WO1996020870A1 - Packaging film for respiring materials - Google Patents

Packaging film for respiring materials

Info

Publication number
WO1996020870A1
WO1996020870A1 PCT/US1995/016112 US9516112W WO9620870A1 WO 1996020870 A1 WO1996020870 A1 WO 1996020870A1 US 9516112 W US9516112 W US 9516112W WO 9620870 A1 WO9620870 A1 WO 9620870A1
Authority
WO
WIPO (PCT)
Prior art keywords
films
packaging
packaging film
permeability
film
Prior art date
Application number
PCT/US1995/016112
Other languages
French (fr)
Inventor
Jean-Claude Cardinal
Original Assignee
E.I. Du Pont De Nemours And Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from EP95201390A external-priority patent/EP0744434A1/en
Application filed by E.I. Du Pont De Nemours And Company filed Critical E.I. Du Pont De Nemours And Company
Publication of WO1996020870A1 publication Critical patent/WO1996020870A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
    • B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D85/00—Containers, packaging elements or packages, specially adapted for particular articles or materials
    • B65D85/50—Containers, packaging elements or packages, specially adapted for particular articles or materials for living organisms, articles or materials sensitive to changes of environment or atmospheric conditions, e.g. land animals, birds, fish, water plants, non-aquatic plants, flower bulbs, cut flowers or foliage
    • B65D85/52—Containers, packaging elements or packages, specially adapted for particular articles or materials for living organisms, articles or materials sensitive to changes of environment or atmospheric conditions, e.g. land animals, birds, fish, water plants, non-aquatic plants, flower bulbs, cut flowers or foliage for living plants; for growing bulbs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • the present invention relates to packaging films for the food and flower industry, more particularly to packaging films suitable for packaging materials which respire.
  • MAP modified atmosphere packaging
  • CAP controlled atmosphere packaging
  • Certain ⁇ lymer films have been proposed for such applications: Micro-perforated polypropylene films are commonly used, but have the disadvantage that they do not function as a barrier to certain microorganisms.
  • C.f. also US Patent No 5,254,354 wherein films are described as being made from a polymer having a side- chain crystallizable polymer and a permeability which increases by a factor of greater than 2.5 in response to a 10°C temperature increase;
  • US Patent 4,842,741 describes a heterogeneous film having a porous core layer and nonporous outer layers, and containing a filler;
  • FR 2 351 877 describes film of polyurethane suitable for packaging meats and cheeses, though does not mention modified or controlled atmosphere packaging.
  • the present invention relates to the use of a homogeneous packaging film of a block copolyether ester or a block copolyether amide to package an actively respiring biological material such as a food product or a flower, and to the resulting packaged article.
  • Bio materials which respire refer generally to fresh fruits, vegetables and flowers, and to dairy products such as cheeses.
  • packaging films of this invention when used to package fruits and vegetables, such as tomatoes, mushrooms, green beans, lettuce, beansprouts, figs, apricots, strawberries and raspberries.
  • the particular packaging films of the present invention i.e., block copolyether esters and block copolyether amides, are known per se, and commercially available.
  • these polymers have thicknesses ranging from 10 to 120 microns, and demonstrate the following permeabilities at 1 atm pressure, 100% humidity, and 23 °C: 02 permeability of ⁇ 25,000 ml/m ⁇ -day, preferably ⁇ 15, 000 ml/m 2 -day, suitably from 3,000 to 20,000 ml/m 2 -day; C ⁇ 2 permeability of >75,000 ml/m ⁇ -day, more preferably >100,000 ml/m ⁇ -day, suitably from 85,000 to 1,000,000 ml/m ⁇ -day.
  • the films of the present invention will be homogenous and do not require a filler (unlike those films described in US Patent 4,842,741).
  • Preferred block copolyether esters are segmented elastomers having soft polyether segments and hard polyester segments (c.f. U.S. Patent No. 4,739,012), available from the DuPont Company under the name Hytrel® .
  • Suitable block copolyether amides for use in the invention are described in US Patent 5,069,955 and are available under the name Pebax® from Elf Atochem.
  • the packaging films according to the present invention may be free-standing, or may support or be supported by additional films in multilayer film constructions.
  • additional films will be made of highly porous materials, such as paper or the films described in the patent publications mentioned herein.
  • the biological materials can be packaged in any of a variety of known styles.
  • the packaging may be made 100% from the films, or the films may comprise a part of the packaging.
  • a support which holds the biological matters can be used, which is then sealed shut with the packaging film of the present invention.
  • Such support may be made from any conventional material which is a gas barrier, such as polypropylene, polystyrene, etc.
  • the packaging material of the present invention can be formed as a "window" in a sealing film made from another material.
  • the film for sealing the support can be of a conventional gas barrier polymer, such as polyethylene, polyester, etc., into which is formed (by conventional techniques) a window of packaging film of the present invention.
  • any such packaging design is that sufficient surface area of packaging film for the present invention be used to provide modified or controlled atmosphere packaging.
  • the specific amount of surface area will, of course, depend upon the size and design of the package, and the type of biological material that is packaged.
  • Cultivated mushrooms are obtained from Ferme de la Gontiere
  • closed velum normal appearance at harvesting stretched velum: velum is fully attached to stem but begins to stretch torn velum: mushroom starts to separate from the stem and is torn in several places open velum: velum has completely separated from the stem
  • the 02 and C02 permeabilities of Hytrel films can be calculated under actual conditions of use from measurements of the level of 02 and C02 in the bags at
  • the C02 prevents the opening of the carpophores.
  • the most impermeable films prevent the ripening of the mushroom (for mushrooms packed in the films OPP, P+ 5000 and P+ 10000: 100 % of velum stretch after 6 days of conservation at 8 - 9 °C).
  • the mushrooms packed in the films P+100000 and P+ 200000 behave like those packed in Hytrel® films (about 20 % of velum tears).
  • the external color of the mushrooms packed in Hytrel® films is statistically lighter (average L less than 91 ) than the one of mushrooms packed with oriented polypropylene film (L increases from 86 to 90 according to the permeability of the film).
  • the internal color is also much more attractive for the mushrooms packed in Hytrel® films.

Abstract

A packaged respiring biological material such as food and flowers wherein the package includes a packaging film comprising a block copolyether ester or a block copolyether amide. Due to the particular gas permeability of the film, preservation of the respiring biological material is enhanced.

Description

PACKAGING FILM FOR RESPIRING MATERIALS
The present invention relates to packaging films for the food and flower industry, more particularly to packaging films suitable for packaging materials which respire.
Background of the Invention
Various packaging materials have been proposed for preserving respiring biological materials, such as foods and flowers, after they are harvested or produced. One means for so doing is to package the biological materials in "modified atmosphere packaging" (MAP) or "controlled atmosphere packaging" (CAP). Such packaging is designed to modify the levels of carbon dioxide (Cθ2), oxygen (02) and/or other gases to which the packaged articles are exposed, in order to retard deterioration. A number of theories have been proposed as to the effect varying the levels of these gases has on the rate of decomposition of respiring biological materials (c.f. "Storage of Common Mushroom under Controlled Atmospheres", Briones et al., International Journal of
Food Science and Technology. (1992) 27, 493-505; "Modified Atmosphere Packaging of Common Mushroom", International Journal of Food Science and Technology. (1993) 28, 57-68; "Recent Developments in the Processing of Fruit and Vegetables in France", Varoquaux, The European Food and Drink Review.
Autumn 1993; "Ready-to-use Fresh Fruits and Vegetables", Varoquaux, Rev. Gen. Froid. July 1991).
Certain υlymer films have been proposed for such applications: Micro-perforated polypropylene films are commonly used, but have the disadvantage that they do not function as a barrier to certain microorganisms. C.f. also US Patent No 5,254,354 wherein films are described as being made from a polymer having a side- chain crystallizable polymer and a permeability which increases by a factor of greater than 2.5 in response to a 10°C temperature increase; US Patent 4,842,741 describes a heterogeneous film having a porous core layer and nonporous outer layers, and containing a filler; FR 2 351 877 describes film of polyurethane suitable for packaging meats and cheeses, though does not mention modified or controlled atmosphere packaging.
It has now been found that homogeneous packaging films made from block copolyether esters and block copolyether amides are able to create particularly desirable modified atmospheres for the packaging of respiring biological materials.
Summary of the Invention
Accordingly, the present invention relates to the use of a homogeneous packaging film of a block copolyether ester or a block copolyether amide to package an actively respiring biological material such as a food product or a flower, and to the resulting packaged article.
Detailed description of the Invention
As used herein, certain terms have the following meanings.
"Biological materials which respire" refer generally to fresh fruits, vegetables and flowers, and to dairy products such as cheeses.
Particularly good results can be obtained with the packaging films of this invention when used to package fruits and vegetables, such as tomatoes, mushrooms, green beans, lettuce, beansprouts, figs, apricots, strawberries and raspberries.
The particular packaging films of the present invention, i.e., block copolyether esters and block copolyether amides, are known per se, and commercially available. As films, these polymers have thicknesses ranging from 10 to 120 microns, and demonstrate the following permeabilities at 1 atm pressure, 100% humidity, and 23 °C: 02 permeability of <25,000 ml/m^-day, preferably < 15, 000 ml/m2-day, suitably from 3,000 to 20,000 ml/m2-day; Cθ2 permeability of >75,000 ml/m^-day, more preferably >100,000 ml/m^-day, suitably from 85,000 to 1,000,000 ml/m^-day. Furthermore, the films of the present invention will be homogenous and do not require a filler (unlike those films described in US Patent 4,842,741).
Preferred block copolyether esters are segmented elastomers having soft polyether segments and hard polyester segments (c.f. U.S. Patent No. 4,739,012), available from the DuPont Company under the name Hytrel® .
Suitable block copolyether amides for use in the invention are described in US Patent 5,069,955 and are available under the name Pebax® from Elf Atochem.
The packaging films according to the present invention may be free-standing, or may support or be supported by additional films in multilayer film constructions. Such additional films will be made of highly porous materials, such as paper or the films described in the patent publications mentioned herein.
The biological materials can be packaged in any of a variety of known styles. For example, the packaging may be made 100% from the films, or the films may comprise a part of the packaging. In the latter case, a support which holds the biological matters can be used, which is then sealed shut with the packaging film of the present invention. Such support may be made from any conventional material which is a gas barrier, such as polypropylene, polystyrene, etc.
Alternatively, the packaging material of the present invention can be formed as a "window" in a sealing film made from another material. In this case, the film for sealing the support can be of a conventional gas barrier polymer, such as polyethylene, polyester, etc., into which is formed (by conventional techniques) a window of packaging film of the present invention.
The only governing feature of any such packaging design is that sufficient surface area of packaging film for the present invention be used to provide modified or controlled atmosphere packaging. The specific amount of surface area will, of course, depend upon the size and design of the package, and the type of biological material that is packaged.
Examples
MATERIAL AND METHODS
1. Raw material:
Cultivated mushrooms are obtained from Ferme de la Gontiere
(France). 200 to 250 grams of whole mushrooms, with bases removed, are evaluated for organoleptic qualities (color and velum opening) and subsequently stored in bags, having a surface area of 800 cm2, made from various plastics having different permeabilities.
2. Reference films:
A film of oriented polypropylene (OPP) and films "P+" from
Sidlaw Packaging, U.K., are used, having the permeability grades listed in Table 1. Table 1 : Permeability of reference films
Ref. Film 02 Permeability Cθ2 Permeability
(ml/m2.day.atm) (ml/m .day.atm)
OPP 900 4000
P+ 5000 5000 9000
P+ 10000 10000 14000
P+ 25000 25000 29000
P+ 50000 50000 54000
P+ 100000 100000 104000
P+ 200000 200000 204000
3. Hytrel® Films studied:
G-4078, G-3548W, HTR-8206, G-4778; all commercially available grades from the DuPont Company.
4. Conservation conditions:
Temperature: 8-9 °C
Sampling every second day up to the 8th day.
5. Organoleptic evaluation:
Evaluation of the velum opening through visual observation and positioning on the BURTON simplified scale (c.f. LOPEZ-
BRIONES et al.).
closed velum: normal appearance at harvesting stretched velum: velum is fully attached to stem but begins to stretch torn velum: mushroom starts to separate from the stem and is torn in several places open velum: velum has completely separated from the stem
6. Evaluation of the color of the mushrooms:
Reflectometric measuring of the color with a HUNTERLAB COLORQUEST apparatus.
a) measurement of the external color: 3 measurements on the top of 10 carpophores
b) measurement of internal color: after removal of a 5 mm top section.
Interpretation in the CIE LAB system. The L parameter (luminance) is noted down to evaluate the darkening.
RESULTS
1. Permeability measurements:
1.1 Permeability to 02 and Cθ
The 02 and C02 permeabilities of Hytrel films can be calculated under actual conditions of use from measurements of the level of 02 and C02 in the bags at
8 °C, saturated humidity conditions (internal face of the film) after 2, 4 and 6 days. These are reported in Tables 1 and 2. Table 1 : 0?^ permeability of Hytrel® films
Figure imgf000009_0001
Table 2: Cθ2 permeability of Hvtrel® films
Figure imgf000009_0002
2. Effect of the film on the organoleptic qualities:
2.1 Effect on the opening of the velum:
It is known that the C02 prevents the opening of the carpophores. Thus, the most impermeable films prevent the ripening of the mushroom (for mushrooms packed in the films OPP, P+ 5000 and P+ 10000: 100 % of velum stretch after 6 days of conservation at 8 - 9 °C). The mushrooms packed in the films P+100000 and P+ 200000 behave like those packed in Hytrel® films (about 20 % of velum tears). 2.2 Effect on the color:
After 2 days of conservation, the external color of the mushrooms packed in Hytrel® films is statistically lighter (average L less than 91 ) than the one of mushrooms packed with oriented polypropylene film (L increases from 86 to 90 according to the permeability of the film). The internal color is also much more attractive for the mushrooms packed in Hytrel® films.
The positive effect of Hytrel® films on the external color of the mushrooms is apparent until the sixth day of conservation; afterwards, the improvement in color is less apparent. However, mushrooms packed in Hytrel® retain the advantage that even beyond the sixth day of conservation they do not become slimy; mushrooms packed in oriented polypropylene, in contrast, ferment and become slimy.

Claims

CLAIM S
1. A packaged article comprising a biological material selected from the group consisting of foods and flowers which are actively respiring, and a homogeneous packaging film comprising a block copolyether ester and a block copolyether amide.
2. A packaged article according to claim 1 wherein the biological materials are fruits, vegetables or dairy products.
3. A packaged article according to claims 1 or 2 wherein the packaging film comprises a block copolyether ester and has an 02 permeability of <25,000 ml/m -day and Cθ2 permeability of >75,000 ml/m -day at 1 atm pressure, 100% humidity, and
23 °C.
A packaged article according to claim 1 wherein the packaging film supports or is supported by one or more additional films.
PCT/US1995/016112 1994-12-29 1995-12-13 Packaging film for respiring materials WO1996020870A1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP94203785 1994-12-29
EP94203785.4 1994-12-29
EP95201390A EP0744434A1 (en) 1995-05-26 1995-05-26 Packaging film for respiring materials
EP95201390.2 1995-05-26

Publications (1)

Publication Number Publication Date
WO1996020870A1 true WO1996020870A1 (en) 1996-07-11

Family

ID=26136869

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1995/016112 WO1996020870A1 (en) 1994-12-29 1995-12-13 Packaging film for respiring materials

Country Status (1)

Country Link
WO (1) WO1996020870A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8858985B2 (en) * 2004-05-12 2014-10-14 E I Du Pont De Nemours And Company Films comprising a liquid-absorbant inner layer, an antimicrobial material and an impermeable outer layer
JP2020006972A (en) * 2018-07-04 2020-01-16 住友ベークライト株式会社 Bean sprout packaging container, manufacturing method of bean sprout-containing package, and freshness keeping method of bean sprout

Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3423212A (en) * 1964-11-20 1969-01-21 Union Carbide Corp Method for packaging food products
US3450543A (en) * 1966-01-10 1969-06-17 United Fruit Co Method of packaging perishable plant foods to prolong storage life
US3450544A (en) * 1966-01-10 1969-06-17 United Fruit Co Method of packaging ripening perishable plant foods to prolong storage life
US3630759A (en) * 1970-01-02 1971-12-28 Brown Co Package for respiratory products
US3795749A (en) * 1972-03-31 1974-03-05 Borden Inc Packaging lettuce in carbon dioxide permeable film
US3804961A (en) * 1972-03-31 1974-04-16 Borden Inc Packaging tomatoes in carbon dioxide permeable film
US4423080A (en) * 1975-03-10 1983-12-27 Bedrosian And Associates Controlled atmosphere produce package
US4769262A (en) * 1985-11-19 1988-09-06 Bunzl Flexpack Limited Packaging of fresh fruit and vegetables
US4842875A (en) * 1986-10-06 1989-06-27 Hercules Incorporated Controlled atmosphere package
US4910032A (en) * 1988-11-16 1990-03-20 Hercules Incorporated Water-permeable controlled atmosphere packaging device from cellophane and microporous film
US4923703A (en) * 1988-03-14 1990-05-08 Hercules Incorporated Container comprising uniaxial polyolefin/filler films for controlled atmosphere packaging
US5002786A (en) * 1988-02-22 1991-03-26 Idaho Research Foundation, Inc. Method of killing larvae in infested fruit
US5045331A (en) * 1987-08-14 1991-09-03 Hercules Incorporated Container for controlled atomsphere packaging
US5160768A (en) * 1988-10-25 1992-11-03 Hercules Incorporated Curable silicone-coated microporous films for controlled atmosphere packaging
US5165947A (en) * 1990-03-26 1992-11-24 Dowbrands, Inc. Controlled atmosphere, controlled humidity package for red-ripe tomatoes
US5254354A (en) * 1990-12-07 1993-10-19 Landec Corporation Food package comprised of polymer with thermally responsive permeability
US5458899A (en) * 1990-09-05 1995-10-17 Weyerhaeuser Company Method of packaging perishable food or horticultural products

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3423212A (en) * 1964-11-20 1969-01-21 Union Carbide Corp Method for packaging food products
US3450543A (en) * 1966-01-10 1969-06-17 United Fruit Co Method of packaging perishable plant foods to prolong storage life
US3450544A (en) * 1966-01-10 1969-06-17 United Fruit Co Method of packaging ripening perishable plant foods to prolong storage life
US3630759A (en) * 1970-01-02 1971-12-28 Brown Co Package for respiratory products
US3795749A (en) * 1972-03-31 1974-03-05 Borden Inc Packaging lettuce in carbon dioxide permeable film
US3804961A (en) * 1972-03-31 1974-04-16 Borden Inc Packaging tomatoes in carbon dioxide permeable film
US4423080A (en) * 1975-03-10 1983-12-27 Bedrosian And Associates Controlled atmosphere produce package
US4769262A (en) * 1985-11-19 1988-09-06 Bunzl Flexpack Limited Packaging of fresh fruit and vegetables
US4842875A (en) * 1986-10-06 1989-06-27 Hercules Incorporated Controlled atmosphere package
US5045331A (en) * 1987-08-14 1991-09-03 Hercules Incorporated Container for controlled atomsphere packaging
US5002786A (en) * 1988-02-22 1991-03-26 Idaho Research Foundation, Inc. Method of killing larvae in infested fruit
US4923703A (en) * 1988-03-14 1990-05-08 Hercules Incorporated Container comprising uniaxial polyolefin/filler films for controlled atmosphere packaging
US5160768A (en) * 1988-10-25 1992-11-03 Hercules Incorporated Curable silicone-coated microporous films for controlled atmosphere packaging
US4910032A (en) * 1988-11-16 1990-03-20 Hercules Incorporated Water-permeable controlled atmosphere packaging device from cellophane and microporous film
US5165947A (en) * 1990-03-26 1992-11-24 Dowbrands, Inc. Controlled atmosphere, controlled humidity package for red-ripe tomatoes
US5458899A (en) * 1990-09-05 1995-10-17 Weyerhaeuser Company Method of packaging perishable food or horticultural products
US5254354A (en) * 1990-12-07 1993-10-19 Landec Corporation Food package comprised of polymer with thermally responsive permeability

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8858985B2 (en) * 2004-05-12 2014-10-14 E I Du Pont De Nemours And Company Films comprising a liquid-absorbant inner layer, an antimicrobial material and an impermeable outer layer
JP2020006972A (en) * 2018-07-04 2020-01-16 住友ベークライト株式会社 Bean sprout packaging container, manufacturing method of bean sprout-containing package, and freshness keeping method of bean sprout

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