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EP1090064A1 - Film thermoplastique mousse a partir de matieres biodegradables - Google Patents

Film thermoplastique mousse a partir de matieres biodegradables

Info

Publication number
EP1090064A1
EP1090064A1 EP99923786A EP99923786A EP1090064A1 EP 1090064 A1 EP1090064 A1 EP 1090064A1 EP 99923786 A EP99923786 A EP 99923786A EP 99923786 A EP99923786 A EP 99923786A EP 1090064 A1 EP1090064 A1 EP 1090064A1
Authority
EP
European Patent Office
Prior art keywords
acid
acids
optionally
mixture
bifunctional
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Withdrawn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
EP99923786A
Other languages
German (de)
English (en)
Inventor
Jürgen LOERCKS
Harald Schmidt
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.)
BioTec Biologische Naturverpackungen GmbH and Co KG
Original Assignee
BioTec Biologische Naturverpackungen 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 BioTec Biologische Naturverpackungen GmbH and Co KG filed Critical BioTec Biologische Naturverpackungen GmbH and Co KG
Publication of EP1090064A1 publication Critical patent/EP1090064A1/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Withdrawn legal-status Critical Current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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
    • 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
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/03—Extrusion of the foamable blend
    • 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
    • C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products

Definitions

  • thermoplastic film made from biodegradable materials
  • the present invention relates to a foamed, thermoplastically processable, thermoformable and weldable semi-finished product or molding or molding consisting of a biodegradable and compostable material / polymer and a process for its production, which is characterized in that the biodegradable and compostable thermoplastic polymer in The extruder is converted into a melt, the melt is gassed with a low-boiling blowing agent directly under pressure, the blowing agent is incorporated into the melt, the melt-blowing agent mixture is cooled to the required molding temperature, extruded through a nozzle at the end of the extruder, and formed into a cellular semi-finished product or molding material or molded part is shaped and expanded, the foamed semi-finished product or molded part having a volume density many times lower than that of its framework substances and as a biodegradable and compostable polymer foam semi-finished product or molded part v is used.
  • Biodegradable foams are already known from a large number of documents that deal with the topic and also show how eminently important the realization of lightweight, fully biodegradable foam plastics is to be assessed. This is because packaging materials or insulating materials are to be made available which are completely biodegradable after use and are particularly light, material-saving, shock-absorbing and insulating due to a foam structure.
  • WO95 / 04104 proposes a foamed, thermoplastic starch polymer which foams when processed by splitting off water by using fibers which bind capillary-active water.
  • WO94 / 05492 describes a biodegradable layered composite material on the basis of hardened starch foam, in which the starch foam is produced by water vapor in a syringe expansion process.
  • WO96 / 07693 discloses a molded part made of starch foam, which is produced by extruding starch into starch foam profiles and further processing into molded parts.
  • WO96 / 07539 in turn shows a sandwich panel with a starch foam core.
  • Patent applications EP-B-0 413 798, EP-A-0 667 369, EP-A-0 696 611 and EP-A-0 696 612 deal with foamed starch-based materials.
  • WO83 / 02955 describes a process in which starch is processed in the presence of water and a blowing agent in an extruder at elevated temperature to form a foam product.
  • EP 0 375 831 and EP 0 376 201 disclose starch foam products and processes for their production from starches containing high amylose.
  • EP 0 696 611, EP 0 667 369 and EP 0 696 612 deal with "loose fillers” based on starch and polymer blends with PVOH, EVOH, PVAc, PU, polyester. Packaging materials can also be produced from these "loose fillers” by agglomeration.
  • a process for producing a foam based on starch is described in DE 23 04 736, the Starch is inflated under the influence of heat and a blowing agent mixture.
  • DE 32 06 751 a starch foam is obtained by an extrusion process using blowing agents that release carbon dioxide.
  • DE 23 65 523 also deals with starch foam.
  • CA-A-2 057 668 proposes a biodegradable polymer foam which, on the one hand, consists of 50% to 100% of one or more homopolymers, which are biodegradable, and from 0% to 50% of a polymer, which is hardly or is not biodegradable at all.
  • the homopolymers are preferably polylactic acid or polymers based on a lactide.
  • synthetic polymers such as polyester, polycarbonate, polysulfone, etc., are mentioned as hardly or not biodegradable polymers, which makes the biodegradability of the proposed foam questionable.
  • the foamed, biodegradable materials have significant disadvantages when used with foamed plastics such as EPS
  • the invention has for its object to provide a biodegradable, compostable foam as a semifinished product or molding or molding with a uniform pore distribution and thermoplastic processing properties, for example as a thermally deformable, foamed film or injection molded foamed molding or molding, the manufacture of End products from the semi-finished product according to the invention with the usual methods of the plastics processing industry by thermoplastic forming, hot forming or deep drawing into biodegradable end products with versatile applications, for example for cups, plates, trays, cups, bowls, portion packs, blister backs, trays, packaging bowls for fruit, vegetables and fresh meat, egg packaging, protective films, sandwich elements, laminated foam films.
  • the foamed semi-finished product according to the invention which has a particularly light density in the sealing range below 300 g / l, consists of biodegradable thermoplastic materials, which are preferably produced on the basis of renewable raw materials such as starch or cellulose and polymer mixtures based on starch or cellulose, from the melt Extrusion produced by continuously introducing a low-boiling blowing agent into the extruder Polymer melt is metered. Depending on the properties of the biodegradable polymers, the melt is gassed directly in the extruder at pressures of 150 - 400 bar. The melt / fuel mixture is then cooled in the extruder to the required molding temperature, continuously injected, molded and directly foamed. The melt-fuel mixture can also be injected into a mold and foamed therein.
  • melt / fuel mixture it is also possible to first extrude, cool and granulate the melt / fuel mixture or to form it as a semi-finished granulate.
  • These granules loaded with fuel or gas can then be foamed in a further separate process step to give molded parts in accordance with customary methods, or can be processed into foamed molded parts by means of hot air / hot steam.
  • thermoplastic polymers The following can be used as biodegradable thermoplastic polymers:
  • Thermoplastic polysaccharides and derivatives thereof such as chitin and its derivatives, cellulose derivatives and starch derivatives - Starch blends with the aforementioned, biodegradable polymers, as well
  • Fluorocarbons as blowing agents or partially halogenated blowing agents are deliberately avoided in this area of application for reasons of environmental compatibility, although the technical function is suitable.
  • Nitrogen and / or carbon dioxide are used as a particularly preferred blowing agent, which take into account the special ecological balance advantages of biodegradable materials based on renewable raw materials such as starch as foam plastics.
  • the biodegradable foam products are extruded in the extruder by direct gassing with the gaseous blowing agent into the polymer melt and continuous or discontinuous further processing in customized plant technology.
  • the individual manufacturing processes are divided into sensible process steps, which are combined depending on the task.
  • the method is used in which the shape and density of the product are achieved in one operation, regardless of the type of blowing agent.
  • the extruder used is preferably a single-shaft extruder with a large cylinder length of approximately L / D 40: 1.
  • the length of the extruder results from the process sequences and is designed for conveying and melting the granulated bioplastic raw material, mixing in the blowing agent and cooling the melt / blowing agent mixture to the molding temperature.
  • the propellant is supplied by suitable, precise metering pumps with the necessary injection pressure while maintaining a constant
  • the foamed semi-finished products are made from biodegradable polymers according to the principle of free expansion on the tool. For this reason, the BAW melt mixture is horizontally formed into a tube during film production. The foam film tube is then pulled over a temperature-adjustable calibration mandrel and stretched and cooled radially and axially. The even expansion and rec- ken is achieved by constant air supply in the space between the nozzle and the calibration mandrel. On the back of the calibration mandrel there are cutting devices on which the foamed tubular films are cut in two webs and laid flat.
  • the procedure according to the invention as a semi-finished or molded material, for example as a film of particularly light density, in the density range below 300 g / l, consisting of biodegradable thermoplastic materials, is produced by this procedure described by way of example.
  • Another variant consists in that the mixture of the polymer melt and the blowing agent is injected, foamed and molded into an enclosed space (mold), as in the injection molding process or blow molding.
  • the foamed molding materials according to the invention have the advantage that they are semi-finished, e.g. as foamed film, have a particularly low density of less than 300 g / 1, have a uniform pore distribution with closed-pore outside and with the usual processing methods of the plastics processing industry, such as hot forming, deep-drawing or pressing, to be processed into light, compostable molded parts and packaging can.
  • the characteristic of compostability can be determined with the standard DIN 54900, or according to the standard CEN 261, if this comes into force.
  • thermoplastically deformable, weldable, foamed semi-finished products or molded parts are particularly suitable for Provision of completely biodegradable and compostable packaging materials, insulation materials, foam foils, heat, cold and sound insulation as well as for the production of fast food dishes, packaging trays for fruit, vegetables and meat, egg packaging, protective films, trays, sandwich elements, cans, bottles, Coatings for paper or cardboard.
  • This list contains only a number of examples and is by no means exhaustive.
  • the biodegradable polymer such as a polymer blend containing thermoplastic starch and optionally further polymers and additives
  • the biodegradable polymer is entered at point 11.
  • zone 4 in the extruder, direct gassing with carbon dioxide or injection of the gaseous nitrogen takes place.
  • Zone 8 forms a liquid-cooled cylinder extension, and zone 10 has a foam foil tool.
  • a temperature-controlled cooling mandrel with a cutting device is designated by the reference number 12 and a draw-off for the foam sheets is given the reference number 13. 2.
  • test protocols listed below the tests with recipe 0640GS8209 and fumigation with carbon dioxide are provided with test numbers 1 to 6. Due to the relatively high melting temperatures, the proportion of carbon dioxide had to be reduced to 0.6% in the course of the tests from 1 to 6, as breakdowns occurred at higher values. It was shown that the screw was too heavily relined for a metering setting of 30%, which is why the metering speed was increased for the last attempts.
  • Test 10 gave a 1.7 mm thick film with a density of 316 kg / m 3 and a smooth surface. However, there is a very coarse-cell foam structure with an average bubble size of approx. 2 mm x 0.5 mm on the surface.
  • cylinder zones 2-4 were raised to 200 ° C for experiments 12 to 17. Previous studies have shown that this temperature has to be exceeded for a certain time in order to ensure the complete decomposition of the nucleating agent.
  • the increased pressures in zones 5 and 6 also indicate that there is an additional decomposition of the nucleating agent.
  • some of the samples show a clear yellowing. This coloring indicates that the sensitive starch may be degraded by acid groups or thermally degraded by the high cylinder temperatures. Since there is no further reduction in density of samples 12 - 17 compared to sample 11 B, the higher cylinder temperatures for this material should be avoided.
  • tests 26 to 31 are identified as tests 26 to 31 in the following test table. Since the material according to recipe 4 has a high hen pressure built up and the cylinder temperature could not be increased further, the screw had to be driven relined. Foaming the material without the addition of nucleating agent (test 27) resulted in a uniform, thick foam with a density of 214 kg / m 3 and an average bubble size of approx. 1 mm. The strong longitudinal folds in the film can be traced back to the fact that the film was not fully drawn over the cooling mandrel that was placed.
  • tests 21 to 24 The tests with recipe 3 0640GS8207 and nitrogen as blowing agent are identified as tests 21 to 24 in the following test protocol.
  • the settings according to test 10 were adopted from the tests with carbon dioxide as a blowing agent.
  • a film with a density of 500 kg / m 3 was obtained (test 21).
  • the film had an excellent surface, but foamed very irregularly.
  • Various measures to achieve the solubility of the propellant and to improve the homogenization of the melt did not bring any significant improvement in the foam quality.
  • test 25 In the test protocol listed below, the test with formulation 0640GS8208 and nitrogen as blowing agent is identified as test 25.
  • the mixtures with 0640GS8209 showed the better foaming behavior with carbon dioxide as a blowing agent.
  • the result was a relatively fine-cell structure with good surface quality.
  • the existing cracks and stripes can be eliminated by optimizing the trigger conditions.
  • the density of the foam was in the range of 540 kg / m 3 and was therefore relatively high. Further attempts should show here whether the density can be further reduced by varying the proportion of blowing agent and nucleating agent.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

L'invention concerne un produit semi-fini ou une matière moulable ou une pièce moulée biodégradables et compostables, réalisés en matière alvéolaire et moussée, ayant des propriétés thermoplastiques et donc pouvant être transformés par formage à chaud. Pour obtenir ce produit, on introduit des gonflants gazeux à faible température d'ébullition sous pression dans la masse en fusion du matériau et puis on procède à une opération de moussage. Le produit semi-fini, pouvant être transformé thermoplastiquement, peut faire l'objet d'une utilisation universelle. Les avantages de la matière moulable ou de la pièce moulée moussée sont la biodégradabilité, l'aptitude au compostage et la faible densité favorable en termes de réduction des coûts.
EP99923786A 1998-06-17 1999-06-11 Film thermoplastique mousse a partir de matieres biodegradables Withdrawn EP1090064A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CH130498 1998-06-17
CH130498 1998-06-17
PCT/IB1999/001070 WO1999065977A1 (fr) 1998-06-17 1999-06-11 Film thermoplastique mousse a partir de matieres biodegradables

Publications (1)

Publication Number Publication Date
EP1090064A1 true EP1090064A1 (fr) 2001-04-11

Family

ID=4207316

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99923786A Withdrawn EP1090064A1 (fr) 1998-06-17 1999-06-11 Film thermoplastique mousse a partir de matieres biodegradables

Country Status (3)

Country Link
EP (1) EP1090064A1 (fr)
AU (1) AU4054199A (fr)
WO (1) WO1999065977A1 (fr)

Families Citing this family (14)

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NL1012919C2 (nl) * 1999-08-26 2001-07-10 Geldrop Mode B V H O D N Groen Werkwijze voor de vervaardiging van natuurlijk afbreekbare producten.
EP1528079A1 (fr) * 2003-11-03 2005-05-04 Coopbox Europe S.P.A. Mousses dégradables en acide polylactique et procédé pour leur préparation
ITMI20040947A1 (it) * 2004-05-11 2004-08-11 Novamont Spa Foglia estrusa semi e4spansa prodotti da essa formati e loro processo di preparazione
WO2008057797A2 (fr) * 2006-11-06 2008-05-15 Meadwestvaco Corporation Emballage alvéolaire thermoformee biodégradable
PL2121838T3 (pl) 2007-02-15 2010-12-31 Basf Se Warstwa piankowa na bazie biodegradowalnej mieszaniny poliestrowej
CN101831140B (zh) * 2010-03-17 2011-09-07 无锡卡卡生物科技有限公司 用于制备聚乳酸的成核剂及其应用
CN102079853B (zh) * 2010-12-22 2012-07-25 无锡卡卡生物科技有限公司 一种利用二氧化碳制备聚乳酸的成核剂及其应用
DE102013005568B4 (de) * 2012-04-02 2018-09-27 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur Herstellung von Lebensmittelverpackungen und nach diesem Verfahren hergestellte Lebensmittelverpackung
US20220363857A1 (en) * 2019-09-25 2022-11-17 Eastman Chemical Company Foamed cellulose esters
WO2021150540A1 (fr) * 2020-01-20 2021-07-29 Eastman Chemical Company Compositions biodégradables et articles fabriqués à partir d'acétate de cellulose
US20230064720A1 (en) * 2020-01-20 2023-03-02 Eastman Chemical Company Biodegradable compositions and articles made from cellulose acetate
US20230076268A1 (en) * 2020-01-27 2023-03-09 Ricoh Company, Ltd. Foamed sheet, manufacture, and method for producing foamed sheet
WO2021257599A1 (fr) * 2020-06-15 2021-12-23 Westrock Mwv, Llc Emballage étanche durable et son procédé de fabrication
CN114854182A (zh) * 2022-04-19 2022-08-05 天津科技大学 一种可降解发泡缓冲包装材料及制备方法

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DE4035867A1 (de) * 1990-11-10 1992-05-14 Nmc Sa Verbundformkoerper aus zwei verschiedenen schaumstoffen sowie verfahren zu ihrer herstellung
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Also Published As

Publication number Publication date
AU4054199A (en) 2000-01-05
WO1999065977A1 (fr) 1999-12-23

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