WO1998007782A1 - Biodegradable thermoplastically deformable materials for food packaging - Google Patents
Biodegradable thermoplastically deformable materials for food packaging Download PDFInfo
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- WO1998007782A1 WO1998007782A1 PCT/DE1997/001725 DE9701725W WO9807782A1 WO 1998007782 A1 WO1998007782 A1 WO 1998007782A1 DE 9701725 W DE9701725 W DE 9701725W WO 9807782 A1 WO9807782 A1 WO 9807782A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/04—Starch derivatives, e.g. crosslinked derivatives
- C08L3/06—Esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
Definitions
- the invention relates to molding compositions for the production of biodegradable or compostable thermoplastically deformable materials, which are particularly suitable for use in the field of food packaging, fast food, etc. and from biodegradable or compostable blends, in particular from starch esters and polyesters and other biological compatible additives exist.
- biodegradable materials show that the use of such materials is possible in many areas. However, it is still difficult to cover the wide range of properties known for conventional plastics with new, environmentally compatible materials. In addition, there are often costs that are too high to prevent their widespread use.
- Blends of starch or starch derivatives and synthetic polymers are generally known (including DE 42 37 535).
- Copolymers used include: EVOH, poly- ⁇ -caprolactone, polyhydroxybutyric acid, ethyl cellulose, special polyamides or polyester amides. '
- starch or low-substituted starch derivatives are usually the main component in these blends, there are a number of application problems for the products made from them:
- the plasticizers used are mostly hydrophilic and migrate very quickly in the aqueous medium. This in turn prohibits applications in the food sector.
- DE 4114185 proposes a coester with longer-chain fatty acids, which is processed using plasticizers, such as ethyl citrate, glycerol acetate and lactic acid esters.
- EP 0638609 proposes a blend of starch acetate (DS 1, 8-2.6) and polyethylene glycol (MG 200-2000) using various auxiliaries.
- DE 4443539 proposes blends of starch esters and polyalkylene carbonates.
- the solution proposed there with plasticizer mixtures of polyalkylene glycols as the primary plasticizer for starch acetate and a second, secondary plasticizer component for determining the compatibility between the two polymer components brings considerable advantages with regard to the mechanical properties and the water resistance of the products. These variants are not yet satisfactory in terms of plasticizer migration and heat resistance
- the invention is therefore based on the object of providing materials which are biodegradable and thermoplastically processable at an economically justifiable cost and which are suitable for applications in the open air area and / or in the ground due to lower migration values for applications in the food sector or due to their improved weather stability and increased heat resistance
- the blends according to the invention consist of starch esters based on starches which have an amylopectin content of 20-80%, preferably starch acetate with a degree of substitution 1.5-2.6, preferably 1.8-2, and aliphatic polycarbonates with or without addition of oxydicarboxylic acids and / or oxytricarboxylic acids with 2 to 10 carbon atoms in a ratio of 100: 2 to 1000: 1 starch ester to polyfunctional carboxylic acid using plasticizers and customary additives.
- plasticizers for starch acetate instead of the usual plasticizers for starch acetate, so-called secondary plasticizers for starch acetate are used, which at the same time act as a compatibilizer.
- Such secondary plasticizers are preferably biologically compatible compounds.
- Esters of polyols with aliphatic monocarboxylic acids or esters of polyfunctional carboxylic acids with short-chain alkanols are well suited.
- the weight ratio of the carboxylate groups to the CH, CH 2 and CH 3 groups can be between 1 • 0.5 to 1 4, preferably between 1 1 to 1 2.
- These include, for example, citric acid t ⁇ alkyl (-ethyl or -butyl) ester, glycennecarboxylate (-t ⁇ butyrate), adipic acid ester with Ci - to C -alcohols, T ethyie ⁇ gyikolt ⁇ acetat
- the aliphatic polycarbonates are polymers containing carbonic acid ester groups, the chemical structure of the formula
- polyethylene, polypropylene and polybutylene carbonate are particularly favorable.
- PEC polyethylene carbonate
- polypropylene carbonate (PPC) and polybutylene carbonate (PBC) offers u. a. in the case of moldings which are to have certain mechanical properties over relatively long periods (2-8 years), but which can then be left to decay, for example, in the base.
- the mixtures according to the invention can also contain conventional fillers and pigments such as, for. B. talc, chalk, titanium dioxide, cellulose powder or starch in the order of 0-30% based on the total mass.
- the ratio of starch ester to aliphatic polycarbonates can be 5:95 to 95: 5.
- the proportion of additives and plasticizers should be 0 to 15% by mass, preferably 3 to 12% by mass.
- the solid components are placed in a high-speed mixer and to be used during the intensive ven mixing the liquid components are added by spraying. These mixtures can then be extruded and granulated. It is also possible to meter the plasticizer component directly into the extrusion process or to add all the subcomponents separately. Granules produced in this way can be processed at temperatures of 130 ° C to 180 ° C on conventional injection molding machines. The resulting products are largely insensitive to water, although they still have a water absorption of 5 - 10%.
- transparent objects can also be shaped, for example.
- the amounts of polyalkylene carbonates used can be varied to a lesser extent in other areas, and those of the other blend components mentioned.
- a high heat resistance is achieved by keeping the plasticizer content low.
- An advantage of the procedure proposed here is that the mixtures described can still be processed very well and also show good mechanical characteristics.
- Table 2 contains some of the key parameters of the examples given. The characteristic values were based on the abovementioned. Specimens determined as follows:
- PEG 400 polyethylene glycol
- Ball indentation hardness 30 "[N / mm 2 ] 70 59 38 56 62 51 25 29 61 48
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Abstract
Description
Bioabbaubare thermoplastisch verformbare Materialien für LebensmittelverpackungenBiodegradable thermoplastic materials for food packaging
Die Erfindung bezieht sich auf Formmassen für die Herstellung von bioabbaubaren bzw. kompostierbaren thermoplastisch verformbaren Materialien, die sich insbesondere für den Einsatz im Bereich Lebensmittelverpackungen, Fast food etc. eignen und aus biologisch abbaubaren bzw. kompostierbaren Blends, insbesondere aus Stärkeestern und Polyestem und weiteren biologisch verträglichen Zusätzen bestehen.The invention relates to molding compositions for the production of biodegradable or compostable thermoplastically deformable materials, which are particularly suitable for use in the field of food packaging, fast food, etc. and from biodegradable or compostable blends, in particular from starch esters and polyesters and other biological compatible additives exist.
Ressourcenverknappung und wachsende Müllberge lassen die Nachfrage nach biologisch abbaubaren Werkstoffen bzw. Werkstoffen auf der Basis nachwachsender Rohstoffe auf Gebieten, die bisher herkömmlichen thermoplastischen Kunststoffen vorbehalten waren, stetig wachsen.Resource scarcity and growing mountains of garbage mean that the demand for biodegradable materials or materials based on renewable raw materials in areas that were previously reserved for conventional thermoplastic materials is growing steadily.
Die bisher bekannten bioabbaubaren Werkstoffe zeigen, daß der Einsatz solcher Materialien auf vielen Gebieten möglich ist. Es ist aber nach wie vor schwierig, die breiten Eigenschaftsspektren, die für herkömmliche Kunststoffe bekannt sind, mit neuen, umweltverträglichen Werkstoffen abzudecken. Hinzu kommen oft noch zu hohe Kosten, die ihren breiten Einsatz bisher verhindern.The previously known biodegradable materials show that the use of such materials is possible in many areas. However, it is still difficult to cover the wide range of properties known for conventional plastics with new, environmentally compatible materials. In addition, there are often costs that are too high to prevent their widespread use.
Ein Lösungsansatz, der beiden Forderungen, biologische Abbaubarkeit und niedrige Produktionskosten, gerecht wird, wurde in der jüngeren Vergangenheit im Einsatz von Stärke und Stärkederivaten gesehen.A solution that meets both requirements, biodegradability and low production costs, has been seen in the recent past in the use of starch and starch derivatives.
Blends aus Stärke bzw. Stärkederivaten und synthetischen Polymeren sind allgemein bekannt (u. a. DE 42 37 535).Blends of starch or starch derivatives and synthetic polymers are generally known (including DE 42 37 535).
Sofern Stärkederivate beschrieben sind, beziehen sich die entsprechenden Angaben auf niedrig substituierte Produkte mit einem DS (Degree of Substitution) <1.If starch derivatives are described, the corresponding information relates to low-substituted products with a DS (Degree of Substitution) <1.
Als Copolymere werden u. a. eingesetzt : EVOH, Poly-ε-caprolacton, Po- lyhydroxybuttersäure, Ethylcellulose, spezielle Polyamide oder Polyesteramide. 'Copolymers used include: EVOH, poly-ε-caprolactone, polyhydroxybutyric acid, ethyl cellulose, special polyamides or polyester amides. '
Da Stärke bzw. niedrig substituierte Stärkederivate in diesen Blends meist die Hauptkomponente sind, resultieren für die daraus hergestellten Produkte eine Reihe von Problemen bei der Anwendung :Since starch or low-substituted starch derivatives are usually the main component in these blends, there are a number of application problems for the products made from them:
- Die verwendeten Weichmacher sind meist hydrophil und migrieren im wäßrigen Medium sehr schnell. Das wiederum verbietet Anwendungen im Lebensmittelbereich.- The plasticizers used are mostly hydrophilic and migrate very quickly in the aqueous medium. This in turn prohibits applications in the food sector.
- Die Nichtmischbarkeit der Komponenten bedingt, daß es sich nicht um klare durchsichtige Massen handelt.- The immiscibility of the components means that they are not clear, transparent masses.
- Die erreichten Wärmeformbeständigkeiten reichen oftmals für die angestrebten Anwendungsgebiete nicht aus.- The heat resistance achieved is often not sufficient for the intended areas of application.
Für höher substituierte und damit wasserunempfindliche Ester der Stärke (DS > 1 ,8) wird in der DE 4114185 ein Coester mit längerkettigen Fettsäuren vorgeschlagen, der mittels Weichmachern, wie Zitronensäureethylester, Glycerinacetat und Milchsäureester verarbeitet wird.For more highly substituted and therefore water-insensitive esters of starch (DS> 1.8), DE 4114185 proposes a coester with longer-chain fatty acids, which is processed using plasticizers, such as ethyl citrate, glycerol acetate and lactic acid esters.
In EP 0638609 wird ein Blend aus Stärkeacetat (DS 1 ,8 - 2,6) und Polyethy- iengiycol (MG 200 - 2000) unter Verwendung verschiedener Hilfsmittel vorgeschlagen.EP 0638609 proposes a blend of starch acetate (DS 1, 8-2.6) and polyethylene glycol (MG 200-2000) using various auxiliaries.
Beide Varianten zeigen eine erhebliche Verbesserung der Wasserstabilität, das Problem der Migration wasserlöslicher Bestandteile ist aber noch nicht ausreichend gelöst. Auch die Wärmeformbestäπdigkeit ist für viele Anwendungen zu niedrig.Both variants show a considerable improvement in water stability, but the problem of the migration of water-soluble components has not yet been sufficiently solved. The heat resistance is too low for many applications.
In DE 4443539 werden Blends aus Stärkeestem und Polyalkylencarbonaten vorgeschlagen. Die dort vorgeschlagene Lösung mit Weichmachergemischen von Polyalkylenglykolen als primäre Weichmacher für Stärkeacetat und einer zweiten, sekundären Weichmacherkomponente zur Verträglichkeitsermittluπg zwischen den beiden Polymerkomponeπten bringt erhebliche Vorteile bezüglich der mechanischen Eigenschaften und der Wasserbeständigkeit der Produkte. Noch nicht befriedigend sind diese Varianten hinsichtlich Weichmachermigration und WärmeformbestandigkeitDE 4443539 proposes blends of starch esters and polyalkylene carbonates. The solution proposed there with plasticizer mixtures of polyalkylene glycols as the primary plasticizer for starch acetate and a second, secondary plasticizer component for determining the compatibility between the two polymer components brings considerable advantages with regard to the mechanical properties and the water resistance of the products. These variants are not yet satisfactory in terms of plasticizer migration and heat resistance
Damit können viele für die angestrebte Produktgruppe interessante Anwendungsgebiete nicht berücksichtigt werden.This means that many areas of application that are interesting for the desired product group cannot be considered.
Der Erfindung egt deshalb die Aufgabe zugrunde, mit ökonomisch vertretbarem Aufwand Materialien bereitzustellen, die biologisch abbaubar und thermoplastisch verarbeitbar sind sowie aufgrund geringerer Migrationswerte für Anwendungen im Lebensmittelbereich oder aufgrund ihrer verbesserten Witterungsstabilität und erhöhter Wärmeformbestandigkeit für Anwendungen im Freiluftbereich und/oder in der Erde geeignet sindThe invention is therefore based on the object of providing materials which are biodegradable and thermoplastically processable at an economically justifiable cost and which are suitable for applications in the open air area and / or in the ground due to lower migration values for applications in the food sector or due to their improved weather stability and increased heat resistance
Die erfindungsgemäßen Blends bestehen aus Stärkeestern, die auf Stärken basieren, die einen Amylopektingehalt von 20 - 80 % aufweisen, vorzugsweise Stärkeacetat mit einem Substitutionsgrad 1 ,5 - 2,6, vorzugsweise 1 ,8 - 2 und aliphati- schen Polycarbonaten mit oder ohne Zusatz von Oxydicarbonsäuren und/oder Oxytricarboπsauren mit 2 - 10 C-Atomen im Verhältnis 100 : 2 bis 1000 : 1 Stärkeester zu polyfunktioneller Carbonsäure unter Verwendung von Weichmachern und üblichen Zusätzen.The blends according to the invention consist of starch esters based on starches which have an amylopectin content of 20-80%, preferably starch acetate with a degree of substitution 1.5-2.6, preferably 1.8-2, and aliphatic polycarbonates with or without addition of oxydicarboxylic acids and / or oxytricarboxylic acids with 2 to 10 carbon atoms in a ratio of 100: 2 to 1000: 1 starch ester to polyfunctional carboxylic acid using plasticizers and customary additives.
Anstelle der bisher üblichen Weichmacher für Stärkeacetat kommen sogenannte sekundäre Weichmacher für Stärkeacetat zum Einsatz, die gleichzeitig die Funktion eines Verträglichkeitsvermittlers übernehmen.Instead of the usual plasticizers for starch acetate, so-called secondary plasticizers for starch acetate are used, which at the same time act as a compatibilizer.
Als solche sekundäre Weichmacher kommen vorzugsweise biologisch kompatible Verbindungen in Betracht.Such secondary plasticizers are preferably biologically compatible compounds.
Gut eignen sich Ester von Polyolen mit aliphatischen Monocarbonsauren oder Ester von polyfunktionellen Carbonsäuren mit kurzkettigen Alkanoleπ. Das Gewichtsverhältnis der Carboxylatgruppen zu den CH-, CH2- und CH3-Grupρen kann zwischen 1 • 0,5 bis 1 4, vorzugsweise zwischen 1 1 bis 1 2 betragen. Dazu gehören zum Beispiel Zitronensäuretπalkyl (-ethyl oder -butyl) ester, Gly- cenncarboxylate (-tπbutyrat), Adipinsaureester mit Ci - bis C -Alkoholen, T ethyieπgyikoltπacetat Die aliphatischen Polycarbonate sind Kohlensäureestergruppen enthaltende Polymere, deren chemischer Aufbau der FormelEsters of polyols with aliphatic monocarboxylic acids or esters of polyfunctional carboxylic acids with short-chain alkanols are well suited. The weight ratio of the carboxylate groups to the CH, CH 2 and CH 3 groups can be between 1 • 0.5 to 1 4, preferably between 1 1 to 1 2. These include, for example, citric acid tπalkyl (-ethyl or -butyl) ester, glycennecarboxylate (-tπbutyrate), adipic acid ester with Ci - to C -alcohols, T ethyieπgyikoltπacetat The aliphatic polycarbonates are polymers containing carbonic acid ester groups, the chemical structure of the formula
Besonders günstig ist die Verwendung von Polyethylen-, Polypropylen- und Polybutylencarbonat.The use of polyethylene, polypropylene and polybutylene carbonate is particularly favorable.
Aus Gründen der besseren biologischen Abbaubarkeit sollte vorrangig Polyethy- lencarbonat (PEC) eingesetzt werden.For reasons of better biodegradability, primarily polyethylene carbonate (PEC) should be used.
Der Einsatz von Polypropylencarbonat (PPC) und Polybutylencarbonat (PBC) bietet sich u. a. bei Formkörpern an, die über relativ lange Zeiträume (2 - 8 Jahre) bestimmte mechanische Eigenschaften aufweisen sollen, danach jedoch beispielsweise im Boden der Verrottung überlassen werden können. Die erfindungsgemäßen Gemische können auch übliche Füllstoffe und Pigmente wie z. B. Talkum, Kreide, Titandioxid, Cellulosepulver oder Stärke in der Größenordnung 0-30 % bezogen auf die Gesamtmasse enthalten.The use of polypropylene carbonate (PPC) and polybutylene carbonate (PBC) offers u. a. in the case of moldings which are to have certain mechanical properties over relatively long periods (2-8 years), but which can then be left to decay, for example, in the base. The mixtures according to the invention can also contain conventional fillers and pigments such as, for. B. talc, chalk, titanium dioxide, cellulose powder or starch in the order of 0-30% based on the total mass.
Das Verhältnis Stärkeester zu aliphatischen Polycarbonaten kann 5 : 95 bis 95 : 5 betragen. Der Anteil der Additive und Weichmacher sollte 0 bis 15 Masse-%, vorzugsweise 3 bis 12 Masse-% betragen.The ratio of starch ester to aliphatic polycarbonates can be 5:95 to 95: 5. The proportion of additives and plasticizers should be 0 to 15% by mass, preferably 3 to 12% by mass.
Um die beschriebenen Formmassen herzustellen, ist es zweckmäßig, daß die festen Komponenten in einem Schnellmischer vorgelegt und während des intensi- ven Mischens die flüssigen Komponenten im Sprühverfahren zugesetzt werden. Anschließend können diese Mischungen extrudiert und granuliert werden. Ebenso ist ein direktes Zudosieren der Weichmacherkomponente in den Extrusi- onsprozeß bzw. eine getrennte Zugabe alier Teilkomponenten möglich. Auf diese Weise hergestellte Granulate können bei Temperaturen von 130 °C bis 180 °C auf herkömmlichen Spritzgußmaschinen verarbeitet werden. Die resultierenden Produkte sind weitgehend wasserunempfindlich, obwohl sie noch eine Wasseraufnahme von 5 - 10 % aufweisen.To produce the molding compositions described, it is expedient for the solid components to be placed in a high-speed mixer and to be used during the intensive ven mixing the liquid components are added by spraying. These mixtures can then be extruded and granulated. It is also possible to meter the plasticizer component directly into the extrusion process or to add all the subcomponents separately. Granules produced in this way can be processed at temperatures of 130 ° C to 180 ° C on conventional injection molding machines. The resulting products are largely insensitive to water, although they still have a water absorption of 5 - 10%.
Bei Versuchen konnte nachgewiesen werden, daß die wesentlichen mechanischen Eigenschaften der erfindungsgemäßen Blends über einen für viele Anwendungszwecke relevanten Zeitraum von 1 Jahr erhalten werden, bei Einsatz von PPC über 2 - 3 Jahre.Tests have shown that the essential mechanical properties of the blends according to the invention are obtained over a period of 1 year which is relevant for many applications, and with PPC over 2-3 years.
Die Migrationswerte in verschiedenen Testlebensmitteln werden durch eine erfindungsgemäße Gestaltung der Blends weit unter die gesetzlich zulässigen Grenzwerte gesenkt.The migration values in various test foods are reduced far below the legally permissible limit values by designing the blends according to the invention.
Je nach Gestaltung der Blends lassen sich beispielsweise auch durchsichtige Gegenstände formen. Dabei sind die eingesetzten Mengen Polyalkylencarbonate in weiteren Bereichen, die der anderen genannten Blendkomponenten in geringerem Maße variierbar.Depending on the design of the blends, transparent objects can also be shaped, for example. The amounts of polyalkylene carbonates used can be varied to a lesser extent in other areas, and those of the other blend components mentioned.
Eine hohe Wärmeformbeständigkeit wird erreicht, indem die Weichmacheranteile gering gehalten werden. Ein Vorzug der hier vorgeschlagenen Vorgehensweise ist, daß sich die beschriebenen Mischungen auch dann noch sehr gut verarbeiten lassen und auch gute mechanische Kennwerte zeigen.A high heat resistance is achieved by keeping the plasticizer content low. An advantage of the procedure proposed here is that the mixtures described can still be processed very well and also show good mechanical characteristics.
Zur Veranschaulichung der erfindungsgemäßen Mischungen wurden Spritzgußkörper hergestellt. Die Zusammensetzung der einzelnen Proben ist Tabelle 1 zu entnehmen. bInjection molded articles were produced to illustrate the mixtures according to the invention. The composition of the individual samples is shown in Table 1. b
Tabelle 2 enthält einige der wesentlichen Kennwerte der angeführten Beispiele. Die Kennwerte wurden an den o. g. Prüfkörpern wie folgt ermittelt:Table 2 contains some of the key parameters of the examples given. The characteristic values were based on the abovementioned. Specimens determined as follows:
Schmelzindex (150 °C, 2,16 kp, MFI DIN ISO 1133Melt index (150 ° C, 2.16 kp, MFI DIN ISO 1133
Schlagbiegefestigkeit DIN 53488Impact resistance DIN 53488
Biegefestigkeit DIN 53452Flexural strength DIN 53452
Biege-E-Modul DIN 53457Bending modulus of elasticity DIN 53457
Zugfestigkeit DIN 53455Tensile strength DIN 53455
Reißfestigkeit DIN 53455Tear resistance DIN 53455
Reißdehnung DIN 53455Elongation at break DIN 53455
Kugeldruckhärte DIN ISO 2039Ball indentation hardness DIN ISO 2039
HDTA ( 1 ,82 ) DIN 53461HDTA (1, 82) DIN 53461
Die Migration wurde nach EG-Richtlinie 9318, EWG (Durchführung nach ASU B 80.30 - 1-3 EG) 1 bei 70 °C jeweils in Wasser und in Oel geprüft. An den Beispielen ist deutlich zu erkennen, daß die nach der vorgeschlagenen Verfahrensweise hergestellten Muster vor allem bessere Migrationswerte aufweisen.The migration was tested according to EC directive 9318, EEC (implementation according to ASU B 80.30 - 1-3 EC) 1 at 70 ° C in water and in oil. The examples clearly show that the patterns produced according to the proposed procedure above all have better migration values.
Aber auch die Schlagbiegefestigkeit und die Reißdehnung sind zum Teil deutlich verbessert. But the impact resistance and the elongation at break are also significantly improved in some cases.
Tabelle 1Table 1
Zusammensetzung der BeispielmischungenComposition of the sample mixtures
Beispiel Stac WeichStabilisator BlendFüllstoff/ macher komponente PigmenteExample Stac soft stabilizer blend filler / make component pigments
[Ma.-%- prim. Anteil sec. Anteil Art Anteil Art Anteil Art Anteil Art [Ma.-%] Art [Ma.-%] [Ma.-%] [Ma.-%1 [Ma.-%][% By mass - prim. Share sec. Share Type Share Type Share Type Share Type [Ma .-%] Kind [Ma .-%] [Ma .-%] [Ma .-% 1 [Ma .-%]
1 vergl. 83,3 PEG 400 16,5 / / WS 0,2 / / / /1 see 83.3 PEG 400 16.5 / / WS 0.2 / / / /
2 vergl. 62,2 PEG 400 18,7 / / WS 0,3 / / Talkum 18,72 see 62.2 PEG 400 18.7 // WS 0.3 // talc 18.7
3 vergl. 55,7 PEG 400 20 / / WS 0,3 PEC 24 / /3 see 55.7 PEG 400 20 / / WS 0.3 PEC 24 / /
4 vergl. PEG 400 / / / / PEC / / /4 see PEG 400 / / / / PEC / / /
5 erf.gem. 37 / TBC 11 ,9 WS 0,2 PEC 37 Talkum 13,95 acc. 37 / TBC 11.9 WS 0.2 PEC 37 talc 13.9
6 erf.gem. 50 / TBC 10 / / PEC 40 / /6 acc. To 50 / TBC 10 / / PEC 40 / /
7 erf.gem. 55,4 / ADE 11 ,1 WS 0,3 PEC 33, 2 / /7 acc. To 55.4 / ADE 11, 1 WS 0.3 PEC 33, 2 / /
8 erf.gem. 55,4 / TB 11 ,1 WS 0,3 PEC 33, 2 / / θ erf.gem. 55,4 / SDE 11.1 WS 0,3 PEC 33, 2 / /8 acc. 55.4 / TB 11, 1 WS 0.3 PEC 33, 2 / / θ in accordance with 55.4 / SDE 11.1 WS 0.3 PEC 33, 2 / /
10 erf.gem. 70 / / TB 10 WS 0,2 PPC 19,8 / /10 acc. To 70 / / TB 10 WS 0.2 PPC 19.8 / /
Stac Stärkeacetat DS 2,20Stac starch acetate DS 2.20
PEG 400 Polyethylenglykol, MG 400PEG 400 polyethylene glycol, MG 400
TBC TributylcitratTBC tributyl citrate
ADE AdipinsäurediethylesterADE diethyl adipate
TB TributyrinTB tributyrin
PEC PolyethylencarbonatPEC polyethylene carbonate
CDE SebacinsäurediethylesterCDE diethyl sebacate
PPC Polypropylencarbonat PPC polypropylene carbonate
Tabelle 2Table 2
Prüfwerte der aus den Mischungen hergestellten MusterTest values of the samples made from the mixtures
Probenbezeichnung 1 2 3 4 5 6 7 8 9 10Sample name 1 2 3 4 5 6 7 8 9 10
PrüfwerteTest values
Migration in Wasser [mg/dm2] 239 123 23 33 0,6 0.5 10,3 2,1 1 ,1 8,3Migration in water [mg / dm 2 ] 239 123 23 33 0.6 0.5 10.3 2.1 1, 1 8.3
Migration in Oel [mg/dm2] 21 18 6 5 0 0 0 0 0 0Migration in oil [mg / dm 2 ] 21 18 6 5 0 0 0 0 0 0
Schlagbiegefestigkeit [KJ/m2] 4,1 18,6 36 12,9 18,2 12,8 27,5 19,4 8,1 15,3Impact resistance [KJ / m 2 ] 4.1 18.6 36 12.9 18.2 12.8 27.5 19.4 8.1 15.3
Grenzbiegefestigkeit [Mpa] 48,8 36,3 25,3 32,9 45,1 42,5 32,6 27,7 44,8 36,1Ultimate bending strength [Mpa] 48.8 36.3 25.3 32.9 45.1 42.5 32.6 27.7 44.8 36.1
E-Modul [Mpa] 1581 2307 820 1605 2118 1380 971 919 1440 1260E-module [Mpa] 1581 2307 820 1605 2118 1380 971 919 1440 1260
Zugfestigkeit [Mpa] 22,5 28,0 15,4 35,6 23,0 21 ,1 18,3 22,9 28,7 29,6Tensile strength [Mpa] 22.5 28.0 15.4 35.6 23.0 21.1 18.3 22.9 28.7 29.6
Reißfestigkeit [Mpa] 8,3 26,4 13,8 28,6 18,5 17,7 10,1 17,1 18,0 24,0Tear resistance [Mpa] 8.3 26.4 13.8 28.6 18.5 17.7 10.1 17.1 18.0 24.0
ReiBdehnung [%] 5,0 2,2 86 18,6 2,5 3 52 85,6 8 13Elongation at break [%] 5.0 2.2 86 18.6 2.5 3 52 85.6 8 13
Kugeldruckhärte 30" [N/mm2] 70 59 38 56 62 51 25 29 61 48Ball indentation hardness 30 "[N / mm 2 ] 70 59 38 56 62 51 25 29 61 48
MFI (150 °C/ 2,16 kp) 5,6 5,9 11.7 12,3 1 ,5 0,3 1.9 0,4 1.2 0,5MFI (150 ° C / 2.16 kp) 5.6 5.9 11.7 12.3 1, 5 0.3 1.9 0.4 1.2 0.5
HDT(A) 46 49 45 36 52 56 58 57 56 60 HDT (A) 46 49 45 36 52 56 58 57 56 60
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19633476A DE19633476A1 (en) | 1996-08-20 | 1996-08-20 | Biodegradable thermoplastically deformable materials for food packaging |
| DE19633476.4 | 1996-08-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1998007782A1 true WO1998007782A1 (en) | 1998-02-26 |
Family
ID=7803080
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/DE1997/001725 Ceased WO1998007782A1 (en) | 1996-08-20 | 1997-08-11 | Biodegradable thermoplastically deformable materials for food packaging |
Country Status (2)
| Country | Link |
|---|---|
| DE (1) | DE19633476A1 (en) |
| WO (1) | WO1998007782A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100360610C (en) * | 2005-10-20 | 2008-01-09 | 中山大学 | Degradable plastic composition and preparation method thereof |
| CN100365064C (en) * | 2005-10-20 | 2008-01-30 | 中山大学 | Fully degradable polymethylethylene carbonate/ethylene vinyl alcohol copolymer composite foam material and preparation method thereof |
| US20120183779A1 (en) * | 2011-01-18 | 2012-07-19 | Sk Innovation Co., Ltd. | Multilayer film |
| US8795745B2 (en) | 2008-10-13 | 2014-08-05 | Roquette Freres | Thermoplastic or elastomeric compositions based on esters of a starchy material and method for preparing such compositions |
| CN113214615A (en) * | 2021-06-03 | 2021-08-06 | 中国科学院长春应用化学研究所 | Ternary complete biodegradable film and preparation method thereof |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19822979A1 (en) | 1998-05-25 | 1999-12-02 | Kalle Nalo Gmbh & Co Kg | Film with starch or starch derivatives and polyester urethanes and process for their production |
| US20100175586A1 (en) * | 2005-03-24 | 2010-07-15 | Madrisano Catinari | Biodegradable plastic material |
| CN102020838A (en) * | 2010-11-11 | 2011-04-20 | 中山大学 | Completely-degradable poly propylene carbonate blending material and preparation method thereof |
Citations (5)
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|---|---|---|---|---|
| DE1950028A1 (en) * | 1969-02-28 | 1970-09-17 | Owens Illinois Inc | Electrophotographic printer or copier device |
| DE1951949A1 (en) * | 1969-10-15 | 1971-04-29 | Westfaelische Metall Industrie | Car headlight parabolic reflector mfr |
| DE1961348A1 (en) * | 1969-12-06 | 1971-10-21 | Hueck Fa E | Procedure for fastening a corner drive to window or door frame profiles and corner drive |
| EP0638609A2 (en) * | 1993-08-04 | 1995-02-15 | Buna Gmbh | Biodegradable thermoformable materials made of starch esters |
| WO1996017888A1 (en) * | 1994-12-07 | 1996-06-13 | Buna Sow Leuna Olefinverbund Gmbh | Biodegradable deformable thermoplastic materials and packages made thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4228016C1 (en) * | 1992-08-24 | 1994-03-31 | Biotec Biolog Naturverpack | Process for producing biodegradable films from vegetable raw materials |
| DE4411051C2 (en) * | 1994-03-30 | 1998-04-09 | Buna Sow Leuna Olefinverb Gmbh | Disposable containers for food, especially for drinking water |
| DE4443539A1 (en) * | 1994-12-07 | 1996-06-13 | Buna Sow Leuna Olefinverb Gmbh | Biodegradable thermoplastic materials for packaging cigarettes etc. |
| DE19519495A1 (en) * | 1995-05-27 | 1996-11-28 | Reynolds Tobacco Gmbh | Biodegradable thermoplastic materials for packaging cigarettes etc. |
| DE19516361A1 (en) * | 1995-05-04 | 1996-11-07 | Buna Sow Leuna Olefinverb Gmbh | Biodegradable packaging material |
-
1996
- 1996-08-20 DE DE19633476A patent/DE19633476A1/en not_active Withdrawn
-
1997
- 1997-08-11 WO PCT/DE1997/001725 patent/WO1998007782A1/en not_active Ceased
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1950028A1 (en) * | 1969-02-28 | 1970-09-17 | Owens Illinois Inc | Electrophotographic printer or copier device |
| DE1951949A1 (en) * | 1969-10-15 | 1971-04-29 | Westfaelische Metall Industrie | Car headlight parabolic reflector mfr |
| DE1961348A1 (en) * | 1969-12-06 | 1971-10-21 | Hueck Fa E | Procedure for fastening a corner drive to window or door frame profiles and corner drive |
| EP0638609A2 (en) * | 1993-08-04 | 1995-02-15 | Buna Gmbh | Biodegradable thermoformable materials made of starch esters |
| WO1996017888A1 (en) * | 1994-12-07 | 1996-06-13 | Buna Sow Leuna Olefinverbund Gmbh | Biodegradable deformable thermoplastic materials and packages made thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100360610C (en) * | 2005-10-20 | 2008-01-09 | 中山大学 | Degradable plastic composition and preparation method thereof |
| CN100365064C (en) * | 2005-10-20 | 2008-01-30 | 中山大学 | Fully degradable polymethylethylene carbonate/ethylene vinyl alcohol copolymer composite foam material and preparation method thereof |
| US8795745B2 (en) | 2008-10-13 | 2014-08-05 | Roquette Freres | Thermoplastic or elastomeric compositions based on esters of a starchy material and method for preparing such compositions |
| US20120183779A1 (en) * | 2011-01-18 | 2012-07-19 | Sk Innovation Co., Ltd. | Multilayer film |
| US9050743B2 (en) * | 2011-01-18 | 2015-06-09 | Sk Innovation Co., Ltd. | Multilayer film |
| CN113214615A (en) * | 2021-06-03 | 2021-08-06 | 中国科学院长春应用化学研究所 | Ternary complete biodegradable film and preparation method thereof |
| CN113214615B (en) * | 2021-06-03 | 2023-10-13 | 中国科学院长春应用化学研究所 | A ternary completely biodegradable film and its preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| DE19633476A1 (en) | 1998-02-26 |
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