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(12) Patent Application Publication (10) Pub. No.: US 2011/0171074 A1 Naka0 Et Al

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(12) Patent Application Publication (10) Pub. No.: US 2011/0171074 A1 Naka0 Et Al US 2011 0171074A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2011/0171074 A1 Naka0 et al. (43) Pub. Date: Jul. 14, 2011 (54) DEOXIDIZING MULTILAYERED BODY Publication Classification (75) Inventors: Kimitaka Nakao, Chiba (JP); (51) Int. Cl. Emiko Yokose, Tokyo (JP) A62B 7/08 (2006.01) (52) U.S. Cl. ........................................................ 422/120 (73) Assignee: MTSUBISHIGAS CHEMICAL COMPANY, INC., Chiyoda-ku, (57) ABSTRACT Tokyo (JP) The present invention provides a deoxidizing multilayered body, which sufficiently suppresses the production of odor (21) Appl. No.: 13/060,644 ous organic components produced with oxidation, and which absorbs oxygen at a fast rate. The present invention is the (22) PCT Filed: Aug. 26, 2009 deoxidizing multilayered body that is constituted by laminat (86). PCT No.: PCT/UP2009/004129 ing at least an isolation layer (A) that contains athermoplastic resin, an odor absorption layer (B), which is made from an S371 (c)(1), odor absorbent resin composition (b) that contains an oxidiz (2), (4) Date: Apr. 1, 2011 able thermoplastic resin, a transition metal catalyst, and an odor absorbent, an oxygen absorption layer (C), which is (30) Foreign Application Priority Data made from an oxygen absorbent resin composition (c) that contains an oxidizable thermoplastic resin and a transition Aug. 26, 2008 (JP) ................................. 2008-216736 metal catalyst, and an oxygen barrier layer (D), which con Apr. 3, 2009 (JP) ................................. 2009-091034 tains an oxygen barrier Substance, in this order. 1 O (D) 22 u-(C) ^2/622 a a C2 a 2 Y22 2 21 2 (B) (A) Patent Application Publication Jul. 14, 2011 Sheet 1 of 2 US 2011/0171074 A1 F I G. 1 (D) 2 2Z N a p 2 2 Øy / 2/2 2 2/42 2 2 2 2 2 2 M 2 (B) (A) Patent Application Publication Jul. 14, 2011 Sheet 2 of 2 US 2011/0171074 A1 F I G. 2 y O O (A) (B) (C) (D) O US 2011/0171074 A1 Jul. 14, 2011 DEOXDZING MULTILAYERED BODY 0007 Patent Document 2: Japanese Patent Application TECHNICAL FIELD Publication (JP-B) No. 2991437 0001. The present invention relates to a deoxidizing mul 0008 Patent Document 3: JP-B No. 3183704 tilayered body. The deoxidizing multilayered body of the 0009 Patent Document 4: JP-A No. 05-247276 present invention can be used for part or whole of a deoxidiz 0010 Patent Document 5: JP-A No. 06-100042 ing container, sheet, or film. O011 Patent Document 6: JP-B No. 3306071 0002. In the present specification, the term “deoxidize” 0012 Patent Document 7:JP-B No. 2837057 means that the oxygen concentration becomes 0.1 vol% or 0013 Patent Document 8:JP-A No. 2007-204892 less under a sealed environment and the term “deoxidizer” means a chemical agent, a material, and the like which are used for the purpose of achieving a deoxidized state. Further, SUMMARY OF THE INVENTION the term "deoxidizing has the same meaning as the expres Problems to be Solved by the Invention sion "has a function of a deoxidizer. Still further, the term "oxygen absorb means that the chemical agent, material, and 0014. The present inventors found the followings. the like take in the oxygen contained in the environment 0015 Specifically, as described above, the deoxidizing regardless of the reached oxygen concentration. multilayered film which contains an oxygen absorption layer BACKGROUND ART made of oxidizable organic components or resin components 0003 For the purpose of preserving for a long period of and a metal catalyst is problematic in that odorous organic time the various products that are prone to deteriorate or components are produced with oxidation of the organic com degrade under the influence of oxygen, and that are repre ponents or the resin components during deoxidization pro sented by food products, beverages, pharmaceuticals, medi cess. In particular, when the deoxidizing multilayered film is cal products, cosmetics, metal products, and electronic prod used for packaging of a food product, flavor of the food ucts by preventing their oxidation by oxygen, a deoxidizer product is impaired even by production of weak odor, yield which eliminates oxygen contained in a packaging container ing a significant problem of lowering the value of the food or a packaging bag storing such products has been used. The product. shape which has been developed at early stage and still used 0016. Accordingly, an object of the present invention is to commonly as the deoxidizer is a shape in which a deoxidizer provide a deoxidizing multilayered body, which suppresses consisted of powdery or granular iron powder, or ascorbic the production of odorous components produced with oxida acid, or the like is filled in a air-permeable sachet. tion, and which can absorb oxygen at a practically sufficient 0004. In recent years, a film type deoxidizer having good rate. handleability, wide application range, and very little possibil ity of accidental ingestion is also being used. With respect to Means for Solving the Problems the film type deoxidizer, various suggestions have been made in terms of an oxygen absorbent composition and a film 0017. The present inventors conducted a research on a constitution. A basic deoxidizing multilayered body, that is deoxidizing multilayered body, and as a result found that by obtained by adding a deoxidizer like iron powder or ascorbic laminating an odor absorption layer containing an odor absor acid to a resin, molding the resin into a film, a sheet, or the bent and an oxygen absorption layer, and laminating at the like, laminating an isolation layer having heat sealability on same time an isolation layer on the odor absorption layer side one side, and laminating a gas barrier layer on the other side, and an oxygen barrier layer side on the oxygen absorption is known (Patent Document 1). Further, a packaging film layer, a deoxidizing multilayered body which Suppresses the containing a layer made from oxidizable organic components production of odorous organic components produced with or resin components and a transition metal catalyst is also oxidation and can absorb oxygen at a practically sufficient known (Patent Documents 2 and 3). Further, for the purpose rate is obtained, and accomplished the present invention. of suppressing odor produced by a deoxidizer consisted of an 0018 Specifically, the present invention is a deoxidizing organic material with the oxidation, including an adsorbent multilayered body constituted by laminating at least an iso like Zeolite, etc. in an oxygen absorbent composition, prepar lation layer (A) that contains a thermoplastic resin, an odor ing a deoxidizing multilayered film which is obtained by absorption layer (B), which is made from an odor absorbent laminating layers containing an adsorbent, or preparing a resin composition (b) that contains an oxidizable thermoplas deoxidizing multilayered film which is obtained by laminat tic resin, a transition metal catalyst, and an odor absorbent, an ing layers containing a base as a neutralizing agent of an oxygen absorption layer (C), which is made from an oxygen acidic gas, that is a cause of odor has been Suggested (Patent absorbent resin composition (c) that contains an oxidizable Documents 4 to 6). thermoplastic resin and a transition metal catalyst, and an 0005. Further, with respect to an agent of eliminating alde oxygen barrier layer (D), which contains an oxygen barrier hyde-based gas as a cause of unusual Smell, an amine com Substance, in this order. pound, a hydrazide compound, a hydrazine compound or a 0019. Further, in the deoxidizing multilayered body of the hydrazine derivative Supported on an inorganic material is present invention, the isolation layer (A) is preferably an known mainly for the purpose of the elimination of tobacco acidic gas absorbent isolation layer (Aa), which is made from Smell and a counter measureagainst a sick building syndrome an acidic gas absorbent resin composition (a) that contains an (Patent Documents 7 and 8). acidic gas absorbent and a thermoplastic resin. 0020. The odor absorbent used in the present invention PRIOR ART DOCUMENTS preferably contains a hydrazine derivative, a urea derivative, Patent Documents or a guanidine derivative, and particularly preferably, it is 0006 Patent Document 1: Japanese Patent Application constituted by having a hydrazine derivative, a urea deriva Laid-Open (JP-A) No. 55-90535 tive, or a guanidine derivative Supported on a carrier. US 2011/0171074 A1 Jul. 14, 2011 0021. Further, it is preferable that the hydrazine derivative layer side. However, since the odor absorption layer acts as is an aminoguanidine derivative and/or a hydrazine double resistance to oxygen permeation, the oxygen absorption rate salt. was decreased. 0022. The acidic gas absorbent used in the present inven 0031. Meanwhile, when an odor absorbent is included in tion is preferably a base compound, and particularly prefer the oxygen absorbent resin composition containing an oxi ably magnesium oxide. dizable thermoplastic resin and a transition metal catalyst, it 0023 The deoxidizing multilayered body of the present was possible to obtain both the oxygen absorption rate and the invention may further contain a photoinitiator in the odor odor Suppressing effect. However, when the resin composi absorbent resin composition (b) and/or the oxygen absorbent tion is used for the oxygen absorption layer to provide a resin composition (c). deoxidizing multilayered body having three layers of an iso 0024. In the deoxidizing multilayered body of the present lation layer, the oxygen absorption layer, and an oxygen invention, it is preferable that the oxygen absorbent resin barrier layer, the oxygen absorption rate was significantly composition (c) further contains at least one component decreased although it was possible to obtain the odor Sup selected from a group consisting of a photoinitiator, another pressing effect. thermoplastic resin that is different from the oxidizable ther 0032.
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