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WO2005061610A1 - Emballage pour aliments impregne ou recouvert de polyvinylamines a base de cellulose regeneree - Google Patents

Emballage pour aliments impregne ou recouvert de polyvinylamines a base de cellulose regeneree Download PDF

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Publication number
WO2005061610A1
WO2005061610A1 PCT/EP2004/014264 EP2004014264W WO2005061610A1 WO 2005061610 A1 WO2005061610 A1 WO 2005061610A1 EP 2004014264 W EP2004014264 W EP 2004014264W WO 2005061610 A1 WO2005061610 A1 WO 2005061610A1
Authority
WO
WIPO (PCT)
Prior art keywords
food casing
casing according
cellulose
food
polyvinylamine
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.)
Ceased
Application number
PCT/EP2004/014264
Other languages
German (de)
English (en)
Inventor
Theresia Rieser
Volker Effern
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.)
Kalle GmbH and Co KG
Original Assignee
Kalle GmbH and Co KG
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 Kalle GmbH and Co KG filed Critical Kalle GmbH and Co KG
Publication of WO2005061610A1 publication Critical patent/WO2005061610A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • A—HUMAN NECESSITIES
    • A22—BUTCHERING; MEAT TREATMENT; PROCESSING POULTRY OR FISH
    • A22C—PROCESSING MEAT, POULTRY, OR FISH
    • A22C13/00—Sausage casings
    • A22C2013/0096—Sausage casings cellulosic

Definitions

  • the invention relates to a coated or impregnated food casing based on cellulose, a process for its production and its use as an artificial sausage casing.
  • Water is removed from the so-called gel tube by drying.
  • the viscose solution can also be applied to a fiber paper formed into a tube.
  • the cellulose in the fiber casings thus formed is then regenerated in the same way.
  • the viscose process is extremely complex in terms of equipment and requires extensive measures for the purification of waste water and waste air. Therefore, the much less complex amine oxide process has recently been developed.
  • the cellulose is dissolved therein in an aqueous amine oxide of a tertiary amine, particularly preferably in N-methyl-morpholine-N-oxide (NMMO) monohydrate.
  • NMMO N-methyl-morpholine-N-oxide
  • the NMMO / cellulose solution can be extruded into seamless tubes using ring dies.
  • the cellulose is precipitated in a precipitation bath which contains dilute aqueous amine oxide.
  • the NMMO / cellulose solution can also be applied to fiber paper, so that cellulose fiber casings can also be produced by this process.
  • casings which have a layer with barrier properties for water vapor and / or oxygen, for example made of vinylidene chloride copolymers, and casings which are impregnated with a biocide. Also described are coatings for increasing the thickness of the cellulose casings.
  • a plasticizer such as glycerol
  • additives to their inner surface which influence the adhesion to the filling material in the desired manner. Because on the one hand the casing should be easy to peel, on the other hand it should adhere sufficiently to the sausage meat during the production of the sausage.
  • casings which have a layer with barrier properties for water vapor and / or oxygen, for example made of vinylidene chloride copolymers, and casings which are impregnated with a biocide. Also described are coatings for increasing the
  • Components that improve the properties of the cellulose hydrate shell can also be added directly to the viscose solution or the cellulose / amine oxide solution. By this measure, the liability of the shell can be
  • EP-B 0 635 211 and EP-B 0 878 133 are food casings based on regenerated cellulose, in the production of which cationic resins or mixtures of cationic resins were mixed with viscose proteins.
  • Melamine / formaldehyde and polyamine / polyamide / epichlorohydrin resins are specifically disclosed.
  • such resins are disadvantageous in a number of ways.
  • Melamine / formaldehyde resins contain or form small amounts of formaldehyde, which is why they are hardly used for food commodities in general and food packaging in particular still be used.
  • Polyamine / polyamide / epichlorohydrin resins increase the proportion of AOX in wastewater during the production of the casings and can contain substances that are hazardous to health, such as monochloropropanediol and dichloropropanol.
  • the permissible limit values for these connections have been lowered several times in recent years. Cases with these additives must also cure at elevated temperature or - for a correspondingly longer period - at room temperature.
  • DE-A 36 20 165 discloses a tubular food casing based on regenerated cellulose, which on the inside increases the
  • Meat cling is coated.
  • the inner coating comprises a film-forming plastic resin, in particular a polyamine-polyamide-epichlorohydrin resin, a polyethyleneimine resin, a urea or melamine-formaldehyde resin, and also a protein coagulant, such as tartaric acid, citric acid, ascorbic acid or sorbic acid.
  • DE-A 37 11 712 also describes a tubular food casing based on regenerated cellulose.
  • the casing contains, mixed with the cellulose, alkali-soluble or alkali-dispersible and hydrolysis-resistant protein compounds and crosslinking agents.
  • the shell can have an inner coating of cross-linked cationic compounds.
  • cross-linked protein compounds especially casein cross-linked with glyoxal.
  • DE-A 199 57 454 describes an optionally fiber-reinforced food casing based on regenerated cellulose, which has a layer which is impermeable to water vapor on the outside and also has a coating on the inside.
  • the coating comprises a crosslinked polyamine / polyamide / epichlorohydrin resin, a wax, for example montan wax or beeswax, and optionally a synthetic polymer, such as
  • the coating on the inside increases the adhesion to the sausage meat. It was therefore the task of providing cellulose-based food casings with a coating or impregnation which brings about a defined and uniform adhesion of the casing to the respective food.
  • the coating or impregnation should, if possible, also do without additional crosslinking agents, and the cellulase resistance of the casing should also be improved.
  • Polyvinylamines show surprisingly good adhesion to cellulose. This is attributed to the large number of primary amino groups.
  • the present invention accordingly relates to an impregnated or coated food casing based on cellulose, which is characterized in that the impregnation or coating comprises at least one polymer containing vinylamine units.
  • the sheath is preferably tubular.
  • the polymer containing vinylamine units is preferably a polyvinylamine.
  • Polyvinylamines as such are known and commercially available, for example under the names ⁇ Luresin PR 8086, ⁇ Polymin PR 8182, ⁇ Catiofast
  • polyvinylamines with a proportion of 5 to 100 mol%, preferably 30 to 95 mol%, of vinylamine units are suitable for causing the cellulose casing to adhere to the sausage meat.
  • Polyvinylamines such as polyvinylamine hydrochloride can be used.
  • a common process for the production of polyvinylamines consists in the hydrolysis of polymers with units made of N-vinylcarboxamides.
  • R and R 2 independently represent a hydrogen atom or C r to C 6 alkyl.
  • R 1 is H or C r to C 6 alkyl
  • the hydrolyzed polymers are accessible.
  • the primary or secondary amino groups obtained can also be present as hydrochlorides or in another salt-like form.
  • polyvinylamine should therefore also be understood to mean polymers with N-vinylcarboxamide groups in which more than 5 mol%, preferably 75 to 95 mol%, of the N-vinylcarboxamide units are hydrolyzed hydrolyzed homopolymers of N-vinylformamide, N-
  • copolymers are also suitable in principle. They generally contain at least 5 mol%, preferably at least 30 mol%, of vinylamine units. The further units can be derived from largely any monomers copolymerizable with N-vinylcarboxylic acid amides. They can also have functional groups, preferably basic or neutral.
  • Such monomers are, for example, ethylene and / or propylene, but preferably monoethylenic unsaturated monomers from the group of vinyl acetate, Vinyl propionate, the C r to C 4 alkyl vinyl ether, the esters, nitriles and amides of acrylic acid and methacrylic acid and N-vinyl pyrrolidone.
  • copolymers are also to be understood as meaning polymers which contain more than two different monomer units, that is to say also terpolymers, etc.
  • the hydrolysis of the N-vinylcarboxylic acid unit can by suitable mineral acids, such as hydrogen halide (gaseous or in aqueous solution), sulfuric, nitric or phosphoric acid, C 1 -C 5 carboxylic acids, such as formic, acetic or propionic acid, or by aromatic sulfonic acids, such as methane,
  • suitable mineral acids such as hydrogen halide (gaseous or in aqueous solution), sulfuric, nitric or phosphoric acid, C 1 -C 5 carboxylic acids, such as formic, acetic or propionic acid, or by aromatic sulfonic acids, such as methane,
  • Benzene or toluenesulfonic acids can also be carried out.
  • bases such as alkali metal or alkaline earth metal oxides (for example sodium or calcium hydroxide)
  • Ammonia or alkyl derivatives thereof can also be used.
  • Hydrolysis is also possible with the help of enzymes. A neutralization of the solutions is often carried out after the acidic or basic hydrolysis.
  • the average molecular weight M w of the vinylamine polymers is generally about 500 to 3,000,000 daltons, preferably about 100,000 to 2,000,000 daltons. Due to the large number of free primary amino groups combine
  • the application amount of the vinylamine polymers is generally about 10 to 1500 mg / m 2 , preferably 50 to 500 mg / m 2 , particularly preferably 60 to 200 mg / m 2 .
  • the adhesion of the casing to the food can be adjusted according to the requirements by the quantity applied.
  • the inner coating or impregnation can also comprise further components. These are, in particular, organic and / or inorganic particles, such as cellulose powder or fibers or silica particles.
  • Liquid smoke or bioeide can also be added. In some cases it may make sense if the impregnation or coating contains substances which reduce the adhesion of the casing to the food. Diketenes with long-chain (10 to 18 carbon atoms) alkyl radicals, chromium fatty acid complexes, lecithins, cellulose ethers (in particular carboxymethyl, hydroxyethyl and methyl cellulose), fats, oils and / or waxes are particularly suitable for this.
  • the impregnation or coating can discolor the surface. This can be suppressed by adding suitable additives such as gluconic acid ⁇ -lactone.
  • crosslinking can also be carried out.
  • Suitable crosslinkers are, in particular, dialdehydes, such as glyoxal or glutaraldehyde, and also diiisocyanates or diepoxides.
  • the coating or impregnation containing polyvinylamine is located on the outside of the casing. It increases the resistance of the shell to cellulitic enzymes (cellulases), such as those formed by molds.
  • cellulases cellulitic enzymes
  • the shell can be equipped with a barrier layer for oxygen and / or water vapor.
  • a barrier layer for oxygen and / or water vapor is a layer based on
  • Vinylidene chloride copolymers A previous coating or impregnation with polyvinylamine acts as an adhesion promoter for such additional layers.
  • the coating or impregnation containing polyvinylamine can be applied to a pure cellulose casing.
  • the cellulose casing according to the invention preferably also comprises a fiber reinforcement, preferably from a wet-strength fiber paper, particularly preferably from a hemp fiber paper.
  • the required wet strength can be achieved by treatment with a resin, with a dilute viscose solution or in a similar manner known to the person skilled in the art.
  • the fiber reinforcement has a (dry) weight of generally 15 to 29 g / m 2 , preferably 17 to 25 g / m 2 . It is shaped into a tube and is charged with the cellulose from the inside and / or outside.
  • the proportion of polyvinylamine in or on the shell can be calculated by a nitrogen determination according to Kjeldahl.
  • the nitrogen content must be taken into account, which may be due to the fiber reinforcement and / or the
  • the food casing according to the invention can be further modified in subsequent treatment steps, e.g. B. by treatment with a plasticizer, such as glycerol, and / or a bioid.
  • a plasticizer such as glycerol
  • bioid e.g. glycerol
  • Cover with a barrier layer or be impregnated with liquid smoke. A combination of several of these measures is also possible.
  • Envelopes with a moisture content of 8 to 13% by weight typically contain 17 to 25% by weight of glycerin.
  • the casing weight is generally 65 to 140 g / m 2 , preferably 70 to 120 g / m 2 .
  • the diameter of the tubular casing is generally 40 to 300 mm, preferably 49 to 250 mm.
  • the casings according to the invention are produced with the aid of methods and devices which are known per se to the person skilled in the art.
  • other additives e.g. B. cellulose ether added.
  • the mixture is then extruded using a ring die.
  • the viscose mixture is applied from the inside, from the outside or from both sides to a fiber insert which is shaped into a tube (known as internal, external or double viscosity).
  • the fiber-reinforced hose, if necessary, an acidic precipitation bath then runs in which the cellulose xanthate is regenerated to cellulose.
  • the gel tube then runs through further precipitation and washing baths, is then dried and then conditioned to the desired final moisture by spraying with water.
  • the final moisture is generally 8 to 13% by weight.
  • the casing can also be pre-moistened ready for filling. Then she has one
  • the casing according to the invention is produced by the amine oxide process, it is dissolved in water-containing amine oxide, in particular in NMMO monohydrate
  • spinning solution is extruded through an annular die.
  • the cellulose is then precipitated in a bath containing a dilute aqueous solution
  • the preferred amine oxide is N-methyl-morpholine-N-oxide.
  • Fiber casings can also be produced using the NMMO process.
  • Spinning solution is then applied to a fiber material formed into a tube.
  • the coating or impregnation is then applied by methods which are known in principle to the person skilled in the art.
  • the food casing according to the invention is primarily used as an artificial sausage casing which can be used for raw, scalded or cooked sausage.
  • the casing can be available as rolled goods, in the form of individual sections tied off at one end or otherwise closed and / or in an increased form to form so-called shirred sticks.
  • the moisture in the shirred sticks is 14 to 35%, preferably 16 to 30%, depending on the field of application.
  • Percentages are percentages by weight unless otherwise stated or can be seen from the context.
  • a sausage meat from 70% meat (from the shoulder of the pork) and 30% bacon (back bacon from the pork), which was stored at -30 ° C., and 24 g / kg nitrite curing salt were used.
  • the water activity (a w value) was 0.98-0.99 and the pH 6.0 (measured 24 hours after slaughter).
  • the ingredients were at
  • a meat sausage was made; the filled intestine was heated with the caliber 4560-70 min and with the caliber for 902 hours at 75-78 ° C.
  • Example 1 a standard NaloFiber type, single-viscosity, with a diameter of 45 mm (caliber 45) and a weight per unit area of about 77 g / m 2 was used. While in Example 1 the casing remained uncoated for comparison purposes, in Examples 2 to 3 it was coated on the inside with polyvinylamine ( ⁇ Luresin PR 8086 from BASF Aktiengesellschaft). For this purpose, solutions were used which, in addition to polyvinylamine, also contained water and 4% glycerol in the proportions given in the table. The solutions were adjusted to a pH of 6.5 to 7.0. They were in the form of a
  • Liquid bubble passed through the tube (“slug coating”).
  • the shell was then dried by standard methods known to the person skilled in the art.
  • a standard NaloFiber type, double-viscous, caliber 90 with a basis weight of about 87 g / m 2 was used in Examples 5 to 8.
  • the cellulose was divided into 50% each of the inside and outside viscose.
  • the casing according to Comparative Example 5 was not impregnated on the inside.
  • the casings according to Examples 6 to 8 were impregnated on the inside with polyvinylamine as described (pH value of the solutions again 6.5 to 7.0).
  • the adhesive properties of the casing can be specifically adjusted to the respective food by varying the amount of polyvinylamine.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Food Science & Technology (AREA)
  • Packging For Living Organisms, Food Or Medicinal Products That Are Sensitive To Environmental Conditiond (AREA)
  • Processing Of Meat And Fish (AREA)

Abstract

L'invention concerne un emballage pour aliments recouvert ou imprégné à base de cellulose, dont l'imprégnation et le revêtement comprend au moins un polymère contenant des unités de vinylamine. L'invention concerne également un procédé de production et d'utilisation dudit emballage en tant qu'enveloppe artificielle pour saucisses.
PCT/EP2004/014264 2003-12-19 2004-12-15 Emballage pour aliments impregne ou recouvert de polyvinylamines a base de cellulose regeneree Ceased WO2005061610A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10360609.2 2003-12-19
DE2003160609 DE10360609A1 (de) 2003-12-19 2003-12-19 Mit Polyvinylaminen imprägnierte oder beschichtete Nahrungsmittelhülle auf Basis von regenerierter Cellulose

Publications (1)

Publication Number Publication Date
WO2005061610A1 true WO2005061610A1 (fr) 2005-07-07

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Family Applications (1)

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PCT/EP2004/014264 Ceased WO2005061610A1 (fr) 2003-12-19 2004-12-15 Emballage pour aliments impregne ou recouvert de polyvinylamines a base de cellulose regeneree

Country Status (2)

Country Link
DE (1) DE10360609A1 (fr)
WO (1) WO2005061610A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008055857A3 (fr) * 2006-11-10 2009-02-19 Basf Se Revêtements à effet biocide

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB814760A (en) * 1955-10-12 1959-06-10 Union Carbide Corp Casings and method of making same
DE3711712A1 (de) * 1987-04-07 1988-10-27 Hoechst Ag Lebensmittelhuelle auf basis von cellulose mit vernetzten eiweissverbindungen
WO1997036799A1 (fr) * 1996-04-01 1997-10-09 Cryovac, Inc. Film de transfert d'agent modifiant et procede de cuisson d'une denree alimentaire
EP0878133A1 (fr) * 1997-05-14 1998-11-18 Devro-Teepak, Inc. Enveloppes pour aliments ayant des propriétés de décollage améliorées et leur procédé de fabrication
US6451884B1 (en) * 1998-01-15 2002-09-17 Acordis Kelheim Gmbh Cellulosic particles and methods of making them

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB814760A (en) * 1955-10-12 1959-06-10 Union Carbide Corp Casings and method of making same
DE3711712A1 (de) * 1987-04-07 1988-10-27 Hoechst Ag Lebensmittelhuelle auf basis von cellulose mit vernetzten eiweissverbindungen
WO1997036799A1 (fr) * 1996-04-01 1997-10-09 Cryovac, Inc. Film de transfert d'agent modifiant et procede de cuisson d'une denree alimentaire
EP0878133A1 (fr) * 1997-05-14 1998-11-18 Devro-Teepak, Inc. Enveloppes pour aliments ayant des propriétés de décollage améliorées et leur procédé de fabrication
US6451884B1 (en) * 1998-01-15 2002-09-17 Acordis Kelheim Gmbh Cellulosic particles and methods of making them

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008055857A3 (fr) * 2006-11-10 2009-02-19 Basf Se Revêtements à effet biocide

Also Published As

Publication number Publication date
DE10360609A1 (de) 2005-07-28

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