EP1999517A2 - Recipient a paroi expansee dote d'un aspect argente - Google Patents

Recipient a paroi expansee dote d'un aspect argente

Info

Publication number
EP1999517A2
EP1999517A2 EP07752928A EP07752928A EP1999517A2 EP 1999517 A2 EP1999517 A2 EP 1999517A2 EP 07752928 A EP07752928 A EP 07752928A EP 07752928 A EP07752928 A EP 07752928A EP 1999517 A2 EP1999517 A2 EP 1999517A2
Authority
EP
European Patent Office
Prior art keywords
container
preform
polymer
reactive gas
container according
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.)
Withdrawn
Application number
EP07752928A
Other languages
German (de)
English (en)
Other versions
EP1999517A4 (fr
Inventor
Frank E. Semersky
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Plastic Technologies Inc
Original Assignee
Plastic Technologies Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US11/384,979 external-priority patent/US7790255B2/en
Application filed by Plastic Technologies Inc filed Critical Plastic Technologies Inc
Publication of EP1999517A2 publication Critical patent/EP1999517A2/fr
Publication of EP1999517A4 publication Critical patent/EP1999517A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/0005—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor characterised by the material
    • B29C49/0006—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor characterised by the material for heating or cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
    • B65D81/38—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents with thermal insulation
    • B65D81/3865—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents with thermal insulation drinking cups or like containers
    • B65D81/3867—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents with thermal insulation drinking cups or like containers formed of foam material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
    • B29C44/08—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles using several expanding or moulding steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
    • B29C49/06—Injection blow-moulding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
    • B29C2049/023—Combined blow-moulding and manufacture of the preform or the parison using inherent heat of the preform, i.e. 1 step blow moulding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/42—Component parts, details or accessories; Auxiliary operations
    • B29C49/78—Measuring, controlling or regulating
    • B29C49/786—Temperature
    • B29C2049/7861—Temperature of the preform
    • B29C2049/7862—Temperature of the preform characterised by temperature values or ranges
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/10—Polymers of propylene
    • B29K2023/12—PP, i.e. polypropylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
    • B29K2027/06—PVC, i.e. polyvinylchloride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
    • B29K2105/041—Microporous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
    • B29K2105/046—Condition, form or state of moulded material or of the material to be shaped cellular or porous with closed cells
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/25—Solid
    • B29K2105/253—Preform
    • B29K2105/258—Tubular
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
    • B29K2995/0022—Bright, glossy or shiny surface

Definitions

  • the present invention relates generally to a foamed-wall polymer container having a unique appearance. More particularly, the invention is directed to a container comprising micro cellular foam, wherein the foam micro cells contain a non-reactive gas such as nitrogen, and the container has a silvery appearance. Also contemplated as a part of the present invention is a method of manufacturing the foamed-wall container having a silvery appearance.
  • Biaxially oriented single and multi-layered bottles may be manufactured from polymer materials such as, for example, polyethylene terephthalate (PET) using a hot preform process, wherein a single or multi- layered preform is heated to its desired orientation temperature and drawn and blown into conformity with a surrounding mold cavity.
  • PET polyethylene terephthalate
  • the preform may be prepared by any conventional process such as, for example, by extruding a preform comprising single or multiple layers of polymer, or by injecting subsequent layers of polymer over a previously injection molded preform.
  • multiple layers are used for beverage containers, to add diffusion barrier properties not generally found in single layer containers.
  • a foamed-wall container having a unique appearance has surprisingly been discovered.
  • the container comprises a micro cellular foamed polymer, and a non-reactive gas contained within the micro cellular foam cells, wherein the container has a silvery appearance without the addition of a coloring agent.
  • Also contemplated as an embodiment of the invention is a process for preparing a foamed-wall container having a unique appearance.
  • the process comprises the steps of injection molding a polymer preform having a non-reactive gas entrapped within the walls thereof, cooling the preform to a temperature below the polymer softening temperature, reheating the preform to a temperature above the polymer softening temperature, and blow molding the preform, to prepare a container comprising a micro cellular foamed polymer having a non-reactive gas contained within the micro cellular foam cells, wherein the container has a silvery appearance.
  • the container according to the present invention is particularly useful for packaging carbonated beverages.
  • the present invention is directed to a foamed-wall container having a unique appearance, comprising a micro cellular foamed polymer, and a non- reactive gas contained within the micro cellular foam cells, wherein the container has a silvery appearance.
  • Another embodiment of the present invention is directed to a process for making a foamed-wall container having a unique appearance, comprising injection molding a polymer preform having a non-reactive gas entrapped within the walls thereof, cooling the preform to a temperature below the polymer softening temperature, reheating the preform to a temperature above the polymer softening temperature, and blow molding the preform, to prepare a container comprising a micro cellular foamed polymer having a non- reactive gas contained within the micro cellular foam cells, wherein the container has a silvery appearance.
  • Suitable polymers from which the container may be prepared include, but are not necessarily limited to, polyethylene terephthalate (PET) and other polyesters, polypropylene, acrylonitrile acid esters, vinyl chlorides, polyolefins, polyamides, and the like, as well as derivatives, blends, and copolymers thereof.
  • PET polyethylene terephthalate
  • a suitable polymer for commercial purposes is PET.
  • Polymer flakes are melted in a conventional plasticizing screw extruder, to prepare a homogeneous stream of hot polymer melt at the extruder discharge. Typically, the temperature of the polymer melt stream discharged from the extruder ranges from about 225 degrees Centigrade to about 325 degrees Centigrade.
  • the temperature of the polymer melt stream will be determined by several factors, including the kind of polymer flakes used, the energy supplied to the extruder screw, etc.
  • PET is conventionally extruded at a temperature from about 260 degrees Centigrade to about 290 degrees Centigrade.
  • a non-reactive gas is injected under pressure into the extruder mixing zone, to ultimately cause the entrapment of the gas as micro cellular voids within the polymer material.
  • non-reactive gas as it is used herein is meant a gas that is substantially inert vis-a-vis the polymer.
  • Preferred non-reactive gases comprise carbon dioxide, nitrogen, and argon, as well as mixtures of these gases with each other or with other gasses.
  • the extrudate is injection molded to form a polymer preform having the non-reactive gas entrapped within the walls thereof. Methods and apparatus for injection molding a polymer preform are well-known in the art
  • the density of amorphous PET is 1.335 grams per cubic centimeter. It is also known that the density of PET in the melt phase is about 1.200 grams per cubic centimeter. Thus, if the preform injection cavity is filled completely with molten PET and allowed to cool, the resulting preform would not exhibit the proper weight and would have many serious deficiencies, such as sink marks.
  • the prior art injection molding literature teaches that, in order to offset the difference in the densities of amorphous and molten PET, a small amount of polymer material must be added to the part after the cavity has been filled and as the material is cooling. This is called the packing pressure.
  • the packing pressure phase of the injection molding cycle is likewise used for polymer materials other than PET.
  • the polymer preform is injection molded and simultaneously foamed using a non-reactive gas. The gas is entrained in the material during the injection phase. Contrary to the prior art injection molding process, wherein additional polymer material is injected during the packing phase, the present invention utilizes minimal packing pressure.
  • the partial pressure of the non-reactive gas is sufficient to permit the release of the dissolved gas from the polymer into the gas phase where it forms the micro cellular foam structure.
  • the preform made by the inventive process weighs less than, but has the same form and geometry as, the polymer preforms produced by the conventional injection molding operations that employ the packing process.
  • the micro cells may contain one or more of a variety of gases typically used in processes for making micro cellular foam structures.
  • the non-reactive gas comprises carbon dioxide in a concentration of at least ten percent by weight of the total weight of the non-reactive gas. This level of carbon dioxide concentration provides adequate partial pressure to retard the diffusion of carbon dioxide from a carbonated beverage within the inventive container to the exterior atmosphere.
  • the micro cellular foam tends to act as an effective thermal insulator, to retard the conduct of heat energy from the atmosphere to the chilled carbonated beverage within the container
  • the preform Upon completion of the injection molding step, the preform is cooled to a temperature below the polymer softening temperature.
  • the softening temperature for PET is approximately 70 degrees Centigrade.
  • This cooling step conditions the polymer and preserves its desirable properties for the successful preparation of a blow molded container.
  • This cooling step is also useful when employing polymers such as polyesters, which cannot be blow molded directly from an extruded parison.
  • This cooling step may be effected by any conventional process used in the polymer forming art such as, for example, by passing a stream of a cooling gas over the surfaces of the preform, or cooling the preform while in-mold by cooling the forming mold.
  • the preform is thereafter reheated to a temperature above the polymer softening temperature.
  • This heating step may be effected by well- known means such as, for example, by exposure of the preform to a hot gas stream, by flame impingement, by exposure to infra-red energy, by passing the preform through a conventional oven, or the like.
  • PET is generally reheated to a temperature twenty to twenty-five degrees above its softening temperature for the subsequent blow molding operation. If PET is reheated too far above its glass transition temperature, or held at a temperature above its softening temperature for an excessive period of time, the PET undesirably will begin to crystallize and turn white.
  • the preform is heated to a temperature above which the mechanical properties of the material are exceeded by the increasing pressure of the non-reactive gas in the micro cells, the micro cells undesirably will begin to expand thus distorting the preform.
  • the preform is blow molded, to prepare a container, consisting essentially of a micro cellular foamed polymer having a non- reactive gas contained within the micro cellular foam cells.
  • Methods and apparatus for blow molding a container from a polymer preform are well- known.
  • the blow molded foamed-wall polymer container so produced has a silvery appearance; as though the container were made of metal.
  • the blow molded container is silvery in color, and may exhibit Pantone Color Formula Guide numbers in the range of about 420 through 425, 877, 8001, 8400, and 8420. While not wishing to be bound by any particular theory regarding the reason that the ultimately produced container has a unique silvery appearance, it is believed that, as the preform cavity is being filled with polymer, bubbles of gas are formed at the flow front of the polymer due to the pressure drop between the dissolved gas and the relatively lower pressure in the preform cavity. The bubbles formed at the flow front of the polymer material as it is introduced into the preform cavity are subsequently deposited on the outside and inside surfaces of the preform.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
  • Containers Having Bodies Formed In One Piece (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Molding Of Porous Articles (AREA)

Abstract

La présente invention concerne un récipient comprenant un polymère expansé microcellulaire et un gaz non réactif occlus dans les cellules de mousse microcellulaire, ce récipient ayant un aspect argenté. Le procédé de fabrication du récipient consiste à mouler par injection une préforme polymère comprenant un gaz non réactif occlus dans les parois de la préforme, à refroidir la préforme à une température inférieure à celle de ramollissement du polymère, à chauffer à nouveau la préforme à une température supérieure à celle de ramollissement du polymère et à mouler par soufflage la préforme, pour préparer un récipient comprenant un polymère expansé microcellulaire ayant un gaz non réactif occlus dans les cellules de mousse microcellulaire.
EP07752928A 2006-03-20 2007-03-12 Recipient a paroi expansee dote d'un aspect argente Withdrawn EP1999517A4 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US11/384,979 US7790255B2 (en) 2006-03-20 2006-03-20 Foamed-wall container having a silvery appearance
PCT/US2007/006264 WO2007109009A2 (fr) 2006-03-20 2007-03-12 Recipient a paroi expansee dote d'un aspect argente

Publications (2)

Publication Number Publication Date
EP1999517A2 true EP1999517A2 (fr) 2008-12-10
EP1999517A4 EP1999517A4 (fr) 2012-07-18

Family

ID=39760539

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07752928A Withdrawn EP1999517A4 (fr) 2006-03-20 2007-03-12 Recipient a paroi expansee dote d'un aspect argente

Country Status (7)

Country Link
EP (1) EP1999517A4 (fr)
JP (1) JP2009530205A (fr)
AU (1) AU2007227660C1 (fr)
BR (1) BRPI0708939A2 (fr)
CA (1) CA2646320C (fr)
MX (1) MX2008011900A (fr)
WO (1) WO2007109009A2 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101639743B1 (ko) 2012-03-26 2016-07-14 도요세이칸 그룹 홀딩스 가부시키가이샤 금속색의 외관을 갖는 연신 발포 플라스틱 성형체
JP7610336B2 (ja) 2021-02-04 2025-01-08 東洋製罐グループホールディングス株式会社 合成樹脂製容器、及びプリフォーム

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3558751A (en) * 1964-07-22 1971-01-26 Owens Illinois Inc Method of making a foamed container having an integral neck portion
JPS6019511A (ja) * 1983-07-14 1985-01-31 Orion Kasei Kk 中空断熱容器の製造方法
JPS6153021A (ja) * 1984-08-23 1986-03-15 Mitsubishi Gas Chem Co Inc 発泡容器の製造法
US6352426B1 (en) * 1998-03-19 2002-03-05 Advanced Plastics Technologies, Ltd. Mold for injection molding multilayer preforms
EP1056585A1 (fr) * 1997-12-23 2000-12-06 Coraltech Limited Thermoformage ou moulage par soufflage de preformes moulees par injection
US6169266B1 (en) * 1998-03-25 2001-01-02 Xirom, Inc. Etching of multi-layered coated surfaces to add graphic and text elements to an article
US6939071B1 (en) * 2000-02-29 2005-09-06 Fragrance Systems International Roll-on applicator
US20020122838A1 (en) * 2001-01-04 2002-09-05 Anderson Jere R. Blow molding method and system
JP4391887B2 (ja) * 2004-05-31 2009-12-24 株式会社吉野工業所 積層成形体
US6794117B2 (en) * 2002-10-28 2004-09-21 Kodak Polychrome Graphics Process to produce a custom-color overlay
US20050181161A1 (en) * 2004-02-17 2005-08-18 Semersky Frank E. Container having a foamed wall
BRPI0511664A (pt) * 2004-06-10 2008-01-02 Advanced Plastics Technologies métodos e sistemas para o controle de temperaturas de moldes

Also Published As

Publication number Publication date
MX2008011900A (es) 2008-10-17
AU2007227660A1 (en) 2007-09-27
JP2009530205A (ja) 2009-08-27
CA2646320A1 (fr) 2007-09-27
WO2007109009A3 (fr) 2007-11-29
AU2007227660C1 (en) 2012-09-20
CA2646320C (fr) 2014-09-16
AU2007227660B2 (en) 2012-04-05
BRPI0708939A2 (pt) 2011-06-14
WO2007109009A2 (fr) 2007-09-27
EP1999517A4 (fr) 2012-07-18

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