WO2017188906A1 - Packaging film for packing fresh fruits and vegetables under modified atmosphere - Google Patents
Packaging film for packing fresh fruits and vegetables under modified atmosphere Download PDFInfo
- Publication number
- WO2017188906A1 WO2017188906A1 PCT/TR2017/050157 TR2017050157W WO2017188906A1 WO 2017188906 A1 WO2017188906 A1 WO 2017188906A1 TR 2017050157 W TR2017050157 W TR 2017050157W WO 2017188906 A1 WO2017188906 A1 WO 2017188906A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- film
- packaging
- temperature
- films
- vegetables
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- 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
-
- 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
- B65D85/00—Containers, packaging elements or packages, specially adapted for particular articles or materials
- B65D85/30—Containers, packaging elements or packages, specially adapted for particular articles or materials for articles particularly sensitive to damage by shock or pressure
- B65D85/34—Containers, 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6696—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
-
- 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
-
- 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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
Definitions
- the invention is related to the packaging of fresh fruits and vegetables in food industry.
- the present invention describes the synthesis of polyurethane films having different compositions by using monomers having distinct physical and chemical properties and the method of transforming them into films by the casting method and the hot press method, and the packaging film produced by said method and the use of this film.
- Modified Atmosphere Packaging refers to changing the composition of the atmosphere around the food product inside the package. Modified atmosphere packaging allows the control of chemical, enzymatic or microbiological reactions and therefore prevents or reduces the effect of the factors which will cause deterioration of the product.
- MAP Modified Atmosphere Packaging
- packaging materials having a high gas barrier feature is required for many food products
- materials having particular gas permeability are required in the packaging of fresh fruits and vegetables.
- MA Modified Atmosphere
- the exposure of fresh fruits and vegetables packed under Modified Atmosphere (MA) to ambient temperature after the cold chain has been broken during storage and marketing causes the inner package stability MA to deteriorate and depending on this, the product quality and shelf life is affected adversely. This results from the fact that the temperature and the breathing rate increase more, relative to gas permeability.
- the heat sensitivity of the gas permeability of the present commercial packing materials is insufficient. Packing materials whose gas permeability increases with heat, in a similar level to the breathing rate of fruits and vegetables can eliminate this problem.
- polyethylene ethylene vinyl acetate and low density polyethylene (LDPE) based
- K-Resin ® styrene butadiene block copolymer
- Attane ® LDPE octane copolymer
- Affinity ® series polyolefin octane copolymer
- Micro perforation is another method implemented in order to obtain gas permeability of desired levels in packaging fresh products.
- perforations are made whose size (20-200 ⁇ ) and number per unit area varies relevant to the product and package and the permeability of the material is increased in this way.
- LDPE polyethylene
- HDPE polyethylene
- Gas permeability of polyethylene can be insufficient for fresh fruit and vegetable products having high breathing rate. It is necessary to develop new packaging films having high gas permeability. Moreover, as the product breathing rate and packaging material barrier features are affected from environmental features (temperature, humidity) on different levels this negatively affects the stability MA targeted inside the package. Taking the storage, transportation and sale conditions for fresh fruits and vegetables into consideration, it is seen that the cold chain is broken and the product is exposed to normal ambient temperatures. In such a case, the breathing rate increases substantially together with heat. Change of the breathing rate depending on temperature is generally expressed by Qi 0 value standing for the reaction rate observed at 10°C temperature increase. In fresh fruits and vegetables, for every 10°C temperature increase, the breathing rate increases 2 - 3 fold (Table 2).
- gas permeability Qi 0 values of the gas permeability of the present packaging materials are lower than the breathe rate Qi 0 values of many fresh fruits and vegetables. If the product breathing rate is higher than breathing rate of package permeability; this causes the reduction of 0 2 inside the package and increase of C0 2 . In such a case, physical deteriorations take place as a result of the anaerobic fermentation and C0 2 damage depending on the low 0 2 first and the high C0 2 inside the package.
- micro perforation technique is another method implemented in order to obtain the desired level gas permeability in packaging fresh products.
- micro perforated films allow the passage of C0 2 and 0 2 at the same level in contrary to normal plastic films, it is not suitable to use these films, for products which are damaged by high C02 values such as green leafy vegetables, apples or pears.
- the synthesized polyurethane films have high oxygen, carbon dioxide and water vapour permeability
- the temperature-dependant permeability is changed 2,8 fold at room temperature by an increase of 10°C in the range of 0-40°C and these values are parallel to the breathing rate increase of fresh fruits and vegetable products
- synthesizing is possible using natural sources such as castor oil and without using catalysers or solvents
- these films are inert and stable in chemical terms, they are concordant with the legal regulation related to the materials contacting the food and they have sufficient mechanical force.
- Polyurethane films having different formulations have been synthesized by the single step mass polymerization method without using a catalyser or solvent.
- Polyethylene glycol (PEG) chosen as the polyol source is a polyether and it is used due to reasons such as having low transition temperature, good tensile strength, being hydrophilic and providing non-toxic deterioration products.
- Soft parts composed of polyols provide polyurethane elastomeric features.
- the hard parts formed by diisocyanates are efficient in forming cross bonds.
- Castor oil (HY) has been used as a vegetable oil based cross bond since it is cost-efficient and easily obtained and it is efficient in the formation of the hard parts in the polymer together with the chain lengthened
- Film A (PU1500-50-40) has been synthesized using PEG 1500 g/mol, 50% castor oil and 40% 1,4-butanediol. In order to remove the humidity which can stop the reaction before the preparation of the reaction mixture in the Film A synthesis from the materials used, PEG 1500 g/mol has been liquefied in the rotary evaporator between 90-95°C under vacuum for 6 hours.
- HY has been kept under vacuum for 1 night at 80°C and 1,4 butanediol (BDO) at 50°C.
- BDO 1,4 butanediol
- PEG and HY which are the source of polyol were stirred at 90-95°C in the rotary evaporator until a homogenous mixture is obtained and then the stirring was continued after the addition of the chain lengthener BDO.
- the prepared reaction mixture was transferred into a three neck reaction flask and stirred at 50°C under nitrogen atmosphere. 1,6-hexamethylene diisocyanate (HDI) was added to the reaction medium slowly so an amount of isocyanate equivalent to the hydroxyl group in the mixture is present.
- HDI 1,6-hexamethylene diisocyanate
- the oxygen permeability rate of the obtained Film A is 3218 ml/m2.day.atm at 23°C with 0% relative humidity and 5235 ml/m2.day.atm at 98% relative humidity.
- the reason behind this humidity-dependant increase is the existence of polar groups in the structure of the polymer film.
- the oxygen permeability rate of Film A is 2 fold at 0% relative humidity from LDPE which is a commercial film and approximately 4 fold more at 98% relative humidity.
- the purpose of conducting the analysis at high relative humidity is that the fresh fruit and vegetable products that breathe, represent the packaging atmosphere better, in comparison to the standard 0% relative humidity at which the measurements are taken. According to the results, Film A may be more appropriate for the fruit and vegetable products that have high breathing rate.
- Carbondioxide permeability rate of Film A is approximately 10 fold more compared to the LDPE, which is a commercial film, at 98% relative humidity (Table 3).
- Qi 0 value is 2,8; which is close to the room temperature in the range of 0-40°C at 0% humidity (Table 4). This value can be increased by changing the PEG molecular weight and castor oil percentage. Moreover, it is two times higher in comparison to LDPE, which is a commercial film. A material whose heat sensitivity is higher in comparison to the prior inventions and Qi 0 values closer to the fruits and vegetables have been obtained.
- Activation energy (Ep) for the oxygen permeability of Film A is 63 kJ/mole at 23°C(Table 3). This value is closer to the breathing activation values (65 kJ/mole) of products having high breathing rates such as strawberries; and is higher than the Ep values of commercial films. According to the results, the obtained material has better potential for packaging fresh fruits and vegetables depending on high gas permeability and heat sensitivity.
- the melting temperature of the crystal region in the structure of Film A can be shown as the changing point of the entire gas permeability.
- the DSC chart of Film A the melting peak which is 24°C can be seen. This temperature can be obtained at the desired temperature in the range of 15-40°C by changing the PEG molecular weight, castor oil and chain lengthener percentages.
- the obtained films show thermal stability up to 300°C. This shows that the films can be commercially processed by extrusion as well as hot press.
- the maximum tensile strength of Film A was calculated as 2,08 MPa, having a maximum extension of 7,9%.
- Young's modulus (E) obtained from the ratio of tension to the deformation is 100 MPa.
- a material was obtained, having mechanical elastic resistance close to LDPE (190 MPa) or to rubber (10-100 MPa).
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Packages (AREA)
- Wrappers (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Packging For Living Organisms, Food Or Medicinal Products That Are Sensitive To Environmental Conditiond (AREA)
- Storage Of Fruits Or Vegetables (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2018517379A JP2019515055A (en) | 2016-04-26 | 2017-04-22 | Packaging film for fresh fruits and vegetables in a controlled atmosphere |
DE112017000128.5T DE112017000128T5 (en) | 2016-04-26 | 2017-04-22 | Packaging film for the packaging of fresh fruits and vegetables in a protective atmosphere |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
TR201605385 | 2016-04-26 | ||
TR2016/05385 | 2016-04-26 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2017188906A1 true WO2017188906A1 (en) | 2017-11-02 |
Family
ID=59914508
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/TR2017/050157 WO2017188906A1 (en) | 2016-04-26 | 2017-04-22 | Packaging film for packing fresh fruits and vegetables under modified atmosphere |
Country Status (3)
Country | Link |
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JP (1) | JP2019515055A (en) |
DE (1) | DE112017000128T5 (en) |
WO (1) | WO2017188906A1 (en) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1992010414A1 (en) | 1990-12-07 | 1992-06-25 | Landec Labs, Inc. | Food package comprised of polymer with thermally responsive permeability |
US5254354A (en) * | 1990-12-07 | 1993-10-19 | Landec Corporation | Food package comprised of polymer with thermally responsive permeability |
WO2006064085A2 (en) * | 2004-12-15 | 2006-06-22 | Ionphase Oy | Novel polymers and method for the production thereof |
US20100242798A1 (en) * | 2006-02-17 | 2010-09-30 | Mitsui Chemicals Polyurethanes, Inc. | Laminating Adhesive |
US20140255560A1 (en) * | 2013-03-06 | 2014-09-11 | H.B. Fuller Company | Gas transmitting polyurethane adhesive |
-
2017
- 2017-04-22 JP JP2018517379A patent/JP2019515055A/en active Pending
- 2017-04-22 WO PCT/TR2017/050157 patent/WO2017188906A1/en active Application Filing
- 2017-04-22 DE DE112017000128.5T patent/DE112017000128T5/en active Pending
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1992010414A1 (en) | 1990-12-07 | 1992-06-25 | Landec Labs, Inc. | Food package comprised of polymer with thermally responsive permeability |
US5254354A (en) * | 1990-12-07 | 1993-10-19 | Landec Corporation | Food package comprised of polymer with thermally responsive permeability |
EP0560901B1 (en) | 1990-12-07 | 1997-05-14 | Landec Labs. Inc. | Packages with temparature-sensitive permeability for foods and flowers |
WO2006064085A2 (en) * | 2004-12-15 | 2006-06-22 | Ionphase Oy | Novel polymers and method for the production thereof |
US20100242798A1 (en) * | 2006-02-17 | 2010-09-30 | Mitsui Chemicals Polyurethanes, Inc. | Laminating Adhesive |
US20140255560A1 (en) * | 2013-03-06 | 2014-09-11 | H.B. Fuller Company | Gas transmitting polyurethane adhesive |
WO2014138218A1 (en) | 2013-03-06 | 2014-09-12 | H.B. Fuller Company | Gas transmitting polyurethane adhesive |
Non-Patent Citations (1)
Title |
---|
DENIZ TURAN ET AL: "Synthesis, Characterization and O 2 Permeability of Shape Memory Polyurethane Films for Fresh Produce Packaging : Shape-Memory Polyurethane Films for Fresh Produce Packaging", PACKAGING TECHNOLOGY AND SCIENCE, vol. 29, no. 7, 26 May 2016 (2016-05-26), UK, pages 415 - 427, XP055413446, ISSN: 0894-3214, DOI: 10.1002/pts.2222 * |
Also Published As
Publication number | Publication date |
---|---|
DE112017000128T5 (en) | 2018-06-14 |
JP2019515055A (en) | 2019-06-06 |
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