WO1999047600A1 - Films stabilises pour resister a l'hydrolyse, constitues de polymeres biodegradables, et procede de production de tels films - Google Patents

Films stabilises pour resister a l'hydrolyse, constitues de polymeres biodegradables, et procede de production de tels films Download PDF

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Publication number
WO1999047600A1
WO1999047600A1 PCT/EP1999/001473 EP9901473W WO9947600A1 WO 1999047600 A1 WO1999047600 A1 WO 1999047600A1 EP 9901473 W EP9901473 W EP 9901473W WO 9947600 A1 WO9947600 A1 WO 9947600A1
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Prior art keywords
acid
film
acids
film according
bifunctional
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PCT/EP1999/001473
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German (de)
English (en)
Inventor
Michael Kleemiss
Original Assignee
Wolff Walsrode Ag
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Application filed by Wolff Walsrode Ag filed Critical Wolff Walsrode Ag
Priority to AU33289/99A priority Critical patent/AU3328999A/en
Publication of WO1999047600A1 publication Critical patent/WO1999047600A1/fr

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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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • 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
    • B29K2069/00—Use of PC, i.e. polycarbonates or derivatives thereof, as moulding material
    • 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
    • B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
    • 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
    • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
    • 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
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0059—Degradable
    • B29K2995/006—Bio-degradable, e.g. bioabsorbable, bioresorbable or bioerodible

Definitions

  • the invention relates to a single-layer or multilayer, thermoplastic film made from biodegradable and compostable polymers, which has improved hydrolysis stability by filling the polymers with inorganic fillers.
  • the object of the present invention is to produce a single-layer or multilayer film from biodegradable and compostable polymers, which has an improved resistance to hydrolysis.
  • This goal is achieved in that, in the case of a multilayer film, at least one layer or, in the case of a single-layer film, this is filled with inorganic fillers, which cause buffering compared to hydrolysis.
  • Hydrolysis is understood here primarily as the decomposition of the material by acidic or alkaline media.
  • several or all of the layers can also be filled with the fillers with the same or different concentrations, it being possible for the concentration of inorganic fillers to influence the rate of degradation by hydrolysis.
  • Each layer can consist of a single or a mixture of several biodegradable polymers.
  • the film can be equipped for better production or better processing.
  • the film according to the invention is produced by an extrusion process.
  • the invention relates to a single-layer or multi-layer hydrolysis-stabilized, biodegradable and compostable film which, in the case of the single-layer film, is filled with inorganic fillers and, in the case of the multi-layer film, can be filled in one, more or all layers with inorganic fillers, in a preferred form the layer is filled with inorganic fillers which is exposed to the hydrolyzing medium.
  • the invention relates to a hydrolysis-stabilized, biodegradable and compostable film, the layers of which are made of biodegradable polymers or
  • Biodegradable polymers exist in addition to the inorganic fillers with a maximum of 5% by weight of nucleating agents and a maximum of 5% by weight of the usual stabilizers and neutralizing agents and a maximum of 5% by weight of the usual lubricants and release agents in one, several or contains all layers and a maximum of 5% by weight of the usual antiblocking agents, preferably in the outer cover layers.
  • the nucleating agents or antiblocking agents can also count among the inorganic fillers and likewise bring about an improvement in the hydrolysis stability.
  • the hydrolysis-stabilized, biodegradable and compostable film can additionally be treated with a corona and / or flame and / or plasma pretreatment and / or an oxidizing substance and / or a depositable / depositable substance and / or a mixture of substances from oxidative acting and / or attachable substances, e.g. B. gases with radical components such as ozone or a plasma-excited gas mixture of, for example, hexamethyldisiloxane
  • the proportion of inorganic fillers may not exceed 49% by weight.
  • the proportion of the fillers can also be greater than 49% by weight, preferably less than 85% by weight.
  • polyesters represent an important class within these materials. Synthetic raw materials which only contain aliphatic monomers have a relatively good biodegradability, and because of their material properties they can be used only to a very limited extent; see Witt et al. in
  • Aromatic polyesters show significantly deteriorated, biodegradability with good material properties.
  • Microorganisms such as those found in compost, are given in DIN V 54 900, among others. Due to the thermoplastic behavior, these biodegradable materials can be processed into semi-finished products such as cast or blown films. However, the use of these semi-finished products is very limited. On the one hand, these films are characterized by poor mechanical properties and on the other hand, the barrier properties with regard to water vapor and gases in the - 4 - - -
  • Suitable polymers for the film according to the invention are:
  • A) aliphatic bifunctional alcohols preferably linear C 2 to C 10 di-alcohols such as, for example, ethanediol, butanediol, hexanediol or particularly preferably butanediol and / or optionally cycloaliphatic bifunctional alcohols, preferably having 5 or 6 carbon atoms in the cycloaliphatic ring, for example Cyclohexanedimethanol, and / or partially or completely instead of the diols, monomeric or oligomeric polyols based on ethylene glycol, propylene glycol, tetrahydrofuran or copolymers thereof with molecular weights of up to 4000, preferably up to 1000, and / or optionally small amounts of branched bifunctional alcohols, preferably C 3 -C, 2 -alkyldiols, such as neopentyglycol, and additionally optionally small amounts of higher-functional alcohols, such as 1,
  • C) aliphatic bifiin mecanicellen alcohols preferably linear C 2 to C, 0 alcohols, di-, such as ethanediol, butanediol, hexanediol, more preferably butanediol and / or optionally cycloaliphatic bifunctional alcohols, preferably C 5 - or C 6 ring -cycloaliphaticianm , such as cyclohexanedimethanol, and / or partially or completely instead of the diols, monomeric or oligomeric polyols based on ethylene glycol, propylene glycol, tetrahydrofuran or copolymers thereof with molecular weights up to 4000, preferably up to 1000, and / or optionally small amounts of branched bifunctional alcohols, preferably
  • C 3 -C 12 alkyldiols such as neopentyglycol, and additionally optionally small amounts of higher-functional alcohols, preferably C 3 -C 12 alkyl polyols, such as 1,2,3-propanetriol or trimethylolpropane, and from aliphatic bifunctional acids, preferably C 2 -C 12 alkyl dicarboxylic acids, such as and preferred
  • Succinic acid, adipic acid, and / or optionally aromatic bifunctional acids such as, for example, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and additionally optionally small amounts of higher functional acids such as, for example, trimellitic acid or
  • ester fraction C) and / or D) is at least 75% by weight, based on the sum of C), D) and E);
  • aliphatic bifunctional alcohols preferably linear C 2 to C 10 dialcohols such as, for example, ethanediol, butanediol, hexanediol or particularly preferably butanediol and / or optionally cycloaliphatic bifunctional alcohols, preferably having 5 to 8 C atoms in the cycloaliphatic ring, such as, for example, cyclohexanedimethanol, and / or partially or completely instead of the diols monomeric or oligomeric polyols - 7 - - -
  • branched bifunctional alcohols preferably with C 2 -C 12 -alkyl dicarboxylic acids, such as neopentyglycol and additionally optionally small amounts of higher-functional alcohols such as for example 1,2,3-propanetriol, trimethylolpropane and from aliphatic bifunctional acids such as, for example and preferably, succinic acid, adipic acid and / or optionally aromatic bifunctional acids such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and additionally optionally small amounts of higher functional acids such as trimellitic acid or
  • G from acid- and alcohol-functionalized building blocks, preferably with 2 to 12 carbon atoms in the alkyl chain, for example hydroxybutyric acid,
  • Hydroxyvaleric acid lactic acid, or their derivatives, for example ⁇ -caprolactone or dilactide,
  • ester fraction F) and / or G) is at least 70% by weight, based on the sum of F), G) and H);
  • aliphatic bifunctional alcohols preferably linear C 2 to C 10 -
  • Dialcohols such as ethanediol, butanediol, hexanediol, particularly preferably butanediol, and / or optionally cycloaliphatic bifunctional alcohols, preferably having 5 to 8 carbon atoms, such as cyclohexanedimethanol, and / or partially or completely instead of the diols, monomeric or oligomeric polyols based on ethylene glycol , Propylene glycol, tetrahydrofuran or copolymers thereof with molecular weights up to 4000, preferably up to 1000, and / or optionally small amounts of branched bifunctional alcohols, preferably C 3 -C 12 alkyl diols, such as neopentyl glycol and additionally, if appropriate, low
  • Amounts of higher functional alcohols preferably C 3 -C 12 alkyl polyols, such as 1,2,3-propanetriol, trimethylolpropane and from aliphatic bifunctional acids, preferably with 2 to 12 C atoms in the alkyl chain, such as and preferably succinic acid, adipic acid and / or optionally aromatic bifunctional acids such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and additionally optionally small amounts of higher functional acids such as trimellitic acid or
  • Naphthalenedicarboxylic acid and, if necessary, small amounts of higher functional acids, preferably with 2 to 10 carbon atoms, or
  • the ester portion I) and / or K) being at least 30% by weight, based on the sum of I), K), L) and M), preferably the weight portion of the Ester structures 30 to 70 wt .-%, the proportion of the amide structures is 70 to 30 wt .-%.
  • the polymers according to the invention can be both pure polymers and mixtures of various of the polymers mentioned. - 10 -
  • the invention furthermore relates to the use of a certain class of materials of the biodegradable and compostable polymers for the production of the film, this class of material being polyester amide.
  • the film according to the invention can consist of a polyester amide or a mixture of different polyester amides.
  • the invention relates to a hydrolysis-stabilized, biodegradable and compostable single-layer or multilayer film made of a polymer or a mixture of different polymers, which is / are biodegradable and compostable and filled with inorganic fillers and thus are Fillers may have a maximum proportion of 49% by weight.
  • the proportion of inorganic fillers can be greater than 49% by weight, preferably less than 85% by weight.
  • the inorganic fillers are distributed in the polymer matrix and have a maximum particle diameter of 60 ⁇ m (D98%) and a medium one
  • the inorganic fillers used have a maximum particle diameter of 30 ⁇ m (D98%) and an average particle diameter of less than or equal to 6 ⁇ m (D50%).
  • the invention relates to a hydrolysis-stabilized, biodegradable and compostable single or multilayer film made of polymers or a mixture of different polymers which are biodegradable and compostable and enriched with inorganic fillers, the inorganic ones
  • Fillers in a preferred form are chalk.
  • the chalk used for the most part (at least 94% by weight) consists of CaCO 3 (textbook of inorganic chemistry; Holleman, AF, Wiberg, E .; de Gruyter-Verlag 1985).
  • MgCO 3 and Fe 2 O 3 generally occur as further inorganic constituents, but they have a significantly lower proportion than CaCO 3 . - 11 -
  • the fillers can be mixed by a masterbatch, the content of fillers of which is correspondingly high, so that the film or the corresponding layer of the multilayer film has the desired content of fillers, or by compounding directly with the polymer or polymers and then processed.
  • masterbatch in the context of the present invention is to be understood as a masterbatch, in particular a granular, dust-free concentrate of a plastic raw material with high amounts of fillers or other additives, which is used as an intermediate product in bulk preparation (as a material additive to one or only partially or incompletely granules equipped with fillers or additives), in order to produce films therefrom which contain a certain amount of fillers or additives.
  • the masterbatch is admixed in such quantities with the raw materials which are not or only partially or incompletely equipped with fillers or additives, so that the desired weight percentages of fillers are achieved in the films.
  • the invention relates to a hydrolysis-stabilized, biodegradable and compostable single-layer or multilayer film made of polymers which are filled with inorganic fillers and additionally with a maximum of 5% by weight of nucleating agents and a maximum of 5% by weight of the usual stabilizers and neutralizing agents and a maximum of 5% by weight .-% of the usual lubricants and release agents and a maximum of 5 wt .-% of the usual antiblocking agents in a multilayer film preferably in the outer cover layers.
  • the nucleating agents or antiblocking agents can also count among the inorganic fillers and likewise bring about an improvement in the hydrolysis stability.
  • the film according to the invention can contain a maximum of 5% by weight of nucleating agents typically used for polyester (for example 1,5-naphthalenedisodium sulfonate or layered silicates, for example talc, or nucleating agents of nanoparticle size, i.e. average particle diameter ⁇ 1 ⁇ m, for example from
  • the usual stabilizing compounds for polyester compounds can be used as stabilizers and neutralizing agents. Their
  • the maximum amount added is 5% by weight.
  • Phenolic stabilizers, alkaline earth alkaline stearates and / or alkaline earth alkaline carbonates are particularly suitable as stabilizers.
  • Phenolic stabilizers are preferred in an amount of 0 to 3% by weight, in particular 0.15 to 0.3% by weight and with a molar mass of more than 500 g / mol.
  • Pentaerythrityl tetrakis 3 (3,5-di-tertiary-butyl-4-hydroxyphenyl) propionate or 1,3,5-trimethyl-2,4,6-tris (3,5-di-tertiary-butyl-4-hydroxybenzyl) -benzene are particularly advantageous.
  • Neutralizing agents are preferably dihydrotalcite, calcium stearate, calcium carbonate and / or calcium montanate with an average particle size of at most 0.7 ⁇ m, an absolute particle size of less than 10 ⁇ m and a specific surface area of at least 40 m 2 / g.
  • the film has a nucleating agent content of 0.0001 to 2% by weight and a stabilizer and neutralizing agent content of 0.0001 to 2% by weight.
  • Lubricants and release agents are higher aliphatic amides, tertiary amines, aliphatic acid amides, higher aliphatic acid esters, and low-molecular polar modified
  • Waxes montan waxes, cyclic waxes, phthalates, metal soaps and silicone oils. - 13 -
  • Aliphatic acid amides are amides of a water-insoluble monocarboxylic acid (so-called fatty acids) with 8 to 24 carbon atoms, preferably 10 to 18 carbon atoms. Erucic acid amide, stearic acid amide and oleic acid amide are preferred among them.
  • release agents or lubricants are compounds which contain both esterais and amide groups, such as stearamide ethyl stearate or 2 stear amido ethyl stearate.
  • Suitable cyclic waxes are components such as cyclic adipic acid tetramethylene esters or 1,6-dioxa-2,7-dioxocyclododecane, or the homologous hexamethylene derivative. Such substances are known as commercial products
  • Suitable silicone oils are polydialkylsiloxanes, preferably polydimethylsiloxane, polymethylphenylsiloxane, olefininodified silicone, silicone modified with polyethers such as e.g. B. polyethylene glycol and polypropylene glycol and epoxyamino- and alcohol-modified silicone.
  • the viscosity of the suitable silicone oils is in the range from 5,000 to 1,000,000 mm 2 / s. Polydimenthylsiloxane with a viscosity of 10,000 to 100,000 mm 2 / s is preferred.
  • the amount of lubricant added is at most 5% by weight. In a particularly preferred embodiment of the film, it has a proportion of lubricant - 14 -
  • the film has a lubricant content of 0.05 to 1% by weight.
  • one or more or all of the layers can contain lubricants.
  • Suitable antiblocking agents are both inorganic and organic additives, which protrude from the film surface as an elevation and thus produce a spacer effect.
  • the outer cover layers preferably contain the antiblocking agents.
  • the nucleating agents or antiblocking agents can belong to the inorganic fillers and also one
  • the following substances or mixtures of these substances are used as inorganic fillers, which are used for hydrolysis stabilization and can also serve as antiblocking agents, the
  • Mixtures generally represent natural occurrences (e.g. chalk,
  • Aluminum silicates for example kaolin or kaolin clay
  • aluminum oxides for example ⁇ -aluminum oxide
  • Micro glass balls, and the following substances are used as organic antiblocking agents: organic polymers incompatible with the biodegradable polymer such as
  • Polycarbonate cross-linked and uncross-linked polymethyl methacrylate cross-linked polysiloxane e.g. Tospearl
  • polar-modified polyethylene e.g. maleic anhydride-grafted polyethylene
  • polar-modified polypropylene e.g. maleic anhydride-grafted polypropylene
  • Benzoguanamine formaldehyde polymers aliphatic and partially aromatic polyesters with different melting points than that
  • the effective amount of antiblocking agent is up to a maximum of 5% by weight.
  • the film contains 0.005 to 4% by weight of antiblocking agent.
  • the film contains 0.05 to 1% by weight of antiblocking agent.
  • the average particle size is between 1 and
  • the polymers for the film provided with additives are provided with the desired amounts by weight of organic and / or inorganic fillers in the production of raw materials. This takes place when the raw material is granulated, for example in twin-screw extruders, where the additives are added to the raw material. In addition to this type of additive, there is also the possibility that some or all of the necessary additives are added to a raw material that is not or only partially finished in the form of a masterbatch.
  • the preferred materials from which the masterbatches are produced in addition to the additives are substances which are compatible with the polymers mentioned in this invention.
  • the materials from which the masterbatches are produced in addition to the additives are likewise biodegradable and compostable or biologically harmless or neutral.
  • the procedure is expediently such that the film is passed between two conductor elements serving as electrodes, such a high voltage, usually alternating voltage (approximately 5 to 20 kV and 5 to 30 kHz), being applied between the electrodes that spray or corona discharges can take place.
  • a high voltage usually alternating voltage (approximately 5 to 20 kV and 5 to 30 kHz)
  • alternating voltage approximately 5 to 20 kV and 5 to 30 kHz
  • the applied voltage is between 400 and - 17 -
  • the applied voltage gives the ionized atoms increased acceleration and impacts the polymer surface with greater kinetic energy.
  • the chemical bonds within the polymer molecule are broken more easily and the radical formation takes place more quickly.
  • the thermal load on the polymer is much lower than in the standard flame treatment, and films can be obtained in which the sealing properties of the treated side are even better than those of the untreated side.
  • gases e.g.
  • Monomer radicals are formed - some already in plasma - short-chain oligomers, which then condense and polymerize on the surface to be coated. A homogeneous film is deposited on the coating material.
  • Foil surface is firmly connected. With a suitable material composition, this results in an increase in the surface tension on the film.
  • the invention also relates to the process for producing a hydrolysis-stabilized, biodegradable and compostable single or multilayer film.
  • the hydrolysis-stabilized, biodegradable and compostable single or multilayer film according to the invention is expediently produced using an extrusion process.
  • the filled, or in the case of a multilayer film, unfilled polymers in the form of granules are melted in extruders, homogenized, compressed and discharged via a single or multilayer nozzle.
  • the nozzle can be an annular nozzle for producing a seamless tubular film.
  • the carried out or e.g. Film pulled out by roller pressers is then cooled until solidification.
  • the cooling can take place both over air and over water or also by means of cooling rollers.
  • the cooling can take place on one or both sides, in the case of a tubular film on the inside and outside or only on the inside or only on the outside.
  • the tubular film can also be cut on one or both sides, so that a single or multilayer flat film is obtained.
  • the invention also relates to an extrusion process for producing the hydrolysis-stabilized film according to the invention, in which the single- or multi-layer die is designed as a flat die for producing a single- or multi-layer flat film.
  • the discharged film is then cooled until solidification.
  • the cooling can take place over water by means of cooling rollers.
  • the finished film can possibly be pre-treated in-line on one or both sides.
  • the film according to the invention has a thickness which is less than 1000 ⁇ m.
  • the film according to the invention has a thickness which is less than 500 ⁇ m.
  • the film according to the invention has a thickness which is less than 80 ⁇ m.
  • the invention also relates to the use of the invention
  • This film is used as a hydrolysis-stabilized, single or multi-layer film in pretreated or untreated and in printed, unprinted form for packaging in the food and non-food sectors or as a hydrolysis-stabilized, single or multi-layer film in pretreated or untreated form for protection and separation functions in connection with cosmetics and hygiene articles, for example for baby diapers or sanitary napkins or as hydrolysis-stabilized, single or multi-layer film in pretreated or untreated form for surface protection or surface finishing in the area of cardboard, paper and letter window lamination or as a refined film, which can be used in pre-treated or untreated as well as printed or unprinted form and provided with adhesive as a label or adhesive strip.
  • hydrolysis-stabilized, one- or multi-layer film made from biodegradable and compostable polymers in pretreated or untreated form for greenhouse covers, mulch films or for lining plant growing boxes (eg for mushroom growing) in the fields of horticulture or agriculture or for sacks refined for the storage and transport of goods, for example organic waste, are used, the multilayered by the concentration and / or the type of inorganic fillers - 20 -
  • Structure and orientation of the molecules / crystals can be controlled to control the hydrolytic and biotic degradation rate.
  • the invention also relates to the use of the multilayer film according to the invention as a coated film or in a film composite.
  • the overall composite is also biodegradable and compostable in accordance with DIN V 54 900.
  • the invention furthermore relates to the use of the multilayer film according to the invention as a starting material for the production of a bag which releases its contents after the disintegration by the biodegradation process.
  • the bag can be produced by gluing and sealing the film and can both be closed and have an opening with a corresponding closure or connection.
  • the invention also relates to the use of the multilayer film or composites according to the invention as a starting material for the production of a packaging or separating or surface protection film with very high water vapor permeability by piercing this film with a cold or tempered needle roller.
  • the purpose of this film is the packaging of moisture-releasing goods, for example bread or various types of fruit or vegetables, or as a separating and protective film in the hygiene area.
  • a single-layer blown film was made from an unfilled, biodegradable and compostable polyester amide.
  • the material had an MFI of 7 (in g / lOmin at 190 ° C, 2.16kg, measured according to DIN 53 735), a melting point of 125 ° C, measured according to ISO 3146 / C2, a proportion of lubricant of 1 wt. -% and an antiblock content of 0.1 wt .-%.
  • the maximum extrusion temperature was 175 ° C.
  • the melt was discharged through an annular die and cooled by air.
  • the maximum nozzle temperature was 170 ° C.
  • a film with a thickness of 40 ⁇ m could be produced.
  • a single-layer blown film was made from an unfilled biodegradable and compostable polyester amide.
  • the material had one
  • MFI of 10 in g / lOmin at 190 ° C, 2.16kg, measured according to DIN 53 735), a melting point of 140 ° C, measured according to ISO 3146 / C2, a percentage of lubricant of 0.4% by weight and an antiblock content of 0.1% by weight.
  • the maximum extrusion temperature was 190 ° C, the maximum die temperature was 175 ° C.
  • a film with a thickness of 40 ⁇ m could be produced using the same method as in Example 1.
  • the mechanical quantities of tensile strength and elongation at break in the longitudinal direction of the samples produced were determined in accordance with DIN 53 455.
  • the modulus of elasticity in the longitudinal direction was determined in accordance with DIN 53 457.
  • the thickness of the individual samples was determined in accordance with DIN 53 370.
  • the samples were then stored in a buffer solution (Titrisol pH 2, Merck, hydrochloric acid solution with sodium citrate buffer) and the measurement of the mechanical properties mentioned above was repeated at certain intervals.
  • the hydrolytic degradation of the polymer can be investigated by the decrease in tear strength and elongation at break depending on the storage time.
  • the values ⁇ and ⁇ correspond to the measured values before storage.

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Abstract

La présente invention concerne un film stabilisé pour résister à l'hydrolyse, monocouche ou multicouche, constitué de polymères biodégradables et compostables. On désigne ici comme hydrolyse particulièrement la décomposition du film par des milieux acides. La vulnérabilité par rapport à l'hydrolyse est réduite par le fait que le film monocouche, ou bien, dans le cas d'un film multicouche, une couche, plusieurs couches ou toutes les couches de celui-ci sont remplies d'une matière de charge inorganique, ce qui résulte en un tampon. Le film monocouche ou multicouche stabilisé à l'hydrolyse, biodégradable et compostable peut être pourvu d'additifs supplémentaires améliorant son aptitude au façonnage. Ces additifs peuvent être également des agents de nucléation ou des agents anti-adhérents, qui font partie des matières de charge inorganiques et entraînent également une amélioration de la stabilité à l'hydrolyse.
PCT/EP1999/001473 1998-03-18 1999-03-08 Films stabilises pour resister a l'hydrolyse, constitues de polymeres biodegradables, et procede de production de tels films WO1999047600A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU33289/99A AU3328999A (en) 1998-03-18 1999-03-08 Hydrolytically stabilised films consisting of biodegradable polymers and method for producing films of this type

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19811225.4 1998-03-18
DE19811225A DE19811225A1 (de) 1998-03-18 1998-03-18 Verbesserung der Hydrolysestabilität von Folien aus biologisch abbaubaren Polymeren und Verfahren zur Herstellung solcher Folien

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WO1999047600A1 true WO1999047600A1 (fr) 1999-09-23

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PCT/EP1999/001473 WO1999047600A1 (fr) 1998-03-18 1999-03-08 Films stabilises pour resister a l'hydrolyse, constitues de polymeres biodegradables, et procede de production de tels films

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AU (1) AU3328999A (fr)
DE (1) DE19811225A1 (fr)
WO (1) WO1999047600A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113978083A (zh) * 2021-10-20 2022-01-28 天津万华股份有限公司 一种用于电子元件的无硅亚光聚酯薄膜

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2572875A1 (fr) * 2011-09-26 2013-03-27 Tscheulin-Rothal GmbH Matériaux d'emballage biodégradables
ITPG20110034A1 (it) * 2011-11-08 2013-05-09 Polycart S R L Apparato di supporto per etichette biodegradabili adesive e relativo metodo di realizzazione

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0444880A2 (fr) * 1990-02-28 1991-09-04 Director-General Of The Agency Of Industrial Science And Technology Matière moulable biodégradable
EP0765911A2 (fr) * 1995-09-26 1997-04-02 Bayer Ag Matières plastiques biodégradables renforcées
WO1998004412A1 (fr) * 1996-07-26 1998-02-05 Wolff Walsrode Ag Feuille de support compostable
WO1998004627A2 (fr) * 1996-07-26 1998-02-05 Wolff Walsrode Ag Feuille biodegradable et compostable a etirage biaxial
WO1998004626A2 (fr) * 1996-07-26 1998-02-05 Wolff Walsrode Ag Feuille biodegradable et compostable a etirage biaxial
WO1998004619A1 (fr) * 1996-07-26 1998-02-05 Wolff Walsrode Ag Feuille biodegradable et compostable a etirement monoaxial et a proprietes ameliorees
WO1998025992A2 (fr) * 1996-12-13 1998-06-18 Wolff Walsrode Ag Films elastiques a biodegradabilite amelioree et leur procede de production

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU1088895A (en) * 1993-11-24 1995-06-13 E.I. Du Pont De Nemours And Company Improvements in and relating to compostable copolyesters and products therefrom

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0444880A2 (fr) * 1990-02-28 1991-09-04 Director-General Of The Agency Of Industrial Science And Technology Matière moulable biodégradable
EP0765911A2 (fr) * 1995-09-26 1997-04-02 Bayer Ag Matières plastiques biodégradables renforcées
WO1998004412A1 (fr) * 1996-07-26 1998-02-05 Wolff Walsrode Ag Feuille de support compostable
WO1998004627A2 (fr) * 1996-07-26 1998-02-05 Wolff Walsrode Ag Feuille biodegradable et compostable a etirage biaxial
WO1998004626A2 (fr) * 1996-07-26 1998-02-05 Wolff Walsrode Ag Feuille biodegradable et compostable a etirage biaxial
WO1998004619A1 (fr) * 1996-07-26 1998-02-05 Wolff Walsrode Ag Feuille biodegradable et compostable a etirement monoaxial et a proprietes ameliorees
WO1998025992A2 (fr) * 1996-12-13 1998-06-18 Wolff Walsrode Ag Films elastiques a biodegradabilite amelioree et leur procede de production

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113978083A (zh) * 2021-10-20 2022-01-28 天津万华股份有限公司 一种用于电子元件的无硅亚光聚酯薄膜
CN113978083B (zh) * 2021-10-20 2024-01-23 天津万华股份有限公司 一种用于电子元件的无硅亚光聚酯薄膜

Also Published As

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DE19811225A1 (de) 1999-09-30
AU3328999A (en) 1999-10-11

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