EP1893673A1 - Element de moulage a base de collagenes - Google Patents

Element de moulage a base de collagenes

Info

Publication number
EP1893673A1
EP1893673A1 EP06754121A EP06754121A EP1893673A1 EP 1893673 A1 EP1893673 A1 EP 1893673A1 EP 06754121 A EP06754121 A EP 06754121A EP 06754121 A EP06754121 A EP 06754121A EP 1893673 A1 EP1893673 A1 EP 1893673A1
Authority
EP
European Patent Office
Prior art keywords
collagen
shaped body
extrudate
prefilm
precipitation bath
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Withdrawn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
EP06754121A
Other languages
German (de)
English (en)
Inventor
Herbert Gord
Klaus-Dieter Hammer
Jürgen MELLE
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 EP1893673A1 publication Critical patent/EP1893673A1/fr
Withdrawn legal-status Critical Current

Links

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
    • A22C13/0016—Chemical composition of synthetic sausage casings based on proteins, e.g. collagen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • B29C48/10—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels flexible, e.g. blown foils
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/919—Thermal treatment of the stream of extruded material, e.g. cooling using a bath, e.g. extruding into an open bath to coagulate or cool the material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2093/00—Use of natural resins, e.g. shellac, or derivatives thereof, as moulding material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2389/00—Characterised by the use of proteins; Derivatives thereof
    • C08J2389/04—Products derived from waste materials, e.g. horn, hoof or hair
    • C08J2389/06—Products derived from waste materials, e.g. horn, hoof or hair derived from leather or skin

Definitions

  • the invention relates to moldings based on collagen, a process for their preparation and the use of the moldings, in particular as a food casing or for medical purposes.
  • Shaped bodies of collagen fibrils are known. However, these are extremely roughly structured. They contain pores and are not sufficiently firm and supple. They can not be made to have a compact and dense structure. Alternatively, molded bodies of hydrolyzed collagen, i. made of gelatin, developed. However, the degree of hydrolysis varies greatly. The gelatin obtained in the hydrolysis is a mixture of
  • Polypeptide chains of different lengths and therefore different molecular weight are polypeptide chains of different lengths and therefore different molecular weight.
  • Fiber masses in sheet-like material are also known (US Pat. Nos. 2,934,446 and 2,934,447).
  • films of synthetic polymers for example of polyamide, polyolefin (in particular of polyethylene or polypropylene), polyurethane, polylactide or mixtures thereof.
  • these materials are unsuitable because they are not sufficiently compatible with the body's own tissue. They remain foreign bodies and usually have to be removed because of incompatibility. If the films are used as artificial food casings, then they are not for
  • Co-consumption suitable is suitable.
  • This also applies to the tubular films according to DE-A 199 61 843.
  • the solution is then shaped by extrusion bubbles and the molding solidified in an aqueous precipitation bath.
  • the casings made from a mixture of cellulose, a globular protein and an insoluble filler, likewise produced by the NMMO process are edible (DE-A 101 29 5391).
  • the moldings should be compatible with body tissue, so that they can also be used in surgery. For use in the medical field, it is particularly important that they are free of cellulose.
  • moldings in film form should be able to be used as artificial food casings which are suitable for co-consumption. Not only do they have to be chewable, they also have to be digestible.
  • collagen fibrils can be homogeneously dissolved in N-methylmorpholine N-oxide monohydrate at 80 to 110 ° C. and give a transparent, viscous solution which does not change even after prolonged heating. Treating with a precipitating fluid, such as water or a dilute aqueous NMMO solution, may cause the collagen fibrils to precipitate out again.
  • a precipitating fluid such as water or a dilute aqueous NMMO solution
  • the present invention thus provides a process for the production of collagen-based shaped articles which is characterized in that collagen fibrils are homogeneously dissolved in an optionally hydrous amine oxide, the mass is extruded with the dissolved collagen fibrils or shaped into a prefilm in that the extrudate or the precursor film is treated with an aqueous precipitation bath liquid in which the collagen polypeptides are precipitated and the extrudate or prefilm is solidified into a shaped article.
  • Fibril-producing collagens belong to the multidomain proteins with 3 collagen ⁇ -chains wound into a triple helix. Unlike any other In known processes, the polypeptide chains of the collagen fibrils undergo virtually no hydrolytic degradation in the process according to the invention. They are not split but go into solution at their original length. In the first dissolution step, the numerous tropocollagens that are assembled into a fibril are separated. In the second release step, the three
  • Polypeptide chains each forming a triple helix, separated from each other.
  • the secondary and tertiary structure of the collagen is thus eliminated in the solution.
  • Each of the peptide chains has about 1,000 amino acids linked to it. They have a length of about 2,800 ⁇ (corresponding to 280 nm), and a thickness of about 14 ⁇ (corresponding to 1, 4 nm).
  • the preferred solvent for the collagen fibrils is N-methylmorpholine N-oxide monohydrate (NMMO-MH).
  • the solution generally contains about 6 to 30% by weight of collagen, preferably about 10 to 15% by weight. Even after prolonged heating of the solution virtually no polypeptide chains are cleaved, recognizable by a constant viscosity. The viscosity of the solution is determined by the concentration of the polypeptide chains and the temperature of the solution.
  • the collagen By extruding the hot, viscous solution in water or a dilute aqueous amine oxide solution, the collagen can be precipitated again.
  • the extrusion dies can be used as thread spinning nozzles, slot dies or
  • Ring nozzles are formed so that threads, flat films or tubular films arise.
  • precipitation liquid is expediently also conducted into the interior of the tubes.
  • the structure of the precipitated collagen, and thus the mechanical properties and the permeability of the moldings, can be varied within wide limits and adapted to the particular application.
  • the composition and the temperature also affect the structure of the precipitated collagen. The higher the amine oxide concentration in the precipitation bath, i. in particular, the higher the NMMO concentration, the slower and the more compact the polypeptide is precipitated. A very compact structure is obtained using an aqueous precipitation bath which
  • Porous films useful, for example, as a wound-covering material, on the other hand, are obtained when extruded into an aqueous precipitation bath having a lower NMMO concentration (generally less than 10% by weight).
  • the film thickness can also be selected within a wide range. It can be from 10 ⁇ m - or even less - to 100 ⁇ m and more. Preferably, the thickness is about 20 to 85 microns, more preferably 30 to 70 microns. To this
  • the collagen can be replaced by up to 49%, preferably 5 to 25%, by cellulose. In exceptional cases, the collagen can even be replaced by cellulose up to 90%.
  • the cellulose is dissolved purely physically in the aforementioned warm NMMO-MH, i. without being chemically altered. Their average degree of polymerization (DP) therefore does not decrease practically.
  • the DP determined by the Cuoxam method, is preferably about 300 to 900, preferably 500 to 850.
  • dilute aqueous amine oxide in particular in dilute aqueous NMMO, the cellulose is also reprecipitated, together with the collagen.
  • Fillers are, for example, bran, in particular wheat bran, ground natural fibers, in particular ground flax, hemp or cotton fibers, cotton linters, guar gum, locust bean gum, powdered SiO 2 and / or ground calcium carbonate.
  • the maximum diameter of the filler particles should preferably be not more than 100 .mu.m, preferably not more than 65 .mu.m.
  • the proportion of filler is generally 3 to 50 wt .-%, preferably 4 to 40 wt .-%, each based on the dry weight of the film.
  • hydrophilic additives the chewability can be further improved.
  • the additives are generally soluble in NMMO-MH.
  • Preferred additives are starch and starch derivatives, such as starch acetate, chitin,
  • hydrophilic additives is generally about 0.5 to 15 wt .-%, preferably about 1 to 10 wt .-%, each based on the total weight of the film.
  • the spinning solution is generally not extruded directly into the precipitation bath, but previously passes through an air gap.
  • the air gap has expediently a length of a few millimeters up to 10 cm or even more.
  • a tubular extrudate can be inflated and stretched by an internal gas pressure.
  • the orientation of the polypeptide chains in the longitudinal direction which prevails immediately after the extrusion, can thereby be changed. If the polypeptide chains are arranged by stretching on average at an angle of 45 ° to the extrusion direction, then a film with uniform properties in the longitudinal and transverse directions is obtained.
  • the shaped body After leaving the spinning bath, the shaped body is washed with water until it is free of amine oxides. This is expediently carried out in a countercurrent process.
  • the molded article in particular the film, can still be impregnated with a plasticizer, such as glycerol or sorbitol.
  • a plasticizer such as glycerol or sorbitol.
  • the molding - with or without plasticizer - is then usually dried, for example by hot air.
  • Thicker films in particular those for medical and surgical purposes, can be produced by cast film processes.
  • the dope is poured into the desired thickness in a mold, the molded mass then treated with Klallbadproblemkeit and finally washed until the cast film is free of amine oxides.
  • the dope is poured into the desired thickness in a mold, the molded mass then treated with Klallbadproblemkeit and finally washed until the cast film is free of amine oxides. In this way can be foils of several millimeters
  • Thickness (up to about 10 mm), which can then be processed into cartilage replacement material.
  • the moldings can be further modified, for example by treatment with lubricants.
  • lubricants are in particular triglycerides of long-chain fatty acids, such as stearic acid or erucic acid.
  • natural waxes for. B. carnauba wax.
  • Such lubricant-containing films can inter alia as cartilage replacement material, the friction in joints, for example in artificial
  • Films to be used as wound cover can also be made porous with the addition of slightly water-soluble salts, such as sodium lactate or sodium hydrogen carbonate, which are then dissolved out.
  • Novel, particularly well-tolerated suture materials, biocompatible wound-covering materials, medical films and tubes can be produced in a simple and cost-effective manner by the method according to the invention.
  • edible, ie suitable for co-consumption, packaging materials for food can be produced by the process according to the invention.
  • these are edible sausage casings. You can serve as a serving for sausages, sausage or sausage. They then generally have a dry tensile strength of 22 to 35 N / mm 2 in the longitudinal direction and
  • the tear strength is therefore significantly lower in the wet state than in the dry state.
  • the elongation at break when wet is about 10 to 20% in the longitudinal direction and about 25 to 30% in the transverse direction, in the dry state about 10 to 30% in the longitudinal direction and about 20 to 25% in the transverse direction.
  • the present invention also relates to the shaped bodies themselves produced by the process according to the invention.
  • NMMO solution was converted almost completely into NMMO monohydrate.
  • the dope was then at a temperature of 90 ° C by a
  • Annular gap nozzle extruded with a diameter of 40 mm The tube thus obtained passed through a 10 cm long air gap, in which it was held wrinkle-free by supporting air acting from inside, before it entered the precipitation bath.
  • the precipitation bath consisted of a 25% aqueous NMMO solution which had been heated to 25 ° C.
  • Precipitation bath liquid of the same composition also reached the interior of the film tube
  • the level of this so-called inner bath was kept at approximately the same level as that of the outer bath
  • the tubing was passed through a pulley placed near the bottom of the precipitating bath, thus passing through an effective felling distance of 3 m, the tube being stretched so far that its flat width after leaving the spinning vat 70 mm was. He went through after 8 wash vats, each with 8 deflection rollers, m a bath depth of 2.5, and m is an air gap of 0.5.
  • the tubes By cutting the tubes could produce films with a width of 140 mm and virtually any length. They were very supple and resistant to abrasion. The thickness of the films was about 40 microns.
  • the precipitation of the polypeptides was then carried out by treating the tube from the inside and the outside in a bath containing a 10% aqueous NMMO solution, which was heated to 10 ° C. Under these conditions, the polypeptide spontaneously precipitated and assumed a porous structure. The felling distance was again 3 m, the tube was deflected in the same way halfway. After leaving the spinning vat, the flat width of the hose was 64 mm. It was followed by an intensive washing process, in which the hose passed 8 skids with 8 pulleys. Water was in the Passed countercurrently through the wash baths. The temperature increased to 80 0 C in the last wash. The tube was then dried as described in Example 1 in a hot air dryer to a final moisture content of 10 to 12%. He was then wound up in flattened form.
  • the tube had a wall thickness of about 55 microns. Slicing was used to produce films, which were used i.a. suitable as wound cover.
  • Example 4 4.48 kg of wheat bran (particle size smaller than 63 ⁇ m) became a 60 in 68 kg
  • % aqueous NMMO solution stirred. To the suspension was then added 3.2 kg of collagen fibrils. By adding NaOH, a pH of 11 was set. For stabilization, an additional 12 g of propyl gallate were added. In a stirred tank with internals to increase the shear, water was distilled off at reduced pressure (25 mbar) and increasing temperature until the aqueous NMMO was present as NMMO monohydrate.
  • the spinning mass thus obtained had a refractive index of 1, 4885 and a zero shear viscosity of 7,100 Pa s, each determined at 85 ° C. At a temperature of 90 0 C, the spinning mass through a ring die with a diameter of 20 mm and a gap width of 0 Extruded 5 mm.
  • the tubular extrudate passed through a 10 cm long air gap, in which it was kept wrinkle-free by compressed air acting from inside. He then entered a precipitation bath containing 15 ° C tempered 15% aqueous NMMO solution. The same cooled precipitation bath liquid was also introduced into the interior of the tube with the level of the inner precipitation bath being maintained at about the same level as that of the outer bath. The mecanicalbad was continuously renewed, as in all other examples. Overall, the hose passed through a felling path with a length of 3 m, where it was deflected at half distance by a roller located at the bottom of the bath. The hose was then stretched so far that he had a flat width of 35 mm when leaving the spinning vat.
  • the hose was passed through a softener vat containing a 10% aqueous solution of glycerine, leaving the glycerine vial with a flat width of 35 mm
  • the air needed for inflation was held between two sets of squeeze rollers as described above, the hot air dryer had several temperature zones, the temperature decreasing from one zone to the next, and the temperature in the entry zone was still 120 ° C C it fell to 80 ° C.
  • the finished casing showed a dry tensile strength of 28.5 N / mm 2 in the longitudinal direction and 22, 5 N / mm 2 in the transverse direction and a wet tensile strength of 7.5 N / mm 2 in the longitudinal direction and 5.5 N / mm 2 in the transverse direction one to
  • Clip device filled with sausage meat, steamed and smoked.
  • the characteristics of the sausages were just as good as those of sausages in the usual skin fiber intestines.
  • the precipitation was then carried out by treating the tube from the inside as well as from the outside in a bath containing a 10% aqueous NMMO solution on
  • the hose was excellently suited as a sausage casing and, when cut open, could also be used for other packaging purposes, in particular in the food sector.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Zoology (AREA)
  • Food Science & Technology (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials For Medical Uses (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention concerne un procédé pour réaliser des éléments de moulage à base de collagènes, selon lequel des fibrilles de collagène sont dissoutes de manière homogène dans un oxyde d'amine éventuellement aqueux, la solution est ensuite extrudée ou moulée en une ébauche de feuille, le produit extrudé ou l'ébauche de feuille est traité dans un bain de précipitation aqueux, dans lequel les polypeptides de collagènes sont précipités et le produit extrudé ou l'ébauche de feuille est solidifié en un élément de moulage. La présente invention porte également sur un élément de moulage réalisé selon ce procédé et sur son utilisation comme matière de suture chirurgicale, de couverture de plaie ou de substitution du cartilage, et comme enveloppe comestible de produits alimentaires, notamment en tant que boyau synthétique comestible pour saucisses.
EP06754121A 2005-06-09 2006-06-03 Element de moulage a base de collagenes Withdrawn EP1893673A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005026747A DE102005026747A1 (de) 2005-06-09 2005-06-09 Formkörper auf Basis von Kollagen
PCT/EP2006/005339 WO2006131285A1 (fr) 2005-06-09 2006-06-03 Element de moulage a base de collagenes

Publications (1)

Publication Number Publication Date
EP1893673A1 true EP1893673A1 (fr) 2008-03-05

Family

ID=36799318

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06754121A Withdrawn EP1893673A1 (fr) 2005-06-09 2006-06-03 Element de moulage a base de collagenes

Country Status (3)

Country Link
EP (1) EP1893673A1 (fr)
DE (1) DE102005026747A1 (fr)
WO (1) WO2006131285A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120201995A1 (en) * 2009-09-30 2012-08-09 Melle Juergen Moulded body having cladding material and carrier material and method for the production thereof
CN103751848B (zh) * 2014-01-27 2016-02-10 东南大学 一种抗菌修复型静电纺丝胶原蛋白-细菌纤维素复合纳米纤维支架的制备方法及其应用

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4615033B1 (fr) * 1967-09-16 1971-04-22
DE19841649A1 (de) * 1998-09-11 2000-04-27 Thueringisches Inst Textil Verfahren zur Herstellung und produktorientierten Verarbeitung von konzentrierten Lösungen fibrillärer Proteine in NMMNO-Monohydrat
DE19961843A1 (de) * 1999-12-21 2001-07-05 Fraunhofer Ges Forschung Schlauchfolien aus Cellulose-Protein-Blends

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2006131285A1 *

Also Published As

Publication number Publication date
DE102005026747A1 (de) 2006-12-21
WO2006131285A1 (fr) 2006-12-14

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