JP6969667B2 - 金属板被覆用フィルム及び樹脂被覆金属板 - Google Patents
金属板被覆用フィルム及び樹脂被覆金属板 Download PDFInfo
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- JP6969667B2 JP6969667B2 JP2020506389A JP2020506389A JP6969667B2 JP 6969667 B2 JP6969667 B2 JP 6969667B2 JP 2020506389 A JP2020506389 A JP 2020506389A JP 2020506389 A JP2020506389 A JP 2020506389A JP 6969667 B2 JP6969667 B2 JP 6969667B2
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- film
- metal plate
- stretching
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/752—Corrosion inhibitor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/40—Closed containers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/40—Closed containers
- B32B2439/66—Cans, tins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/22—Thermoplastic resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Description
株式会社インテスコ製精密万能材料試験機(210XL型)を用いて、23℃条件下にて測定した。サンプルサイズは、測定方向(長手方向又は幅方向)が150mm、測定方向と直角の方向が10mmとなるように切り出した。原長50mm、引張り速度300mm/分で伸張して、JIS−K7127(1999)に規定された方法に従いヤング率を測定した。なお、長手方向及び幅方向共に、それぞれ上記測定を5回繰り返した。長手方向の5回測定の平均値を長手方向ヤング率EMD、幅方向の5回測定の平均値を幅方向のヤング率ETDとした。
株式会社日立ハイテクサイエンス製熱機械分析装置(TMA7100C)を用いて測定した。サンプルは、測定方向(長手方向又は幅方向)のチャック間が10mm、測定方向と直角の方向が4mmとなるように切り出してチャック間に固定した。測定モードは引張モード(測定荷重29.4mN)とし、流量100ml/分の窒素雰囲気下において、30℃から250℃までを5℃/分で昇温した。測定にて得られたチャートより200℃時のTMA値(変位量)を求めた。なお、変位量は収縮を正、膨張若しくは伸長を負の値とした。測定前のチャック間をL0とし、200℃での変位量をL1とした場合、以下に示す数式で計算される値を200℃熱収縮率とした。
本発明のフィルム5mgを試料としてアルミニウム製パンに採取し、TAインスツルメント社製示差走査熱量計(DSCQ100)を用いて測定した。まず、窒素雰囲気下で−50℃まで冷却し、そこから290℃まで20℃/分で昇温した。測定にて得られたチャートより最も低温側に存在する融解ピーク温度を求めた。なお、上記測定を3回繰り返し、その平均値を本フィルムの最も低温側に存在する融解ピーク温度Tm1とした。
株式会社ミツトヨ製ダイヤルゲージスタンド7001−10に設置した同じく株式会社ミツトヨ製のダイヤルゲージ2110S−10(超硬ボール付測定子)にて測定した。測定は場所をかえて10回行い、その平均値をフィルム厚みとした。
金属板として厚さ0.22mmのT3CAを原板としたTFS(金属Cr層:120mg/m2、Cr酸化物層:金属Cr換算で10mg/m2)を用いた。熱圧着ラミネート法(フィルムラミネート法)を利用して金属板の両面に以下の実施例及び比較例にて製造された金属板被覆用フィルムを被覆した。具体的なラミネート条件は、ラミネート直前の金属板温度250℃、ラミネートロール温度60℃とした。なお、ラミネート時の温度は、放射温度計によってラミネート前の温度を測定した(ニップ位置から100mmの位置)。その後、熱圧着から1秒経過後に水冷することにより、金属板の両面に樹脂被覆層を被覆した樹脂被覆金属板を得た。
上記(5)にて得られた樹脂被覆金属板のフィルム幅を確認し、ラミネート前のフィルム幅に対するラミネート後のフィルム幅変化収縮率を算出し、下記判断基準により熱圧着ラミネート性を評価した。
B(良好):ラミネートによる幅方向フィルム収縮率が1.0%以上5.0%未満
C(不可):ラミネートによる幅方向フィルム収縮率が5.0%以下
上記(5)にて得られた樹脂被覆金属板の表面を顕微鏡にて観察し、500μm×500μm視野内の正常被覆部に対する気泡の面積比率を算出し、下記判断基準により熱圧着ラミネート性を評価した。
B(良好):気泡混入面積率1.0%以上5.0%未満
C(不可):気泡混入面積率5.0%以上
得られた樹脂被覆金属板200mm×200mmの範囲において、シワの混入状態を目視観察し、下記判断基準により熱圧着ラミネート性を評価した。
B(良好):シワが1本混入
C(不可):シワが2本以上混入
上記(5)にて得られた樹脂被覆金属板をDRD(ドロー&リドロー)成形し、2ピース缶用缶胴を作製した。1重量%食塩水を缶容量の8割まで充填させ、陰極を食塩水内に浸し、陽極を缶口部の金属が露出した箇所に設置した。電極間に6.2Vの電圧を印加し、4秒通電後の電流値を計測した。計測された電流値から下記判断基準により金属缶耐食性を評価した。
B(良好):0.1mA以上5mA未満
C(不可):5mA以上
フィルムの原料樹脂として、融点が224℃のポリブチレンテレフタレート(以下、PBTと記載)、及び融点が258℃のポリエチレンテレフタレート(以下、PETと記載)のペレットを準備した。それぞれ水分を含まないように真空高温下にて十分に乾燥させた。その後、PBT60質量%、PET40質量%となるようにペレットをブレンドし、後に金属板と熱圧着する際の金属板と接着する層(A層)用の樹脂組成物Aとした。さらに、PBT80質量%、PET20質量%となるようにペレットをブレンドし、後に金属板と熱圧着する際の金属板と接着しない層(B層)、すなわち表層側用の樹脂組成物Bとした。樹脂組成物A,Bをそれぞれ異なる2台の単軸押出機に投入し270℃で溶融混練した。次いで、25μmカットの焼結フィルターを介して異物除去を行った後、A層とB層の積層比率が2:8に設計されたフィードブロックにて合流させ厚み方向に2層積層させた。積層された溶融樹脂をTダイから吐出し、30℃に表面温度を制御したキャスティングドラム上で冷却固化させて厚さ18μmの無延伸フィルムを得た。次いで加熱したセラミックロールを用いてフィルム温度が100℃になるように予熱を行い、フィルムの長手方向に3.0倍延伸を行った。その後、加熱した鏡面HCrメッキロールを用いて120℃で熱固定を行った。なお、この際2本の連続する鏡面HCrメッキロール間の速度差を利用して長手方向に3.0%の弛緩を施した。最後に室温まで徐冷し、端部を除去したフィルムを巻取機で巻き取り、厚み6.0μmの金属板被覆用フィルムを得た。得られたフィルムの物性を以下の表1に示す。
無延伸フィルムの厚みを12μmとし、長手方向の延伸倍率を2.0倍とした以外は実施例1と同様に作製し、厚み6.0μmの金属板被覆用フィルムを得た。得られたフィルムの物性を以下の表1に示す。
フィルムの原料樹脂として、融点が258℃のPETのペレットを準備し、水分を含まないように真空高温下にて十分に乾燥させた。これを単軸押出機に投入し280℃で溶融混練した。次いで、25μmカットの焼結フィルターを介して異物除去を行った後、Tダイから吐出し、35℃に表面温度を制御したキャスティングドラム上で冷却固化させて厚さ150μmの無延伸フィルムを得た。次いで、加熱したセラミックロールを用いてフィルム温度が110℃になるように予熱を行い、フィルムの長手方向に3.5倍延伸を行った。その後、テンター式延伸機に端部をクリップで把持させて導入し、120℃で4.0倍に幅方向に延伸した。そのまま、140℃で熱固定しながら幅方向に1.5%の弛緩を施した。その後、室温まで徐冷し、端部を除去したフィルムを縦延伸機に導入した。加熱したセラミックロールを用いてフィルム温度が120℃になるように予熱を行い、フィルムの長手方向に2.0倍の再延伸を行った。その後、加熱した鏡面HCrメッキロールを用いて140℃で熱固定を行った。なお、この際2本の連続する鏡面HCrメッキロール間の速度差を利用して長手方向に3.0%の弛緩を施した。最後に室温まで徐冷し、端部を除去したフィルムを巻取機で巻き取り、厚み6.0μmの金属板被覆用フィルムを得た。得られたフィルムの物性を以下の表1に示す。
無延伸フィルムの厚みを190μmとし、長手方向の再延伸倍率を2.8倍とした以外は実施例3と同様に作製し、厚み6.0μmの金属板被覆用フィルムを得た。得られたフィルムの物性を以下の表1に示す。
無延伸フィルムの厚みを11.4μmとし、長手方向の延伸倍率を1.9倍とした以外は実施例1と同様に作製し、厚み6.0μmの金属板被覆用フィルムを得た。得られたフィルムの物性を以下の表1に示す。
長手方向への再延伸後の熱固定温度を160℃とした以外は実施例4と同様に作製し、厚み6.0μmの金属板被覆用フィルムを得た。得られたフィルムの物性を以下の表1に示す。
フィルムの原料として、融点が258℃のPET、及び融点が208℃のイソフタル酸共重合PET(以下、CoPETと記載)のペレットを準備した。A層側がPET、B層側がCoPETとなるように積層させ、長手方向の延伸温度を95℃とした以外は実施例1と同様に作製し、厚み6.0μmの金属板被覆用フィルムを得た。得られたフィルムの物性を以下の表1に示す。
無延伸フィルムの厚みを15μmとした以外は実施例1と同様に作製し、厚み5.0μmの金属板被覆用フィルムを得た。得られたフィルムの物性を以下の表1に示す。
無延伸フィルムの厚みを8.5μmとした以外は実施例1と同様に作製し、厚み2.8μmの金属板被覆用フィルムを得た。得られたフィルムの物性を以下の表1に示す。
無延伸フィルムの厚みを45μmとした以外は実施例1と同様に作製し、厚み15μmの金属板被覆用フィルムを得た。得られたフィルムの物性を以下の表1に示す。
無延伸フィルムの厚みを80μmとした以外は実施例1と同様に作製し、厚み26μmの金属板被覆用フィルムを得た。得られたフィルムの物性を以下の表1に示す。
無延伸フィルムの厚みを15μmとし、長手方向の延伸倍率を2.5倍とした以外は実施例1と同様に作製し、厚み6.0μmの金属板被覆用フィルムを得た。得られたフィルムの物性を以下の表1に示す。
無延伸フィルムの厚みを24μmとし、長手方向の延伸倍率を4.0倍とした以外は実施例1と同様に作製し、厚み6.0μmの金属板被覆用フィルムを得た。得られたフィルムの物性を以下の表1に示す。
長手方向への再延伸後の弛緩率を0.5%とした以外は実施例3と同様に作製し、厚み6.0μmの金属板被覆用フィルムを得た。得られたフィルムの物性を以下の表1に示す。
無延伸フィルムの厚みを120μmとし、長手方向の再延伸倍率を1.2倍とした以外は実施例3と同様に作製し、厚み6.0μmの金属板被覆用フィルムを得た。得られたフィルムの物性を以下の表1に示す。
実施例1のTダイからの樹脂吐出量を調節した以外は同様の方法で無延伸フィルムを得て、その無延伸フィルムの端部を除去したフィルムを巻取機で巻き取り、厚み6.0μmの金属板被覆用フィルムを得た。得られたフィルムの物性を以下の表1に示す。
実施例3のTダイからの樹脂吐出量を調節した以外は同様の方法で二軸延伸を行い、横延伸後に端部を除去したフィルムを巻取機で巻き取り、厚み6.0μmの金属板被覆用フィルムを得た。得られたフィルムの物性を以下の表1に示す。
長手方向への再延伸後に熱固定および弛緩を行わなかった以外は実施例3と同様に作製し、厚み6.0μmの金属板被覆用フィルムを得た。得られたフィルムの物性を以下の表1に示す。
長手方向の延伸後に弛緩を行わなかった以外は実施例1と同様に作製し、厚み6.0μmの金属板被覆用フィルムを得た。得られたフィルムの物性を以下の表1に示す。
実施例1〜15及び比較例1〜4の熱圧着ラミネート性の評価結果を以下の表1に併せて示す。表1に示すように、比較例1〜4では、フィルム幅変化、気泡混入、及びシワ混入のうちの少なくとも一つがC(不可)評価であった。これに対して、実施例1〜15では、フィルム幅変化、気泡混入、及びシワ混入のいずれもがB(良好)評価以上であった。このことから、本発明によれば、熱圧着ラミネート法により金属板に被覆する際に、特に高温下における熱収縮が小さいため幅広い製品を製造でき、且つ、シワの発生や気泡の混入も抑制できることが確認された。
Claims (6)
- 幅方向のヤング率ETDに対する長手方向のヤング率EMDの比(EMD/ETD)が1.2以上3.5以下の範囲内にあり、熱機械分析装置によって測定される200℃での熱収縮率が長手方向及び幅方向のいずれも20%以下であり、全成分中に占めるポリエステル樹脂の割合が80質量%以上であることを特徴とする金属板被覆用フィルム。
- 長手方向のヤング率EMDと幅方向のヤング率ETDの和(EMD+ETD)が3000MPa以上12000MPa以下の範囲内にあることを特徴とする請求項1に記載の金属板被覆用フィルム。
- 最も低温側に存在する融解ピーク温度Tm1が210℃以上280℃以下の範囲内にあることを特徴とする請求項1又は2に記載の金属板被覆用フィルム。
- フィルム厚みが3.0μm以上25μm以下の範囲内にあることを特徴とする請求項1〜3のうち、いずれか1項に記載の金属板被覆用フィルム。
- 容器の表面被覆用として用いられることを特徴とする請求項1〜4のうち、いずれか1項に記載の金属板被覆用フィルム。
- 請求項1〜5のうち、いずれか1項に記載の金属板被覆用フィルムを少なくとも片面に備えることを特徴とする樹脂被覆金属板。
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WO2002047889A1 (fr) * | 2000-12-11 | 2002-06-20 | Teijin Limited | Film polyester biaxialement oriente et procede de production de ce film |
TWI295963B (ja) * | 2001-05-11 | 2008-04-21 | Toray Industries | |
JP4194450B2 (ja) * | 2003-08-27 | 2008-12-10 | 富士フイルム株式会社 | 磁気記録再生方法および磁気記録媒体 |
EP1734067B1 (en) * | 2004-02-17 | 2011-11-30 | Toray Industries, Inc. | Biaxially oriented polyester film |
JP4370983B2 (ja) * | 2004-06-15 | 2009-11-25 | 東洋紡績株式会社 | 金属板被覆用ポリエステル系フィルム、ポリエステル系フィルム被覆金属板、及びポリエステル系フィルム被覆金属容器 |
KR101253353B1 (ko) * | 2005-07-04 | 2013-04-11 | 데이진 듀폰 필름 가부시키가이샤 | 가스 배리어 가공용 폴리에스테르 필름 및 그것으로이루어지는 가스 배리어성 적층 폴리에스테르 필름 |
JP5428337B2 (ja) * | 2007-03-28 | 2014-02-26 | 東レ株式会社 | 成形部材用二軸配向ポリエステルフィルム、それを用いた成形用積層体及びその製造方法 |
JP5256754B2 (ja) * | 2008-02-01 | 2013-08-07 | 東レ株式会社 | 積層フィルム |
JP2011126056A (ja) * | 2009-12-16 | 2011-06-30 | Toray Ind Inc | ポリエステル系積層フィルム、それを用いた蒸着フィルム、ラミネート体、および包装体 |
WO2012043281A1 (ja) * | 2010-09-27 | 2012-04-05 | 東レ株式会社 | 二軸配向ポリエステルフィルムおよびリニア磁気記録媒体 |
JP2012171328A (ja) * | 2011-02-24 | 2012-09-10 | Teijin Dupont Films Japan Ltd | 二軸配向ポリエステルフィルム |
CN107001666B (zh) * | 2014-11-28 | 2020-09-01 | 东丽株式会社 | 聚酯膜 |
JP2017132990A (ja) * | 2016-01-22 | 2017-08-03 | 東レ株式会社 | ポリエステルフィルム |
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MY196228A (en) | 2023-03-24 |
AU2019369562B2 (en) | 2022-10-27 |
WO2020090552A1 (ja) | 2020-05-07 |
EP3854837A1 (en) | 2021-07-28 |
PH12021550714A1 (en) | 2021-11-22 |
CN113056507A (zh) | 2021-06-29 |
CA3116825C (en) | 2023-09-26 |
US20210370655A1 (en) | 2021-12-02 |
JPWO2020090552A1 (ja) | 2021-02-15 |
EP3854837A4 (en) | 2021-10-20 |
AU2019369562A1 (en) | 2021-05-06 |
EP3854837B1 (en) | 2024-01-10 |
CN113056507B (zh) | 2023-11-10 |
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