Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
  • C08J2377/12—Polyester-amides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/018—Additives for biodegradable polymeric composition

Definitions

• the invention relates to a monoaxially stretched, biodegradable and compostable film.
• polymeric materials can undergo biodegradation.
• Mainly materials to be mentioned here are those that are obtained from naturally occurring polymers directly or after modification, for example polyhydroxyalkanoates such as polyhydroxybutyrate, plastic celluloses, cellulose esters, plastic starches, chitosan and pullulan.
• a targeted variation of the polymer composition or the stucco, as it is desirable from the polymer application, is difficult and often only possible to a very limited extent due to the natural synthesis process.
• biodegradable polymers have been known recently (see DE 44 32 161). These have the property that they are easy to process thermoplastically and, on the other hand, are biodegradable, ie 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. A corresponding test in a natural environment under the influence of microorganisms, such as that prevailing in compost, is given in DIN 54 900, among others. Due to their 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. For one thing, these films are characterized by poor mechanical Properties from and on the other hand, the barrier properties with regard to water vapor and gases are very poor compared to films made from typical, but not biodegradable plastics such as polyethylene, polypropylene or polyamide.
• the object of the present invention is to produce a biodegradable and compostable film with improved mechanical and optical properties as well as improved splice properties. This goal is achieved by subjecting a biodegradable and compostable polymer or a mixture of several biodegradable and compostable polymers to a monoaxial orientation
• Biodegradable and compostable polymers or films are understood in the sense of this invention goods that are tested for “biodegradability” according to the test according to DIN 54 900 from the 1996 draft.
• biodegradable polymers can also be oriented monoaxially in addition to thermoplastic processing, and that this orientation process can significantly improve the physical properties of the film. This includes a significant increase in strength, an improvement in the optical properties and an improved splicing property of the film.
• the invention relates to a film which has a monoaxial orientation and consists of one or more all biodegradable and compostable polymers 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.
• the film can additionally be treated with a corona and / or flame and / or plasma pretreatment and / or an oxidative substance and / or a depositable / depositable substance and / or a mixture of substances with an oxidative effect and / or depositable substances , e.g. B. gases with radical components such as ozone or a plasma-excited gas mixture of, for example, hexamethyldisiloxane with nitrogen (N- > ) and / or oxygen (O 2 ), are treated on the surface.
• gases with radical components such as ozone or a plasma-excited gas mixture of, for example, hexamethyldisiloxane with nitrogen (N- > ) and / or oxygen (O 2 )
• N- > hexamethyldisiloxane with nitrogen
• O 2 oxygen
• the invention also relates to the use of certain biodegradable and compostable polymers or a mixture of these polymers for the production of the film
• Suitable polymers are:
• linear bifunctional alcohols for example ethylene glycol, hexanediol or preferably butanediol, and / or optionally cycloaliphatic bifunctional alcohols, for example cyclohexanedimethanol and additionally, if appropriate, small amounts of high-functionality alcohols, for example 1,2,3-propanetriol or neopentyl glycol, and also from linear bifunctional acids , for example succinic acid or adipic acid.
• linear bifunctional alcohols for example ethylene glycol, hexanediol or preferably butanediol
• cycloaliphatic bifunctional alcohols for example cyclohexanedimethanol
• high-functionality alcohols for example 1,2,3-propanetriol or neopentyl glycol
• linear bifunctional acids for example succinic acid or adipic acid.
• cycloaliphatic bifunctional acids for example cyclohexanedicarboxylic acid, and / or optionally aromatic bifunctional acids, for example terephthalic acid or isophthalic acid or naphthalenediocarboxylic acid, and additionally optionally small amounts of high-functional acids, for example T ⁇ melhtsaure, or
• aromatic acids make up no more than 50% by weight based on all acids
• the acids can also be used in the form of derivatives, for example acid chloride or esters Aliphatic polyester urethanes
• linear bifunctional alcohols for example ethylene glycol, butanediol, hexanediol, preferably butanediol, and / or optionally cycloaliphatic bifunctional alcohols, for example cyclohexanedimethanol, and additionally optionally small amounts of high-functionality alcohols, for example 1,2,3-propanetriol or neopentyl glycol , and from linear bifunctional acids, for example succinic acid or adipic acid, and / or optionally cycloaliphatic and / or aromatic bifunctional acids, for example cyclohexanediocarboxylic acid and terephthalic acid, and additionally, if appropriate, small amounts of highly functional acids, for example trimellitic acid, or
• ester content C) and / or D) is at least 75% by weight based on the sum of C), D) and E)
• an ester fraction from linear bifunctional alcohols for example ethylene glycol, butanediol, hexanediol, preferably butanediol, and / or cycloaliphatic bifunctional alcohols, for example cyclohexane-dimethanol, and additionally, if appropriate, small amounts of higher-frequency tional alcohols, for example 1,2,3-propanetriol or neopentyl glycol, and from linear bifunctional acids, for example succinic acid or adipic acid, and / or optionally cycloaliphatic bifunctional acids, for example cyclohexanedicarboxylic acid, and additionally, if appropriate, small amounts of highly functional acids, for example
• linear bifunctional alcohols for example ethylene glycol, butanediol, hexanediol, preferably butanediol, and / or cycloaliphatic bifunctional alcohols, for example cyclohexane-dimethanol, and
• G from an ester fraction from acid and alcohol-functionalized building blocks, for example hydroxybutyric acid or hydroxyvalenic acid, or their derivatives, for example ⁇ -caprolactone,
• a carbonate component which is produced from aromatic bifunctional phenols, preferably bisphenol A and carbonate donors, for example phosgene,
• ester fraction F) and / or G) is at least 70% by weight based on the sum of F), G) and H)
• ester fraction from linear and / or cycloaliphatic bifunctional alcohols, for example ethylene glycol, hexanediol or butanediol. preferably butanediol or cyclohexanedimethanol, and optionally small amounts of high-functional alcohols, for example
• 1,2,3-propanetriol or neopentylgycol and from linear and / or cycloaliphatic bifunctional acids, for example succinic acid, adipic acid, cyclohexanedicarboxylic acid, preferably adipic acid and additional, if appropriate, small amounts of highly functional acids, for example t ⁇ mellitic acid, or
• an amide component from linear and / or cycloaliphatic bifunctional and additionally optionally small amounts of higher-functional amines, for example tetramethylendiamine, hexamethylenediamine, isophorondiamine, and from linear and / or cycloaliphatic bifunctional acids and, if appropriate, small amounts of highly functional acids, for example succinic acid or adipic acid, or
• ester fraction I) and / or K) at least 30% by weight based on the
• the biodegradable and compostable raw materials 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 the nanoparticle size, i.e. medium
• Particle diameter ⁇ 1 ⁇ m from, for example, titanium nitride, aluminum hydroxyl hydrate, barium sulfate or zirconium compounds) and with a maximum of 5% by weight of the usual stabilizers and neutralizing agents and with a maximum of 5% by weight of the usual lubricants and release agents and a maximum of 5% by weight of the usual Antiblocking agent, equipped and possibly with a corona or flame or
• Plasma pretreatment or an oxidizing substance or mixture of substances for example gases with radical components such as ozone or a plasma-excited gas mixture of, for example, hexamethyldisiloxane with nitrogen (N 2 ) and / or oxygen (O 2 ), have been treated on the surface.
• gases with radical components such as ozone or a plasma-excited gas mixture of, for example, hexamethyldisiloxane with nitrogen (N 2 ) and / or oxygen (O 2 ) have been treated on the surface.
• the usual stabilizing compounds for polyester compounds can be used as stabilizers and neutralizing agents.
• the maximum amount added is 5% by weight.
• Particularly suitable stabilizers are phenolic stabilizers, alkali
• 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 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 one
• 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, low molecular weight, 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
• the aliphatic amides include, in particular, the supply forms of
• 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. Erucasaureamide, stearic acid amide and oleic acid amide are preferred among them
• release agents or lubricants are compounds that both
• ester 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 16-dioxa-2.7-dioxocyclododecane, or the homologous hexamethylene 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 2 / s polydimenthylsiloxane with a viscosity of 10,000 to 100,000 mm 2 / s is preferred
• the amount of lubricant added is a maximum of 5% by weight. In a particularly preferred embodiment of the film, it has a lubricant content of 0.005 to 4% by weight. In a very particularly preferred embodiment of the film, it has a lubricant content of 0.05 to 1% by weight.
• Suitable antiblocking agents are both inorganic and organic additives which, after the monoaxial stretching, protrude from the surface of the foal and thus produce 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
• Polycarbonate crosslinked and uncrosslinked polymethyl methacrylate crosslinked 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 in the range up to a maximum of 5% by weight.
• the film contains 0.005 to 4% by weight of antiblocking agent.
• the film contains
• the average particle size is between 1 and 6 ⁇ m, in particular 2 and 5 ⁇ m, particles with a spherical shape, as 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 polymers for the film provided with additives are provided with the desired amounts by weight of organic or inorganic fillers in the production of raw materials. This takes place when granulating the raw material, for example in twin-screw extruders, where the additives are added to the raw material Additization is also possible in that part or all of the necessary additives are added to a raw material that has not or only partially been finished in the form of a masterbatch.
• masterbatch means a masterbatch, in particular a granular, dust-free concentrate of a plastic raw material with high
• Amounts of additives that are 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 that contain a certain amount of additives.
• the masterbatch is prepared before the Polymer granules are mixed in the extruder in such amounts to the raw materials which are not or only partially or incompletely equipped with additives, so that the desired percentages by weight of fillers are achieved in the films
• the preferred materials from which the masterbatches are made in addition to the additives are substances that are compatible with the biodegradable raw materials mentioned in this invention.
• the materials from which the masterbatches are made in addition to the additives are also biological degradable materials
• the procedure is expediently such that the film is felt 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
• 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
• an electrical direct voltage is applied between a burner (negative pole) and a cooling roller.
• the amount of the voltage applied is between 400 and 3,000 V, preferably it is in the range from 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 formation of radicals takes place more quickly.
• the 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
• a high-energy field e.g. B. microwave radiation exposed.
• High-energy electrons are created, which hit the molecules and transfer their energies. This creates local radical structures, the excitation states of which correspond to temperatures of a few
• Foil surface is firmly connected. With a suitable material composition, this results in an increase in the surface tension on the film
• 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 be produced from a polyester amide or a mixture of different polyester amides.
• the invention also relates to a method for producing the film according to the invention. This process is characterized in that the biodegradable and compostable materials are first broken down by the action of heat and shear, this melt is discharged in a tool, cooled to solidification, then in the case of partially crystalline materials
• the film can optionally be fixed in each case.
• the film thus produced can possibly be pretreated in-line.
• the pretreatment can be carried out with a corona, a flame, a plasma or an oxidative substance or mixture of substances, e.g. gases with radical components such as ozone or a plasma-excited gas mixture from, for example, hexamethyldisiloxane with nitrogen (N 2 ) and / or oxygen (O 2 ), in such a way that there is an increase in the surface tension on the film
• the monoaxial stretching is characterized in that the total stretch ratio in the longitudinal direction 1. 1, 5 to 1 15 amounts
• the monoaxial stretching is characterized in that the total stretching ratio in the longitudinal direction is 1 2.8 to 1 8
• 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 film according to the invention.
• This film is used as a solo film in pretreated or untreated as well as in printed or unprinted form for packaging in the food and non-food sectors or as a solo film in pretreated or untreated form
• the film surface can be bonded during manufacture and / or subsequently during further processing with a corona, a flame, a plasma or another oxidative substance or mixture of substances, for example gases with radical components such as ozone or a plasma-excited gas mixture of, for example, hexamethyldisiloxane with nitrogen (N,) and / or
• the invention furthermore relates to the use of the film according to the invention as a coated film or in a film composite.
• the other films in the composite may be non-degradable films or else biodegradable and compostable films.
• the coating or adhesives used can be both belong to the normal non-degradable systems as well as to the biodegradable and compostable raw materials
• the invention furthermore relates to the use of the film according to the invention or the coated film or the composite as a starting material for the production of tapes or tear strips by cutting open the film or the coated film or the composite in a further working step
• the invention furthermore relates to the use of the tapes according to the invention for the production of fabrics or braids or knitted fabrics or nonwovens.
• a biodegradable polyester amide with a melt viscosity of 250 Pas at 190 ° C (measured according to DIN 54 81 1 - B) and a melting point of 125 ° C measured according to ISO 3146 / C2, which has a lubricant content of 1% by weight and an antiblock content of 0 , 1% by weight was among the following
• Tempe ⁇ erwalzen at temperatures of 65 ° C to the stretching temperature was heated
• the actual stretching rollers were operated at a temperature of 70 ° C
• the flat film was in two stages once by the ratio 1 1.5 and then by the ratio of 1 3.25 in the longitudinal direction stretched This resulted in a total stretch ratio of 1 4,875 die in the longitudinal direction
• Post-heating rollers over which the film then ran had a temperature of 85 ° C.
• the production speed after stretching was 30.0 m / min.
• a film with a thickness of 30 ⁇ m could be produced
• the same biodegradable polyester amide from Examples 1 and 2 was processed on a foal blowing system.
• the melt temperature measured at the die outlet was 152 ° C.
• the cylinder temperature of the extruder was regulated to max. 145 ° C. and the die to 145 ° C.
• the diameter of the die used was 400 mm.
• the bed width of the finished film was 950 mm. It was produced at a take-off speed of 6.3 m / min
• the thickness of the blown film was 30 ⁇ m
• the splice property of the finished film is determined using an approx. 5 mm long
• the surface gloss was determined as optical properties on the films in accordance with DIN 67 530 at a test angle of 20 ° and the haze was determined in accordance with ASTM D 1003. The gloss measurement was carried out on both sides of the film. The values determined were then used to form an average and reported as the result

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Manufacturing & Machinery (AREA)
• Engineering & Computer Science (AREA)
• Crystallography & Structural Chemistry (AREA)
• Materials Engineering (AREA)
• Biological Depolymerization Polymers (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)
• Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
• Laminated Bodies (AREA)
• Wrappers (AREA)

Priority Applications (5)

Applications Claiming Priority (2)

Publications (1)

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Family Applications (1)

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Cited By (3)

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Citations (6)

• 1996
  • 1996-07-26 DE DE19630232A patent/DE19630232A1/de not_active Withdrawn
• 1997
  • 1997-07-14 CA CA002261977A patent/CA2261977A1/en not_active Abandoned
  • 1997-07-14 EP EP97933672A patent/EP0914371A1/de not_active Withdrawn
  • 1997-07-14 WO PCT/EP1997/003743 patent/WO1998004619A1/de not_active Application Discontinuation
  • 1997-07-14 AU AU36946/97A patent/AU725049B2/en not_active Ceased
  • 1997-07-14 KR KR1019997000613A patent/KR20000029555A/ko not_active Application Discontinuation
  • 1997-07-14 CN CN97196778A patent/CN1226266A/zh active Pending
  • 1997-07-14 JP JP10508430A patent/JP2000516972A/ja active Pending
  • 1997-07-14 BR BR9710603-8A patent/BR9710603A/pt not_active Application Discontinuation
  • 1997-07-14 IL IL12807597A patent/IL128075A0/xx unknown

Patent Citations (6)

Non-Patent Citations (2)

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