US20040142129A1 - Modified container - Google Patents

Modified container Download PDF

Info

Publication number: US20040142129A1
Authority: US; United States
Prior art keywords: article; oxygen; polyester; coating; epoxy
Prior art date: 2000-12-21
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.): Abandoned

Application number

US10/450,540

Other languages

English (en)

Inventor

Lindsay Mulholland

Nina Goodrich

David Senior

Boris Chiu

Steven Li

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.)

Amcor Packaging Canada Inc

Original Assignee

Amcor Twinpak North America 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.)

2000-12-21

Filing date

2001-12-21

Publication date

2004-07-22

2001-12-21 Application filed by Amcor Twinpak North America Inc filed Critical Amcor Twinpak North America Inc

2003-12-01 Assigned to AMCOR TWINPAK-NORTH AMERICA INC. reassignment AMCOR TWINPAK-NORTH AMERICA INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CHIU, BORIS, GOODRICH, NINA, LI, STEVEN, MULHOLLAND, LINDSAY, SENIOR, DAVID

2004-07-22 Publication of US20040142129A1 publication Critical patent/US20040142129A1/en

Status Abandoned legal-status Critical Current

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Classifications

- 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
- B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
- B65D81/26—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants with provision for draining away, or absorbing, or removing by ventilation, fluids, e.g. exuded by contents; Applications of corrosion inhibitors or desiccators
- B65D81/266—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants with provision for draining away, or absorbing, or removing by ventilation, fluids, e.g. exuded by contents; Applications of corrosion inhibitors or desiccators for absorbing gases, e.g. oxygen absorbers or desiccants
- 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
- B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
- B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
- B65D1/0207—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]

Definitions

This invention relates to a packaging article, specifically a normally air-permeable container, which has been modified to reduce its gas permeability.
PET Polyethylene-terephalate
gases such as oxygen and carbon dioxide
One method for use of such active absorbent is a sandwich arrangement in which the gas scavenging material is provided as an inner layer while the outer layers are formed of PET or other polyester packaging material.
the gas scavenging material may be uniformly distributed in the wall structure.
gas scavenging material including poly(1,2-butadiene), as described, for example, in U.S. Pat. No. 5,310,497, polyamide, as described, for example, in U.S. Pat. No. 5,639,815, and condensation polymers comprising predominantly polyester segments and an oxygen scavenging amount of polyolefin oligomer segments, such as unhydrogenated polybutadiene, as described, for example, in U.S. Pat. No. 6,083,585.
poly(1,2-butadiene) as described, for example, in U.S. Pat. No. 5,310,497
polyamide as described, for example, in U.S. Pat. No. 5,639,815
condensation polymers comprising predominantly polyester segments and an oxygen scavenging amount of polyolefin oligomer segments, such as unhydrogenated polybutadiene, as described, for example, in U.S. Pat. No. 6,083,585.
the oxygen transmission rate and capacity of the gas scavenging material may be greatly improved by applying an external passive barrier to gas flow both from exterior of the bottle and from interior of the bottle to at least the walls of the container.
a packaging article having at least a wall constructed of a polyester and having an oxygen scavenging material therein and having an external barrier to gas flow therein. Since the oxygen barrier performance of the wall is improved, the quantity of active oxygen scavenger material can be significantly reduced while, at the same time, achieving an improved shelf-life.
FIGS. 1 to 5 are graphical representative of data generated with respect to oxygen permeability, as described in detail in the Examples below.
the packaging article provided herein preferably is in the form of a bottle, which may have any convenient volume and generally is formed by blow moulding. At least a wall and preferably the entire article, is constructed of a linear polyester, preferably PET, prepared by condensation of an aromatic dicarboxylic acid component and a diol component. For the provision of PET, terephthaltic acid and diethylene glycol are condensed.
the polyester contains at least one oxygen scavenging material, which may be provided as a discrete layer or preferably is uniformly distributed throughout the container wall.
the oxygen scavenging material may be any of the materials known to be useful in the art for such purposes, but preferably is a polyester copolymer comprising predominantly polyester segments and an oxygen scavenging amount of polyolefin oligomer segments.
polyester copolymers are described in detail in U.S. Pat. No. 6,083,585, the disclosure of which is incorporated herein by reference. Such materials are available commercially under the trademark AMOSORB.
the polyester segment of the polyester copolymer usually is the same polyester used to construct the container, preferably PET.
the polyolefin oligomer segments are distributed throughout the predominant polyester segments of the copolymer and are present in sufficient quantity in the copolymer to provide the needed oxygen scavenging capacity.
the hydrocarbon segments are the only moieties present which have oxygen scavenging propensity and capacity.
the polyester copolymer preferably has an oxygen scavenging capacity of at least about 0.4 cc of oxygen per gram of copolymer at a temperature in the range of about 4° to about 60° C., preferably at least 10 cc of oxygen per gram of copolymer and more preferably at least 20 cc per gram.
the polyolefin segments may be provided by polypropylene, poly(4-methyl) 1-pentene, unhydrogenated polybutadiene or mixtures thereof, preferably dihydroxy-terminated unhydrogenated polybutadiene, which may have a molecular weight in the range of about 100 to about 10,000, preferably in the range of about 1000 to about 3000.
the polyolefin segments may comprise about 0.5 to about 12 wt % of the polyester copolymer.
polyester copolymer often is employed in amounts of about 4 to 5 wt % of the container wall.
this amount of oxygen scavenging material may be significantly reduced to about 1 wt % and still provide improved performance.
the external coating of barrier material is applied as a very thin continuous layer, often less than a micron in thickness, at least to the walls of the container and preferably also to the neck and base of a bottle. Depending on the size of the bottle and the nature of the coating, a coating applied to the walls only may be sufficient.
the external coating may be applied in any convenient manner, depending on the material used to provide the coating, preferably by spraying. Generally, sufficient material only is used to provide a continuous coating of barrier layer on the desired portion of the bottle so as to minimize the material costs and to provide transparency to the coating. Each coating may have a thickness of about 0.3 to about 0.5 mil (about 5 to 15 microns).
the material used to provide the external barrier coating should be a material generally impervious to gaseous flow therethrough, particularly oxygen, and, where the container is to be used for carbonated beverages, also by carbon dioxide.
the material utilized to provide the barrier coating may be an epoxy resin, plasma-deposited silica or carbons, vapor-deposited silica or an ester-based UV-curable polymeric material. Any other suitable material which provides a passive barrier to the passage of air and/or carbon dioxide may be employed.
the barrier coating is provided by an epoxy-amine resin.
an epoxy-amine resin Such barrier materials are described in U.S. Pat. Nos. 5,300,541, 5,637,365 and 4,309,367 among others, the disclosures of which are incorporated herein by reference.
film-forming epoxy-amine resins are generally formed by reacting a polyamine and a polyepoxide.
the barrier material is provided by an epoxy-amine copolymer constructed as described in the aforementioned U.S. Pat. No. 5,637,365.
Such materials employ an amine hydrogen to epoxy equivalent cure ratio lower than 1.5 to 1.
the amino contents of the cured coating may be less than seven percent with good results being obtainable as low as four percent or lower.
the relatively lower amino content of the coating generally has the advantage of less yellowing of the coating over time.
Such material are sold by PPG Industries under the trademark BAIROCADE.
the barrier coating when employed in conjunction with a PET constructed of a monolayer of material having an active oxygen scavenger material distributed throughout the walls, then the amount of oxygen scavenger material which is used can be reduced and an improved bottle performance can be achieved.
This ability to employ less oxygen scavenger material is advantageous, in terms of cost of materials and has the effect of improving bottle clarity.
the barrier coating herein in conjunction with the oxygen scavenger material, the overall performance of the container in terms of gas permeability is improved. Both the empty bottle and full bottle shelf-lives are improved. In the case of carbonated beverages, the barrier coating prevents carbon dioxide from exiting the container through the walls, thereby improving the shelf-life for such materials.
the presence of an epoxy-amine polymer coating on bottles constructed of PET having an oxygen scavenger uniformly distributed in the walls generally improves both the barrier to oxygen transmission and oxygen absorbing capacity, as compared to the absence of such coating. While permitting bottles to stand prior to filling reduces the combined effectiveness of the epoxy-amine polymer coating on an oxygen-scavenger containing wall, the total oxygen transmittance can be significantly reduced and the package with the combination is much more effective for bottling all types of beer and other oxygen-sensitive foods and beverages.
the oxygen permeance measurements made in the Example are obtained by a liquid oxygen sensitive indicator method, which represents oxygen ingress into the liquid.
the method correlates were with oxidative degradation of a model ascorbic acid solution and with results by trained taste pnaelists.
a 34 g PET beer bottle having 1% of an oxygen scavenger dispersed in the walls was provided with an epoxy-amine coating.
An improvement in oxygen barrier rate when compared to the absence of the epoxy-amine coating was determined to be 3.8 times.
This Example illustrates the significant effect of an oxygen scavenger in conjunction with an external barrier layer.
PET Polyethylene-terephthalate
Amosorb is a proprietary oxygen scavenging copolymer material supplied by BP chemicals.
the copolymer is a copolymer of PET having polybutadiene oligomer segments and is produced as described in the aforementioned U.S. Pat. No. 6,083,585.
the bottles were spray coated on the outside of the bottles with a contiguous outer film of an epoxy-amine resin supplied by PPG Industries under the trademark “BAIROCADE” and produced as described in the aforementioned U.S. Pat. No. 5,637,365. The thickness of the layer was about 0.4 mil.
Control bottles were also prepared in which there was only no modification to the bottle walls, in which only 1% Amosorb was present and in which only the epoxy-amine resin coating was present.
OTR oxygen transmission rate
This Example illustrates the synergistic effect of an oxygen scavenger material in conjunction with an external barrier layer.
Example 2 The procedure of Example 2 was repeated except that a comparison was made between bottles which were filled immediately after the bottles were made and these which were filled after 5 weeks standing empty (“aged”).
This Example describes a study of the effect of Amosorb and PPG on total oxygen absorbance over a four month period.
Beer in plastic bottles has a finite shelf-life due to oxygen permeation. A four-month period of time usually is considered acceptable. For light-flavoured beer, less oxygen absorbance is tolerable than for stronger-flavoured beer.
Example 2 The procedure of Example 2 was repeated except that 0.473 L (16 oz) bottles were prepared, and filled immediately following manufacture or after 5 weeks (“aged”). Bottles were prepared with no alteration to the bottle, 1 wt % Amosorb, 4 wt % Amosorb, epoxy-amine coating and 1% Amosorb plus epoxy-amine coating. The total ppm oxygen absorbed by oxygen-sensitive liquid during a 4 month period was determined and the results are shown graphically in FIG. 5.
Example illustrates the use of a different barrier layer material.
PCT bottles were blown from a blend of commercial PET and 2 wt % Amosorb with 700 ml capacity.
the bottles are coated with silica by high vacuum deposition on the outside of the bottles with a spray-applied polymeric top coat.
the coating materials are sold under the tradename BestPET by Krones.
the present invention provides containers having walls constructed of polyester with an oxygen scavenging material therein and a barrier coating applied thereto to provide an improved performance with respect to gas permeation. Modifications are possible within the scope of the invention.

US10/450,540 2000-12-21 2001-12-21 Modified container Abandoned US20040142129A1 (en)

Applications Claiming Priority (2)

Application Number	Priority Date	Filing Date	Title
US25696300P	2000-12-21	2000-12-21
PCT/CA2001/001840 WO2002049923A2 (fr)	2000-12-21	2001-12-21	Contenant modifie

Publications (1)

Publication Number	Publication Date
US20040142129A1 true US20040142129A1 (en)	2004-07-22

Family

ID=22974320

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
US10/450,540 Abandoned US20040142129A1 (en)	2000-12-21	2001-12-21	Modified container

Country Status (4)

Country	Link
US (1)	US20040142129A1 (fr)
AU (1)	AU2002218903A1 (fr)
CA (1)	CA2432511A1 (fr)
WO (1)	WO2002049923A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
WO2010096430A2 (fr)	2009-02-18	2010-08-26	Invista Technologies S.A. R.L.	Composition de polyester et bouteille pour produits pasteurisés gazéifiés

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US9382028B2 (en)	2002-02-01	2016-07-05	Invista North America S.A.R.L.	Opaque polyester containers
US7368153B2 (en)	2002-12-06	2008-05-06	Cryovac, Inc.	Oxygen detection system for a rigid container
US7078100B2 (en)	2003-08-28	2006-07-18	Cryovac, Inc.	Oxygen scavenger compositions derived from isophthalic acid and/or terephthalic acid monomer or derivatives thereof
US7754798B2 (en)	2003-08-28	2010-07-13	Cryovac, Inc.	Oxygen scavenger block copolymers and compositions
US7534615B2 (en)	2004-12-03	2009-05-19	Cryovac, Inc.	Process for detecting leaks in sealed packages
US10894625B1 (en)	2020-07-29	2021-01-19	Verre Vert, Inc.	Lightweight polymer bottle for wine and spirits

Citations (9)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US4309367A (en) *	1981-02-02	1982-01-05	Warren F. B. Lindsley	Carburetor employing fuel air mixture means operative prior to carburetion
US4735832A (en) *	1984-05-11	1988-04-05	Terumo Kabushiki Kaisha	Container made of synthetic resin and method for manufacture thereof
US5300541A (en) *	1988-02-04	1994-04-05	Ppg Industries, Inc.	Polyamine-polyepoxide gas barrier coatings
US5310497A (en) *	1992-10-01	1994-05-10	W. R. Grace & Co.-Conn.	Oxygen scavenging compositions for low temperature use
US5637365A (en) *	1994-12-16	1997-06-10	Ppg Industries, Inc.	Epoxy-amine barrier coatings with aryloxy or aryloate groups
US5639815A (en) *	1987-07-27	1997-06-17	Carnaudmetalbox Plc	Packaging
US5759653A (en) *	1994-12-14	1998-06-02	Continental Pet Technologies, Inc.	Oxygen scavenging composition for multilayer preform and container
US5804236A (en) *	1996-09-26	1998-09-08	Frisk; Peter	Oxygen scavenging container
US6083585A (en) *	1996-09-23	2000-07-04	Bp Amoco Corporation	Oxygen scavenging condensation copolymers for bottles and packaging articles

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
DK0932561T3 (da) *	1996-09-23	2000-08-28	Bp Amoco Corp	Plastflaske uden oxygengennemtrængning til øl og andre anvendelser
WO1999032548A1 (fr) *	1997-12-19	1999-07-01	E.I. Du Pont De Nemours And Company	Composition de polyester, ayant des proprietes d'arret des gaz accrues

2001
- 2001-12-21 WO PCT/CA2001/001840 patent/WO2002049923A2/fr not_active Application Discontinuation
- 2001-12-21 US US10/450,540 patent/US20040142129A1/en not_active Abandoned
- 2001-12-21 AU AU2002218903A patent/AU2002218903A1/en not_active Abandoned
- 2001-12-21 CA CA002432511A patent/CA2432511A1/fr not_active Abandoned

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US4309367A (en) *	1981-02-02	1982-01-05	Warren F. B. Lindsley	Carburetor employing fuel air mixture means operative prior to carburetion
US4735832A (en) *	1984-05-11	1988-04-05	Terumo Kabushiki Kaisha	Container made of synthetic resin and method for manufacture thereof
US5639815A (en) *	1987-07-27	1997-06-17	Carnaudmetalbox Plc	Packaging
US5300541A (en) *	1988-02-04	1994-04-05	Ppg Industries, Inc.	Polyamine-polyepoxide gas barrier coatings
US5310497A (en) *	1992-10-01	1994-05-10	W. R. Grace & Co.-Conn.	Oxygen scavenging compositions for low temperature use
US5759653A (en) *	1994-12-14	1998-06-02	Continental Pet Technologies, Inc.	Oxygen scavenging composition for multilayer preform and container
US5637365A (en) *	1994-12-16	1997-06-10	Ppg Industries, Inc.	Epoxy-amine barrier coatings with aryloxy or aryloate groups
US6083585A (en) *	1996-09-23	2000-07-04	Bp Amoco Corporation	Oxygen scavenging condensation copolymers for bottles and packaging articles
US6406766B1 (en) *	1996-09-23	2002-06-18	Bp Corporation North America Inc.	Active oxygen scavenger packaging
US5804236A (en) *	1996-09-26	1998-09-08	Frisk; Peter	Oxygen scavenging container

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
WO2010096430A2 (fr)	2009-02-18	2010-08-26	Invista Technologies S.A. R.L.	Composition de polyester et bouteille pour produits pasteurisés gazéifiés
EP2398712A2 (fr) *	2009-02-18	2011-12-28	INVISTA Technologies S.à.r.l.	Composition de polyester et bouteille pour produits pasteurisés gazéifiés
EP2398712A4 (fr) *	2009-02-18	2015-04-15	Invista Technologies Srl	Composition de polyester et bouteille pour produits pasteurisés gazéifiés

Also Published As

Publication number	Publication date
CA2432511A1 (fr)	2002-06-27
WO2002049923A3 (fr)	2002-09-06
WO2002049923A2 (fr)	2002-06-27
AU2002218903A1 (en)	2002-07-01
WO2002049923A8 (fr)	2004-04-22

Legal Events

Date

Code

Title

Description

2003-12-01

AS

Assignment