WO2006112840A1 - Composition en polyester a barriere au gaz amelioree, articles ainsi elabores, et procedes - Google Patents

Composition en polyester a barriere au gaz amelioree, articles ainsi elabores, et procedes Download PDF

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Publication number
WO2006112840A1
WO2006112840A1 PCT/US2005/013226 US2005013226W WO2006112840A1 WO 2006112840 A1 WO2006112840 A1 WO 2006112840A1 US 2005013226 W US2005013226 W US 2005013226W WO 2006112840 A1 WO2006112840 A1 WO 2006112840A1
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WO
WIPO (PCT)
Prior art keywords
polyester composition
polyester
additive
weight
dihydroxy naphthalene
Prior art date
Application number
PCT/US2005/013226
Other languages
English (en)
Inventor
Yu Shi
Original Assignee
The Coca-Cola Company
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 The Coca-Cola Company filed Critical The Coca-Cola Company
Priority to CNA2005800495323A priority Critical patent/CN101166783A/zh
Priority to JP2008507607A priority patent/JP2008537006A/ja
Priority to EP05735791A priority patent/EP1902092A1/fr
Priority to PCT/US2005/013226 priority patent/WO2006112840A1/fr
Publication of WO2006112840A1 publication Critical patent/WO2006112840A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • 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
    • C08K2201/008—Additives improving gas barrier properties

Definitions

  • This invention relates to polyester and polyester articles.
  • this invention relates to polyesters for use in applications such as packaged beverages wherein enhanced gas barrier or oxygen scavenging is desirable.
  • PET Polyethylene terephthalate and its copolyesters
  • the permeation rate of carbon dioxide through PET containers is in the range of 3 to 14 cc's per day or 1.5 to 2% per week loss rate at room temperature depending on the size of the container.
  • a smaller container has a larger surface to volume ratio resulting in a higher relative loss rate.
  • PET containers are currently used only as larger containers for packaging carbonated soft drinks, while metal cans and glass containers are the choice for smaller carbonated soft drink containers.
  • a barrier additive for the PET or a polymer with inherent barrier properties would be preferred solutions. Neither such solution requires additional capital investment, and therefore, does not have the limitations inherent with other technologies.
  • a barrier additive can also be added during the injection molding process which gives more flexibility for downstream operations.
  • HO-Ar-COOR HO-Ar-COORlCOO-AR-OH, HO-AR-CONHR, HO-AR-CO- NHR3 -COO-AR-OH, H0-AR-C0NHR2NHC0-AR-0H
  • AR is selected from the group consisting of substituted or unsubstituted phenylene or naphthalene.
  • Rl, R2, and R3 are selected from the group consisting from Cl to C6 alkyl groups, a phenyl group, and a naphthyl group.
  • PET with a significantly lower IV cannot be used in blow molding containers, such as beverage containers.
  • lower IV PET makes containers with poor mechanical performance, such as creep, drop impact, and the like.
  • PET containers made from lower IV PET have poor stress cracking resistance, which is undesirable in container applications.
  • PET has been modified or blended with other components to enhance the gas barrier of the PET.
  • examples include polyethylene naphthalate (PEN)/PET copolymers or blends, isophthalate (IPA) modified PET, PET blended with polyethylene isophthalate (PEI) or a polyamide, such as nylon, and PET modified with resorcinol based diols.
  • PEN polyethylene naphthalate
  • PET PET copolymers or blends
  • PET modified with resorcinol based diols For a PET copolymer to achieve moderate barrier enhancement of 2X or higher, the modification is normally more than 10 to 20 weight or mole % of the total co-monomers.
  • PET is modified to such a high level, the stretching characteristics of the PET are changed dramatically such that the normal PET container preform design could not be used in the manufacture of containers.
  • PET copolymers to mold conventional PET container preforms results in preforms that can not be fully stretched and the ultimate containers are very difficult, if not impossible, to make. Even if such a container can be made, it does not show improved barrier performance and shows deteriorated physical performance such that it can not be used to package carbonated soft drinks.
  • U.S. Patents 5,888,598 and 6,150,450 disclose redesigned PET container preforms with thicker side walls to compensate for the increased stretch ratio. This thicker preform, however, requires new molds which require additional capital investment and is also made at a lower rate of productivity because it takes longer to cool and heat the thicker wall preform.
  • PET blends with polyamide such as nylon developed yellowness and haze and are not clear like conventional PET.
  • the monolayer oxygen scavengers provide additional benefits over the multi-layered oxygen scavenger in that the monolayer oxygen scavenger can react with the headspace oxygen in the container, in addition to blocking the oxygen ingress to the container. Therefore, the monolayer oxygen scavenger can prevent the product oxidation from the headspace oxygen.
  • the oxygen scavenger compositions disclosed in these and other similar patents all contain transition metals as catalysts. The transition metals can cause degradation in PET and cause discoloration in PET. In addition, in certain countries, certain transition metals also raise environmental and regulatory concerns.
  • This invention addresses the above described need for enhanced gas barrier PET by providing a polyester composition comprising a polyester and an organic gas barrier enhancing additive having the chemical formula OH-AR-OH, wherein AR is substituted or unsubstituted naphthalene.
  • the polyester in the polyester composition comprises a poly(ethylene terethphalate) based copolymer (PET copolymer).
  • PET copolymer poly(ethylene terethphalate) based copolymer
  • the polyester comprises a PET copolymer having less than 20% diacid component modification and/or less than 10% diol component modification, based on 100 mole % diacid component and 100 mole % diol component.
  • this invention encompasses a method for enhancing gas barrier of a polyester composition
  • a method for enhancing gas barrier of a polyester composition comprising blending a polyester and an organic gas barrier enhancing additive having the chemical formula OH-AR-OH, wherein AR is substituted or unsubstituted naphthalene.
  • the polyester is a PET copolymer.
  • this invention encompasses an article comprising a polyester and an organic gas barrier enhancing additive having the chemical formula OH-AR-OH, wherein AR is substituted or unsubstituted naphthalene.
  • the article is a container and in other preferred embodiments is a stretch blow molded container.
  • the polyester is a PET copolymer.
  • this invention encompasses a method for making an article with enhancing gas barrier comprising the steps of blending a polyester and an organic gas barrier enhancing additive having the chemical formula
  • the polyester is a PET copolymer.
  • the article is a stretch blow molded container.
  • polyesters such as PET copolymers, with enhanced gas barrier, and in particular, enhanced barrier to carbon dioxide and oxygen. This makes certain embodiments of this invention particularly suited for packaging carbonated soft drinks and oxygen sensitive beverages and foods.
  • Fig. 1 is a schematic illustration of a system for making a PET container with enhanced gas barrier in accordance with an embodiment of this invention.
  • Fig. 2 is a sectional elevation view of a molded container preform made in accordance with an embodiment of this invention.
  • Fig. 3 is a sectional elevation view of a blow molded container made from the preform of Fig. 2 in accordance with an embodiment of this invention.
  • Fig. 4 is a perspective view of a packaged beverage made in accordance with an embodiment of this invention.
  • This invention encompasses a polyester composition with enhanced gas barrier or oxygen scavenging capability or both, a method for enhancing gas barrier or oxygen scavenging capability of a polyester composition, articles comprising such a polyester composition, and a method for making such articles.
  • embodiments of this invention provide a polyester composition and articles made therewith which exhibit enhanced barrier to gases or oxygen scavenging capability while maintaining physical properties.
  • Suitable polyesters include those that are suitable for packaging carbonated or non-carbonated beverages and oxygen sensitive beverages or food products.
  • Suitable polyesters for use in embodiments of this invention include PET copolymers, polyethylene naphthalate (PEN), polyethylene isophthalate, and the like. PET copolymers are particularly useful because they are used for many barrier applications such as films and containers.
  • Suitable containers include but are not limited to bottles, drums, carafes, coolers, and the like.
  • PET copolymers suitable for use in embodiments of this invention comprise a diol component having repeat units from ethylene glycol and a diacid component having repeat units from terephthalic acid. Desirably, in some embodiments, the PET copolymer has less than 20% diacid component modification and/or less than 10% diol component modification, based on 100 mole % diacid component and 100 mole % diol component. Such PET copolymers are well known.
  • suitable organic gas barrier enhancing additives are those having the chemical formula OH-AR-OH, wherein AR is substituted or unsubstituted naphthalene.
  • Suitable additives include, but are not limited to, 1,2-dihydroxy naphthalene, 1,3-dihydroxy naphthalene, 1,5-dihydroxy naphthalene, 1 ,6-dihydroxy naphthalene, and 2,6-dihydroxy naphthalene. 1,5- dihydroxy naphthalene degrades at polyester melt processing temperatures, and therefore is not a preferred additive, but is useful at lower melt processing temperatures. 2,7-dihydroxy naphthalene is not listed because it has an even lower degradation temperature and is not suitable for use as an additive for PET.
  • the organic gas barrier enhancing additive compound is added to the polyester in an amount sufficient to enhance the gas barrier properties of the polyester.
  • the polyester is present in the polyester composition in amount from 99.9% to 90% by weight of the polyester composition and the organic gas barrier enhancing additive is present in the polyester composition in an amount of 0.1% to about 10% by weight of the polyester composition.
  • the PET copolymer is present in the polyester composition in an amount from 99.9% to about 95% by weight of the polyester composition and the additive is present in the polyester composition in an amount from about 0.1% to about 5% by weight of the polyester composition.
  • the PET copolymer is present in the polyester composition in an amount from about 99.9% to about 97% by weight of the polyester composition and the additive is present in the polyester composition in an amount from about 0.1% to about 3% by weight of the polyester composition.
  • Polyesters including PET copolymers, have free volume between polymer chains.
  • the amount of free volume in polyesters such as PET copolymers determines their barrier to gas molecules. The lower the free volume, the lower the gas diffusion, and the higher the barrier to gas molecules.
  • the additive is at least partially disposed in the free volume of the polyester between the polyester chains and solidifies in the free volume when the blend is cooled down to room temperature after melt processing. Due to the presence of the two hydroxyl groups, it is possible that the additive reacts with the polyester chain and causes the intrinsic viscosity (IV) to drop although the reactivity of the hydroxy group in the current additive is very low.
  • the additive when melt blending the additive with polyester, it is possible that the additive partially reacts with the polyester and forms a mixture of polyester/dihydroxy naphthalene copolymer, polyester, and the additive.
  • the additive when the additive is 1,3-dihydroxy naphthalene, it is believed that the additive at least partially reacts with the polyester and becomes part of the polyester backbone chain.
  • the polyester comprises a poly(ethylene terephthalate) based copolymer (PET copolymer) and, based on 100 mole % diacid component and 100 mole % diol component, the PET copolymer has less than 20% diacid component modification and less than 10% diol component modification, and at least a portion of the additive is reacted with the PET copolymer such that the diol component comprises 0.1 to about 5 mole % of the additive.
  • PET copolymer poly(ethylene terephthalate) based copolymer
  • the additive may be incorporated into the polyester in different ways.
  • the additive can be incorporated directly into polyester during the injection molding process, can be preblended in the polyester resin making process, or can be incorporated into melt polyester prior to the discharge of the polyester in the melt polymerization process.
  • the additives can be preblended with the polyester, melt extruded and solid state polymerized to the desired IV. The solid stated mixture can then be injection molded into container performs as described in more detail below.
  • any residual polycondensation catalyst in the polyester include commonly used catalyst such as compounds containing antimony, titanium, tin, and the like, and are deactivated by phosphorus containing compounds.
  • the phosphorus containing compounds include both organic and inorganic compounds. Examples include but are not limited to phosphoric acid, polyphosphoric acid, and tris(2,4-di-t-butylphenyl) phosphite, tris monononylphenyl phosphite. These additives are typically added in amounts less than 2000 ppm. As described above, the polyester composition of this invention is useful for making articles in which enhanced gas barrier is desirable.
  • Such articles are made by forming the above described polyester compositions into the desired article by conventional methods such as melt forming.
  • Suitable melt forming processes include, but are not limited to, injection molding, extrusion, thermal forming and compression molding.
  • embodiments of this invention are suitable for making containers for packaging applications in the carbonated and non-carbonated soft drink industry and the food industry.
  • a common manufacturing method for forming these containers includes injection molding container preforms, and then, making the containers from the preforms in single stage, two stage, and double blow molding manufacturing systems.
  • Such methods are well known to those skilled in the art and examples of suitable preform and container structures and are disclosed in U.S. Patent 5,888,598, the disclosure of which is expressly incorporated herein by reference in its entirety.
  • a container preform is formed by injection molding the polyester into a blowable geometric form.
  • the preform or blowable form is then contained within a mold cavity having the volumetric configuration of the desired container and the preform is expanded by blowing it with compressed air within the confines of the mold cavity.
  • Suitable containers in accordance with embodiments of this invention may be blow-molded from a cylindrical injection-molded preform having an open top end and neck finish.
  • the preform may have a tapered shoulder-forming portion, substantially uniform thickness along the sides of the cylinder, and a base-forming portion preferably in a champagne design, but including a hemispherical base with a base cup or a footed design such as a petaloid design.
  • the preform is amorphous and substantially transparent and is injection molded.
  • container preforms are subsequently placed in a blow molding apparatus having an upper mold section which engages the neck finish, a middle mold section having an interior cavity forming the shape of the container side wall, and a lower mold section having an upper surface forming the outwardly concave dome portion of the container base.
  • the injection-molded preform is first reheated to a temperature suitable for stretching and orientation of about 70 to 130 0 C, placed in the blow mold, and an axial stretch rod is then inserted into the open upper end and moved downwardly to axially stretch the preform.
  • Fig. 1 illustrates a system 10 in accordance with an embodiment of this invention for making a rigid container preform 12 (illustrated in Fig. 2) and a rigid container 14 (illustrated in Fig. 3) from the preform. As is shown in Fig.
  • solid PET copolymer pellets 20 and an organic gas barrier enhancing additive such as dimethyl terephthalate 22 are added to a feeder or hopper 24 that delivers the components to a hot melt extruder 26 in which the components are melted and blended.
  • the hot melt extruder 26 then extrudes the molten mixture of PET copolymer and organic gas barrier enhancing additive into an injection molding device 28 to form the preform 12.
  • the preform is cooled and removed from the injection molding device 28 and delivered to a blow molding device 30 which blow molds the preform 12 into a finished rigid container 14.
  • the melt residence time of the preform production is preferably less than three minutes and more preferably from about 100 to about 120 seconds.
  • the melt temperatures desirably from 270 to about 300 0 C and more desirably from about 270 to about 290 0 C.
  • the melt residence time begins when the PET copolymer and organic barrier enhancing additive enter the melt extruder 26 and start melting, and ends after injection of the molten blend into the injection mold to form the preform 12.
  • a polyester container preform 12 is illustrated.
  • This preform 12 is made by injection molding PET based resin and comprises a threaded neck finish 112 which terminates at its lower end in a capping flange 114.
  • a capping flange 114 Below the capping flange 114, there is a generally cylindrical section 116 which terminates in a section 118 of gradually increasing external diameter so as to provide for an increasing wall thickness.
  • an elongated body section 120 Below the section 118 there is an elongated body section 120.
  • the preform 12 illustrated in Fig. 2 can be blow molded to form a container 14 illustrated in Figs. 3 and 4.
  • the container 14 comprises a shell 124 comprising a threaded neck finish 126 defining a mouth 128, a capping flange 130 below the threaded neck finish, a tapered section 132 extending from the capping flange, a body section 134 extending below the tapered section, and a base 136 at the bottom of the container.
  • the container 14, for the most part, is highly biaxially oriented, but the neck finish 126 is non-oriented.
  • the container 14 is suitably used to make a packaged beverage 138, as illustrated in Fig. 4.
  • the packaged beverage 138 includes a beverage such as a carbonated soda beverage disposed in the container 14 and a closure 140 sealing the mouth 128 of the container.
  • the preform 12, container 14, and packaged beverage 138 are but examples of applications using the preforms of the present invention. It should be understood that the process and apparatus of the present invention can be used to make preforms and containers having a variety of configurations.
  • Example 1 A commercially available polyester container grade resin was used as a control.
  • the polyester composition (PET) had a diacid component of 97.2 mole% terephthalic acid and 2.8 mole% isophthalic acid and a glycol component of 97.2 to 97.3 mole% ethylene glycol and 2.7 to 2.8 mole% diethylene glycol.
  • the PET was dried in a vacuum oven at 14O 0 C overnight to a moisture level below 50 ppm.
  • the additives listed in Table 1 were dried in a vacuum oven at 70 0 C overnight to remove absorbed moisture.
  • the PET and 5 weight % of different additives were mixed prior to injection molding.
  • a lab scale Arburg unit cavity injection molding machine was used for injection molding.
  • a 24.5-g preform was used to make a 500 ml container.
  • the preforms were blow molded with a Sidel SBO 2/3 blow molding machine to make acceptable 500 ml contour containers.
  • the oxygen transmission rate of the containers was then measured using a Macon 2/60 model instrument at 22.2°C and 50% relative humidity (RH) with the 99%N 2 /1%H 2 purging rate of 10 ml/min on one side and air on the other side.
  • RH relative humidity
  • the results are shown in Table 1.
  • the barrier improvement factor (BIF) was defined as the ratio of the oxygen transmission rate of the control and the additive package. BIF is a measurement of the barrier enhancement as comparison to control.
  • the resins and additives listed in Table 2 were dried, mixed and injection molded as in Example 1. Instead of 5 weight % of additive loading, a 3 weight % of additive loading was used.
  • a 24.5-g preform was used to make a 500 ml container. The preforms were blow molded with a Sidel SBO 2/3 blow molding machine to make acceptable 500 ml contour containers.
  • the oxygen transmission rate of the containers was then measured using a Macon 2/60 model instrument at 22.2 0 C and 50% RH with the 99%N 2 /1%H 2 purging rate of 10 ml/min on one side and air on the other side. The results are shown in Table 2.
  • Table 2 Table 2
  • a commercially available carbonated soft drink grade PET resin and 3 weight % 1, 3-dihydroxy naphthalene were dried, mixed and injection molded as in Example 1.
  • a 24.5g preform was used to make a 500 ml container.
  • the preforms were blow molded with a Sidel SBO 2/3 blow molding machine to make acceptable 500 ml contour containers.
  • the bottle sidewalls were then cut into a 2 in by 2 in square and mounted into a Mocon Permeatran to measure the CO 2 transmission rate.
  • a PET control film was also used for the CO 2 transmission rate. The results are shown in table 3.
  • a commercially available carbonated soft drink grade PET resin and 5 weight % of 1, 3 dihydroxy naphthalene additive were dried, mixed and injection molded as in Example 1.
  • a 24.5 -g preform was used to make a 500 ml container.
  • the preforms were blow molded with a Sidel SBO 2/3 blow molding machine to make acceptable 500 ml contour containers.
  • the oxygen transmission rate of the containers were then measured using a Macon 2/60 model instrument at 22.2°C and 50% RH with the 99%N 2 /1%H 2 purging rate of 10 ml/min on one side and air on the other side. The results are shown in Table 4.
  • Example 5 Comparison examples
  • the resins and additives were dried, mixed and injection molded as in Example
  • the oxygen transmission rate of the containers were then measured using a Macon 2/60 model instrument at 22.2°C and 50% RH with the 99%N 2 /1%H 2 purging rate of 10 ml/min on one side and air on the other side. The results are shown in Table 5.
  • embodiments of this invention have much higher gas barrier than containers made with conventional barrier additives.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Containers Having Bodies Formed In One Piece (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Wrappers (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

Composition en polyester à propriétés de barrière au gaz améliorées, comprenant un polyester et un additif organique augmentant la barrière au gaz, de formule chimique OH-AR-OH, sachant qu'AR est naphtalène avec ou sans substitution. Egalement, articles à barrière au gaz améliorée et procédés d'élaboration de polyesters et d'articles à barrière au gaz améliorée.
PCT/US2005/013226 2005-04-19 2005-04-19 Composition en polyester a barriere au gaz amelioree, articles ainsi elabores, et procedes WO2006112840A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CNA2005800495323A CN101166783A (zh) 2005-04-19 2005-04-19 具有提高的气体阻挡性能的聚酯组合物，用其制造的制品和方法
JP2008507607A JP2008537006A (ja) 2005-04-19 2005-04-19 ガスバリアが向上したポリエステル組成物、それによって製造された物品、および方法
EP05735791A EP1902092A1 (fr) 2005-04-19 2005-04-19 Composition en polyester a barriere au gaz amelioree, articles ainsi elabores, et procedes
PCT/US2005/013226 WO2006112840A1 (fr) 2005-04-19 2005-04-19 Composition en polyester a barriere au gaz amelioree, articles ainsi elabores, et procedes

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2005/013226 WO2006112840A1 (fr) 2005-04-19 2005-04-19 Composition en polyester a barriere au gaz amelioree, articles ainsi elabores, et procedes

Publications (1)

Publication Number Publication Date
WO2006112840A1 true WO2006112840A1 (fr) 2006-10-26

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EP (1) EP1902092A1 (fr)
JP (1) JP2008537006A (fr)
CN (1) CN101166783A (fr)
WO (1) WO2006112840A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013040020A1 (fr) * 2011-09-12 2013-03-21 Constar International Llc Bouteilles en polyéthylène téréphtalate (pet) formant une barrière monocouche au dioxyde de carbone

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4474918A (en) * 1983-05-31 1984-10-02 Eastman Kodak Company Thermoplastic polyester compositions having improved barrier properties
US4574148A (en) * 1985-06-21 1986-03-04 Eastman Kodak Company Polyester resins capable of forming containers having improved gas barrier properties
EP0678554A1 (fr) * 1988-11-08 1995-10-25 Mitsui Petrochemical Industries, Ltd. Copolyester, composition de polyester contenant le copolyester et structure laminée de polyester ayant une couche composée du copolyester ou de la composition de polyester
US6489386B1 (en) * 1999-08-12 2002-12-03 E. I. Du Pont De Nemours And Company Method and composition for improving gas barrier properties of polymeric containers and films
US20040116619A1 (en) * 2000-09-12 2004-06-17 Graeme Moad Polyester resins with improved properties

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4474918A (en) * 1983-05-31 1984-10-02 Eastman Kodak Company Thermoplastic polyester compositions having improved barrier properties
US4574148A (en) * 1985-06-21 1986-03-04 Eastman Kodak Company Polyester resins capable of forming containers having improved gas barrier properties
EP0678554A1 (fr) * 1988-11-08 1995-10-25 Mitsui Petrochemical Industries, Ltd. Copolyester, composition de polyester contenant le copolyester et structure laminée de polyester ayant une couche composée du copolyester ou de la composition de polyester
US6489386B1 (en) * 1999-08-12 2002-12-03 E. I. Du Pont De Nemours And Company Method and composition for improving gas barrier properties of polymeric containers and films
US20040116619A1 (en) * 2000-09-12 2004-06-17 Graeme Moad Polyester resins with improved properties

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013040020A1 (fr) * 2011-09-12 2013-03-21 Constar International Llc Bouteilles en polyéthylène téréphtalate (pet) formant une barrière monocouche au dioxyde de carbone
CN103917369A (zh) * 2011-09-12 2014-07-09 普莱斯提派克包装公司 单层二氧化碳屏障pet瓶
AU2012308752B2 (en) * 2011-09-12 2015-09-24 Plastipak Packaging, Inc. Monolayer carbon dioxide barrier PET bottles
RU2579595C2 (ru) * 2011-09-12 2016-04-10 Пластипэк Пэкэджинг, Инк. Пэт бутылки с однослойным барьером для диоксида углерода
US10011714B2 (en) 2011-09-12 2018-07-03 Plastipak Packaging, Inc. Monolayer carbon dioxide barrier PET bottles

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JP2008537006A (ja) 2008-09-11
CN101166783A (zh) 2008-04-23
EP1902092A1 (fr) 2008-03-26

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