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WO2000036014A2 - Corps extrudes thermoplastiques biodegradables presentant une stabilite a l'hydrolyse et une resistance au fendillement par contrainte ameliorees - Google Patents

Corps extrudes thermoplastiques biodegradables presentant une stabilite a l'hydrolyse et une resistance au fendillement par contrainte ameliorees Download PDF

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Publication number
WO2000036014A2
WO2000036014A2 PCT/EP1999/009526 EP9909526W WO0036014A2 WO 2000036014 A2 WO2000036014 A2 WO 2000036014A2 EP 9909526 W EP9909526 W EP 9909526W WO 0036014 A2 WO0036014 A2 WO 0036014A2
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WO
WIPO (PCT)
Prior art keywords
acid
blend
bifunctional
aliphatic
acids
Prior art date
Application number
PCT/EP1999/009526
Other languages
German (de)
English (en)
Other versions
WO2000036014A3 (fr
Inventor
Michael Kleemiss
Annett Kaeding
Gunter Weber
Heiko Tamke
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
Priority claimed from DE19951021A external-priority patent/DE19951021A1/de
Application filed by Wolff Walsrode Ag filed Critical Wolff Walsrode Ag
Priority to JP2000588268A priority Critical patent/JP2002532603A/ja
Priority to CA002354514A priority patent/CA2354514A1/fr
Priority to BR9916117-6A priority patent/BR9916117A/pt
Priority to EP99963396A priority patent/EP1144507A3/fr
Priority to AU19709/00A priority patent/AU1970900A/en
Publication of WO2000036014A2 publication Critical patent/WO2000036014A2/fr
Publication of WO2000036014A3 publication Critical patent/WO2000036014A3/fr

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Classifications

    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • 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
    • C08L69/005—Polyester-carbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2230/00—Compositions for preparing biodegradable polymers

Definitions

  • the invention relates to biodegradable, thermoplastic, extruded moldings, in particular single-layer or multilayer films with improved hydrolysis stability and stress crack resistance.
  • polymers like other materials, can be subject to biological degradation.
  • the main materials to be mentioned here are those that are obtained directly or after modification from naturally occurring polymers, for example polyhydroxyalkanolates such as polyhydroxybutyrate, plastic celluloses, cellulose ether esters, cellulose esters, plastic starches, chitosan and pullulan.
  • biodegradable and compostable polymers or molded articles are understood to mean goods which are tested for "biodegradability” in accordance with the test according to DIN V 54 900 from 1998/1999.
  • biodegradable, synthetic polymers based on polyester or polyester amide have become known. These have the property that they are easy to process thermoplastically and, on the other hand, are biodegradable, i.e. their entire polymer chain is broken down by microorganisms (bacteria and fungi) by means of enzymes and completely broken down into carbon dioxide, water and biomass, so that they can be broken down accordingly Test in a natural environment under the influence of microorganisms meet the conditions for biodegradability according to DIN V 54 900. Due to the thermoplastic behavior, these biodegradable materials can be processed into semi-finished products such as cast or blown films.
  • the object of the present invention was therefore to provide moldings, in particular single-layer or multilayer films, made of biodegradable polymers with improved hydrolysis resistance and improved stress crack resistance.
  • Hydrolysis is understood to mean the destruction of the shaped body by aqueous media, which may also have an acidic or alkaline pH.
  • Stress crack formation is understood to mean damage mechanisms that occur under the influence of the environment, physical and / or chemical, due to an interaction with the surrounding media in the presence of internal or external mechanical stresses or strains.
  • ESC Euvironnetal Stress Cracking and Crazing
  • EJ Kramer Environmental Cracking of Polymers, in Developments in Polymer Fracture-1, Edited by EH Andrews, Science publishers LTD London, 55-120 (1979) .
  • the goal is achieved in that the diffusion of the permeating surrounding aqueous medium into the microstructure of the shaped body takes place so slowly that failure of the shaped body due to chain breakage, if not prevented, is nevertheless delayed.
  • a multiphase morphology of the shaped bodies is provided for this purpose, which is preferably generated by a binary blend of two biodegradable polymers.
  • a multi-phase morphology can also be generated by blends with more than just two biodegradable polymers as blend partners.
  • the damage mechanisms under the interaction with the non-existent medium are advantageously reduced in that a blend partner shows only a slight interaction with the medium.
  • a particularly advantageous multiphase morphology exists when the diffusion path of the surrounding medium through the shaped body becomes as large as possible, e.g. with a layer-like or lamellar structure of the glare partner in microscopic dimensions.
  • the blend partners must be selected so that there is a high degree of phase compatibility, but not necessarily molecular miscibility, of the blend partners.
  • the occurrence of mixture gaps should be avoided.
  • the phase compatibility can be increased both by similar melt viscosities of the blend partners and by extrusion conditions.
  • the preferred embodiment of the moldings according to the invention contains additives and auxiliary substances, as will be explained below.
  • Shaped bodies which are particularly preferred according to the invention are single-layer or multilayer films which can be produced by coextrusion, coating, lamination according to the prior art.
  • the corresponding films consist overall of a blend according to the invention and, if appropriate, customary additives and auxiliaries, as are explained below.
  • at least one layer consists of a blend according to the invention, as described above, and, if appropriate, the usual additives and auxiliaries mentioned.
  • this layer is arranged as an outer layer on that side of the film which is in contact with the hydrolyzing medium during use.
  • several or all layers of the multilayer film can also be constructed as described above for the single-layer film, the ratio of the blend partners and the additives and auxiliaries depending on the type and amount in each layer being different.
  • blend partner (I) and blend partner (II) preferably at least one polymer from each of the two subsequent groups labeled blend partner (I) and blend partner (II) is used.
  • thermoplastic molded articles according to the invention in particular single-layer or multilayer films with improved resistance to hydrolysis and stress cracking are:
  • Biodegradable aliphatic or partially aromatic polyesters in which the aromatic acids make up a proportion of not more than 60% by weight, based on all acids, preferably formed from
  • aliphatic bifunctional alcohols preferably linear C 2 to C 10 dialcohols such as, in particular, ethanediol, hexanediol or very particularly preferably adds butanediol and / or cycloaliphatic bifunctional alcohols, preferably with 5 or 6 carbon atoms in the cycloaliphatic ring, such as in particular 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 optionally small amounts of branched bifunctional alcohols, preferably C 3 -C 12 -alkyldiols, in particular neopentyl glycol, and additionally optionally small amounts of higher-functional alcohols such as preferably 1,2,3-propanetriol or Trimethyl
  • acid- and alcohol-functionalized building blocks preferably with 2 to 12 carbon atoms in the alkyl chain, preferably hydroxybutyric acid, hydroxyvaleric acid, lactic acid, or their derivatives, for example ⁇ -caprolactone or dilactide,
  • blend partners (I) are biodegradable, aliphatic or partially aromatic polyester urethanes derived from the above biodegradable aliphatic or partially aromatic polyesters, which in addition to the above preferably contain ester groups formed from building blocks a) and / or b), which are preferably formed from
  • Atoms or 5 to 8 carbon atoms in the case of cycloaliphatic isocyanates preferably tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, optionally additionally with linear and / or branched and / or cycloaliphatic bifunctional and / or higher-functional alcohols, preferably C 3 -C 12 - Alkyl di- or polyols or cycloaliphatic alcohols with 5 to 8 carbon atoms, preferably ethanediol, hexanediol, butanediol, cyclohexanedimethanol, and / or optionally additionally with linear and / or branched and / or cycloaliphatic bifunctional and / or higher functional amines and / or amino alcohols with preferably 2 to 12 carbon atoms in the alkyl chain, preferably ethylenediamine or aminoethanol, and / or optionally further modified amines
  • ester portion preferably formed from a) and / or b) is at least 75
  • blend partners (I) are aliphatic or partially aromatic polyester carbonates derived from the above aliphatic or partially aromatic polyesters, which in addition to building blocks a) and / or b) contain carbonate groups, which are preferably formed from:
  • a carbonate fraction which is prepared from aromatic bifunctional phenols, preferably bisphenol-A, and carbonate donors, in particular phosgene, or a carbonate fraction which is derived from aliphatic carbonic acid esters or their derivatives, such as preferably chlorocarbonic acid esters or aliphatic table carboxylic acids or their derivatives such as salts and carbonate donors, in particular phosgene, is produced, wherein
  • ester fraction preferably formed from a) and / or b) is at least 70% by weight, based on the total weight.
  • Particularly suitable as blend partners (I) are aliphatic or partially aromatic polyester amides derived from the above aliphatic or partially aromatic polyesters, which in addition to the building blocks a) and / or b) contain amide groups, which were preferably formed from
  • aliphatic and / or cycloaliphatic bifunctional amines preferably linear aliphatic C 2 to C 10 diamines, in particular isophoronediamine and very particularly preferably hexamethylenediamine, where these amines may contain small amounts of branched bifunctional amines and / or higher-functional amines and also from linear and / or cycloaliphatic bifunctional acids, preferably with 2 to 12 C atoms in the alkyl chain or C 5 or C 6 ring in the case of cycloaliphatic acids, preferably adipic acid, and optionally small amounts of branched bifunctional and / or optionally aromatic bifunctional acids such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and additionally optionally small amounts of higher functional acids, preferably with 2 to 10 carbon atoms, or
  • Atoms in the cycloaliphatic chain preferably co-laurolactam, particularly preferably ⁇ -caprolactam,
  • ester fraction preferably formed from a) and / or b) being at least 20% by weight, based on the total weight, preferably the ester content is 20 to 80% by weight, and the content of the amide structures is 80 to 20% by weight.
  • the blend partners (I) used in thermoplastic molded articles according to the invention can be both pure polymers and mixtures of various of the polymers mentioned, in the case of mixtures preferably polymers of only one of the aforementioned classes of compounds ( Polyesters, polyester urethanes, polyester carbonates, polyester amides) can be used. Polyester amides or mixtures of different polyester amides are particularly preferably used.
  • Suitable blend partners (II) for moldings according to the invention are suitable aliphatic polyesters made from linear bifunctional alcohols, such as preferably ethylene glycol, hxanediol or particularly preferably butanediol and / or cycloaliphatic bifunctional alcohols, such as preferably cyclohexane dimethanol and additionally optionally small amounts of higher-functional alcohols, such as preferably 1,2,3-propanetriol or neopenthyl glycol and from linear bifunctional acids, such as preferably succinic acid or adipic acid and / or optionally cycloaliphatic bifunctional acids, such as preferably
  • linear bifunctional alcohols such as preferably ethylene glycol, hxanediol or particularly preferably butanediol and / or cycloaliphatic bifunctional alcohols, such as preferably cyclohexane dimethanol and additionally optionally small amounts of higher-functional alcohols, such as preferably 1,2,3-propanetriol or
  • Blend partners (II) are aliphatic polyesters, polycaprolactone and polylactides formed from these monomers, in particular polylactic acid, polyhydroxybutyric acid, polyhydroxybenzoic acid, polyhydroxybutyric acid / hydroxivaleric acid copolymers and mixtures of these polymers and copolymers from the monomers forming these mixtures.
  • Poly- ⁇ -caprolactone is very particularly suitable. According to the invention, the polymers used as blend partners (I) and blend partners (II) must not be composed of identical monomers.
  • the blend according to the invention is subjected to an orienting stress in the production of the extruded molded articles according to the invention, as it inevitably occurs in the extrusion process if the blend is mixed in the desired composition by mixing and / or metering systems is plasticized and melted in the extrusion system and emerges from the nozzle.
  • the thermoplastic molded body as a single-layer or multilayer film, targeted stretching of the molded body after the melt extrusion allows further improvements in the hydrolysis stability and the stress crack resistance to be achieved, which are due to the choice of the nozzle gap width, the rate of melt withdrawal and in the case of
  • Blown film production of the inflation ratio can be influenced.
  • composition of the blend according to the invention can be varied over a wide range.
  • the proportion of the blend partner (I) can be between 1 and 99% by weight and that of the blend partner (II) can be between 99 and 1% by weight based on the total of the blend partners, and the desired properties can be set by the proportion of the blend partners of the molded body such as hydrolysis stability, stress crack resistance and the rate of damage caused by biological and / or physical / chemical degradation.
  • blend partner (II) only leads to a slight improvement in the resistance to hydrolysis and stress cracking, while a high proportion of blend partner (II) increases the tendency to block, particularly when extruding foils, so that either the processing speed is reduced or generally undesirably high proportion of lubricant must be added.
  • the proportion of the blend partner (I) is therefore preferably from 10 to 90% by weight and that of the blend partner (II) from 90 to 10% by weight.
  • thermoplastic molded articles according to the invention can additionally contain customary additives and auxiliaries.
  • additives and auxiliaries are preferably used:
  • nucleating agents typically used for polyester for example 1,5-naphthalene disodium sulfonate or layered silicates, for example talc, or nucleating agents of nanoparticle size, ie average particle diameter ⁇ 1 ⁇ m, for example of titanium nitride, aluminum hydroxyl hydrate, barium sulfate or zirconium compounds
  • nucleating agents typically used for polyester for example 1,5-naphthalene disodium sulfonate or layered silicates, for example talc, or nucleating agents of nanoparticle size, ie average particle diameter ⁇ 1 ⁇ m, for example of titanium nitride, aluminum hydroxyl hydrate, barium sulfate or zirconium compounds
  • customary stabilizers and neutralizing agents and / or 0 to a maximum of 5% by weight of the usual lubricants and release agents and / or 0 to a maximum of 5% by weight of the customary antiblocking agents and optionally pigments Coloring.
  • the usual stabilizing compounds for polyester compounds can be used as stabilizers and neutralizing agents.
  • the amount added is 0 to a maximum of 5% by weight.
  • Phenolic stabilizers alkali / earth alkali stearates and / or alkali earth alkali 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 0.00001 to 2% by weight and a stabilizer and neutralizing agent content of 0.00001 to 2% by weight.
  • Lubricants and release agents are higher aliphatic amides, tertiary amines, aliphatic
  • Acid amides higher aliphatic acid esters, low-molecular polar-modified waxes, montan waxes, cyclic waxes, phthalates, metal soaps and silicone oils.
  • the addition of higher aliphatic acid amides and silicone oils is particularly suitable.
  • 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.
  • cyclic waxes are components such as cyclic adipic acid tetramethylene esters or 1.6-dioxa-2.7-dioxocyclododecane, or the homologous hexa- suitable methylene derivative. Such substances are known as commercial products with the name Glycolube VL.
  • Suitable silicone oils are polydialkylsiloxanes, preferably polydimethylsiloxane, polymethylphenylsiloxane, olefin-modified silicone, silicone modified with polyethers such as, for. 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 / s. Polydimenthylsiloxane with a viscosity of 10,000 to 100,000 mm 2 s is preferred.
  • the amount of lubricant added is 0 to a maximum of 5% by weight.
  • it has a lubricant content of 0.005 to 4% by weight.
  • it has a lubricant content of 0.05 to 1% by weight.
  • one, more or all layers can contain lubricants.
  • Suitable antiblocking agents are both inorganic and organic additives which, because of their particle size and / or shape, protrude from the surface of the film and thus cause a spacer effect.
  • the following substances are used as inorganic antiblocking agents:
  • Aluminum silicates for example kaolin or kaolin clay
  • Aluminum oxides for example ⁇ aluminum oxide
  • Ceramics made of silica-aluminum oxides, barium sulfate, natural and synthetic silicas Layered silicates, for example asbestos,
  • Zinc oxide micro glass balls and the following substances are used as organic antiblocking agents: organic polymers incompatible with the biodegradable polymer such as
  • Polystyrene cross-linked and uncross-linked polymethyl methacrylate cross-linked polysiloxane e.g. Tospearl
  • polar-modified polyethylene e.g. maleic anhydride-grafted polyethylene
  • polypropylene e.g.
  • maleic anhydride-grafted polypropylene statistical copolymer based on ethylene or acrylic or methacrylic acid or acrylic or methacrylic acid or acrylic or methacrylic acid or acrylic or methacrylic acid or acrylic or methacrylic acid or acrylic or methacrylic acid or acrylic or methacrylic acid or acrylic or methacrylic acid or acrylic or methacrylic acid or acrylic or methacrylic acid or acrylic or methacrylic acid or acrylic or methacrylic acid or acrylic or methacrylic acid or acrylic or methacrylic acid or acrylic or methacrylic acid or acrylic or methacrylic acid or acrylic or methacrylic acid or acrylic or methacrylic acid or acrylic or methacrylic acid or acrylic or methacrylic acid - Reester or metal salts of methacrylic acid or metal salts of methacrylic acid esters
  • the effective amount of antiblocking agent is in the range from 0 to a maximum of 5% by weight.
  • the film contains 0.005 to 4% by weight
  • the film contains
  • the average particle size is between 1 and 20 ⁇ m, in particular 2-12 ⁇ m, particles with a spherical or ellipsoidal shape, as described in EP-A-0 236 945 and DE-A-38 01 535, are particularly suitable.
  • Combinations of different spacer systems are also particularly suitable.
  • the spacer systems are added to the outer cover layers in multilayer films.
  • the moldings according to the invention in particular in the form of single or multilayer films, can have 0 to max. Contain 10% by weight pigments for coloring. These can be organic or inorganic pigments. In a particularly preferred form, the pigments are biologically harmless and / or have a concentration of less than 1% by weight.
  • the polymers for the film are provided with the desired amounts by weight of organic or inorganic additives and / or auxiliaries in the production of raw materials in accordance with the customary prior art. This happens at
  • Granulation of the raw material for example in twin-screw extruders, where the additives are added to the raw material.
  • additives are added to the raw material.
  • masterbatch in the context of the present invention is a
  • masterbatch in particular a granular, dust-free concentrate of a plastic raw material with high amounts of additives, which is used in the mass preparation as an intermediate product (as a material additive to a granulate that is not or only partially or incompletely equipped with additives) in order to produce films therefrom, that contain a certain amount of additives.
  • Masterbatch is mixed into the extruder in such amounts before the polymer granules are added to the polymer raw materials which are not or only partially or incompletely equipped with additives, so that the desired percentages by weight of additives and / or auxiliaries are achieved.
  • the preferred materials from which the masterbatches are produced in addition to the additives and / or auxiliaries are substances which are compatible with the polymers mentioned in this invention.
  • the moldings according to the invention are produced using a conventional extrusion process.
  • the polymers in granular form optionally including the desired additives and auxiliaries, are melted in one or more extruders, homogenized, compressed and discharged via a single- or multi-layer nozzle.
  • the single-layer or multi-layer film can be an annular nozzle for producing a seamless tubular film or a flat nozzle for producing a flat film.
  • the carried out or e.g. foil 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.
  • 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 orientation and thus the hydrolysis stability and the stress crack resistance can be influenced by the choice of the nozzle gap size, the withdrawal speed and, in the case of a tubular film, the inflation ratio.
  • the tubular film can also be cut on one or both sides, so that a multilayer flat film is obtained.
  • the film After cooling, the film can be tempered below the crystalline melting temperature in the case of partially crystalline materials and above the glass transition temperature in the case of amorphous materials, and then stretched one or more times monoaxially or biaxially, the biaxial stretching being able to take place successively or, in particular in the case of tubular films, simultaneously. After the stretching stage or stages, the film can optionally be fixed by heat treatment.
  • a particularly suitable stretching method is for simultaneous biaxial
  • Stretching tubular films using the so-called double bubble technology in which the A primary bladder is stretched over an applied internal pressure.
  • the film can then be subjected to a heat treatment in order to adjust the shrinkage properties.
  • the film can be heated up to just below the crystalline melting temperature.
  • the procedure is expediently such that the film is passed through 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.
  • alternating voltage approximately 5 to 20 kV and 5 to 30 kHz
  • the air above the film surface is ionized by the spray or corona discharge and reacts with the molecules of the film surface, so that additional polar deposits occur in the polymer matrix.
  • an electrical direct voltage is applied between a burner (negative pole) and a cooling roller.
  • the applied voltage is between 400 and 3,000 V, preferably in the range of 500 to 2,000 V.
  • the applied voltage gives the ionized atoms increased acceleration and hits 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. B. oxygen or nitrogen or carbon dioxide or methane or halogenated hydrocarbons or
  • High-energy electrons are created, which hit the molecules and transfer their energies.
  • Monomer radicals and ions are formed. The resulting monomer radicals form - partly 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.
  • the shaped body according to the invention has a thickness of preferably less than 1000 ⁇ m, in particular less than 500 ⁇ m and very particularly preferably less than 80 ⁇ m.
  • the invention also relates to the use of the thermoplastic molded articles according to the invention in the preferred embodiment as a single-layer or multilayer film.
  • the preferred application is the use of this film, in particular as a multilayer film in pretreated or untreated as well as in printed or unprinted form for the packaging in the areas
  • the hydrolysis-stabilized, single-layer or multilayer film can be refined in pretreated or untreated form for greenhouse covers, mulch films or for lining plant-growing boxes (for example for mushroom cultivation) in the horticultural or agricultural sectors or for sacks for the storage and transport of goods
  • organic waste is used, whereby the proportion of the blend partners, the multilayer structure and the orientation of the molecules / crystals can be used to control the hydrolytic and biotic degradation rate.
  • the invention furthermore relates to the use of a 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 biological degradation 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 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 packaging or release 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.
  • the material had an MFI of 7 (in g / 10 min at 190 ° C, 2.16 kg, measured according to DIN 53 735), a melting point of 125 ° C, measured according to ISO 3146 7 C2, a proportion of lubricant of
  • the maximum extrusion temperature was 165 ° C
  • the maximum nozzle temperature was 155 ° C.
  • blend partner (I) from a mixture of the polymer from Example 1 as blend partner (I) and a blend partner (II) (poly- ⁇ -caprolactone clays P 787, Union Carbide), the proportion of blend partner (II) being 20% by weight the same system from Example 1, a single-layer blown film.
  • the blend partner (I ⁇ ) had an MFI of 2.8 (in g / 10 min at 190 ° C, 2.16 kg, measured according to DIN 53 735) and a melting point of 60 ° C, measured according to ISO 3146 / C2.
  • the maximum extrusion temperature was 160 ° C, the maximum nozzle temperature was 155 ° C.
  • a flat film tube with a total thickness of 80 ⁇ m could be produced using the same method as in Example 1.
  • Example 3 Example 3
  • a single-layer blown film was produced on the same system from Example 1 from the same materials from Example 2, but here the proportion of the blend partner (II) was 40% by weight.
  • the maximum extrusion temperature was
  • Example 2 the maximum nozzle temperature was 150 ° C.
  • a flat film tube with a total thickness of 80 ⁇ m could be produced using the same method as in Example 1.
  • a single-layer blown film was produced from the same materials from Example 2, but the proportion of the blend partner (II) here was 60% by weight, using the same system from Example 1.
  • the maximum extrusion temperature was 155 ° C, the maximum die temperature was 135 ° C. It could do the same
  • the mechanical quantities of tensile strength and elongation at break in the longitudinal and transverse directions were determined in accordance with DIN 53 455 on the samples produced.
  • the E module in the longitudinal and transverse directions was determined in accordance with DIN 53 457.
  • the thickness of the individual samples was determined in accordance with DIN 53 370.
  • the tear strength was measured as the maximum force and the tear resistance (tear strength based on sample thickness) in the longitudinal and transverse directions. The samples were then stored in water for 24 hours.
  • Tear strength, elongation at break and tear resistance depending on the storage time, the hydrolytic degradation and the stress crack resistance can be influenced by the choice of the nozzle gap size, the withdrawal speed and in the case of a tubular film the inflation ratio, the orientation and thus the hydrolysis stability and the stress crack resistance can be influenced.
  • the results of the tests on the samples from Examples 1, 2, 3 and 4 are listed in Table 1 and shown graphically in Fig. 1.
  • Bags were welded from the film sample using a separating seam welder. Five bags were made from each film sample. The bags were filled with fresh organic household waste and stored dry at an ambient temperature of approx. 15 ° C. The bags were examined for damage caused by degradation at intervals of one day.
  • the shelf life in relation to deposited compost is shown graphically in FIG. 1.
  • Samples 1, 2 and 7 have insufficient compost resistance with the damage pattern of cracks in the area of folds.
  • the damage pattern mainly shows seam cracks, from the 3rd week small round holes appear in the area of the filling material, which after a few days grow into irregular areas due to bacterial degradation.
  • the compost resistance is significantly improved from a 40% share of blend partner (II), the mixture of 60% blend partner (II) and 40% blend partner (I) was the most stable in this experiment.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Bag Frames (AREA)
  • Wrappers (AREA)
  • Food Preservation Except Freezing, Refrigeration, And Drying (AREA)

Abstract

Corps extrudés thermoplastiques biodégradables, en particulier feuilles à une ou plusieurs couches, qui possèdent une stabilité à l'hydrolyse, une résistance au fendillement par contrainte et une biodégradabilité améliorées. Lesdits corps sont constitués d'un mélange d'au moins deux polymères biodégradables différents.
PCT/EP1999/009526 1998-12-15 1999-12-06 Corps extrudes thermoplastiques biodegradables presentant une stabilite a l'hydrolyse et une resistance au fendillement par contrainte ameliorees WO2000036014A2 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP2000588268A JP2002532603A (ja) 1998-12-15 1999-12-06 改良された加水分解安定性と改良された耐応力亀裂性を示す生分解性で熱可塑性の成形体
CA002354514A CA2354514A1 (fr) 1998-12-15 1999-12-06 Corps extrudes thermoplastiques biodegradables presentant une stabilite a l'hydrolyse et une resistance au fendillement par contrainte ameliorees
BR9916117-6A BR9916117A (pt) 1998-12-15 1999-12-06 Corpos moldados termoplásticos, biodegradáveis, exibindo uma estabilidade melhorada com respeito à hidrólise e uma resistência melhorada à rachadura por tensão
EP99963396A EP1144507A3 (fr) 1998-12-15 1999-12-06 Corps extrudes thermoplastiques biodegradables presentant une stabilite a l'hydrolyse et une resistance au fendillement par contrainte ameliorees
AU19709/00A AU1970900A (en) 1998-12-15 1999-12-06 Biodegradable, thermoplastic shaped bodies exhibiting an improved stability withregard to hydrolysis and an improved resistance to stress cracking

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19857655 1998-12-15
DE19857655.2 1998-12-15
DE19951021.0 1999-10-22
DE19951021A DE19951021A1 (de) 1998-12-15 1999-10-22 Biologisch abbaubare, thermoplastische Formkörper mit verbesserter Hydrolysestabilität und Spannungsrissbeständigkeit

Publications (2)

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WO2000036014A2 true WO2000036014A2 (fr) 2000-06-22
WO2000036014A3 WO2000036014A3 (fr) 2001-11-29

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EP (1) EP1144507A3 (fr)
JP (1) JP2002532603A (fr)
AU (1) AU1970900A (fr)
BR (1) BR9916117A (fr)
CA (1) CA2354514A1 (fr)
WO (1) WO2000036014A2 (fr)

Cited By (1)

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JP2004506792A (ja) * 2000-08-23 2004-03-04 イー　カショーギ　インダストリーズ　エルエルシー 積層被覆物としての使用に適した生分解性ポリマーフィルムおよびシートならびにラップその他のパッケージング材料

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US7297394B2 (en) 2002-03-01 2007-11-20 Bio-Tec Biologische Naturverpackungen Gmbh & Co. Kg Biodegradable films and sheets suitable for use as coatings, wraps and packaging materials
CN105713356B (zh) * 2016-03-07 2017-05-31 杨红梅 一种可生物降解聚酯组合物
CN105585824A (zh) * 2016-03-07 2016-05-18 金发科技股份有限公司 一种可生物降解聚酯组合物

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US5227415A (en) * 1990-04-06 1993-07-13 Director-General Of Agency Of Industrial Science And Technology Biodegradable plastic composition
NO302481B1 (no) * 1990-10-16 1998-03-09 Takeda Chemical Industries Ltd Polymer for et preparat med forlenget frigjöring, samt preparat med forlenget frigjöring
US5320624A (en) * 1991-02-12 1994-06-14 United States Surgical Corporation Blends of glycolide and/or lactide polymers and caprolactone and/or trimethylene carbonate polymers and absorbable surgical devices made therefrom
US5480962A (en) * 1993-07-22 1996-01-02 Eastman Chemical Company Copolyesters having repeat units derived from succinic acid
DE4327024A1 (de) * 1993-08-12 1995-02-16 Bayer Ag Thermoplastisch verarbeitbare und biologisch abbaubare aliphatische Polyesteramide
DE4432161A1 (de) * 1994-09-09 1996-03-14 Biotechnolog Forschung Gmbh Biologisch abbaubare Polyester-Copolymere mit aromatischen Anteilen
JP2882756B2 (ja) * 1994-10-12 1999-04-12 昭和高分子株式会社 脂肪族ポリエステル組成物からなる延伸中空成形体
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WO1997034953A1 (fr) * 1996-03-19 1997-09-25 The Procter & Gamble Company Compositions de polymeres biodegradables et produits associes
DE19638488A1 (de) * 1996-09-20 1998-03-26 Basf Ag Biologisch abbaubare Polyester
JP2001507737A (ja) * 1996-12-31 2001-06-12 ザ・ダウ・ケミカル・カンパニー ポリエステルブレンド

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004506792A (ja) * 2000-08-23 2004-03-04 イー　カショーギ　インダストリーズ　エルエルシー 積層被覆物としての使用に適した生分解性ポリマーフィルムおよびシートならびにラップその他のパッケージング材料
JP2008255349A (ja) * 2000-08-23 2008-10-23 E Khashoggi Industries Llc 積層被覆物としての使用に適した生分解性ポリマーフィルムおよびシートならびにラップその他のパッケージング材料

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WO2000036014A3 (fr) 2001-11-29
AU1970900A (en) 2000-07-03
EP1144507A3 (fr) 2002-01-30
CA2354514A1 (fr) 2000-06-22
JP2002532603A (ja) 2002-10-02
EP1144507A2 (fr) 2001-10-17
BR9916117A (pt) 2001-09-04

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