JP3824915B2 - Freshness-keeping packaging material, fruit and vegetable packaging, and freshness-keeping packaging method - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、青果物などの包装に適した包装材、包装体、及びそれを用いた鮮度保持方法に関し、更に詳しくは、青果物の呼吸量と包装材のガス透過量とのバランスで青果物の存在する雰囲気中のガス濃度を調整し、青果物を低呼吸状態に維持することによって鮮度を長く保持することができる鮮度保持包装材、包装体、及び鮮度保持方法に関するものである。
【０００２】
【従来の技術】
従来、青果物などの鮮度保持方法は種々提案されている。特開昭６１−２１６６４０号公報には、炭酸ガス透過度と酸素ガス透過度との比が一定範囲のフィルムが記載されている。しかし、ブロッコリーなどの呼吸量の多い青果物によっては、嫌気障害を起こす可能性が大きいことが判明した。特公平８−２２４１号公報には、炭酸ガス透過係数と酸素透過係数の比、及び水蒸気透過係数が一定範囲にある合成樹脂フィルムが記載されている。このフィルムは透過係数が前記範囲内にあっても、フィルム厚さが厚くなるとガス透過量が低下するために、嫌気障害が起こり易くなって鮮度低下を早める可能性があることが推定される。更に、上記の従来技術は、青果物の呼吸を利用した所謂ＭＡ（Modified Atmosphere）保存であり、一般的にＭＡ状態へ到達するには数日間を要するために、それまでの期間は空気中での呼吸状態に近く、保存開始時からガス濃度が調整された所謂ＣＡ（Controlled atmosphere）保存と比較すると鮮度保持効果が低いおそれがある。特表２００１−５０４８７５号公報には、特定密度、特定分子量分布Ｍｗ／Ｍｎ、示差走査熱量計で測定して単一溶融ピーク、特定のメルトインデックスを有する少なくとも１種の均一線状もしくは実質的に線状であるエチレンポリマーとプロピレンと随意にエチレンからなり、特定メルトフロー率を有するホモポリマーまたはコポリマーである少なくとも１種のポリプロピレンポリマー、及び任意に、スリップ、アンチブロック、ポリマー加工助剤、アンチフォッグ、アンチスタット及びロールリリースからなる群から選択されて１種以上の添加剤を含むブレンド物を含んでなるフィルムを少なくとも１層含む腐敗し易い食品の包装で用いる穴無しフィルム構造物が記載されている。
また、ＷＯ９９／５１６６５公報には、フィルム厚さ、水蒸気の透過度、酸素ガスの透過度、およびエチレンガスの透過度を一定範囲に規定した単層または多層フィルムに関する発明が記載されている。この気体透過性フィルムは、酸素ガスの取り込み、エチレンガスの発散を十分に維持した上で、水蒸気の発散を適度に抑制し得る結果、青果物の瑞々しさを長く維持できる効果を奏し得ると記載されている。
【０００３】
【発明が解決しようとする課題】
本発明は、上記従来技術に鑑みてなされたものであり、その目的は、呼吸量の少ない青果物から呼吸量の多い青果物まで鮮度保持が可能で、フィルムのガス透過度のバラツキの少ない包装材を提供することにある。また、別の目的として、ＭＡ状態への到達時間を短縮できる青果物の保存方法を提供するにある。
【０００４】
【課題を解決するための手段】
本発明者らは、エチレン−オクテン共重合体とポリプロピレン−エチレン共重合体の特定割合の混合樹脂からなるフィルムがかかる問題点を解決し得ることを見い出し、本発明を完成するに至った。
【０００５】
すなわち本発明は、エチレン−オクテン−１共重合体７０〜９５重量％とプロピレン−エチレン共重合体５〜３０重量％のブレンドからなるポリオレフィン樹脂からなり、２３℃、８０％ＲＨにおける酸素ガス透過度が６５００〜９５００ｃｍ３／ｍ２・ｄａｙ・ａｔｍで、２３℃、８０％ＲＨにおける二酸化炭素ガス透過度が２３０００〜３８０００ｃｍ３／ｍ２・ｄａｙ・ａｔｍであり、二酸化炭素ガス透過度と酸素ガス透過度の比（ＣＯ２／Ｏ２）が３．５〜４．１であり、且つ、水蒸気透過度が８〜３５ｇ／ｍ２・ｄａｙ・ａｔｍである鮮度保持包装材を提供する。貯蔵弾性率が１１０〜１２００ＭＰａである前記発明の鮮度保持包装材を提供する。貯蔵弾性率をＥ（ＭＰａ）、フィルム厚さをｔ（μｍ）としたときＥ×ｔ３が５０×１０３〜５０×１０６である前記発明の鮮度保持包装材を提供する。ポリオレフィン樹脂からなる前記発明の鮮度保持包装材を提供する。更に、アンチブロッキング剤、スリップ剤、防曇剤を含んでなる前記発明の鮮度保持包装材を提供する。フィルムである前記発明の鮮度保持包装材及び密封可能な開封部を有する袋である前記発明の鮮度保持包装材を提供する。
本発明は、前記発明の鮮度保持包装材で青果物を包装した包装体を提供する。
また、前記発明の鮮度保持包装材を用いて青果物を包装する際に、青果物と共に脱酸素剤を封入する青果物の鮮度保持方法を提供する。
【０００６】
【発明の実施の形態】
以下に本発明を詳細に説明する。
本発明の鮮度保持包装材は、酸素ガス透過度が２３℃、８０％ＲＨにおいて６５００〜９５００ｃｍ3／ｍ2・ｄａｙ・ａｔｍ、好ましくは７８００〜９４００ｃｍ3／ｍ2・ｄａｙ・ａｔｍ、更に好ましくは８０００〜９３００ｃｍ3／ｍ2・ｄａｙ・ａｔｍであり、２３℃、８０％ＲＨにおける二酸化炭素ガス透過度が２３０００〜３８０００ｃｍ3／ｍ2・ｄａｙ・ａｔｍ、好ましくは２８０００〜３７０００ｃｍ3／ｍ2・ｄａｙ・ａｔｍ、更に好ましくは２９０００〜３８０００ｃｍ3／ｍ2・ｄａｙ・ａｔｍであり、二酸化炭素ガス透過度と酸素ガス透過度の比（ＣＯ2／Ｏ2）が３．５〜４．１、好ましくは３．６〜４．０、更に好ましくは３．８〜４．０である。これらの要件を満たす材料樹脂としては、例えば、以下のポリオレフィン樹脂から選択することができる。ＣＯ2／Ｏ2 が４．１を越える場合は、系内のＣＯ2濃度が低下し、酵素活性の働き、または、エチレン生成を抑制する効果が低くなるため鮮度保持効果が少なくなるおそれがあり、３．５未満の場合は、系内のＣＯ2濃度が高くなり、ＣＯ2障害が起こり、鮮度が落ちることがあるので、規定の範囲にあることが必要である。
【０００７】
前記ガス透過度に関する条件を満足する包装材は、種々の樹脂又はそれらの組合せにより選択できる。それらの樹脂の例としては、エチレン−ブテン−１共重合体、エチレン−４−メチルペンテン−１共重合体、エチレン−ヘキセン−１共重合体、エチレン−オクテン−１共重合体等のエチレン−α−オレフィン共重合体；高密度ポリエチレン（ＨＤＰＥ）、低密度ポリエチレン、線状低密度ポリエチレン、超低密度ポリエチレン等のポリエチレン類；ポリエチレン系アイオノマー、エチレン−酢酸ビニル共重合体、エチレン−アクリル酸共重合体、エチレン−メチルメタクリレート共重合体、エチレン−プロピレン共重合体、ポリプロピレン、ポリスチレン、ポリスチレン−アクリロニトリル共重合体、ポリウレタン、ポリブタジエン、ポリ塩化ビニル、スチレンブタジエンゴム、シリコンゴム、ポリテトラフルオロエチレン、ポリカーボネート、ナイロン１２、ポリ４−メチルペンテン−１、ポリサルホン、三酢酸セルローズ、エチルセルロース、酢酸ブチルセルローズ、ポリジメチルシロキサン、ポリ乳酸、ポリブチレンサシネート−アジテート共重合体、ポリカプロラクトン、ポリヒドロキシブチレート−バリレート共重合体、主成分がブタンジオールとテレフタル酸とアジピン酸とスルホネート化合物からなるポリエステル共重合体、ポリブチレンサクシネート−カーボネート共重合体等を挙げることができる。これらの樹脂から包装対象物の呼吸量、及び包装体としたときの外観、包装材のガス透過度、ＣＯ2／Ｏ2などを考慮して適宜、選択する。
【０００８】
更に、青果物を包装する場合、青果物の有する水分が包装体内に曇り状となって付着するのを防ぐためには、包装材自体の水蒸気透過度が８〜３５ｇ／ｍ2・ｄａｙ・ａｔｍ、好ましくは１５〜２８ｇ／ｍ2・ｄａｙ・ａｔｍ、更に好ましくは１８〜２５ｇ／ｍ2・ｄａｙ・ａｔｍである。これらの条件が満たされると呼吸量のすくない青果物から呼吸量の多い青果物まで鮮度保持が可能な包装材を得ることができる。
水蒸気透過度を満足する包装材としては、前記のエチレン−α−オレフィン共重合体、前記ポリエチレン類、ポリエチレン系アイオノマー、エチレン−酢酸ビニル共重合体、ポリ塩化ビニリデン共重合体、ナイロン１１、ナイロン１２、ポリエチレンテレフタレート、ポリプロピレン、ポリＰＥニルサルファイド、ポリエーテルエーテルケトン、ポリテトラフルオロエチレン、塩酸ゴムなどを挙げることができるが、前記のガス透過度の条件と水蒸気透過度の条件を同時に満たすものの中から選ぶことができる。好ましい樹脂の例としてはエチレン−α−オレフィン共重合体を主体とした樹脂、α−オレフィンとしては、例えば、オクテン−１を５〜１５重量％含む共重合体、エチレン−オクテン−１共重合体（オクテン含量約１２％）７０〜９５重量％とプロピレン−エチレンランダム共重合体（エチレン含量約３％）５〜３０重量％とのブレンド物を挙げることができる。このブレンド物からなるフィルムの厚さは、酸素ガス透過度、二酸化炭素ガス透過度、二酸化炭素ガス透過度と酸素ガス透過度の比、及び水蒸気透過度が本発明で規定する範囲に入るように設定すればよい。
本発明の鮮度保持包装材料のフィルム厚さは、特別の制限はないが実用的には２０〜５０μｍ、更には３０〜４５μｍが好ましい。また、ＨＤＰＥ１０重量％とエチレン−オクテン−１共重合体（オクテン含量約１２重量％）９０重量％の樹脂からなるフィルム厚さ２３μｍのフィルム、プロピレン−エチレンランダム共重合体（エチレン含量約３重量％）２０重量％とエチレン−オクテン−１共重合体（オクテン含量約１２重量％）８０重量％の樹脂からなるフィルム厚さ３０μｍのフィルム等が挙げられる。尚、これらの樹脂は、フィルムに成形後、袋に加工されることがあるので超音波シール、熱シール可能な熱シール性を有することが好ましい。
本発明の鮮度保持包装材は、前記ガス透過度、及び水蒸気透過度の条件が満たされている限り、延伸されていても、未延伸であってもよい。
【０００９】
本発明の鮮度保持包装材は、取り扱い易さ、適度な硬さ、密封性の観点から貯蔵弾性率は、１１０〜１２００ＭＰａ、更には１４０〜２５０ＭＰａであることが好ましい。貯蔵弾性率がこの範囲内にあることにより、柔らかすぎることがなく、取り扱い易さが良好なので好ましい。また、貯蔵弾性率をＥ（ＭＰａ）、フィルム厚さをｔ（μｍ）としたときＥ×ｔ3の数値が５０×１０3〜５０×１０6で、更には５×１０6〜１５×１０6であることが密封性、取り扱い性の観点から好ましい。尚、フィルム厚さには、特に制限はないが、通常２０〜６０μｍ、更には３０〜５０μｍであることが好ましい。本発明においては、ガス透過性を所定の水準に合わせるためにフィルム厚さを調整することができる。
【００１０】
本発明の鮮度保持包装材は、フェノール系、有機イオウ系、有機窒素系、有機リン系の酸化防止剤や熱安定剤、金属石ケンや他の脂肪酸エステルなどの脂肪酸誘導体等の滑剤、アンチブロッキング剤、スリップ剤、防曇剤、帯電防止剤、炭酸カルシウム、ホワイトカーボン、チタンホワイト、炭酸マグネシウム、ケイ酸マグネシウム、カーボンブラック、各種クレイ、天然又は合成ゼオライト等の無機系充填剤或いは他の着色料などの配合剤を包装材樹脂１００重量部に対して０．５〜８重量部配合することができる。
【００１１】
本発明の鮮度保持包装材は、Ｔダイ法、インフレーション法を用いて製膜することができる。また、本発明の条件を満たす限り、他の樹脂との共押出、或いは樹脂フィルムとのラミネートであってもよい。包装材は、種々の形態で青果物の包装に適用でき、その使用形態には特に制限はない。密封可能な袋などが好ましく用いられる。本発明の包装材は青果物を単独で包装してもよいが、場合により青果物と共に脱酸素剤を封入する鮮度保持方法をとってもよい。
【００１２】
【実施例】
以下、実施例により本発明を具体的に説明するが、本発明はこれらに限定されるものではない。なお、物性などの測定法は、次の通りである。
１．ガス透過度
試料を２３℃、５０％相対湿度（ＲＨ）の雰囲気中で２４時間放置した後、GL Sciences社製、フィルム両面加湿ガス透過測定装置を用いて２３℃、８０％ＲＨにおける酸素ガス透過度、及び二酸化炭素ガス透過度を測定した。
２．水蒸気透過度
試料を２３℃、５０％相対湿度（ＲＨ）の雰囲気中で２４時間放置した後、LYSSY社製、水蒸気透過量測定装置 Ｌ８０−４０００を用いて４０℃、９０％ＲＨにおける水蒸気透過度を測定した。
３．酸素ガス濃度
東レエンジニアリング社製、酸素濃度計ＬＣ−７５０を用いて袋内酸素ガス濃度を測定した。
４．二酸化炭素ガス濃度
Ｙａｎａｃｏ社製、ガスクロマトグラフＧ３８００を用いて袋内部の二酸化炭素ガス濃度を測定した。
５．貯蔵弾性率
試料を２３℃、５０％相対湿度（ＲＨ）の雰囲気中で２４時間放置した後、レオメトリックス社製、動的粘弾性測定装置ＲＳＡIIを用いて、周波数１０Ｈｚで温度２０℃における貯蔵弾性率（動的弾性率）を測定した。
【００１３】
（実施例１）
エチレン−オクテンコポリマー（ダウ・ケミカル日本（株）、オクテン含量約１２％、ＰＬ１８８０）のペレット９０重量％、プロピレン−エチレンコポリマー（日本ポリケム（株）、ＥＧ７ＦＴ）のペレット１０重量％をブレンドし、これらの樹脂成分に対してアンチブロッキング剤マスターバッチ（三井化学株式会社製、ＬＤＺ５０−２０）を２ｐｈｒ、スリップ剤マスターバッチ（理研ビタミン（株）、ＥＬＭ−０８０）を２ｐｈｒ、防曇剤マスターバッチ（理研ビタミン、ＫＰ−４１０）を３ｐｈｒ添加し、Ｔダイ法により厚さ４５μｍの未延伸フィルムを得た。このフィルム（貯蔵弾性率が１４３ＭＰａ、Ｅ×ｔ3＝１３．０×１０6）を用いて、大きさが２５ｃｍ×２５ｃｍの正方形で、正方形の３辺をインパルスシーラーでシールした袋を作製し、苺を約３００ｇ（１パック）入れた後に残りの１辺をインパルスシールして５℃で保存した。
【００１４】
（実施例２）
実施例１と同一の原料処方で、Ｔダイ法によって厚さ３５μｍのフィルムを得た。このフィルム（貯蔵弾性率が１４３ＭＰａ、Ｅ×ｔ3＝６．１×１０6）を用いて、大きさが２５ｃｍ×２５ｃｍの正方形で、正方形の３辺をインパルスシーラーでシールした袋を作製し、苺を約３００ｇ（１パック）入れた後に残りの１辺をインパルスシーラーでシールして５℃で保存した。また、同様にして作製した袋にブロッコリーを１房（約２５０ｇ）入れて、残りの１辺をインパルスシーラーでシールして７℃で保存した。
【００１５】
（実施例３）
実施例１と同一の原料処方で、ダイレクトブロー法により厚さ３５μｍのフィルムを得た。このフィルム（貯蔵弾性率が２２２ＭＰａ、Ｅ×ｔ3＝９．５×１０6）を用いて、大きさが２５ｃｍ×２５ｃｍの正方形で、正方形の３辺をインパルスシーラーでシールした袋を作製し、苺を約３００ｇ（１パック）入れた後に残りの１辺をインパルスシーラーでシールして５℃で保存した。
【００１６】
（比較例１）
エチレン−オクテンコポリマー（ダウ・ケミカル日本（株）、ＰＬ１８８０）にアンチブロッキング剤マスターバッチ（三井化学株式会社製、ＬＤＺ５０−２０）を２ｐｈｒ、スリップ剤マスターバッチ（理研ビタミン（株）、ＥＬＭ−０８０）を２ｐｈｒ添加し、Ｔダイ法で厚さ４５μｍのフィルムを得た。このフィルムを用いて、大きさが２５ｃｍ×２５ｃｍの正方形で、正方形の３辺をインパルスシーラーでシールした袋を作製し、苺を約３００ｇ（１パック）入れた後に残りの１辺をインパルスシーラーでシールして５℃で保存した。
【００１７】
（比較例２）
エチレン−オクテンコポリマー（ダウ・ケミカル日本（株）、ＰＬ１８８０）８０重量％、プロピレン−エチレンランダムコポリマー（日本ポリケム（株）、ＥＧ７ＦＴ、エチレン含量約３％）２０重量％をブレンドし、これらの樹脂成分に対してアンチブロッキング剤マスターバッチ（三井化学株式会社製、ＬＤＺ５０−２０）を２ｐｈｒ、スリップ剤マスターバッチ（理研ビタミン（株）、ＥＬＭ−０８０）を２ｐｈｒ添加し、Ｔダイ法により厚さ４５μｍの未延伸フィルムを得た。このフィルムを用いて、大きさが２５ｃｍ×２５ｃｍの正方形で、正方形の３辺をインパルスシーラーでシールした袋を作製し、苺を約３００ｇ（１パック）入れた後に残りの１辺をインパルスシールして５℃で保存した。また、同様にして作製した袋にブロッコリーを一房（約２５０ｇ）入れ、残りの１辺をインパルスシールして７℃で保存した。
【００１８】
（実施例４）
実施例１と同一の袋を作製し、この袋に脱酸素剤（三菱ガス化学（株）製、エージレスＳＳ−１００）と共に苺を約３００ｇ（１パック）入れて残りの１辺をインパルスシーラーでシールし、５℃で保存した。
【００１９】
（実施例５）
実施例１で得たフィルム（貯蔵弾性率が１４３ＭＰａ、Ｅ×ｔ3＝１３．０×１０6）を用いて、大きさが２５ｃｍ×２５ｃｍの正方形で、正方形の３辺をインパルスシーラーでシールし、残りの１辺を密着可能な巾着式にして、ブロッコリーを１房（約２５０ｇ）入れて開口部を絞ってストッパーで止閉し、７℃で８日間保存した結果、袋内部の酸素ガス濃度は開口部をインパルスシーラーでシールした実施例２と同じレベル（２．８％）であった。
（実施例６）
実施例２で得たフィルム（貯蔵弾性率が１４３ＭＰａ、Ｅ×ｔ3＝６．１×１０6）を用いて、実施例５と同様な巾着袋を作製し、ブロッコリーを１房（約２５０ｇ）入れて開口部を絞ってストッパーで止閉し、７℃で８日間保存した結果、袋内部の酸素ガス濃度は開口部をインパルスシーラーでシールした実施例２と同じレベル（３．７％）であった。
【００２０】
（比較例３）
厚さ３５μｍのポリプロピレン−エチレン共重合体製のフィルム（貯蔵弾性率が１２５０ＭＰａ、Ｅ×ｔ3＝５４×１０6）を用いて、実施例５と同様な巾着袋を作製し、ブロッコリーを１房（約２５０ｇ）入れて開口部を絞ってストッパーで止閉し、７℃で８日間保存した結果、袋内部の酸素ガス濃度は空気中と同じ２１％であった。
実施例１〜３、及び比較例１〜２で得たフィルムのガス透過度、ガス透過の比、及び水蒸気透過度を表１に、実施例１〜４、及び比較例１〜２の苺包装試験の包装内部のガス濃度、外観の変化を表２に示した。また、実施例６及び比較例２のブロッコリー包装試験の包装内部のガス濃度、外観の変化を表３に示した。
【００２１】
【表１】
【表２】
【表３】
（実施例７）
実施例３と同様な袋を用いて、保存品を替え、保存温度７℃で、７日間保存した際の、包装内部のガス濃度、外観の変化を表４に示した。
【００２５】
【表４】
【発明の効果】
本発明によれば、鮮度保持効果が大きく、青果物の包装時に脱酸素剤を併用することによって、包装袋内部の酸素濃度の低下時間を早めることが可能になり、鮮度の保持効果が更に大きい包装材を与えることが可能になった。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a packaging material suitable for packaging fruits and vegetables, a package, and a freshness maintaining method using the packaging material, and more particularly, the presence of fruits and vegetables in a balance between the respiration rate of fruits and vegetables and the gas permeation rate of the packaging material. The present invention relates to a freshness-keeping packaging material, a package, and a freshness-keeping method that can maintain freshness for a long time by adjusting the gas concentration in the atmosphere and maintaining the fruits and vegetables in a low-breathing state.
[0002]
[Prior art]
Conventionally, various methods for maintaining the freshness of fruits and vegetables have been proposed. Japanese Patent Application Laid-Open No. 61-216640 describes a film in which the ratio of carbon dioxide gas permeability to oxygen gas permeability is within a certain range. However, it was found that some fruits and vegetables with high respiration rate such as broccoli are likely to cause anaerobic injury. Japanese Examined Patent Publication No. 8-2241 describes a synthetic resin film in which the ratio of the carbon dioxide gas permeability coefficient to the oxygen permeability coefficient and the water vapor permeability coefficient are within a certain range. Even if the permeability coefficient of the film is within the above range, it is estimated that an increase in the thickness of the film results in a decrease in the amount of gas permeation. Furthermore, the above-mentioned conventional technique is so-called MA (Modified Atmosphere) preservation using the respiration of fruits and vegetables, and generally it takes several days to reach the MA state. Compared with so-called CA (Controlled atmosphere) storage in which the gas concentration is adjusted from the beginning of storage close to the breathing state, the freshness maintaining effect may be low. JP-T-2001-504875 discloses a specific density, a specific molecular weight distribution Mw / Mn, a single melting peak measured by a differential scanning calorimeter, at least one uniform linear or substantially having a specific melt index. At least one polypropylene polymer that is a homopolymer or copolymer of ethylene polymer, propylene, and optionally ethylene, with a specific melt flow rate, and optionally slip, antiblock, polymer processing aid, antifog A non-perforated film structure for use in packaging of perishable foods comprising at least one film comprising a blend comprising at least one additive selected from the group consisting of antistat and roll release Yes.
In addition, WO99 / 51665 describes an invention relating to a single layer or multilayer film in which film thickness, water vapor permeability, oxygen gas permeability, and ethylene gas permeability are defined within a certain range. This gas permeable film is said to be able to maintain the freshness of fruits and vegetables for a long time as a result of being able to moderately suppress the diffusion of water vapor while maintaining sufficient oxygen gas uptake and ethylene gas emission. Has been.
[0003]
[Problems to be solved by the invention]
The present invention has been made in view of the above prior art, and its purpose is to provide a packaging material that can maintain freshness from fruits and vegetables with a low respiration rate to fruits and vegetables with a high respiration rate and has little variation in gas permeability of the film. It is to provide. Another object is to provide a method for preserving fruits and vegetables that can shorten the time to reach the MA state.
[0004]
[Means for Solving the Problems]
The present inventors have found that a film made of a mixed resin of a specific ratio of an ethylene-octene copolymer and a polypropylene-ethylene copolymer can solve such problems, and has completed the present invention.
[0005]
That is, the present invention comprises a polyolefin resin composed of a blend of 70 to 95% by weight of ethylene-octene-1 copolymer and 5 to 30% by weight of propylene-ethylene copolymer, and oxygen gas permeability at 23 ° C. and 80% RH. Is 6500-9500 cm 3 / m 2 · day · atm, carbon dioxide gas permeability at 23 ° C. and 80% RH is 23,000 to 38000 cm 3 / m 2 · day · atm, carbon dioxide gas permeability and oxygen gas permeability A freshness-maintaining packaging material having a ratio of degrees (CO 2 / O 2 ) of 3.5 to 4.1 and a water vapor permeability of 8 to 35 g / m 2 · day · atm is provided. The freshness-keeping packaging material of the invention having a storage elastic modulus of 110 to 1200 MPa is provided. Provided is the freshness-keeping packaging material according to the invention, wherein E × t 3 is 50 × 10 3 to 50 × 10 6 when the storage elastic modulus is E (MPa) and the film thickness is t (μm). A freshness-keeping packaging material according to the invention comprising a polyolefin resin is provided . Further, the providing anti-blocking agent, slip agent, a freshness-keeping packaging material of the invention comprising anti-fogging agent. The freshness-keeping packaging material of the invention, which is a film, and the freshness-keeping packaging material of the invention, which is a bag having a sealable opening portion.
The present invention provides a package in which fruits and vegetables are packaged with the freshness-keeping packaging material of the invention.
Moreover, when packaging fruits and vegetables using the freshness maintenance packaging material of the said invention, the freshness maintenance method of fruits and vegetables which enclose an oxygen absorber with fruits and vegetables is provided.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
Freshness-keeping packaging materials of the present invention, the oxygen gas permeability 23 ℃, 6500~9500cm in 80% RH 3 / m 2 · day · atm, preferably 7800~9400cm 3 / m 2 · day · atm, more preferably 8000~9300cm a 3 / m 2 · day · atm , 23 ℃, carbon dioxide gas permeability at 80% RH is 23000~38000cm 3 / m 2 · day · atm, preferably 28000~37000cm 3 / m 2 · day Atm, more preferably 29000 to 38000 cm 3 / m 2 · day · atm, and the ratio of carbon dioxide gas permeability to oxygen gas permeability (CO 2 / O 2 ) is 3.5 to 4.1, preferably 3.6 to 4.0, more preferably 3.8 to 4.0. As material resin which satisfy | fills these requirements, it can select from the following polyolefin resin, for example. When CO 2 / O 2 exceeds 4.1, the CO 2 concentration in the system decreases, and the effect of inhibiting enzyme activity or ethylene production is reduced, so there is a possibility that the effect of maintaining freshness may be reduced. If it is less than 3.5, the CO 2 concentration in the system becomes high, CO 2 failure occurs, and the freshness may decrease. Therefore, it is necessary to be within the specified range.
[0007]
The packaging material that satisfies the conditions relating to the gas permeability can be selected from various resins or combinations thereof. Examples of these resins include ethylene-butene-1 copolymers, ethylene-4-methylpentene-1 copolymers, ethylene-hexene-1 copolymers, ethylene-octene-1 copolymers and other ethylene- α-olefin copolymers; polyethylenes such as high density polyethylene (HDPE), low density polyethylene, linear low density polyethylene, and ultra low density polyethylene; polyethylene ionomers, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers Polymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, polypropylene, polystyrene, polystyrene-acrylonitrile copolymer, polyurethane, polybutadiene, polyvinyl chloride, styrene butadiene rubber, silicon rubber, polytetrafluoroethylene, polycarbonate , Nylon 12, poly-4-methylpentene-1, polysulfone, cellulose triacetate, ethyl cellulose, butyl cellulose acetate, polydimethylsiloxane, polylactic acid, polybutylene succinate-agitate copolymer, polycaprolactone, polyhydroxybutyrate- Examples thereof include a valerate copolymer, a polyester copolymer composed mainly of butanediol, terephthalic acid, adipic acid, and a sulfonate compound, and a polybutylene succinate-carbonate copolymer. These resins are appropriately selected in consideration of the respiration rate of the object to be packaged, the appearance of the package, the gas permeability of the packaging material, CO 2 / O 2, and the like.
[0008]
Furthermore, when packaging fruits and vegetables, in order to prevent the moisture contained in the fruits and vegetables from becoming cloudy and adhering to the package, the water vapor permeability of the packaging material itself is 8 to 35 g / m 2 · day · atm, preferably 15 to 28 g / m 2 · day · atm, more preferably 18 to 25 g / m 2 · day · atm. If these conditions are satisfied, it is possible to obtain a packaging material capable of maintaining freshness from fruits and vegetables with low respiration rate to fruits and vegetables with high respiration rate.
Examples of the packaging material satisfying the water vapor permeability include the ethylene-α-olefin copolymer, the polyethylenes, the polyethylene ionomer, the ethylene-vinyl acetate copolymer, the polyvinylidene chloride copolymer, nylon 11, and nylon 12. , Polyethylene terephthalate, polypropylene, polyPEnyl sulfide, polyetheretherketone, polytetrafluoroethylene, hydrochloric acid rubber and the like. Among those satisfying the above gas permeability condition and water vapor permeability condition at the same time You can choose. Examples of preferable resins include resins mainly composed of ethylene-α-olefin copolymers. Examples of α-olefins include copolymers containing 5 to 15% by weight of octene-1 and ethylene-octene-1 copolymers. Mention may be made of blends of 70 to 95% by weight (octene content of about 12%) and 5 to 30% by weight of propylene-ethylene random copolymer (ethylene content of about 3%). The thickness of the film made of this blend is such that the oxygen gas permeability, the carbon dioxide gas permeability, the ratio of the carbon dioxide gas permeability to the oxygen gas permeability, and the water vapor permeability are within the ranges defined in the present invention. You only have to set it.
The film thickness of the freshness-keeping packaging material of the present invention is not particularly limited, but is practically 20 to 50 μm, more preferably 30 to 45 μm. Further, a film having a film thickness of 23 μm comprising a resin of 10% by weight of HDPE and 90% by weight of an ethylene-octene-1 copolymer (octene content of about 12% by weight), a propylene-ethylene random copolymer (ethylene content of about 3% by weight) And a film having a film thickness of 30 μm and a resin comprising 20% by weight and 80% by weight of an ethylene-octene-1 copolymer (octene content of about 12% by weight). In addition, since these resin may be processed into a bag after being formed into a film, it is preferable that the resin has a heat sealing property capable of ultrasonic sealing and heat sealing.
The freshness-keeping packaging material of the present invention may be stretched or unstretched as long as the gas permeability and water vapor permeability conditions are satisfied.
[0009]
The freshness-keeping packaging material of the present invention preferably has a storage elastic modulus of 110 to 1200 MPa, more preferably 140 to 250 MPa, from the viewpoints of ease of handling, moderate hardness, and hermeticity. It is preferable that the storage elastic modulus is in this range because it is not too soft and easy to handle. Further, when the storage elastic modulus is E (MPa) and the film thickness is t (μm), the numerical value of E × t 3 is 50 × 10 3 to 50 × 10 6 , and further 5 × 10 6 to 15 × 10 6. 6 is preferable from the viewpoints of sealing properties and handling properties. In addition, although there is no restriction | limiting in particular in film thickness, Usually, it is preferable that it is 20-60 micrometers, and also 30-50 micrometers. In the present invention, the film thickness can be adjusted to adjust the gas permeability to a predetermined level.
[0010]
The freshness-keeping packaging material of the present invention includes phenolic, organic sulfur-based, organic nitrogen-based, organic phosphorus-based antioxidants and heat stabilizers, lubricants such as fatty acid derivatives such as metal soaps and other fatty acid esters, and anti-blocking. Agent, slip agent, antifogging agent, antistatic agent, calcium carbonate, white carbon, titanium white, magnesium carbonate, magnesium silicate, carbon black, various clays, natural or synthetic zeolite and other inorganic fillers or other colorants The compounding agent such as 0.5 to 8 parts by weight can be blended with respect to 100 parts by weight of the packaging material resin.
[0011]
The freshness-maintaining packaging material of the present invention can be formed using a T-die method or an inflation method. Moreover, as long as the conditions of this invention are satisfy | filled, the coextrusion with other resin or the lamination with a resin film may be sufficient. The packaging material can be applied to the packaging of fruits and vegetables in various forms, and the usage form is not particularly limited. A sealable bag or the like is preferably used. Although the packaging material of the present invention may package fruits and vegetables alone, it may take a freshness maintaining method in which an oxygen scavenger is enclosed together with fruits and vegetables.
[0012]
【Example】
EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, the measuring methods, such as a physical property, are as follows.
1. The gas permeability sample was allowed to stand in an atmosphere of 23 ° C. and 50% relative humidity (RH) for 24 hours, and then oxygen gas permeation at 23 ° C. and 80% RH using a film double-side humidified gas permeation measuring device manufactured by GL Sciences. Degree and carbon dioxide gas permeability were measured.
2. Water Vapor Permeability Samples were allowed to stand in an atmosphere of 23 ° C. and 50% relative humidity (RH) for 24 hours, and then water vapor permeability at 40 ° C. and 90% RH using a water vapor transmission amount measuring device L80-4000 manufactured by LYSSY. Was measured.
3. Oxygen gas concentration The oxygen gas concentration in the bag was measured using an oxygen concentration meter LC-750 manufactured by Toray Engineering.
4). Carbon dioxide gas concentration The carbon dioxide gas concentration inside the bag was measured using a gas chromatograph G3800 manufactured by Yanaco.
5). A storage elastic modulus sample was allowed to stand in an atmosphere of 23 ° C. and 50% relative humidity (RH) for 24 hours, and then the storage elasticity at a frequency of 10 Hz and a temperature of 20 ° C. using a dynamic viscoelasticity measuring device RSAII manufactured by Rheometrics. The modulus (dynamic elastic modulus) was measured.
[0013]
Example 1
Blending 90% by weight of pellets of ethylene-octene copolymer (Dow Chemical Japan Co., Ltd., octene content of about 12%, PL1880) and 10% by weight of propylene-ethylene copolymer (Nippon Polychem Co., Ltd., EG7FT) Anti-blocking agent master batch (Mitsui Chemicals, LDZ50-20) 2 phr, slip agent master batch (RIKEN Vitamin Co., Ltd., ELM-080) 2 phr, anti-fogging agent master batch (RIKEN) Vitamin, KP-410) was added by 3 phr, and an unstretched film having a thickness of 45 μm was obtained by a T-die method. Using this film (storage elastic modulus is 143 MPa, E × t 3 = 13.0 × 10 6 ), a bag having a size of 25 cm × 25 cm and three sides of the square sealed with an impulse sealer is produced, After about 300 g (1 pack) of soot was added, the remaining one side was impulse sealed and stored at 5 ° C.
[0014]
(Example 2)
A film having a thickness of 35 μm was obtained by the T-die method using the same raw material formulation as in Example 1. Using this film (storage modulus is 143 MPa, E × t 3 = 6.1 × 10 6 ), a bag having a square size of 25 cm × 25 cm and three sides of the square sealed with an impulse sealer is produced. After about 300 g (1 pack) of soot was added, the remaining one side was sealed with an impulse sealer and stored at 5 ° C. Further, one bunch of broccoli (about 250 g) was put in a bag produced in the same manner, and the remaining one side was sealed with an impulse sealer and stored at 7 ° C.
[0015]
Example 3
A film having a thickness of 35 μm was obtained by the direct blow method using the same raw material formulation as in Example 1. Using this film (storage modulus is 222 MPa, E × t 3 = 9.5 × 10 6 ), a bag with a size of 25 cm × 25 cm and three sides of the square sealed with an impulse sealer is produced, After about 300 g (1 pack) of soot was added, the remaining one side was sealed with an impulse sealer and stored at 5 ° C.
[0016]
(Comparative Example 1)
Anti-blocking agent master batch (Mitsui Chemicals, LDZ50-20) 2 phr, slip agent master batch (RIKEN Vitamin Co., Ltd., ELM-080) on ethylene-octene copolymer (Dow Chemical Japan Co., Ltd., PL1880) 2 phr was added, and a 45 μm thick film was obtained by the T-die method. Using this film, make a bag with a size of 25cm x 25cm and 3 sides of the square sealed with an impulse sealer. After about 300g (1 pack) of bag, put the other side with an impulse sealer. Sealed and stored at 5 ° C.
[0017]
(Comparative Example 2)
A blend of 80% by weight of ethylene-octene copolymer (Dow Chemical Japan Co., Ltd., PL1880) and 20% by weight of propylene-ethylene random copolymer (Nippon Polychem Co., Ltd., EG7FT, ethylene content of about 3%), and these resin components 2 phr of anti-blocking agent master batch (Mitsui Chemicals, LDZ50-20) and 2 phr of slip agent master batch (RIKEN Vitamin Co., Ltd., ELM-080) were added, and the thickness was 45 μm by T-die method. An unstretched film was obtained. Using this film, make a bag with a size of 25cm x 25cm and sealed the three sides of the square with an impulse sealer. After about 300g (one pack) of bag, put the remaining one side with an impulse seal. And stored at 5 ° C. Moreover, a bunch of broccoli (about 250 g) was put in a bag produced in the same manner, and the remaining one side was impulse-sealed and stored at 7 ° C.
[0018]
Example 4
The same bag as Example 1 is produced, and about 300g (1 pack) of soot is put into this bag together with an oxygen scavenger (Mitsubishi Gas Chemical Co., Ltd., Ageless SS-100), and the remaining one side is an impulse sealer. Sealed and stored at 5 ° C.
[0019]
(Example 5)
Using the film obtained in Example 1 (storage modulus is 143 MPa, E × t 3 = 13.0 × 10 6 ), the size is a square of 25 cm × 25 cm, and three sides of the square are sealed with an impulse sealer. The other side was made into a drawstring type that can be in close contact with each other, put one broccoli (about 250g), squeezed the opening, closed with a stopper, and stored at 7 ° C for 8 days. As a result, the oxygen gas concentration inside the bag Was the same level (2.8%) as Example 2 in which the opening was sealed with an impulse sealer.
(Example 6)
Using the film obtained in Example 2 (storage elastic modulus is 143 MPa, E × t 3 = 6.1 × 10 6 ), a drawstring bag similar to that in Example 5 is prepared, and one bunch of broccoli (about 250 g) The opening was squeezed, closed with a stopper, and stored at 7 ° C for 8 days. As a result, the oxygen gas concentration inside the bag was the same level (3.7%) as Example 2 where the opening was sealed with an impulse sealer. there were.
[0020]
(Comparative Example 3)
Using a film made of a polypropylene-ethylene copolymer having a thickness of 35 μm (storage elastic modulus is 1250 MPa, E × t 3 = 54 × 10 6 ), a drawstring bag similar to that in Example 5 is produced, and one bunch of broccoli is produced. (Approx. 250 g), the opening was squeezed, closed with a stopper, and stored at 7 ° C. for 8 days. As a result, the oxygen gas concentration inside the bag was 21%, the same as in air.
Table 1 shows the gas permeability, gas permeability ratio, and water vapor permeability of the films obtained in Examples 1 to 3 and Comparative Examples 1 and 2, and the packaging of Examples 1 to 4 and Comparative Examples 1 to 2 Table 2 shows changes in gas concentration and appearance inside the test package. Table 3 shows changes in gas concentration and appearance inside the package in the broccoli packaging test of Example 6 and Comparative Example 2.
[0021]
[Table 1]
[Table 2]
[Table 3]
(Example 7)
Table 4 shows changes in gas concentration and appearance inside the package when the stored product was changed using the same bag as in Example 3 and stored at a storage temperature of 7 ° C. for 7 days.
[0025]
[Table 4]
【The invention's effect】
According to the present invention, the effect of maintaining the freshness is large, and by using an oxygen scavenger together when packaging fruits and vegetables, it becomes possible to shorten the time for reducing the oxygen concentration inside the packaging bag, and the packaging with a greater effect of maintaining freshness. It became possible to give timber.
Claims (8)
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| KR20180138541A (en) * | 2017-06-21 | 2018-12-31 | 아사히 가세이 가부시키가이샤 | Packaging, preservation apparatus and preservation method for fruit and vegetable |
| JP2019058636A (en) * | 2017-09-27 | 2019-04-18 | 三井化学株式会社 | Cold insulation vessel |
| CN114007941A (en) * | 2019-06-12 | 2022-02-01 | 珀弗泰科有限公司 | Package and method for preserving respiratory agricultural products |
-
2001
- 2001-12-03 JP JP2001369020A patent/JP3824915B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018210955A1 (en) | 2017-05-16 | 2018-11-22 | Cryovac, Inc. | New packaging method for fruits and vegetables |
| US11485120B2 (en) | 2017-05-16 | 2022-11-01 | Cryovac, Llc | Packaging method for fruits and vegetables |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2003169598A (en) | 2003-06-17 |
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