JP2019131632A - 酸素吸収性樹脂組成物及び容器 - Google Patents
酸素吸収性樹脂組成物及び容器 Download PDFInfo
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- JP2019131632A JP2019131632A JP2018012622A JP2018012622A JP2019131632A JP 2019131632 A JP2019131632 A JP 2019131632A JP 2018012622 A JP2018012622 A JP 2018012622A JP 2018012622 A JP2018012622 A JP 2018012622A JP 2019131632 A JP2019131632 A JP 2019131632A
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- oxygen
- mass
- resin composition
- container
- absorbing resin
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Images
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Abstract
Description
本発明に係る酸素吸収性樹脂組成物は、鉄粉及びハロゲン化金属を含む酸素吸収剤と、樹脂とを含む。ここで、該酸素吸収性樹脂組成物は、アルミニウムの含有量が50質量ppm以下である。
本発明において酸素吸収剤は、鉄粉及びハロゲン化金属を含む。該鉄粉としては、還元鉄粉、アトマイズ鉄粉、電解鉄粉、カルボニル鉄粉等、公知の鉄粉を使用することができる。これらの中でも、多孔質であり比較的比表面積の大きい還元鉄粉、特にロータリー還元鉄粉を好適に用いることができる。ロータリー還元鉄粉は、純度が高く、比表面積が大きいことから、酸素吸収性能に優れている。これらの鉄粉は一種を用いてもよく、二種以上を併用してもよい。酸素吸収剤中の鉄粉の含有量は、3〜40質量%であることが好ましく、5〜30質量%であることがより好ましい。
本発明に係る酸素吸収性樹脂組成物に含まれる樹脂としては特に限定されないが、熱可塑性樹脂を用いることができる。具体的には、低−、中−又は高−密度のポリエチレン、ポリプロピレン、エチレン−プロピレン共重合体、ポリブテン−1、エチレン−ブテン−1共重合体、プロピレン−ブテン−1共重合体、エチレン−プロピレン−ブテン−1共重合体、ポリメチルペンテン−1、エチレン−酢酸ビニル共重合体、エチレン−(メタ)アクリル酸共重合体、イオン架橋オレフィン共重合体(アイオノマー)、エチレン−ビニルアルコール共重合体或いはこれらのブレンド物等のオレフィン系樹脂、ポリスチレン、スチレン−ブタジエン共重合体、スチレン−イソプレン共重合体、ABS樹脂等のスチレン系樹脂、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリテトラメチレンテレフタレート、グリコール変性ポリエチレンテレフタレート、ポリ乳酸、ポリブチレンサクシネート等のポリエステル、ナイロン6、ナイロン66等のポリアミド、ポリカーボネート等が挙げられる。これらの中でも、オレフィン系樹脂が好ましく、ポリプロピレンがより好ましい。これらの樹脂は一種を用いてもよく、二種以上を併用してもよい。
本発明に係る酸素吸収性樹脂組成物は、前記酸素吸収剤を前記樹脂に配合して混合することにより得ることができる。混合は、メルトブレンドでもドライブレンドでもよい。少量の酸素吸収剤を配合する場合には、酸素吸収剤を高濃度で含有するマスターバッチを調製し、該マスターバッチを樹脂に混合することが好ましい。
本発明に係る酸素吸収性樹脂組成物において、アルミニウムの含有量は50質量ppm以下である。アルミニウムの含有量が50質量ppmを超えると、酸素吸収性能が低下する。アルミニウムの含有量は45質量ppm以下が好ましく、40質量ppm以下がより好ましく、30質量ppm以下がさらに好ましく、20質量ppm以下が特に好ましい。なお、アルミニウムの含有量の範囲の下限は特に限定されず、アルミニウムの含有量がより少ない方が鉄と酸素との反応がより阻害されないため好ましい。なお、アルミニウムの含有量はICP分析装置(商品名:720−ES、Varian製)により測定される値である。
本発明に係る酸素吸収性樹脂組成物において、前記酸素吸収剤の含有量は30質量%以下であることが好ましく、10質量%以上30質量%以下であることがより好ましく、20質量%以上27質量%以下であることがさらに好ましい。本発明に係る酸素吸収性樹脂組成物では、鉄が高い酸素吸収性能を発揮できるため、組成物中の酸素吸収剤の含有量を30質量%以下にすることができ、製造コストを低減することができる。また、成形性や容器としての特性を向上させることができる。
本発明に係る容器は、本発明に係る酸素吸収性樹脂組成物からなる酸素吸収層を有する。本発明に係る酸素吸収性樹脂組成物は高い酸素吸収性能を有するため、該組成物からなる酸素吸収層を有する本発明に係る容器は、高い酸素吸収性能を示し、高い内容物保存性を示す。特に、該酸素吸収層は高い酸素吸収性能を有するため、本発明に係る容器では酸素バリア層、酸素吸収層の厚さを低減することができ、製造コストを低減することができる。
酸素吸収層は、本発明に係る酸素吸収性樹脂組成物からなる。容器全体の質量(100質量%)に対する、酸素吸収層の質量の割合(厚みに関する質量比率)は20質量%以下が好ましく、1質量%以上15質量%以下がより好ましく、5質量%以上10質量%以下がさらに好ましい。酸素吸収層を構成する本発明に係る酸素吸収性樹脂組成物では、鉄が高い酸素吸収性能を発揮できるため、該割合を20質量%以下にすることができ、製造コストを低減することができる。また、容器の軽量化を図ることができる。酸素吸収層の厚さは、5μm以上300μm以下が好ましく、10μm以上200μm以下がより好ましい。
酸素バリア層の材料としては、エチレン−ビニルアルコール共重合体、ナイロンMXD6、ポリグリコール酸等のガスバリア性樹脂を用いることができる。これらの中でも、酸素の遮断性が高い観点から、エチレン−ビニルアルコール共重合体が好ましい。これらの材料は一種を用いてもよく、二種以上を併用してもよい。また、前記材料とポリオレフィン系樹脂との混合物を用いることもできる。アルミニウム、スチール等の金属箔、無機薄膜蒸着フィルム、ポリビニルアルコールやポリアクリル酸等のガスバリア性材料を基材フィルムに塗布したガスバリア性コーティングフィルムを酸素バリア層として用いてもよい。
内層及び外層の材料としては、特に限定されないが、例えば低−、中−又は高−密度のポリエチレン、ポリプロピレン、エチレン−プロピレン共重合体、ポリブテン−1、エチレン−ブテン−1共重合体、プロピレン−ブテン−1共重合体、エチレン−プロピレン−ブテン−1共重合体、ポリメチルペンテン−1、エチレン−酢酸ビニル共重合体、エチレン−(メタ)アクリル酸共重合体、イオン架橋オレフィン共重合体(アイオノマー)或いはこれらのブレンド物等のオレフィン系樹脂、ポリスチレン、スチレン−ブタジエン共重合体、スチレン−イソプレン共重合体、ABS樹脂等のスチレン系樹脂、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリテトラメチレンテレフタレート、グリコール変性ポリエチレンテレフタレート、ポリ乳酸、ポリブチレンサクシネート等のポリエステル、ナイロン6、ナイロン66等のポリアミド、ポリカーボネート等が挙げられる。これらの材料は一種を用いてもよく、二種以上を併用してもよい。また、内層の材料と外層の材料とは同一であってもよく、異なっていてもよい。内層及び外層の厚さは特に限定されないが、例えば30〜1000μmであることができる。
接着層の材料としては、特に限定されないが、例えばエチレン−アクリル酸共重合体、イオン架橋オレフィン共重合体、無水マレイン酸グラフトポリエチレン、無水マレイン酸グラフトポリプロピレン、アクリル酸グラフトポリオレフィン、エチレン−酢酸ビニル共重合体、共重合ポリエステル、共重合ポリアミド等が挙げられる。これらの材料は一種を用いてもよく、二種以上を併用してもよい。接着層の厚さは特に限定されないが、例えば1〜20μmであることができる。
本発明に係る容器の製造方法は特に限定されない。例えば、各層に対応する材料を押出機で溶融混練した後、T−ダイ、サーキュラーダイ等の多層多重ダイスを通して所定の形状に押出す多層同時押出であってもよい。また、各層に対応する射出機で各材料を溶融混練した後、射出金型中に共射出又は逐次射出して、多層容器又は容器用のプリフォームを製造してもよい。更に、ドライラミネーション、サンドイッチラミネーション、押出コート等の積層方式も採用し得る。
本発明に係る容器は酸素吸収性能に優れるため、例えば米飯、コーヒー、スープ等の容器として好適に用いることができる。
スチール箔を積層した内容積85mlのガス不透過性のプラスチックカップ容器内部に、酸素吸収性樹脂組成物ペレット3g及び蒸留水1mlを、両者が接触しないように設置した。その後、ガス不透過性の金属箔積層フィルムを用いて、該容器を空気中でヒートシールし、密封した。該容器を50℃にて1日保管後、該容器内部の酸素濃度をガスクロマトグラフ(商品名:CP4900、Agilent製)を用いて測定した。得られた測定結果から、酸素吸収性樹脂組成物ペレットの質量当たりの酸素吸収量を算出した。結果を表1に示す。なお、表1では酸素吸収量を、実施例1の酸素吸収性樹脂組成物ペレット(アルミニウム含有量:7質量ppm)の酸素吸収量を100.0%としたときの相対比率(単位:%)として示した。
容器内部に米飯を入れ、ガス不透過性の金属箔積層フィルムを用いて、該容器を1%の酸素濃度雰囲気下でヒートシールし、密封した。この時、容器の有効面積は220cm3、容器内部のヘッドスペースは50mlであった。該容器を23℃−50%RH下で300日間保管後、該容器内部の酸素濃度をガスクロマトグラフ(商品名:CP4900、Agilent製)を用いて測定した。保管後の容器内の酸素濃度から内容物保存性を以下の基準で評価した。結果を表2に示す。
○:保管後の容器内の酸素濃度が1%未満である。
△:保管後の容器内の酸素濃度が1%以上1.15%未満である。
×:保管後の容器内の酸素濃度が1.15%以上である。
(酸素吸収剤の調製)
ロータリー還元鉄粉(金属鉄量90質量%、平均粒径45μm)100質量部、塩化ナトリウム2質量部及び水酸化カルシウム1質量部を混合し、振動ボールミルを用いて10時間粉砕処理を行った。その後、180meshのふるいにて分級して90μm以上の粗大粒子を除去し、混合微粉砕物を得た。得られた混合微粉砕物50kgを内容積230Lのバッチ式回転炉内に充填し、回転数6rpm、窒素ガス流量10L/分、550℃の条件で8時間熱処理を行った(昇温2時間、冷却8時間)。なお、熱処理の際、窒素ガスの代わりに空気を10L/分の流量で6時間流入させることにより、表面酸化を促進させた。その後、180meshのふるいにて分級して90μm以上の粗大粒子を除去し、酸素吸収剤を得た。
前記酸素吸収剤29質量部と、ランダムポリプロピレン(ランダムPP)(密度:0.91g/cm3、メルトインデックス(MI):0.6g/10min、230℃)71質量部とを二軸押出機(商品名:TEM−35B、東芝機械製)により溶融混練し、成形して酸素吸収性樹脂組成物ペレットを作製した。該酸素吸収性樹脂組成物ペレットのアルミニウム含有量は7質量ppmであった。なお、該アルミニウム含有量はICP分析装置(商品名:720−ES、Varian製)により測定した。得られた酸素吸収性樹脂組成物ペレットについて、前記方法により酸素吸収性能を評価した。結果を表1及び図2に示す。
酸素吸収性樹脂組成物ペレットの作製において、用いるランダムPPを変更することで酸素吸収性樹脂組成物ペレットのアルミニウム含有量を表1に示すように変更した以外は、実施例1と同様に酸素吸収性樹脂組成物ペレットを作製し、評価した。結果を表1及び図2に示す。
実施例1における酸素吸収性樹脂組成物ペレットの作製において、用いるランダムPPを変更することで、実質的にアルミニウムを含まない酸素吸収性樹脂組成物ペレット(アルミニウム含有量:10質量ppm未満)を作製した。また、酸素バリア層の材料としてエチレン−ビニルアルコール共重合体(EVOH、エチレン含有量32モル%、ケン化度99.6モル%)、内層及び外層の材料として8質量%のチタン白顔料を含有する白色ブロックポリプロピレン(白色ブロックPP)、接着層の材料として無水マレイン酸変性ポリプロピレン(無水マレイン酸変性PP)(MI:1.0g/10min、230℃)を準備した。
層構成を、外層(40質量%)/接着層(2質量%)/酸素バリア層(6質量%)/接着層(2質量%)/酸素吸収層(7質量%)/内層(43質量%)に変更した以外は、実施例4と同様の方法により容器を作製し、評価した。結果を表2に示す。
酸素吸収性樹脂組成物ペレットの作製において、前記酸素吸収剤26質量部と、前記ランダムPP 74質量部とを用いた以外は、実施例4と同様の方法により容器を作製し、評価した。結果を表2に示す。
酸素吸収性樹脂組成物ペレットの作製において、用いるランダムPPを変更することで、アルミニウムを140質量ppm以上含む酸素吸収性樹脂組成物ペレットを作製した。該酸素吸収性樹脂組成物ペレットを用いた以外は、実施例4と同様の方法により容器を作製し、評価した。結果を表2に示す。
2a、2b 接着層
3 酸素バリア層
4 酸素吸収層
5 内層
Claims (7)
- 鉄粉及びハロゲン化金属を含む酸素吸収剤と、樹脂とを含む酸素吸収性樹脂組成物であって、
アルミニウムの含有量が50質量ppm以下であることを特徴とする酸素吸収性樹脂組成物。 - 前記酸素吸収剤の含有量が30質量%以下である請求項1に記載の酸素吸収性樹脂組成物。
- 前記酸素吸収性樹脂組成物がハイドロタルサイトを含まない請求項1又は2に記載の酸素吸収性樹脂組成物。
- 請求項1から3のいずれか一項に記載の酸素吸収性樹脂組成物からなる酸素吸収層を有することを特徴とする容器。
- 前記酸素吸収層よりも外側に、さらにエチレン−ビニルアルコール共重合体を含む酸素バリア層を有する請求項4に記載の容器。
- 前記容器全体の質量に対する、前記酸素バリア層の質量の割合が10質量%以下である請求項5に記載の容器。
- 前記容器全体の質量に対する、前記酸素吸収層の質量の割合が20質量%以下である請求項4から6のいずれか一項に記載の容器。
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