EP0944667A2 - Films elastiques a biodegradabilite amelioree et leur procede de production - Google Patents

Films elastiques a biodegradabilite amelioree et leur procede de production

Info

Publication number
EP0944667A2
EP0944667A2 EP97953730A EP97953730A EP0944667A2 EP 0944667 A2 EP0944667 A2 EP 0944667A2 EP 97953730 A EP97953730 A EP 97953730A EP 97953730 A EP97953730 A EP 97953730A EP 0944667 A2 EP0944667 A2 EP 0944667A2
Authority
EP
European Patent Office
Prior art keywords
ester
film according
amide
film
acid
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Withdrawn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
EP97953730A
Other languages
German (de)
English (en)
Inventor
Dirk Schultze
Gunter Weber
Ralf Schledjewski
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.)
Dow Produktions und Vertriebs GmbH and Co oHG
Original Assignee
Wolff Walsrode AG
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 Wolff Walsrode AG filed Critical Wolff Walsrode AG
Publication of EP0944667A2 publication Critical patent/EP0944667A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L28/00—Materials for colostomy devices
    • A61L28/0007—Materials for colostomy devices containing macromolecular materials
    • A61L28/0026—Mixtures of macromolecular compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/06—Polyurethanes from polyesters
    • 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
    • C08L77/12—Polyester-amides
    • 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/06—Polyurethanes from polyesters
    • 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
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/12—Polyester-amides

Definitions

  • This invention relates to elastic films which are distinguished by an improved biodegradability of the polymer resins used for their production.
  • Films are obtained using mixtures of thermoplastic ester-amide copolymers and thermoplastic polyurethanes (TPU).
  • TPU thermoplastic polyurethanes
  • TPU as a class of substances, their properties and processing options are described in the Plastics Manual, Volume 7, Polyurethane, ed. G. Oertel, 2nd edition, Hanser-Verlag, Kunststoff 1983.
  • the calender process known from the prior art for forming web-shaped semifinished products is, however, only of limited suitability, in particular for the thermal digestion of (partially) crystalline polymers such as TPU or polyester amides, since the heat of fusion is not sufficient on calender systems high machine throughput, as Krüger or Hoppe used in plastic
  • Blends of TPU and various other polymer resins are also described in the literature. TPU / ABS blends have been known since 1978, as described by Utracki in Polymer Engineering and Science, 35 Jhrg (1995), No. 1, pages 2-17. Blends made from reactive resins, but which have impaired deep-drawing behavior, are, for example, in DE 39 27 720 mentioned
  • Compatibilizers can be added to improve the homogeneity of the mixture
  • At least partial biodegradability is expected from ostomy aids today. They should also nestle softly and elastically to body movements. Soft, skin-friendly wrappings with a high level are required for this
  • the present invention thus relates to films with soft elastic
  • Biodegradable resins or resin mixtures or foils are defined in accordance with DIN 54 900 (draft 1996) with regard to their biodegradability.
  • the present invention relates to foils which, with regard to their biodegradability, are degraded from aromatic thermoplastic polyurethanes better than those known from the prior art
  • the films according to the invention had an appealing level of mechanical properties. These properties go hand in hand with an unusually low half-life for biodegradability for thermoplastics According to the invention, preference is given to films having a Shore D hardness of less than 55, measured in accordance with DIN 53 505.
  • thermoplastic polyurethane elastomers for the mixtures according to the invention are preferably composed of predominantly linear thermoplastic polyurethane elastomers, the longer-chain diol component of which is a polyester or polyether, and which have a Shore hardness of preferably 75-95 A, particularly preferably 85-92 A according to DIN 53 505.
  • thermoplastic polyurethanes are, for example, under the trade names
  • the suitable thermoplastic polyurethanes have a molecular weight of at least 10,000 g / mol and have a block-like sequence of the hard and soft segment starting materials (monomers) in the polymer resin.
  • the films according to the invention have elastic urethane elastomer formulation components, the soft segment phase of which is predominantly formed from ester soft segment building blocks.
  • thermoplastic ester-amide copolymers for the inventive
  • Mixtures are preferably formed from predominantly linear, thermoplastic ester-amide copolymers
  • ester fraction from linear and / or cycloaliphatic bifunctional alcohols for example ethylene glycol, hexanediol or butanediol, is preferred
  • Butanediol or cyclohexanedimethanol and in addition, if appropriate, small amounts of higher-functional alcohols, for example 1,2,3-propanetriol or neopentyl glycol, and also from linear and / or cycloaliphatic bifunctional acids, for example succinic acid, adipic acid, cyclohexanedicarboxylic acid, preferably adipic acid and additional, if appropriate, small
  • Amounts of higher functional acids for example trimellitic acid, or B) an ester fraction from acid- and alcohol-functionalized building blocks, for example hydroxybutyric acid or hydroxyvaleric acid, or their derivatives, for example ⁇ -caprolactone,
  • an amide component from linear and / or cycloaliphatic bifunctional and additionally optionally small amounts of higher functional amines, for example tetramethylene diamine, hexamethylene diamine, isophorone diamine, and from linear and / or cycloaliphatic bifunctional acids, for example succinic acid or adipic acid or
  • ester fraction A) and / or B) is at least 30% by weight based on the sum of A), B), C) and D).
  • the biodegradable and compostable polyester amides have a molecular weight of at least 10,000 g / mol and have a statistical distribution of the starting materials (monomers) in the polymer.
  • thermoplastic polyurethanes and polyesteramide copolymers mix in a compatible manner, i.e. the properties of the blend components correspond proportionately to those of the pure raw material components used.
  • mechanical strength properties of the resin mixtures according to the invention are not as with incompatible ones
  • Plastics usually fall below the parameters of the raw materials used.
  • separation images are used, for example, for mixtures of thermoplastic Polyurethanes with low-density polyethylene resins have been observed, for which it is known to those skilled in the relevant art that strengths are observed with these blends which are 10 N / mm 2 below the level of pure polyethylene.
  • such blends have strongly anisotropic segregation structures have, in which the different phases form domains oriented in the processing direction
  • the polymer resins mixed for this invention already have multiphase structures in themselves, so that in the present invention there is a mutual expansion of the network-like structures Structures of the mixing partners must be assumed.
  • the mixtures according to the invention can be processed into films which have properties which do not obviously represent the corresponding proportionate properties of the mixed polymer resins used
  • Films which are particularly suitable according to the invention are distinguished in that they have a thermoplastic ester-amide content of at least 30% by weight and a thermoplastic polyurethane content of at least 20% by weight
  • a suitable embodiment of the films according to the invention additionally contains useful additives from the group I. antiblocking agents, inorganic or organic spacers,
  • Particularly suitable inorganic additives come from the group comprehensively
  • V natural and synthetic silica or silicates, also layered silicates, VT. Titanium dioxide,
  • Films with a total thickness between 20 ⁇ m and 500 ⁇ m are preferred according to the invention.
  • the conventional thermal forming processes for processing plastics into sheet-like structures by extrusion, which is preferably carried out by the blown film process, are particularly suitable for producing the film according to the invention.
  • the films according to the invention can be modified on one or both sides in their surface properties using the known physical and chemical treatment methods such as, for example, the corona treatment.
  • Polymer mixtures, blends or blends can be produced by mechanically mixing melts, latices or solutions of two separately produced polymer resins or in-situ polymerisation of monomers in the presence of a pre-formed polymer resin. This is advantageously done by melt mixing two separately produced polymer resins.
  • the polymer resins which are usually in the form of bales, granules or powders, are mixed in kneaders or with extruders.
  • the thermoplastic polymer resins suitable according to the invention are heated above the glass or melting temperature. Good mixing is achieved at higher temperatures and / or under strong shear fields.
  • the polymer resins used for film extrusion are subjected to a premixing in a softened state in a compounding step.
  • Suitable tools for such a mixing step are the compounding agents known in their type. Tools Tools with several screws, but especially the two-screw kneaders popular for compounding, have proven to be advantageous.
  • the film according to the invention is suitable in the form of film tubes but also in the form of individual layers or webs for welding against itself. However, it is also suitable for welding against stiffer films, for example for shaping air-filled orthopedic support pillows with a preferred direction of deformation under pressure.
  • the welding can be carried out according to all techniques common for ester-amide copolymers or TPU, also by thermal or high-frequency or ultrasonic welding against oneself or other suitable substrate materials.
  • thermo- The construction of screw tools suitable for plastic resins is described, for example, by Wortberg, Mahlke and Effen in: Kunststoffe, 84 (1994) 1131-1138, by Pearson in: Mechanics of Polymer Processing, Elsevier Publishers, New York, 1985, by Stevens and Covas in: Extruder Principles and Operation, Chapman & Hall, 2nd ed., London 1995 or Davis Standard in: Paper, Film & Foil Converter 64 (1990) pp. 84-90. Tools for shaping the melt into foils are explained by Michaeli in: Extrusions-Werkmaschinee, Hanser Verlag, Kunststoff 1991.
  • a film was produced for which a prefabricated compound was used as the raw material.
  • the compound consisted of 49% by weight ester-amide copolymer resin with a Shore A hardness greater than 95.
  • the extrusion device was operated at temperatures between 130 ° C and 180 ° C.
  • the compound melt flow was in a blown film head with a
  • the ring-shaped melt plume was cooled by blowing with air, then laid flat, trimmed in the edge area and wound up in the form of 50 ⁇ m-thick individual webs.
  • a film was produced analogously to Example A with a thickness of 50 ⁇ m.
  • the raw materials were combined shortly before the extruder was drawn in, the composition of the blend being 68.5% by weight of TPU, 29% by weight of ester-amide copolymer resin, 1.5% by weight of silicate and 1% by weight .-% waxes is represented.
  • a film was again produced analogously to Example A in a thickness of 50 ⁇ m.
  • the composition of the blend was 58.5% by weight of ester-amide copolymer, 39.5% by weight of TPU, 1% by weight of waxes and 1% by weight of silicate. Comparative Example 1:
  • a TPU film was produced under the parameters mentioned for example A.
  • the composition of the translucent 50 ⁇ m thick film was 97% by weight of a TPU of Shore A hardness 92 with a polyadipate-based soft segment phase and
  • a 50 ⁇ m thick ester-amide copolymer film was produced using 98% by weight copolyesteramide with a Shore A hardness greater than 95, 1% by weight silicate and 1% by weight amide wax.
  • the processing parameters corresponded to Example A, but the extrusion tool was only operated at temperatures of 130-170 ° C, the melt temperature was 190 ° C.
  • the films produced in the examples and comparative examples were evaluated in part with regard to properties relevant to the application, such as skin / handle friendliness or haptic properties, and biodegradability.
  • the evaluation of these relevant properties was obtained by subjective evaluation by several independent persons and the evaluations are given in Table 1. As far as possible, the subjective assessments were verified using standardized test procedures.
  • the feel is a property that is a mixture of Shore hardness, analogous to DIN 53 505, tension at low deformations (for elastomers here: 100%) according to ISO 527 and friction coefficients according to DIN 53 375.
  • the haptics were assessed manually on the manufactured film webs.
  • the mechanical parameters of tear resistance and tensile strength as well as the characteristics of the tensile test, tension at 100% elongation, tensile strength and elongation at break were determined in accordance with DIN 53 515 and ISO 527.
  • the softening range determines both the processing properties when
  • the oxygen permeability (O2-Du, DIN 53 380, part 3) reflects important application-relevant variables. Good odor-tightness is of great importance for use in ostomy aids. For the filling with metabolic products it is of great importance that the filling medium or its gas or vapor phase does not escape, or at least is significantly inhibited.
  • the table below shows characteristic data of the films produced in the examples and comparative examples.
  • the films shown in the examples are clearly superior to the films from the comparative examples known from the prior art, in particular with regard to their biodegradability.
  • the films according to the invention offer advantages in terms of wearing comfort and elasticity.
  • the films according to the invention improved the properties of the TPU film.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • Materials Engineering (AREA)
  • General Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Epidemiology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

Ce film en matières polymères moulables est sensiblement constitué de mélanges de polymères d'esters et d'amides et de polyuréthannes. Les polymères d'esters et d'amides sont à leur tour sensiblement constitués de copolymères d'esters et d'amides surtout linéaires dont le poids moléculaire dépasse 10.000 g/mol et les polyuréthannes thermoplastiques ont un point de fusion inférieur à 200 DEG C.
EP97953730A 1996-12-13 1997-12-01 Films elastiques a biodegradabilite amelioree et leur procede de production Withdrawn EP0944667A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE1996152037 DE19652037A1 (de) 1996-12-13 1996-12-13 Elastische Folien mit verbesserter biologischer Abbaubarkeit sowie Verfahren für ihre Herstellung
DE19652037 1996-12-13
PCT/EP1997/006729 WO1998025992A2 (fr) 1996-12-13 1997-12-01 Films elastiques a biodegradabilite amelioree et leur procede de production

Publications (1)

Publication Number Publication Date
EP0944667A2 true EP0944667A2 (fr) 1999-09-29

Family

ID=7814705

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97953730A Withdrawn EP0944667A2 (fr) 1996-12-13 1997-12-01 Films elastiques a biodegradabilite amelioree et leur procede de production

Country Status (5)

Country Link
EP (1) EP0944667A2 (fr)
JP (1) JP2001505945A (fr)
AU (1) AU5753498A (fr)
DE (1) DE19652037A1 (fr)
WO (1) WO1998025992A2 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19811225A1 (de) * 1998-03-18 1999-09-30 Wolff Walsrode Ag Verbesserung der Hydrolysestabilität von Folien aus biologisch abbaubaren Polymeren und Verfahren zur Herstellung solcher Folien
EP1022127A3 (fr) * 1999-01-25 2001-08-08 Cryovac, Inc. Film barrière biodégradable pour poche d'ostomie
US7220816B2 (en) * 2003-12-16 2007-05-22 Advanced Cardiovascular Systems, Inc. Biologically absorbable coatings for implantable devices based on poly(ester amides) and methods for fabricating the same
US7435788B2 (en) 2003-12-19 2008-10-14 Advanced Cardiovascular Systems, Inc. Biobeneficial polyamide/polyethylene glycol polymers for use with drug eluting stents
US8685431B2 (en) * 2004-03-16 2014-04-01 Advanced Cardiovascular Systems, Inc. Biologically absorbable coatings for implantable devices based on copolymers having ester bonds and methods for fabricating the same
JP4978426B2 (ja) * 2007-10-31 2012-07-18 横浜ゴム株式会社 硬化性樹脂組成物
FR2992652B1 (fr) * 2012-06-27 2014-06-20 Arkema France Utilisation d'un alliage d'amidon thermoplastique et de tpe pour la fabrication d'un film ultra-fin imper-respirant adhesif.

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DK0442786T3 (da) * 1990-02-13 1996-01-02 Atochem Elf Sa Fremgangsmåde til omdannelse af termoplastiske polyurethaner ved ekstrudering og modificeringsmidler anvendt ved denne fremgangsmåde
NZ239723A (en) * 1990-09-18 1993-06-25 Chicopee Blends comprising a hydrophilic block poly (ether-co-amide) and a hydrophobic polymer
DE4035140A1 (de) * 1990-11-06 1992-05-07 Bayer Ag Thermoplastische polyurethan-formmassen
EP0657505A1 (fr) * 1993-12-10 1995-06-14 Toyo Boseki Kabushiki Kaisha Composition à base de polyamide

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9825992A3 *

Also Published As

Publication number Publication date
AU5753498A (en) 1998-07-03
DE19652037A1 (de) 1998-06-18
JP2001505945A (ja) 2001-05-08
WO1998025992A3 (fr) 1998-07-23
WO1998025992A2 (fr) 1998-06-18

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