EP1497120A2 - Enveloppe d'emballage tubulaire multicouche - Google Patents

Enveloppe d'emballage tubulaire multicouche

Info

Publication number
EP1497120A2
EP1497120A2 EP03722404A EP03722404A EP1497120A2 EP 1497120 A2 EP1497120 A2 EP 1497120A2 EP 03722404 A EP03722404 A EP 03722404A EP 03722404 A EP03722404 A EP 03722404A EP 1497120 A2 EP1497120 A2 EP 1497120A2
Authority
EP
European Patent Office
Prior art keywords
layer
aliphatic
cycloolefinic
copolymer
sausage
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP03722404A
Other languages
German (de)
English (en)
Inventor
Ekkehard Beer
Wolfram Goerlitz
Bernd Hoecker
Dieter Flieger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Topas Advanced Polymers GmbH
Original Assignee
Ticona GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ticona GmbH filed Critical Ticona GmbH
Publication of EP1497120A2 publication Critical patent/EP1497120A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • 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
    • B32B1/00—Layered products having a non-planar shape
    • B32B1/08—Tubular products
    • 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
    • B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a multilayer, tubular packaging casing for pasty filling material, in particular artificial sausage casing based on a cycloolefinic copolymer. It essentially consists of an outer layer based on aliphatic polyamide, aliphatic copolyamide and / or cycloolefinic copolymer or a polymer mixture of at least one of these compounds, a middle layer which either consists of EVOH or else at least one partially crystalline polyolefin and from more than 5% by weight of at least one cycloolefinic copolymer and, if appropriate, adhesion-promoting component and an inner layer based on aliphatic and / or partially aromatic polyamides and / or aliphatic and / or partially aromatic copolyamides and / or cycloolefinic copolymer and, if appropriate, adhesion mediating layer between the outer and inner layer.
  • Casings based on polyamide are increasingly used for packaging food, in particular as artificial sausage casings.
  • a casing material is required for different types of sausage, which has a low water vapor permeability, so that the weight loss when storing the sausage due to water release of the sausage mass remains as small as possible.
  • the sausage then shows a wrinkle-free, tight-fitting casing even after prolonged storage; there are no gaps between the sausage mass and the inside of the casing, which leads to jelly sales of the sausage mass.
  • EP-A-0 305 959 describes a multilayer polyamide film which, for. B. is provided in the form of a heat sealable bag for packaging meat and poultry. It consists of a barrier layer for oxygen from a partially aromatic copolyamide (PA 6I / 6T), which consists of units of hexamethylenediamine, terephthalic acid and isophthalic acid. This copolyamide layer forms the core layer of the film.
  • PA 6I / 6T partially aromatic copolyamide
  • polyolefin layers which form a water vapor barrier, the inner polyolefin layer being intended to prevent the escape of moisture from the packaged food into the core layer made from copolyamide.
  • Pure polyolefin layers are disadvantageous as the inside of sausage casings because they lead to insufficient adhesion between the sausage mass and the inner wall of the sausage casing and promote jelly sales.
  • EP-A-0 467 039 attempts to solve the disadvantages mentioned by means of a multilayer film structure based on polyamide, an outer layer consisting of aliphatic polyamide, aliphatic copolyamide or a polymer mixture.
  • Another layer based on polyethylene or polypropylene or mixtures of these polymers is to take on the function of the water vapor barrier. It turns out, however, that these polymers only adequately fulfill the barrier effect against water vapor, alone or in a mixture, if they are present in such a film structure in a sufficient layer thickness.
  • the increased layer thickness of these polymers is also necessary in order to give the tubular packaging envelope the necessary rigidity so that the pasty filling material remains in a defined shape.
  • the present invention is therefore based on the object of providing a tubular packaging casing which, after being filled, has sufficient adhesion to the coated filling material, in particular sausage mass, has little or no jelly sales, and has sufficient rigidity to give the filling material in a defined form hold, the shirring process of the casing can be carried out without the addition of anti-blocking agents and no additional pretreatment of the inside of the casing is necessary.
  • the casing should be easy to use as an artificial sausage casing, especially for cooked and cooked sausages. It should have a greatly reduced permeability with respect to water vapor and atmospheric oxygen.
  • Sausages with this coating should not show any noticeable loss of moisture even after four to six weeks of storage, which is reflected in a decrease in the weight of the sausage and a wrinkled appearance, nor should peeling of the casing from the sausage mass between the casing wall and the sausage mass should result in jelly drop.
  • the envelope is also intended for oxygen-tight packaging of air-sensitive goods, such as. B. sausage masses of the liver sausage type, be suitable so that they do not change during the storage period, especially not discolour in an unsightly manner.
  • a multilayer, tubular packaging envelope for pasty filling material characterized in that it is essentially composed of: an outer layer based on aliphatic polyamide, aliphatic copolyamide, and / or cycloolefinic copolymer or a polymer mixture containing at least one of these connections; a middle layer, which either consists of ethyl vinyl alcohol or contains at least a partially crystalline polyolefin and at least 5% by weight of a cycloolefinic copolymer and adhesion-promoting components if there is no adhesion-promoting agent between the outer and / or inner layer and the middle layer Layer is located; an inner layer based on aliphatic and / or partially aromatic polyamides and / or aliphatic and / or partially aromatic copolyamides and / or cycloolefinic copolymer and at least one adhesion-promoting layer which is located between the outer and / or inner layer and the middle layer if the middle layer
  • the casing shows a wall thickness which is comparatively very thin for multilayer packaging casings made of polyolefins and polyamide with good barrier properties, which is essentially due to the use of the cycloolefinic copolymer. It is preferably 30 to 60, in particular 40 to 50, micrometers. The lower limit is around 25 to 30 micrometers.
  • the hose caliber is adapted to the intended use. When using the casing for cooked and cooked sausages, the tube caliber is generally 30 to 160, in particular 40 to 135 mm.
  • the proportion of the outer layer in the total thickness of the shell is 45 to 80%, the middle layer 15 to 75% and the inner layer 2 to 35%.
  • the proportion of optional additional adhesion-promoting layers is between 0 and 35%.
  • the packaging wrapper consists of at least three layers, namely an outer, a middle and an inner layer, the outer and the inner layer made of polyamides, optionally and / or cycloolefinic copolymer, and the middle layer made of a polymer mixture of a cycloolefinic copolymer and another, partly crystalline Polyolefins exist. If necessary, the three-layer structure is expanded to a five- or multi-layer structure in which there is at least one layer around the middle layer that improves the adhesion of the middle layer to the inner and outer layer or other intermediate layers.
  • the middle layer usually has the greatest thickness compared to the other layers.
  • the thickness is generally 10 to 50 ⁇ m with a total thickness of the film of 25 to 60 ⁇ m. This layer can therefore generally be regarded as the actual carrier layer of the multilayer casing.
  • the middle layer of the packaging envelope shows practically no water and water vapor absorption and, above all, practically no water vapor permeability.
  • the middle layer should have a minimum thickness of 2 ⁇ m. In general, a thickness of 5 to 25 ⁇ m is sufficient to achieve the water vapor impermeability required for sausage casings for scalded and cooked sausages.
  • the middle layer consists of a mixture of a cycloolefinic copolymer and partially crystalline polyolefin and optionally an adhesion-promoting component, which improves the adhesion between the inner or outer layer with the middle layer.
  • the middle layer is made up of a single layer
  • the middle layer preferably consists of a polyolefin core and in each case a layer of polyolefin / adhesion promoter or only adhesion promoter on the surfaces of the polyolefin core, so that in the first case one a total of three layers, in the second case a total of five layers, of the shell wall.
  • the barrier effect against water vapor as well as the mechanical stiffness in contrast to the use of conventional alpha-olefins at a given thickness, can be increased or increased significantly, e.g. greater than 25% the layer containing the cycloolefinic copolymer can be made significantly thinner in order to achieve the same barrier effect against water vapor and mechanical rigidity.
  • the glass transition temperature Tg is preferably matched to the melting points of the other, partially crystalline polymers in order to be able to ensure a homogeneous melting of the polymer mixtures.
  • the adhesion-promoting component is incorporated into the middle layer , This increases the binding force between the middle layer and the adjacent layers with a sufficient amount of the adhesion-promoting component, so that at The coextrusion of the three layers creates a firm bond, which does not experience any separation of layers even when exposed to hot water when the sausage is scalded.
  • the proportion of the adhesion-promoting components is generally 5 to 50% by weight, in particular 10 to 35% by weight, based on the polymer mixture present in the middle layer. It should be noted, however, that the water vapor permeability of the middle layer increases somewhat due to the functional groups of the adhesion promoter, which is why this addition should be as small as possible in a three-layer film structure. In general, 20 to 25% by weight, based on the polymer mixture of the middle layer, is therefore sufficient.
  • the problem of reducing the barrier effect against water vapor in the middle layer can be avoided in that the component imparting the adhesion forms its own layer. Furthermore, this layer which improves the adhesion can be made so thin that, in relation to the necessary addition of the adhesion promoter in the middle layer, smaller amounts of the adhesion promoter can be used, so that the entire film structure becomes less expensive.
  • a five- or seven-layer embodiment is preferred in which EVOH is used in the middle layer or in one of the layers on the inside.
  • the layers around the EVOH layer consist of a mixture of partially crystalline polymers and cycloolefinic copolymer.
  • the adhesion-promoting layers are in a separate form above these layers.
  • the adhesion-promoting component may be in the layer in which the cycloolefinic copolymers and partially crystalline polymers are located.
  • the outer and inner layers based on aliphatic polyamide, aliphatic copolyamide and / or cycloolefinic copolymer or a polymer mixture of at least one of these compounds are located above these layers or the adhesion-promoting layers.
  • the middle layer is a mixture containing a cycloolefinic copolymer and a partially crystalline polyolefin.
  • Suitable copolymers are C 2 / C 3 and C 3 / C 4 copolymers and C 2 / C 3 / C 4 terpolymers, e.g. B. a mixture of C 3 / C copolymer and C 2 / C 3 / C terpolymer.
  • Suitable materials are known in principle to the person skilled in the art and are described, for example, in Sachtling, Plastic Pocket Book, 27th Edition 1998 on pages 375 to 415, to which reference is made.
  • the cycloolefinic copolymer has a glass transition temperature of greater than 60 ° C., which is matched to the glass or melting temperature of the other polymers, and an average molecular weight Mw of 500 to 500,000, preferably 3,000 to 150,000.
  • the cycloolefinic copolymer is advantageously a copolymer of ethylene and / or an alpha-olefin and a cyclic, bicyclic or polycyclic olefin.
  • the cycloolefinic copolymer derived from at least one cyclic or polycyclic olefin of the formula I to VII is particularly advantageous
  • radicals R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 of the formulas I to VI may be the same or different, and H, C 6 -C 2 o-aryl, C ⁇ -C 20 alkyl, F, Cl, Br, I mean, n is an integer from 0 to 5, and m is an integer from 2 to 10, in particular copolymers of one or more of the cyclic or polycyclic olefins of the formula I to VII with ethylene.
  • the cycloolefinic copolymer is very particularly advantageously a copolymer of ethylene and norbornene.
  • the cycloolefinic copolymer is present in the middle layer in an amount of more than 5% by weight, particularly advantageously in amounts of 5 to 100% by weight, in particular 5 to 50% by weight.
  • the adhesion-promoting component is an agent as is known for the production of coextruded composites from polar and non-polar plastics such as polyamide and polyolefin. It usually consists of a polyolefin resin modified with functional groups, which is composed of ethylene and / or propylene units, optionally also further linear alpha-olefins having 3 to 10 carbon atoms.
  • the olefinic chain ensures compatibility with the polyolefin of the middle layer and the extrudability of the adhesion-promoting component.
  • the functional groups are in particular units of vinyl acetate, vinyl alcohol, ethylenically unsaturated carboxylic acids such as acrylic acid and methacrylic acid, and the esters and salts, in particular Na and Zn salts, and also also ethylenically unsaturated carboxylic acid anhydride groups. They lead to a sufficient the wettability of the polyamide and polyolefin melt during coextrusion, so that a firmly adhering bond is created.
  • Suitable adhesion promoters also consist of graft polymers, copolymers or terpolymers with ethylene or propylene units with at least one comonomer from the group comprising (meth) acrylic acid, (meth) acrylic acid esters (esters of n-alkanols with 1 to 6 carbon atoms, e.g. butyl acrylate), ethylene vinyl acetate and / or maleic anhydride.
  • the proportion of units with functional groups is usually 3 to 12% by weight, based on the weight of the adhesion-promoting polymer.
  • the modified polyolefin resins also include rubber modified polyethylene.
  • the adhesion-promoting component is present in the middle layer in an amount of 0 to 50% by weight, advantageously 5 to 50% by weight, in particular 10 to 35% by weight.
  • the casing is to be colored, it is expedient to incorporate the dye or the color pigments into the middle layer so that they do not come into direct contact with the filling material.
  • This measure has the advantage that the stretching process is not disturbed by the nucleating effect of color pigments. It has also been shown that color pigments can be dispersed particularly easily and uniformly in the middle layer.
  • the outer layer usually has an equal or less thickness in relation to the middle layer, but in special embodiments it can also be thicker than the middle layer.
  • the thickness is generally greater than 5 ⁇ m to 50 ⁇ m with a total thickness of the film of, for example, 25 to 60 ⁇ m.
  • the layer can thus either serve as a cover layer or, owing to its share of the total thickness, can sometimes assume a certain carrier function, the middle layer, as a result of the selection of the polymers, in particular the cycloolefinic copolymer and thus also the rigid polymer, generally also the carrier function of the Whole film is inside, if it should be thinner than other layers in a special embodiment.
  • the outer layer is made up of a single layer and shows a higher water absorption than the middle layer The outer layer absorbs water when the sausage is scalded or boiled, which is gradually released again when the sausage is cooled and stored. As a result, the outer layer shrinks when drying, so that the sausage casing lies tightly against the cooled sausage mass and without wrinkles.
  • the outer layer consists essentially of an aliphatic polyamide, aliphatic copolyamide and / or cycloolefinic copolymer or a polymer mixture of at least one of these compounds.
  • Polyamides of this type are known to the person skilled in the art and are described, for example, in Sachtling, Kunststoff-Taschenbuch, Hanser Verlag, 27th edition 1998 on pages 465 to 478, to which reference is made.
  • the aliphatic polyamide is a homopolycondensate of aliphatic primary diamines, in particular with 4 to 8 C atoms, and aliphatic dicarboxylic acids, in particular with 4 to 10 C atoms, or a homopolymer of omega-aminocarboxylic acids with 8 to 12 C atoms or their lactams.
  • the aliphatic copolyamide contains the same units and is e.g. a polymer based on one or different aliphatic diamines and one or different aliphatic dicarboxylic acids and / or one or different omega
  • Aminocarboxylic acids or their lactams are adipic acid, azelaic acid, sebacic acid and dodecanedicarboxylic acid, suitable diamines are tetra-, penta-, hexa- and octa-methylenediamine, and hexamethylenediamine is particularly preferred.
  • An example of omega-aminocarboxylic acids is 11-aminoundecanoic acid
  • lactams are epsilon-caprolactam and omega-laurolactam.
  • Particularly preferred aliphatic polyamides are polycaprolactam (PA 6) and polyhexamethylene adipinamide (PA 66) or mixtures of these polyamides.
  • the aliphatic copolyamide contains various of the units mentioned.
  • a preferred aliphatic copolyamide consists of caprolactam, hexamethylene diamine and adipic acid units (PA 6/66).
  • the outer layer of the tubular packaging casing has a higher water absorption capacity than the middle layer and, in a preferred embodiment, also as the inner layer, so that it functions well as a sausage casing before the filling process water and shows the required suppleness.
  • the middle layer with the reduced water absorption and water vapor permeability enhances the barrier properties with respect to the inner layer.
  • PA 6 and PA 66 which are also in a mixture with other water-absorbent polymers, including polyester, are therefore particularly suitable for the outer layer.
  • the addition of polyester facilitates the biaxial stretching of the tube, ie the required stretching force is surprisingly reduced, and the strength of the envelope is also increased overall.
  • Suitable polyesters are condensation products of diols and aromatic dicarboxylic acids, in particular terephthalic acid and optionally additionally isophthalic acid. Polyesters are known to the person skilled in the art and are described, for example, in Sachtling, Kunststoff-Taschenbuch, Hanser Verlag, 27th edition 1998 on pages 478 to 495, to which reference is made. To a small extent, the polyester can be modified with aliphatic dicarboxylic acids, such as adipic acid.
  • Polybutylene terephthalate is preferably used in the polymer mixture.
  • the proportion of the polyester ester is usually 5 to 15% by weight, based on the polymer mixture of the outer layer of the packaging casing.
  • Suitable, additional polymers are, for example, polyolefins, ie homopolymers or copolymers of alpha-olefins having 2 to 8 carbon atoms, in particular ethylene, propylene and butylene, preferably polyethylene, in particular LDPE and LLDPE, and also modified polyolefins with functional groups, such as those used in the middle layer as a suitable adhesion-promoting component, for example polyolefins with carboxyl radicals, that is to say groups which consist of acids, esters, anhydrides and salts of carboxylic acids and / or cycloolefinic copolymers.
  • the polyolefin and the modified polyolefin improve the adhesion of the outer layer to the middle layer and increase the smoothness of the casing. However, they are generally A maximum of only 3 to 10% by weight is present in the outer layer in order not to significantly impair the water absorption capacity and the strength of the outer layer.
  • the outer layer may contain conventional additives, for example matting agents, in order to reduce the gloss. Furthermore, the outer layer shows good color adhesion and can be printed on the entire surface without any problems.
  • the inner layer consists of aliphatic polyamide, aliphatic copolyamide and / or cycloolefinic copolymer or a polymer mixture of at least one of these compounds.
  • Other polymers e.g. Polyolefins, polyesters or ionomers can be present in the inner polyamide layer in a proportion of up to 15% by weight.
  • This layer thus consists of a polymer or a polymer mixture, as has already been described above for the outer layer.
  • the aliphatic polyamide of the inner layer preferably shows a lower water absorption capacity than the aliphatic polyamide of the outer layer. For the inner layer, therefore, aliphatic polyamides with relatively long methylene chains such as. B.
  • PA 11 or PA 12 or copolyamides used with these units The adhesion of the inner layer to the sausage mass can be improved by adding ionomers to the aliphatic polyamide.
  • the layer of aliphatic polyamide or copolyamide prevents direct contact between the polyolefin and the sausage mass.
  • the oxygen barrier property of this inner layer is comparatively low. If the shell is to have a reduced oxygen permeability, the inner layer consists of a partially aromatic polyamide and / or partially aromatic copolyamide or of ethyl vinyl alcohol.
  • the partially aromatic polyamide or copolyamide consists of aliphatic and aromatic units.
  • the diamine units predominantly or exclusively form the aromatic units.
  • the dicarboxylic acid units of this embodiment are predominantly or exclusively aliphatic and usually contain 4 to 10 C atoms.
  • Preferred aliphatic dicarboxylic acid units are sebacic acid and azelaic acid, in particular adipic acid.
  • the diamine units predominantly or exclusively form the aliphatic units, while the Dicarboxylic acid units consist predominantly or completely of residues of aromatic dicarboxylic acids, in particular isophthalic acid and terephthalic acid.
  • the aliphatic diamine units usually consist of 4 to 8 carbon atoms, preferably caprolactam and / or hexamethylene diamine units.
  • the preferred partially aromatic copolyamide of the second embodiment consists of caprolactam and / or hexamethylenediamine units as well as terephthalic acid and / or isophthalic acid units, in particular PA 6I / 6T.
  • the first embodiment of the partially aromatic polyamide or copolyamide optionally contains up to 5 mol% of aliphatic diamine units and up to 5 mol% of aromatic dicarboxylic acid units.
  • the second embodiment of the partially aromatic polyamide or copolyamide can contain up to 5 mol% of aromatic diamine units and up to 5 mol% of aliphatic dicarboxylic acid units.
  • inner layers made of pure partially aromatic polyamide and / or pure partially aromatic copolyamide are relatively stiff and hard and lead to the fact that the inner sides of the flattened casing lying on top of one another tend to stick together.
  • the inner layer additionally contains aliphatic polyamides and / or copolyamides.
  • the partially aromatic polyamide or copolyamide consists of the second embodiment mentioned, the partially aromatic polyamide is present in a mixture with a saturated, linear aliphatic polyamide and / or a saturated linear, aliphatic copolyamide.
  • a shell with an inner layer made of this polymer mixture is also particularly easy to stretch biaxially.
  • This additional aliphatic polyamide in the polymer mixture of the inner layer consists of the reaction product of an aliphatic dicarboxylic acid, preferably with 4 to 10 C atoms, with aliphatic primary diamines, preferably with 4 to 8 C atoms.
  • suitable dicarboxylic acids are adipic acid, azelaic acid, sebacic acid and dodecanedicarboxylic acid
  • suitable diamines are tetra-, penta-, hexa- and octa-methylenediamine, hexamethylenediamine is particularly preferred.
  • the additional aliphatic polyamide of the polyamide mixture can also be composed of units of omega-aminocarboxylic acids having 6 to 12 carbon atoms or their lactams, for example of 11- Amioundecanoic acids with 6 to 12 carbon atoms epsilon-caprolactam or omega-laurolactam.
  • the aliphatic copolyamides in the mixture with the partially aromatic polyamide or copolyamide contain various of the units of the aliphatic polyamide mentioned.
  • a preferred aliphatic copolyamide consists of caprolactam, hexamethylenediamine and adipic acid units.
  • PA 6, PA 66, PA 6/66, PA 11 and PA 12 or mixtures of these polymers are particularly preferred as an additional component in addition to the partially aromatic polyamide and / or copolyamide in the inner layer.
  • Layer is preferably 5 to 85, in particular 10 to 40 wt .-%, based on the polymer mixture of partially aromatic and aliphatic polyamides and copolyamides. In this range of the mixing ratio, a smooth, yet relatively oxygen-impermeable inner layer is achieved.
  • the proportion of the partially aromatic polyamide / copolyamide increases, the adhesion of the sausage mass to the inner wall of the casing increases, so that the casing properties can also be varied in this regard by increasing the proportion of the partially aromatic polyamide / copolyamide.
  • the proportion of COC can also be varied from 0 to 25% by weight.
  • the tubular casing is preferably produced by coextrusion of the polymers forming the individual layers through an annular nozzle, for example using a system as described in EP-A-0 305 874. Due to the biaxial stretching, the shell is oriented and consequently shows excellent resistance to deformation and elastic elasticity. The stretching takes place at 70 to 95 ° C in a stretch ratio of 2.4 to 3.8, in each case in the longitudinal and transverse directions. The area stretch ratio is 7 to 12. To improve the dimensional stability, partial or complete heat setting may be carried out after stretching. This is usually done at 120 to 160 ° C.
  • the film shows only a relatively small shrinkage of less than 20, in particular less than 15%, in the longitudinal and transverse directions when exposed to heat up to about 90 ° C.
  • the packaging casing can be easily processed into sausage casings.
  • the gathering process can surprisingly be carried out without the addition of inorganic or organic antiblocking agents. It is sufficient if only the usual gathering aids such as paraffin oil and water are used.
  • the pleats are completely removed after the skin has been removed and filled and are no longer recognizable from the finished sausage.
  • the casing can be filled with sausage mass plump and wrinkle-free without the filling pressure causing undesired bulging of the casing or delamination of the layers. Even with heavy sausages with one .
  • the subsequent cooking process to a core temperature of 80 ° C., there is no formation of long corners, no pear-shaped deformations and no "bag-in-bag” formation.
  • the sausages obtained are cylindrical and have a uniform cross section. Due to the high material strength and the excellent elastic resilience, there is no costly cooling of the sausages in cold water. A short, intermittent cooling shower with a subsequent cooling phase in air is sufficient.
  • a cooked sausage with the casing according to the invention can be stored for at least 8 weeks without serious weight loss and without wrinkling.
  • the graying of the sausage material occurs much later compared to stretch-oriented PA 6 casings (of the same film thickness), which can be attributed to an improved oxygen barrier.
  • the casing according to the invention is particularly suitable for use as a sausage casing, in particular as a casing for liver sausage, scalded sausage, meat sausage, blood sausage and cooked sausage.
  • Such sausages are described, for example, in DE 298 03 965 U1, DE 299 14 336 U1, DE 198 37 733 A1, DE 29824273 U1, DE 20013974 U1, DE 20007988 U1, DE 02639177 C2 and DE 29517106 U1.
  • the invention is illustrated by the following examples. Percentages are in percent by weight.
  • a 5-layer pipe is constructed using 4 single-screw extruders and a downstream co-extrusion round die (state of the art according to EP-A-0 467 039):
  • This tube is brought to stretching temperature (about 80 ° C.) within 2 seconds by means of IR radiation.
  • the thickness of the resulting film is 58 ⁇ m.
  • a determination of the individual layer thicknesses results in:
  • Middle layer blend of 70% ULDPE (Atane SL4102)
  • Inner layer 34 ⁇ m
  • This tube is brought to stretching temperature (about 80 ° C.) within 2 seconds by means of IR radiation.
  • the thickness of the resulting film is 58 ⁇ m.
  • a determination of the individual layer thicknesses gives: 18.1 ⁇ m outer layer 8.5 ⁇ m adhesion promoter
  • Middle layer blend of 70% ULDPE (Atane SL4102)
  • Middle layer 136 ⁇ m bonding agent 62 ⁇ m
  • Inner layer 34 ⁇ m.
  • This tube is brought to stretching temperature (about 80 ° C.) within 2 seconds by means of IR radiation.
  • a pressure of about 1 bar inside the heated tube it is stretched biaxially by an area factor of 7.33 and heat-set, laid flat and wound up in a second bubble.
  • the thickness of the resulting film is 58 ⁇ m.
  • a determination of the individual layer thicknesses gives: 18.1 - ⁇ m outer layer 8.5 ⁇ m adhesion promoter
  • Middle layer blend of 70% ULDPE (Atane SL4102)
  • the thickness of the resulting film is 52 ⁇ m.
  • a determination of the individual layer thicknesses results in:
  • the thickness of the resulting film is 46 ⁇ m.
  • a determination of the individual layer thicknesses results in:
  • Tubular film with a higher proportion (40% by weight) of COC in the middle layer :
  • Middle layer blend of 60% ULDPE (Atane SL4102)
  • the thickness of the resulting film is 52 ⁇ m.
  • a determination of the individual layer thicknesses results in:
  • tubular film with 100% by weight COC in the middle layer tubular film with 100% by weight COC in the middle layer:
  • the thickness of the resulting film is 45 ⁇ m.
  • a determination of the individual layer thicknesses results in:
  • the thickness of the resulting film is 35 ⁇ m.
  • a determination of the individual layer thicknesses results in: 21.3 ⁇ m outer layer 7.9 ⁇ m middle layer 5.2 ⁇ m inner layer.
  • Outer layer PA 6 (Grilon F 47)
  • Middle layer Dry blend made from 80% HDPE (Lupolen 2411 D)
  • This tube is brought to stretching temperature (about 80 ° C.) within 2 seconds by means of IR radiation.
  • the tube By applying a pressure of about 1 bar inside the heated tube, the tube is stretched biaxially by an area factor of 8.6 and heat-set, laid flat and wound up in a second bubble.
  • the thickness of the resulting film is 40 ⁇ m.
  • a determination of the individual layer thicknesses gives:
  • a 3-layer pipe is made analogously to Example 1 with a structure of (also prior art according to EP-A-0 467 039):
  • Middle layer Dryblend made of 80% HDPE (Lupolen 2441 D) and 20% adhesion promoter based on LLDPE / methacrylic acid copolymer (Plexar OH 002).
  • Inner layer Dryblend made of 70% PA 6 (Grilon F 47) and 30% PA 61 / 6T (Grivory G 21)
  • Example 1 produced and stretched to form a hose and heat-set as in Example 1.
  • the layer thickness distribution corresponds to Example 1.
  • a single-layer hose made of an oriented polyamide / polybutylene terephthalate blend (oPAx PBT blend according to DE-A-34 36 682, b) an unoriented single-layer blow hose made of polyamide-12 (PA-12) and c) a multi-layer cover with the structure of polyamide bonding agent-polyethylene
  • Table 1 contains mechanical characteristics and the barrier properties of these sleeves.
  • Table 2 shows the application comparison based on meat sausage or. Liverwurst fillings.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)

Abstract

L'invention concerne une enveloppe d'emballage tubulaire multicouche conçue pour une matière de remplissage pâteuse. L'enveloppe d'emballage selon l'invention présente une perméabilité fortement réduite vis-à-vis de la vapeur d'eau et de l'oxygène atmosphérique.
EP03722404A 2002-04-12 2003-04-05 Enveloppe d'emballage tubulaire multicouche Withdrawn EP1497120A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10216473A DE10216473B4 (de) 2002-04-12 2002-04-12 Mehrschichtige, schlauchförmige Verpackungshülle für pastöses Füllgut
DE10216473 2002-04-12
PCT/EP2003/003565 WO2003086751A2 (fr) 2002-04-12 2003-04-05 Enveloppe d'emballage tubulaire multicouche

Publications (1)

Publication Number Publication Date
EP1497120A2 true EP1497120A2 (fr) 2005-01-19

Family

ID=28798410

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03722404A Withdrawn EP1497120A2 (fr) 2002-04-12 2003-04-05 Enveloppe d'emballage tubulaire multicouche

Country Status (4)

Country Link
EP (1) EP1497120A2 (fr)
AU (1) AU2003229612A1 (fr)
DE (1) DE10216473B4 (fr)
WO (1) WO2003086751A2 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102016213838A1 (de) * 2016-07-27 2018-02-01 Sig Technology Ag Flächenförmiger Verbund zum Herstellen formstabiler Nahrungsmittelbehälter mit einer biobasierten Barriereschicht

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2639177A1 (de) * 1976-08-31 1978-03-02 Hohenester Hermann Verfahren zur herstellung diaetetischer fleischpasteten mit geringem fettgehalt
FI66278C (fi) * 1978-11-18 1984-10-10 Becker & Co Naturinwerk Slangfolie foer foerpackning och omhoeljande av pastaartade lismedel speciellt korv och smaeltost foerpackad i form av kenrv
US4606922A (en) * 1983-04-21 1986-08-19 W. R. Grace & Co., Cryovac Div. Cook-in meat packaging
DE3816942C2 (de) * 1987-05-21 2000-06-15 Gunze Kk Lebensmittel-Verpackungsmaterial und Herstellungsverfahren dafür
US4911963A (en) * 1987-08-31 1990-03-27 Viskase Corporation Multilayer film containing amorphous nylon
DE4001131C2 (de) * 1990-01-17 1999-04-08 Hoechst Ag Mehrschichtige künstliche Wursthülle auf Polyamidbasis
DE4017046A1 (de) * 1990-05-26 1991-11-28 Hoechst Ag Mehrschichtige, schlauchfoermige verpackungshuelle
DE4128081A1 (de) * 1991-08-23 1993-02-25 Wolff Walsrode Ag Coextrudierte biaxial gereckte schlauchfolie
DE4130486A1 (de) * 1991-08-23 1993-02-25 Wolff Walsrode Ag 5-schichtige, coextrudierte biaxial gereckte schlauchfolie mit mindestens 3 pa-schichten
US5698279A (en) * 1992-09-23 1997-12-16 Viskase Corporation Heat shrinkable nylon food casing having a functionalized ethylenic polymer core layer
US6165573A (en) * 1994-07-05 2000-12-26 Mitsui Petrochemical Industries Ltd Multi-layer laminates and uses thereof
DE19529603A1 (de) * 1995-08-11 1997-02-13 Wolff Walsrode Ag Polyamid-Wursthülle mit verbesserter Schälcharakteristik
DE29517106U1 (de) * 1995-10-19 1995-12-14 Greifert Gerd Kochwurstprodukt mit reduziertem Fettgehalt, insbesondere Blutwurst
JPH10119204A (ja) * 1996-10-25 1998-05-12 Tousero Kk 積層フィルム
DE19938434A1 (de) * 1999-08-13 2001-03-01 Mathews Plc Bernard Fleischware und Verfahren zu deren Verbesserung
DE19752249A1 (de) * 1997-10-24 1999-04-29 Bernhard Bartsch Gmbh Verfahren zur Herstellung einer Wurst und vorzugsweise nach diesem Verfahren hergestellte Wurst
US5942587A (en) * 1997-11-21 1999-08-24 Exxon Chemical Patents Inc. Ethylene polymers with a norbornene comonomer for LLDPE like resins of improved toughness and processibility for film production
DE19837733A1 (de) * 1998-08-20 2000-02-24 Heinrich Hans Georg Verfahren zur Herstellung eines Grundbräts für Brühwurst, und einer Leberwurstgrundmasse; Grundbrät; Leberwurstgrundmase; Wurstware
DE29914336U1 (de) * 1999-08-16 1999-11-18 Quadt Bernd Leberwurst, insbesondere mit Äpfeln und einer Wurstmasse
DE20007988U1 (de) * 2000-05-04 2000-08-24 Lutz Fleischwaren Ag Wurst, insbesondere Brühwurst
DE10026167A1 (de) * 2000-05-26 2001-11-29 Mitsubishi Polyester Film Gmbh Weiße, hochglänzende, UV-stabilisierte Polyesterfolie enthaltend Cycloolefincopolymer (COC), Verfahren zu ihrer Herstellung und ihre Verwendung
DE10030235A1 (de) * 2000-06-20 2002-01-03 Mitsubishi Polyester Film Gmbh Weiße, siegelfähige, thermoformbare, biaxial orientierte und koextrudierte Polyesterfolie mit Cycloolefincopolymer, Verfahren zu ihrer Herstellung und ihre Verwendung
EP1213138B1 (fr) * 2000-12-06 2006-08-02 Huhtamaki Deutschland GmbH & Co. KG Procédé de fabrication d'une feuille stratifiée

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO03086751A3 *

Also Published As

Publication number Publication date
AU2003229612A8 (en) 2003-10-27
DE10216473B4 (de) 2004-10-28
AU2003229612A1 (en) 2003-10-27
WO2003086751A3 (fr) 2004-05-06
WO2003086751A2 (fr) 2003-10-23
DE10216473A1 (de) 2003-11-06

Similar Documents

Publication Publication Date Title
EP0467039B1 (fr) Enveloppe tubulaire d'emballage à plusieurs couches
DE4001131C2 (de) Mehrschichtige künstliche Wursthülle auf Polyamidbasis
DE4001612C2 (de) Mehrschichtige Verpackungshülle auf Basis von Polyamid
DE4339337C2 (de) Fünfschichtige, biaxial verstreckte Schlauchfolie zur Verpackung und Umhüllung von pastösen Lebensmitteln
EP0530549B1 (fr) Feuille tubulaire étirée biaxialement et coextrudée contenant au moins 3 couches, la couche intérieure se composant de polyamide
EP1084962B9 (fr) Feuille multicouche synthétique étirée biaxialement pour boyaux de saucisses avec barrière à oxygène
EP0530539A1 (fr) Film tubulaire coextrudé orienté biaxialement
EP0815732A2 (fr) Enveloppe d'emballage plissée
DE60216189T2 (de) Polyamid-Nahrungsmittelhülle mit einer undurchlässigen Mittelschicht
EP0722664B1 (fr) Enveloppe pour saucisses à base de polyamide
EP1299000A1 (fr) Boyau artificiel en polyamide a additifs nanodisperses et son utilisation comme enveloppe d'aliment
EP0603676B1 (fr) Boyau de saucisses multicouche coextrudé et étiré biaxialement sans soudure avec barrière à oxygène amélioré
DE102006047779A1 (de) Mehrschichtige nahtlose Schlauchhülle auf Basis von Polyamid für die Formenkochung
EP1677980B1 (fr) Enveloppe a base de polyamide pour denrees alimentaires, impregnee de fumee
DE4306274A1 (de) Mehrschichtig coextrudierte, biaxial verstreckte Schlauchfolie mit verbesserter Sauerstoffbarriere
EP0658310B1 (fr) Enveloppe tubulaire transparente, étirée biaxialement et coextrudée, contenant au moins quatre couches, et ayant des propriétés de barrière améliorées à la perméation de vapeur d'eau et d'oxygène et à la transmission de lumière
DE10319006A1 (de) Nahrungsmittelhülle mit antimikrobieller Ausrüstung
DE10216473B4 (de) Mehrschichtige, schlauchförmige Verpackungshülle für pastöses Füllgut
EP1338204A1 (fr) Bâton de boyau plissé et procédé de préparation d'un boyau d'emballage plissé
EP0993940B1 (fr) Feuille thermorétractable revêtue ou laminée ayant des propriétés de barrière améliorées et film tubulaire délivré avec joint soudé
EP1290948B1 (fr) Film tubulaire multicouche à base de polyamide
DE19833986A1 (de) Schlauchfolie

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20041112

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: TOPAS ADVANCED POLYMERS GMBH

17Q First examination report despatched

Effective date: 20100512

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20100923