WO2004016417A2 - Film metallise traite au plasma - Google Patents

Film metallise traite au plasma Download PDF

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Publication number
WO2004016417A2
WO2004016417A2 PCT/US2003/025582 US0325582W WO2004016417A2 WO 2004016417 A2 WO2004016417 A2 WO 2004016417A2 US 0325582 W US0325582 W US 0325582W WO 2004016417 A2 WO2004016417 A2 WO 2004016417A2
Authority
WO
WIPO (PCT)
Prior art keywords
plastic film
metallized
film
plasma
plasma treatment
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/US2003/025582
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English (en)
Other versions
WO2004016417A3 (fr
Inventor
Robert T. Korowicki
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Individual
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Individual
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
Application filed by Individual filed Critical Individual
Priority to AU2003262703A priority Critical patent/AU2003262703A1/en
Priority to CA002495244A priority patent/CA2495244A1/fr
Priority to US10/524,924 priority patent/US20060159860A1/en
Publication of WO2004016417A2 publication Critical patent/WO2004016417A2/fr
Publication of WO2004016417A3 publication Critical patent/WO2004016417A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/021—Cleaning or etching treatments
    • C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/20—Metallic material, boron or silicon on organic substrates

Definitions

  • the present invention relates to metallized films, particularly for use in the food and liquid packaging and decorative balloon industries.
  • the present invention relates generally to various types of metallized plastic films.
  • Metallized plastic films are known in the art, and are used to provide barriers between the interior and external environment of a package or product. Such barriers can be used, for example, for food and liquid packaging or for decorative balloons.
  • the barrier provided by the film packaging safeguards the enclosed product against the major causes of loss of food freshness and flavor, namely, oxygen or water vapor flow into the package and/or exposure to ultraviolet light.
  • the barrier protects against undesirable loss of gas caused by diffusion through the film and out of the balloon, such diffusion resulting in shrinkage and short balloon life.
  • the various surface treatments have two major disadvantages, however.
  • the treatment values are found to decrease with time from the moment that treatment of the surface is complete to the time of metallization in the vacuum chamber.
  • the surface energy will decrease due to the diffusion of some chemical groups into the surface of the film.
  • the additional processes involved in the surface treatment add to the final price of the film.
  • a plasma metallized film is provided, particularly for the food and liquid packaging and balloon industries, wherein the film is provided with improved barrier characteristics over prior films in the art while being simple and inexpensive to manufacture.
  • a method is provided in which a plastic film is subjected to plasma treatment inside the vacuum chamber of a metallization apparatus and is coated on one or both surfaces of the treated film with a desired coating material (e.g. aluminum vapor).
  • a film is produced exhibiting excellent oxygen and moisture barrier properties. Due to these increased barrier properties, shelf life and the floating time can be extended dramatically while maintaining the aesthetic appeal of the metallized film, a strong advantage in merchandising food and decorative balloon products.
  • a method for providing a film having improved barrier properties.
  • the film provides an improved barrier to oxygen and water vapor transmission, and to ultraviolet light.
  • an improved barrier is provided, while providing a method which is simple to implement and resulting in a film which is relatively inexpensive to manufacture.
  • the film can be used in the food and liquid packaging industries, or for decorative balloons.
  • the initial film can be of polyester, polypropylene, polyethylene, polyvinyl chloride or nylon.
  • the film is processed in a vacuum system machine which is used to deposit the coating material onto the film.
  • the apparatus used for metallization of the film is a Galileo Vacuum System machine, and further preferably a Galileo Mega2 Model, such as the Mega 4-2410B.
  • various components are provided for processing and metallization of the film, including, for example, the winding system, the vacuum chamber, the pumping system, controls, evaporation system, etc.
  • the rolls of plastic are fed through the winding system portion of the machine, which includes the drive system, the tension control, and so forth.
  • the vacuum chamber is the portion of the machine where a vacuum is produced for use during the coating process, and which has the evaporators for evaporation of the coating material into a gas for deposition onto the film. Pumping of gas within the machine is accomplished by the pumping equipment.
  • the roll of film is set up inside of the metallization machine on a section referred to as "the unwind shaft", where the film is unwound off of the roll for passage through the remainder of the machine. From the unwind shaft, the film is threaded through the machine for it to eventually pass through the plasma treater over some additional rollers and through the evaporation zone until it reaches the empty core of the rewind shaft (the rewind station) .
  • This process begins with setup of the clear roll in the winding system section. After the setup is complete, the machine is closed and hermetically sealed for commencement of the pumping down process.
  • plasma treatment involves modification of the surface of the plastic film, and is used to promotes adhesion of the coating material (e.g. a metal) to the film's surface.
  • plasma treatment can enhance the moisture and gas barrier properties of the resulting metallized film.
  • high voltage power preferably 7-25 KW
  • a high magnetic field and a gas mixture are provided.
  • a preferred gas blend for use in the plasma treatment is a mixture of 80% Nitrogen and 20% Argon ("Gas B" of Table 1, also referred to as "Plasma B").
  • Gas B Nitrogen and 20% Argon
  • a gas blend of 30% Oxygen and 70% Argon, or 50% Oxygen and 50% Argon can be used.
  • one or more of the gases Argon, Nitrogen and/or Oxygen can be used, whether individually as pure gases or as a mixture in any combination suitable for the desired application.
  • other gases may be used for treatment of the film surface providing that they are suitable to provide the desired final characteristics of the film achieved herein.
  • ions and electrons are constrained in the magnetic field above the generator where the film is passed through.
  • some systems can be magnetically enhanced to open the field lines toward the film by placing permanent magnets behind the film as it passes through the treater. Those permanent magnets have the effect of directing the ions and electrons toward the film surface.
  • the electrical system in conjunction with the gas blend fed into the plasma treater will clean and activate the film surface for chemical modification. This change in the surface characteristics occurs just prior to the deposition of the coating material (e.g. aluminum vapor). It is believed that oxygen species are generated on the film surface under the metal layer resulting in oxidized surfaces. That oxygen is either added to the surface by the gas or is drawn to the surface from the polymer itself.
  • the plasma treater is provided in an area within the machine which is located before the evaporation zone, and which is sealed from the evaporation zone. After passing through the plasma treater, the film is moved into that evaporation zone. Isolation of the plasma treater from the evaporation zone is provided so that the gas from the plasma treater will not interfere with the evaporation process.
  • the plasma treated film moves into and through the evaporation zone, where the evaporators melt and evaporate the coating component to be applied to the film.
  • solid coating material is fed into the evaporators (e.g. aluminum wire or any other desired coating material), and as the evaporators heat up to reach the desired temperature (e.g. 1400 degrees centigrade in the case of aluminum) the coating material is vaporized.
  • the machine is simultaneously activated to pump out gas to reach the desired vacuum pressure, while power is provided to the plasma treaters and the evaporators are heated to the necessary temperature, before beginning to move the film within the machine.
  • This allows the film to be rapidly and efficiendy moved through the entire machine from section to section once the various sections of the machine are ready, without needing to wait in one section for a subsequent section to be available for use.
  • it is necessary to wait several minutes until the coating material has been fed into all of the evaporators (also known as "boats"), and until that material has filled all of the pores in the ceramic and begun to vaporize uniformly before beginning a run of film through the metallization machine.
  • the evaporators are warmed up and all of the boats in the line are stabilized prior to initiating treatment of the film with the plasma treater, so that the film can pass from the plasma treater into the evaporation zone and onward without delay.
  • the plasma treated film comes into contact with the coating material.
  • the temperatures for the evaporators depend on the material to be evaporated.
  • pure aluminum is evaporated for deposit on the film, e.g. at temperatures beginning from approximately 1400 degrees Centigrade (1400 ° C).
  • silver or gold or tin or other metals, or glass could be utilized. Accordingly, while aluminum is generally referred to in the illustrations herein as an example of a preferred embodiment, it is to be understood that the present invention is not limited to such preferred material.
  • coating material molecules travel throughout the evaporation zone in a vacuum.
  • pumping equipment is provided in communication with the evaporation zone to improve the coating process within that zone.
  • the aluminum it is important that the aluminum not come into contact with any oxygen molecules, since pure aluminum is to be deposited on the film, with the presence of any aluminum oxide being highly undesirable.
  • aluminum can boil and evaporate more efficiently at the lower pressure.
  • the vacuum also facilitates the free travel of the aluminum molecules to provide an even coat from one edge to another of the film, such that dark and light areas are not produced on the film.
  • the pumping out of oxygen helps avoid damage to the ceramic evaporators, since the presence of oxygen molecules around those high temperature evaporators (running at approximately 1400° C or higher) will degrade tho evaporators and decrease their effective life.
  • the aluminum comes into contact with the surface of the plastic film, which may pass over a chill roller.
  • the chill roller is a roller maintained at a sufficiendy low temperature to maintain the dimensional stability of the plastic film when it is exposed to the excessive heat of the vapor, and further preferably to maintain the film at a sufficiently low temperature to promote condensation of the aluminum thereon.
  • the vapor may be approximately 1400° C
  • the film may be approximately 70-80 degrees Fahrenheit.
  • a chill roller is needed for those films which are very sensitive to heat, a chill roller is not essential for the process. Some films resist heat and therefore do not need special cooling. With those films, the ambient temperature of the film or the cold temperature of vacuum can itself provide a sufficient temperature difference to cause condensation, and the movement of the film at a rapid line speed results in insufficent time for the film to melt. Likewise, the film does not need to be supported by the chill roller during the evaporation, but rather can be free spanning, i.e. metallized while running between two rollers. When the film is free spanning, it can be cooled after the evaporation step, if desired, using a chill roller or by a cooling tower.
  • a coat of material is thereby provided on the substrate in the sufficient thickness to seal the surface pores of the substrate.
  • a coating of, for example, 120-200 or more preferably, 10-1000 Angstroms is used, although any other desired thickness may be employed if desired.
  • a greater coating thickness may be used in the embodiments utilizing multiple coating layers on one or both sides of the film to further reduce transmission through the material, i.e. to increase the barrier properties, albeit at higher cost.
  • the film After deposition of the aluminum on the film, the film is rewound on the empty core, producing the finished roll.
  • the pumping valves are closed, power is turned off of the evaporators, and an inlet air valve is opened to put more air into the machine to reach atmospheric pressure. At that point, the machine is opened and the finished roll can be removed.
  • reaction conditions including, for example, the gas in use, the blend ratio and the flow rate.
  • reaction conditions have been developed which optimize the barrier properties produced in accordance with the invention.
  • the preferred reaction conditions for producing improved metallized films with various film types in accordance with the invention are shown in Table 1 as follows:
  • a highly effective film is produced at decreased cost.
  • a saving of at least 15% can be achieved by metallizing a plain film with the plasma treatment methods of the present invention rather than using a film with a special formulation.
  • Tables 2 and 3 below shows a comparison of some common values that can be produced using the present invention, followed by some typical values for barrier properties of past metallized and clear products at .5 mil:
  • a three-zone geometry is used (as is available, for example, in the Galileo Mega2).
  • in-line surface treatment i.e. plasma treatment within the metallization machine
  • Metallizing takes place in a second vacuum zone, and can be conducted at a line speed as fast as 3,000 fpm. Due to the multi-zone geometry, the machine can achieve and maintain a vacuum in the 10 "5 mbar range, which improves metal density and prevents spit holes.
  • the Mega 2 machines can deposit aluminum for microwave applications as well as for complete opacity.
  • the web is cooled in the third vacuum zone, where it is possible to maintain the web's temperature within two degrees, even at a high level of metal deposition.
  • This cooling system allows running of plastic films that are heat sensitive and extensible.
  • a different vacuum level can be maintained in each of the three zones if desired. For example, a higher degree of vacuum can be maintained in the evaporation zone than in the winding zone, where as high a level of vacuum is not necessary.
  • one side of the substrate film can be metallized ("Metal One Side” or “MOS” of Table 1), with the film plasma treated on one or or both sides of the film (surface A or B).
  • the substrate film can be plasma treated on a surface of the film (surface A or B) and metallized on that plasma treated side in one pass.
  • the substrate film can be plasma treated on surface A or B, and then metallized on that plasma treated surface, and then remetallized again on that metal side (two pass).
  • the substrate film can be metallized on surface A or B (before any plasma treatment), then plasma treated on that metallized side, then remetallized again on that plasma treated metal surface (two pass).
  • the substrate film can be plasma treated on surface A or B, and then metallized on the plasma treated surface, then plasma treated again on that metallized side, and remetallized again on the plasma treated metallized surface (two pass).
  • both sides of the substrate film can be metallized ("Metal Both Sides" or "MBS" of Table 1).
  • the substrate film can be plasma treated on both surfaces A & B, and then metallized once on each surface (one pass each side) .
  • the substrate film can be plasma treated only on one surface (surface A or B) and metallized on both surfaces (one pass each side).
  • the substrate film can be plasma treated on both surfaces A & B, with side A and side B each metallized once, then plasma treated again on one side, and remetallized for a second time on that same side (one pass side A and two pass side B).
  • the substrate film can be metallized on both surfaces A & B (before any plasma treatment), then surface A or surface B can be plasma treated, followed by remetallization for a second time over that plasma treated side (one side one pass, the second side two pass).
  • the substrate film can have surface A just metallized and surface B both plasma treated and metallized, followed by surface B being plasma treated again and remetallized for a second time (one pass surface A and two pass surface B).
  • the substrate film can have surface A both plasma treated and metallized, and surface B initially just metallized, followed by surface B being plasma treated (on that metallized surface) and then remetallized for a second time (one pass surface A and two pass surface B).
  • a super high barrier plasma treated plastic film e.g. polyester, polypropylene, polyethylene, polyvinyl chloride or nylon
  • a super high barrier plasma treated plastic film e.g. polyester, polypropylene, polyethylene, polyvinyl chloride or nylon
  • is metallized on one or both surfaces of the film and which can be used, for example, for food or liquid packaging or for decorative balloons, at low cost.
  • the oxygen transmission rate (OTR) through the treated film achieved via the invention is less than 0.01 cc/100in 2 / day and the water vapor transmission rate (WNTR) is reduced to 0.02 - 0.35 or even to less than 0.02 gr/100in 2 /day at 100 °F / 100% RH, depending on the selected substrate.
  • the oxygen transmission rate is reduced from 0.07 cc/100in 2 /day with prior art methods to 0.015 cc/100in 2 /day.
  • the OTR is reduced from 0.070 cc/100in 2 /day to 0.0025 cc/100in 2 /day.
  • the OTR is reduced from 0.050 - 0.070 to a range of 0.015 - 0.030 cc/100in 2 /day.
  • the water vapor transmission rate (WVTR) also was reduced from 0.070 - 0.100 gr/100in 2 /day at 100 ° F and 100% RH to 0.020 - 0.035 gr/100in 2 /day.
  • OPP WVTR was reduced from the normal 0.050 gr/100in 2 /day to as low as 0.015 gr/100in 2 /day at 100°F and 100% RH.
  • the metal adhesion bond was also increased using the invention from 250 gr/in to 400-500 gr/in.
  • the choice of using one or two sides for metallization and/or plasma treatment, and of conducting plasma and/or metallization treatment one time or multiple times (whether twice, three times or more), can be made to yet further increase the barrier properties of the invention to whatever extent desired.
  • Such variations are highly effective, albeit at increased cost. Accordingly, while the barrier properties listed above are typical values produced at relatively inexpensive cost, an even more impermeable barrier can nonetheless be achieved, if desired, in accordance with the invention.
  • the metallized film preferably has a thickness in the range of .20 mil to 10 mil where the thickness is chosen depending on the desired stiffness of the package needed for the final product.
  • that metallized film is further comprised of plain plastic film, the film being plasma treated on one or both surfaces and metallized on one or both surfaces of the film.
  • the substrate surface of the film may be chemically or corona treated prior to plasma treatment or metallization, using known methods.
  • chemically treated SP91 film or SP95 film can be utilized, as available from SKC Materials, Inc. of Covington, Georgia.
  • the gases used for the plasma treatment can be Argon, Nitrogen and/or Oxygen at various ratios, or other desired gases.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)
  • Laminated Bodies (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention concerne un film plastique métallisé traité au plasma, présentant de propriétés de barrière ultra-élevées et fabriqué à un coût sensiblement bas.
PCT/US2003/025582 2002-08-13 2003-08-14 Film metallise traite au plasma Ceased WO2004016417A2 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AU2003262703A AU2003262703A1 (en) 2002-08-14 2003-08-14 Plasma treated metallized film
CA002495244A CA2495244A1 (fr) 2002-08-14 2003-08-14 Film metallise traite au plasma
US10/524,924 US20060159860A1 (en) 2002-08-13 2003-08-14 Plasma treated metallized film

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US40329502P 2002-08-14 2002-08-14
US60/403,394 2002-08-14
US44885903P 2003-02-21 2003-02-21
US60/448,859 2003-02-21

Publications (2)

Publication Number Publication Date
WO2004016417A2 true WO2004016417A2 (fr) 2004-02-26
WO2004016417A3 WO2004016417A3 (fr) 2004-06-03

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PCT/US2003/025582 Ceased WO2004016417A2 (fr) 2002-08-13 2003-08-14 Film metallise traite au plasma

Country Status (3)

Country Link
CN (1) CN100457959C (fr)
AU (2) AU2003262703A1 (fr)
WO (1) WO2004016417A2 (fr)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1634699A1 (fr) * 2004-09-10 2006-03-15 Syrom 90 S.P.A. Film métallisé multicouche et procédé de production
ITRM20080449A1 (it) * 2008-08-08 2010-02-09 Michele Colajanni Foglio plastico laminato con metallo prezioso
US7799399B2 (en) * 2006-06-07 2010-09-21 Toray Plastics (America), Inc. High barrier laminate and process
US7951438B2 (en) * 2007-12-10 2011-05-31 Toray Plastics (America), Inc. Biaxially oriented polylactic acid film with high barrier
US8236399B2 (en) 2006-06-07 2012-08-07 Toray Plastics (America), Inc. Lighter than air balloon made from a biaxially oriented polyester film
WO2012142639A1 (fr) * 2011-04-21 2012-10-26 Nico Ros Emballage doté d'une barrière thermique enveloppante
US8318289B2 (en) 2002-04-12 2012-11-27 Dupont Teijin Films U.S. Limited Partnership Coated polymeric substrates having improved surface smoothness suitable for use in flexible electronic and opto-electronic devices
US9186593B2 (en) 2006-06-07 2015-11-17 Toray Plastics (America), Inc. Stretchable and formable lighter than air balloons made from a biaxially oriented polyester film
US9314999B2 (en) 2008-08-15 2016-04-19 Toray Plastics (America), Inc. Biaxially oriented polylactic acid film with high barrier
US9561676B2 (en) 2011-07-08 2017-02-07 Toray Plastics (America), Inc. Biaxially oriented bio-based polyester thin films and laminates for thermal transfer printing
US10137625B2 (en) 2011-07-08 2018-11-27 Toray Plastics (America), Inc. Biaxially oriented bio-based polyester films and laminates
US11318721B2 (en) 2016-06-28 2022-05-03 Toray Plastics (America), Inc. Method of forming a formable polyester film

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9150004B2 (en) 2009-06-19 2015-10-06 Toray Plastics (America), Inc. Biaxially oriented polylactic acid film with improved heat seal properties
EP2480710B1 (fr) 2009-09-25 2018-01-24 Toray Plastics (America) , Inc. Film d'acide polylactique multicouche très étanche à la vapeur et son procédé de production
US9221213B2 (en) 2009-09-25 2015-12-29 Toray Plastics (America), Inc. Multi-layer high moisture barrier polylactic acid film
US9492962B2 (en) 2010-03-31 2016-11-15 Toray Plastics (America), Inc. Biaxially oriented polylactic acid film with reduced noise level and improved moisture barrier
WO2011123165A1 (fr) 2010-03-31 2011-10-06 Toray Plastics (America), Inc. Film d'acide polyactique à orientation biaxiale doté de niveau de bruit réduit
CN106480406B (zh) * 2016-10-17 2018-11-13 东丽薄膜加工（中山）有限公司 金属化薄膜及其制备方法和电容器

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US3828960A (en) * 1972-11-10 1974-08-13 Dow Chemical Co Heat insulating container having plastic walls retaining vacuum
CA2160079A1 (fr) * 1994-10-07 1996-04-08 Frank Harry Bria Aerostats
US5981079A (en) * 1997-01-29 1999-11-09 Mobil Oil Corporation Enhanced barrier vacuum metallized films
US6110599A (en) * 1997-04-21 2000-08-29 Eastman Chemical Company Blends of polyethylene for extrusion coating

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8318289B2 (en) 2002-04-12 2012-11-27 Dupont Teijin Films U.S. Limited Partnership Coated polymeric substrates having improved surface smoothness suitable for use in flexible electronic and opto-electronic devices
US8501300B2 (en) * 2002-04-12 2013-08-06 Dupont Teijin Films U.S. Limited Partnership Coated polymeric substrates having improved surface smoothness suitable for use in flexible electronic and opto-electronic devices
WO2006027033A1 (fr) 2004-09-10 2006-03-16 Syrom 90 S.P.A. Film metallise multicouche et procede d'elaboration
EP1634699A1 (fr) * 2004-09-10 2006-03-15 Syrom 90 S.P.A. Film métallisé multicouche et procédé de production
US9186593B2 (en) 2006-06-07 2015-11-17 Toray Plastics (America), Inc. Stretchable and formable lighter than air balloons made from a biaxially oriented polyester film
US8236399B2 (en) 2006-06-07 2012-08-07 Toray Plastics (America), Inc. Lighter than air balloon made from a biaxially oriented polyester film
US8323759B2 (en) 2006-06-07 2012-12-04 Toray Plastics (America), Inc. Lighter than air balloon made from a biaxially oriented polyester film
US8399080B2 (en) 2006-06-07 2013-03-19 Toray Plastics (America), Inc. Lighter than air balloon made from a biaxially oriented polyester film
US7799399B2 (en) * 2006-06-07 2010-09-21 Toray Plastics (America), Inc. High barrier laminate and process
US7951438B2 (en) * 2007-12-10 2011-05-31 Toray Plastics (America), Inc. Biaxially oriented polylactic acid film with high barrier
ITRM20080449A1 (it) * 2008-08-08 2010-02-09 Michele Colajanni Foglio plastico laminato con metallo prezioso
US9314999B2 (en) 2008-08-15 2016-04-19 Toray Plastics (America), Inc. Biaxially oriented polylactic acid film with high barrier
CN103917459A (zh) * 2011-04-21 2014-07-09 尼科·罗斯 带有包围的热壁垒的包装件
CN103917459B (zh) * 2011-04-21 2016-03-09 雷普Ip股份公司 带有优化的绝热值的绝缘部件、其制造方法及具有其的包装容器
WO2012142639A1 (fr) * 2011-04-21 2012-10-26 Nico Ros Emballage doté d'une barrière thermique enveloppante
US9598221B2 (en) 2011-04-21 2017-03-21 Rep Ip Ag Packaging having a surrounding heat barrier
US9561676B2 (en) 2011-07-08 2017-02-07 Toray Plastics (America), Inc. Biaxially oriented bio-based polyester thin films and laminates for thermal transfer printing
US10137625B2 (en) 2011-07-08 2018-11-27 Toray Plastics (America), Inc. Biaxially oriented bio-based polyester films and laminates
US11318721B2 (en) 2016-06-28 2022-05-03 Toray Plastics (America), Inc. Method of forming a formable polyester film

Also Published As

Publication number Publication date
CN1685076A (zh) 2005-10-19
AU2009233624A1 (en) 2009-11-26
WO2004016417A3 (fr) 2004-06-03
CN100457959C (zh) 2009-02-04
AU2003262703A1 (en) 2004-03-03

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