoter (like 2nd layer), 15 μm

5th layer (inner layer): mixture 90% polyamide 6/12, Grilon CF6S from EMS-

Chemistry and 10% ionomer resin, Surlyn 1652 from Du Pont de Nemours GmbH, 10 μm

The coextruded tubular film was cut open and wound up as a flat film.

The following values for the weld seam strength were determined: Welding method 1:

Sealing temperature 120 ° C: 181 N / 25 mm. Sealing temperature 200 ° C: 115 N / 25 mm

Welding method 2:

Sealing temperature 180 ° C: 93 N / 25 mm

Sealing temperature 200 ° C: 94 N / 25 mm

Example 2:

Five-layer flat film:

The individual polymers for the different layers were plasticized and homogenized in five extruders on a tubular film coextrusion system. The five melt streams were fed to a five-layer extrusion head in accordance with the desired individual wall thickness ratios and formed into a primary tube, biaxially stretched and heat-set. The primary pipe had a diameter of 67.5 mm and an average total wall thickness of 0.66 mm. It was heated to 126 ° C. with infrared radiation and stretched with an area stretch ratio of 10.1. The biaxially stretched The tube was heat set, laid flat and wound up. The mean total wall thickness of the hose was 65 μm. The lying width was 355 mm.

1st layer (outer layer): Mix 85% polyamide 6/12, Grilon CF6S from EMS-

Chemistry and 5% polyamide 61161, Grivory G21 from EMS-Chemie and 10% ionomer resin, Surlyn 1652 from Du Pont de Nemours GmbH, 10 μm

2nd layer: ethylene vinyl alcohol copolymer, Soarnol AT4406 from

Nippon Gohsei, 6 μm

3rd layer: polyamide 6, Durethan B 40 F from Bayer AG, 19 μm

4th layer: adhesion promoter, modified polyethylene, Bynel 4140 from

Du Pont de Nemours GmbH, 20 μm

5th layer (inner layer): mixture 85% polyamide 6/12, Grilon CF6S from EMS-

Chemistry and 5% polyamide 6I / 6T, Grivory G21 from EMS-Chemie and 10% ionomer resin, Surlyn 1652 from Du Pont de Nemours GmbH, 10 μm

The coextruded tubular film was cut open and wound up as a flat film.

Seal temperature 120 ° C: 190 N / 25 mm Seal temperature 200 ° C: 115 N / 25 mm

Welding method 2:

Sealing temperature 180 ° C: 86 N / 25 mm Sealing temperature 200 ° C: 96 N / 25 mm

Comparative example

A five-layer flat film was produced as in Example 1, with the difference that the first and fifth layers consisted of pure polyamide 6/12, Grilon CF6S from EMS-Chemie.

Sealing temperature 120 ° C: 167 N / 25 mm. Sealing temperature 200 ° C: 114 N / 25 mm

Welding method 2:

Sealing temperature 180 ° C: 78 N / 25 mm

Sealing temperature 200 ° C: 80 N / 25 mm

Claims

claims:

1. Coextruded, multilayer, biaxially stretched, weldable flat film for the production of welded tubular films, characterized in that the two surface layers of the flat film are weldable and made of at least one copolyamide and at least one amorphous polyamide and or at least one homopolyamide and / or at least one modified polyolefin consist.

2. Flat film according to claim 1, characterized in that the copolyamides of the surface layers are made from monomers selected from the group prolactam, laurolactam, omegaaminoundecanoic acid, adipic acid, azelaic acid, sebazic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, terephthalic acid, isophthalic acid, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, octamethylene diamine and xylylenediamine.

3. Flat film according to claim 2, characterized in that the copolyamides are present in the surface layers each in amounts of 50 to 95% by weight.

4. Flat film according to one of claims 1 to 3, characterized in that the surface layers contain amorphous polyamides whose glass transition temperature in the dry state is between 50 and 200 ° C.

5. Flat film according to claim 4, characterized in that the glass transition temperature of the amorphous polyamides is preferably between 90 and 160 ° C.

6. Flat film according to one of claims 1 to 5, characterized in that the surface layers contain homopolyamides which are made from monomers which are selected from the group caprolactam, laurolactam, omegaaminoundecanoic acid, adipic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, terephthalic acid, Isophthalic acid, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, octamethylene diamine and xylylene diamine.

, Flat film according to one of claims 1 to 6, characterized in that the surface layers contain modified polyolefins, the copolymers of ethylene or propylene and optionally further linear alpha olefins having 3 to 8 carbon atoms with alpha-beta-unsaturated carboxylic acids, preferably acrylic acid, methacrylic acid and / or their metal salts and / or their alkyl esters or corresponding graft copolymers of the monomers mentioned onto polyolefins or partially saponified ethylene / vinyl acetate copolymers, which are optionally graft-polymerized with an alpha-beta-unsaturated carboxylic acid and have a low degree of saponification or mixtures thereof.

8. Flat film according to claims 1 to 7, characterized in that the further components contained in the surface layers, amorphous polyamide, homopolyamide and modified polyolefin, in amounts of 0 to 30% by weight, based on the respective surface layer, can be admixed ,

9. Flat film according to claims 1 to 8, characterized in that the wall thickness of the respective surface layer is between 5 and 16 microns.

10. Flat film according to claim 1, characterized in that there is at least one further layer between the surface layers.

11. Flat film according to claims 1 to 10, characterized in that the further layer or layers arranged between the surface layers consist of materials or mixtures thereof, which are selected from the groups of polyamides, polyolefins, modified polyolefins and ethylene vinyl alcohol. copolymers.

12. Flat film according to claims 1 to 11, characterized in that the further layer arranged between the surface layers of polyamide consists of at least one homopolyamide and / or at least one copolyamide, which are made from monomers selected from the group caprolactam, laurolactam , Omega aminoundecanoic acid, adipic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, terephthalic acid, isophthalic acid, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, octamethylene diamine and xylylene diamine.

13. Flat film according to claim 12, characterized in that the wall thickness of the polyamide layer is between 5 and 30 microns.

14. Flat film according to claims 1 to 13, characterized in that the further layer of polyolefin arranged between the surface layers is composed of homopolymers of ethylene or propylene and / or copolymers of linear alpha olefins having 2 to 8 carbon atoms.

15. Flat film according to claim 14, characterized in that the wall thickness of the polyolefin layer is between 5 and 30 μm.

16. Flat film according to claims 1 to 15, characterized in that the further layer of modified polyolefin arranged between the surface layers of copolymers of ethylene or propylene and optionally further linear alpha olefins having 3 to 8 carbon atoms with alpha-beta-unsaturated carboxylic acids such as Acrylic acid, methacrylic acid and / or their metal salts and / or their alkyl esters or corresponding graft copolymers of the monomers mentioned on polyolefins or partially saponified ethylene / vinyl acetate copolymers, which are optionally graft-polymerized with an alpha-beta-unsaturated carboxylic acid and have a low degree of saponification or mixtures thereof is.

17. Flat film according to claim 16, characterized in that the wall thickness of the modified polyolefin layer is between 5 and 30 microns.

18. Flat film according to claims 1 to 17, characterized in that the further layer of ethylene vinyl alcohol copolymer arranged between the surface layers contains a copolymer whose ethylene content is between 27 and 48 mol%, preferably between 34 and 48 mol%.

19. Flat film according to claim 18, characterized in that the wall thickness of the ethylene-vinyl alcohol copolymer layer is between 3 and 20 μm.

0. Flat film according to claims 1 to 19, characterized in that modified homopolymers or copolymers of ethylene and / or propylene and optionally further linear alpha-olefins having 3 to 8 carbon atoms, the monomers from the group of the alpha-beta, as adhesion promoters unsaturated dicarboxylic acids, such as maleic acid, fumaric acid, itaconic acid or their acid anhydrides, containing grafted acid esters, acid amides or acid imides.

21. Flat film according to claim 20, characterized in that the wall thickness of the adhesive layer is between 3 and 20 microns.

22. Flat film according to claims 1 to 21, characterized in that the total wall thickness is 30 to 100, preferably 40 to 80 microns.

23. Multi-layer, weldable flat film, produced by coextrusion of a flat film with subsequent biaxial stretching and heat setting.

24. Multi-layer, weldable flat film, produced by coextrusion of a tubular film with subsequent biaxial stretching and heat setting and cutting the tubular film into a flat film.

25. Use of a flat film according to one of claims 1 to 24 for the production of a tubular film.

26. Use of a tubular film according to claim 25 for the packaging and wrapping of food.