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An Oxygen Absorbent Package

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An Oxygen Absorbent Package ~" ' MM II II II II I Ml MM Ml II II I II J European Patent Office tsAts w%n © Publication number: 0 268 848 B1 Office europeen* des.. brevets , EUROPEAN PATENT SPECIFICATION @ Date of publication of patent specification: 20.05.92 % Int. CI.5: B65D 81/26 @ Application number: 87115671.7 (§) Date of filing: 26.10.87 © An oxygen absorbent package. ® Priority: 27.10.86 JP 253759/86 CHEMICAL ABSTRACTS, vol. 102, no. 14, 8th 13.11.86 JP 268542/86 April 1985, abstract no. 114740w, Columbus, 10.03.87 JP 52963/87 Ohio, US; & JP-A-59 163 175 (MITSUBISHI GAS CHEMICAL CO. INC.) 14-09-1984 @ Date of publication of application: 01.06.88 Bulletin 88/22 @ Proprietor: MITSUBISHI GAS CHEMICAL COM- PANY, INC. © Publication of the grant of the patent: 5-2, Marunouchl 2-chome Chlyoda-Ku 20.05.92 Bulletin 92/21 Tokyo, 100(JP) @ Designated Contracting States: @ Inventor: Inoue, Yoshlakl DE FR GB 14-20, Mlnamlmlzumoto-2-chome Katsushlka-ku Tokyo(JP) @ References cited: EP-A- 0 151 489 GB-A- 1 175 739 0 Representative: Patentanwalte Grunecker, GB-A- 2 068 991 Klnkeldey, Stockmalr & Partner US-A- 4 297 402 Maximilianstrasse 58 US-A- 4 579 223 W-8000 Munchen 22(DE) ABSTRACT BULLETIN OF THE INSTITUTE OF PAPER CHEMISTRY, vol. 54, no. 4, October 1983, page 417, abstract no. 3794, Appleton, 00 Wisconsin, US; R.C. YOUNG: "Fluorochemlcal additives for paper and 00 board specialties"; & INNOVATION PAPER 00 IND. CORPORATE EXEC. CONF. (VENICE) PROC.: 108-111 (MAY 1980) 00 CO CM Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid (Art. 99(1) European patent convention). Rank Xerox (UK) Business Services (3.08/2. 19/2.0) EP 0 268 848 B1 Description This invention is directed to an oxygen absorbent package used for storage of foodstuff of high water content, foodstuff containing alcohols and foodstuff containing a large amount of oil, and is also directed to 5 an oxygen absorbent package used for storage of retort foods. Use of oxygen absorbents is known as a technique for storage of foodstuff. According to this technique, foodstuff to be stored and an air-permeable package packed with an oxygen absorbent are enveloped in a gas-barrier packaging material and the sealed system is brought into a substantially oxygen-free state to thereby prevent oxidation of packed foodstuff and development of bacteria or mold on or in such foodstuff io (See US Patents 4,113,652, 4,104,192, 4,119,472, 4,127,503, 4,166,807 and 4,192,773). This technique is used for storage of a variety of foods. There is also known a retort pouching technique for long-time preservation of foodstuff. This technique features heating of the packed foodstuff at 100-1 50 °C for 2-80 min to kill the bacteria causative of putrefaction to thereby allow long-time storage of foodstuff. It has been, however, extremely difficult to 75 exterminate even the spores of thermophilic bacteria in the retort food, and it has been quite probable that the spores of a bacterium germinate and grow in the retort food to cause its deterioration, or that the foodstuff, especially the oil or fat contained in the foodstuff is oxidized by oxygen present in the spaces in the retort pouch to change the taste or quality of foodstuff before the retort food is served to the consumers. If the foodstuff storage technique by use of oxygen absorbents can be applied to said retort foods, it 20 becomes possible not only to inhibit germination and growth of the spores of thermophilic bacteria in retort foods but also prevent the oxidation of oil and fat and accordingly the change of taste of foodstuff, thus realizing an elongation of safe storage period of retort foods. Generally, when air-permeable packages used as oxygen absorbent packages are applied to the field of foodstuff, it is essential that such packages satisfy the requirements for waterproofness, resistance to 25 breakage and hygienic safety in addition to air permeability. Further, in case such packages are used for storage of foodstuff of high water content, foodstuff containing alcohols or foodstuff containing a large amount of oil, they are required to have proofness against alcohols and oils beside waterproofness. Heat resistance is also required for the packages when they are used for storage of retort foods. As materials used for oxygen absorbent packages, there are known microporous films made of porous 30 plastic materials, such as Celgard (Celanese Corp.), Nitto Flon NTF (Nitto Electric Industrial Co., Ltd), and NF sheet (Tokuyama Soda Chemical Co.) and nonwoven fabrics made of polyethylene fibre, polyamide fibre, polyester fibre, polypropylene fibre or the like, such as Tyvek (E.I. Du Pont) and Spubond (Asahi Kasei Co., Ltd). These packaging materials, however, have the following defects. 35 (1) When contacted with foodstuff containing oil or alcohol, said packaging materials are impregnated with oil or alcohol from the portion contacted therewith. (2) Since the sealing material is polyethylene having a low softening point, the sealed portion may peel off to break the package when the package is applied to retort foods and subjected to heat sterilization. (3) Oil or alcohol can penetrate into the packed substance to obstruct absorption of oxygen, making the 40 oxygen absorbent unable to perform its food preserving activity. For the improvement of resistance to oils and alcohols, Japanese Patent Application Kokai (Laid-Open) No. 64959/83 and Abstract Bulletin of the Institute of Paper Chemistry 3794, Vol 54, No. 4, October 1983, disclose a method in which the packaging material composed of a microporous film or nonwoven fabric is impregnated or coated with a fluorine resin. 45 This method, however, has the disadvantage that since the microporous film or nonwoven fabric used for the packaging material is hydrophobic, the fluorine resin applied does not spread all over the packaging material but merely stays in the surface of the packaging material, thus imposing a limitation to the degree of proofness against oils and alcohols that the packaging material can provide. Further, since there locally exist parts with large openings in said microporous film or nonwoven fabric, 50 even if it is impregnated or coated with a fluorine resin, oil or alcohol enters from the parts with large openings and can infiltrate into the side of the packaging material or even into the oxygen absorbent packed therein. When an oxygen absorbent package using paper made from fluorine resin-added natural pulp as a part of packaging material is contacted with an oil-containing moist food such as doughnut or fried fish ball, oil 55 soaks into the packaging material along with water in a relatively short time. Thus, it is difficult to provide such oxygen absorbent packages with satisfactory oil resistance in practical use. 2 EP 0 268 848 B1 Japanese Utility Model Publication No. 22048/84 discloses an oxygen absorbent package comprising a laminate package made by bonding a microporous film and a sheet having a higher softening point than said film. This package, however, cannot be applied to retort foods containing an oil or alcohol because the 5 microporous film is not provided with resistance to oils and alcohols. EP-A-151489 discloses an oxygen absorbent package which is partly formed with an air permeable sheet made from plastic fibre produced by a wet processing and drying which sheet can be treated with a water or oil repellent. It is the object of the present invention to provide an oxygen absorbent package which does not permit io penetration of oil or alcohol into the package and can fulfill its function even if it is packed with retort foods containing an oil or alcohol along with water and subjected to heat sterilization. Said object is achieved by an oxygen absorbent package according to claims 1 to 18 and a retort food according to claims 19 and 20. It has been found that a sheet material obtained by wet processing plastic fibre such as polyethylene or is polypropylene followed by drying has no water resistance and sucks up water when contacted with water. When this sheet material after drying is impregnated with a fluorine resin in the form of an emulsion or solution and dried, the fluorine resin is adhered to the whole of fibre, and when this sheet material is hot pressed, it is provided with not only air permeability and water resistance but also a high degree of resistance to alcohols and oils. 20 The thus obtained sheet is suitable for use as a material for forming an oxygen absorbent package. It was further found that the incorporation of a specific reinforcing material for reinforcing the strength of said sheet can provide a sheet improved in strength against stress in the longitudinal direction. Further a package bonded with a porous composite film (b) made by laminating a resin layer having a lower softening point than said sheet and a resin layer having a higher softening point than said sheet and 25 perforating the laminate is provided with high heat resistant, eliminating any fear of breakage even under high temperatures, in addition to air permeability and water resistance, and also has a high degree of resistance to alcohols and oils which cannot be expected from conventional packaging materials.
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