EP1289855A2 - Packaging of bananas - Google Patents

Packaging of bananas

Info

Publication number
EP1289855A2
EP1289855A2 EP01959756A EP01959756A EP1289855A2 EP 1289855 A2 EP1289855 A2 EP 1289855A2 EP 01959756 A EP01959756 A EP 01959756A EP 01959756 A EP01959756 A EP 01959756A EP 1289855 A2 EP1289855 A2 EP 1289855A2
Authority
EP
European Patent Office
Prior art keywords
bananas
container
ethylene
sealed
less
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.)
Granted
Application number
EP01959756A
Other languages
German (de)
French (fr)
Other versions
EP1289855B1 (en
Inventor
Raymond Clarke
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.)
Apio Inc
Original Assignee
Landec Corp
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 Landec Corp filed Critical Landec Corp
Priority to EP04027190A priority Critical patent/EP1516827B1/en
Publication of EP1289855A2 publication Critical patent/EP1289855A2/en
Application granted granted Critical
Publication of EP1289855B1 publication Critical patent/EP1289855B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS 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
    • B65D85/00Containers, packaging elements or packages, specially adapted for particular articles or materials
    • B65D85/30Containers, packaging elements or packages, specially adapted for particular articles or materials for articles particularly sensitive to damage by shock or pressure
    • B65D85/34Containers, packaging elements or packages, specially adapted for particular articles or materials for articles particularly sensitive to damage by shock or pressure for fruit, e.g. apples, oranges or tomatoes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65BMACHINES, APPARATUS OR DEVICES FOR, OR METHODS OF, PACKAGING ARTICLES OR MATERIALS; UNPACKING
    • B65B25/00Packaging other articles presenting special problems
    • B65B25/02Packaging agricultural or horticultural products
    • B65B25/04Packaging fruit or vegetables
    • B65B25/041Packaging fruit or vegetables combined with their conservation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS 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
    • B65D81/00Containers, 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
    • B65D81/24Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants

Definitions

  • This invention relates to the packaging of bananas.
  • a respiring material should be stored in a container whose permeability to O 2 and CO 2 is correlated with (i) the atmosphere outside the package, (ii) the rates at which the material consumes O 2 and produces CO 2 , and (iii) the temperature, to produce the desired atmosphere within the container.
  • CAP controlled atmosphere packaging
  • MAP modified atmosphere packaging
  • Bananas are respiring biological materials whose storage and ripening present the most serious problems because
  • the conventional procedure is to harvest the bananas when they are hard, green and unripe; to transport the green bananas, at 13-14 °C, to the location where they will be consumed; to ripen the green bananas by exposing them to ethylene in a ripening room at that location; and to place the ripened bananas on sale.
  • the time at which the bananas are harvested depends on the time needed to transport them to the point- of-sale. Thus bananas are typically harvested at week 11 (i.e. 11 weeks after the flower emerges from the plant) or week 12.
  • the green bananas are shipped in bags made of polyethylene about 0.04 to 0.06 mm (1.5-2.5 mil) thick, with each bag containing about 18 kg (40 lb) of bananas and being supported by a cardboard box.
  • each bag containing about 18 kg (40 lb) of bananas and being supported by a cardboard box.
  • most of the air is exhausted from the bag, and the bag is then sealed; this is the procedure generally described in US Patent No. 3,450,542 (Badran).
  • the bag contains vent holes.
  • a serious disadvantage of the conventional procedure is the need to harvest the bananas a good while before they are fully grown. It would be desirable to harvest the bananas at a later time, when they are larger. However, the later the bananas are picked, the greater the propensity for their climacteric to be triggered by small concentrations of ethylene, and experience has shown that if the bananas are harvested later than the presently established timetables, this results in prematurely ripe bananas when the bananas are shipped in vented bags, and in so-called "green-ripe" bananas when the bananas are shipped in sealed bags. Green-ripe bananas soften, but remain green, and have an unpleasant flavor.
  • Another serious disadvantage of the conventional procedure is that, in order to ripen the green bananas by exposing them to ethylene, it is necessary to open each of the shipping bags if, as in most cases, the bags have been sealed during shipping.
  • Another serious disadvantage of the conventional procedure is that the bananas, once ripened, must be sold within a few days, or scrapped.
  • Another serious disadvantage of the conventional procedure is that the heat generated by the ripening of the bananas is generated over a relatively short period of time, which heats the bananas to an extent that causes dehydration of the bananas and/or increases the demand on the refrigeration equipment used to keep the bananas cool.
  • the present invention mitigates or overcomes one or more of these disadvantages by packaging bananas in a bag (or other container) having designed permeabilities to oxygen (O 2 ) and carbon dioxide (CO 2 ), and in many aspects of the invention, also to ethylene.
  • Some embodiments of the invention make it possible to maintain bananas, before and/or after their climacteric in a packaging atmosphere which enables storage and/or ripening of green bananas in a controlled fashion.
  • Other embodiment of the invention make it possible to store bananas, after their climacteric, within a desired range of color stages (e.g. within the range most attractive for retail sale) for a longer period than is possible under conventional practice.
  • the containers used in the present invention preferably, but not necessarily, include at least one atmosphere control member which provides a pathway for O 2 and CO 2 , and which comprises a gas-permeable membrane comprising (1) a microporous film, and
  • the atmosphere control member is preferably a control member as described in one or more of copending, commonly assigned US Patent Application Serial Nos. 08/759,602 and 09/121 ,082 and US Patent No. 6,013,293 incorporated by reference herein.
  • Different aspects of the invention make it possible to ripen bananas in a sealed container, for example in a conventional ripening room or while the bananas are being transported; and/or to harvest bananas at a later time than is now possible; and/or to preserve bananas in a satisfactory ripened state for longer than is now possible,
  • this invention provides a container which is suitable for packaging bananas and which has at least one, and preferably both, of the following characteristics
  • the container can be sealed around a quantity of bananas, said quantity being at least 4 kg, preferably at least 15 kg, especially 16 to 22 kg, and, when sealed around the bananas, has an O 2 permeability at 13 °C, per kg of bananas in the container (OP13/kg), of at least 700, preferably at least 1000, particularly at least 1500, ml/atm.24 hrs and an R ratio at 13 °C of at least 2, preferably at least 3, and preferably has an ethylene permeability at 13 °C, per kg of bananas in the container (EtOP13/kg) which is at least 3 times, preferably at least 4 times, the OP13/kg of the container; and (2) the container includes at least one permeable control member which (i) provides a pathway for O 2 , CO 2 and ethylene to enter or leave the packaging atmosphere and (ii) comprises a gas-permeable membrane comprising
  • this invention provides a package which comprises
  • the sealed container having an O 2 permeability at 13 °C, per kg of bananas in the container (OP13/kg), of at least 700, preferably at least 1000, particularly at least 1500, ml/atm.24 hrs and an R ratio at 13 °C of at least 2, preferably at least 3.
  • this invention provides a method of ripening green bananas which comprises
  • this invention provides a sealed package which comprises (a) a sealed container, and (b) within the sealed container, green bananas and a packaging atmosphere around the green bananas; the sealed container having an O 2 permeability at 13 °C, per kg of bananas in the container (OP13/kg), of at least 700, preferably at least 1000, particularly at least 1500, ml/atm.24 hrs, an R ratio at 13 °C of at least 2, preferably at least 3, and an ethylene permeability at 13 °C, per kg of bananas in the container (EtOP13/kg) which is at least 3 times, preferably at least 4 times, the OP13/kg of the container; and (B) placing the sealed package in an atmosphere containing ethylene.
  • this invention provides a method of ripening green bananas which comprises
  • the sealed container having an O 2 permeability at 13 °C, per kg of bananas in the container (OP13/kg), of at least 700, preferably at least 1000, particularly at least 1500, ml/atm.24 hrs, an R ratio at 13 °C of at least 2, preferably at least 3, and an ethylene permeability at 13 °C, per kg of bananas in the container (EtOP13/kg) which is at least 3 times, preferably at least 4 times, the OP13/kg of the container; and (C) exposing the bananas in the sealed package to ethylene from the source of ethylene in the sealed container.
  • O 2 permeability at 13 °C, per kg of bananas in the container OP13/kg
  • the sealed container having an O 2 permeability at 13 °C, per kg of bananas in the container (OP13/kg), of at least 700, preferably at least 1000, particularly at least 1500, ml/atm.24 hrs, an R ratio at 13 °C of at least 2, preferably at
  • this invention provides a method of storing green bananas which comprises
  • this invention provides a package which is stored in air and which comprises
  • the sealed container including at least one permeable control member which provides a pathway for O 2 and CO 2 to enter or leave the packaging atmosphere and which comprises a gas- permeable membrane comprising (1 ) a microporous film, and
  • this invention provides a package which comprises
  • the sealed container including at least one permeable control member which provides a pathway for O 2 ,CO 2 and ethylene to enter or leave the packaging atmosphere and which comprises a gas-permeable membrane comprising
  • this invention provides a method of ripening green bananas which comprises
  • the sealed container including at least one permeable control member which provides a pathway for O 2 ,CO 2 and ethylene to enter or leave the packaging atmosphere and which comprises a gas-permeable membrane comprising
  • this invention provides a method of ripening green bananas which comprises
  • the sealed container including at least one permeable control member which provides a pathway for O 2 ,CO 2 and ethylene to enter or leave the packaging atmosphere and which comprises a gas-permeable membrane comprising
  • this invention provides a method of storing green bananas which comprises (A) placing the green bananas in a container which comprises an atmosphere control member which comprises
  • this invention relates to the use, in packaging bananas, of a container including at least one permeable control member which provides a pathway for O 2 and CO 2 , and which comprises a gas-permeable membrane comprising
  • OTR O 2 permeability
  • COTR CO 2 permeability
  • EtTR ethylene transmission rate
  • OTR, COTR and EtTR values are given in ml/m 2 .atm.24 hrs; in some cases, the equivalent in cc/100 inch 2 .atm.24 hrs is given in parentheses.
  • OTR and COTR values referred to herein can be measured using a permeability cell (supplied by Millipore) in which a mixture of O 2 , CO 2 and helium is applied to the sample, using a pressure of 0.7 kg/cm 2 (10 psi) except where otherwise noted, and the gases passing through the sample were analyzed for O 2 and CO 2 by a gas chromatograph.
  • the cell could be placed in a water bath to control the temperature.
  • the abbreviation P 1 0 is used to denote the ratio of the oxygen permeability at a first temperature T ⁇ °C to the oxygen permeability at a second temperature T 2 , where T 2 is (T- ⁇ -10)°C, Ti being 10 S C and T 2 being 0 Q C unless otherwise noted.
  • the abbreviation R or R ratio is used to denote the ratio of C0 2 permeability to O 2 permeability, both permeabilities being measured at 20°C unless otherwise noted.
  • Pore sizes given in this specification are measured by mercury porosimetry or an equivalent procedure. Parts and percentages are by weight, except for percentages of gases, which are by volume; temperatures are in degrees Centigrade, and molecular weights are weight average molecular weights expressed in Daltons.
  • T 0 is used to denote the onset of melting
  • T p is used to denote the crystalline melting point
  • ⁇ H is used to denote the heat of fusion.
  • T 0 , T p and ⁇ H are measured by means of a differential scanning calorimeter (DSC) at a rate of 10°C/minute and on the second heating cycle.
  • DSC differential scanning calorimeter
  • T p is the temperature at the peak of the DSC curve
  • T 0 is the temperature at the intersection of the baseline of the DSC peak and the onset line, the onset line being defined as the tangent to the steepest part of the DSC curve below T p .
  • sealing bags containing bananas can be, but generally is not, hermetic sealing.
  • Conventional methods for sealing bags of bananas can conveniently be used in this invention. Such conventional methods include, for example, the use of a cable tie to seal the neck of the bag.
  • a moon seal made by conventional methods is not a hermetic seal, and has the advantage that it permits equilibration of the pressures inside and outside the bag. If the bag is sealed hermetically, it will generally be desirable to include one or more pinholes in the bag, to achieve such equilibration.
  • this invention preferably makes use of an atmosphere control member comprising (a) a microporous polymeric film, and (b) a polymeric coating on the microporous film.
  • the microporous polymeric film preferably comprises a network of interconnected pores having an average pore size of less than 0.24 micron, with at least 70% of the pores having a pore size of less than 0.24 micron.
  • the pores in the microporous film constitute 35 to 80% by volume of the microporous film.
  • Preferred microporous films comprise a polymeric matrix comprising (i) an essentially linear ultrahigh molecular weight polyethylene having an intrinsic viscosity of at least 18 deciliters/g, or (ii) an essentially linear ultrahigh molecular weight polypropylene having an intrinsic viscosity of at least 6 deciliters/g, or (iii) a mixture of (i) and (ii).
  • the microporous film may contain 30 to 90% by weight, based on the weight of the film, of a finely divided particulate substantially insoluble filler which is distributed throughout the film.
  • a preferred process for preparing suitable microporous films comprises (A) preparing a uniform mixture comprising the polymeric matrix material in the form of a powder, the filler, and a processing oil;
  • step (E) passing the sheet from step (D) to a first extraction zone in which the processing oil is substantially removed by extraction with an organic extraction liquid which is a good solvent for the processing oil, a poor solvent for the polymeric matrix material, and more volatile than the processing oil;
  • step (F) passing the sheet from step (E) to a second extraction zone in which the organic extraction liquid is substantially removed by steam or water or both;
  • the polymeric coating on the control member preferably comprises a crystalline polymer having a peak melting temperature Tp of -5 to 40 °C, e.g. 0 to 15°C, or 10 to 20 °C, an onset of melting temperature T 0 such that ( T p - T 0 ) is less than 10 °C, and a heat of fusion of at least 5 J/g.
  • the polymer preferably comprises a side chain crystalline polymer moiety comprising, and optionally consisting of, units derived from (i) at least one n-alkyl acrylate or methacrylate (or equivalent monomer, for example an amide) in which the n-aikyl group contains at least 12, preferably at least 14, for example 16-50, preferably 16-22, carbon atoms, for example in amount 35-100%, preferably 50-100%, often 80-100%, and (ii) one or more comonomers selected from acrylic acid, methacrylic acid, and esters of acrylic or methacrylic acid in which the esterifying group contains less than 10 carbon atoms.
  • the polymer can be a block copolymer in which one of blocks is a crystalline polymer as defined and the other block(s) is crystalline or amorphous.
  • Preferred block copolymers comprise polysiloxane polymeric blocks, and (ii) crystalline polymeric blocks having a Tp of -5 to 40 a C.
  • Such a polymer can be prepared by copolymenzing a mixture of reactants which comprises (i) at least one n-alkyl acrylate or methacrylate in which the n-alkyl group contains at least 12 carbon atoms and (ii) a polysiloxane having a copolymerizable group at one end thereof.
  • the gas-permeable membrane preferably has one or more of the following properties
  • control member comprises
  • the apertured cover member being composed of (i) a barrier portion having an O 2 permeability, OTR ar , which is less than 0.5 times, preferably less than 0.01 times, OTR P e rm , and
  • an aperture portion which comprises at least one aperture having an area of at least 0.015 in ,2 and through which the gas-permeable membrane is exposed to the air surrounding the package, the aperture portion being such that the control member has a permeability ratio, Rconhoi, which is at most 0.9, preferably at most 0.8, times R P erm, and which is preferably greater than 1.00.
  • the aperture portion of the cover member may have an area A op ⁇ n which is at most 0.04 times Ape rm , where A pe rm is the area of the gas-permeable membrane.
  • the aperture portion can consist of one or more apertures, each aperture having an area, Ap er t ure , less than 0.155 in 2 .
  • the permeability of the container can be influenced by perforating the container in order to make a plurality of pinholes therein.
  • green bananas are ripened while in a sealed container.
  • This method can be carried out in a conventional ripening room containing ethylene, typically but not necessarily at a concentration of 500 to 1000 ppm. It was surprising to discover that, when using suitable containers, it was unnecessary to follow the conventional practice of opening the bags, and that the bananas would ripen satisfactorily in this way.
  • An important advantage of this method of ripening bananas is that the ripening takes place in a more controlled fashion, resulting in lower peak temperatures in the bananas, which in turn results in reduced dehydration of the bananas and reduced demand upon the refrigeration equipment when the ripening is carried out at temperatures below room temperature.
  • the temperature at which ripening is carried out and the concentration of ethylene in the atmosphere influence the rate at which ripening takes place. In general, slower ripening results in bananas which remain in a desired range of color stage for a longer period. On the other hand, this must be balanced against delivery dates required by retail outlets and inventory constraints. Generally the ethylene-containing atmosphere will be maintained at the temperature less than 22 °C, preferably less than 20 °C, for example 16-21 °C.
  • the atmosphere within the bags will change substantially during the ripening process, as the bananas consume O 2 and generates CO 2 .
  • the packaging atmosphere for at least part of the period before the bananas reach their climacteric, contains at least 10% preferably at least 12%, particularly 14 to 19%, of O 2 , and less than 10%, preferably less than 4%, of CO 2> with the total quantity of O 2 and CO 2 being less than 20 %, preferably less than 17 %.
  • the packaging atmosphere preferably contains at least 0.8%, preferably 1.5 to 6%, especially 1.5 to 3%, of O 2 , and less than 15%, preferably less than 7%, of CO 2 , with the total quantity of O 2 and CO 2 being less than 16%, preferably less than 10 %.
  • green bananas are ripened by means of a source of ethylene placed with the bananas in the sealed container.
  • This aspect of the invention is particularly useful for ripening bananas while they are being transported, for example on a ship.
  • the ripening process can be controlled so that the bananas are at a desired color stage when the bananas reach their destination. During the ripening process, there is no need to alter the normal atmosphere in which the bags of bananas are being transported (though the invention does not exclude the possibility that a controlled atmosphere is used).
  • the source of ethylene can make ethylene available immediately after packaging the bananas, or after a desired delay.
  • relatively slow ripening of the bananas is generally desired, and in consequence the temperature around the bags of bananas is generally controlled, during at least part of the ripening process, at a temperature less than 18 °C, preferably less than 16 °C, for example at 14-15 °C.
  • 2CPA 2- chloroethyl phosphonic acid
  • 2CPA can be used in the form of an aqueous solution, for example of concentration 3-4%.
  • the rate at which 2CPA generates ethylene increases with increasing pH of the aqueous solution, which can be adjusted, for example to more than 4, particularly more than 7, by the addition of suitable materials, for example buffer solutions and/or sodium bicarbonate solutions.
  • a 2CPA solution and any pH adjuster are adsorbed on the same or different absorbent pads, e.g. paper pads, and the pad(s) placed in the bottom of the bag and covered with a polymeric sheet before the bananas are placed in the bag.
  • a solution of 2CPA is applied to the green bananas, for example by dipping or spraying, before the bananas are placed in the bag.
  • the atmosphere within the sealed bags containing the source of ethylene will change during the ripening process.
  • the atmospheres in the bag, for at least part of the periods before and after the climacteric, are preferably as stated above when the bananas are ripened in an ethylene-containing atmosphere. Quantities of bananas
  • the invention can in principle be used for any quantity of bananas. However, when the invention is used for ripening bananas, or for storing green bananas, it is particularly valuable when relatively large quantities are involved. Thus it is generally preferred that the sealed container contains at least 4 kg, preferably least 15 kg, especially 16 to 22 kg of bananas. However, in the sixth aspect of the invention, much smaller quantities (1 to 2.5 kg (2 to 5 lb.) are used in order to increase the shelf life of the bananas at a desired color stage.
  • the invention is illustrated in the following Examples, a number of which are comparative Examples, designated by the letter C before the number of the example.
  • the bananas, bags and control members used in the Examples were as follows. Bananas
  • the bananas were Cavendish bananas, from Ecuador in Examples 1A-B, C11-12, 2, C2, 4A-B and C41-42, from Costa Rica in Examples 5 A-C and C5, and from Colombia in the other Examples. Bags The large bags were about 0.96 m (38 in.) wide and about 1.2 m (50 in.) long, and were made from polyethylene film about 0.056 mm (2.2 mil) thick (available from Roplast Industries under the tradename RA 3030).
  • the polyethylene film had an OTR at 13 °C of about 2915 (188) and at 22 °C of about 4,650 (300), and EtTR at 13 °C of about 11 ,400 (735) and at 22 °C of about 18,100 (1 ,170), an R ratio of about 4.5, and a P10 ratio (between 0 and 10 °C.) of about 1.76.
  • the small bags were about 0.3 m (12 in.) wide and about 0.46 m (18 in.) long, and were made from the same polyethylene film. Control Members
  • the Type S control members were as described in copending commonly assigned U.S. Application Serial No. 09/121 ,082 and corresponding International Publication No. WO 00/04787 and comprised a microporous polyethylene film coated with a polysiloxane/SCC block copolymer.
  • the Type S members had an OTR at 13 °C of about 3,803,850 (245,410) and at 22 °C of about 5,000,000 (324,000), an EtTR at 13 °C of about 16,280,000 (1 ,050,300) and at 22 °C of about 19,500,000 (1 ,260,000), an R ratio of about 3.8, and a P10 ratio (between 0 and 10 °C.) of about 1.8.
  • the microporous polyethylene film contained 50-60% silica, had a thickness of about 0.18 mm (0.007 inch), a tear strength of about 90g, a porosity of about 65%, an average pore size of about 0.1 micron and a largest pore size of 4-10 microns (available from PPG industries under the tradename Teslin SP 7).
  • the block copolymer was prepared by the reaction of a polydimethyl siloxane terminated one end only by a methacryloxypropyl group (available from Gelest under the tradename MCR M17), 40 parts, dodecyl acrylate, 26.8 parts and tetradecyl acrylate, 33.2 parts, as described in Example A7 of U.S. Application Serial No. 09/121 ,082 and corresponding International Publication No. WO 00/04787.
  • the Type A control members were as described in copending commonly assigned U.S. Application Serial No. 08/759,602 and corresponding International Publication No. WO 96/38495, and comprised the same microporous polyethylene film coated with an SCC polymer of dodecyl acrylate, 42 parts, tetradecyl acrylate, 53 parts, and acrylic acid, 5 parts.
  • the Type A members had an OTR at 22 °C of about 1 ,705,000 (110,000), an R ratio of about 4, and a P10 ratio (between 0 and 10 °C.) of about 1.4.
  • control member was secured to a portion of the bag in which one or more round holes had been cut.
  • the effective area of the control member is about equal to the area of the hole or holes in the portion of the bag to which the control member is attached.
  • the periphery of the control member was heat sealed to the interior of the bag, thus creating a control member of the kind described in United States Patent No. 6,013,293.
  • the control member was secured to the exterior of the bag by means of a layer of a pressure sensitive adhesive on the peripheral margin of the control member.
  • Bananas are preferably at color stage 3.5 to 5 when put on retail sale. Many of the Examples are summarized in Tables 1-8 below. In the Tables, when more than one result is given for a particular Example, this reflects the fact that more than one test was carried out under the same conditions. Examples 1A-B. C11-12. 2 and C2
  • each bag has one S-type control member placed under two or more holes in the bag.
  • the control member had an area of 1935 mm 2 (3 in 2 ) and was placed under two holes, each of diameter 20.6 mm (0.81 in.).
  • the control member had an area of 6450 mm 2 (10 in 2 ) and was placed under 6 holes, each of diameter 20.6 mm (0.81 in.).
  • the control member had an area of 12,900 mm 2 (20 in 2 ) and was placed under 6 holes, each of diameter 28.7 mm (1.13 in).
  • Each bag was packed with about 20 kg (44 lb) of green bananas.
  • the bananas had been harvested at week 11 and maintained at 13-14 °C for about 11 days after harvest before being packed. Except in Examples C12 and C2, excess air was extracted from the bags using a vacuum pump, and the bags were then sealed using tie wraps. In Examples C12 and C2, the bags were left open. The bags were maintained at 13 °C. for an extended time,
  • Example 2 (generated by the ripening of the bananas) remained in the test chamber from Example 1 and caused the bananas to ripen more rapidly than in the otherwise substantially identical Example
  • each bag has one S-type control member placed under one or more holes in the bag.
  • the control member had an area of 967 mm 2 (1.5 in 2 ) and was placed under a single hole of diameter 20.6 mm (0.81 in.).
  • the control member had an area of 1935 mm 2 (3 in 2 ) and was placed under 2 holes, each of diameter 20.6 mm (0.81 in.).
  • the control member had an area of 3225 mm 2 (5 in 2 ) and was placed under 4 holes, each of diameter 19 mm (0.75 in.).
  • Example 3 the control member had an area of 12,900 mm 2 (20 in 2 ) and was placed under 6 holes, each of diameter 25 mm (1 in.).
  • Example C34 the bag did not have a control member.
  • Each bag was packed with about 18.1 kg (40 lb) of green bananas. The bananas had been harvested at week 13, and maintained at 13-14°C for about 11 days after harvest before being packed. Except in Example C34, excess air was extracted from the bags using a vacuum pump, and then securely tied (the bags were not, however, as completely sealed as in Examples 1 and 2). In Example C34, the bags were left open. The sealed bags were cooled to about 13 °C and shipped to Gulfport, Mississippi, and then to San Francisco, California, maintaining the temperature at about 13 °C.
  • each bag has one A-type control member placed over four or five holes in the bag.
  • the control member had an area of 145 mm 2 (5.7 in 2 ) and was placed over four holes each of diameter 19 mm (0.75 in.).
  • the control member had an area of 4516 mm 2 (7 in 2 ) and was placed over 5 holes, each of diameter 19 mm (0.75 in.).
  • the control member and the holes under it were as in Example 4A, except that the control member was an uncoated microporous film.
  • the bag was intact except for 200 pinholes each about 0.5 mm (26 gauge) in diameter.
  • Example C42 Each bag was packed with about 1.35 kg (3 lb) of green bananas which had been maintained at 13-14 °C for about 11 days after harvest. Except in Example C42, excess air was extracted from the bags using a vacuum pump, and the bags were then securely tied. In Example C42, the bags were left open. After three days, to allow the packaging atmosphere to equilibrate, the bags were exposed to ethylene (500-1000 ppm) in a ripening room. The results are shown in Table 3 below. These Examples demonstrate that small quantities of bananas can be ripened in a suitably designed bag, and can remain in the bag in excellent condition for several days longer than bananas exposed to the air. Table 3
  • Example C5 Each control member was placed over a single hole in the bag, the hole having an diameter of 70 mm (2.75 in.) in Example 5A, 74.4 mm (2.93 in.) in Example 5B, and 78.7 mm (3.1 in.) in Example 5C.
  • the bag was perforated so that the bananas were surrounded by air.
  • the bags were then sealed with rubber bands.
  • the sealed bags were placed in a refrigerated room at about 13 °C. After about 84 hours, the temperature of the room was raised to about 16.7 °C and after about 12 hours, an ethylene generator was used to provide an initial ethylene concentration in the room of 500-1000 ppm. About 24 hours after the generation of ethylene had begun, the room was vented.
  • the temperature of the bananas was monitored for about 15 days, and reached a peak at about 60 hours after the generation of ethylene had begun. At that time, the concentration of O 2 and CO 2 was measured. The results are shown in Table 4 below. It will be seen that the peak temperature was substantially lower in the bags containing control members than in the perforated bag. Table 4
  • Each of these Examples uses a large bag having two S-type control members, each control member having an area of 11 ,300 mm 2 (17.5 in 2 ). Each control member was placed over seven holes in the bag, each hole of diameter 25.4 mm (1 in). A paper pad about 300 x 400 mm (12 x 16 in.) impregnated with an aqueous solution of 2CPA (3.9%) was placed in the bottom of each bag and covered with a sheet of polyethylene. The amount of the solution varied from Example to Example, and is shown in Table 5 below. About 18.1 kg (40 lb.) of green bananas were then placed in each bag, and the bags were sealed with rubber bands. The green bananas had been maintained at 13-14 °C for about 11 days after harvest. The sealed bags were left in a cold room at 13-14 °C. The color stage of the bananas was monitored, and Table 5 below shows the time in days taken to reach color stages 4 and 5.5.
  • Examples 7A-D there was a single hole, diameter 82.5 mm (3.25 in.), under each of the two control members. The total area of the holes was 10,700 mm 2 .
  • Example 7A, 7B and 7C and in comparative Examples C72 and C73 a paper pad impregnated with 0.1 N NaHCO 3 solution was placed adjacent to the paper pad impregnated with 2CPA solution, thus increasing the pH of the 2CPA solution and increasing the rate at which ethylene was generated.
  • the amount of the NaHCO 3 solution varied from Example to Example as shown in Table 6 below.
  • Comparative Examples C71 -74 were carried out in which no ethylene was used (C71 ), or the bag was sealed but did not have a control member (C 72-73), or the bag was not sealed (C74). 5. The ethylene concentration in the bags was measured at various times after packing. The results obtained are shown in Table 6 below.
  • Examples 8A-J and C 81-83 followed the same procedure as Examples 7A-C and C71- 74 except for the changes noted below.
  • the second paper pad was impregnated with 30 mL of an aqueous buffer solution (i) containing potassium phthalate and having a pH of 4, (ii) containing dibasic sodium phosphate, monobasic potassium phosphate, sodium chromate and potassium dichromate, and having a pH of 7, or (iii) containing sodium carbonate and sodium bicarbonate and having a pH of 10.
  • aqueous buffer solution containing potassium phthalate and having a pH of 4
  • dibasic sodium phosphate, monobasic potassium phosphate, sodium chromate and potassium dichromate and having a pH of 7
  • sodium carbonate and sodium bicarbonate having a pH of 10.
  • Example 8G the sealed bags were left in a room at about 21 °C (in the other Examples, the room was at 13-14 °C).
  • Example C83 the bag was not sealed. The results are shown in Table 7 below.
  • Example 6 The procedure of Example 6 was followed, except for the changes noted below.
  • Comparative Examples C91 and C92 were carried out in which the bag did not have a control member (C91) or the bananas were not treated with 2CPA solution (C92). Comparative Example C91 is the same as the comparative Example C71.
  • Table 9 shows, for each of the bags in Examples 5A-C, 6A-E and 7A-E, the permeability of the bag to O 2 and to ethylene ("Et" in Table 9), and the respective contributions of the control member and the remainder of the bag.
  • Et the size of the bag, after sealing, was assumed to be 0.96 x 1.04 m (38 in. x 41 in.), i.e. to have a total area of 2 m 2 (3115 in 2 ).

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Abstract

Packaging of bananas in containers having designed permeabilities to oxygen, carbon dioxide, and ethylene. The containers preferably include a gas-permeable membrane comprising (1) a microporous film, and (2) a polymeric coating on the microporous film. The container enable storage and/or ripening of bananas under controlled conditions. Using the new containers, bananas can be ripened while they are being transported, or in conventional ripening rooms without opening the bags in which they have been transported. In addition, bananas can be preserved in a satisfactory ripened state for longer periods of time.

Description

PACKAGING OF BANANAS
This invention relates to the packaging of bananas.
Respiring biological materials consume oxygen (O2) and produce carbon dioxide (CO2) at rates which depend upon temperature and the stage of their development. Ideally, a respiring material should be stored in a container whose permeability to O2 and CO2 is correlated with (i) the atmosphere outside the package, (ii) the rates at which the material consumes O2 and produces CO2, and (iii) the temperature, to produce the desired atmosphere within the container. This is the principle behind the technology of controlled atmosphere packaging (CAP) and modified atmosphere packaging (MAP), as discussed, for example, in US Patent Nos. 3,450,542 (Badran), 3,450,544 (Badran et al.), 3,798,333 (Cummin et al. 4,734,324 (Hill), 4,830,863 (Jones), 4,842,875 (Anderson), 4,879,078 (Antoon), 4,910,032 (Antoon), 4,923,703 (Antoon), 5,045,331 (Antoon), 5,160,768 (Antoon), 5,254,354 (Stewart) and 6,013,293 (De Moor), copending commonly assigned US Patent Application Serial Numbers 08/759,602 (Clarke et al.) and 09/121 ,082 (Clarke et al.), International Publication Numbers WO 94/12040 (Fresh Western), WO 96/38495 (Landec) and WO 00/04787 (Landec), and European Patent Applications Nos. 0,351 ,115 and 0,351 ,116 (Courtaulds). The disclosure of each of these patents, applications and publications is incorporated herein by reference.
Bananas are respiring biological materials whose storage and ripening present the most serious problems because
(i) bananas are grown in locations far distant from the locations at which they are consumed;
(ii) they are damaged by storage at temperatures below about 14.4 °C, with the extent of the damage depending upon the time spent below that temperature and how far the temperature is below 14.4 °C (58 °F);
(iii) they go through a climacteric when they ripen, thus producing a very large increase in respiration rate and the generation of heat;
(iv) they generate ethylene as they ripen, and they ripen at a rate which increases with the concentration of ethylene around them ~ as a result, a single prematurely ripe banana can trigger premature ripening of many others; and
(iv) once they have ripened, and have been exposed to air, they rapidly become overripe. These problems have not yet been solved. The conventional procedure is to harvest the bananas when they are hard, green and unripe; to transport the green bananas, at 13-14 °C, to the location where they will be consumed; to ripen the green bananas by exposing them to ethylene in a ripening room at that location; and to place the ripened bananas on sale. The time at which the bananas are harvested depends on the time needed to transport them to the point- of-sale. Thus bananas are typically harvested at week 11 (i.e. 11 weeks after the flower emerges from the plant) or week 12. The green bananas are shipped in bags made of polyethylene about 0.04 to 0.06 mm (1.5-2.5 mil) thick, with each bag containing about 18 kg (40 lb) of bananas and being supported by a cardboard box. In many cases, after the bananas have been placed in the bag, most of the air is exhausted from the bag, and the bag is then sealed; this is the procedure generally described in US Patent No. 3,450,542 (Badran). In other cases, the bag contains vent holes.
A serious disadvantage of the conventional procedure is the need to harvest the bananas a good while before they are fully grown. It would be desirable to harvest the bananas at a later time, when they are larger. However, the later the bananas are picked, the greater the propensity for their climacteric to be triggered by small concentrations of ethylene, and experience has shown that if the bananas are harvested later than the presently established timetables, this results in prematurely ripe bananas when the bananas are shipped in vented bags, and in so-called "green-ripe" bananas when the bananas are shipped in sealed bags. Green-ripe bananas soften, but remain green, and have an unpleasant flavor.
Another serious disadvantage of the conventional procedure is that, in order to ripen the green bananas by exposing them to ethylene, it is necessary to open each of the shipping bags if, as in most cases, the bags have been sealed during shipping. Another serious disadvantage of the conventional procedure is that the bananas, once ripened, must be sold within a few days, or scrapped.
Another serious disadvantage of the conventional procedure is that the heat generated by the ripening of the bananas is generated over a relatively short period of time, which heats the bananas to an extent that causes dehydration of the bananas and/or increases the demand on the refrigeration equipment used to keep the bananas cool.
The present invention mitigates or overcomes one or more of these disadvantages by packaging bananas in a bag (or other container) having designed permeabilities to oxygen (O2) and carbon dioxide (CO2), and in many aspects of the invention, also to ethylene. Some embodiments of the invention make it possible to maintain bananas, before and/or after their climacteric in a packaging atmosphere which enables storage and/or ripening of green bananas in a controlled fashion. Other embodiment of the invention make it possible to store bananas, after their climacteric, within a desired range of color stages (e.g. within the range most attractive for retail sale) for a longer period than is possible under conventional practice.
The containers used in the present invention preferably, but not necessarily, include at least one atmosphere control member which provides a pathway for O2 and CO2, and which comprises a gas-permeable membrane comprising (1) a microporous film, and
(2) a polymeric coating on the microporous film.
The atmosphere control member is preferably a control member as described in one or more of copending, commonly assigned US Patent Application Serial Nos. 08/759,602 and 09/121 ,082 and US Patent No. 6,013,293 incorporated by reference herein. Different aspects of the invention make it possible to ripen bananas in a sealed container, for example in a conventional ripening room or while the bananas are being transported; and/or to harvest bananas at a later time than is now possible; and/or to preserve bananas in a satisfactory ripened state for longer than is now possible, In a first aspect, this invention provides a container which is suitable for packaging bananas and which has at least one, and preferably both, of the following characteristics
(1 ) the container can be sealed around a quantity of bananas, said quantity being at least 4 kg, preferably at least 15 kg, especially 16 to 22 kg, and, when sealed around the bananas, has an O2 permeability at 13 °C, per kg of bananas in the container (OP13/kg), of at least 700, preferably at least 1000, particularly at least 1500, ml/atm.24 hrs and an R ratio at 13 °C of at least 2, preferably at least 3, and preferably has an ethylene permeability at 13 °C, per kg of bananas in the container (EtOP13/kg) which is at least 3 times, preferably at least 4 times, the OP13/kg of the container; and (2) the container includes at least one permeable control member which (i) provides a pathway for O2, CO2 and ethylene to enter or leave the packaging atmosphere and (ii) comprises a gas-permeable membrane comprising
(a) a microporous polymeric film, and
(b) a polymeric coating on the microporous film. In a second aspect, this invention provides a package which comprises
(a) a sealed container, and
(b) within the sealed container, bananas and a packaging atmosphere around the bananas; the sealed container having an O2 permeability at 13 °C, per kg of bananas in the container (OP13/kg), of at least 700, preferably at least 1000, particularly at least 1500, ml/atm.24 hrs and an R ratio at 13 °C of at least 2, preferably at least 3.
In a third aspect, this invention provides a method of ripening green bananas which comprises
(A) providing a sealed package which comprises (a) a sealed container, and (b) within the sealed container, green bananas and a packaging atmosphere around the green bananas; the sealed container having an O2 permeability at 13 °C, per kg of bananas in the container (OP13/kg), of at least 700, preferably at least 1000, particularly at least 1500, ml/atm.24 hrs, an R ratio at 13 °C of at least 2, preferably at least 3, and an ethylene permeability at 13 °C, per kg of bananas in the container (EtOP13/kg) which is at least 3 times, preferably at least 4 times, the OP13/kg of the container; and (B) placing the sealed package in an atmosphere containing ethylene. In a fourth aspect, this invention provides a method of ripening green bananas which comprises
(A) placing, in a sealable container,
(a) the green bananas, and
(b) a source of ethylene;
(B) sealing the container around the green bananas and the source of ethylene, thus providing a sealed package which comprises
(a) a sealed container, and
(b) within the sealed container, the green bananas, the source of ethylene, and a packaging atmosphere around the green bananas; the sealed container having an O2 permeability at 13 °C, per kg of bananas in the container (OP13/kg), of at least 700, preferably at least 1000, particularly at least 1500, ml/atm.24 hrs, an R ratio at 13 °C of at least 2, preferably at least 3, and an ethylene permeability at 13 °C, per kg of bananas in the container (EtOP13/kg) which is at least 3 times, preferably at least 4 times, the OP13/kg of the container; and (C) exposing the bananas in the sealed package to ethylene from the source of ethylene in the sealed container.
In a fifth aspect, this invention provides a method of storing green bananas which comprises
(A) placing the green bananas in a container which comprises an atmosphere control member which comprises (1 ) a microporous film, and
(2) a polymeric coating on the microporous film;
(B) sealing the container, thus providing a sealed package which comprises (a) a sealed container, and
(a) within the sealed container, the green bananas, and a packaging atmosphere around the green bananas; and
(C) maintaining the sealed bag at the temperature of 13-18 °C. In a sixth aspect, this invention provides a package which is stored in air and which comprises
(a) a sealed container, and
(b) within the sealed container, 1 to 2.5 kg (2 to 5 lb) of bananas which have passed their climacteric and which are at a color stage less than 5, and a packaging atmosphere around the bananas; the sealed container including at least one permeable control member which provides a pathway for O2 and CO2 to enter or leave the packaging atmosphere and which comprises a gas- permeable membrane comprising (1 ) a microporous film, and
(2) a polymeric coating on the microporous film; and the packaging atmosphere containing at least 0.8%, preferably 1.5 to 6%, especially 1.5 to 3%, of O2l and less than 15%, preferably less than 7%, of CO2 , with the total quantity of O2 and CO2 being less than 16%, preferably less than 10 %. In a seventh aspect, this invention provides a package which comprises
(a) a sealed container, and
(b) within the sealed container, bananas and a packaging atmosphere around the bananas; the sealed container including at least one permeable control member which provides a pathway for O2 ,CO2 and ethylene to enter or leave the packaging atmosphere and which comprises a gas-permeable membrane comprising
(a) a microporous polymeric film, and
(b) a polymeric coating on the microporous film.
In an eighth aspect, this invention provides a method of ripening green bananas which comprises
(A) providing a sealed package which comprises
(a) a sealed container, and
(b) within the sealed container, green bananas and a packaging atmosphere around the green bananas; the sealed container including at least one permeable control member which provides a pathway for O2 ,CO2 and ethylene to enter or leave the packaging atmosphere and which comprises a gas-permeable membrane comprising
(a) a microporous polymeric film, and
(b) a polymeric coating on the microporous film; and (B) placing the sealed package in an atmosphere containing ethylene. In a ninth aspect, this invention provides a method of ripening green bananas which comprises
(A) placing, in a sealable container, (a) the green bananas, and (b) a source of ethylene;
(B) sealing the container around the green bananas and the source of ethylene, thus providing a sealed package which comprises
(a) a sealed container, and
(b) within the sealed container, the green bananas, the source of ethylene, and a packaging atmosphere around the green bananas; the sealed container including at least one permeable control member which provides a pathway for O2 ,CO2 and ethylene to enter or leave the packaging atmosphere and which comprises a gas-permeable membrane comprising
(a) a microporous polymeric film, and (b) a polymeric coating on the microporous film; and
(C) exposing the bananas in the sealed package to ethylene from the source of ethylene in the sealed container.
In a tenth aspect, this invention provides a method of storing green bananas which comprises (A) placing the green bananas in a container which comprises an atmosphere control member which comprises
(1) a microporous film, and
(2) a polymeric coating on the microporous film;
(B) sealing the container, thus providing a sealed package which comprises (a) a sealed container, and
(b) within the sealed container, the green bananas, and a packaging atmosphere around the green bananas; and
(C) maintaining the sealed bag at the temperature of 13-18 °C.
In an eleventh aspect, this invention relates to the use, in packaging bananas, of a container including at least one permeable control member which provides a pathway for O2 and CO2, and which comprises a gas-permeable membrane comprising
(1) a microporous film, and
(2) a polymeric coating on the microporous film.
In this specification, including the Examples and the Claims below, reference is made to particular features of the invention. It is to be understood that the disclosure of the invention in this specification includes all appropriate combinations of such particular features. For example, where a particular feature is disclosed in the context of a particular aspect or embodiment of the invention, or a particular claim, that feature can also be used, to the extent appropriate, in the context of other particular aspects and embodiments of the invention, and in the invention generally. In describing and claiming the invention below, the following abbreviations, definitions, and methods of measurement are used. OTR is O2 permeability. COTR is CO2 permeability. EtTR is ethylene transmission rate. OTR, COTR and EtTR values are given in ml/m2.atm.24 hrs; in some cases, the equivalent in cc/100 inch2.atm.24 hrs is given in parentheses. OTR and COTR values referred to herein can be measured using a permeability cell (supplied by Millipore) in which a mixture of O2, CO2 and helium is applied to the sample, using a pressure of 0.7 kg/cm2 (10 psi) except where otherwise noted, and the gases passing through the sample were analyzed for O2 and CO2 by a gas chromatograph. The cell could be placed in a water bath to control the temperature. The abbreviation P10 is used to denote the ratio of the oxygen permeability at a first temperature Tι°C to the oxygen permeability at a second temperature T2, where T2 is (T-ι-10)°C, Ti being 10SC and T2 being 0QC unless otherwise noted. The abbreviation R or R ratio is used to denote the ratio of C02 permeability to O2 permeability, both permeabilities being measured at 20°C unless otherwise noted. Pore sizes given in this specification are measured by mercury porosimetry or an equivalent procedure. Parts and percentages are by weight, except for percentages of gases, which are by volume; temperatures are in degrees Centigrade, and molecular weights are weight average molecular weights expressed in Daltons. For crystalline polymers, the abbreviation T0 is used to denote the onset of melting, the abbreviation Tp is used to denote the crystalline melting point, and the abbreviation ΔH is used to denote the heat of fusion. T0, Tp and ΔH are measured by means of a differential scanning calorimeter (DSC) at a rate of 10°C/minute and on the second heating cycle. T0 and Tp are measured in the conventional way well known to those skilled in the art. Thus Tp is the temperature at the peak of the DSC curve, and T0 is the temperature at the intersection of the baseline of the DSC peak and the onset line, the onset line being defined as the tangent to the steepest part of the DSC curve below Tp.
Where reference is made herein to sealing bags containing bananas, it is to be understood that the sealing can be, but generally is not, hermetic sealing. Conventional methods for sealing bags of bananas can conveniently be used in this invention. Such conventional methods include, for example, the use of a cable tie to seal the neck of the bag. A moon seal made by conventional methods is not a hermetic seal, and has the advantage that it permits equilibration of the pressures inside and outside the bag. If the bag is sealed hermetically, it will generally be desirable to include one or more pinholes in the bag, to achieve such equilibration. Control Members
As noted above, this invention preferably makes use of an atmosphere control member comprising (a) a microporous polymeric film, and (b) a polymeric coating on the microporous film. The microporous polymeric film preferably comprises a network of interconnected pores having an average pore size of less than 0.24 micron, with at least 70% of the pores having a pore size of less than 0.24 micron. Preferably the pores in the microporous film constitute 35 to 80% by volume of the microporous film. Preferred microporous films comprise a polymeric matrix comprising (i) an essentially linear ultrahigh molecular weight polyethylene having an intrinsic viscosity of at least 18 deciliters/g, or (ii) an essentially linear ultrahigh molecular weight polypropylene having an intrinsic viscosity of at least 6 deciliters/g, or (iii) a mixture of (i) and (ii). The microporous film may contain 30 to 90% by weight, based on the weight of the film, of a finely divided particulate substantially insoluble filler which is distributed throughout the film. A preferred process for preparing suitable microporous films comprises (A) preparing a uniform mixture comprising the polymeric matrix material in the form of a powder, the filler, and a processing oil;
(B) extruding the mixture as a continuous sheet;
(C) forwarding the continuous sheet, without drawing, to a pair of heated calender rolls; (D) passing the continuous sheet through the calender rolls to form a sheet of lesser thickness;
(E) passing the sheet from step (D) to a first extraction zone in which the processing oil is substantially removed by extraction with an organic extraction liquid which is a good solvent for the processing oil, a poor solvent for the polymeric matrix material, and more volatile than the processing oil;
(F) passing the sheet from step (E) to a second extraction zone in which the organic extraction liquid is substantially removed by steam or water or both; and
(G) passing the sheet from step (F) through a forced air dryer to remove residual water and organic extraction liquid. The polymeric coating on the control member preferably comprises a crystalline polymer having a peak melting temperature Tp of -5 to 40 °C, e.g. 0 to 15°C, or 10 to 20 °C, an onset of melting temperature T0 such that ( Tp- T0) is less than 10 °C, and a heat of fusion of at least 5 J/g. The polymer preferably comprises a side chain crystalline polymer moiety comprising, and optionally consisting of, units derived from (i) at least one n-alkyl acrylate or methacrylate (or equivalent monomer, for example an amide) in which the n-aikyl group contains at least 12, preferably at least 14, for example 16-50, preferably 16-22, carbon atoms, for example in amount 35-100%, preferably 50-100%, often 80-100%, and (ii) one or more comonomers selected from acrylic acid, methacrylic acid, and esters of acrylic or methacrylic acid in which the esterifying group contains less than 10 carbon atoms. The polymer can be a block copolymer in which one of blocks is a crystalline polymer as defined and the other block(s) is crystalline or amorphous. Preferred block copolymers comprise polysiloxane polymeric blocks, and (ii) crystalline polymeric blocks having a Tp of -5 to 40aC. Such a polymer can be prepared by copolymenzing a mixture of reactants which comprises (i) at least one n-alkyl acrylate or methacrylate in which the n-alkyl group contains at least 12 carbon atoms and (ii) a polysiloxane having a copolymerizable group at one end thereof.
Other polymers which can be used to the coat the microporous film include cis- polybutadiene, poly (4-methyIpentene), polydimethyl siloxane, and ethylene-propylene rubber. The gas-permeable membrane preferably has one or more of the following properties
(i) a P10 ratio, over at least one 10eC range between -5 and 15 °C or between 10 and
20 °C, of at least 2.0 to 2.8; (ii) an oxygen permeability at all temperatures between 209 and 259C of 2,480,000 to 7,000,000 ml/m2.atm.24 hr. (160,000 to 450,000 cc/100 in2.atm.24hr); and (iii) an R ratio of at least 2.0, preferably at least 3.0, particularly at least 3.5.
In one embodiment, the control member comprises
(a) the gas-permeable membrane; and
(b) an apertured cover member which lies between the gas-permeable membrane and the air surrounding the package; the gas permeable membrane having, in the absence of the apertured cover member,
(i) an O2 permeability, OTRperm, of at least 155,000 ml/m2 • atm «24 hr
(10,000 cc/100 in2 • atm • 24 hr), and (ii) a permeability ratio, RPerm, of at least 2, and the apertured cover member being composed of (i) a barrier portion having an O2 permeability, OTR ar, which is less than 0.5 times, preferably less than 0.01 times, OTRPerm, and
(ii) an aperture portion which comprises at least one aperture having an area of at least 0.015 in ,2 and through which the gas-permeable membrane is exposed to the air surrounding the package, the aperture portion being such that the control member has a permeability ratio, Rconhoi, which is at most 0.9, preferably at most 0.8, times RPerm, and which is preferably greater than 1.00. The aperture portion of the cover member may have an area Aopθn which is at most 0.04 times Aperm, where Aperm is the area of the gas-permeable membrane. The aperture portion can consist of one or more apertures, each aperture having an area, Aperture, less than 0.155 in2. For further details of such atmosphere for control members, reference should be made to U.S. Patent No. 6,013,293.
The permeability of the container, whether or not it includes an atmosphere control member, can be influenced by perforating the container in order to make a plurality of pinholes therein.
Ripening bananas in an ethylene atmosphere
In the third and eight aspects of the invention, green bananas are ripened while in a sealed container. This method can be carried out in a conventional ripening room containing ethylene, typically but not necessarily at a concentration of 500 to 1000 ppm. It was surprising to discover that, when using suitable containers, it was unnecessary to follow the conventional practice of opening the bags, and that the bananas would ripen satisfactorily in this way. An important advantage of this method of ripening bananas is that the ripening takes place in a more controlled fashion, resulting in lower peak temperatures in the bananas, which in turn results in reduced dehydration of the bananas and reduced demand upon the refrigeration equipment when the ripening is carried out at temperatures below room temperature.
The temperature at which ripening is carried out and the concentration of ethylene in the atmosphere influence the rate at which ripening takes place. In general, slower ripening results in bananas which remain in a desired range of color stage for a longer period. On the other hand, this must be balanced against delivery dates required by retail outlets and inventory constraints. Generally the ethylene-containing atmosphere will be maintained at the temperature less than 22 °C, preferably less than 20 °C, for example 16-21 °C.
The atmosphere within the bags will change substantially during the ripening process, as the bananas consume O2 and generates CO2 . Preferably, the packaging atmosphere, for at least part of the period before the bananas reach their climacteric, contains at least 10% preferably at least 12%, particularly 14 to 19%, of O2 , and less than 10%, preferably less than 4%, of CO2> with the total quantity of O2 and CO2 being less than 20 %, preferably less than 17 %. For at least part of the period after the bananas have passed their climacteric, the packaging atmosphere preferably contains at least 0.8%, preferably 1.5 to 6%, especially 1.5 to 3%, of O2, and less than 15%, preferably less than 7%, of CO2 , with the total quantity of O2 and CO2 being less than 16%, preferably less than 10 %.
Ripening bananas using a source of ethylene within the container In the third and ninth aspects of the invention, green bananas are ripened by means of a source of ethylene placed with the bananas in the sealed container. This aspect of the invention is particularly useful for ripening bananas while they are being transported, for example on a ship. The ripening process can be controlled so that the bananas are at a desired color stage when the bananas reach their destination. During the ripening process, there is no need to alter the normal atmosphere in which the bags of bananas are being transported (though the invention does not exclude the possibility that a controlled atmosphere is used). The source of ethylene can make ethylene available immediately after packaging the bananas, or after a desired delay. In these aspects of the invention, relatively slow ripening of the bananas is generally desired, and in consequence the temperature around the bags of bananas is generally controlled, during at least part of the ripening process, at a temperature less than 18 °C, preferably less than 16 °C, for example at 14-15 °C.
Any convenient source of ethylene can be used, i have obtained good results using 2- chloroethyl phosphonic acid, which is often referred to herein as 2CPA. 2CPA can be used in the form of an aqueous solution, for example of concentration 3-4%. The rate at which 2CPA generates ethylene increases with increasing pH of the aqueous solution, which can be adjusted, for example to more than 4, particularly more than 7, by the addition of suitable materials, for example buffer solutions and/or sodium bicarbonate solutions. In one embodiment, a 2CPA solution and any pH adjuster are adsorbed on the same or different absorbent pads, e.g. paper pads, and the pad(s) placed in the bottom of the bag and covered with a polymeric sheet before the bananas are placed in the bag. In another embodiment, a solution of 2CPA is applied to the green bananas, for example by dipping or spraying, before the bananas are placed in the bag. As in the aspects of the invention which involve ripening in an ethylene-containing atmosphere, the atmosphere within the sealed bags containing the source of ethylene will change during the ripening process. The atmospheres in the bag, for at least part of the periods before and after the climacteric, are preferably as stated above when the bananas are ripened in an ethylene-containing atmosphere. Quantities of bananas
The invention can in principle be used for any quantity of bananas. However, when the invention is used for ripening bananas, or for storing green bananas, it is particularly valuable when relatively large quantities are involved. Thus it is generally preferred that the sealed container contains at least 4 kg, preferably least 15 kg, especially 16 to 22 kg of bananas. However, in the sixth aspect of the invention, much smaller quantities (1 to 2.5 kg (2 to 5 lb.) are used in order to increase the shelf life of the bananas at a desired color stage. EXAMPLES
The invention is illustrated in the following Examples, a number of which are comparative Examples, designated by the letter C before the number of the example. The bananas, bags and control members used in the Examples were as follows. Bananas
The bananas were Cavendish bananas, from Ecuador in Examples 1A-B, C11-12, 2, C2, 4A-B and C41-42, from Costa Rica in Examples 5 A-C and C5, and from Colombia in the other Examples. Bags The large bags were about 0.96 m (38 in.) wide and about 1.2 m (50 in.) long, and were made from polyethylene film about 0.056 mm (2.2 mil) thick (available from Roplast Industries under the tradename RA 3030). The polyethylene film had an OTR at 13 °C of about 2915 (188) and at 22 °C of about 4,650 (300), and EtTR at 13 °C of about 11 ,400 (735) and at 22 °C of about 18,100 (1 ,170), an R ratio of about 4.5, and a P10 ratio (between 0 and 10 °C.) of about 1.76. The small bags were about 0.3 m (12 in.) wide and about 0.46 m (18 in.) long, and were made from the same polyethylene film. Control Members
The Type S control members were as described in copending commonly assigned U.S. Application Serial No. 09/121 ,082 and corresponding International Publication No. WO 00/04787 and comprised a microporous polyethylene film coated with a polysiloxane/SCC block copolymer. The Type S members had an OTR at 13 °C of about 3,803,850 (245,410) and at 22 °C of about 5,000,000 (324,000), an EtTR at 13 °C of about 16,280,000 (1 ,050,300) and at 22 °C of about 19,500,000 (1 ,260,000), an R ratio of about 3.8, and a P10 ratio (between 0 and 10 °C.) of about 1.8. The microporous polyethylene film contained 50-60% silica, had a thickness of about 0.18 mm (0.007 inch), a tear strength of about 90g, a porosity of about 65%, an average pore size of about 0.1 micron and a largest pore size of 4-10 microns (available from PPG industries under the tradename Teslin SP 7). The block copolymer was prepared by the reaction of a polydimethyl siloxane terminated one end only by a methacryloxypropyl group (available from Gelest under the tradename MCR M17), 40 parts, dodecyl acrylate, 26.8 parts and tetradecyl acrylate, 33.2 parts, as described in Example A7 of U.S. Application Serial No. 09/121 ,082 and corresponding International Publication No. WO 00/04787.
The Type A control members were as described in copending commonly assigned U.S. Application Serial No. 08/759,602 and corresponding International Publication No. WO 96/38495, and comprised the same microporous polyethylene film coated with an SCC polymer of dodecyl acrylate, 42 parts, tetradecyl acrylate, 53 parts, and acrylic acid, 5 parts. The Type A members had an OTR at 22 °C of about 1 ,705,000 (110,000), an R ratio of about 4, and a P10 ratio (between 0 and 10 °C.) of about 1.4.
In each Example, the control member was secured to a portion of the bag in which one or more round holes had been cut. The effective area of the control member is about equal to the area of the hole or holes in the portion of the bag to which the control member is attached. However, in Examples 1A-B, C11 -12, 2, C2, 3A-D and C31-33, the periphery of the control member was heat sealed to the interior of the bag, thus creating a control member of the kind described in United States Patent No. 6,013,293. In the other Examples, the control member was secured to the exterior of the bag by means of a layer of a pressure sensitive adhesive on the peripheral margin of the control member.
The color stages referred to in the Examples are those accepted by the industry and as shown below.
Bananas are preferably at color stage 3.5 to 5 when put on retail sale. Many of the Examples are summarized in Tables 1-8 below. In the Tables, when more than one result is given for a particular Example, this reflects the fact that more than one test was carried out under the same conditions. Examples 1A-B. C11-12. 2 and C2
Each of these Examples uses a large bag. In Examples C 11 ,1 A-B and 2, each bag has one S-type control member placed under two or more holes in the bag. In Example C11 , the control member had an area of 1935 mm2 (3 in2) and was placed under two holes, each of diameter 20.6 mm (0.81 in.). In Example 1 A, the control member had an area of 6450 mm2 (10 in2) and was placed under 6 holes, each of diameter 20.6 mm (0.81 in.). In Examples 1 B and 2, the control member had an area of 12,900 mm2 (20 in2) and was placed under 6 holes, each of diameter 28.7 mm (1.13 in). Each bag was packed with about 20 kg (44 lb) of green bananas. The bananas had been harvested at week 11 and maintained at 13-14 °C for about 11 days after harvest before being packed. Except in Examples C12 and C2, excess air was extracted from the bags using a vacuum pump, and the bags were then sealed using tie wraps. In Examples C12 and C2, the bags were left open. The bags were maintained at 13 °C. for an extended time,
Examples 1 A, 1 B, C11 and C12 being terminated at day 62, and Examples 2 and C2 being terminated at day 40. The results are given in Table 1 below. In Example 2, traces of ethylene
(generated by the ripening of the bananas) remained in the test chamber from Example 1 and caused the bananas to ripen more rapidly than in the otherwise substantially identical Example
1 B. This demonstrates the desirability of excluding ethylene when long storage periods are needed (and conversely, the ability to accelerate ripening when desired).
Table 1
UGH unripe, green and hard. * the bananas had a color of 4.5 when the test was terminated at day 62
Exct excellent taste and texture
# test terminated at this point; extrapolation indicates that time to change from color 3.5 to 5 would be 5.9 days.
* Bananas removed on day 26 because they were over-ripe. Examples 3 and C31 -33
Each of these Examples uses a large bag. In Examples C31-33 and 3, each bag has one S-type control member placed under one or more holes in the bag. In Example C31 , the control member had an area of 967 mm2 (1.5 in2) and was placed under a single hole of diameter 20.6 mm (0.81 in.). In Example C32, the control member had an area of 1935 mm2 (3 in2) and was placed under 2 holes, each of diameter 20.6 mm (0.81 in.). In Example C33, the control member had an area of 3225 mm2 (5 in2) and was placed under 4 holes, each of diameter 19 mm (0.75 in.). In Example 3, the control member had an area of 12,900 mm2 (20 in2) and was placed under 6 holes, each of diameter 25 mm (1 in.). In Example C34, the bag did not have a control member. Each bag was packed with about 18.1 kg (40 lb) of green bananas. The bananas had been harvested at week 13, and maintained at 13-14°C for about 11 days after harvest before being packed. Except in Example C34, excess air was extracted from the bags using a vacuum pump, and then securely tied (the bags were not, however, as completely sealed as in Examples 1 and 2). In Example C34, the bags were left open. The sealed bags were cooled to about 13 °C and shipped to Gulfport, Mississippi, and then to San Francisco, California, maintaining the temperature at about 13 °C. In San Francisco, 36 days after packing, half the bags in each Example were opened, and the other half left intact. All the bags were then exposed to ethylene (500-1000 ppm) in a commercial ripening room for about 24 hours. The bananas in the opened bags ripened rapidly in the expected way; thus by day 43, their color was 6, by day 46 their color was greater than 7, and by day 49, they were overripe. The bags which were still sealed were opened on day 49. The results for the bags opened on day 49 are shown in Table 2 below. These Examples demonstrate that bananas harvested at 13 weeks can be transported in a suitably designed bag, and can be ripened into an excellent product by exposure to ethylene, either through the bag or after opening the bag. TABLE 2
SGU soft, green and unpalatable
DDU dehydrated, decayed and unpalatable by day 47 (day 11 after exposure to ethylene) Exct excellent taste and texture
Examples 4A, 4B. C41 and C42
Each of these Examples uses a small bag. In Examples 4A-B, each bag has one A-type control member placed over four or five holes in the bag. In Example 4A, the control member had an area of 145 mm2 (5.7 in2) and was placed over four holes each of diameter 19 mm (0.75 in.). In Example 4B, the control member had an area of 4516 mm2 (7 in2) and was placed over 5 holes, each of diameter 19 mm (0.75 in.). In Example C41 , the control member and the holes under it were as in Example 4A, except that the control member was an uncoated microporous film. In Example C42, the bag was intact except for 200 pinholes each about 0.5 mm (26 gauge) in diameter. Each bag was packed with about 1.35 kg (3 lb) of green bananas which had been maintained at 13-14 °C for about 11 days after harvest. Except in Example C42, excess air was extracted from the bags using a vacuum pump, and the bags were then securely tied. In Example C42, the bags were left open. After three days, to allow the packaging atmosphere to equilibrate, the bags were exposed to ethylene (500-1000 ppm) in a ripening room. The results are shown in Table 3 below. These Examples demonstrate that small quantities of bananas can be ripened in a suitably designed bag, and can remain in the bag in excellent condition for several days longer than bananas exposed to the air. Table 3
* uncoated microporous film Exct excellent taste and texture
Examples 5A. 5B. 5C and C5
These Examples show that the bananas generate heat more evenly when ripened in a container including an atmosphere control member. In each Example, a large bag was packed with about 18.1 kg (40 lb.) of green bananas. The green bananas had been harvested 13 days previously and had been stored at 13-14 °C since harvest. A temperature sensor (available from Sensitech, Beverly, Massachusetts, under the tradename Temptale P) was inserted into one banana in each bag. In each of Examples 5A, 5B and 5C, the bag had two S-type control members, each having an area of 11 ,300 mm2 (17.5 in2). Each control member was placed over a single hole in the bag, the hole having an diameter of 70 mm (2.75 in.) in Example 5A, 74.4 mm (2.93 in.) in Example 5B, and 78.7 mm (3.1 in.) in Example 5C. In Example C5, the bag was perforated so that the bananas were surrounded by air. The bags were then sealed with rubber bands. The sealed bags were placed in a refrigerated room at about 13 °C. After about 84 hours, the temperature of the room was raised to about 16.7 °C and after about 12 hours, an ethylene generator was used to provide an initial ethylene concentration in the room of 500-1000 ppm. About 24 hours after the generation of ethylene had begun, the room was vented. The temperature of the bananas was monitored for about 15 days, and reached a peak at about 60 hours after the generation of ethylene had begun. At that time, the concentration of O2 and CO2 was measured. The results are shown in Table 4 below. It will be seen that the peak temperature was substantially lower in the bags containing control members than in the perforated bag. Table 4
Examples 6 A-E
Each of these Examples uses a large bag having two S-type control members, each control member having an area of 11 ,300 mm2 (17.5 in2). Each control member was placed over seven holes in the bag, each hole of diameter 25.4 mm (1 in). A paper pad about 300 x 400 mm (12 x 16 in.) impregnated with an aqueous solution of 2CPA (3.9%) was placed in the bottom of each bag and covered with a sheet of polyethylene. The amount of the solution varied from Example to Example, and is shown in Table 5 below. About 18.1 kg (40 lb.) of green bananas were then placed in each bag, and the bags were sealed with rubber bands. The green bananas had been maintained at 13-14 °C for about 11 days after harvest. The sealed bags were left in a cold room at 13-14 °C. The color stage of the bananas was monitored, and Table 5 below shows the time in days taken to reach color stages 4 and 5.5.
Table 5
* this color stage had not been reached when the experiment was terminated after 27 days. Examples 7 A-D and C71-74
The procedure of Example 6 was followed except for the changes noted below.
1. In Examples 7A-D, there was a single hole, diameter 82.5 mm (3.25 in.), under each of the two control members. The total area of the holes was 10,700 mm2.
2. In Examples 7A, 7B and 7C and in comparative Examples C72 and C73, a paper pad impregnated with 0.1 N NaHCO3 solution was placed adjacent to the paper pad impregnated with 2CPA solution, thus increasing the pH of the 2CPA solution and increasing the rate at which ethylene was generated. The amount of the NaHCO3 solution varied from Example to Example as shown in Table 6 below.
3. In Examples 7D and C74, 2CPA was not used, but three days after packing, the bags were exposed to ethylene for 24 hours in a conventional ripening room at 16.7 °C and containing 500-1000 ppm of ethylene.
4. Comparative Examples C71 -74 were carried out in which no ethylene was used (C71 ), or the bag was sealed but did not have a control member (C 72-73), or the bag was not sealed (C74). 5. The ethylene concentration in the bags was measured at various times after packing. The results obtained are shown in Table 6 below.
Table 6
*this color stage had not been reached when the experiment was terminated. Examples 8A-J and C81-83
Examples 8A-J and C 81-83 followed the same procedure as Examples 7A-C and C71- 74 except for the changes noted below.
1. The ethylene, O2 and CO2 concentrations were determined at different times.
2. In some of the examples, the second paper pad was impregnated with 30 mL of an aqueous buffer solution (i) containing potassium phthalate and having a pH of 4, (ii) containing dibasic sodium phosphate, monobasic potassium phosphate, sodium chromate and potassium dichromate, and having a pH of 7, or (iii) containing sodium carbonate and sodium bicarbonate and having a pH of 10. These buffer solutions are available from Orion Research lnc.,Beverley, Massachusetts USA
3. In Examples 8H and C83, the bag was taken to the ripening room 3 days after packing.
4. In Example 8G, the sealed bags were left in a room at about 21 °C (in the other Examples, the room was at 13-14 °C).
5. In Example C83, the bag was not sealed. The results are shown in Table 7 below.
Table 7
* this color stage had not been reached when the experiment was terminated after 17 days. Examples 9A-C and C91-92
The procedure of Example 6 was followed, except for the changes noted below.
1. There was a single hole, diameter 82.5 mm (3.25 in.), under each control member. The total area of the hole was 5350 mm2.
2. No 2CPA-impregnated paper pad was placed in the bag. 3. The bananas, before being packed into the bag, were dipped into a dilute aqueous solution of 2CPA. The concentration of the 2CPA varied from Example to Example as shown in Table 8 below.
4. Comparative Examples C91 and C92 were carried out in which the bag did not have a control member (C91) or the bananas were not treated with 2CPA solution (C92). Comparative Example C91 is the same as the comparative Example C71.
The results obtained are shown in Table 8 below.
Table 8
* this color stage had not been reached when the experiment was terminated after 27 days Table 9 below shows, for each of the bags in Examples 5A-C, 6A-E and 7A-E, the permeability of the bag to O2 and to ethylene ("Et" in Table 9), and the respective contributions of the control member and the remainder of the bag. For this calculation, the size of the bag, after sealing, was assumed to be 0.96 x 1.04 m (38 in. x 41 in.), i.e. to have a total area of 2 m2 (3115 in2).
Table 9

Claims

Claims
1.. A container which is suitable for packaging bananas and which has at least one, and preferably both, of the following characteristics (1) the container can be sealed around a quantity of bananas, said quantity being at least 4 kg, preferably at least 15 kg, especially 16 to 22 kg, and, when sealed around the bananas, has an O2 permeability at 13 °C, per kg of bananas in the container (OP13/kg), of at least 700, preferably at least 1000, particularly at least 1500, ml/atm.24 hrs and an R ratio at 13 °C of at least 2, preferably at least 3, and preferably has an ethylene permeability at 13 °C, per kg of bananas in the container (EtOP13/kg) which is at least 3 times, preferably at least 4 times, the OP13/kg of the container; and (2) the container includes at least one permeable control member which (i) provides a pathway for O2, CO2 and ethylene to enter or leave the packaging atmosphere and (ii) comprises a gas-permeable membrane comprising (a) a microporous polymeric film, and
(b) a polymeric coating on the microporous film.
2. A container according to Claim 1 which has both characteristic (1) and characteristic (2) and wherein the gas-permeable membrane
(i) has a P-|0 ratio, over at least one 109C range between -5 and 25 °C, e.g. between - 5 and 15 °C, or between 10 and 20 °C, of at least 1.3, preferably at least 1.5, e.g. 1.5 to
2.8 or 2.0 to 2.8; and
(ii) has an oxygen permeability (OTR), at all temperatures between 20 and 25SC, preferably at all temperatures between 13 and 25°C, of at least 775,000 ml/m2.atm.24 hrs (50,000 cc/100 inch2.atm.24 hrs, preferably at least 2,480,000 ml/m2.atm.24 hrs (160,000 cc/100 inch2.atm.24 hrs), e.g. 2,480,000 to 7,000,000 ml/m2.atm.24 hrs(160,000 to 450,000 cc/100 inch2.atm.24 hrs).
3. A container according to Claim 1 or 2 wherein the microporous polymeric film comprises a network of interconnected pores having an average pore size of less than 0.24 micron, with at least 70% of the pores having a pore size of less than 0.24 micron.
4. A container according to any one of the preceding claims wherein the microporous film is a film which was prepared by a process comprising
(A) preparing a uniform mixture comprising the polymeric matrix material in the form of a powder, the filler, and a processing oil;
(B) extruding the mixture as a continuous sheet; (C) forwarding the continuous sheet, without drawing, to a pair of heated calender rolls; (D) passing the continuous sheet through the calender rolls to form a sheet of lesser thickness;
(E) passing the sheet from step (D) to a first extraction zone in which the processing oil is substantially removed by extraction with an organic extraction liquid which is a good solvent for the processing oil, a poor solvent for the polymeric matrix material, and more volatile than the processing oil;
(F) passing the sheet from step (E) to a second extraction zone in which the organic extraction liquid is substantially removed by steam or water or both; and
(G) passing the sheet from step (F) through a forced air dryer to remove residual water and organic extraction liquid.
5. A container according to any one of the preceding claims, wherein
(1 ) the pores in the microporous film constitute 35 to 80% by volume of the microporous film; and
(2) the microporous film comprises
(a) a polymeric matrix comprising (i) an essentially linear ultrahigh molecular weight polyethylene having an intrinsic viscosity of at least 18 deciliters/g, or (ii) an essentially linear ultrahigh molecular weight polypropylene having an intrinsic viscosity of at least 6 deciliters/g, or (iii) a mixture of (i) and (ii); and (c) 30 to 90% by weight, based on the weight of the film, of a finely divided particulate substantially insoluble filler which is distributed throughout film.
6. A container according to any one of the preceding claims wherein the polymeric coating comprises a crystalline polymeric moiety which has a Tp of -5 to 25 °C, preferably 0 to 15 °C and which is a side chain crystalline polymer comprising units derived from (i) at least one n-alkyl acrylate or methacrylate in which the n-alkyl group contains at least 12 carbon atoms and (ii) one or more comonomers selected from acrylic acid, methacrylic acid, and esters of acrylic or methacrylic acid in which the esterifying group contains less than 10 carbon atoms.
7. A container according to any one of the preceding claims wherein the polymeric coating comprises a block copolymer which has a heat of fusion ΔH of at least 5 J/g, and which comprises (i) polysiloxane polymeric blocks, and (ii) crystalline polymeric blocks having a melting point, Tp> of -5 to 40 °C.
8. A container according to Claim 7, wherein the crystalline polymeric blocks comprise units derived from (i) at least one n-alkyl acrylate or methacrylate in which the n-alkyl group contains at least 12 carbon atoms and (ii) one or more comonomers selected from acrylic acid, methacrylic acid, and esters of acrylic or methacrylic acid in which the esterifying group contains less than 10 carbon atoms.
9. A container according to Claim 7 or 8, wherein the block copolymer was prepared by copolymenzing a mixture of reactants which comprises (i) at least one n-alkyl acrylate or methacrylate in which the n-alkyl group contains at least 12 carbon atoms and (ii) a polysiloxane having a copolymerizable group at one end thereof.
10. A container according to any one of claims 1 to 5 wherein the polymer coating on the microporous film is composed of cis-polybutadiene, poly (4-methylpentene), polydimethyl siloxane, and ethylene-propylene rubber.
11. A container according to any one of the preceding claims wherein the control member comprises
(a) the gas-permeable membrane; and
(b) an apertured cover member which lies between the gas-permeable membrane and the air surrounding the package; the gas permeable membrane having, in the absence of the apertured cover member,
(i) an O2 permeability, OTRperm. of at least 155,000 ml/m2» atm »24 hr
(10,000 cc/100 in2* atm • 24 hr), and (ii) a permeability ratio, Rperm, of at least 2, and the apertured cover member being composed of (i) a barrier portion having an O2 permeability, OTR ar, which is less than 0.5 times OTRperm, and (ii) an aperture portion which comprises at least one aperture having an area of at least 0.015 in2 and through which the gas-permeable membrane is exposed to the air surrounding the package, the aperture portion being such that the control member has a permeability ratio, RControi, of at most
0.9 times Rperm-
12. A container according to any one of the preceding claims wherein at least 75% of the O2 which enters the packaging atmosphere, after the container has been sealed around the bananas, passes through said at least one atmosphere control member.
13. A package which comprises
(a) a sealed container, and
(b) within the sealed container, bananas and a packaging atmosphere around the bananas; the sealed container having an O2 permeability at 13 °C, per kg of bananas in the container (OP13/kg), of at least 700, preferably at least 1000, particularly at least 1500, ml/atm.24 hrs and an R ratio at 13 °C of at least 2, preferably at least 3.
14. A package according to Claim 13 wherein the container has an ethylene permeability at 13 °C, per kg of bananas in the container (EtOP13/kg) which is at least 2 times, preferably at least 4 times, the OP13/kg of the container.
15. A package according to Claim 13 or 14 wherein the bananas have not yet reached their climacteric, and the packaging atmosphere contains at least 10% preferably at least 12%, particularly 14 to 19%, of O2 , and less than 10%, preferably less than 4%, of CO2, with the total quantity of O2 and CO2 being less than 20 %, preferably less than 17 %.
16. A package according to Claim 13 or 14 wherein the bananas have passed their climacteric, and the packaging atmosphere contains at least 0.8%, preferably 1.5 to 6%, especially 1.5 to 3%, of O2, and less than 15%, preferably less than 7%, of CO2 , with the total quantity of O2 and CO2 being less than 16%, preferably less than 10 %.
17. A package according to any one of claims 13 to 16 wherein the container includes at least one permeable control member which provides a pathway for O2 ,CO2 and ethylene to enter or leave the packaging atmosphere and which comprises a gas-permeable membrane comprising
(a) a microporous polymeric film, and
(b) a polymeric coating on the microporous film.
18. A package according to Claim 17 wherein the permeable control member is as defined in any one of claims 2 to 12.
19. A package according to any one of claims 13 to 18 wherein the sealed container contains at least 4 kg, preferably at least 15 kg, especially 16 to 22 kg of bananas.
20. A method of ripening green bananas which comprises
(A) providing a sealed package which comprises (a) a sealed container, and (b) within the sealed container, green bananas and a packaging atmosphere around the green bananas; the sealed container having an O2 permeability at 13 °C, per kg of bananas in the container (OP13/kg), of at least 700, preferably at least 1000, particularly at least 1500, ml/atm.24 hrs, an R ratio at 13 °C of at least 2, preferably at least 3, and an ethylene permeability at 13 °C, per kg of bananas in the container (EtOP13/kg) which is at least 3 times, preferably at least 4 times, the OP13/kg of the container; and
(B) placing the sealed package in an atmosphere containing ethylene.
21. A method according to Claim 20 wherein step (B) comprises placing the sealed package in a ripening room containing ethylene, preferably in amount 500 to 1000 ppm.
22. A method according to Claim 20 or 21 , when at least part of step (B) is carried out at a temperature less than 22 °C, preferably less than 20 °C, for example at 16-21°C.
23. A method according to any one of claims 20 to 22 wherein the packaging atmosphere, for at least part of the period before the bananas reach their climacteric, contains at least 10% preferably at least 12%, particularly 14 to 19%, of O2 , and less than 10%, preferably less than 4%, of CO2, with the total quantity of O2 and CO2 being less than 20 %, preferably less than 17 %.
24. A method according to any one of claims 20 to 23 wherein the packaging atmosphere, for at least part of the period after the bananas have passed their climacteric, contains at least 0.8%, preferably 1.5 to 6%, especially 1.5 to 3%, of O2, and less than 15%, preferably less than 7%, of CO2 , with the total quantity of O2 and CO2 being less than 16%, preferably less than 10 %.
25. A method according to any one of claims 20 to 24 wherein the sealed container contains at least 4 kg, preferably at least 15 kg, especially 16 to 22 kg of bananas.
26. A method according to any one of claims 20 to 25 wherein the container includes at least one permeable control member which provides a pathway for O2 ,CO2 and ethylene to enter or leave the packaging atmosphere and which comprises a gas-permeable membrane comprising
(a) a microporous polymeric film, and
(b) a polymeric coating on the microporous film.
27. A method according to Claim 26 wherein the permeable control member is as defined in any one of claims 2 to 12.
28. A method of ripening green bananas which comprises
(A) placing, in a sealable container, (a) the green bananas, and (b) a source of ethylene;
(B) sealing the container around the green bananas and the source of ethylene, thus providing a sealed package which comprises
(a) a sealed container, and
(b) within the sealed container, the green bananas, the source of ethylene, and a packaging atmosphere around the green bananas; the sealed container having an O2 permeability at 13 °C, per kg of bananas in the container (OP13/kg), of at least 700, preferably at least 1000, particularly at least 1500, ml/atm.24 hrs, an R ratio at 13 °C of at least 2, preferably at least 3, and an ethylene permeability at 13 °C, per kg of bananas in the container (EtOP13/kg) which is at least 3 times, preferably at least 4 times, the OP13/kg of the container; and (C) exposing the bananas in the sealed package to ethylene from the source of ethylene in the sealed container.
29. A method according to Claim 28, wherein the source of ethylene is 2-chloroethyl phosphonic acid, the 2-chloroethyl phosphonic acid, during step (C), preferably being at a pH of more than 4, particularly more than 7.
30. A method according to Claim 28 or 29, when at least part of step (C) is carried out at a temperature less than 18 °C, preferably less than 16 °C, for example at 14-15°C.
31. A method according to any one of claims 28 to 30 wherein the packaging atmosphere, for at least part of the period before the bananas reach their climacteric, contains at least 10% preferably at least 12%, particularly 14 to 19%, of O2 , and less than 10%, preferably less than 4%, of CO2, with the total quantity of O2 and CO2 being less than 20 %, preferably less than 17 %.
32. A method according to any one of claims 28 to 31 wherein the packaging atmosphere, for at least part of the period after the bananas have passed their climacteric, contains at least 0.8%, preferably 1.5 to 6%, especially 1.5 to 3%, of O2, and less than 15%, preferably less than 7%, of CO2 , with the total quantity of O2 and CO2 being less than 16%, preferably less than 10 %.
33. A method according to any one of claims 28 to 32 wherein the sealed container contains at least 4 kg, preferably at least 15 kg, especially 16 to 22 kg of bananas.
34. A method according to any one of claims 28 to 33 wherein the container includes at least one permeable control member which provides a pathway for O2 ,CO2 and ethylene to enter or leave the packaging atmosphere and which comprises a gas-permeable membrane comprising
(a) a microporous polymeric film, and
(b) a polymeric coating on the microporous film.
35. A method according to Claim 34 wherein the permeable control member is as defined in any one of claims 2 to 12.
36. A method of storing green bananas which comprises
(A) placing the green bananas in a container which comprises an atmosphere control member which comprises (1) a microporous film, and
(2) a polymeric coating on the microporous film;
(B) sealing the container, thus providing a sealed package which comprises (a) a sealed container, and
(d) within the sealed container, the green bananas, and a packaging atmosphere around the green bananas; and
(C) maintaining the sealed bag at the temperature of 13-18 °C.
37. A method according to Claim 36 wherein the packaging atmosphere contains at least 10% preferably at least 12%, particularly 14 to 19%, of O2 , and less than 10%, preferably less than 4%, of CO2, with the total quantity of O2 and CO2 being less than 20 %, preferably less than 17 %.
38. A method according to Claim 36 or 37 wherein the sealed container contains at least 4 kg, preferably at least 15 kg, especially 16 to 22 kg of bananas.
39. A package according to any one of claims 36 to 38 wherein the container includes at least one permeable control member which provides a pathway for O2 ,CO2 and ethylene to enter or leave the packaging atmosphere and which comprises a gas-permeable membrane comprising
(a) a microporous polymeric film, and
(b) a polymeric coating on the microporous film.
40. A package according to Claim 39 wherein the permeable control member is as defined in any one of claims 2 to 12.
41. A package which is stored in air and which comprises (a) a sealed container, and
(c) within the sealed container, 1 to 2.5 kg (2 to 5 lb) of bananas which have passed their climacteric and which are at a color stage less than 5, and a packaging atmosphere around the bananas; the sealed container including at least one permeable control member which provides a pathway for O2 and CO2 to enter or leave the packaging atmosphere and which comprises a gas- permeable membrane comprising
(1 ) a microporous film, and
(2) a polymeric coating on the microporous film; and the packaging atmosphere containing at least 0.8%, preferably 1.5 to 6%, especially 1.5 to 3%, of O2, and less than 15%, preferably less than 7%, of CO2 , with the total quantity of O2 and CO2 being less than 16%, preferably less than 10 %.
42. A package according to Claim 41 wherein the membrane is as defined in any one of claims 2 to 12.
43. A package which comprises
(a) a sealed container, and
(b) within the sealed container, bananas and a packaging atmosphere around the bananas; the sealed container including at least one permeable control member which provides a pathway for O2 ,CO2 and ethylene to enter or leave the packaging atmosphere and which comprises a gas-permeable membrane comprising (a) a microporous polymeric film, and
(b) a polymeric coating on the microporous film.
44. A method according to Claim 43 wherein the membrane is as defined in any one of claims 2 to 12.
45. A method of ripening green bananas which comprises (A) providing a sealed package which comprises
(a) a sealed container, and
(b) within the sealed container, green bananas and a packaging atmosphere around the green bananas; the sealed container including at least one permeable control member which provides a pathway for O2 ,CO2 and ethylene to enter or leave the packaging atmosphere and which comprises a gas-permeable membrane comprising
(a) a microporous polymeric film, and
(b) a polymeric coating on the microporous film; and (B) placing the sealed package in an atmosphere containing ethylene.
46. A method according to Claim 45 wherein the membrane is as defined in any one of claims 2 to 12.
47. A method of ripening green bananas which comprises
(A) placing, in a sealable container, (a) the green bananas, and
(b) a source of ethylene;
(B) sealing the container around the green bananas and the source of ethylene, thus providing a sealed package which comprises
(a) a sealed container, and (b) within the sealed container, the green bananas, the source of ethylene, and a packaging atmosphere around the green bananas; the sealed container including at least one permeable control member which provides a pathway for O2 ,CO2 and ethylene to enter or leave the packaging atmosphere and which comprises a gas-permeable membrane comprising (a) a microporous polymeric film, and
(b) a polymeric coating on the microporous film; and
(C) exposing the bananas in the sealed package to ethylene from the source of ethylene in the sealed container.
48. A method according to Claim 47 wherein the membrane is as defined in any one of claims 2 to 12.
49. A method of storing green bananas which comprises (A) placing the green bananas in a container which comprises an atmosphere control member which comprises
(1 ) a microporous film, and
(2) a polymeric coating on the microporous film; (B) sealing the container, thus providing a sealed package which comprises
(a) a sealed container, and
(e) within the sealed container, the green bananas, and a packaging atmosphere around the green bananas; and (C) maintaining the sealed bag at the temperature of 13-18 °C.
50. A method according to Claim 49 wherein the membrane is as defined in any one of claims 2 to 12.
51. The use, in packaging bananas, of a container including at least one permeable control member which provides a pathway for O2 and CO2, and which comprises a gas-permeable membrane comprising (1) a microporous film, and
(3) a polymeric coating on the microporous film.
52. The use according to Claim 51 wherein the container is as defined in any one of claims 2 to 12.
EP01959756A 2000-05-26 2001-05-15 Packaging of bananas Expired - Lifetime EP1289855B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP04027190A EP1516827B1 (en) 2000-05-26 2001-05-15 Packaging of bananas

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US580379 1990-09-10
US58037900A 2000-05-26 2000-05-26
PCT/US2001/040732 WO2001092118A2 (en) 2000-05-26 2001-05-15 Packaging of bananas

Related Child Applications (1)

Application Number Title Priority Date Filing Date
EP04027190A Division EP1516827B1 (en) 2000-05-26 2001-05-15 Packaging of bananas

Publications (2)

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EP1289855A2 true EP1289855A2 (en) 2003-03-12
EP1289855B1 EP1289855B1 (en) 2005-01-12

Family

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EP04027190A Expired - Lifetime EP1516827B1 (en) 2000-05-26 2001-05-15 Packaging of bananas
EP01959756A Expired - Lifetime EP1289855B1 (en) 2000-05-26 2001-05-15 Packaging of bananas

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EP (2) EP1516827B1 (en)
JP (1) JP2003534991A (en)
AT (2) ATE367983T1 (en)
AU (1) AU2001281278A1 (en)
CA (1) CA2409358C (en)
DE (2) DE60108381T2 (en)
DK (1) DK1516827T3 (en)
WO (1) WO2001092118A2 (en)

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Also Published As

Publication number Publication date
WO2001092118A2 (en) 2001-12-06
DE60108381D1 (en) 2005-02-17
EP1289855B1 (en) 2005-01-12
CA2409358A1 (en) 2001-12-06
DK1516827T3 (en) 2007-11-12
WO2001092118A3 (en) 2002-04-04
DE60108381T2 (en) 2006-04-06
CA2409358C (en) 2009-11-24
EP1516827B1 (en) 2007-07-25
JP2003534991A (en) 2003-11-25
AU2001281278A1 (en) 2001-12-11
ATE286838T1 (en) 2005-01-15
DE60129612T2 (en) 2008-05-21
EP1516827A1 (en) 2005-03-23
DE60129612D1 (en) 2007-09-06
ATE367983T1 (en) 2007-08-15

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