JP3566114B2 - Retort food packaging film and method for producing the same - Google Patents

Retort food packaging film and method for producing the same Download PDF

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Publication number
JP3566114B2
JP3566114B2 JP36458298A JP36458298A JP3566114B2 JP 3566114 B2 JP3566114 B2 JP 3566114B2 JP 36458298 A JP36458298 A JP 36458298A JP 36458298 A JP36458298 A JP 36458298A JP 3566114 B2 JP3566114 B2 JP 3566114B2
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film
food packaging
weight
propylene
retort food
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JP2000186159A (en
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孝典 久米
茂樹 木代
洋一郎 門田
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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Description

【0001】
【発明の属する技術分野】
本発明はレトルト食品包装用フィルムおよびその製造方法に関する。さらに詳しくは、低温での耐衝撃性と耐ブロッキング性、ヒートシール性に優れ、且つフィッシュアイの少ないレトルト食品包装用フィルムおよびその製造方法に関するものである。
【0002】
【従来の技術】
ポリプロピレンは耐熱性、包装適性等に優れているため、食品包装、繊維包装などの包装分野で広く使用されている。
近年、食品包装分野などにおいて耐衝撃性、耐熱性、耐ブロッキング性、ヒートシール性を兼ね備えた材料が要望されている。しかし、プロピレン単独重合体、プロピレンとα−オレフィンのランダム共重合体は低温での耐衝撃性が不十分であり使用に制限があった。
耐衝撃性を付与させるための方法として、主にポリプロピレンブロック共重合体を用いて改良する試みがいくつかなされている。
プロピレン(以下、Pと記載する)とエチレン・プロピレン(以下、EPと記載する)共重合体のブロック共重合体として、特開平6−93061号公報にはチーグラー・ナッタ型触媒を用いて、実質的に不活性溶剤の不存在下に第一工程でプロピレンを主体とした重合体部分を重合し、次いで第二工程中で気相中にてエチレン・プロピレン共重合体を重合したP−EPブロック共重合体が提案されている。
しかしながら、気相中での重合においては従来の溶剤法での重合体に比べ低温での耐衝撃性が良好である材料が得られるものの、ブロッキング性、ヒートシール性が低下する問題があった。
また、連続重合法においてはフィッシュアイの発生による外観不良を抑えるために、P部とEP部の極限粘度比を限定する必要があり、フィルム性能にも限界があった。
【0003】
【発明が解決しようとする課題】
本発明の課題は、従来公知のプロピレン系ブロック共重合体からなるレトルト食品包装用フィルムの欠点を改良し、耐熱性などポリプロピレンブロック共重合体が本来有する好ましい特性を損なうことなく、低温での耐衝撃性が良好であり、外観、耐ブロッキング性、ヒートシール性が良好なレトルト食品包装用フィルムを提供することにある。
【0004】
【課題を解決するための手段】
本発明者らは種々の検討の結果、フィルムの20℃キシレン可溶部(以下、CXS部という)を制御することにより、良好な特性を発現するフィルムとなることを見出し、更に、フィルム製膜時の分解によるCXS部の極限粘度(以下、[η]という)の低下をある範囲に抑えるフィルムの製造方法により、より良好な特性を発現することを見出し本発明に至った。
【0005】
即ち、本発明は、第一工程で実質的に不活性溶剤の不存在下にプロピレンを主体とした重合体部分(A成分)を重合し、次いで第二工程を気相中でエチレン含有量が20〜50重量%のプロピレンとエチレンとの共重合体部分(B成分)を重合して得られるブロック共重合体とトコフェロール類を溶融混練してなり、230℃のメルトフローレートが2〜5g/10分であり、20℃キシレン可溶部の極限粘度が2.4dl/g以上である組成物を製膜してなるフィルムであって、以下の物性を満足するレトルト食品包装用フィルムに係るものである。
(1)フィルムの20℃キシレン可溶部が8〜25重量%
(2)フィルムの20℃キシレン可溶部の極限粘度が2dl/g以上
(3)フィルムの曇値(HAZE)が45%以上
(4)直径200μm以上のフィッシュアイが1m2あたり100個以下
【0006】
また、本発明は、レトルト食品包装用フィルムの製造方法であって、第一工程で実質的に不活性溶剤の不存在下にプロピレンを主体とした重合体部分(A成分)を重合し、次いで第二工程を気相中でエチレン含有量が20〜50重量%のプロピレンとエチレンとの共重合体部分(B成分)を重合して得られるブロック共重合体とトコフェロール類を溶融混練してなり、230℃のメルトフローレートが2〜5g/10分であり、20℃キシレン可溶部の極限粘度が2.4dl/g以上である組成物を製膜して、得られるフィルムの20℃キシレン可溶部の極限粘度([η]b)と製膜される組成物の極限粘度([η]a)との比[η]b/[η]a0.75以上にするレトルト食品包装用フィルムの製造方法に係るものである。
【0007】
以下、本発明を具体的に記載する。
本発明のレトルト食品包装用フィルムに使用されるポリプロピレン系組成物は、第一工程で実質的に不活性溶剤の不存在下にプロピレンを主体とした重合体部分(A成分)を重合し、次いで第二工程を気相中でエチレン含有量が20〜50重量%のプロピレンとエチレンとの共重合体部分(B成分)を重合して得られるブロック共重合体を溶融混練してなるものである。触媒としてはチーグラー・ナッタ型触媒を用いることができる。
【0008】
A成分とB成分の割合は、必要な耐衝撃強度特性に応じて任意に選択することが可能であるが、フィルムのCXS部の量が8〜25重量%となるように選択する必要がある。8重量%未満の場合は耐衝撃強度が低下するため好ましくなく、25重量%を超える場合は耐ブロッキング性が悪化するため好ましくない。特に、9〜16重量%の範囲が耐衝撃性と耐ブロッキング性のバランスからより好ましい。
また、B成分のエチレン含有量は20〜50重量%であることが必要である。好ましい範囲は、30〜50重量%である。
エチレン含有量が20重量%未満の場合は、耐ブロッキング性が劣るため好ましくなく、50重量%を超える場合は、耐衝撃性が劣るため好ましくない。
【0009】
本発明のレトルト食品包装用に使用されるポリプロピレン系組成物はフィルム加工性を考慮すると230℃のメルトフローレートは2〜5g/10分である
メルトフローレートが1.5g/10分未満の場合は押出特性が悪化するため好ましくなく、10g/10分を超える場合は引き取り特性が悪化するため好ましくない。
【0010】
本発明のレトルト食品包装用フィルムはフィルムのCXS部の[η]が2dl/g以上であることが必要である。2dl/g未満の場合は、耐ブロッキング性、ヒートシール性が低下するため好ましくない。好ましい範囲は、2.1dl/g以上である。
また、フィルムの曇値(以下、HAZEという)は45%以上が必要である。好ましい範囲は、50%以上である。
HAZEの増加は表面の微少凹凸を促進することであり、耐ブロッキング性を改良することができる。HAZEが45%未満の場合は耐ブロッキング性が悪化するため好ましくない。
【0011】
本発明のレトルト食品包装用フィルムは外観、特性の観点から直径200μm以上のフィッシュアイが1mあたり100個以下であることが必要である。
好ましい範囲は、50個以下である。
【0012】
本発明のレトルト食品包装用フィルムは、Tダイ法、チューブラー法などの公知のフィルム製膜法で製造することが可能であるが、特にTダイ法による未延伸フィルムの製造法により好適に製造される。
フィルムの厚みは特に限定されないが、10〜250μmが好ましく、さらに好ましくは30〜150μmである。
【0013】
本発明のレトルト食品包装用フィルムには、酸化防止剤として、CXS部の [ η ] 低下抑制の観点から、トコフェロール類が添加される
また、本発明のレトルト食品包装用フィルムには、中和剤、その他の酸化防止剤、紫外線吸収剤、帯電防止剤、滑剤、抗ブロッキング剤、造核剤などを必要に応じて添加することが可能である。
特に、中和剤としてはハイドロタルサイト類化合物、水酸化カルシウムなどが加工時の発煙低下には好ましい
【0014】
本発明のレトルト食品包装用フィルムは、その他のフィルム、例えばポリプロピレン二軸延伸フィルム、延伸ナイロンフィルム、延伸ポリテレフタル酸エチルフィルムやアルミニウム箔などのドライラミネート法、または押出ラミネート法などの方法で製造される複合フィルムの少なくとも一層としても好適に使用することが可能である。
【0015】
本発明のレトルト食品包装用フィルムには、通常工業的に採用されている方法によって、コロナ放電処理、火炎処理、プラズマ処理、オゾン処理などの表面処理を施すこともできる。
【0016】
本発明のレトルト食品包装用フィルムの製造方法は20℃キシレン可溶部の極限粘度が2.4dl/g以上である組成物をフィルムの20℃キシレン可溶部の極限粘度([η]b)と組成物の極限粘度([η]a)との比[η]b/[η]aが0.75以上となる様にすることが必要である。
好ましい範囲は、0.80以上である。
[η]b/[η]aが0.75未満の場合は、CXS部の分解が促進されるため耐ブロッキング性が悪化して好ましくない。
[η]b/[η]aは、組成物の安定剤処方、加工機の構造、加工温度等の加工条件によりコントロールすることが出来る。[η]b/[η]aを高くするためには、例えば、組成物の安定剤の強化、低せん断の加工機の選択、低温での加工などが効果的である。
【0017】
特に、組成物の直径200μm以上のフィッシュアイ個数がN(個/m)であり、フィルムのフィッシュアイ個数をN(個/m)としたとき、製造時にフィルター等を用いて、NとNの関係を、N≦0.2×N、N≦100を満足するようにすることがより好ましい。
フィルターとしては例えば、ろ過精度10〜150μmの金属製フィルターを1枚以上、数百枚まで重ねて使用することができ、特にろ過精度40〜80μmの焼結繊維で構成されたフィルターを用いることが、加工性とフィッシュアイの削減効果から好ましい。
【0018】
本発明のレトルト食品包装用フィルムは外観、耐熱性、低温での耐衝撃性、ヒートシール性、更には耐ブロッキング性に優れ、特に、低温下での重量物包装用途で好適に使用される。
【0019】
【実施例】
以下、実施例によって本発明をより具体的に説明するが、本発明の範囲は何ら実施例のみに限定されるものではない。なお、発明の詳細な説明および実施例中の各項目の測定値は、下記の方法で測定した。
【0020】
(1)プロピレン−エチレン共重合体部分(B成分)中のエチレン濃度
高分子ハンドブック(1995年、紀伊国屋書店発行)の616ページに記載されている13C−NMRの測定を行い、組成物のエチレン含量を求めた。B成分中のエチレン濃度は物質収支から求めたB成分含有量を用いて次式により計算した。
(組成物のエチレン濃度)×100/(B成分含有量 (重量%))
(2)極限粘度([η])
ウベローデ型粘度計を用いて135℃テトラリン中で測定を行った。
(3)20℃キシレン可溶部(CXS)
ポリプロピレン5gを沸騰キシレン500mlに完全に溶解させた後、20℃に降温し、4時間以上放置する。その後、これを析出物と溶液とにろ別し可溶部と不溶部に分離した。可溶部はろ液を乾固して減圧下70℃で乾燥し、その重量を測定して含有量(重量%)を求めた。
【0021】
(4)メルトフローレイト
JIS K7210に従い、条件−14の方法で測定した。
(5)耐衝撃性
試料を0℃に保持しておき、2mの高さから535.1gの鉄球を落とし、試料を破壊貫通した時の落下速度と、試料のない場合の鉄球のみの落下速度との、速度差から耐衝撃エネルギーを求めた。
その計算は次式による。
E=(1/2)・M・L(1/t −1/t
E:耐衝撃エネルギー[J]
M:ボールの重量[0.5351kg]
L:二つの光電管管の距離[0.1m]
:フィルムのない場合の鉄球通過時間[S]
:フィルムを破壊貫通時の鉄球通過時間[S]
【0022】
(6)透明性(ヘイズ)
JIS K7105に従い測定した。
(7)フィッシュアイ(FE)
組成物のFE個数(N)は、φ50押出機で#80/#100/#120のスクリーンメッシュを使用して製膜した厚み50μmのフィルムを目視により、直径が200μm以上のFE個数を観測した。
本発明フィルムのFEの個数(N)は本特許記載のフィルターを使用して製膜したフィルムを目視により、直径が200μm以上のFE個数を観測した。
(8)耐ブロッキング性
225mm×50mmのフィルムを用いて、フィルム同志を重ねあわせ、100mm×50mmの範囲を40g/cmの荷重下で60℃、80℃で3時間状態調整を行った。その後、23℃、湿度50%の雰囲気下に30分以上放置し、島津製作所製ブロッキングテスターを用いて20g/分の剥離荷重速度で試料の剥離に要する強度を測定した。
(9)ヒートシール強度
東洋テスター工業(株)性ヒートシーラーを使用し次の条件でシールし、次いでシール片を15mm幅に切り、剥離角90°で(株)オリエンテック製テンシロンを用いて測定した。
[シール条件]
シールバー:平面両面加熱、シール温度:200℃
シール圧力:1.0kg/cm、シール時間:1.0秒
裏打ち補強剤:PET#12/AL#9/CPP#70構成のドライラミネートフィルム
【0023】
実施例1
チーグラーナッタ型触媒を用いて第一工程で気相中でプロピレン単独重合体部分を重合し、次いで第二工程を気相中でエチレン含有量が34重量%のプロピレンとエチレンとの共重合体部分を重合した。得られた共重合体100部に水酸化カルシウム0.03部、ビタミンE0.05部を加えて溶融混練し組成物とした。組成物に含まれるCXS量は13.7重量%、CXS部の[η]は3.29dl/g、フィッシュアイ個数は2150個/mであった。
本組成物をろ過精度60μmの金属フィルターを使用して濾過し、次いでTダイ加工法により、270℃の温度で製膜して厚み70μmのレトルト食品包装用フィルムを得た。
得られたフィルムのCXS量は12.8重量%、CXS部の[η]は2.57dl/g、フィッシュアイ個数は98個/mであった。
フィルムの物性は表1、表2に示す様に、フィッシュアイは多めであるが、耐ブロッキング性、耐衝撃性、ヒートシール強度の良好なフィルムであった。
【0024】
実施例2
チーグラーナッタ型触媒を用いて第一工程で気相中でプロピレン単独重合体部分を重合し、次いで第二工程を気相中でエチレン含有量が36重量%のプロピレンとエチレンとの共重合体部分を重合した。得られた共重合体100部に水酸化カルシウムを0.01部、ビタミンEを0.05部を加えて溶融混練して組成物とした。組成物に含まれるCXS量は13.5重量%CXS部の η 2.62dl/g、フィッシュアイ個数は680個/m であった。実施例1と同様にレトルト食品包装用フィルムを得た。
得られたフィルムのCXS量は13.3重量%、CXS部の[η]は2.17dl/g、フィッシュアイ個数は20個/mであった。
フィルムの物性は表1、表2に示す様に、フィッシュアイが少なく、耐ブロッキング性、耐衝撃性、ヒートシール強度の良好なフィルムであった。
【0025】
実施例3
実施例2の共重合体100部に水酸化カルシウムを0.01部、ビタミンEを0.03部、イルガノックス1010(商品名:チバスペシャリティーケミカルズ社製)0.1部を用いたこと以外は実施例2と同様にレトルト食品包装用フィルムを得た。
得られたフィルムのCXS量は13.7重量%、CXS部の[η]は2.17dl/g、フィッシュアイ個数は10個/mであった。
フィルムの物性は表1、表2に示す様に、フィッシュアイが更に少なく、耐ブロッキング性、耐衝撃性、ヒートシール強度の良好なフィルムであった。
【0026】
比較例1
チーグラーナッタ型触媒を用いて第一工程で気相中でプロピレン単独重合体部分を重合し、次いで第二工程を気相中でエチレン含有量が41重量%のプロピレンとエチレンとの共重合体部分を重合した。共重合体100部に水酸化カルシウム0.03部、イルガノックス1010を0.2部、イルガノックス3114(商品名:チバスペシャリティーケミカルズ社製)を0.075部、イルガフォス168(商品名:チバスペシャリティーケミカルズ社製)を0.05部を加えて組成物とした。組成物に含まれるCXS量は14.8重量%、CXS部の[η]は1.64dl/g、フィッシュアイ個数は170個/mであった。
本組成物を実施例1と同様の方法にてレトルト食品包装用フィルムを得た。得られたフィルムのCXS量は12.2重量%、CXS部の[η]は1.56dl/g、フィッシュアイ個数は7個/mであった。
フィルムの物性は表1、表2に示す様に、フィッシュアイは少ないが、耐ブロッキング性、耐衝撃性が劣るフィルムであった。
【0027】
比較例2
実施例2で得られた共重合体100重量部、水酸化カルシウム0.03部、イルガノックス1010を0.2部を用いた以外は実施例2と同様にレトルト食品包装用フィルムを得た。
得られたフィルムのCXS量は13.4重量%、CXS部の[η]は1.95dl/gとCXS部の分解が進んでいた。
フィルムの物性は表1、表2に示す様に、耐ブロッキング性、耐衝撃性が劣るフィルムであった。
【0028】
【表1】

Figure 0003566114
【0029】
【表2】
Figure 0003566114
【0030】
【発明の効果】
本発明により、低温での耐衝撃性が良好であり、外観、耐ブロッキング性、ヒートシール性が良好なレトルト食品包装用フィルムおよびその製造法が提供される。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a retort food packaging film and a method for producing the same. More specifically, the present invention relates to a retort food packaging film having excellent low-temperature impact resistance, anti-blocking properties, and heat-sealing properties and having little fish eyes, and a method for producing the same.
[0002]
[Prior art]
Polypropylene is widely used in packaging fields such as food packaging and fiber packaging because of its excellent heat resistance and packaging suitability.
In recent years, materials having both impact resistance, heat resistance, blocking resistance, and heat sealability have been demanded in the field of food packaging and the like. However, propylene homopolymers and random copolymers of propylene and α-olefins have insufficient impact resistance at low temperatures, and their use has been limited.
As a method for imparting impact resistance, some attempts have been made mainly to improve the impact resistance by using a polypropylene block copolymer.
As a block copolymer of propylene (hereinafter, referred to as P) and ethylene / propylene (hereinafter, referred to as EP) copolymer, a Ziegler-Natta type catalyst is disclosed in JP-A-6-93061. P-EP block obtained by polymerizing a polymer portion mainly composed of propylene in the first step in the absence of an inert solvent and then polymerizing an ethylene-propylene copolymer in the gas phase in the second step Copolymers have been proposed.
However, in the polymerization in the gas phase, although a material having better impact resistance at a lower temperature than that of a polymer obtained by a conventional solvent method can be obtained, there is a problem that the blocking property and the heat sealing property are deteriorated.
In addition, in the continuous polymerization method, it is necessary to limit the limiting viscosity ratio between the P part and the EP part in order to suppress appearance defects due to generation of fish eyes, and there is a limit in film performance.
[0003]
[Problems to be solved by the invention]
An object of the present invention is to improve the drawbacks of a conventionally known retort food packaging film made of a propylene-based block copolymer, and to withstand the low-temperature resistance without impairing the inherent characteristics of the polypropylene block copolymer, such as heat resistance. An object of the present invention is to provide a retort food packaging film having good impact properties and good appearance, blocking resistance and heat sealability.
[0004]
[Means for Solving the Problems]
As a result of various studies, the present inventors have found that controlling the xylene-soluble portion (hereinafter referred to as CXS portion) at 20 ° C. of a film results in a film exhibiting good characteristics. The present inventors have found out that better properties are exhibited by a method for producing a film in which a decrease in the intrinsic viscosity (hereinafter referred to as [η]) of the CXS portion due to decomposition during a certain period is exhibited, and the present invention has been accomplished.
[0005]
That is, in the present invention, in the first step, a polymer portion mainly composed of propylene (component (A)) is polymerized in the substantially absence of an inert solvent, and then the ethylene content in the gas phase in the second step is reduced. A block copolymer obtained by polymerizing 20 to 50% by weight of a copolymer portion (component B) of propylene and ethylene and a tocopherol are melt-kneaded, and the melt flow rate at 230 ° C is 2 to 5 g / 10 min, a film with an intrinsic viscosity of 20 ° C. xylene-soluble portion formed by film formation of the composition is 2.4 dl / g or more, relates to a retort food packaging film which satisfies the following physical properties It is.
(1) The xylene-soluble portion at 20 ° C. of the film is 8 to 25% by weight.
(2) The limiting viscosity of the xylene-soluble portion of the film at 20 ° C. is 2 dl / g or more. (3) The haze value (HAZE) of the film is 45% or more. (4) 100 or less fish eyes with a diameter of 200 μm or more per 1 m 2 [ [0006]
Further, the present invention is a method for producing a film for retort food packaging, wherein in the first step, a polymer portion mainly composed of propylene (A component) is polymerized substantially in the absence of an inert solvent, In the second step, a block copolymer obtained by polymerizing a copolymer part (component B) of propylene and ethylene having an ethylene content of 20 to 50% by weight in a gas phase and a tocopherol are melt-kneaded. , a melt flow rate of 230 ° C. is 2-5 g / 10 min, 20 ° C. the intrinsic viscosity of the xylene-soluble portion is to form a film of the composition is 2.4 dl / g or more, 20 ° C. xylene resulting film the intrinsic viscosity of the soluble portion ([η] b) the intrinsic viscosity of film-forming composition being ([eta] a) the ratio [η] b / [η] retort food packaging to 0.75 or more a The present invention relates to a method for producing a film for use.
[0007]
Hereinafter, the present invention will be specifically described.
The polypropylene composition used in the retort food packaging film of the present invention is obtained by polymerizing a propylene-based polymer portion (A component) in the first step in the absence of an inert solvent, In the second step, a block copolymer obtained by polymerizing a copolymer portion (component B) of propylene and ethylene having an ethylene content of 20 to 50% by weight in a gas phase is melt-kneaded. . As the catalyst, a Ziegler-Natta type catalyst can be used.
[0008]
The ratio between the component A and the component B can be arbitrarily selected according to the required impact resistance characteristics, but it is necessary to select the ratio so that the amount of the CXS portion of the film is 8 to 25% by weight. . If the amount is less than 8% by weight, the impact resistance is lowered, which is not preferable. In particular, the range of 9 to 16% by weight is more preferable from the balance of impact resistance and blocking resistance.
Further, the ethylene content of the component B needs to be 20 to 50% by weight. A preferred range is 30 to 50% by weight.
If the ethylene content is less than 20% by weight, the blocking resistance is poor, which is not preferable. If it exceeds 50% by weight, the impact resistance is poor, which is not preferable.
[0009]
The polypropylene-based composition used for retort food packaging of the present invention has a melt flow rate at 230 ° C. of 2 to 5 g / 10 minutes in consideration of film processability.
If the melt flow rate is less than 1.5 g / 10 minutes, the extrusion characteristics deteriorate, and if it exceeds 10 g / 10 minutes, the take-off characteristics deteriorate, which is not preferable.
[0010]
In the retort food packaging film of the present invention, it is necessary that the [η] of the CXS portion of the film is 2 dl / g or more. If it is less than 2 dl / g, the blocking resistance and the heat sealing property are undesirably reduced. A preferred range is 2.1 dl / g or more.
Further, the haze value of the film (hereinafter, referred to as HAZE) needs to be 45% or more. A preferred range is 50% or more.
An increase in HAZE is to promote fine irregularities on the surface, and the blocking resistance can be improved. If the HAZE is less than 45%, the blocking resistance is undesirably deteriorated.
[0011]
The retort food packaging film of the present invention is required to have not more than 100 fish eyes having a diameter of 200 μm or more per 1 m 2 from the viewpoint of appearance and properties.
A preferred range is 50 or less.
[0012]
The retort food packaging film of the present invention can be produced by a known film forming method such as a T-die method or a tubular method, but is particularly suitably produced by a method of producing an unstretched film by the T-die method. Is done.
The thickness of the film is not particularly limited, but is preferably from 10 to 250 µm, and more preferably from 30 to 150 µm.
[0013]
Tocopherols are added to the retort food packaging film of the present invention as an antioxidant from the viewpoint of suppressing the decrease of [ η ] in the CXS part .
In addition, the retort food packaging film of the present invention may contain a neutralizing agent, another antioxidant, an ultraviolet absorber, an antistatic agent, a lubricant, an anti-blocking agent, a nucleating agent, and the like, if necessary. It is possible.
In particular, as the neutralizing agent, hydrotalcite compounds, calcium hydroxide, and the like are preferable for reducing smoke generation during processing.
[0014]
The retort food packaging film of the present invention is manufactured by a method such as a dry lamination method such as a biaxially stretched polypropylene film, a stretched nylon film, a stretched polyethyl terephthalate film or an aluminum foil, or an extrusion lamination method. The composite film can be suitably used as at least one layer.
[0015]
The retort food packaging film of the present invention can be subjected to a surface treatment such as a corona discharge treatment, a flame treatment, a plasma treatment, and an ozone treatment by a method generally employed in industry.
[0016]
In the method for producing a film for packaging a retort food according to the present invention, the composition having an intrinsic viscosity of a 20 ° C. xylene-soluble part of 2.4 dl / g or more is used as an intrinsic viscosity ([η] b) of a 20 ° C. xylene-soluble part of the film. It is necessary that the ratio [η] b / [η] a of the composition and the intrinsic viscosity ([η] a) of the composition be 0.75 or more.
A preferred range is 0.80 or more.
When [η] b / [η] a is less than 0.75, the decomposition of the CXS portion is promoted, so that the blocking resistance deteriorates, which is not preferable.
[Η] b / [η] a can be controlled by processing conditions such as the formulation of the stabilizer for the composition, the structure of the processing machine, and the processing temperature. In order to increase [η] b / [η] a, for example, it is effective to strengthen the stabilizer of the composition, select a low-shear processing machine, and process at low temperature.
[0017]
In particular, when the number of fish eyes having a diameter of 200 μm or more of the composition is N 1 (pieces / m 2 ) and the number of fish eyes of the film is N 2 (pieces / m 2 ), a filter or the like is used during production, More preferably, the relationship between N 1 and N 2 satisfies N 2 ≦ 0.2 × N 1 and N 2 ≦ 100.
As the filter, for example, one or more metal filters with a filtration accuracy of 10 to 150 μm can be used by stacking up to several hundreds, and in particular, a filter made of sintered fibers with a filtration accuracy of 40 to 80 μm can be used. It is preferable from the viewpoint of workability and the effect of reducing fish eyes.
[0018]
The retort food packaging film of the present invention is excellent in appearance, heat resistance, low-temperature impact resistance, heat-sealing property, and blocking resistance, and is particularly suitably used in heavy-duty packaging at low temperatures.
[0019]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples, but the scope of the present invention is not limited to the examples. In addition, the measured value of each item in the detailed description of the invention and the examples was measured by the following method.
[0020]
(1) Ethylene Concentration in Propylene-Ethylene Copolymer Part (Component B) 13C-NMR measurement described on page 616 of Handbook of Polymers (1995, published by Kinokuniya Bookstore) was carried out, and ethylene in the composition was measured. The content was determined. The ethylene concentration in the B component was calculated by the following equation using the B component content obtained from the material balance.
(Ethylene concentration of composition) × 100 / (B component content (% by weight))
(2) Intrinsic viscosity ([η])
The measurement was performed at 135 ° C. in tetralin using an Ubbelohde viscometer.
(3) Xylene soluble part at 20 ° C (CXS)
After completely dissolving 5 g of polypropylene in 500 ml of boiling xylene, the temperature is lowered to 20 ° C. and left for 4 hours or more. Thereafter, this was separated by filtration into a precipitate and a solution, and separated into a soluble part and an insoluble part. The soluble part of the filtrate was dried and dried at 70 ° C. under reduced pressure, and its weight was measured to determine its content (% by weight).
[0021]
(4) Melt flow rate Measured according to JIS K7210 under the condition -14.
(5) Impact resistance The sample was kept at 0 ° C., 535.1 g of iron balls were dropped from a height of 2 m, and the drop speed when breaking through the sample and the iron ball only when there was no sample were measured. The impact energy was determined from the speed difference from the falling speed.
The calculation is based on the following equation.
E = (1/2) · M · L 2 (1 / t 0 2 -1 / t 1 2)
E: Impact resistance [J]
M: Weight of ball [0.5351 kg]
L: distance between two phototubes [0.1 m]
t 0: iron ball passing time in the absence of film [S]
t 1 : Iron ball passage time when breaking through the film [S]
[0022]
(6) Transparency (haze)
It was measured according to JIS K7105.
(7) Fisheye (FE)
The number of FEs having a diameter of 200 μm or more was observed by visually observing a 50 μm thick film formed using a # 80 / # 100 / # 120 screen mesh with a φ50 extruder using the FE number (N 1 ) of the composition. did.
Regarding the number of FEs (N 2 ) of the film of the present invention, the number of FEs having a diameter of 200 μm or more was visually observed for a film formed using the filter described in the present patent.
(8) Blocking resistance Using a film of 225 mm × 50 mm, the films were superposed on each other, and the condition of 100 mm × 50 mm was adjusted at 60 ° C. and 80 ° C. for 3 hours under a load of 40 g / cm 2 . Thereafter, the sample was allowed to stand in an atmosphere of 23 ° C. and a humidity of 50% for 30 minutes or more, and the strength required for peeling the sample was measured at a peeling load speed of 20 g / min using a blocking tester manufactured by Shimadzu Corporation.
(9) Heat seal strength Sealing was performed using a heat sealer manufactured by Toyo Tester Co., Ltd. under the following conditions. Then, a seal piece was cut to a width of 15 mm, and measured at a peel angle of 90 ° using Tensilon manufactured by Orientec. did.
[Seal conditions]
Seal bar: heating both sides of the plane, sealing temperature: 200 ° C
Sealing pressure: 1.0 kg / cm 2 , Sealing time: 1.0 second Backing reinforcing agent: Dry laminated film composed of PET # 12 / AL # 9 / CPP # 70
Example 1
In a first step, a propylene homopolymer portion is polymerized in a gas phase using a Ziegler-Natta type catalyst, and then in a second step, a copolymer portion of propylene and ethylene having an ethylene content of 34% by weight in a gas phase. Was polymerized. To 100 parts of the obtained copolymer, 0.03 part of calcium hydroxide and 0.05 part of vitamin E were added and melt-kneaded to obtain a composition. The CXS amount contained in the composition was 13.7% by weight, [η] of the CXS part was 3.29 dl / g, and the number of fish eyes was 2150 / m 2 .
This composition was filtered using a metal filter having a filtration accuracy of 60 µm, and then formed into a film at a temperature of 270 ° C by a T-die processing method to obtain a 70 µm-thick retort food packaging film.
The CXS amount of the obtained film was 12.8% by weight, [η] in the CXS portion was 2.57 dl / g, and the number of fish eyes was 98 / m 2 .
As shown in Tables 1 and 2, the physical properties of the film were such that the fish eyes were large, but the film had good blocking resistance, impact resistance and heat seal strength.
[0024]
Example 2
In a first step, a propylene homopolymer portion is polymerized in the gas phase using a Ziegler-Natta type catalyst, and then in a second step, a copolymer portion of propylene and ethylene having an ethylene content of 36% by weight in the gas phase. Was polymerized. To 100 parts of the obtained copolymer, 0.01 part of calcium hydroxide and 0.05 part of vitamin E were added and melt-kneaded to obtain a composition. CXS content in the composition 13.5 wt%, the CXS portion [eta] is 2.62dl / g, the fisheye number was 680 pieces / m 2. A retort food packaging film was obtained in the same manner as in Example 1.
The CXS amount of the obtained film was 13.3% by weight, [η] in the CXS portion was 2.17 dl / g, and the number of fish eyes was 20 / m 2 .
As shown in Tables 1 and 2, the physical properties of the film were such that there were few fish eyes, and the film had good blocking resistance, impact resistance and heat seal strength.
[0025]
Example 3
Except that 0.01 part of calcium hydroxide, 0.03 part of vitamin E and 0.1 part of Irganox 1010 (trade name: manufactured by Ciba Specialty Chemicals) were used for 100 parts of the copolymer of Example 2. In the same manner as in Example 2, a retort food packaging film was obtained.
The CXS amount of the obtained film was 13.7% by weight, [η] in the CXS portion was 2.17 dl / g, and the number of fish eyes was 10 / m 2 .
As shown in Tables 1 and 2, the physical properties of the film were such that the film had less fish eyes and had good blocking resistance, impact resistance and heat seal strength.
[0026]
Comparative Example 1
In a first step, a propylene homopolymer portion is polymerized in a gas phase using a Ziegler-Natta type catalyst, and then in a second step, a copolymer portion of propylene and ethylene having an ethylene content of 41% by weight in a gas phase. Was polymerized. To 100 parts of the copolymer, 0.03 part of calcium hydroxide, 0.2 part of Irganox 1010, 0.075 part of Irganox 3114 (trade name, manufactured by Ciba Specialty Chemicals), and Irgafos 168 (trade name: Ciba) Specialty Chemicals) (0.05 parts) was added to give a composition. The amount of CXS contained in the composition was 14.8% by weight, [η] of the CXS part was 1.64 dl / g, and the number of fish eyes was 170 / m 2 .
A retort food packaging film was obtained from this composition in the same manner as in Example 1. The CXS amount of the obtained film was 12.2% by weight, [η] in the CXS portion was 1.56 dl / g, and the number of fish eyes was 7 / m 2 .
As shown in Tables 1 and 2, the physical properties of the film were low in fish eyes, but were poor in blocking resistance and impact resistance.
[0027]
Comparative Example 2
A retort food packaging film was obtained in the same manner as in Example 2, except that 100 parts by weight of the copolymer obtained in Example 2, 0.03 part of calcium hydroxide, and 0.2 part of Irganox 1010 were used.
The CXS amount of the obtained film was 13.4% by weight, and [η] of the CXS portion was 1.95 dl / g, indicating that decomposition of the CXS portion was in progress.
As shown in Tables 1 and 2, the physical properties of the film were poor in blocking resistance and impact resistance.
[0028]
[Table 1]
Figure 0003566114
[0029]
[Table 2]
Figure 0003566114
[0030]
【The invention's effect】
According to the present invention, there is provided a retort food packaging film having good impact resistance at low temperatures, good appearance, blocking resistance, and good heat sealability, and a method for producing the same.

Claims (4)

第一工程で実質的に不活性溶剤の不存在下にプロピレンを主体とした重合体部分(A成分)を重合し、次いで第二工程を気相中でエチレン含有量が20〜50重量%のプロピレンとエチレンとの共重合体部分(B成分)を重合して得られるブロック共重合体とトコフェロール類を溶融混練してなり、230℃のメルトフローレートが2〜5g/10分であり、20℃キシレン可溶部の極限粘度が2.4dl/g以上である組成物を製膜してなるフィルムであって、以下の物性を満足することを特徴とするレトルト食品包装用フィルム。
(1)フィルムの20℃キシレン可溶部が8〜25重量%
(2)フィルムの20℃キシレン可溶部の極限粘度が2dl/g以上
(3)フィルムの曇値(HAZE)が45%以上
(4)直径200μm以上のフィッシュアイが1m2あたり100個以下
In the first step, a polymer portion mainly composed of propylene (component (A)) is polymerized substantially in the absence of an inert solvent, and then the second step is carried out in a gas phase with an ethylene content of 20 to 50% by weight. A block copolymer obtained by polymerizing a copolymer portion (component (B)) of propylene and ethylene and a tocopherol are melt-kneaded. The melt flow rate at 230 ° C is 2 to 5 g / 10 minutes, and 20 ℃ intrinsic viscosity of the xylene-soluble portion is a film obtained by film formation of the composition is 2.4 dl / g or more, retort food packaging film which satisfies the following physical properties.
(1) The xylene-soluble portion at 20 ° C. of the film is 8 to 25% by weight.
(2) The limiting viscosity of the xylene-soluble portion of the film at 20 ° C. is 2 dl / g or more. (3) The haze value (HAZE) of the film is 45% or more. (4) 100 or less fish eyes with a diameter of 200 μm or more per m 2.
第一工程で実質的に不活性溶剤の不存在下にプロピレンを主体とした重合体部分(A成分)を重合し、次いで第二工程を気相中でエチレン含有量が20〜50重量%のプロピレンとエチレンとの共重合体部分(B成分)を重合して得られるブロック共重合体100重量部に対して、トコフェロール類0.03〜0.05重量部を溶融混練してなることを特徴とする請求項1記載のレトルト食品包装用フィルム。In the first step, a polymer portion mainly composed of propylene (component (A)) is polymerized substantially in the absence of an inert solvent, and then the second step is carried out in a gas phase with an ethylene content of 20 to 50% by weight. It is characterized in that 0.03-0.05 parts by weight of tocopherols is melt-kneaded with respect to 100 parts by weight of a block copolymer obtained by polymerizing a copolymer portion (component B) of propylene and ethylene. The retort food packaging film according to claim 1, wherein 請求項1又は2記載のレトルト食品包装用フィルムの製造方法であって、第一工程で実質的に不活性溶剤の不存在下にプロピレンを主体とした重合体部分(A成分)を重合し、次いで第二工程を気相中でエチレン含有量が20〜50重量%のプロピレンとエチレンとの共重合体部分(B成分)を重合して得られるブロック共重合体とトコフェロール類を溶融混練してなり、230℃のメルトフローレートが2〜5g/10分であり、20℃キシレン可溶部の極限粘度が2.4dl/g以上である組成物を製膜して、得られるフィルムの20℃キシレン可溶部の極限粘度([η]b)と製膜される組成物の極限粘度([η]a)との比[η]b/[η]a0.75以上にすることを特徴とするレトルト食品包装用フィルムの製造方法。 The method for producing a retort food packaging film according to claim 1 or 2, wherein a polymer portion mainly composed of propylene (A component) is polymerized in the first step substantially in the absence of an inert solvent, Next, in the second step, a block copolymer obtained by polymerizing a copolymer portion (component B) of propylene and ethylene having an ethylene content of 20 to 50% by weight in a gas phase and a tocopherol are melt-kneaded. it is the 2-5 g / 10 min melt flow rate of 230 ° C., and film formation the intrinsic viscosity of 20 ° C. xylene solubles is 2.4 dl / g or more compositions, 20 ° C. of the obtained film to the intrinsic viscosity of the xylene soluble portion of ([η] b) the intrinsic viscosity of film-forming composition being ([η] a) the ratio of [η] b / [η] a to 0.75 or more A method for producing a film for packaging retort foods, which is characterized in that : 請求項3記載のレトルト食品包装用フィルムの製造方法であって、組成物の直径200μm以上のフィッシュアイ個数をN1(個/m2)、フィルムのフィッシュアイ個数をN2(個/m2)とした場合に、N1とN2との関係が、N2≦0.2×N1、N2≦100を満足することを特徴とするレトルト食品包装用フィルムの製造方法。The method for producing a retort food packaging film according to claim 3, wherein the number of fish eyes having a diameter of 200 µm or more of the composition is N 1 (pieces / m 2 ), and the number of fish eyes of the film is N 2 (pieces / m 2). ) when the relationship between N 1 and N 2 the method for producing a retort food packaging film, characterized by satisfying the N 2 ≦ 0.2 × N 1, N 2 ≦ 100.
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