JP2004042617A - Method for manufacturing polyester film-coated metallic sheet - Google Patents
Method for manufacturing polyester film-coated metallic sheet Download PDFInfo
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- JP2004042617A JP2004042617A JP2003134653A JP2003134653A JP2004042617A JP 2004042617 A JP2004042617 A JP 2004042617A JP 2003134653 A JP2003134653 A JP 2003134653A JP 2003134653 A JP2003134653 A JP 2003134653A JP 2004042617 A JP2004042617 A JP 2004042617A
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- Prior art keywords
- polyester
- film
- resin
- olefin
- layer
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- 229920006267 polyester film Polymers 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 40
- 229920005989 resin Polymers 0.000 claims abstract description 106
- 239000011347 resin Substances 0.000 claims abstract description 106
- 229920000728 polyester Polymers 0.000 claims abstract description 95
- 238000002844 melting Methods 0.000 claims abstract description 34
- 230000008018 melting Effects 0.000 claims abstract description 34
- 238000001816 cooling Methods 0.000 claims abstract description 19
- 238000005520 cutting process Methods 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims description 61
- 239000002184 metal Substances 0.000 claims description 61
- -1 polyethylene Polymers 0.000 claims description 41
- 150000001336 alkenes Chemical class 0.000 claims description 38
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 38
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- 229920001971 elastomer Polymers 0.000 claims description 19
- 239000000806 elastomer Substances 0.000 claims description 19
- 229920000642 polymer Polymers 0.000 claims description 19
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 18
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 18
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 17
- 238000010030 laminating Methods 0.000 claims description 14
- KKEYFWRCBNTPAC-UHFFFAOYSA-N terephthalic acid group Chemical group C(C1=CC=C(C(=O)O)C=C1)(=O)O KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 9
- 229920001577 copolymer Polymers 0.000 claims description 7
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical group CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 238000009998 heat setting Methods 0.000 claims 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 26
- 238000010438 heat treatment Methods 0.000 abstract description 12
- 238000000576 coating method Methods 0.000 abstract description 10
- 239000011248 coating agent Substances 0.000 abstract description 8
- 229920000098 polyolefin Polymers 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 238000001125 extrusion Methods 0.000 abstract description 3
- 230000001954 sterilising effect Effects 0.000 abstract description 3
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 3
- 230000003245 working effect Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 67
- 239000002994 raw material Substances 0.000 description 30
- 238000003860 storage Methods 0.000 description 29
- 229910052782 aluminium Inorganic materials 0.000 description 25
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 25
- 230000002087 whitening effect Effects 0.000 description 20
- 238000005266 casting Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 11
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 9
- 230000007423 decrease Effects 0.000 description 8
- 230000006866 deterioration Effects 0.000 description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 229910000838 Al alloy Inorganic materials 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 238000003475 lamination Methods 0.000 description 6
- 238000010409 ironing Methods 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- 230000037303 wrinkles Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 150000007519 polyprotic acids Polymers 0.000 description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 2
- 238000006748 scratching Methods 0.000 description 2
- 230000002393 scratching effect Effects 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- HOPNITFHNCUXTG-UHFFFAOYSA-N 3-ethoxycarbonylbenzoic acid Chemical group CCOC(=O)C1=CC=CC(C(O)=O)=C1 HOPNITFHNCUXTG-UHFFFAOYSA-N 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009924 canning Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 239000005043 ethylene-methyl acrylate Substances 0.000 description 1
- 229920005680 ethylene-methyl methacrylate copolymer Polymers 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 239000005029 tin-free steel Substances 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
Abstract
Description
【０００１】
【発明の属する技術分野】
ポリエステル系フィルム被覆金属板の製造方法に関するものである。さらに詳細には、製缶性（例えば、絞り・しごき加工性）と耐衝撃性に優れ、かつ温水殺菌処理が実施される金属缶に好適なポリエステル系フィルム被覆金属板の製造方法に関するものである。
【０００２】
【従来技術】
従来、金属缶の缶内面及び缶外面は腐蝕防止を目的として、エポキシ系，フェノール系等の各種熱硬化性樹脂を溶剤に溶解又は分散させたものを塗布し、金属表面を被覆することが広く行われてきた。しかしながら、この熱硬化性樹脂の被覆方法では塗料の乾燥に長時間を要するため生産性が低下したり、多量の有機溶剤による環境汚染など好ましくない問題を発生させることが多いという欠点があった。
【０００３】
かかる欠点を解決するため、金属板に熱可塑性樹脂を溶融押出法で被覆する方法が開示されている（例えば、特許文献１参照。）。
【０００４】
又、溶融押出した熱可塑性樹脂を一旦冷却固化させた後、加熱された金属板に圧着する方法が開示されている（例えば、特許文献２参照。）。しかしながら、これらの熱可塑性樹脂の被覆方法では、Ｔダイから層状に溶融樹脂を押出す際、溶融樹脂膜の巾減少（ネックインと称す）が大きく、被覆に必要な樹脂巾に対して数１０ｃｍ広い巾で製膜する必要があり、経済性の点から満足される方法ではなかった。
【０００５】
かかる欠点を解決するため、三官能以上の多塩基酸又は多価アルコール成分を共重合させたポリエステルを配合してなるポリエステルを使用することによりネックインを小さくする方法が開示されている（例えば、特許文献３、特許文献４参照。）。しかしながら、これらの被覆方法では、三官能以上の多塩基酸又は多価アルコール成分を共重合させたポリエステルが押出機からＴダイに至る溶融工程で熱劣化しやすく、熱安定剤を併用しても得られた溶融樹脂膜に異物（例えば、ゲル状異物又は劣化物を核とした異物）が発生しやすく、製缶時に樹脂被覆層に異物を起点とした亀裂が入るため、製缶用の樹脂被覆金属板として満足されるものではなかった。
【０００６】
又、絞り・しごき缶に用いられる樹脂被覆金属板の被覆用樹脂では、製缶（絞り・しごき加工）に追従しうる優れた成形性が要求されるばかりでなく、製缶後に美麗化を目的として実施される外面焼付け塗装の加熱においても耐衝撃性が低下しないことが要求される。しかしながら、前記の樹脂被覆金属板は耐衝撃性が低下することが多く、耐衝撃性の要求を満足するものではなかった。
【０００７】
【特許文献１】
特開昭５７−２０３５４５号公報
【特許文献２】
特開平１０−３０９７７５号公報
【特許文献３】
特開平１０−８６３０８号公報
【特許文献４】
特開２０００−７１３８８号公報
【０００８】
【発明が解決しようとする課題】
本発明は前記従来技術の問題点を解消することを目的とするものである。即ち、溶融押出時のネックインが小さく、かつ得られた溶融樹脂膜に異物が発生しにくいため、経済性と製缶性に優れ、かつ製缶後に美麗化を目的として実施される外面焼付け塗装の加熱においても耐衝撃性が低下しにくく、かつ温水殺菌処理が実施される金属缶に好適なポリエステル系フィルム被覆金属板の製造方法を提供するものである。
【０００９】
【課題を解決するための手段】
本発明の目的は、金属板の片面に融点１８０℃以上の結晶性ポリエステルを主体とするフィルム（Ａ）を被覆しもう一方の面に融点１８０℃以上の結晶性ポリエステルよりなるフィルム（Ｂ）を被覆する製造方法において、Ｔダイを用いて両端部にオレフィン系ポリマーが合流された状態で層状に押出した溶融樹脂膜を冷却固化して得た樹脂膜（Ａ）及び（Ｂ）を縦方向に１軸延伸し、次いで熱固定処理し、次いで両端部を切断除去してポリエステル系フィルム（Ａ）及び（Ｂ）を得る方法と該ポリエステル系フィルム（Ａ）及び（Ｂ）を別工程で加熱された金属板にラミネートする方法よりなるポリエステル系フィルム被覆金属板の製造方法であって、かつポリエステル系フィルム（Ａ）は（Ｉ）層／（ＩＩ）層の複合構成であり、（Ｉ）層がポリエチレンテレフタレートとポリブチレンフタレートが６０：４０〜３０：７０（重量％）よりなり、（ＩＩ）層が結晶性ポリエステルとポリエステルエラストマーが９５：５〜７０：３０（重量％）よりなるポリエステルとオレフィン系ポリマーが７０：３０〜１００：０（重量％）よりなるものであって、かつポリエステル系フィルム（Ｂ）はポリエチレンテレフタレートとポリブチレンテレフタレートが６０：４０〜３０：７０（重量％）のポリエステルよりなるものであって、かつポリエステル系フィルム（Ａ）及び（Ｂ）は１５０℃での縦方向の熱収縮率が４〜３０％であることを特徴とするポリエステル系フィルム被覆金属板の製造方法によって達成される。
【００１０】
この場合において、前記ポリエステルエラストマーのハードセグメントがテレフタル酸残基とエチレングリコール残基及び／又はブタンジオール残基を主成分とするポリエステルであり、ソフトセグメントがポリテトラメチレンオキサイドであることが好適である。
【００１１】
また、この場合において、前記樹脂膜（Ａ）の両端部と（ＩＩ）層のオレフィン系ポリマー及び樹脂膜（Ｂ）の両端部のオレフィン系ポリマーが同一であることが好適である。
【００１２】
さらにまた、この場合において、オレフィン系ポリマーがポリエチレン及び／又はエチレン系共重合体であることが好適である。
【００１３】
さらにまた、この場合において、前記樹脂膜（Ａ）の（Ｉ）層と樹脂膜（Ｂ）のポリエステルのポリエチレンテレフタレートとポリブチレンテレフタレートの比率が同一であることが好適である。
【００１４】
【発明の実施の形態】
本発明にける樹脂膜（Ａ）の（Ｉ）層及び樹脂膜（Ｂ）ではポリエチレンテレフタレート及びポリブチレンテレフタレートの特性を損なわない範囲でテレフタル酸以外のジカルボン酸成分とエチレングリコール及びブタンジオール以外のグリコール成分を使用できる。例えば、ジカルボン酸として、イソフタル酸，オルソフタル酸，ナフタレンジカルボン酸，ジフェニルスルホンジカルボン酸，５−ナトリウムスルホイソフタル酸等の芳香族ジカルボン酸、シュウ酸，コハク酸，アジピン酸，セバシン酸，デカンジカルボン酸，マレイン酸，フマル酸，ダイマー酸等の脂肪族ジカルボン酸、ｐ−オキシ安息香酸等のオキシカルボン酸、シクロヘキサンジカルボン酸等の脂環族ジカルボン酸が使用できる。又、エチレングリコール及びブタンジオール以外のグリコール成分として、プロパンジオール，ペンタンジオール，ヘキサンジオール，ネオペンチルグリコール等の脂肪族グリコール、シクロヘキサンジメタノール等の脂環族グリコール、ビスフェノールＡ，ビスフェノールＳ等の芳香族グリコールが使用できる。
本発明における樹脂膜（Ａ）の（ＩＩ）層を構成する結晶性ポリエステルは、ジカルボン酸成分とグリコール成分からなるポリマーであり、ジカルボン酸として、テレフタル酸，イソフタル酸，オルソフタル酸，ナフタレンジカルボン酸，ジフェニルスルホンジカルボン酸，５−ナトリウムスルホイソフタル酸等の芳香族ジカルボン酸、シュウ酸，コハク酸，アジピン酸，セバシン酸，デカンジカルボン酸，マレイン酸，フマル酸，ダイマー酸等の脂肪族ジカルボン酸、ｐ−オキシ安息香酸等のオキシカルボン酸、シクロヘキサンジカルボン酸等の脂環族ジカルボン酸が使用できる。
又、グリコール成分として、エチレングリコール，プロパンジオール，ブタンジオ−ル，ペンタンジオール，ヘキサンジオール，ネオペンチルグリコール等の脂肪族グリコール、シクロヘキサンジメタノール等の脂環族グリコール、ビスフェノールＡ，ビスフェノールＳ等の芳香族グリコールが使用できる。
【００１５】
本発明における樹脂膜（Ａ）の（ＩＩ）層の結晶性ポリエステルとポリエステルエラストマーの比率は９５：５〜７０：３０（重量％）が必要である。ポリエステルエラストマーが５重量％未満の場合、耐衝撃性が低く好ましくない。逆に、３０重量％を超える場合、Ｔダイからの吐出が不安定となり好ましくない。ポリエステルエラストマーはハードセグメントがテレフタル酸残基とエチレングリコール残基又はブタンジオール残基を主成分とするポリエステルであり、イソフタル酸，オルソフタル酸等の芳香族ジカルボン酸、アジピン酸，セバシン酸，デカンジカルボン酸等の脂肪族ジカルボン酸を含有してもかまわない。又、ソフトセグメントが重量平均分子量４００〜５０００のポリテトラメチレンオキサイドを５〜５０モル％含有することが好ましい。
【００１６】
本発明におけるポリエステルには、必要に応じて酸化防止剤，熱安定剤，紫外線吸収剤，可塑剤，顔料，帯電防止剤，潤滑剤，結晶核剤，無機又は有機粒子よりなる滑剤等を配合させてもよい。
【００１７】
本発明におけるポリエステルの製造方法については特に限定しない。即ち、エステル交換法又は直接重合法のいずれの方法で製造されたものであっても使用できる。又、分子量を高めるために固相重合法で製造されたものであってもかまわない。さらに缶に内容物を充填後に実施されるパストライズ処理，レトルト処理等でのポリエステル樹脂からのオリゴマー量を少なくする点より、減圧固相重合法で製造されたオリゴマー含有量が低いポリエステルを使用することは好ましい。但し、樹脂膜（Ａ）の（Ｉ）層と樹脂膜（Ｂ）のポリエステルのポリエチレンテレフタレートとポリブチレンテレフタレートの比率が同一であることが好ましい。その理由は、樹脂の無駄を省く観点から層状に押出された樹脂（Ａ）及び（Ｂ）を冷却固化後に縦１軸延伸及び熱固定処理して得た樹脂膜（Ａ）及び（Ｂ）の両端部を切断除去して得た樹脂を樹脂膜（Ａ）の（ＩＩ）層で再使用した場合、金属板に被覆されたポリエステル系フィルム（Ａ）の品質が安定するためである。
【００１８】
本発明におけるポリエステルエラストマーの製造方法については特に限定しない。即ち、エステル交換法又は直接重合法のいずれの方法で製造されたものであっても使用できる。
本発明で使用されるポリエステル及びポリエステルエラストマーの融点は１８０℃以上であることが製缶性（絞り・しごき加工において、缶内面側の樹脂ではポンチの離型性の確保、缶外面側の樹脂ではかじり抑制［樹脂皮膜での縦方向のキズ］）から必要である。
【００１９】
本発明では樹脂膜（Ａ）の両端部と（ＩＩ）層及び樹脂膜（Ｂ）の両端部で使用するオレフィン系ポリマーはポリエチレン及び／又はエチレン系共重合体が好ましい。低密度ポリエチレン，中密度ポリエチレン，高密度ポリエチレン，直鎖状低密度ポリエチレン，超高分子量ポリエチレン，エチレンープロピレン共重合体，エチレンーブテン共重合体，エチレンー酢酸ビニル共重合体，エチレンーエチルアクリレート共重合体，エチレンーメチルアクリレート共重合体、エチレンーメチルメタアクリレート共重合体、エチレンーアクリル酸共重合体、エチレンーメタクリル酸共重合体、エチレンーエチルアクリレートー無水マレイン酸共重合体、アイオノマー、エチレンー無水マレイン酸グラフト共重合体、エチレンービニルアルコール共重合体等が使用できる。樹脂膜（Ａ）の両端部と（ＩＩ）層で使用するオレフィン系ポリマー及び樹脂膜（Ｂ）の両端部で使用するオレフィン系ポリマーは同一であることが好ましい。その理由は、樹脂の無駄を省く観点から層状に押出された樹脂（Ａ）及び（Ｂ）を冷却固化後に縦１軸延伸及び熱固定処理して得た樹脂膜（Ａ）及び（Ｂ）の両端部を切断除去して得た樹脂を樹脂膜（Ａ）の（ＩＩ）層で再使用した場合、金属板に被覆されたポリエステル系フィルム（Ａ）の品質が安定するためである。
【００２０】
本発明ではポリエステル系フィルムのポリエステルとオレフィン系ポリマーの比率は７０：３０〜１００：０（重量％）であることが必要である。オレフィン系ポリマーが３０重量％を超える場合、製缶性（ポンチの離型性）が劣るため好ましくない。
【００２１】
本発明ではポリエステルとオレフィン系ポリマーをＴダイから層状に押出す際、両端部（片側が５ｃｍ以下の部分）にオレフィン系ポリマーを使用することが好ましい。
本発明ではポリエステルとオレフィン系ポリマーをドライブレンド又は溶融混合して得たポリマーを公知の１軸又は２軸押出機内で溶融させた後、エッジラミネーションタイプ等の公知のマルチマニホールドダイを使用して層状の溶融樹脂膜を得る。
【００２２】
本発明では冷却固化方法として、回転させた冷却ロールにＴダイから層状に溶融した樹脂を接触させる公知の方法が使用できる。溶融樹脂を冷却ロールに接触させる際、強制的にエアーを吹き付ける方法又は静電気で密着させる方法を採用することが好ましい。又、強制エアー吹き付け法，静電密着法のいずれにおいても層状樹脂の両端部と中央部を独立させて実施する方法がより好ましい。さらに、溶融樹脂が冷却ロールに接触する際、反対側を減圧して随伴流を低減させる方策（例えば、バキュームチャンバー，バキュームボックス等の装置）を併用することがより好ましい。
【００２３】
本発明では冷却固化させた後、必要に応じて両端部を切断除去して得た樹脂膜（Ａ）及び（Ｂ）をポリエステルのガラス転移点以上かつ冷結晶化温度未満の温度で１．３〜６．０倍の縦延伸を実施し、次いで緊張下で５０℃以上かつポリエステルの融点−２０℃の温度で１〜２０秒間熱処理し、次いで樹脂膜の両端部を切断除去してポリエステル系フィルム（Ａ）及び（Ｂ）を得る。
【００２４】
本発明で用いるポリエステル系フィルム（Ａ）及び（Ｂ）は１５０℃での縦方向の熱収縮率を４〜３０％であることが必要である。熱収縮率が４％未満の場合、ラミネート後の密着性が低下するため好ましくない。逆に、熱収縮率が３０％を超える場合、ラミネートまでの保管中に縦方向の経時収縮によりシワ・ブロッキングが発生し、ポリエステル系フィルム被覆金属板にシワ・気泡のスジが発生しやすく好ましくない。
【００２５】
本発明では上記の切断除去した樹脂膜の両端部を細断後、押固める方法又は加熱溶融させる方法等によって得た原料を樹脂膜（Ａ）の（ＩＩ）層で再使用することは可能である。再使用率は特に限定されないが、５〜９０重量％が好ましい。
【００２６】
本発明では金属板として、ティンフリースティール等の表面処理鋼板あるいはアルミニウム板又はアルミニウム合金板あるいは表面処理を施したアルミニウム板又はアルミニウム合金板が使用できる。これらの金属板をポリエステルの融点−２０℃以上かつ融点＋１５０℃に加熱した後、ラミネートロールを使用して金属板にポリエステル系フィルム（Ａ）及び（Ｂ）をラミネートし、引き続いてこのラミネート金属板をポリエステルの融点＋１０℃以上かつ融点＋６０℃で加熱した後、水冷及び／又は空冷してポリエステル系フィルム被覆金属板を得る。但し、ポリエステル系フィルム（Ａ）を金属板にラミネートする場合、（ＩＩ）層側と金属板を接触させることが製缶性を確保するために好ましい。
【００２７】
【実施例】
以下、実施例をもとに本発明を説明する。
［評価方法］
（１）ポリエステルの融点
ポリエステル組成物を３００℃で５分間加熱溶融した後、液体窒素で急冷して得たサンプル１０ｍｇを用い、窒素気流中、示差走査型熱量計（ＤＳＣ）を用いて１０℃／分の昇温速度で発熱・吸熱曲線（ＤＳＣ曲線）を測定したときの、融解に伴う吸熱ピークの頂点温度を融点Ｔｍ（℃）とした。
【００２８】
（２）ネックイン量
Ｔダイの吐出口巾（６０ｃｍ）とｎ＝３で測定した冷却固化後の樹脂膜巾（両端部を切断除去する前の樹脂膜巾）の平均値（Ａｃｍ）を用い、次式でネックイン量（ｃｍ）を求めた。ネックイン量が５ｃｍ以下を実用性ありと評価した。
ネックイン量（ｃｍ）＝６０−Ａ
【００２９】
（３）保管後のロールフィルムの外観と耐切断性
ロール状フィルムを４０℃で相対湿度８０％の条件下で１ケ月保管した後、フィルムの外観とＪＩＳ Ｋ ７１２７に準じた引張試験（縦方向 ｎ＝３０、１５ｍｍ巾の１号試験片、試験速度：２００ｍｍ／分）を実施した。評価基準を以下のとおり設定し、○を実用性ありと評価した。
［外観］
○：シワ・ブロッキング・タルミなし
×：シワ・ブロッキング・タルミあり
［耐切断性］
破断伸度＜５％以下のサンプル数で評価した。（２個／３０個以下を実用性あり と評価した。）
【００３０】
（４）熱収縮率
ＪＩＳ Ｚ １７１５に準じて評価した。
【００３１】
（５）ポリエステル系フィルム被覆金属板の作製方法
２５０℃に加熱したアルミニウム合金板（厚み：０．２６ｍｍの３００４系合金板）の片面にポリエステル系フィルム（Ａ）の（ＩＩ）層が金属板と接触するように，もう一方の面にポリエステル系フィルム（Ｂ）を同時にラミネートした後、２７５℃で加熱した後に水中急冷して被覆アルミニウム板を作製した。
【００３２】
（６）缶内面樹脂と加工ポンチの離型性
被覆アルミニウム板のポリエステル系フィルム（Ａ）が缶内面側になるようにｎ＝１０で製缶し、成形缶上部に起る座屈程度を目視観察した。評価基準は以下のとおり設定し、○を実用性ありと評価した。
○：缶開口部の座屈未発生
△：缶開口部円周の約１／３に座屈発生
×：缶開口部円周の１／３以上に座屈発生
【００３３】
（７）缶外面の耐かじり性（缶外面のポリエステル系フィルムでの縦方向のキズ）
被覆アルミニウム板のポリエステル系フィルム（Ａ）が缶内面側になるようにｎ＝１０で製缶し、成形した缶体胴壁部の外面ポリエステル系フィルム（Ｂ）のキズ発生程度を目視観察した。評価基準は以下のとおり設定し、○を実用性ありと評価した。
○：キズ未発生
△：外面の約１／３にキズ発生
×：外面の１／３以上に激しいキズ発生
【００３４】
（８）耐衝撃性
被覆アルミニウム板を製缶して得た缶を２８０℃で４０秒加熱後水中急冷した缶の胴壁中央部より７ｃｍ角のサンプルを切り出す。このサンプルの缶外面に相当する面に先端径１０ｍｍの重り（６００ｇ）を高さ１０ｃｍから落して衝撃を付与する。ついで７％の希塩酸を満たしたガラス容器上にサンプルを置き（サンプルの凸部が浸漬する状態で置き）、３日後に凸部の腐蝕状態を目視観察した。評価基準は以下のとおり設定し、○を実用性ありと評価した。
○：凸部の腐蝕未発生
×：凸部の腐蝕発生
【００３５】
（９）温水処理後の缶外面の白化程度
被覆アルミニウム板を製缶して得た缶を２７０℃で４０秒間加熱した後水中急冷したものをサンプルとする。このサンプルを８０℃の温水中に１０分間浸漬した後、水中急冷して得た缶外面を目視観察した。評価基準は以下のとおり設定 し、○を実用性ありと評価した。
○：白化が目立たない
△：明らかに白化しているが、アルミニウム合金板の色が見える
×：白化によりアルミニウム合金板の色がみえない
【００３６】
［実施例・比較例に用いたポリエステルとオレフィン系ポリマーの略号と内容］
（１）ＰＥＴ ：ポリエチレンテレフタレート
（２）ＰＢＴ ：ポリブチレンテレフタレート
（３）ＰＥＴ−Ｉ ：ポリエチレンテレフタレート・イソフタレート（エチレイソフタレートの繰り返し単位１０モル％）
（４）エラストマー ：ポリブチレンテレフタレートとポリブチレンオキサイドの共重合体（重量平均分子量が１０００のブチレンオキサイドの繰り返し単位１５モル％）
（５）ＣＯ−ＰＥＳ ：テレフタル酸とエチレングリコール／シクロヘキサンジメタノール（モル％ ７０／３０）との共重合ポリエステル
（６）オレフィンＡ ：低密度ポリエチレン（住友化学社製、スミカセンＧ４０１：商品名）
（７）オレフィンＢ ：エチレンーブテン共重合体（三井化学社製、タフマーＡ４０８５：商品名）
（８）オレフィンＣ ： アイオノマー（三井デュポンポリケミカル社製、ハイ ミラン１７０６：商品名）
（９）オレフィンＤ ：エチレンーメチルアクリレート共重合体（イーストマンケミカル社製、ＥＭＡＣ ＳＰ２２０５：商品名）
（１０）オレフィンＦ ：ポリプロピレン（住友化学社製、ノーブレンＦＳ２０１１ＤＧ２：商品名）
【００３７】
［実施例 １］
樹脂膜（Ａ）の（Ｉ）層原料としてＰＥＴ／ＰＢＴ＝４０／６０（重量％）のポリエステル、（ＩＩ）層原料として（Ｉ）層原料／エラストマー＝８５／１５（重量％）のポリエステルを２８０℃で溶融させ、樹脂膜（Ａ）の両端部の原料としてオレフィンＡ単体を２５０℃で溶融させ、エッジラミネーションタイプのＴダイ（両端部の吐出口巾／中央部の吐出口巾／両端部の吐出口巾＝２ｃｍ／５６ｃｍ／２ｃｍ、２６０℃に加熱）を用いて、層状に冷却ロール（周速２０ｍ／分）へキャスト（Ｔダイから冷却ロールでの溶融樹脂の接地点までの距離１５ｃｍ、中央部と両端部は別々の装置で強制的にエアーを吹付け）して樹脂膜（Ａ）を得た。
樹脂膜（Ａ）を予熱温度６５℃、延伸温度１００℃で３．０倍縦延伸し、クリップ把持方式のセッターを用い１５０℃で３秒間熱処理した後、両端部（片側５ｃｍ）を切断除去して巻取り、厚みが２５μｍ（（Ｉ）層厚み１２．５μｍ，（ＩＩ）層厚み１２．５μｍ）で長さが１００ｍのロール状ポリエステル系フィルム（Ａ）を得た。
【００３８】
又、樹脂膜（Ｂ）の中央部の原料としてＰＥＴ／ＰＢＴ＝４０／６０（重量％）のポリエステルを２７０℃で溶融させ、樹脂膜（Ｂ）の両端部の原料としてオレフィンＡ単体を２５０℃で溶融させ、エッジラミネーションタイプのＴダイ（両端部の吐出口巾／中央部の吐出口巾／両端部の吐出口巾＝２ｃｍ／５６ｃｍ／２ｃｍ、２６０℃に加熱）を用いて、層状に冷却ロール（周速２０ｍ／分）へキャスト（Ｔダイから冷却ロールでの溶融樹脂の接地点までの距離１５ｃｍ、中央部と両端部は別々の装置で強制的にエアーを吹付け）して樹脂膜（Ｂ）を得た。
樹脂膜（Ｂ）を予熱温度６５℃、延伸温度１００℃で３．０倍縦延伸し、クリップ把持方式のセッターを用い１５０℃で３秒間熱処理した後、両端部（片側５ｃｍ）を切断除去して巻取り、厚みが１６μｍで長さが１００ｍのロール状ポリエステル系フィルム（Ｂ）を得た。
【００３９】
ロール状ポリエステル系フィルム（Ａ）及び（Ｂ）を４０℃で相対湿度８０％の条件下で１ケ月保管した後、２５０℃に加熱した３００４系アルミニウム合金板（厚み ０．２６ｍｍ）の両面に前記フィルムを圧着し、２７５℃に加熱した後、水中急冷して被覆アルミニウム板を得た。
【００４０】
こうして得られた被覆アルミニウム板に成形用潤滑剤を塗布した後、加熱して板温７０℃でポリエステル系フィルム（Ａ）が内面側となるように絞り加工を実施した。次いで、得られたカップの温度を４０℃にして金型温度８０℃でしごき加工を実施し、３５０ｍｌサイズのシームレス缶を得た。
【００４１】
ポリエステルの融点，キャスト時のネックイン量，保管後のロールフィルムの外観と耐切断性，熱収縮率，製缶性（缶内面フィルムとポンチの離型性と缶外面フィルムのキズ発生程度），耐衝撃性，温水処理後の缶外面の白化程度を表１に示す。本実施例の方法は、ネックイン量が小さく経済性に優れ、かつ保管後のポリエステル系フィルムの外観不良及び耐切断性の低下がないためラミネート性が良好であり、かつ製缶性に優れ、かつ耐衝撃性と外面の耐温水白化性が優れた金属缶が得られるポリエステル系フィルム被覆金属板の製造方法であるといえる。
【００４２】
［実施例 ２］
樹脂膜Ａの（ＩＩ）層原料をＰＥＴ−Ｉ／エラストマー＝８５／１５（重量％）のポリエステルとした以外は実施例１と同様にして厚みが２５μｍ（（Ｉ）層厚み１２．５μｍ，（ＩＩ）層厚み１２．５μｍ）で長さが１００ｍのロール状ポリエステル系フィルム（Ａ）と厚みが１６μｍで長さが１００ｍのロール状ポリエステル系フィルム（Ｂ）を得た。
【００４３】
ついで、実施例１と同様に被覆アルミニウム板を作製し、製缶して３５０ｍｌサイズのシームレス缶を得た。
【００４４】
ポリエステルの融点，キャスト時のネックイン量，保管後のロールフィルムの外観と耐切断性，熱収縮率，製缶性（缶内面フィルムとポンチの離型性と缶外面フィルムのキズ発生程度），耐衝撃性，温水処理後の缶外面の白化程度を表１に示す。本実施例の方法は、ネックイン量が小さく経済性に優れ、かつ保管後のポリエステル系フィルムの外観不良及び耐切断性の低下がないためラミネート性が良好であり、かつ製缶性に優れ、かつ耐衝撃性と外面の耐温水白化性が優れた金属缶が得られるポリエステル系フィルム被覆金属板の製造方法であるといえる。
【００４５】
［実施例 ３］
樹脂膜Ａの（ＩＩ）層原料を（Ｉ）層原料／エラストマー＝８５／１５（重量％）のポリエステル ８７重量％とオレフィンＡ １３重量％とした以外は実施例１と同様にして厚みが２５μｍ（（Ｉ）層厚み１２．５μｍ，（ＩＩ）層厚み１２．５μｍ）で長さが１００ｍのロール状ポリエステル系フィルム（Ａ）と厚みが１６μｍで長さが１００ｍのロール状ポリエステル系フィルム（Ｂ）を得た。
【００４６】
ついで、実施例１と同様に被覆アルミニウム板を作製し、製缶して３５０ｍｌサイズのシームレス缶を得た。
【００４７】
ポリエステルの融点，キャスト時のネックイン量，保管後のロールフィルムの外観と耐切断性，熱収縮率，製缶性（缶内面フィルムとポンチの離型性と缶外面フィルムのキズ発生程度），耐衝撃性，温水処理後の缶外面の白化程度を表１に示す。本実施例の方法は、ネックイン量が小さく経済性に優れ、かつ保管後のポリエステル系フィルムの外観不良及び耐切断性の低下がないためラミネート性が良好であり、かつ製缶性に優れ、かつ耐衝撃性と外面の耐温水白化性が優れた金属缶が得られるポリエステル系フィルム被覆金属板の製造方法であるといえる。
【００４８】
［実施例 ４］
樹脂膜Ａの（ＩＩ）層原料を（Ｉ）層原料／エラストマー＝８５／１５（重量％）のポリエステル ８７重量％とオレフィンＢ １３重量％とし、樹脂膜（Ａ）及び（Ｂ）の両端部の原料をオレフィンＢとした以外は実施例１と同様にして厚みが２５μｍ（（Ｉ）層厚み１２．５μｍ，（ＩＩ）層厚み１２．５μｍ）で長さが１００ｍのロール状ポリエステル系フィルム（Ａ）と厚みが１６μｍで長さが１００ｍのロール状ポリエステル系フィルム（Ｂ）を得た。
【００４９】
ついで、実施例１と同様に被覆アルミニウム板を作製し、製缶して３５０ｍｌサイズのシームレス缶を得た。
【００５０】
ポリエステルの融点，キャスト時のネックイン量，保管後のロールフィルムの外観と耐切断性，熱収縮率，製缶性（缶内面フィルムとポンチの離型性と缶外面フィルムのキズ発生程度），耐衝撃性，温水処理後の缶外面の白化程度を表１に示す。本実施例の方法は、ネックイン量が小さく経済性に優れ、かつ保管後のポリエステル系フィルムの外観不良及び耐切断性の低下がないためラミネート性が良好であり、かつ製缶性に優れ、かつ耐衝撃性と外面の耐温水白化性が優れた金属缶が得られるポリエステル系フィルム被覆金属板の製造方法であるといえる。
【００５１】
［実施例 ５］
樹脂膜Ａの（ＩＩ）層原料を（Ｉ）層原料／エラストマー＝８５／１５（重量％）のポリエステル ８７重量％とオレフィンＣ １３重量％とし、樹脂膜（Ａ）及び（Ｂ）の両端部の原料をオレフィンＣとした以外は実施例１と同様にして厚みが２５μｍ（（Ｉ）層厚み１２．５μｍ，（ＩＩ）層厚み１２．５μｍ）で長さが１００ｍのロール状ポリエステル系フィルム（Ａ）と厚みが１６μｍで長さが１００ｍのロール状ポリエステル系フィルム（Ｂ）を得た。
【００５２】
ついで、実施例１と同様に被覆アルミニウム板を作製し、製缶して３５０ｍｌサイズのシームレス缶を得た。
【００５３】
ポリエステルの融点，キャスト時のネックイン量，保管後のロールフィルムの外観と耐切断性，熱収縮率，製缶性（缶内面フィルムとポンチの離型性と缶外面フィルムのキズ発生程度），耐衝撃性，温水処理後の缶外面の白化程度を表１に示す。本実施例の方法は、ネックイン量が小さく経済性に優れ、かつ保管後のポリエステル系フィルムの外観不良及び耐切断性の低下がないためラミネート性が良好であり、かつ製缶性に優れ、かつ耐衝撃性と外面の耐温水白化性が優れた金属缶が得られるポリエステル系フィルム被覆金属板の製造方法であるといえる。
【００５４】
［実施例 ６］
樹脂膜Ａの（ＩＩ）層原料を（Ｉ）層原料／エラストマー＝８５／１５（重量％）のポリエステル ８７重量％とオレフィンＡ／オレフィンＤ＝７０／３０（重量％）よりなるオレフィン １３重量％とし、樹脂膜（Ａ）及び（Ｂ）の両端部の原料をオレフィンＡ／オレフィンＤ＝７０／３０（重量％）とした以外は実施例１と同様にして厚みが２５μｍ（（Ｉ）層厚み１２．５μｍ，（ＩＩ）層厚み１２．５μｍ）で長さが１００ｍのロール状ポリエステル系フィルム（Ａ）と厚みが１６μｍで長さが１００ｍのロール状ポリエステル系フィルム（Ｂ）を得た。
【００５５】
ついで、実施例１と同様に被覆アルミニウム板を作製し、製缶して３５０ｍｌサイズのシームレス缶を得た。
【００５６】
ポリエステルの融点，キャスト時のネックイン量，保管後のロールフィルムの外観と耐切断性，熱収縮率，製缶性（缶内面フィルムとポンチの離型性と缶外面フィルムのキズ発生程度），耐衝撃性，温水処理後の缶外面の白化程度を表１に示す。本実施例の方法は、ネックイン量が小さく経済性に優れ、かつ保管後のポリエステル系フィルムの外観不良及び耐切断性の低下がないためラミネート性が良好であり、かつ製缶性に優れ、かつ耐衝撃性と外面の耐温水白化性が優れた金属缶が得られるポリエステル系フィルム被覆金属板の製造方法であるといえる。
【００５７】
［実施例 ７］
樹脂膜Ａの（ＩＩ）層原料を（Ｉ）層原料／エラストマー＝８５／１５（重量％）のポリエステル ８５重量％と実施例１でポリエステル系フィルム（Ａ）及び（Ｂ）を得る前に切断除去した両端部（オレフィンＡの比率が８５重量％）を造粒して得たポリマーを１５重量％とした以外は実施例１と同様にして厚みが２５μｍ（（Ｉ）層厚み１２．５μｍ，（ＩＩ）層厚み１２．５μｍ）で長さが１００ｍのロール状ポリエステル系フィルム（Ａ）と厚みが１６μｍで長さが１００ｍのロール状ポリエステル系フィルム（Ｂ）を得た。
【００５８】
ついで、実施例１と同様に被覆アルミニウム板を作製し、製缶して３５０ｍｌサイズのシームレス缶を得た。
【００５９】
ポリエステルの融点，キャスト時のネックイン量，保管後のロールフィルムの外観と耐切断性，熱収縮率，製缶性（缶内面フィルムとポンチの離型性と缶外面フィルムのキズ発生程度），耐衝撃性，温水処理後の缶外面の白化程度を表１に示す。本実施例の方法は、ネックイン量が小さく経済性に優れ、かつ保管後のポリエステル系フィルムの外観不良及び耐切断性の低下がないためラミネート性が良好であり、かつ製缶性に優れ、かつ耐衝撃性と外面の耐温水白化性が優れた金属缶が得られるポリエステル系フィルム被覆金属板の製造方法であるといえる。
【００６０】
［比較例 １］
樹脂膜（Ａ）と樹脂膜（Ｂ）の両端部の原料をＰＥＴ／ＰＢＴ＝４０／６０（重量％）のポリエステルとした以外は実施例１と同様にしてロール状樹脂膜を得ようとしたが、ネックイン量が大きく，かつ両端部を１８ｃｍ切断除去しなければ、厚み分布が一様な中央部が得られないため、この方法はポリエステル系フィルム被覆金属板の製造方法として好ましくない。ポリエステルの融点，キャスト時のネックイン量を表２に示す。
【００６１】
［比較例 ２］
樹脂膜（Ａ）の（Ｉ）層の原料をＰＥＴ／ＰＢＴ＝２０／８０（重量％）のポリエステルとし、樹脂膜（Ｂ）の中央部の原料をＰＥＴ／ＰＢＴ＝２０／８０（重量％）のポリエステルとした以外は実施例１と同様にして製膜しようとしたが、冷却ロールと縦延伸の予熱ロール間で樹脂膜が割れることが多く、さらに縦延伸時に樹脂膜が破断することが多く、ロール状ポリエステル系フィルム（Ａ）及び（Ｂ）を得られないため、この方法はポリエステル系フィルム製造方法として好ましくない。ポリエステルの融点，キャスト時のネックイン量を表２に示す。
【００６２】
［比較例 ３］
樹脂膜（Ａ）の（Ｉ）層の原料をＰＥＴ／ＰＢＴ＝７０／３０（重量％）のポリエステルとし、樹脂膜（Ｂ）の中央部の原料をＰＥＴ／ＰＢＴ＝７０／３０（重量％）のポリエステルとした以外は実施例１と同様にして厚みが２５μｍ（（Ｉ）層厚み１２．５μｍ，（ＩＩ）層厚み１２．５μｍ）で長さが１００ｍのロール状ポリエステル系フィルム（Ａ）と厚みが１６μｍで長さが１００ｍのロール状ポリエステル系フィルム（Ｂ）を得た。
ついで、実施例１と同様に被覆アルミニウム板を作製し、製缶して３５０ｍｌサイズのシームレス缶を得た。
【００６３】
ポリエステルの融点，キャスト時のネックイン量，保管後のロールフィルムの外観と耐切断性，熱収縮率，製缶性（缶内面フィルムとポンチの離型性と缶外面フィルムのキズ発生程度），耐衝撃性，温水処理後の缶外面の白化程度を表２に示す。この方法は、ネックイン量が小さく経済性に優れ、かつ保管後のポリエステル系フィルムの外観不良及び耐切断性の低下がないためラミネート性が良好であり、かつ製缶性に優れ、かつ金属缶の耐衝撃性に優れていたが、外面の耐温水白化性が劣るため、ポリエステル系フィルム被覆金属板の製造方法として好ましくない。
【００６４】
［比較例 ４］
樹脂膜（Ａ）の（Ｉ）層，（ＩＩ）層の原料としてＰＥＴ−Ｉ／エラストマー＝８５／１５（重量％）のポリエステルとした以外は実施例１と同様にして同様にして厚みが２５μｍ（（Ｉ）層厚み１２．５μｍ，（ＩＩ）層厚み１２．５μｍ）で長さが１００ｍのロール状ポリエステル系フィルム（Ａ）と厚みが１６μｍで長さが１００ｍのロール状ポリエステル系フィルム（Ｂ）を得た。
【００６５】
ついで、実施例１と同様に被覆アルミニウム板を作製し、製缶して３５０ｍｌサイズのシームレス缶を得た。
【００６６】
ポリエステルの融点，キャスト時のネックイン量，製缶性（缶内面樹脂膜とポンチの離型性と缶外面樹脂膜のキズ発生程度）を表２に示す。この方法は、ネックイン量が小さく経済性に優れ、かつ保管後のポリエステル系フィルムの外観不良及び耐切断性の低下がないためラミネート性が良好であったが、被覆アルミニウム板を製缶した際、缶内面フィルムと加工ポンチが粘着し缶開口部の全周にわたって座屈が発生したため製缶性が劣っており、ポリエステル系フィルム被覆金属板の製造方法として好ましくない。
【００６７】
［比較例 ５］
樹脂膜（Ａ）の（Ｉ）層と樹脂膜（Ｂ）の中央部の原料をＣＯ−ＰＥＳとした以外は実施例１と同様にして厚みが２５μｍ（（Ｉ）層厚み１２．５μｍ，（ＩＩ）層厚み１２．５μｍ）で長さが１００ｍのロール状ポリエステル系フィルム（Ａ）と厚みが１６μｍで長さが１００ｍのロール状ポリエステル系フィルム（Ｂ）を得た。
【００６８】
ついで、実施例１と同様に被覆アルミニウム板を作製し、製缶して３５０ｍｌサイズのシームレス缶を得た。
【００６９】
ポリエステルの融点，キャスト時のネックイン量，保管後のロールフィルムの外観と耐切断性，熱収縮率，製缶性（缶内面フィルムとポンチの離型性と缶外面フィルムのキズ発生程度）を表２に示す。この方法は、ネックイン量が小さく経済性に優れ、かつ保管後のポリエステル系フィルムの外観不良はなかったが、耐切断性が低下し、又被覆アルミニウム板を製缶した際、缶内面フィルムと加工ポンチが粘着し缶開口部の全周にわたって座屈が発生し、さらに缶外面フィルムの全周にキズが発生したため製缶性が劣っており、ポリエステル系フィルム被覆金属板の製造方法として好ましくない。
【００７０】
［比較例 ６］
樹脂膜（Ａ）の（ＩＩ）層の原料をＰＥＴ／ＰＢＴ＝４０／６０（重量％）のポリエステル ５０重量％とオレフィンＡ ５０重量％とした以外は実施例１と同様にして厚みが２５μｍ（（Ｉ）層厚み１２．５μｍ，（ＩＩ）層厚み１２．５μｍ）で長さが１００ｍのロール状ポリエステル系フィルム（Ａ）と厚みが１６μｍで長さが１００ｍのロール状ポリエステル系フィルム（Ｂ）を得た。
【００７１】
ついで、実施例１と同様に被覆アルミニウム板を作製し、製缶して３５０ｍｌサイズのシームレス缶を得た。
【００７２】
ポリエステルの融点，キャスト時のネックイン量，保管後のロールフィルムの外観と耐切断性，熱収縮率，製缶性（缶内面フィルムとポンチの離型性と缶外面フィルムのキズ発生程度）を表２に示す。この方法は、ネックイン量が小さく経済性に優れ、かつ保管後のポリエステル系フィルムの外観不良及び耐切断性の低下がないためラミネート性が良好であったが、被覆アルミニウム板を製缶した際、加工ポンチの抜けが悪く缶内面開口部の約１／３に座屈が発生したため製缶性が劣っており、ポリエステル系フィルム被覆金属板の製造方法として好ましくない。
【００７３】
［比較例 ７］
実施例１の原料で厚みが２５μｍ（（Ｉ）層厚み１２．５μｍ，（ＩＩ）層厚み１２．５μｍ）と１６μｍの２種類のポリエステル系未延伸フィルム（１００ｍのロール状フィルム）を得た。
ポリエステルの融点，キャスト時のネックイン量，保管後のロールフィルムの外観と耐切断性，熱収縮率を表２に示す。
実施例１と同様に保管した結果、フィルムの耐切断性が悪く、シワ・タルミ・ブロッキングが発生し、外観が良好な被覆アルミニウム板が得られなかったため、ポリエステル系フィルム被覆金属板の製造方法として好ましくない。
【００７４】
［比較例 ８］
縦延伸後の熱処理温度を１９０℃とした以外は実施例１と同様にして厚みが２５μｍ（（Ｉ）層厚み１２．５μｍ，（ＩＩ）層厚み１２．５μｍ）で長さが１００ｍのロール状ポリエステル系フィルム（Ａ）と厚みが１６μｍで長さが１００ｍのロール状ポリエステル系フィルム（Ｂ）を得た。
【００７５】
ついで、実施例１と同様に被覆アルミニウム板を作製し、製缶して３５０ｍｌサイズのシームレス缶を得た。
【００７６】
ポリエステルの融点，キャスト時のネックイン量，保管後のロールフィルムの外観と耐切断性，熱収縮率，製缶性（缶内面フィルムとポンチの離型性と缶外面フィルムのキズ発生程度）を表２に示す。この方法は、ネックイン量が小さく経済性に優れ、かつ保管後のポリエステル系フィルムの外観不良及び耐切断性の低下はなかったが、被覆アルミニウム板を製缶した際、フィルムが剥離したため、ポリエステル系フィルム被覆金属板の製造方法として好ましくない。
【００７７】
［比較例 ９］
縦延伸後に熱処理を実施しなかった以外は実施例１と同様にして厚みが２５μｍ（（Ｉ）層厚み１２．５μｍ，（ＩＩ）層厚み１２．５μｍ）で長さが１００ｍのロール状ポリエステル系フィルム（Ａ）と厚みが１６μｍで長さが１００ｍのロール状ポリエステル系フィルム（Ｂ）を得た。
ポリエステルの融点，キャスト時のネックイン量，保管後のロールフィルムの外観と耐切断性，熱収縮率を表２に示す。
この方法は、ネックイン量が小さく経済性に優れ、かつ保管後のポリエステル系フィルムの耐切断性の低下はなかったが、フィルムの横方向のシワとフィルムの両端部にタルミが発生し、外観が良好な被覆アルミニウム板が得られなかっため、ポリエステル系フィルム被覆金属板の製造方法として好ましくない。
【００７８】
［比較例 １０］
樹脂膜Ａの（ＩＩ）層原料を（Ｉ）層原料／エラストマー＝８５／１５（重量％）のポリエステル ８７重量％とオレフィンＦ １３重量％とし、樹脂膜（Ａ）及び（Ｂ）の両端部の原料をオレフィンＦとした以外は実施例１と同様にしてキャストしたが、ネックイン量が大きいため、この方法は、ポリエステル系フィルム被覆金属板の製造方法として好ましくない。ポリエステルの融点，キャスト時のネックイン量を表２に示す。
【００７９】
【表１】
【表２】
【発明の効果】
本発明のポリエステル系フィルム被覆金属板の製造方法は原料の無駄を省けるため、経済性に優れた製造方法であるばかりでなく、フレーバー性に優れたポリエステル系フィルム被覆金属板が得られる製造方法である。さらに、製缶性（特に、缶内面樹脂膜と加工ポンチの離型性と缶外面樹脂膜の耐キズつき性）に優れ、かつ内容物を充填後に実施される温水殺菌処理で金属缶外面の外観不良（樹脂膜の白化）が発生しにくく、かつ製缶後に美麗化を目的として実施される外面焼付け塗装を想定した加熱を実施しても耐衝撃性が低下しにくいため、極めて有用なポリエステル系フィルム被覆金属板の製造方法といえる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for manufacturing a metal film coated with a polyester film. More specifically, the present invention relates to a method for producing a polyester film-coated metal sheet which is excellent in can-making properties (eg, drawing / ironing workability) and impact resistance, and is suitable for a metal can to be subjected to hot water sterilization. .
[0002]
[Prior art]
Conventionally, the inner surface and outer surface of metal cans are widely coated with a solution in which various thermosetting resins such as epoxy and phenol are dissolved or dispersed in a solvent to prevent corrosion. Has been done. However, this method of coating with a thermosetting resin has disadvantages in that it often takes a long time to dry the paint, resulting in a decrease in productivity and undesired problems such as environmental pollution due to a large amount of organic solvents.
[0003]
In order to solve such a drawback, a method of coating a metal plate with a thermoplastic resin by a melt extrusion method has been disclosed (for example, see Patent Document 1).
[0004]
Further, a method is disclosed in which a melt-extruded thermoplastic resin is once cooled and solidified, and then pressure-bonded to a heated metal plate (for example, see Patent Document 2). However, in these thermoplastic resin coating methods, when the molten resin is extruded in a layer form from a T-die, the width of the molten resin film greatly decreases (referred to as neck-in), and is several tens of cm with respect to the resin width required for coating. It was necessary to form a film with a wide width, and it was not a method that was satisfactory in terms of economy.
[0005]
In order to solve such a drawback, a method of reducing neck-in by using a polyester obtained by blending a polyester obtained by copolymerizing a trifunctional or higher polybasic acid or polyhydric alcohol component is disclosed (for example, See Patent Documents 3 and 4.) However, in these coating methods, a polyester obtained by copolymerizing a trifunctional or higher polybasic acid or polyhydric alcohol component is liable to be thermally degraded in a melting step from an extruder to a T-die, and even when a heat stabilizer is used in combination. Foreign matter (for example, a gel-like foreign matter or a foreign matter with a degraded substance as a nucleus) is likely to be generated in the obtained molten resin film, and a crack originating from the foreign matter is formed in the resin coating layer at the time of can-making. It was not satisfactory as a coated metal plate.
[0006]
In addition, the coating resin of the resin-coated metal plate used for drawing and ironing cans is required not only to have excellent formability that can follow can making (drawing and ironing), but also to beautify after can making. It is required that the impact resistance does not decrease even in the heating of the outer surface baking coating carried out as follows. However, the impact resistance of the resin-coated metal sheet is often lowered, and the impact resistance is not satisfied.
[0007]
[Patent Document 1]
JP-A-57-203545 [Patent Document 2]
JP-A-10-309775 [Patent Document 3]
JP-A-10-86308 [Patent Document 4]
JP 2000-71388 A
[Problems to be solved by the invention]
SUMMARY OF THE INVENTION An object of the present invention is to solve the problems of the conventional technology. That is, since the neck-in at the time of melt extrusion is small and foreign matters are hardly generated in the obtained molten resin film, it is excellent in economy and can making property, and external baking coating performed for the purpose of beautification after can making It is intended to provide a method for producing a polyester-film-coated metal sheet suitable for a metal can to be subjected to a hot water sterilization treatment, in which impact resistance is hardly reduced even by heating.
[0009]
[Means for Solving the Problems]
An object of the present invention is to coat a film (A) mainly composed of a crystalline polyester having a melting point of 180 ° C. or more on one surface of a metal plate and a film (B) composed of a crystalline polyester having a melting point of 180 ° C. or more on the other surface. In the manufacturing method of coating, the resin films (A) and (B) obtained by cooling and solidifying a molten resin film extruded in a layered state in a state where olefin polymers are merged at both ends using a T die are vertically oriented. The polyester film (A) and (B) are uniaxially stretched, then heat-set, and then cut and removed at both ends to obtain the polyester films (A) and (B). A method for producing a polyester-based film-coated metal plate comprising a method of laminating on a metal plate, wherein the polyester-based film (A) has a composite structure of (I) layer / (II) layer; Is a polyester and olefin in which the polyethylene terephthalate and the polybutylene phthalate are composed of 60:40 to 30:70 (% by weight), and the (II) layer is composed of the crystalline polyester and the polyester elastomer in a proportion of 95: 5 to 70:30 (% by weight). And the polyester-based film (B) is a polyester-based film (B) having a polyethylene terephthalate and polybutylene terephthalate ratio of 60:40 to 30:70 (% by weight). Wherein the polyester-based films (A) and (B) have a heat shrinkage in the longitudinal direction at 150 ° C. of 4 to 30% by a method for producing a metal sheet coated with a polyester-based film. Achieved.
[0010]
In this case, it is preferable that the hard segment of the polyester elastomer is a polyester having a terephthalic acid residue and an ethylene glycol residue and / or a butanediol residue as main components, and the soft segment is a polytetramethylene oxide. .
[0011]
In this case, it is preferable that the olefin-based polymer of both ends of the resin film (A) and the (II) layer and the olefin-based polymer of both ends of the resin film (B) are the same.
[0012]
Furthermore, in this case, it is preferable that the olefin-based polymer is polyethylene and / or an ethylene-based copolymer.
[0013]
Further, in this case, it is preferable that the polyester (I) layer of the resin film (A) and the polyester of the resin film (B) have the same ratio of polyethylene terephthalate and polybutylene terephthalate.
[0014]
BEST MODE FOR CARRYING OUT THE INVENTION
In the (I) layer of the resin film (A) and the resin film (B) according to the present invention, a dicarboxylic acid component other than terephthalic acid and a glycol other than ethylene glycol and butanediol are used as long as the properties of polyethylene terephthalate and polybutylene terephthalate are not impaired. Ingredients can be used. For example, as dicarboxylic acids, aromatic dicarboxylic acids such as isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, diphenylsulfonedicarboxylic acid, 5-sodium sulfoisophthalic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, decanedicarboxylic acid, Aliphatic dicarboxylic acids such as maleic acid, fumaric acid and dimer acid, oxycarboxylic acids such as p-oxybenzoic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid can be used. As glycol components other than ethylene glycol and butanediol, aliphatic glycols such as propanediol, pentanediol, hexanediol and neopentyl glycol, alicyclic glycols such as cyclohexanedimethanol, and aromatics such as bisphenol A and bisphenol S Glycol can be used.
The crystalline polyester constituting the layer (II) of the resin film (A) in the present invention is a polymer comprising a dicarboxylic acid component and a glycol component. As the dicarboxylic acid, terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, Aromatic dicarboxylic acids such as diphenyl sulfone dicarboxylic acid and 5-sodium sulfoisophthalic acid; aliphatic dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, sebacic acid, decane dicarboxylic acid, maleic acid, fumaric acid, and dimer acid; -Oxycarboxylic acids such as oxybenzoic acid and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid can be used.
Examples of the glycol component include aliphatic glycols such as ethylene glycol, propanediol, butanediol, pentanediol, hexanediol and neopentyl glycol, alicyclic glycols such as cyclohexanedimethanol, and aromatics such as bisphenol A and bisphenol S. Glycol can be used.
[0015]
In the present invention, the ratio between the crystalline polyester and the polyester elastomer in the layer (II) of the resin film (A) needs to be 95: 5 to 70:30 (% by weight). If the content of the polyester elastomer is less than 5% by weight, the impact resistance is low, which is not preferable. On the other hand, if it exceeds 30% by weight, the discharge from the T-die becomes unstable, which is not preferable. Polyester elastomers are polyesters whose hard segments are mainly composed of terephthalic acid residues and ethylene glycol residues or butanediol residues, and aromatic dicarboxylic acids such as isophthalic acid and orthophthalic acid, adipic acid, sebacic acid and decanedicarboxylic acid. And other aliphatic dicarboxylic acids. Further, the soft segment preferably contains 5 to 50 mol% of polytetramethylene oxide having a weight average molecular weight of 400 to 5000.
[0016]
The polyester of the present invention may contain, if necessary, an antioxidant, a heat stabilizer, an ultraviolet absorber, a plasticizer, a pigment, an antistatic agent, a lubricant, a nucleating agent, a lubricant comprising inorganic or organic particles, and the like. May be.
[0017]
The method for producing the polyester in the present invention is not particularly limited. That is, those produced by either the transesterification method or the direct polymerization method can be used. Further, those produced by a solid-phase polymerization method for increasing the molecular weight may be used. In addition, use a polyester with a low oligomer content produced by a vacuum solid-phase polymerization method in order to reduce the amount of oligomers from the polyester resin in the past lamination process, retort process, etc. performed after filling the contents in the can. Is preferred. However, it is preferable that the polyester (I) of the resin film (A) and the polyester of the resin film (B) have the same ratio of polyethylene terephthalate and polybutylene terephthalate. The reason for this is that the resin films (A) and (B) obtained by subjecting the resin (A) and (B) extruded in layers to cooling unidirectional stretching and heat fixing after cooling and solidifying from the viewpoint of reducing waste of the resin. This is because the quality of the polyester film (A) coated on the metal plate becomes stable when the resin obtained by cutting and removing both ends is reused in the (II) layer of the resin film (A).
[0018]
The method for producing the polyester elastomer in the present invention is not particularly limited. That is, those produced by either the transesterification method or the direct polymerization method can be used.
The melting point of the polyester and the polyester elastomer used in the present invention is 180 ° C. or higher. In canning properties (during drawing and ironing, the resin on the inner surface of the can secures the releasability of the punch. It is necessary because of galling suppression [vertical scratches on the resin film]).
[0019]
In the present invention, the olefin polymer used at both ends of the resin film (A), the (II) layer and both ends of the resin film (B) is preferably polyethylene and / or an ethylene copolymer. Low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, ultra high molecular weight polyethylene, ethylene-propylene copolymer, ethylene butene copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer , Ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-ethyl acrylate-maleic anhydride copolymer, ionomer, ethylene-anhydride A maleic acid graft copolymer, an ethylene-vinyl alcohol copolymer, or the like can be used. It is preferable that the olefin-based polymer used in both ends of the resin film (A) and the (II) layer and the olefin-based polymer used in both ends of the resin film (B) are the same. The reason for this is that the resin films (A) and (B) obtained by subjecting the resin (A) and (B) extruded in layers to cooling unidirectional stretching and heat fixing after cooling and solidifying from the viewpoint of reducing waste of the resin. This is because the quality of the polyester film (A) coated on the metal plate becomes stable when the resin obtained by cutting and removing both ends is reused in the (II) layer of the resin film (A).
[0020]
In the present invention, the ratio of the polyester to the olefin polymer in the polyester film needs to be 70:30 to 100: 0 (% by weight). If the olefin-based polymer exceeds 30% by weight, the can-making properties (punch release properties) are poor, which is not preferable.
[0021]
In the present invention, when the polyester and the olefin-based polymer are extruded in a layer form from a T-die, it is preferable to use the olefin-based polymer at both ends (a portion of one side of which is 5 cm or less).
In the present invention, a polymer obtained by dry blending or melt-mixing a polyester and an olefin-based polymer is melted in a known single-screw or twin-screw extruder, and then layered using a known multi-manifold die such as an edge lamination type. Is obtained.
[0022]
In the present invention, as the cooling and solidifying method, a known method of contacting the molten resin in a layer form from a T-die with a rotated cooling roll can be used. When the molten resin is brought into contact with the cooling roll, it is preferable to employ a method of forcibly blowing air or a method of bringing the resin into close contact with static electricity. In both the forced air spraying method and the electrostatic adhesion method, a method in which both ends and the central portion of the layered resin are performed independently is more preferable. Further, when the molten resin comes into contact with the cooling roll, it is more preferable to use a measure (for example, a device such as a vacuum chamber or a vacuum box) for reducing the entrained flow by reducing the pressure on the opposite side.
[0023]
In the present invention, the resin films (A) and (B) obtained by cutting and removing both ends as necessary after cooling and solidifying are cooled to 1.3 ° C. at a temperature equal to or higher than the glass transition point of the polyester and lower than the cold crystallization temperature. A longitudinal stretching of up to 6.0 times is performed, and then a heat treatment is performed under tension at a temperature of 50 ° C. or more and a melting point of the polyester of −20 ° C. for 1 to 20 seconds, and then both ends of the resin film are cut off to obtain a polyester film. (A) and (B) are obtained.
[0024]
The polyester films (A) and (B) used in the present invention must have a heat shrinkage in the longitudinal direction at 150 ° C. of 4 to 30%. If the heat shrinkage is less than 4%, the adhesion after lamination is undesirably reduced. Conversely, when the heat shrinkage exceeds 30%, wrinkles and blocking occur due to longitudinal shrinkage during storage until lamination, and wrinkles and bubbles are easily generated on the polyester film-coated metal plate, which is not preferable. .
[0025]
In the present invention, it is possible to reuse the raw material obtained by shredding both ends of the cut and removed resin film and then compacting or heating and melting the resin film in the (II) layer of the resin film (A). is there. The reuse rate is not particularly limited, but is preferably 5 to 90% by weight.
[0026]
In the present invention, as the metal plate, a surface-treated steel plate such as tin-free steel, an aluminum plate or an aluminum alloy plate, or an aluminum plate or an aluminum alloy plate subjected to a surface treatment can be used. After heating these metal plates to a melting point of polyester of −20 ° C. or more and a melting point of + 150 ° C., the polyester films (A) and (B) are laminated on the metal plates using a laminating roll. Is heated at the melting point of the polyester + 10 ° C. or higher and the melting point + 60 ° C., and then cooled with water and / or air to obtain a polyester film-coated metal plate. However, when laminating the polyester-based film (A) on a metal plate, it is preferable to contact the (II) layer side with the metal plate in order to ensure can-making properties.
[0027]
【Example】
Hereinafter, the present invention will be described based on examples.
[Evaluation method]
(1) Melting point of polyester The polyester composition was heated and melted at 300 ° C. for 5 minutes, and then quenched with liquid nitrogen to obtain 10 mg of a sample, which was heated to 10 ° C. in a nitrogen stream using a differential scanning calorimeter (DSC). The peak temperature of the endothermic peak accompanying melting when the exothermic / endothermic curve (DSC curve) was measured at a heating rate of / min was defined as the melting point Tm (° C.).
[0028]
(2) Neck-in Amount The average value (Acm) of the discharge port width of the T-die (60 cm) and the resin film width after cooling and solidification (resin film width before cutting off both ends) measured at n = 3 is used. The neck-in amount (cm) was determined by the following equation. A neck-in amount of 5 cm or less was evaluated as practical.
Neck-in amount (cm) = 60-A
[0029]
(3) Appearance of roll film after storage and cut resistance After storing the roll-shaped film at 40 ° C. and a relative humidity of 80% for one month, the appearance of the film and a tensile test according to JIS K 7127 (longitudinal direction) n = 30, No. 1 test piece of 15 mm width, test speed: 200 mm / min). The evaluation criteria were set as follows, and ○ was evaluated as practical.
[appearance]
○: No wrinkle, blocking, and thinning ×: With wrinkle, blocking, and thinning [cutting resistance]
Evaluated by the number of samples having a breaking elongation of <5%. (2/30 or less were evaluated as practical.)
[0030]
(4) Heat shrinkage rate Evaluated according to JIS Z 1715.
[0031]
(5) Method for producing a polyester-based film-coated metal plate On one side of an aluminum alloy plate (thickness: 0.26 mm, 3004-based alloy plate) heated to 250 ° C., a (II) layer of the polyester-based film (A) is formed as a metal plate. A polyester film (B) was simultaneously laminated on the other surface so as to make contact, and then heated at 275 ° C. and then rapidly cooled in water to produce a coated aluminum plate.
[0032]
(6) Releasability of the resin on the inner surface of the can and the processed punch The can was made at n = 10 so that the polyester film (A) of the coated aluminum plate was on the inner surface of the can, and the degree of buckling occurring at the upper part of the molded can was visually observed. Observed. The evaluation criteria were set as follows, and ○ was evaluated as practical.
○: No buckling occurred at the can opening △: Buckling occurred at about 1/3 of the circumference of the can opening ×: Buckling occurred at 1/3 or more of the circumference of the can opening
(7) Galling resistance of the outer surface of the can (vertical scratches on the polyester film on the outer surface of the can)
The can was made at n = 10 so that the polyester film (A) of the coated aluminum plate was on the inner surface side of the can, and the degree of scratching of the outer polyester film (B) of the molded can body wall was visually observed. The evaluation criteria were set as follows, and ○ was evaluated as practical.
：: no scratches Δ: scratches on about 1/3 of the outer surface ×: severe scratches on 1/3 or more of the outer surface
(8) Impact Resistance A can of 7 cm square was cut out from the center of the body wall of a can obtained by heating an aluminum plate at 280 ° C. for 40 seconds and then rapidly cooling in water. A weight (600 g) having a tip diameter of 10 mm is dropped from a height of 10 cm on a surface corresponding to the outer surface of the can of this sample to give an impact. Then, the sample was placed on a glass container filled with 7% diluted hydrochloric acid (placed in a state where the convex portion of the sample was immersed), and after 3 days, the corrosion state of the convex portion was visually observed. The evaluation criteria were set as follows, and ○ was evaluated as practical.
：: no corrosion of the convex portion occurred x: corrosion of the convex portion occurred
(9) A sample obtained by heating a can at a temperature of 270 ° C. for 40 seconds and then quenching in water is used as a sample. After this sample was immersed in warm water at 80 ° C. for 10 minutes, the outer surface of the can obtained by rapid cooling in water was visually observed. The evaluation criteria were set as follows, and ○ was evaluated as practical.
：: Whitening is not conspicuous. 明 ら か に: Whitening is apparent, but the color of the aluminum alloy plate is visible. X: Color of the aluminum alloy plate is not visible due to whitening.
[Abbreviations and contents of polyester and olefin-based polymers used in Examples and Comparative Examples]
(1) PET: polyethylene terephthalate (2) PBT: polybutylene terephthalate (3) PET-I: polyethylene terephthalate / isophthalate (10 mol% of repeating units of ethyl isophthalate)
(4) Elastomer: copolymer of polybutylene terephthalate and polybutylene oxide (15 mol% of repeating units of butylene oxide having a weight average molecular weight of 1,000)
(5) CO-PES: Copolyester of terephthalic acid and ethylene glycol / cyclohexanedimethanol (mol% 70/30) (6) Olefin A: Low density polyethylene (Sumikasen G401, trade name, manufactured by Sumitomo Chemical Co., Ltd.)
(7) Olefin B: ethylene butene copolymer (manufactured by Mitsui Chemicals, Tuffmer A4085: trade name)
(8) Olefin C: Ionomer (manufactured by Mitsui DuPont Polychemicals Co., Ltd., High Milan 1706: trade name)
(9) Olefin D: ethylene-methyl acrylate copolymer (EMAC SP2205: trade name, manufactured by Eastman Chemical Company)
(10) Olefin F: polypropylene (Noblen FS2011DG2: trade name, manufactured by Sumitomo Chemical Co., Ltd.)
[0037]
[Example 1]
Polyester of PET / PBT = 40/60 (% by weight) as the (I) layer raw material of the resin film (A), and polyester of (I) layer / elastomer = 85/15 (% by weight) as the (II) layer raw material. Melt at 280 ° C, melt olefin A alone as a raw material at both ends of the resin film (A) at 250 ° C, and use an edge lamination type T-die (ejection opening width at both ends / ejection opening width at center / ends at both ends) (2 cm / 56 cm / 2 cm, heated to 260 ° C.) and cast into a layered cooling roll (peripheral speed: 20 m / min) (distance from the T-die to the contact point of the molten resin on the cooling roll with 15 cm) The central portion and both end portions were forcibly blown with air by separate devices) to obtain a resin film (A).
The resin film (A) was longitudinally stretched 3.0 times at a preheating temperature of 65 ° C. and a stretching temperature of 100 ° C., and was heat-treated at 150 ° C. for 3 seconds using a clip gripping setter, and then cut off at both ends (5 cm on one side). Then, a roll-shaped polyester film (A) having a thickness of 100 m and a thickness of 25 μm ((I) layer thickness 12.5 μm, (II) layer thickness 12.5 μm) was obtained.
[0038]
Further, a polyester of PET / PBT = 40/60 (% by weight) is melted at 270 ° C. as a raw material at the center of the resin film (B), and olefin A alone is heated at 250 ° C. as a raw material at both ends of the resin film (B). And cooled in layers using an edge lamination type T die (discharge port width at both ends / discharge port width at center / discharge port width at both ends = 2 cm / 56 cm / 2 cm, heated to 260 ° C.) Cast into a roll (peripheral speed: 20 m / min) (distance from the T-die to the contact point of the molten resin with the cooling roll: 15 cm, forced air is blown at the center and both ends by separate devices) and the resin film (B) was obtained.
The resin film (B) was longitudinally stretched 3.0 times at a preheating temperature of 65 ° C. and a stretching temperature of 100 ° C., and was heat-treated at 150 ° C. for 3 seconds using a clip gripping setter. To give a roll-shaped polyester film (B) having a thickness of 16 μm and a length of 100 m.
[0039]
The roll-shaped polyester films (A) and (B) were stored at 40 ° C. for one month under the condition of a relative humidity of 80%, and then the both sides of a 3004 series aluminum alloy plate (0.26 mm thick) heated to 250 ° C. After the film was pressed and heated to 275 ° C., it was rapidly cooled in water to obtain a coated aluminum plate.
[0040]
After applying a forming lubricant to the coated aluminum plate thus obtained, it was heated and drawn at a plate temperature of 70 ° C. so that the polyester film (A) was on the inner surface side. Next, the temperature of the obtained cup was set to 40 ° C., and ironing was performed at a mold temperature of 80 ° C. to obtain a 350 ml-sized seamless can.
[0041]
Melting point of polyester, neck-in amount during casting, appearance and cut resistance of roll film after storage, heat shrinkage, can-making properties (releasability of inner can film and punch and degree of scratch on can outer film), Table 1 shows the impact resistance and the degree of whitening of the outer surface of the can after hot water treatment. The method of this example has a small neck-in amount, is excellent in economic efficiency, and has good laminating properties because there is no deterioration in appearance and cut resistance of the polyester film after storage, and is excellent in can-making properties. It can be said that this is a method for producing a polyester film-coated metal plate that can provide a metal can having excellent impact resistance and hot water whitening resistance on the outer surface.
[0042]
[Example 2]
Except that the raw material of the (II) layer of the resin film A was made of polyester of PET-I / elastomer = 85/15 (% by weight), the thickness was 25 μm ((I) layer thickness 12.5 μm, II) A roll-shaped polyester film (A) having a layer thickness of 12.5 μm) and a length of 100 m and a roll-shaped polyester film (B) having a thickness of 16 μm and a length of 100 m were obtained.
[0043]
Next, a coated aluminum plate was prepared and made in the same manner as in Example 1, to obtain a 350 ml-sized seamless can.
[0044]
Melting point of polyester, neck-in amount during casting, appearance and cut resistance of roll film after storage, heat shrinkage, can-making properties (releasability of inner can film and punch and degree of scratch on can outer film), Table 1 shows the impact resistance and the degree of whitening of the outer surface of the can after hot water treatment. The method of this example has a small neck-in amount, is excellent in economic efficiency, and has good laminating properties because there is no deterioration in appearance and cut resistance of the polyester film after storage, and is excellent in can-making properties. It can be said that this is a method for producing a polyester film-coated metal plate that can provide a metal can having excellent impact resistance and hot water whitening resistance on the outer surface.
[0045]
[Example 3]
The thickness of the resin film A was 25 μm in the same manner as in Example 1 except that the raw material of the (II) layer of the resin film A was changed to 87% by weight of polyester (85/15 (% by weight) / elastomer) and 13% by weight of olefin A. ((I) layer thickness 12.5 μm, (II) layer thickness 12.5 μm) and a roll-shaped polyester film (A) having a length of 100 m (A) and a 16 μm-thick roll-shaped polyester film (B) having a length of 100 m (B) ) Got.
[0046]
Next, a coated aluminum plate was prepared and made in the same manner as in Example 1, to obtain a 350 ml-sized seamless can.
[0047]
Melting point of polyester, neck-in amount during casting, appearance and cut resistance of roll film after storage, heat shrinkage, can-making properties (releasability of inner can film and punch and degree of scratch on can outer film), Table 1 shows the impact resistance and the degree of whitening of the outer surface of the can after hot water treatment. The method of this example has a small neck-in amount, is excellent in economic efficiency, and has good laminating properties because there is no deterioration in appearance and cut resistance of the polyester film after storage, and is excellent in can-making properties. It can be said that this is a method for producing a polyester film-coated metal plate that can provide a metal can having excellent impact resistance and hot water whitening resistance on the outer surface.
[0048]
[Example 4]
The raw material of the (II) layer of the resin film A is (raw material of the (I) layer / elastomer = 87/15 (weight%) of polyester (87% by weight) and olefin B (13% by weight), and both ends of the resin films (A) and (B). A roll-shaped polyester film having a thickness of 25 μm ((I) layer thickness of 12.5 μm, (II) layer thickness of 12.5 μm) and a length of 100 m was prepared in the same manner as in Example 1 except that olefin B was used as the raw material for (1). A) and a roll-shaped polyester film (B) having a thickness of 16 μm and a length of 100 m were obtained.
[0049]
Next, a coated aluminum plate was prepared and made in the same manner as in Example 1, to obtain a 350 ml-sized seamless can.
[0050]
Melting point of polyester, neck-in amount during casting, appearance and cut resistance of roll film after storage, heat shrinkage, can-making properties (releasability of inner can film and punch and degree of scratch on can outer film), Table 1 shows the impact resistance and the degree of whitening of the outer surface of the can after hot water treatment. The method of this example has a small neck-in amount, is excellent in economic efficiency, and has good laminating properties because there is no deterioration in appearance and cut resistance of the polyester film after storage, and is excellent in can-making properties. It can be said that this is a method for producing a polyester film-coated metal plate that can provide a metal can having excellent impact resistance and hot water whitening resistance on the outer surface.
[0051]
[Example 5]
The raw material of the (II) layer of the resin film A is composed of 87% by weight of polyester (85% by weight / elastomer) and 13% by weight of olefin C, and the both ends of the resin films (A) and (B). A roll-shaped polyester film having a thickness of 25 μm ((I) layer thickness of 12.5 μm, (II) layer thickness of 12.5 μm) and a length of 100 m was prepared in the same manner as in Example 1 except that olefin C was used as the raw material for (1). A) and a roll-shaped polyester film (B) having a thickness of 16 μm and a length of 100 m were obtained.
[0052]
Next, a coated aluminum plate was prepared and made in the same manner as in Example 1, to obtain a 350 ml-sized seamless can.
[0053]
Melting point of polyester, neck-in amount during casting, appearance and cut resistance of roll film after storage, heat shrinkage, can-making properties (releasability of inner can film and punch and degree of scratch on can outer film), Table 1 shows the impact resistance and the degree of whitening of the outer surface of the can after hot water treatment. The method of this example has a small neck-in amount, is excellent in economic efficiency, and has good laminating properties because there is no deterioration in appearance and cut resistance of the polyester film after storage, and is excellent in can-making properties. It can be said that this is a method for producing a polyester film-coated metal plate that can provide a metal can having excellent impact resistance and hot water whitening resistance on the outer surface.
[0054]
[Example 6]
13% by weight of (II) layer raw material / elastomer = 85/15 (weight%) polyester 87% by weight and olefin A / olefin D = 70/30 (weight%) olefin 13% by weight And a thickness of 25 μm ((I) layer thickness) in the same manner as in Example 1 except that the raw materials at both ends of the resin films (A) and (B) were changed to olefin A / olefin D = 70/30 (% by weight). (12.5 μm, (II) layer thickness 12.5 μm) and a roll-shaped polyester film (A) having a length of 100 m and a roll-shaped polyester film (B) having a thickness of 16 μm and a length of 100 m were obtained.
[0055]
Next, a coated aluminum plate was prepared and made in the same manner as in Example 1, to obtain a 350 ml-sized seamless can.
[0056]
Melting point of polyester, neck-in amount during casting, appearance and cut resistance of roll film after storage, heat shrinkage, can-making properties (releasability of inner can film and punch and degree of scratch on can outer film), Table 1 shows the impact resistance and the degree of whitening of the outer surface of the can after hot water treatment. The method of this example has a small neck-in amount, is excellent in economic efficiency, and has good laminating properties because there is no deterioration in appearance and cut resistance of the polyester film after storage, and is excellent in can-making properties. It can be said that this is a method for producing a polyester film-coated metal plate that can provide a metal can having excellent impact resistance and hot water whitening resistance on the outer surface.
[0057]
[Example 7]
The raw material of the (II) layer of the resin film A was cut into 85% by weight of the polyester of the (I) raw material / elastomer = 85/15 (% by weight) and 85% by weight of the polyester film in Example 1 before obtaining the polyester films (A) and (B) Except that the polymer obtained by granulating the removed both ends (the ratio of olefin A was 85% by weight) was changed to 15% by weight, the thickness was 25 μm ((I) layer thickness 12.5 μm, (II) A roll-shaped polyester film (A) having a layer thickness of 12.5 μm) and a length of 100 m and a roll-shaped polyester film (B) having a thickness of 16 μm and a length of 100 m were obtained.
[0058]
Next, a coated aluminum plate was prepared and made in the same manner as in Example 1, to obtain a 350 ml-sized seamless can.
[0059]
Melting point of polyester, neck-in amount during casting, appearance and cut resistance of roll film after storage, heat shrinkage, can-making properties (releasability of inner can film and punch and degree of scratch on can outer film), Table 1 shows the impact resistance and the degree of whitening of the outer surface of the can after hot water treatment. The method of this example has a small neck-in amount, is excellent in economic efficiency, and has good laminating properties because there is no deterioration in appearance and cut resistance of the polyester film after storage, and is excellent in can-making properties. It can be said that this is a method for producing a polyester film-coated metal plate that can provide a metal can having excellent impact resistance and hot water whitening resistance on the outer surface.
[0060]
[Comparative Example 1]
An attempt was made to obtain a roll-shaped resin film in the same manner as in Example 1 except that the raw materials at both ends of the resin film (A) and the resin film (B) were made of PET / PBT = 40/60 (wt%) polyester. However, unless the neck-in amount is large and both ends are cut and removed by 18 cm, a central portion having a uniform thickness distribution cannot be obtained, so this method is not preferable as a method for producing a polyester film-coated metal sheet. Table 2 shows the melting point of polyester and the amount of neck-in during casting.
[0061]
[Comparative Example 2]
The raw material of the layer (I) of the resin film (A) is polyester of PET / PBT = 20/80 (% by weight), and the raw material of the central part of the resin film (B) is PET / PBT = 20/80 (% by weight). An attempt was made to form a film in the same manner as in Example 1 except that the polyester was used. However, the resin film often cracked between the cooling roll and the longitudinally extending preheating roll, and more often the resin film was broken during longitudinal stretching. This method is not preferable as a method for producing a polyester film, since roll-type polyester films (A) and (B) cannot be obtained. Table 2 shows the melting point of polyester and the amount of neck-in during casting.
[0062]
[Comparative Example 3]
The raw material of the (I) layer of the resin film (A) is polyester of PET / PBT = 70/30 (% by weight), and the raw material of the central part of the resin film (B) is PET / PBT = 70/30 (% by weight). A roll-shaped polyester film (A) having a thickness of 25 μm ((I) layer thickness 12.5 μm, (II) layer thickness 12.5 μm) and a length of 100 m was prepared in the same manner as in Example 1 except that the polyester was used. A roll-shaped polyester film (B) having a thickness of 16 μm and a length of 100 m was obtained.
Next, a coated aluminum plate was prepared and made in the same manner as in Example 1, to obtain a 350 ml-sized seamless can.
[0063]
Melting point of polyester, neck-in amount during casting, appearance and cut resistance of roll film after storage, heat shrinkage, can-making properties (releasability of inner can film and punch and degree of scratch on can outer film), Table 2 shows the impact resistance and the degree of whitening of the outer surface of the can after the hot water treatment. This method has a small neck-in amount, is excellent in economical efficiency, has good laminating properties because there is no deterioration in appearance and cut resistance of the polyester film after storage, has excellent can-making properties, and has a metal can. Was excellent in impact resistance, but was inferior in hot water whitening resistance on the outer surface, which was not preferable as a method for producing a polyester film-coated metal sheet.
[0064]
[Comparative Example 4]
The thickness of the resin film (A) was 25 μm in the same manner as in Example 1, except that the polyester of PET-I / elastomer = 85/15 (% by weight) was used as a raw material of the layers (I) and (II). ((I) layer thickness 12.5 μm, (II) layer thickness 12.5 μm) and a roll-shaped polyester film (A) having a length of 100 m (A) and a 16 μm-thick roll-shaped polyester film (B) having a length of 100 m (B) ) Got.
[0065]
Next, a coated aluminum plate was prepared and made in the same manner as in Example 1, to obtain a 350 ml-sized seamless can.
[0066]
Table 2 shows the melting point of the polyester, the neck-in amount at the time of casting, and the can-making properties (the releasability between the resin film on the inner surface of the can and the punch and the degree of scratching on the resin film on the outer surface of the can). This method has a small neck-in amount, is excellent in economical efficiency, and has good laminating properties because there is no poor appearance of the polyester film after storage and no decrease in cut resistance, but when a coated aluminum plate is made, Since the inner surface of the can and the processed punch adhere to each other and buckling occurs over the entire periphery of the opening of the can, the can-making property is inferior, which is not preferable as a method for producing a polyester film-coated metal sheet.
[0067]
[Comparative Example 5]
The thickness was 25 μm ((I) layer thickness 12.5 μm, (I) layer thickness) in the same manner as in Example 1 except that CO-PES was used as the raw material of the (I) layer of the resin film (A) and the central portion of the resin film (B). II) A roll-shaped polyester film (A) having a layer thickness of 12.5 μm) and a length of 100 m and a roll-shaped polyester film (B) having a thickness of 16 μm and a length of 100 m were obtained.
[0068]
Next, a coated aluminum plate was prepared and made in the same manner as in Example 1, to obtain a 350 ml-sized seamless can.
[0069]
Melting point of polyester, amount of neck-in during casting, appearance and cut resistance of roll film after storage, heat shrinkage, can-making properties (releasability of can inner film and punch and degree of scratch on outer film of can) It is shown in Table 2. This method has a small neck-in amount, is excellent in economic efficiency, and there is no appearance defect of the polyester film after storage, but the cut resistance is lowered, and when the coated aluminum plate is made into a can, the can inner film and The processing punch adheres and buckling occurs over the entire circumference of the can opening, and furthermore, the entire circumference of the can outer surface film is scratched, resulting in poor can-making properties, which is not preferable as a method for producing a polyester film-coated metal plate. .
[0070]
[Comparative Example 6]
The thickness was 25 μm (in the same manner as in Example 1 except that the raw material of the layer (II) of the resin film (A) was changed to 50% by weight of a polyester of PET / PBT = 40/60 (% by weight) and 50% by weight of an olefin A. (I) 12.5 μm layer thickness, (II) 12.5 μm layer thickness) and 100 m long roll-shaped polyester film (A) and 16 μm thick 100 m long roll-shaped polyester film (B) Got.
[0071]
Next, a coated aluminum plate was prepared and made in the same manner as in Example 1, to obtain a 350 ml-sized seamless can.
[0072]
Melting point of polyester, amount of neck-in during casting, appearance and cut resistance of roll film after storage, heat shrinkage, can-making properties (releasability of can inner film and punch and degree of scratch on outer film of can) It is shown in Table 2. This method has a small neck-in amount, is excellent in economical efficiency, and has good laminating properties because there is no poor appearance of the polyester film after storage and no decrease in cut resistance, but when a coated aluminum plate is made, In addition, the punch was not easily removed, and buckling occurred in about one third of the opening on the inner surface of the can, resulting in poor can-making properties, which is not preferable as a method for producing a polyester film-coated metal sheet.
[0073]
[Comparative Example 7]
Two kinds of polyester-based unstretched films (100 m roll-shaped film) having a thickness of 25 μm ((I) layer thickness 12.5 μm, (II) layer thickness 12.5 μm) and 16 μm were obtained from the raw materials of Example 1.
Table 2 shows the melting point of the polyester, the neck-in amount at the time of casting, the appearance, cut resistance, and heat shrinkage of the roll film after storage.
As a result of storage in the same manner as in Example 1, the cut resistance of the film was poor, wrinkles and blocking occurred, and a coated aluminum plate having a good appearance could not be obtained. Not preferred.
[0074]
[Comparative Example 8]
Except for setting the heat treatment temperature after the longitudinal stretching at 190 ° C., the same as in Example 1 was carried out in a roll shape having a thickness of 25 μm ((I) layer thickness 12.5 μm, (II) layer thickness 12.5 μm) and length 100 m. A polyester film (A) and a roll-shaped polyester film (B) having a thickness of 16 μm and a length of 100 m were obtained.
[0075]
Next, a coated aluminum plate was prepared and made in the same manner as in Example 1, to obtain a 350 ml-sized seamless can.
[0076]
Melting point of polyester, amount of neck-in during casting, appearance and cut resistance of roll film after storage, heat shrinkage, can-making properties (releasability of can inner film and punch and degree of scratch on outer film of can) It is shown in Table 2. This method has a small amount of neck-in and is excellent in economical efficiency, and there was no poor appearance of the polyester film after storage and no decrease in cut resistance.However, when the coated aluminum plate was canned, the film was peeled off. It is not preferable as a method for producing a system-film-coated metal plate.
[0077]
[Comparative Example 9]
Roll-like polyester having a thickness of 25 μm ((I) layer thickness 12.5 μm, (II) layer thickness 12.5 μm) and a length of 100 m in the same manner as in Example 1 except that the heat treatment was not performed after the longitudinal stretching. A film (A) and a roll-shaped polyester film (B) having a thickness of 16 μm and a length of 100 m were obtained.
Table 2 shows the melting point of the polyester, the neck-in amount at the time of casting, the appearance, cut resistance, and heat shrinkage of the roll film after storage.
This method has a small amount of neck-in and is economical, and there is no decrease in the cut resistance of the polyester film after storage. Is not preferable as a method for producing a polyester film-coated metal plate, since a coated aluminum plate having a good quality cannot be obtained.
[0078]
[Comparative Example 10]
The raw material of the (II) layer of the resin film A is (raw material of the (I) layer / elastomer = 87/15 (weight%) of polyester (87% by weight) and olefin F (13% by weight), and both ends of the resin films (A) and (B). Casting was carried out in the same manner as in Example 1 except that olefin F was used as the raw material for the above, but this method is not preferable as a method for producing a polyester film-coated metal plate because of a large neck-in amount. Table 2 shows the melting point of polyester and the amount of neck-in during casting.
[0079]
[Table 1]
[Table 2]
【The invention's effect】
The method for producing a polyester-based film-coated metal sheet of the present invention is not only an economical production method for eliminating waste of raw materials, but also a production method capable of obtaining a polyester-based film-coated metal sheet having excellent flavor properties. is there. Furthermore, it has excellent can-making properties (especially, the releasability of the resin film on the inner surface of the can and the processing punch and the scratch resistance of the resin film on the outer surface of the can). An extremely useful polyester because it is unlikely to have poor appearance (whitening of the resin film) and it is unlikely that the impact resistance will decrease even if heating is performed assuming baking on the exterior surface for the purpose of beautification after can-making. It can be said to be a method for producing a system film-coated metal plate.
Claims (5)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006199916A (en) * | 2004-12-22 | 2006-08-03 | Toyobo Co Ltd | Polyester film for laminating metal plate, laminated metal plate and metal container |
| JP2006199917A (en) * | 2004-12-22 | 2006-08-03 | Toyobo Co Ltd | Polyester film for laminating metal plate, laminated metal plate and metal container |
| JP2006328187A (en) * | 2005-05-25 | 2006-12-07 | Toyobo Co Ltd | Method for producing polyester film for laminating metal plate |
| CN108886115A (en) * | 2016-04-06 | 2018-11-23 | 大日本印刷株式会社 | Battery use packing material, its manufacturing method and battery |
-
2003
- 2003-05-13 JP JP2003134653A patent/JP4264810B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006199916A (en) * | 2004-12-22 | 2006-08-03 | Toyobo Co Ltd | Polyester film for laminating metal plate, laminated metal plate and metal container |
| JP2006199917A (en) * | 2004-12-22 | 2006-08-03 | Toyobo Co Ltd | Polyester film for laminating metal plate, laminated metal plate and metal container |
| JP4670484B2 (en) * | 2004-12-22 | 2011-04-13 | 東洋紡績株式会社 | Polyester film for laminating metal plates, laminated metal plates and metal containers |
| JP2006328187A (en) * | 2005-05-25 | 2006-12-07 | Toyobo Co Ltd | Method for producing polyester film for laminating metal plate |
| JP4701834B2 (en) * | 2005-05-25 | 2011-06-15 | 東洋紡績株式会社 | Manufacturing method of polyester film for inner surface of metal can and film laminated metal plate |
| CN108886115A (en) * | 2016-04-06 | 2018-11-23 | 大日本印刷株式会社 | Battery use packing material, its manufacturing method and battery |
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