WO2007027163A2 - Film en polypropylène biorienté dégradable et/ou biodégradable - Google Patents

Film en polypropylène biorienté dégradable et/ou biodégradable Download PDF

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Publication number
WO2007027163A2
WO2007027163A2 PCT/TR2005/000040 TR2005000040W WO2007027163A2 WO 2007027163 A2 WO2007027163 A2 WO 2007027163A2 TR 2005000040 W TR2005000040 W TR 2005000040W WO 2007027163 A2 WO2007027163 A2 WO 2007027163A2
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WO
WIPO (PCT)
Prior art keywords
degradable
biodegradable
polypropylene film
mono
multilayer
Prior art date
Application number
PCT/TR2005/000040
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English (en)
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WO2007027163A3 (fr
Inventor
M. Necdet Kileci
Turgut Selbasti
Philippe Lavoisier
Sibel Tilfarligil
Eda Elgin Kilic
Mehmet Hayri Genc
Radu Baciu
Original Assignee
Super Film Ambalaj Sanayi Ve Ticaret A. S.
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
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Application filed by Super Film Ambalaj Sanayi Ve Ticaret A. S. filed Critical Super Film Ambalaj Sanayi Ve Ticaret A. S.
Priority to PCT/TR2005/000040 priority Critical patent/WO2007027163A2/fr
Priority to TR2008/01372T priority patent/TR200801372T2/xx
Publication of WO2007027163A2 publication Critical patent/WO2007027163A2/fr
Publication of WO2007027163A3 publication Critical patent/WO2007027163A3/fr

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Classifications

    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • C08K5/0033—Additives activating the degradation of the macromolecular compound
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/518—Oriented bi-axially
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/716—Degradable
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/716—Degradable
    • B32B2307/7163—Biodegradable
    • 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
    • B32B2323/00—Polyalkenes
    • B32B2323/10—Polypropylene
    • 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
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/16—Biodegradable polymers
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • 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 main objective of the present invention is to provide a chemically degradable and/or biodegradable biaxially oriented film of a polypropylene that is suitable for all industrial applications such as packaging or non-packaging applications.
  • the film is rendered degradable and/or biodegradable by addition of agents that promote the degradability by combination of heat and UV in a first step and absorption by microorganism naturally present in soils (those agents promoting degradability are metal carboxylates) in a second step. Film is not accumulated in nature due to a non-hazardous degradation process.
  • Synthetic fossil source have been widely used as base of polymeric plastics in all sectors of industry including packaging due to their superior characteristics and shelf life. With the increase of consumption of the synthetic polymer compounds in all sectors of packaging industry including primary packaging in contact with food, secondary over wrapping packaging and transport bags, the amount of waste of plastics has also incredibly increased.
  • Incineration causes problem due to high heat generation in furnace and risk of emission of toxic substances, but landfill also causes problem of accumulation because they are degrading in very long period of time, also with wind blowing material can migrate to unpolluted areas. It is a major concern for our children to take care of environment.
  • plastic packaging materials such as polyethylene, polypropylene, polyester have been widely used as a packaging material. Since polypropylene remains semi permanently in nature like other polyolefins, it cannot degrade when you disposed it to a landfill.
  • the prior art has attempted to make films biodegradable using some resins such as polylactic acid (PLA), polybutylene succinate (PBS), polyhydroxybutyrate (PHB), polycaprolactone (PCL), polyethylene succinate (PES), polycaprolactone/polybutylene succinate mixtures or copolymers (PCL/PBS), polyethylene terephthalate/polyethylene succinate copolymers (PET/PES), polyhydroxybutyrate/polyhydroxyvalerate copolymers (PHB/PHV), polybutylene succinate/polybutylene adipate mixtures or copolymers (PBS/PBA) and polybutylene terephthalate/polybutylene adipate copolymers (PBT/PBA).
  • PBS/PBA polybutylene terephthalate/polybutylene adipate copolymers
  • PBT/PBA polybutylene terephthalate/polybutylene adipate copo
  • Degradable and/or biodegradable biaxially oriented polypropylene which is developed in this present invention is much more economical, regarding the degradable and biodegradable materials used in the market.
  • Polypropylene is one of the most commonly used polymeric base material for non-biodegradable films used in the various kinds of packaging or non packaging applications, for example flower packaging and labeling which are low cost without degradable products.
  • the degradable additive used in this present invention does not interfere with the additives such as slip, antiblock, antistatic, etc. used for the production of the regular BOPP.
  • the performance of the biodegradable biaxially oriented polypropylene described in this present invention regarding the quality is the same as the regular biaxially oriented polypropylene product.
  • a biodegradable film formable into biodegradable bags includes the blended product of polylactic acid and a suitable biodegradable polymeric resin such as polyester with starch.
  • the blended product includes from about 5% to about 50% by weight polylactic acid.
  • the polylactic acid-containing biodegradable films may be formed into a bag.
  • the biodegradable films of this invention are formed through a blown film process.
  • biaxially oriented polylactic acid-based film and blends have other disadvantages such as their high density 1.25 versus 0.9 for polypropylene, crispy noise when handled in the converting machines, high cost of raw material and green housing incidence (high percentage of acid gas emission and CO2 emission when degrading).
  • US patent application 2005/0008815 discloses biodegradable biaxially oriented polylactic acid-based film suitable for packaging films; such film which is a mixture of crystalline polylactic acid 95 to 60 parts by weigth with 5 to 40 parts of amorphous polylactic acid has tear strength in width direction of 10 to 200 mN.
  • the film disclosed in this patent is suitable for bags and packaging films for various windows, particularly films for outlook window envelopes.
  • the film is biodegradable and, as films for outlook window envelopes, is superior in the coating adaptability for an antistatic agent, a lubricant and an antiblocking agent or the like and in the high-speed cutting property.
  • biaxially oriented polylactic acid films are their tensile strength in machine direction (MD) which are 15,950 psi while biaxially oriented Polypropylene is 27,550 psi. Such material has poor flexibility and therefore are not easy to use for wrapping applications.
  • This invention discloses a biaxially oriented film of a polylactic acid resin comprising not less than 50% by weight of a polylactic acid resin.
  • biodegradable aliphatic thermoplastic polyesters useful for the production of several types of articles such as films, sheets, nets, expanded molded products, and the like, and process for their production.
  • This invention refers biodegradable polyesters of the diacid/diol type comprising at least one at least trifunctional compound in order to obtain articles with enhanced permeability, low gels content and an improved transparency.
  • U.S. Pat. No 2005/0151296 discloses a lactic acid-based resin composition that comprises a lactic acid-based resin (component (A)), and an ethylene-unsaturated carboxylic acid copolymer (component (B)) and/or an ethylene-unsaturated carboxylic acid copolymer ionomer (component (C)).
  • the lactic acid-based resin composition has good physical properties in melt and can be efficiently formed into films and laminates through casting or extrusion lamination.
  • the paper laminates obtained through extrusion lamination with the resin composition have good moisture barrier property, and have the advantages of good antibacterial ability, good biodegradability and low combustion heat.
  • the moldings obtained from the resin composition of the invention have a characteristic which is excellent in impact strength.
  • the films and sheets formed of the resin composition have good low-temperature heat-sealability and hot-tack sealability, and the resin composition well serves as a sealant.
  • the resin composition is favorable to various materials in a broad range, for example, for wrapping and packaging materials for foods, drinks, electronic appliances, medicines and cosmetics, for materials for use in agriculture, civil engineering and construction and for materials for compost, etc.
  • US 2005/0163944 describes a biodegradable film having two biodegradable resin layers and a biodegradable moisture barrier layer interposed between the resin layers.
  • This invention also accomplishes the above object by providing a biodegradable container having a biodegradable container body coated with the biodegradable film of the present invention.
  • This invention also provides biodegradable moistureproof paper having biodegradable paper coated with the biodegradable film of the present invention.
  • This invention also provides a biodegradable container formed of the biodegradable moisture proof paper of the present invention.
  • the film is stretched at least monoaxially.
  • the thin layer formed on the both surfaces of the biodegradable film of the invention is preferably so designed that it is effective for preventing the plasticizer in the film from scattering away and/or bleeding out.
  • the biodegradable oriented film of the invention is useful, for example, for wrapping films. This coating makes of course some additional costs to the film and this thin layer does not degrade even with this thin layers.
  • US patent 5,470,526 issued November 28th 1995, to Minnesota Mining and ' Manufacturing discloses degradable multilayered structures which are compostable.
  • the composition includes thermoplastic polymer with a transition metal salt selected from cobalt, manganese, copper, cerium, vanadium and iron and a fatty acid. Composition will oxidatively degrade to an embrittled state in specific environment conditions.
  • the film disclosed in this patent is not oriented film. Only under appropriate, low temperature conditions (i.e. below 60 0 C), can multilayered structures be uniaxially, biaxially or multiaxially oriented to further enhances their physical properties without loosing the mesophase form of polypropylene, mesopolymer blends, or mesocopolymers.
  • the degradability of another type of the film of this invention is 14 days under 60 0 C.
  • the film produced according to this patent can not be used mainly in general packaging including food or flower packaging, adhesive tape films and labelling, because; • In the BOPP film production the temperature can be between 120 to 250 0 C in different steps of the process,
  • US patent 5,384,183 issued on January 24th, 1995 is also related to degradable film consisting essentially of photodegradable polyethylene sheet with cerium salt of C16- 2 0 fatty acid and with titanium dioxide, this titanium dioxide, normally considered as an opacifying agent is useful to control the rate of polymer degradation.
  • US patent 5,416,133 dated May 16, 1995 is directed to chemically degradable polyolefin film, mainly melt blown polyolefin, especially polyethylene, the incorporation of a metal carboxylate with 25 to 60% filler such as talc are made chemically and thermally degradable. Incorporation of filler is intended to reduce the price of the melt blown film.
  • U.S. Pat. No 2004/0076778 discloses a biodegradable bag for packing a food capable of storing a food such as a snack food which is required to have an oxygen barrier property and a water vapor barrier property, which can be produced at a high speed by a bag making and packaging machine, which can be degraded by naturally occurring microorganisms in soil or water finally to a non-hazardous degradation product, which can be biorecycled, and which is not accumulated in nature.
  • This invention is directed to a biodegradable bag for packing a food, which comprises a laminated film obtainable by laminating in the following order; a sealant layer comprising a biodegradable polymer; a barrier layer having an oxygen barrier property and a water vapor barrier property; and a barrier layer-supporting substrate layer comprising a biodegradable polymer, said laminated film being heat-sealed in order for the sealant layer to be inside.
  • the object of the invention described in U.S. Pat. No 2002/0160201 is to provide a softened biodegradable film which is substantially free from appearance change and morphology change such as transparency reduction, even when stored or used for a long period of time at high temperatures.
  • This invention provides a biodegradable oriented film of a plasticizer-containing biodegradable resin, of which the both surfaces are coated with at least one thin layer to attain these objects.
  • This invention is also related with a coated material requiring further processing unlike the product of this present invention.
  • U.S. Pat. No 2004/0076778 is directed to a biodegradable bag for packing a food, which comprises a laminated film obtainable by laminating in the following order; a sealant layer comprising a biodegradable polymer; a barrier layer having an oxygen barrier property and a water vapor barrier property; and a barrier layer-supporting substrate layer comprising a biodegradable polymer, said laminated film being heat-sealed in order for the sealant layer to be inside.
  • This invention is related only with the biodegradable bags for food packaging.
  • PLA based materials when compared to degradable and/or biodegradable BOPP films developed according to this invention are hereinunder. a) They are produced from non food corns, b) They consume fertilizers and pesticides, c) They have higher density than polypropylene, d) They degrade with 60% more acid gas emission and 40% more CO 2 emission, e) They have higher cost when compared with non degradable materials and other biodegradable materials. f) They have lower tensile strength in both machine and transverse directions, g) They have lower puncture resistance, h) They have low moisture resistance. i) It is difficult to control degradability. The present invention solves these disadvantages.
  • Advantages of this present invention are as follows; b) Product of this present invention is made degradable and/or biodegradable with the addition of limited amount of degradable additives. c) No process parameters change is necessary to make degradable and/or biodegradable product. Therefore, the process parameters of the regular biaxially oriented polypropylene film can be used for the production of biodegradable film described in this present invention. d) No need to modify the production line of the regular BOPP for the production of the material described in this present invention. e) The additive used in this present invention does not interfere with the additives such as slip, antiblock, antistatic, etc. used for the production of the regular BOPP. Consequently, physical properties such as haze, gloss, etc.
  • Biodegradable product described in this invention unlike the PLA based materials is not noisy and crispy material when handled.
  • Biodegradable product described in this invention has wide thickness range from very thin films such as 5 ⁇ m to thicker films such as 100 ⁇ m.
  • the film according to the present invention is preferably produced by using the following process and has the characteristics below.
  • the general definition of the process for the production of the biodegradable BOPP film is as follows: (a) Coextruding the melted materials of individual layer(s) of the film through a die.
  • a method for producing a biaxially oriented film of the present invention is known as a flat tenter process (sequential or simultaneous stretching), but may also be made on a tubular method such as bubble or double bubble process technology as well.
  • the process starts from the gravimetric dosing of each component in each of the layers that will constitute the film.
  • the film can also produced by simultaneous stretching process.
  • the active additive that promotes degradability which is metal carboxylate, is mixed into every layer(s) of the film.
  • the layers constitute polypropylene homopolymer, terpolymer or copolymer of polypropylene according to the final use, and additionally the additives such as slip, antistatic, antiblock (synthetic or polymeric), coloring (organic or inorganic) and cavitating agents (organic or inorganic) or alike in masterbatch or compound form which are necessary for specific end use properties.
  • the prepared raw material is fed in each extruder which are either single screw or twin screw extruder and melt mixed preferably at a temperature below 27O 0 C, where the active additive is not degrading,
  • the melt is then going through a multimanifold die with manual or automatic thickness control system, the melt is then going onto a chill roll where the water bath and roll cooling temperature are adjusted to control the crystallinity.
  • Non oriented crystallized film is then stretched in the machine direction (MD) in a ratio from 4 to 7, more preferably in a range from 5 to 6, the film is preheated to allow MD stretching and heat set at the outlet part of the MD section before entering the TD
  • MD machine direction
  • Transverse direction stretching unit Transverse direction (TD) stretching unit.
  • Transverse direction (TD) stretching is in a ratio from 7-10, more preferably 8-9.
  • Operating temperatures are between 120-140 0 C for preheating, 80 - 130 0 C in the stretching zone and 130-140 0 C on the heat setting zone of MDO (machine direction orienter) section
  • MD oriented film goes into the transverse direction (TD) orienting section, the film is conveyed in an oven by clips, it is preheated, drawed in the TD direction and heat stabilized before leaving the TDO (transverse direction orienter) section.
  • TD transverse direction
  • TDO transverse direction orienter
  • Temperature in the oven are related to thermal exchange within the film, speed and final film thickness; typical temperatures are in a range of 160-180 0 C in the preheating zone , 150-160 0 C in stretching zone and 160-170 0 C in heat setting zone.
  • Biaxially oriented film is then wound in the final width with as complementary steps, going through corona or flame or plasma treatment units and also in an edge cutting section where sides of TD stretch film are cut and going to recycling unit.
  • the recycling material coming from edges are recycled directly in the film without any effect on the film.
  • a tubular method a heat treatment method wherein a film is heated by external hot air and the like, while kept in tensed stage by controlling and maintaining internal pressure of the bubble by sealing internal air.
  • the thickness of the film of the present invention is preferably in the range from 5 to 100 ⁇ m, more preferably in the range from 7 to 50 ⁇ m. In particular, the thickness of the film is preferably in the range from 15 to 50 ⁇ m to provide mechanical and optical properties for different industrial applications.
  • the thickness can be up to 200 ⁇ m.
  • the primary objective of this present invention is to replace the non-degradable BOPP film with the degradable and/or biodegradable counterpart for packaging applications such as fresh vegetable and fruit packaging, food or any good packaging, or any non packaging applications such as flower wrapping, labelling, adhesive tape applications and different industrial applications ...etc.
  • the second aim of this present invention is not to change the physical or mechanical properties of standard non-degradable BOPP to meet the requirements of the specified applications.
  • some active agents are added to each layer of the material of this present invention. By using these active agents added to each layer, the shelf life of the film is controlled.
  • the material of this present invention having monolayer or multilayer structure has the same mechanical and optical properties as normal unfilled polypropylene film before going to landfill.
  • some active agents have been added to each layer. In degradation, large molecules are broken into smaller molecules or fragments. Normally, oxygen is incorporated into these molecular fragments. Typically, strong, tough plastic films become weak and brittle as a result of oxidative degradation. Heat or exposure to UV light initiates the process of degradation and mechanical stress enhances this process.
  • biodegradation is the process by which microorganisms (microbes such as bacteria, fungi or algae) convert materials into biomass, carbon dioxide and water.
  • Biomass is a general term used to refer to the cells of the microorganisms that are using the material as a carbon source to grow on. Biodegradable products can be classified into 5 categories;
  • 5- Fossil source of polymers such as PE, PP, PET with additives that promote their biodegradability.
  • This present invention belongs to 5 th category of degradable polymers.
  • the process parameters of the regular biaxially oriented polypropylene film are used to have the product of this present invention therefore no need to change any process conditions used in the production of regular BOPP film.
  • a flat tenter process technology with draw ratio in machine direction from 4 to 7 and in the transverse direction from 7 to 10 is used to orient the multilayer polypropylene film in both axis.
  • the multilayered biaxially oriented polypropylene film described in this present invention undergoes two step degradation process after completion of its shelf life or when it goes to landfill. In first step of the degradation, heat or exposure to UV light initiates the process of degradation by oxidation and mechanical stress enhances this process. In the second step, the product of this present invention which is fragmented in much shorter oxidized molecules is converted to biomass, carbon dioxide and water by microorganisms accumulated in nature.
  • the density of the product developed in this present invention is lower when compared with PLA based biodegradable material. Consequently, the yield (m 2 /kg) of the product developed in this present invention is higher.
  • Multilayer biaxially oriented polypropylene film of this present invention shows no crispy noise effect that can be seen in PLA based biodegradable material.
  • the multilayer film of the present invention can be produced by the conventional methods such as sequential stretching, simultaneous stretching used in the production of biaxially stretched polyolefins. Since stretching ratios are independently adjustable in sequential stretching, that one is preferable method for the production of the multilayer film of the present invention among the others.
  • the characteristics of the raw materials used in the formulation of the multilayer film of the present invention are as follows; Polypropylene homopolymer having a melting point of 150 0 C or above, melt flow rate between about 2.0 to 4.0 is preferred to be used.
  • Antiblocking agent from the group of inorganic additives such as silicon dioxide, calcium carbonate, aluminum silicate, magnesium silicate, calcium phosphate and the like and/or organic polymers for example polyamides, polyesters and the like.
  • Preferred antiblocking agent is aluminum silicate.
  • Terpolymer of ethylene, propylene and butylene is preferred to be used in this present invention. Such material brings, sealability of film and is mostly used on the skin layers of multilayered film.
  • Slip/antistatic masterbatch having a melt flow rate close to that of homopolymer is preferable.
  • Degradable masterbatch or compound used in this present invention can have as active agents inbodied in polyolefin resins; • transition metal salt selected from cobalt, manganese, copper, cerium, vanadium, aluminum, antimony, barium, cadmium, lead, silver, sodium, zinc, iron and alike, and a fatty ester providing unsaturated species, and free acid, or
  • suitable inorganic ligands includes chlorides, nitrates, sulfates and the like,
  • the preferred active agent of degradable masterbatch or compound used in the present invention are inorganic ligands such as octanoates, acetates, stearates, oleates, naphtenates, linoleates, tallates and the like.
  • Polyolefins are carbon chains containing carbon hydrogen and small amounts of oxygen. These polymers react with oxygen in the air. Since this oxidation reaction is too slow, they cannot be accepted as degradable materials. To accelerate this oxidation reaction, the degradable masterbatch or compounds as catalysts are added in this present invention.
  • hydroperoxides are formed due to oxidation. Free radicals are produced due to the decomposition of hydroperoxides with heat, light or metal catalysts. After that, these free radicals undergo chain reaction to produce oxidation products. Acceleration of oxidation occurs because of the new oxidation reactions of produced free radicals. As a result of these oxidation reactions, carbon chain of the polymer is broken and its chain length is reduced. The final result of all these reactions is that the chain scission of polymer and transition of material from tough state to brittle state. At this state, polymeric material is ready for the attack of microorganisms (microbes such as bacteria, fungi or algae) which convert materials into biomass, carbon dioxide and water.
  • microorganisms microbes such as bacteria, fungi or algae
  • the main feature of the present invention is to add degradable masterbatch or compound into the layer(s) of the mono or multilayer BOPP film to make it degradable and/or biodegradable.
  • the degradable masterbatch or compound is between about 0.5 % to about 10 % by weight of the layer, more preferably from about 1 % to about 3 % by weight of the layer.
  • the mono or multilayered biaxially oriented polypropylene film according to this present invention is produced under the same process parameters as regular unfilled (without degradable masterbatch or compound) biaxially oriented polypropylene film.
  • the mono or multilayered biaxially oriented polypropylene film according to this present invention is extruded before orientation under the same extrusion temperature parameters as regular unfilled film; extrusion and melt temperature does not start activation of film degradation.
  • the mono or multilayered biaxially oriented polypropylene film according to this present invention has lower density than PLA based biodegradable material.
  • the mono or multilayered biaxially oriented polypropylene film according to this present invention has no crispy noise effect in comparison with PLA based biodegradable material.
  • the degradable masterbatch or compound can be added some of the the layer(s) of the multilayer BOPP film to make it degradable and/or biodegradable.
  • the recycling material coming from edges are recycled directly in the film of present invention (up to 25%) without any effect on the film.
  • the mono or multilayered biaxially oriented polypropylene film according to this present invention can be in different color, cavitated, metallized or coated according to the application.
  • compositional characteristics of the multilayer film of the present invention are as follows;
  • Layer 1 (First skin layer) contains between about 92 % and about 99 % by weight of terpolymer, more preferably from about 94 % to 98 % by weight, between about 0.5 % to about 4 % by weight of antiblocking agent, more preferably from about 1 % to about 3 % by weight, between about 0.5 % to about 4 % by weight of degradable masterbatch, more preferably from about 1 % to about 3 % by weight.
  • Layer 2 (First intermediate layer) contains between about 96 % and about 99.5 % by weight of homopolymer, more preferably from about 97 % to 99 % by weight, between about 0.5 % to about 4 % by weight of degradable masterbatch, more preferably from about 1 % to about 3 % by weight.
  • Layer 3 (Main layer) contains between about 92 % and about 99 % by weight of homopolymer, more preferably from about 94 % to 98 % by weight, between about 0.5 % to about 4 % by weight of slip/antistatic masterbatch, more preferably from about 1 % to about 2 % by weight, between about 0.5 % to about 4 % by weight of degradable masterbatch, more preferably from about 1 % to about 3 % by weight.
  • Layer 4 (Second intermediate layer) contains between about 96 % and about 99.5 % by weight of homopolymer, more preferably from about 97 % to 99 % by weight, between about 0.5 % to about 4 % by weight of degradable masterbatch, more preferably from about 1 % to about 3 % by weight. Layer 4 can be totally identical with layer 2 or slight modifications can be made.
  • Layer 5 (Second skin layer) contains between about 96 % and about 99.5 % by weight of terpolymer, more preferably from about 97 % to 99 % by weight, between about 0.5 % to about 4 % by weight of degradable masterbatch, more preferably from about 1 % to about 3 % by weight.
  • the heat sealable degradable and/or biodegradable BOPP film given in the Example 1 is used especially for fresh vegetable and fruit packaging.
  • Example 1 having degradable masterbatch
  • standard film without degradable masterbatch
  • Layer 1 (First skin layer) contains between about 92 % and about 99 % by weight of homopolymer, more preferably from about 94 % to 98 % by weight, between about 0.5 % to about 4 % by weight of antiblocking agent, more preferably from about 1 % to about 3 % by weight, between about 0.5 % to about 4 % by weight of degradable masterbatch, more preferably from about 1 % to about 3 % by weight.
  • Layer 2 (First intermediate layer) contains between about 96 % and about 99.5 % by weight of homopolymer, more preferably from about 97 % to 99 % by weight, between about 0.5 % to about 4 % by weight of degradable masterbatch, more preferably from about 1 % to about 3 % by weight.
  • Layer 3 (Main layer) contains between about 96 % and about 99.5 % by weight of homopolymer, more preferably from about 97 % to 99 % by weight, between about 0.5 % to about 4 % by weight of degradable masterbatch, more preferably from about 1 % to about 3 % by weight.
  • Layer 4 (Second intermediate layer) contains between about 96 % and about 99.5 % by weight of homopolymer, more preferably from about 97 % to 99 % by weight, between about 0.5 % to about 4 % by weight of degradable masterbatch, more preferably from about 1 % to about 3 % by weight. Layer 4 can be totally identical with layer 2 or slight modifications can be made.
  • Layer 5 (Second skin layer) contains between about 92 % and about 99 % by weight of homopolymer, more preferably from about 94 % to 98 % by weight, between about 0.5 % to about 6 % by weight of antiblocking agent, more preferably from about 1 % to about 5 % by weight, between about 0.5 % to about 4 % by weight of non-migratory antiblock masterbatch, more preferably from about 1 % to about 3 % by weight between about 0.5 % to about 4 % by weight of degradable masterbatch, more preferably from about 1 % to about 3 % by weight.
  • Layer 5 can be totally identical with layer 1 or slight modifications can be made.
  • Example 2 is used especially for flower packaging.
  • Example 2 having degradable masterbatch
  • standard film without degradable masterbatch
  • Layer 1 (First skin layer) contains between about 88 % and about 98.5 % by weight of homopolymer, more preferably from about 91 % to 97 % by weight, between about 0.5 % to about 4 % by weight of antiblocking agent, more preferably from about 1 % to about 3 % by weight, between about 0.5 % to about 4 % by weight of antistatic masterbatch, more preferably from about 1 % to about 3 % by weight, between about 0.5 % to about 4 % by weight of degradable masterbatch, more preferably from about 1 % to about 3 % by weight.
  • Layer 2 (First intermediate layer) contains between about 96 % and about 99.5 % by weight of homopolymer, more preferably from about 97 % to 99 % by weight, between about 0.5 % to about 4 % by weight of degradable masterbatch, more preferably from about 1 % to about 3 % by weight.
  • Layer 3 (Main layer) contains between about 96 % and about 99.5 % by weight of homopolymer, more preferably from about 97 % to 99 % by weight, between about 0.5 % to about 4 % by weight of degradable masterbatch, more preferably from about 1 % to about 3 % by weight.
  • Layer 4 (Second intermediate layer) contains between about 96 % and about 99.5 % by weight of homopolymer, more preferably from about 97 % to 99 % by weight, between about 0.5 % to about 4 % by weight of degradable masterbatch, more preferably from about 1 % to about 3 % by weight. Layer 4 can be totally identical with layer 2 or slight modifications can be made.
  • Layer 5 (Second skin layer) contains between about 86 % and about 98.5 % by weight of homopolymer, more preferably from about 89 % to 97 % by weight, between about 0.5 % to about 4 % by weight of antiblocking agent, more preferably from about 1 % to about 3 % by weight, between about 0.5 % to about 4 % by weight of antistatic masterbatch, more preferably from about 1 % to about 3 % by weight more preferably from about 1 % to about 3 % by weight, between about 0.5 % to about 4 % by weight of degradable masterbatch.
  • the non heat sealable degradable and/or biodegradable BOPP film given in the Example 3 is used especially for labeling.
  • Example 3 having degradable masterbatch
  • standard film without degradable masterbatch
  • the examples of the films according to this present invention can be created with many different combinations and different number of layers.
  • Totally brittleness is the state at which the films of the present invention has no or little tear or tensile strength and crumble when folded. This state shows that the polymeric film of the present invention has become totally brittle and this property was tested by hand.
  • A4 size samples of the films with and without degradable masterbatch have been put under UV lamp in the lab for testing photo degradation.
  • the films having degradable masterbatch according to the examples 1, 2 and 3 have become totally brittle in 10 days. But in the non degradable counterpart of the examples no change has occurred.
  • the films having degradable masterbatch according the examples 1, 2 and 3 have become totally brittle in 35 days. But in the non degradable counterpart of the examples no change has occurred.
  • the present invention can be applied directly to cast polypropylene film process without orientation by adding the degradable masterbatch or compound into the layers with the similar ratios stated above.

Abstract

La présente invention concerne un film en polypropylène biorienté (BOPP) dégradable chimiquement et/ou biodégradable qui convient pour toutes les applications industrielles telles que l'emballage ou d'autres applications. Le film est rendu dégradable et/ou biodégradable par l'ajout d'agents qui améliorent la dégradabilité par une combinaison de chaleur et d'UV dans une première étape et par une absorption par des micro-organismes naturellement présents dans les sols (les agents qui améliorent la dégradabilité sont des carboxylates de métaux) dans une seconde étape. Le film ne s'accumule pas dans la nature grâce à un processus de dégradation non toxique. Le film BOPP monocouche ou multicouche dégradable et/ou biodégradable est caractérisé par le fait que la ou les couches comprennent un mélange-maître ou composé dégradable.
PCT/TR2005/000040 2005-09-01 2005-09-01 Film en polypropylène biorienté dégradable et/ou biodégradable WO2007027163A2 (fr)

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TR2008/01372T TR200801372T2 (tr) 2005-09-01 2005-09-01 Bozunabi̇li̇r ve/veya bi̇yobozunabi̇li̇r çi̇ft yönlü gp

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DE102007048090A1 (de) * 2007-10-05 2009-04-09 Wipak Walothen Gmbh Kuvertfenster
GB2464285A (en) * 2008-10-08 2010-04-14 Wells Plastics Ltd Transition metal additives for enhancing polymer degradation
EP2832541A4 (fr) * 2012-03-29 2015-12-09 Extrusion De Resinas Vinilicas S A Film de polypropylène bi-orienté pour des fenêtres d'enveloppes
KR20170044573A (ko) 2015-10-15 2017-04-25 피티. 인도폴리 스와카르사 인더스트리 티비케이 담배 및 일반 포장을 위한 분해가능한 （이축으로） 배향된 필름
CN107253378A (zh) * 2017-03-29 2017-10-17 湛江包装材料企业有限公司 宽容性高收缩高速卷烟包装膜及其制备方法
WO2019108056A1 (fr) 2016-11-29 2019-06-06 Stichting Kennis Exploitatie Rb Feuille à base d'amidon étirée biaxialement
WO2020069711A1 (fr) 2018-10-03 2020-04-09 Eco Packaging Aps Procédé de production d'un polymère biodégradable et neutre vis à vis du dioxyde de carbone et produits d'emballage produits à partir de celui-ci
US10919203B2 (en) 2015-06-30 2021-02-16 BiologiQ, Inc. Articles formed with biodegradable materials and biodegradability characteristics thereof
US10982090B2 (en) 2016-06-21 2021-04-20 3M Innovative Properties Company Graphic articles comprising polylactic acid polymer based film
US10995201B2 (en) 2015-06-30 2021-05-04 BiologiQ, Inc. Articles formed with biodegradable materials and strength characteristics of the same
US11046840B2 (en) 2015-06-30 2021-06-29 BiologiQ, Inc. Methods for lending biodegradability to non-biodegradable plastic materials
US11066551B2 (en) 2016-05-20 2021-07-20 3M Innovative Properties Company Oriented polylactic acid polymer based film
US11111363B2 (en) 2015-06-30 2021-09-07 BiologiQ, Inc. Articles formed with renewable and/or sustainable green plastic material and carbohydrate-based polymeric materials lending increased strength and/or biodegradability
US11111355B2 (en) 2015-06-30 2021-09-07 BiologiQ, Inc. Addition of biodegradability lending additives to plastic materials
US11149144B2 (en) 2015-06-30 2021-10-19 BiologiQ, Inc. Marine biodegradable plastics comprising a blend of polyester and a carbohydrate-based polymeric material
US11254812B2 (en) 2014-12-22 2022-02-22 3M Innovative Properties Company Compositions and films comprising polylactic acid polymer, polyvinyl acetate polymer and plasticizer
US11359088B2 (en) 2015-06-30 2022-06-14 BiologiQ, Inc. Polymeric articles comprising blends of PBAT, PLA and a carbohydrate-based polymeric material
EP4140760A1 (fr) * 2021-08-30 2023-03-01 Hueck Folien Gesellschaft m.b.H. Marque de sûreté pour documents de valeur ou documents de sécurité
CN115819880A (zh) * 2022-09-15 2023-03-21 上海普利特复合材料股份有限公司 一种家禽养殖用的pp/pbs可降解薄膜及其制备方法
US11674014B2 (en) 2015-06-30 2023-06-13 BiologiQ, Inc. Blending of small particle starch powder with synthetic polymers for increased strength and other properties
US11674018B2 (en) 2015-06-30 2023-06-13 BiologiQ, Inc. Polymer and carbohydrate-based polymeric material blends with particular particle size characteristics
US11879058B2 (en) 2015-06-30 2024-01-23 Biologiq, Inc Yarn materials and fibers including starch-based polymeric materials
US11926929B2 (en) 2015-06-30 2024-03-12 Biologiq, Inc Melt blown nonwoven materials and fibers including starch-based polymeric materials
US11926940B2 (en) 2015-06-30 2024-03-12 BiologiQ, Inc. Spunbond nonwoven materials and fibers including starch-based polymeric materials

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DE102007048090A1 (de) * 2007-10-05 2009-04-09 Wipak Walothen Gmbh Kuvertfenster
GB2464285A (en) * 2008-10-08 2010-04-14 Wells Plastics Ltd Transition metal additives for enhancing polymer degradation
EP2832541A4 (fr) * 2012-03-29 2015-12-09 Extrusion De Resinas Vinilicas S A Film de polypropylène bi-orienté pour des fenêtres d'enveloppes
US11787929B2 (en) 2014-12-22 2023-10-17 3M Innovative Properties Company Compositions and films comprising polylactic acid polymer, polyvinyl acetate polymer and plasticizer
US11254812B2 (en) 2014-12-22 2022-02-22 3M Innovative Properties Company Compositions and films comprising polylactic acid polymer, polyvinyl acetate polymer and plasticizer
US11111355B2 (en) 2015-06-30 2021-09-07 BiologiQ, Inc. Addition of biodegradability lending additives to plastic materials
US11674014B2 (en) 2015-06-30 2023-06-13 BiologiQ, Inc. Blending of small particle starch powder with synthetic polymers for increased strength and other properties
US10919203B2 (en) 2015-06-30 2021-02-16 BiologiQ, Inc. Articles formed with biodegradable materials and biodegradability characteristics thereof
US11926940B2 (en) 2015-06-30 2024-03-12 BiologiQ, Inc. Spunbond nonwoven materials and fibers including starch-based polymeric materials
US10995201B2 (en) 2015-06-30 2021-05-04 BiologiQ, Inc. Articles formed with biodegradable materials and strength characteristics of the same
US11926929B2 (en) 2015-06-30 2024-03-12 Biologiq, Inc Melt blown nonwoven materials and fibers including starch-based polymeric materials
US11046840B2 (en) 2015-06-30 2021-06-29 BiologiQ, Inc. Methods for lending biodegradability to non-biodegradable plastic materials
US11879058B2 (en) 2015-06-30 2024-01-23 Biologiq, Inc Yarn materials and fibers including starch-based polymeric materials
US11111363B2 (en) 2015-06-30 2021-09-07 BiologiQ, Inc. Articles formed with renewable and/or sustainable green plastic material and carbohydrate-based polymeric materials lending increased strength and/or biodegradability
US11840623B2 (en) 2015-06-30 2023-12-12 BiologiQ, Inc. Methods for lending biodegradability to non-biodegradable polyolefin and nylon materials
US11149144B2 (en) 2015-06-30 2021-10-19 BiologiQ, Inc. Marine biodegradable plastics comprising a blend of polyester and a carbohydrate-based polymeric material
US11807741B2 (en) 2015-06-30 2023-11-07 BiologiQ, Inc. Articles formed with renewable green plastic materials and starch-based polymeric materials lending increased biodegradability
US11359088B2 (en) 2015-06-30 2022-06-14 BiologiQ, Inc. Polymeric articles comprising blends of PBAT, PLA and a carbohydrate-based polymeric material
US11674018B2 (en) 2015-06-30 2023-06-13 BiologiQ, Inc. Polymer and carbohydrate-based polymeric material blends with particular particle size characteristics
KR20170044573A (ko) 2015-10-15 2017-04-25 피티. 인도폴리 스와카르사 인더스트리 티비케이 담배 및 일반 포장을 위한 분해가능한 （이축으로） 배향된 필름
US11066551B2 (en) 2016-05-20 2021-07-20 3M Innovative Properties Company Oriented polylactic acid polymer based film
US10982090B2 (en) 2016-06-21 2021-04-20 3M Innovative Properties Company Graphic articles comprising polylactic acid polymer based film
WO2019108056A1 (fr) 2016-11-29 2019-06-06 Stichting Kennis Exploitatie Rb Feuille à base d'amidon étirée biaxialement
CN107253378A (zh) * 2017-03-29 2017-10-17 湛江包装材料企业有限公司 宽容性高收缩高速卷烟包装膜及其制备方法
WO2020069711A1 (fr) 2018-10-03 2020-04-09 Eco Packaging Aps Procédé de production d'un polymère biodégradable et neutre vis à vis du dioxyde de carbone et produits d'emballage produits à partir de celui-ci
KR20210069087A (ko) 2018-10-03 2021-06-10 에코팩키징 에이피에스 이산화탄소 중립 및 생분해성 고분자의 제조방법 및 이로부터 제조된 포장재 제품
WO2023028627A1 (fr) * 2021-08-30 2023-03-09 Hueck Folien Gesellschaft M.B.H. Élément de sécurité pour documents de valeur ou documents de sécurité
EP4140760A1 (fr) * 2021-08-30 2023-03-01 Hueck Folien Gesellschaft m.b.H. Marque de sûreté pour documents de valeur ou documents de sécurité
CN115819880A (zh) * 2022-09-15 2023-03-21 上海普利特复合材料股份有限公司 一种家禽养殖用的pp/pbs可降解薄膜及其制备方法

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