JP2018094760A - 多層体、包装容器、及び食品の保存方法 - Google Patents
多層体、包装容器、及び食品の保存方法 Download PDFInfo
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- JP2018094760A JP2018094760A JP2016239658A JP2016239658A JP2018094760A JP 2018094760 A JP2018094760 A JP 2018094760A JP 2016239658 A JP2016239658 A JP 2016239658A JP 2016239658 A JP2016239658 A JP 2016239658A JP 2018094760 A JP2018094760 A JP 2018094760A
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- layer
- oxygen
- multilayer body
- mass
- odor
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Abstract
【解決手段】熱可塑性樹脂を含有するシール層(A)、熱可塑性樹脂と鉄粉とを含有する酸素吸収層(B)、並びに、酸素バリア性を有する酸素バリア層(D)を、この順に積層して備える多層体であって、シール層(A)及び酸素バリア層(D)の少なくとも一方が、熱可塑性樹脂としてアイオノマーを含有する、多層体。
【選択図】 図1
Description
この脱酸素剤として初期に開発され現在も多く使用されている形態は、粉状または粒状の鉄粉やアスコルビン酸などからなる脱酸素剤を通気性の小袋に詰めたものである。
例えば、特許文献1では、臭気原因物質を抑制する積層フィルムを提供することを意図して、外層/第1接着層/バリア層/第2接着層/酸素吸収層/化学吸着層/シール層をこの順に積層して形成される積層フィルムであり、酸素吸収層に鉄粉系酸素吸収剤を用いている。発生する臭気原因物質はアルデヒド類や酸類であり、臭気原因物質を化学的に吸着するアミン系化合物担持二酸化ケイ素を化学吸着層に用いた積層フィルムが提案されている。
また、特許文献2では、酸素吸収性能に優れた酸素吸収剤(酸素吸収材料)等を提供することを意図して、エチレンユニットおよびカルボニル基を主鎖に有するポリマーまたはエチレン・不飽和カルボン酸共重合体のアイオノマーを含有することを特徴とする酸素吸収剤が提案されている。特許文献2では、上記のポリマー及びアイオノマーが酸素吸収能を有し、光もしくはエネルギー線照射または加熱をすることにより酸化反応を開始しうるとされている。
また、特許文献2においては、その実施例でアイオノマーと金属触媒としてのコバルトとを含む酸素吸収剤が開示されており、その技術は、コバルトを触媒としてアイオノマーが酸素と反応し、アイオノマーが酸素を吸収するものである。しかしながら、アイオノマー自体の酸素吸収能は高くないため、その結果として酸素吸収速度が遅くなってしまう。さらに特許文献2は、臭気吸収について全く言及していない。
結局、いずれの文献に記載の積層フィルムや酸素吸収剤も、優れた酸素吸収性を保持すると共に臭気を減少させるには更に改善の余地がある。
(1)熱可塑性樹脂を含有するシール層(A)、熱可塑性樹脂と鉄粉とを含有する酸素吸収層(B)、並びに、酸素バリア性を有する酸素バリア層(D)を、この順に積層して備える多層体であって、前記シール層(A)及び前記酸素吸収層(B)の少なくとも一方が、前記熱可塑性樹脂としてアイオノマーを含有する、多層体。
(2)前記酸素吸収層(B)と前記酸素バリア層(D)との間に、熱可塑性樹脂と無機塩基とを含有する臭気吸収層(C)を更に備える、(1)に記載の多層体。
(3)前記無機塩基は、カルシウムを有する無機塩基である、(2)に記載の多層体。
(4)(1)〜(3)のいずれかに記載の多層体を、熱可塑性樹脂を含有するシール層(A)を内側にし、かつ、酸素バリア性を有する酸素バリア層(D)を外側にして備える、包袋容器。
(5)(4)に記載の包袋容器により食品を封入して保存する、食品の保存方法。
(6)前記食品は、水分活性(Aw)が0.3以上1.0以下である、(5)に記載の保存方法。
(7)前記食品は、脂質を1質量%以上50質量%以下含む、チョコレート菓子及び食肉類のいずれかである、(5)又は(6)に記載の保存方法。
図1は、本実施形態の多層体の一例を模式的に示す部分断面図である。この多層体は、熱可塑性樹脂を含有するシール層(A)、熱可塑性樹脂と鉄粉とを含有する酸素吸収層(B)、並びに、酸素バリア性を有する酸素バリア層(D)をこの順に積層して備え、シール層(A)及び酸素吸収層(B)の少なくとも一方が、熱可塑性樹脂としてアイオノマーを含有する。
また、酸素吸収層(B)に含まれる酸素吸収性の物質が鉄粉であるため、酸素吸収性の物質が有機高分子化合物である場合とは異なり、酸素を吸収しても分解せず、臭気が発生したり、酸素吸収層(B)の物理的強度が低下したりすることを抑制できる。さらに、本実施形態においては、シール層(A)及び/又は酸素吸収層(B)がアイオノマーを含有することにより、臭気の発生を十分に抑制することができる。その臭気発生抑制原理としては、アイオノマーが臭気を吸収するというよりも、例えば食品中の物質、特に油脂や脂肪酸類、が酸素吸収層(B)中の鉄粉と接触して臭気が発生することを抑制するためと、本発明者らは考えている。つまり、アイオノマーが油脂や脂肪酸類と鉄粉との物理的接触を阻害することにより、臭気の発生が抑制されると本発明者らは推定している。ただし、要因はこれに限定されない。また、本実施形態の多層体は、酸素吸収層(B)よりも外側にシール層(A)を備えているため、酸素吸収層(B)が食品に直接接触し水に溶出することはなく、その層に含まれる鉄粉に起因する食品の風味低下を防止することができる。
本実施形態に係るシール層(A)は、少なくとも熱可塑性樹脂を含有する。シール層(A)はシーラントとしての役割を果たすと共に、本実施形態の多層体を用いた包装容器において、食品のような収納物と酸素吸収層(B)とを接触させずに隔離する役割をも果たし得る。また、酸素吸収層(B)による速やかな酸素吸収を妨げないように、効率的な酸素透過を行う役割をも果たし得る。
本実施形態に係る酸素吸収層(B)は、熱可塑性樹脂と鉄粉とを含有する。酸素吸収層(B)は、多層体を透過しようとする酸素、例えば、本実施形態の多層体を用いた包装容器の内部に外気から浸入しようとする酸素、及び該包装容器内部に残存する酸素を吸収する役割を果たす。
本実施形態の多層体は、上記のシール層(A)及び酸素吸収層(B)の少なくとも一方が、熱可塑性樹脂としてアイオノマーを含有するものである。アイオノマーとしては特に限定されないが、本発明による作用効果をより有効かつ確実に奏する観点から、エチレンと不飽和カルボン酸との共重合体のアイオノマー、及び、エチレンと不飽和カルボン酸と不飽和カルボン酸エステルとの共重合体のアイオノマーであると好ましい。
酸素バリア層(D)は、酸素バリア性を有する層であり、例えば酸素バリア性物質を含むことにより、その酸素バリア性を備えることができる。酸素バリア性物質とは、酸素透過度が100cc/(m2・24h・atm)以下の物質を意味する。酸素バリア層(D)に含まれ得る酸素バリア性物質としては、例えば、シリカ若しくはアルミナを蒸着したポリエステル(例えばポリエチレンテレフタレート)、ポリアミド、ナイロンMXD6、エチレン−ビニルアルコール共重合体、及び塩化ビニリデンが挙げられる。また、酸素バリア層(D)は、アルミニウム箔などの金属箔であってもよい。酸素バリア層(D)の厚さは、1μm以上300μm以下であると好ましく、1μm以上100μm以下であるとより好ましい。酸素バリア層(D)の厚さが上記範囲内にあることにより、酸素バリア効果をより高めることができると共に、柔軟性が損なわれることを防止することができる。
本実施形態の多層体は、酸素吸収層(B)と酸素バリア層(D)との間に、熱可塑性樹脂と無機塩基とを含有する臭気吸収層(C)を更に備えると好ましい。臭気吸収層(C)は、多層体と接触する臭気を吸収する役割を果たす。本実施形態の多層体を用いた包装容器においては、食品のような収納物から発生する臭気を吸収することができる。また、このような多層体を用いると、臭気吸収層(C)を備えていても、食品から放出される水分が臭気吸収層(C)と接する前に酸素吸収層(B)と接するので、酸素吸収層(B)に供給される水分量が減少せず、その結果、酸素吸収量が減ったり酸素吸収速度が遅くなったりすることを防止できる。さらに、上記の態様で臭気吸収層(C)を備える多層体は、無機塩基を含有する臭気吸収層(C)よりも外側にシール層(A)を備えているため、無機塩基を含有する臭気吸収層(C)が食品に直接接触し水に溶出することはなく、その層に含まれる無機塩基に起因する食品の風味低下を防止することができる。
本実施形態の多層体は、上記のシール層(A)、酸素吸収層(B)、酸素バリア層(D)、及び任意に備えられる臭気吸収層(C)に加えて、本発明の目的達成を阻害しない範囲で、それら以外の層を備えてもよい。そのような層としては、例えば、接着層、遮光層、易剥離層及び易引裂層が挙げられる。
本実施形態の多層体は、例えば、シール層(A)の材料を含む樹脂組成物、酸素吸収層(B)の材料を含む樹脂組成物及び酸素バリア層(D)の材料を含む組成物の順に積層した多層構造を含む積層体を、多層膜製造装置により共押出して製造することができる。あるいは、シール層(A)の材料を含む樹脂組成物及び酸素吸収層(B)の材料を含む樹脂組成物の順に積層した多層構造を含む積層体を、多層膜製造装置により共押出して製造した後、酸素吸収層(B)に接着剤を用いて酸素バリア層(D)を接着してもよい。多層体が、酸素吸収層(B)と酸素バリア層(D)との間に臭気吸収層(C)を備える場合、例えば、シール層(A)の材料を含む樹脂組成物、酸素吸収層(B)の材料を含む樹脂組成物、臭気吸収層(C)の材料を含む樹脂組成物及び酸素バリア層(D)の材料を含む組成物の順に積層した多層構造を含む積層体を、多層膜製造装置により共押出して製造することができる。あるいは、シール層(A)の材料を含む樹脂組成物、酸素吸収層(B)の材料を含む樹脂組成物及び臭気吸収層(C)の材料を含む樹脂組成物の順に積層した多層構造を含む積層体を、多層膜製造装置により共押出して製造した後、臭気吸収層(C)に接着剤を用いて酸素バリア層(D)を接着してもよい。また、共押出では、各層間で必要があれば接着層を設けてもよい。
本実施形態の多層体は、脱酸素性の包装材料として包装袋などの包装容器の一部又は全部に用いることができる。図2は、本実施形態に係る脱酸素性の包装容器の一例を示す部分断面図であり、図1に示す多層体の酸素吸収層(B)と酸素バリア層(D)との間に臭気吸収層(C)をも備える多層体を用いた例を示している。図2に示すように、包装容器100は、2つの多層体10を備えている。2つの多層体10は、互いにシール層(A)を内側にした状態で貼り合わされている。包装容器100は、例えば多層体10の縁部同士をヒートシールすることによって製造することができる。この包装容器100は、シール層(A)を内側(すなわち収容物と接触する側)にし、かつ、酸素バリア層(D)を外側(すなわち外気に直接触れる側)にしている。なお、図2は、多層体を、包装容器の全部に用いた例を示すものであるが、例えば容器の蓋材やパウチ袋の片面のみのような包装容器の一部に用いてもよい。
本実施形態の食品の保存方法は、上記本実施形態の包装容器により食品を封入して保存する方法である。本実施形態において、酸素の吸収(脱酸素)は、酸素吸収層(B)において水分と反応した鉄粉によりなされるため、食品が所定量の水分を含むことが好ましい。具体的には、食品は、水分活性(Aw)が0.3以上1.0以下であると好ましい。ここで、水分活性とは、物品中の自由水含有量を示す尺度であり、0.0以上1.0以下の数字で示され、水分のない物品は0.0、純水は1.0となる。すなわち、ある物品の水分活性(Aw)は、その物品を密封し平衡状態に到達した後の空間内の水蒸気圧をP、純水の水蒸気圧をP0、同空間内の相対湿度をRH(%)、とした場合、下記式で定義される。
Aw=P/P0=RH/100
多層体から図2に示すような袋状の包装容器を作製した。次いで、その包装容器に、チョコレート、スポンジケーキ及び生クリームを含むチョコレート菓子を、空気と共に収容した後、密封した。チョコレート菓子入りの包装容器を25℃で7日間、暗所にて保存した。その後、包装容器を開封し、チョコレート菓子を取り出し、そのチョコレート菓子のチョコレート部分を口に含んで、そのときの風味を確認した。口に含んだ際の香り及び味が共に良好である場合、すなわち、保存前との変化がほとんど認められない場合を「−」と評価し、チョコレートの味は保持されていたものの、チョコレートの香りが弱くなり、アーモンドを想起させる異臭が目立つ場合を「+」と評価し、チョコレートの風味(香り及び味)はするものの、それらがいずれも弱くなった場合を「++」と評価し、チョコレートとは異質な味がした場合を「+++」と評価した。
多層体から図2に示すような袋状の包装容器を作製した。次いで、その包装容器に、チョコレート、スポンジケーキ及び生クリームを含むチョコレート菓子を、空気と共に収容した後、密封した。チョコレート菓子入りの包装容器を25℃で7日間、暗所にて保存した。保存後の包装容器の開封口から、包装容器内のガスをシリンジで採取し、酸素濃度分析計(Dansensor社製商品名「CheckMate2」)を用いて酸素濃度(%)を測定した。
ポリエチレン(日本ポリエチレン株式会社製商品名「ノバテックLD:LC8001)67.5質量部、鉄粉(ヘガネスジャパン株式会社製商品名「海綿状鉄粉」、平均粒径30μm)30.0質量部、及び酸化カルシウム(カルファイン株式会社製、平均粒径5μm)2.5質量部を、直径37mmのスクリューを2本有する2軸混練押出機を用いて、200℃で溶融混練し、押出機ヘッドからストランドを押し出し、冷却後、ペレタイジングすることにより、酸素吸収層(B1)用の樹脂組成物(b1)を得た。
アイオノマー(エチレンとメタクリル酸との共重合体のアイオノマー、金属イオンの金属種:ナトリウム、三井デュポンポリケミカル株式会社製商品名「ハイミラン1601」)67.5質量部、鉄粉(ヘガネスジャパン株式会社製商品名「海綿状鉄粉」、平均粒径30μm)30.0質量部、及び酸化カルシウム(カルファイン株式会社製、平均粒径5μm)2.5質量部を、直径37mmのスクリューを2本有する2軸混練押出機を用いて、200℃で溶融混練し、押出機ヘッドからストランドを押し出し、冷却後、ペレタイジングすることにより、酸素吸収層(B2)用の樹脂組成物(b2)を得た。シール層(A1)用のアイオノマー(エチレンとメタクリル酸との共重合体のアイオノマー、金属イオンの金属種:ナトリウム、三井デュポンポリケミカル株式会社製商品名「ハイミラン1601」)に代えてシール層(A2)用のポリエチレン(住友化学株式会社製商品名「スミカセンL705」)を用い、樹脂組成物(b1)に代えて樹脂組成物(b2)を用いた以外は実施例1と同様にして、シール層(A1)に代えてシール層(A2)を備え、酸素吸収層(B1)に代えて酸素吸収層(B2)を備える多層体を得た。得られた多層体について、上記「多層体の評価方法1」及び「多層体の評価方法2」により評価した。結果を多層体の構成と共に表1に示す。
ポリエチレン(日本ポリエチレン株式会社製商品名「ノバテックLD:LC606」)88.3質量部、及び酸化カルシウム(カルファイン株式会社製、平均粒径5μm)11.7質量部を、上記の2軸混練押出機を用いて、200℃で溶融混練し、押出機ヘッドからストランドを押し出し、冷却後、ペレタイジングすることにより、臭気吸収層(C3)用の樹脂組成物(c3)を得た。ポリエチレン層(PE)用のポリエチレン(日本ポリエチレン株式会社製商品名「ノバテックLD:LC606」)に代えて樹脂組成物(c3)を用いた以外は実施例1と同様にして、ポリエチレン層(PE)に代えて臭気吸収層(C3)を備える多層体を得た。得られた多層体について、上記「多層体の評価方法1」及び「多層体の評価方法2」により評価した。結果を多層体の構成と共に表1に示す。
ポリエチレン層(PE)用のポリエチレン(日本ポリエチレン株式会社製商品名「ノバテックLD:LC606」)に代えて樹脂組成物(c3)を用いた以外は実施例2と同様にして、ポリエチレン層(PE)に代えて臭気吸収層(C3)を備える多層体を得た。得られた多層体について、上記「多層体の評価方法1」及び「多層体の評価方法2」により評価した。結果を多層体の構成と共に表1に示す。
シール層(A1)用のアイオノマー(エチレンとメタクリル酸との共重合体のアイオノマー、金属イオンの金属種:ナトリウム、三井デュポンポリケミカル株式会社製商品名「ハイミラン1601」)に代えてシール層(A2)用のポリエチレン(住友化学株式会社製商品名「スミカセンL705」)を用いた以外は実施例1と同様にして、シール層(A1)に代えてシール層(A2)を備える多層体を得た。得られた多層体について、上記「多層体の評価方法1」及び「多層体の評価方法2」により評価した。結果を多層体の構成と共に表1に示す。
ポリエチレン(日本ポリエチレン株式会社製商品名「ノバテックLD:LC8001」)64.6質量部、鉄粉(ヘガネスジャパン株式会社製商品名「海綿状鉄粉」、平均粒径30μm)30.0質量部、及び酸化カルシウム(カルファイン株式会社製、平均粒径5μm)5.4質量部を、上記2軸混練押出機を用いて、200℃で溶融混練し、押出機ヘッドからストランドを押し出し、冷却後、ペレタイジングすることにより、樹脂組成物(e2)を得た。酸素吸収層(B2)用の樹脂組成物(b2)に代えて樹脂組成物(e2)を用いた以外は実施例2と同様にして、酸素吸収層(B2)に代えて層(E2)を備える多層体を得た。得られた多層体について、上記「多層体の評価方法1」及び「多層体の評価方法2」により評価した。結果を多層体の構成と共に表1に示す。
ポリエチレン(日本ポリエチレン株式会社製商品名「ノバテックLD:LC8001」)66.3質量部、鉄粉(ヘガネスジャパン株式会社製商品名「海綿状鉄粉」、平均粒径30μm)30.0質量部、酸化カルシウム(カルファイン株式会社製、平均粒径5μm)2.5質量部、及びシリカゲル(富士シリシア化学株式会社製商品名「サイリシア710」)1.3質量部を、上記2軸混練押出機を用いて、200℃で溶融混練し、押出機ヘッドからストランドを押し出し、冷却後、ペレタイジングすることにより、樹脂組成物(e3)を得た。酸素吸収層(B2)用の樹脂組成物(b2)に代えて樹脂組成物(e3)を用いた以外は実施例2と同様にして、酸素吸収層(B2)に代えて層(E3)を備える多層体を得た。得られた多層体について、上記「多層体の評価方法1」及び「多層体の評価方法2」により評価した。結果を多層体の構成と共に表1に示す。
ポリエチレン(日本ポリエチレン株式会社製商品名「ノバテックLD:LC606」)95.5質量部、及びシリカゲル(富士シリシア化学株式会社製商品名「サイリシア710」)4.5質量部を、上記の2軸混練押出機を用いて、200℃で溶融混練し、押出機ヘッドからストランドを押し出し、冷却後、ペレタイジングすることにより、樹脂組成物(e4)を得た。ポリエチレン層(PE)用のポリエチレン(日本ポリエチレン株式会社製商品名「ノバテックLD:LC606」)に代えて樹脂組成物(e4)を用いた以外は実施例2と同様にして、ポリエチレン層(PE)に代えて層(E4)を備える多層体を得た。得られた多層体について、上記「多層体の評価方法1」及び「多層体の評価方法2」により評価した。結果を多層体の構成と共に表1に示す。
ポリエチレン(日本ポリエチレン株式会社製商品名「ノバテックLD:LC606」)91.0質量部、及びシリカゲル(富士シリシア化学株式会社製商品名「サイリシア710」)9.0質量部を、上記の2軸混練押出機を用いて、200℃で溶融混練し、押出機ヘッドからストランドを押し出し、冷却後、ペレタイジングすることにより、樹脂組成物(e5)を得た。シール層(A1)用のアイオノマー(エチレンとメタクリル酸との共重合体のアイオノマー、金属イオンの金属種:ナトリウム、三井デュポンポリケミカル株式会社製商品名「ハイミラン1601」)に代えてシール層(A2)用のポリエチレン(住友化学株式会社製商品名「スミカセンL705」)を用い、ポリエチレン層(PE)用のポリエチレン(日本ポリエチレン株式会社製商品名「ノバテックLD:LC606」)に代えて樹脂組成物(e5)を用いた以外は実施例1と同様にして、シール層(A1)に代えてシール層(A2)を備え、ポリエチレン層(PE)に代えて層(E5)を備える多層体を得た。得られた多層体について、上記「多層体の評価方法1」及び「多層体の評価方法2」により評価した。結果を多層体の構成と共に表1に示す。
ポリエチレン(日本ポリエチレン株式会社製商品名「ノバテックLD:LC606」)97.1質量部、及び酸化カルシウム(カルファイン株式会社製、平均粒径5μm)2.9質量部を、上記の2軸混練押出機を用いて、200℃で溶融混練し、押出機ヘッドからストランドを押し出し、冷却後、ペレタイジングすることにより、臭気吸収層(C6)用の樹脂組成物(c6)を得た。
シール層(A1)用のアイオノマー(エチレンとメタクリル酸との共重合体のアイオノマー、金属イオンの金属種:ナトリウム、三井デュポンポリケミカル株式会社製商品名「ハイミラン1601」)に代えてシール層(A2)用のポリエチレン(住友化学株式会社製商品名「スミカセンL705」)を用い、酸素吸収層(B1)用の樹脂組成物(b1)に代えて易酸化性熱可塑性樹脂(Sealed Air社製商品名「Cryovac(登録商標) OS Films」)を用いた以外は実施例3と同様にして、シール層(A1)に代えてシール層(A2)を備え、酸素吸収層(B1)に代えて易酸化性熱可塑性樹脂層(EO)を備える多層体を得た。得られた多層体について、上記「多層体の評価方法1」及び「多層体の評価方法2」により評価した。結果を多層体の構成と共に表1に示す。
Claims (7)
- 熱可塑性樹脂を含有するシール層(A)、熱可塑性樹脂と鉄粉とを含有する酸素吸収層(B)、並びに、酸素バリア性を有する酸素バリア層(D)を、この順に積層して備える多層体であって、
前記シール層(A)及び前記酸素吸収層(B)の少なくとも一方が、前記熱可塑性樹脂としてアイオノマーを含有する、多層体。 - 前記酸素吸収層(B)と前記酸素バリア層(D)との間に、熱可塑性樹脂と無機塩基とを含有する臭気吸収層(C)を更に備える、請求項1に記載の多層体。
- 前記無機塩基は、カルシウムを有する無機塩基である、請求項2に記載の多層体。
- 請求項1〜3のいずれか1項に記載の多層体を、熱可塑性樹脂を含有するシール層(A)を内側にし、かつ、酸素バリア性を有する酸素バリア層(D)を外側にして備える、包袋容器。
- 請求項4に記載の包袋容器により食品を封入して保存する、食品の保存方法。
- 前記食品は、水分活性(Aw)が0.3以上1.0以下である、請求項5に記載の保存方法。
- 前記食品は、脂質を1質量%以上50質量%以下含む、チョコレート菓子及び食肉類のいずれかである、請求項5又は6に記載の保存方法。
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US20210198022A1 (en) * | 2019-12-30 | 2021-07-01 | Matthew Rubin | Systems and methods for distributing and dispensing personal servings of chocolate |
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