WO2005033187A1 - Enveloppe alimentaire multicouche dont la couche exterieure contient une substance organique a repartition discontinue - Google Patents

Enveloppe alimentaire multicouche dont la couche exterieure contient une substance organique a repartition discontinue Download PDF

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Publication number
WO2005033187A1
WO2005033187A1 PCT/EP2004/010646 EP2004010646W WO2005033187A1 WO 2005033187 A1 WO2005033187 A1 WO 2005033187A1 EP 2004010646 W EP2004010646 W EP 2004010646W WO 2005033187 A1 WO2005033187 A1 WO 2005033187A1
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WO
WIPO (PCT)
Prior art keywords
layer
food casing
casing according
polyamide
polymer
Prior art date
Application number
PCT/EP2004/010646
Other languages
German (de)
English (en)
Inventor
Bernhard Feron
Ulrich Delius
Stefanie Stalberg
Christian Auf Der Heide
Dirk Auf Der Heide
Original Assignee
Kalle Gmbh
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Publication date
Application filed by Kalle Gmbh filed Critical Kalle Gmbh
Priority to EP04765508A priority Critical patent/EP1678243A1/fr
Publication of WO2005033187A1 publication Critical patent/WO2005033187A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • A—HUMAN NECESSITIES
    • A22—BUTCHERING; MEAT TREATMENT; PROCESSING POULTRY OR FISH
    • A22C—PROCESSING MEAT, POULTRY, OR FISH
    • A22C13/00—Sausage casings
    • A22C13/0013—Chemical composition of synthetic sausage casings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • A—HUMAN NECESSITIES
    • A22—BUTCHERING; MEAT TREATMENT; PROCESSING POULTRY OR FISH
    • A22C—PROCESSING MEAT, POULTRY, OR FISH
    • A22C13/00—Sausage casings
    • A22C2013/0053—Sausage casings multilayer casings
    • A—HUMAN NECESSITIES
    • A22—BUTCHERING; MEAT TREATMENT; PROCESSING POULTRY OR FISH
    • A22C—PROCESSING MEAT, POULTRY, OR FISH
    • A22C13/00—Sausage casings
    • A22C2013/0059—Sausage casings thermoplastic casings, casings with at least one layer of thermoplastic material
    • 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
    • B32B2323/00—Polyalkenes
    • B32B2323/04—Polyethylene
    • 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
    • B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
    • 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
    • B32B2371/00—Polyethers, e.g. PEEK, i.e. polyether-etherketone; PEK, i.e. polyetherketone
    • 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
    • B32B2375/00—Polyureas; Polyurethanes
    • 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
    • B32B2377/00—Polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

  • Multilayer food casing with discontinuously distributed organic substance in the outer layer
  • the invention relates to a multilayer, tubular food casing based on thermoplastic material which comprises at least one layer based on polyamide and / or copolyamide.
  • Food casings especially sausage casings, are traditionally made from natural casing
  • thermoplastic materials especially those made of polyamide or polyamide-polyolefin composite systems.
  • the collagen or skin fiber intestine is made from bovine skins after a very complex and polluting process.
  • tissue of the split skin is thereby digested with acids (eg lactic acid) up to the fibrils, the resulting highly viscous mass is then extruded and slowly and compactly precipitated and solidified with gaseous ammonia or ammonium hydroxide.
  • acids eg lactic acid
  • crosslinking then takes place (hardening) in order to give the products sufficient stability so that they survive the brewing process without substantial loss of strength.
  • natural casings as well as skin fiber casings are becoming increasingly less accepted by end users due to various incidents such as the BSE epidemic in cattle and the misuse of antibiotics. There are also legal restrictions. An alternative to the mentioned intestines is therefore desirable. Cellulose casings, even those with fiber reinforcement, can only do this task to a limited extent.
  • thermoplastic sausage casings are their simple, inexpensive production.
  • the end user often has reservations about sausages in these cases.
  • the naturally glossy surface of the plastic often gives the impression of lesser quality of the product. Added to this is the poor grip of the sausages when the plastic surface is moistened with moisture or grease.
  • the fibrous consistency provides a coarse textured, rough surface.
  • the consumer who has known this look for many decades, thus associates a higher value or traditional production of the sausage product.
  • EP-A 596 437 describes mixtures of starch or thermoplastic starch with aliphatic polyesters or polyvinyl alcohol, which can be processed by thermoplastic extrusion into water-resistant, yet biodegradable films.
  • WO 92/19680 discloses blends of a starch component and one or more synthetic polymers, especially homopolymers or copolymers of hydroxycarboxylic acids, polyurethanes, polyamides and vinyl alcohol copolymers. Furthermore, plasticizing aids such as
  • thermoplastic films containing hydrophobically modified starch esters and biodegradable polyesters such as polylactides, polycaprolactone or polyhydroxyalkanoate. These films are distinguished from conventional starch-containing materials by improved water resistance, processability and mechanics.
  • EP-A 479964 discloses moisture-insensitive multilayer films having a central layer of thermoplastic starch and additives to which a layer of polyolefin or a polyolefin-starch blend is attached on both sides. The trapped starch layer should cause a low gas permeability.
  • the primary consideration in this as well as in many other publications is the biodegradability of the material or of the films produced therefrom.
  • thermoplastic starch is described for the first time as a material for sausage casings. This application provides that native strength under
  • the shell should have a correspondingly low gloss. It should have the properties required for a sausage casing, such as strength, elasticity and shrinkage, also be easy and inexpensive to produce.
  • the problem is solved with a multi-layered polymer shell whose outer layer contains organic particles.
  • the invention accordingly provides a multilayer, tubular
  • thermoplastic material which comprises at least one layer based on polyamide and / or copolyamide and thereby characterized in that the outer layer contains at least one organic substance which is discontinuously distributed in the layer.
  • the organic substance is preferably a polysaccharide, a protein or a high-temperature-stable synthetic fiber or a high-temperature-stable plastic powder.
  • This outer layer modified in this way forms an extremely rough, matt surface during the production of the hoses, which surface is very close in optical as well as haptic terms to the surfaces of cellulose fiber casings or collagen casings.
  • the outside of the casing according to the invention has a gloss value of less than 20, preferably less than 15, more preferably less than 8, in each case at an irradiation angle of 60 ° (determined according to DIN 67 530).
  • the further layers bring about the mechanical properties typical of plastic casings, such as tensile strength and elasticity, and, if appropriate, also high gas and water vapor tightness.
  • the casing according to the invention comprises at least one layer based on polyamide and / or copolyamide (abbreviated to (co) polyamide).
  • the polyamide layer may contain one or more aliphatic (co) polyamides, moreover also partially aromatic (co) polyamides.
  • aliphatic polyamides PA6, PA66, PA12; aliphatic copolyamides: PA4 / 6, PA6 / 66, PA6 / 69, PA6 / 9, PA6 / 10, PA6 / 12 polyetheramides, polyesteramides, polyetheresteramides, polyamide urethanes, poly (ether-block-amides); partially aromatic polyamides: PA6-I, nylon-MXD6 (polycondensate of m-xylylenediamine and adipic acid); partially aromatic copolyamides: PA 6-1 / 6-T, PA 6 / 6-1.
  • PA 6 PA 66
  • PA 12 PA 6/66
  • nylon MXD6 PA 6/66
  • PA 6-I / 6-T PA 6/66
  • PA 6/66 PA 12
  • nylon MXD6 PA 6/66
  • PA 6-I / 6-T PA 6/66
  • PA 6/66 PA 12
  • nylon MXD6 PA 6/66
  • PA 6-I / 6-T PA 6/66
  • PA 6/66 PA 12
  • the proportion of partially aromatic (co) polyamides is generally not more than 40% by weight, based on one layer (A).
  • (A) may contain other polymers, for example olefinic
  • Copolymers such as EMAA (ethylene-methacrylic acid copolymer), derived therefrom ionomers, EVOH or (hot) water-soluble synthetic polymers such as polyvinyl alcohol (partially and completely saponified), copolymers of vinyl alcohol with propen-1-ol, polyalkylene glycols, polyvinylpyrrolidone, copolymers from vinylpyrrolidone and at least one .alpha.,. beta.-olefinically unsaturated monomer, polymers of N-vinylalkylamides or (co) polymers of acrylic acid and / or acrylamide.
  • the proportion of the other polymers is preferably not more than 35 wt .-% based on layer (A).
  • layers (A) may also contain pigments and / or other plastic-typical additives.
  • the thickness of these layers is generally 15 to 85 microns, preferably 25 to 65 microns.
  • the polyolefinic layers are generally composed of polyethylene, polypropylene and / or copolymers having units of ethylene, propylene and / or ⁇ -olefins having 4 to 8 C atoms and / or dienes. Also functionalized vinyl monomers, e.g. Vinyl acetate, (IVIeth) acrylic acid and
  • (Meth) acrylic acid esters are suitable as co-building blocks. Particularly suitable are C 2 / C 3 and C 2 / C 8 copolymers.
  • the layers (B) primarily have the function of a moisture barrier, since polyolefins generally have a very low water vapor permeability.
  • layers (B) may still contain pigments, such as those typically used for coloring or UV
  • the layers (B) generally have a thickness in the range of 3 to 20 microns, preferably 4 to 15 microns.
  • layers of plastics with corresponding blocking effect can be added (hereinafter referred to as "C").
  • Suitable plastics for this purpose are ethylene-vinyl alcohol copolymers (partially or completely saponified, "EVOH”), and vinylidene chloride copolymers (for example with vinyl chloride or methyl acrylate as comonomer, "PVDC”). These polymers may also be admixed with additives such as plasticizers and other polymers such as copolyamides or ionomers.
  • the layer (C) generally has a thickness of 3 to 20 ⁇ m, preferably 5 to 15 ⁇ m.
  • adhesion promoters are, in particular, graft copolymers or linear copolymers (where copolymers also contain more than two types of monomer) with ethylene and / or propylene units and also components from the group consisting of (meth) acrylic acid, (meth) acrylic acid ester, vinyl acetate, maleic anhydride.
  • Preferred are u.a. Maleic anhydride grafted polyethylene (LLDPE-g-MAA), ethylene / acrylic acid ester copolymers, and ethylene / vinyl acetate copolymers (EVA).
  • HV layers may contain other polymers, e.g. Polyethylene and other additives or pigments.
  • the adhesive layers are expediently relatively thin. Its thickness is generally 2 to 8 microns, preferably 3 to 6 microns.
  • Individual HV layers may also be eliminated if there is sufficient self-adhesion between the functional layers (e.g., between polyamide or EVOH) or by incorporating the adhesion promoter component into the components of the adjacent B layer.
  • the functional layers e.g., between polyamide or EVOH
  • the adhesion promoter component into the components of the adjacent B layer.
  • the layer disposed on the outer surface of the shell (hereinafter referred to as "Z") generally consists of a blend of at least one poly saccharide and / or at least one high-temperature-stable synthetic fiber or powder and at least one thermoplastic.
  • the polysaccharide may be of natural origin or chemically derivatized, it may be branched, crosslinked or linear.
  • Suitable polysaccharides of this type are, in particular, native or thermoplastic starch (TPS) or starch derivatives.
  • TPS native or thermoplastic starch
  • Starch derivatives are, for example, starch esters (such as starch acetates, maleates, propionates, butyrates, lauroates or oleates), starch xanthates, phosphates, sulfates or nitrates, starch ethers (such as starch methyl ether, ethyl ether, propyl ether, butyl ether, alkenyl ether, hydroxyethyl ether, hydroxypropyl ether), grafted starches (eg grafted with maleic acid or succinic anhydride) or oxidized starches (such as dialdehyde starch, carboxy starch or starch degraded with persulfate).
  • starch esters such as starch acetates, maleates, propionates,
  • starches or starch derivatives As an alternative to or in combination with the above-listed starches or starch derivatives, it is also possible for other components from the family of polysaccharides to be present.
  • vegetable powders or fibers such as, among others, cellulose, cotton, kapok, flax, linen, hemp,
  • organic, synthetic, high temperature stable synthetic fibers or powders are also suitable, e.g. based on polyethylene, polypropylene, polyamide, polyacrylonitrile, polyesters, fluoropolymers, polysulfones, polyethersulfones,
  • Polyether ketones Polyphenylene sulfides, polyaramides, polyimides, aromatic polyesters, polyquinoxalines, polyquinolines, polybenzimidazoles or ladder polymers.
  • Such components have also proven to be very effective for the production of a rough, textured surface in addition to the starches or starch derivatives and other polysaccharides.
  • the organic substance contained in the outer layer expediently has a Particle size of 1 to 200 microns, preferably from 15 to 100 microns. Fibrous organic substances generally arrange parallel to the shell surface, and therefore can be longer than the layer thickness. The length of such fibrous substances is generally 1 to 1000 ⁇ m, preferably 15 to 50 ⁇ m.
  • thermoplastic polyurethanes polyether urethanes
  • aliphatic (co) polyamides aliphatic or partially aromatic (co) polyesters
  • polyester ether urethanes besides vinyl copolymers such as ethylene / vinyl acetate copolymer.
  • polyurethanes polyadducts, e.g. by reaction of tolylene diisocyanate (TDI), isophorone diisocyanate and / or
  • Hexamethylene diisocyanate with poly-1, 2-propanediol (PPG) and / or poly-1, 4-butanediol (PTMG) were prepared.
  • PA 6, PA 12, PA 6/66 and PA 6/12 are preferred.
  • the copolymers mentioned are particularly suitable in that their melting points are below 220.degree. C. and thus permit thermally relatively gentle compounding with the polysaccharide component.
  • PA 66 is also suitable as the polymer matrix.
  • polyesters preferred are polylactide, polycaprolactone, copolymers of aliphatic diols with aliphatic dicarboxylic acids and terephthalic acid, and poly (butylene glycol terephthalate).
  • Layer (Z) may further contain other high or low molecular weight components, e.g. softening substances such as glycerol, polyethylene glycols,
  • thermoplastic polymer matrix and the organic substance discontinuously dissolved therein for layer (Z) are generally carried out in a compounding step preceding the tube extrusion by methods known per se. If the discontinuously dissolved organic substance is starch, it may be thermoplastic
  • TPS Form
  • the destructuring is done by supplying thermal and mechanical energy, e.g. by means of a heated kneader or a twin-screw extruder.
  • plasticizing aids e.g. Water and / or glycerin proven.
  • thermoplasticized (TPS) or native starch is continuously brought together with the intended plastic and unified with further supply of mechanical and thermal energy to a thermoplastic mass. It is advantageous if the plastic forms a continuous matrix in which the starch component is uniformly dispersed.
  • the layer (Z) can be combined with the other layer types mentioned to form different multilayer structures. It is always essential that layer (Z) is arranged on the outer tube surface and that there is at least one layer with a mechanical bearing function underneath.
  • Preferred layer structures are: (for the abbreviations see above): Hose outer side: Hose inner side 1) Z / A 2) Z / A / B 3) Z / HV / A 4) Z / HV / C 5) Z / A / HV / A 6) Z / A / HV / C 7) Z / HV / A / HV 8) Z / HV / C / HV 9) Z / HV / A / HV / A 10) Z / A / HV / B / HV / A 11) Z / A / HV / C / HV / A 12) Z / HV / A / HV / B / HV / A 13) Z / H
  • Structures according to 3), 5) and 11) are particularly preferred.
  • the preparation of the food casing according to one of the structures described is effected by coextrusion and subsequent tube blowing or biaxial tube stretching. Corresponding methods are familiar to the person skilled in the art.
  • the blend of the discontinuously dissolved organic substance and the plastic matrix, and the other polymers or mixtures provided, are melted and plasticized in separate extruders and subsequently combined in a heated coextrusion ring die.
  • the emerging annular melt film can now either be inflated directly to a Fol ienschlauch or be performed by a biaxial stretching process with optionally downstream heat setting.
  • the melt film is solidified by rapid cooling to an amorphous pre-hose and this biaxially by subsequent reheating (about 80 ° C) and by means of an enclosed between two nip rolls air cushion stretched.
  • the subsequent thermosetting can be done by the stretched tube is passed through a further heating zone, optionally with stabilization with a second air cushion.
  • the thermal shrinkage tendency of the shell can be reduced to practical values (ie to about 5 to 20% shrinkage in the longitudinal and transverse directions, measured after 20 minutes storage in 80 ° C warm water).
  • the food casing according to the invention generally has a total thickness of from 35 to 140 ⁇ m, preferably from 50 to 110 ⁇ m.
  • the outer layer has expediently a proportion of 15 to 85 ⁇ m, preferably from 25 to 65 ⁇ m. Because it is made using a ring nozzle, it is seamless.
  • the shell has, depending on the intended use, a diameter of 10 to 300 mm, preferably from 15 to 210 mm.
  • the food casing according to the invention is particularly suitable as an artificial
  • LLCPE Linear Low Density Polyethylene
  • PA12 ® Grilamid L25
  • the total wall thickness of the envelope was 80 ⁇ m to 125 ⁇ m, its diameter 105 mm.
  • the inner layer had a share of 50%, the middle layer of 10% and the outer layer of 40%.
  • This shell construction corresponds to the structure Z / HV / A described above.
  • the outer layer corresponds to the outer layer Z. It is particularly rough and provides extremely low surface gloss.
  • the surface properties of the hose are listed in the table.
  • an inner layer consisting of 80% PA6 (® Grilon F34) nd 20% PA 6l / 6T (® Grivor G21), b) a middle layer consisting grafted of an adhesion promoter on the basis of MSA LLDPE (® Modic-AP L513) and c) an outer layer consisting thermoplasticized from a prepared on a twin-screw kneader compound of 70% copolyamide PA 6/12 (® Grilon CF6S) and 30% starch (TPS) - the latter in turn consisting of 50% native corn starch (® Cerestar gel 03402) and 50 % Glycerin and water as softening and destructuring aids.
  • PA6 ® Grilon F34
  • PA 6l / 6T ® Grivor G21
  • a middle layer consisting grafted of an adhesion promoter on the basis of MSA LLDPE (® Modic-AP L513)
  • an outer layer consisting thermoplasticized from a prepared on a twin
  • the primary tube was cooled rapidly to about 20 ° C and then heated to about 80 ° C and biaxially stretched at this temperature at aarianstreck- ratio of 9.25. In a further heating zone, the tube was then heat-set, so that the thermal shrinkage measured in water at 80 ° C was still about 10 to 12%.
  • Hose was 108 mm with a total wall thickness of 75 microns to 95 microns. It accounted for 40% on the inner layer, 5% on the middle layer and 55% on the outer layer. The latter corresponds to a layer Z described above. It is characterized among other things by an extremely low surface gloss (see following table).
  • Example 2 As described in Example 1, a blown tube was coextruded with the difference that the outer layer Z of a made on a twin kneader compound of 87.5% copolyamide PA 6/12 Grilon CF6S) and 12.5% crystalline cellulose powder ( ® Jelucel PF60 ) consists.
  • the total wall thickness of the shell was 105 .mu.m to 140 .mu.m and a diameter of 40 mm.
  • the inner layer had an average proportion of 50%, the middle layer of 10% and the outer layer of 40%.
  • the natural-intestine-like surface properties of this shell reflect the table.
  • thermoplastic polyurethane (biaxially stretched and heat-set shell with outer layer based on starch and thermoplastic polyurethane) I
  • a biaxially stretched thermo-fixed three-layer hose with a diameter of 108 mm was produced at a total wall thickness of 75 .mu.m to 90 .mu.m.
  • the outer layer Z consisted of one produced on a twin-screw kneader Compound of 50% aromatic thermoplastic polyurethane ( ® lrogran VP456 / 40) and 50% thermoplasticized starch (TPS).
  • the latter in turn, consisted of 70% native maize starch Cerestar Gel 034O2) and 30% of a mixture of glycerine and water as softening and destructuring aids.
  • the outer layer Z was also characterized by a particularly low surface gloss - see table.
  • thermo-set three-layer hose consisting of
  • the total wall thickness here was 50 microns with a diameter of 80 mm.
  • the inner layer portion was 20%, the middle layer portion 40% and the outer layer portion 40%.
  • the surface is very smooth and shiny in spite of the pigmentation compared to the described inventive sheaths as shown in the table below.
  • the table shows how clearly the food casing according to the invention by the externally arranged layer (Z), which is a dispersed organic
  • the roughness values and roughness depths were measured according to DIN 4768.
  • the average roughness value R a is the arithmetic mean of all deviations of the roughness profile from the center line within the total measurement distance.
  • the average roughness R z is the average value of the individual roughness depths of five consecutive individual measuring sections in the roughness profile.
  • the maximum roughness R max is the largest of the five single roughness depths.
  • the gloss values are determined according to DIN 67530 at the three different irradiation angles 20 °, 60 ° and 85 °.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Food Science & Technology (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne une enveloppe alimentaire tubulaire multicouche à base de matière thermoplastique, comprenant au moins une couche à base de polyamide et/ou de copolyamide. La couche extérieure de l'enveloppe contient au moins une substance organique qui est répartie de façon discontinue dans la couche et produit une pigmentation. La couche extérieure de l'enveloppe a de ce fait une action matifiante et s'apparente à un boyau naturel ou un boyau en fibres cellulosiques. L'enveloppe est utilisée de préférence comme enveloppe de saucisse artificielle.
PCT/EP2004/010646 2003-09-30 2004-09-22 Enveloppe alimentaire multicouche dont la couche exterieure contient une substance organique a repartition discontinue WO2005033187A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP04765508A EP1678243A1 (fr) 2003-09-30 2004-09-22 Enveloppe alimentaire multicouche dont la couche exterieure contient une substance organique a repartition discontinue

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10345839A DE10345839A1 (de) 2003-09-30 2003-09-30 Mehrschichtige Nahrungsmittelhülle mit diskontinuierlich verteilter organischer Substanz in der Außenschicht
DE10345839.5 2003-09-30

Publications (1)

Publication Number Publication Date
WO2005033187A1 true WO2005033187A1 (fr) 2005-04-14

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Country Link
EP (1) EP1678243A1 (fr)
DE (1) DE10345839A1 (fr)
WO (1) WO2005033187A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007003656A1 (de) * 2007-01-18 2008-07-31 World-Pac International Ag Verfahren zur Herstellung einer Naturdarm-Hülle
EP4353780A1 (fr) 2022-10-14 2024-04-17 UBE Corporation Europe, S.A.U. Alliages de polyamide-amidon thermoplastique (tps)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004017350A1 (de) 2004-04-08 2005-10-27 Kalle Gmbh Nahrungsmittelhülle mit einer porösen Außenschicht
DE102004022859B4 (de) * 2004-05-06 2006-04-13 Kalle Gmbh Künstliche Nahrungsmittelhülle sowie Verfahren zu deren Herstellung
DE102004038162A1 (de) 2004-08-06 2006-03-16 Kalle Gmbh Mehrschichtige Nahrungsmittelhülle mit grobkörnigen Partikeln in einer mittleren Schicht und Verfahren zu ihrer Herstellung
CA2959423A1 (fr) * 2016-03-10 2017-09-10 Flexopack S.A. Pellicule de doublure

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999061524A1 (fr) * 1998-05-25 1999-12-02 Kalle Nalo Gmbh & Co. Kg Film contenant de l'amidon ou de derives d'amidon et des polyesterurethanes
WO2003028470A1 (fr) * 2001-09-25 2003-04-10 Kalle Gmbh & Co. Kg Enveloppe pour produits alimentaires, contenant de l'amidon, en forme de tuyau et pourvue d'un revetement pouvant etre transfere et procede de fabrication de ladite enveloppe
WO2003073862A2 (fr) * 2002-03-01 2003-09-12 Kalle Gmbh & Co. Kg Enveloppe alimentaire dont la surface presente un aspect rugueux d'apparence naturelle

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999061524A1 (fr) * 1998-05-25 1999-12-02 Kalle Nalo Gmbh & Co. Kg Film contenant de l'amidon ou de derives d'amidon et des polyesterurethanes
WO2003028470A1 (fr) * 2001-09-25 2003-04-10 Kalle Gmbh & Co. Kg Enveloppe pour produits alimentaires, contenant de l'amidon, en forme de tuyau et pourvue d'un revetement pouvant etre transfere et procede de fabrication de ladite enveloppe
WO2003073862A2 (fr) * 2002-03-01 2003-09-12 Kalle Gmbh & Co. Kg Enveloppe alimentaire dont la surface presente un aspect rugueux d'apparence naturelle

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007003656A1 (de) * 2007-01-18 2008-07-31 World-Pac International Ag Verfahren zur Herstellung einer Naturdarm-Hülle
EP4353780A1 (fr) 2022-10-14 2024-04-17 UBE Corporation Europe, S.A.U. Alliages de polyamide-amidon thermoplastique (tps)

Also Published As

Publication number Publication date
DE10345839A1 (de) 2005-04-14
EP1678243A1 (fr) 2006-07-12

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