JP4258807B2 - Polyester film for coating metal plate, method for producing the same, and method for producing polyester film-coated metal plate - Google Patents
Polyester film for coating metal plate, method for producing the same, and method for producing polyester film-coated metal plate Download PDFInfo
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- JP4258807B2 JP4258807B2 JP2003379093A JP2003379093A JP4258807B2 JP 4258807 B2 JP4258807 B2 JP 4258807B2 JP 2003379093 A JP2003379093 A JP 2003379093A JP 2003379093 A JP2003379093 A JP 2003379093A JP 4258807 B2 JP4258807 B2 JP 4258807B2
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- polyester film
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- 229920006267 polyester film Polymers 0.000 title claims description 214
- 229910052751 metal Inorganic materials 0.000 title claims description 136
- 239000002184 metal Substances 0.000 title claims description 136
- 238000004519 manufacturing process Methods 0.000 title claims description 71
- 238000000576 coating method Methods 0.000 title claims description 21
- 239000011248 coating agent Substances 0.000 title claims description 20
- 229920000728 polyester Polymers 0.000 claims description 79
- -1 polyethylene terephthalate Polymers 0.000 claims description 44
- 239000001993 wax Substances 0.000 claims description 34
- 229920005989 resin Polymers 0.000 claims description 31
- 239000011347 resin Substances 0.000 claims description 31
- 230000003746 surface roughness Effects 0.000 claims description 31
- 238000001816 cooling Methods 0.000 claims description 30
- 239000002253 acid Substances 0.000 claims description 27
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 18
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 18
- 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 16
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 10
- 239000000194 fatty acid Substances 0.000 claims description 10
- 229930195729 fatty acid Natural products 0.000 claims description 10
- 238000010030 laminating Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- 230000005611 electricity Effects 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 150000004665 fatty acids Chemical class 0.000 claims description 5
- 235000011187 glycerol Nutrition 0.000 claims description 5
- 239000012188 paraffin wax Substances 0.000 claims description 5
- 230000003068 static effect Effects 0.000 claims description 5
- 238000007711 solidification Methods 0.000 claims description 4
- 230000008023 solidification Effects 0.000 claims description 4
- 238000000034 method Methods 0.000 description 33
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 28
- 229910052782 aluminium Inorganic materials 0.000 description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 239000000539 dimer Substances 0.000 description 15
- 238000002844 melting Methods 0.000 description 15
- 230000008018 melting Effects 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 239000002994 raw material Substances 0.000 description 12
- 230000002087 whitening effect Effects 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 229910000838 Al alloy Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 6
- 230000001954 sterilising effect Effects 0.000 description 6
- 238000004659 sterilization and disinfection Methods 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 238000010409 ironing Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 229920001634 Copolyester Polymers 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
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 3
- 229940117969 neopentyl glycol Drugs 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- 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
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 2
- AMOKUAKXKXBFIW-WJDWOHSUSA-N 9-[(z)-non-3-enyl]-10-octylnonadecanedioic acid Chemical compound OC(=O)CCCCCCCCC(CCCCCCCC)C(CCCCCCCC(O)=O)CC\C=C/CCCCC AMOKUAKXKXBFIW-WJDWOHSUSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 238000006471 dimerization reaction Methods 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
- 238000001125 extrusion Methods 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000011146 organic particle Substances 0.000 description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 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
- 230000000903 blocking effect Effects 0.000 description 1
- YADTZCBJDYCBEH-UHFFFAOYSA-N butane-1,1-diol;pentane-1,1-diol Chemical compound CCCC(O)O.CCCCC(O)O YADTZCBJDYCBEH-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 238000009924 canning Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 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 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 235000014594 pastries Nutrition 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
Description
本発明は金属板被覆用ポリエステルフィルム、その製造方法およびポリエステル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金属板被覆用ポリエステルフィルム、その製造方法およびポリエステルフィルム被覆金属板の製造方法に関するものである。 The present invention relates to a polyester film for coating a metal plate, a method for producing the same, and a method for producing a polyester film-coated metal plate. More specifically, a polyester film for coating a metal plate that is excellent in can manufacturing (for example, drawing and ironing processability) and impact resistance, and suitable for a metal can that is subjected to hot water sterilization, a method for producing the same, and a polyester film The present invention relates to a method for manufacturing a coated metal plate.
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。 Conventionally, the inner surface and outer surface of a metal can have been widely coated with a solution in which various thermosetting resins such as epoxy and phenol are dissolved or dispersed in a solvent for the purpose of preventing corrosion. Has been done. However, this thermosetting resin coating method has a drawback in that it takes a long time to dry the paint, so that productivity is lowered and undesired problems such as environmental pollution due to a large amount of organic solvent often occur.
かかる欠点を回避するため、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） In order to avoid such drawbacks, a method of coating a metal plate with a thermoplastic resin by a melt extrusion method is disclosed. (For example, see Patent Document 1)
しかしながら前記方法では、Ｔダイから金属板までの距離を短くすることが困難であり、その結果、両端部の厚みが非常に厚くなるため、厚みが均一な中央部分（実質的に金属板にラミネートできる部分）が狭くなり、かつ切断除去した両端部を再生使用できないため、材料ロスが大きいラミネート方法であった。 However, in the above method, it is difficult to shorten the distance from the T die to the metal plate, and as a result, the thickness of both ends becomes very thick. Therefore, the central portion having a uniform thickness (substantially laminated to the metal plate). This is a laminating method in which the material loss is large and the both ends cut and removed cannot be reused.
かかる欠点を回避するため、溶融押出後に冷却固化して得たポリエチレンテレフタレートおよび／またはポリブチレンテレフタレートの未配向フィルムを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） In order to avoid such drawbacks, a method is disclosed in which an unoriented film of polyethylene terephthalate and / or polybutylene terephthalate obtained by cooling and solidifying after melt extrusion is bonded to a heated metal plate. (For example, see Patent Document 2)
前記方法は、Ｔダイから金属板までの距離を短くすることが可能であり、その結果、厚みが均一な中央部分（実質的に金属板にラミネートできる部分）が前記方法より広がり、かつ切断除去した両端部を再生使用できるため、材料ロスを少なくすることができるラミネート方法であった。 In the above method, the distance from the T die to the metal plate can be shortened. As a result, a central portion having a uniform thickness (a portion that can be substantially laminated on the metal plate) is wider than the above method and is cut and removed. Since both the end portions can be recycled, the laminating method can reduce material loss.
しかしながら、前記方法は両端部を切断除去する際、フィルムが破断しやすく、また、ポリブチレンテレフタレートの含有率が多くなると（例えば、４０重量％以上では）、ポリエステル製膜で公知なクロムメッキの鏡面ロールを用いて３０ｍ／分以上の速度で製膜した場合、ロールと接触するフィルム表面に５０μｍを超える凹みが発生しやすく、このフィルムをラミネートした場合、凹みに起因した気泡が存在するラミネート金属板となり、製缶時にこの気泡を起点として微細なフィルム破れが発生しやすいという欠点があった。 However, in the above method, when both ends are cut and removed, the film easily breaks, and when the content of polybutylene terephthalate increases (for example, 40% by weight or more), a known chromium-plated mirror surface for polyester film formation When a film is formed at a speed of 30 m / min or more using a roll, a dent exceeding 50 μm is likely to occur on the film surface in contact with the roll, and when this film is laminated, a laminated metal plate in which bubbles due to the dent are present. Thus, there is a drawback that fine film tearing is likely to occur at the time of can making.
また、耐デント性が良好なポリエステル被覆積層体として、（Ｉ）：ポリエチレンテレフタレート・セグメント、（ＩＩ）：ブチレングリコールと芳香族二塩基酸から誘導されたポリエステル・セグメント、（ＩＩＩ）：ブチレングリコールと脂肪族二塩基酸から誘導されたポリエステル・セグメントを（Ｉ）：（ＩＩ）：（ＩＩＩ）＝１０〜７０：１２〜８１：３〜５４の重量比で含有し、さらにヒンダードフェノール系酸化防止剤を０．０１〜１．５重量％含有するポリエステルよりなる積層体が開示されている。（例えば、特許文献３参照） Further, as a polyester-coated laminate having good dent resistance, (I): polyethylene terephthalate segment, (II): polyester segment derived from butylene glycol and aromatic dibasic acid, (III): butylene glycol Contains polyester segments derived from aliphatic dibasic acids in a weight ratio of (I) :( II) :( III) = 10-70: 12-81: 3-54, and hindered phenolic antioxidants A laminate comprising a polyester containing 0.01 to 1.5% by weight of an agent is disclosed. (For example, see Patent Document 3)
さらに、エチレンテレフタレートを主体とするポリエステル樹脂層（Ｉ）とエチレンテレフタレートを主体とするポリエステルとブチレンテレフタレートを主体とし構成単位として脂環族および／または芳香族ダイマー酸成分を３〜８モル％含有する共重合ポリエステルが３０／７０〜９０／１０重量％配合ポリエステル樹脂層（ＩＩ）からなるフィルムが開示されている。（例えば、特許文献４参照） Further, the polyester resin layer (I) mainly composed of ethylene terephthalate, polyester mainly composed of ethylene terephthalate, and butylene terephthalate are mainly composed of 3 to 8 mol% of alicyclic and / or aromatic dimer acid components as structural units. A film comprising a polyester resin layer (II) containing 30/70 to 90/10% by weight of copolyester is disclosed. (For example, see Patent Document 4)
しかしながら、前記積層体を高速で（例えば、８０缶／分の速度で）絞り・しごき加工して金属缶を得ようとした場合、加工ポンチまたはダイスとの離型性が悪く、フィルム破れ、カジリ等が発生しやすいため、ポリエステル被覆積層体として未だ満足できるものではなかった。
本発明は前記従来技術の欠点を解消することを目的とするものである。即ち、厚みが均一な中央部分（実質的に金属板にラミネートできる部分）が広く、かつ切断除去した両端部を再生使用できるため材料ロスが少なく、さらに両端部を切断除去する際、フィルムが破断しにくく、さらに高速（例えば、３０ｍ／分以上の速度）で溶融樹脂膜を冷却固化した場合、ロールと接触するフィルム表面に５０μｍを超える凹みが発生しにくいため製缶性に優れ、また得られた金属缶に内容物を充填・密封後に実施される温水殺菌処理で金属缶外面の外観不良（フィルムの白化）が発生しにくいポリエステルフィルム被覆金属板の製造方法と表面平滑性に優れたポリエステルフィルムを提供するものである。 The present invention aims to eliminate the drawbacks of the prior art. In other words, the central part with a uniform thickness (the part that can be laminated to a metal plate) is wide, and both ends that have been cut and removed can be recycled, so there is little material loss, and the film breaks when both ends are cut and removed. When the molten resin film is cooled and solidified at a higher speed (for example, at a speed of 30 m / min or more), the film surface in contact with the roll is less likely to have a dent exceeding 50 μm, so that it is excellent in can manufacturing ability and is obtained. Polyester film coated with a polyester film coated metal plate that is less likely to have poor appearance (film whitening) on the outer surface of the metal can by hot water sterilization performed after filling and sealing the contents of the metal can. Is to provide.
本願の第１の発明は、（Ｉ）層／（ＩＩ）層／（Ｉ）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の混合比が６０：４０〜３０：７０重量％からなるポリエステルであり、（ＩＩ）層が全酸成分残基の５０モル％以上がテレフタル酸残基かつ５〜５０モル％が炭素数１０以上の脂肪族ジカルボン酸残基であるポリエステルからなり、表面粗さ（Ｒａ）が０．１μｍ以下であり、かつ（Ｉ）層および／または（ＩＩ）層を構成するポリエステル１００重量部に対してワックスが０．０１〜０．１５重量部配合されてなることを特徴とする金属板被覆用ポリエステルフィルムの製造方法であって、表面粗さが０．２μｍ以上、３．５μｍ以下の冷却ロールに３０ｍ／分以上の速度で静電密着させて固化させた後に少なくとも縦方向に１軸延伸すことを特徴とする金属板被覆用ポリエステルフィルム（ポリエステルフィルム（Ａ））の製造方法である。 The first invention of the present application is a composite structure of (I) layer / (II) layer / (I) layer, and the (I) layer has a mixing ratio of polyethylene terephthalate and polybutylene phthalate of 60:40 to 30:70. (II) layer is a polyester in which 50 mol% or more of all acid component residues are terephthalic acid residues and 5 to 50 mol% is an aliphatic dicarboxylic acid residue having 10 or more carbon atoms. The surface roughness (Ra) is 0.1 μm or less, and 0.01 to 0.15 parts by weight of wax is blended with 100 parts by weight of the polyester constituting the (I) layer and / or (II) layer. A method for producing a metal film-covering polyester film, wherein the surface roughness is electrostatically adhered to a cooling roll having a surface roughness of 0.2 μm or more and 3.5 μm or less at a speed of 30 m / min or more. Solidified And a method for producing a polyester film for covering a metal plate (polyester film (A)), wherein the film is stretched uniaxially at least in the longitudinal direction.
本願の第２の発明は、上記第１の発明において、表面粗さ（Ｒａ）が０．２μｍ以上、３．５μｍ以下の梨地状の冷却ロールに層状にキャストし、樹脂の両端部と中央部とを別々の静電気で独立密着させ、前記溶融樹脂膜を固化した後に少なくとも縦方向に１軸延伸することを特徴とする金属板被覆用ポリエステルフィルムの製造方法である。 According to a second invention of the present application, in the first invention, the surface roughness (Ra) is cast in a layered manner on a satin-like cooling roll having a surface roughness (Ra) of 0.2 μm or more and 3.5 μm or less, and both ends and a center of the resin Is made by independently adhering with different static electricity, and after the molten resin film is solidified, it is uniaxially stretched at least in the longitudinal direction.
本願の第３の発明は、（Ｉ）層／（ＩＩ）層／（Ｉ）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の混合比が６０：４０〜３０：７０重量％からなるポリエステルであり、（ＩＩ）層が全酸成分残基の５０モル％以上がテレフタル酸残基かつ５〜５０モル％が炭素数１０以上の脂肪族ジカルボン酸残基であるポリエステルよりなり、（Ｉ）層および／または（ＩＩ）層を構成するポリエステル１００重量部に対してワックスが０．０１〜０．１５重量部配合されてなるポリエステルフィルム（Ａ）と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混合比が６０：４０〜３０：７０重量％からなるポリエステルよりなり、ポリエステル１００重量部に対してワックスが０．０１〜０．１５重量部配合されてなるポリエステルフィルム（Ｂ）が、缶の内面側に相当する金属板表面にはポリエステルフィルム（Ａ）が、缶の外面側に相当する金属表面にはポリエステルフィルム（Ｂ）が被覆されたポリエステルフィルム被覆金属板の製造方法であって、Ｔダイから層状に押出した溶融樹脂膜を表面粗さが０．２μｍ以上、３．５μｍ以下の冷却ロールに層状に３０ｍ／分以上の速度でキャストし、樹脂の両端部と中央部とを別々の静電気で独立密着させて固化させた後に少なくとも縦方向に１軸延伸した後、両端部を切断除去して表面粗さ（Ｒａ）が０．１μｍ以下であるポリエステルフィルム（ポリエステルフィルム（Ａ）および（Ｂ））を得る工程と前記ポリエステルフィルム（Ａ）および（Ｂ）を加熱された金属板にラミネートする工程よりなることを特徴とするポリエステルフィルム被覆金属板の製造方法である。 The third invention of the present application is a composite structure of (I) layer / (II) layer / (I) layer, and (I) layer has a mixing ratio of polyethylene terephthalate and polybutylene phthalate of 60:40 to 30:70. It is a polyester composed of% by weight, and the (II) layer is a polyester in which 50 mol% or more of all acid component residues are terephthalic acid residues and 5 to 50 mol% are aliphatic dicarboxylic acid residues having 10 or more carbon atoms. Polyester film (A), polyethylene terephthalate, and polybutylene terephthalate comprising 0.01 to 0.15 parts by weight of wax with respect to 100 parts by weight of polyester constituting layer (I) and / or (II) The mixing ratio is 60: 40-30: 70% by weight of polyester, and the wax is 0.01-0. The polyester film (B) blended with 15 parts by weight has a polyester film (A) on the metal plate surface corresponding to the inner surface side of the can, and a polyester film (B) on the metal surface corresponding to the outer surface side of the can. A method for producing a coated polyester film-coated metal plate, wherein a molten resin film extruded in a layer form from a T-die is layered on a cooling roll having a surface roughness of 0.2 μm or more and 3.5 μm or less in a layer form of 30 m / min or more. After casting at a speed, the both ends and the center of the resin are solidified by being brought into close contact with each other by static electricity, and then uniaxially stretched at least in the longitudinal direction, both ends are cut and removed, and the surface roughness (Ra) A step of obtaining a polyester film (polyester films (A) and (B)) having a thickness of 0.1 μm or less, and laminating the polyester films (A) and (B) on a heated metal plate A method for producing a polyester film coated metal plate characterized by comprising from preparative to process.
本願の第４の発明は、請求項１又は２記載のワックスがパラフィン系ワックス、ポリエチレンワックス、エステル系ワックス、グリセリン脂肪酸エステル、高級脂肪酸モノアミドから選ばれた１種または２種以上であることを特徴とする金属板被覆用ポリエステルフィルムの製造方法である。 A fourth invention of the present application is characterized in that the wax according to claim 1 or 2 is one or more selected from paraffin wax, polyethylene wax, ester wax, glycerin fatty acid ester, and higher fatty acid monoamide. It is a manufacturing method of the polyester film for metal plate coating which makes it.
本願の第５の発明は、請求項３記載のワックスがパラフィン系ワックス、ポリエチレンワックス、エステル系ワックス、グリセリン脂肪酸エステル、高級脂肪酸モノアミドから選ばれた１種または２種以上であることを特徴とするポリエステルフィルム被覆金属板の製造方法である。
A fifth invention of the present application is characterized in that the wax according to claim 3 is one or more selected from paraffin wax, polyethylene wax, ester wax, glycerin fatty acid ester, and higher fatty acid monoamide. It is a manufacturing method of a polyester film covering metal plate.
本発明のポリエステルフィルム被覆金属板の製造方法は材料ロスを少なくすることができるため、経済性に優れた製造方法であるばかりでなく、外観と製缶性（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）に優れたポリエステルフィルム被覆金属板が得られる製造方法である。さらに、本発明によって得られるポリエステルフィルム被覆金属板を製缶した場合、内容物を充填した後に実施される温水殺菌処理で金属缶外面の外観不良（ポリエステルフィルムの白化）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フィルム被覆金属板の製造方法といえる。 Since the method for producing a polyester film-coated metal sheet of the present invention can reduce material loss, it is not only an economical production method, but also the appearance and can-making properties (particularly, can inner surface resin film and processing punch). This is a production method for obtaining a polyester film-coated metal plate excellent in mold release properties and scratch resistance of the outer resin film of the can. Furthermore, when the polyester film-coated metal plate obtained by the present invention is canned, the appearance of the outer surface of the metal can (whitening of the polyester film) is less likely to occur due to the hot water sterilization performed after filling the contents, and the product is manufactured. Since the impact resistance is unlikely to deteriorate even when heating is performed assuming an external baking coating performed for the purpose of beautification after the can, it can be said to be an extremely useful method for producing a polyester film-coated metal sheet.
本願発明のポリエステルフィルムは、（Ｉ）層／（ＩＩ）層／（Ｉ）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の混合比が６０：４０〜３０：７０重量％からなるポリエステルよりなり、（ＩＩ）層が全酸成分残基の５０モル％以上がテレフタル酸残基かつ５〜５０モル％が炭素数１０以上の脂肪族ジカルボン酸残基であるポリエステルからなるポリエステルの溶融樹脂膜を表面粗さ（Ｒａ）が０．２μｍ以上、４．０μｍ未満の冷却ロールで固化後に少なくとも縦方向に１軸延伸したポリエステルフィルムであって、表面粗さ（Ｒａ）が０．１μｍ以下であり、かつ（Ｉ）層および（ＩＩ）層を構成するポリエステル１００重量部に対してワックスが０．０１〜０．１５重量部配合されてなることを特徴とするポリエステルフィルム（ポリエステルフィルム（Ａ））である。 The polyester film of the present invention has a composite structure of (I) layer / (II) layer / (I) layer, and (I) layer has a mixing ratio of polyethylene terephthalate and polybutylene phthalate of 60:40 to 30:70 weight. (II) layer is made of polyester in which 50 mol% or more of all acid component residues are terephthalic acid residues and 5 to 50 mol% are aliphatic dicarboxylic acid residues having 10 or more carbon atoms. A polyester film obtained by solidifying a polyester molten resin film with a cooling roll having a surface roughness (Ra) of 0.2 μm or more and less than 4.0 μm and then uniaxially stretching in the longitudinal direction, and having a surface roughness (Ra) of 0 0.1 to 0.1 μm or less, and 0.01 to 0.15 parts by weight of a wax is blended with 100 parts by weight of the polyester constituting the layers (I) and (II). A polyester film characterized (polyester film (A)).
ポリエステルフィルム（Ａ）の層構性は（Ｉ）層／（ＩＩ）層／（Ｉ）層である理由は（Ｉ）層／（ＩＩ）層構成に比べ、フィルムのカールが小さく、金属板へラミネートする際、フィルム端部のラミネート状態が良好になるためである。 The reason why the layer structure of the polyester film (A) is (I) layer / (II) layer / (I) layer is that the curl of the film is smaller than that of the (I) layer / (II) layer structure, and the metal film This is because, when laminating, the laminated state of the film end is improved.
本発明のポリエステルフィルム（Ａ）の（Ｉ）層とポリエステルフィルム（Ｂ）で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の混合比が６０／４０〜３０／７０重量％であることが必要である。ポリブチレンテレフタレートが４０重量％未満では得られた金属缶を温水殺菌処理した場合白化するため好ましくない。逆にポリブチレンテレフタレートが７０重量％を超えるとフィルムの製膜性が著しく低下するため好ましくない。 In the polyester film (A) (I) layer and the polyester film (B) of the present invention, the mixing ratio of polyethylene terephthalate and polybutylene terephthalate needs to be 60/40 to 30/70% by weight. If the polybutylene terephthalate is less than 40% by weight, the resulting metal can is whitened when subjected to a hot water sterilization treatment, which is not preferable. On the contrary, when polybutylene terephthalate exceeds 70% by weight, the film-forming property of the film is remarkably lowered.
本発明で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。 In the present invention, a dicarboxylic acid component other than terephthalic acid and a glycol component other than ethylene glycol and butanediol can be used as long as the properties of polyethylene terephthalate and polybutylene terephthalate are not impaired. For example, as dicarboxylic acid, aromatic dicarboxylic acid such as isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, diphenylsulfone dicarboxylic 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 neopentylglycol, alicyclic glycols such as cyclohexanedimethanol, aromatics such as bisphenol A and bisphenol S Glycol can be used.
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されない。即ち、エステル交換法また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。また、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した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。 The method for producing the polyester in the present invention is not particularly limited. That is, it can be used even if it is produced by either the transesterification method or the direct polymerization method. Further, it may be produced by a solid phase polymerization method in order to increase the molecular weight. In addition, polyesters with low oligomer content produced by reduced pressure solid-state polymerization are used from the point of reducing the amount of oligomers from polyester resin in pastry treatment, retort treatment, etc. that are carried out after filling the contents in the can. It is preferable.
本発明で使用されるポリエステルの融点は１８０℃以上であることが製缶時の加工ポンチまたはダイスとの離型性を確保するために必要である。融点が１８０℃未満の場合、製缶時の加工ポンチまたはダイスとの離型性が劣るため好ましくない。 It is necessary for the melting point of the polyester used in the present invention to be 180 ° C. or higher in order to ensure releasability from the processing punch or die during can making. When the melting point is less than 180 ° C., it is not preferable because releasability from a processing punch or die during can making is poor.
本発明では後述の切断除去された両端部を含む樹脂をポリエステルフィルムで再使用できる。再使用する場合、再使用比率は特に限定しないが、５〜６０重量％が好ましい。 In the present invention, a resin containing both ends cut and removed as described later can be reused with a polyester film. When reused, the reuse ratio is not particularly limited, but is preferably 5 to 60% by weight.
本発明で使用されるポリエステルフィルム（Ａ）および（Ｂ）は、上記ポリエステル１００重量部に対し、ワックスを０．０１〜０．１５重量部配合させることが必要である。ワックスが０．０１重量部未満の場合、高速製缶時（例えば、８０缶／分）などの加工ポンチまたはダイスとの離型性が劣る。逆に、０．１５重量部を超える場合、高速製缶時の離型性の改良効果が飽和するだけでなく、コスト的に不利であり、場合によっては、フィルムの透明性が局部的に劣る透明欠点または気泡が生じる。 In the polyester films (A) and (B) used in the present invention, it is necessary to blend 0.01 to 0.15 parts by weight of wax with respect to 100 parts by weight of the polyester. When the wax is less than 0.01 parts by weight, the releasability from the processing punch or die during high-speed can manufacturing (for example, 80 cans / minute) is poor. On the other hand, if it exceeds 0.15 parts by weight, not only is the effect of improving releasability during high-speed can making saturated, but also disadvantageous in cost, and in some cases, the transparency of the film is locally inferior. Transparent defects or bubbles occur.
フィルムに配合されるワックスは製膜の安定性（押出機へ供給する際の取扱い性）の点からパラフィン系ワックス、ポリエチレンワックス、エステル系ワックス、グリセリン脂肪酸エステル、高級脂肪酸モノアミドから選ばれた１種または２種以上であることが好ましい。 The wax blended in the film is one selected from paraffin wax, polyethylene wax, ester wax, glycerin fatty acid ester, and higher fatty acid monoamide from the viewpoint of film formation stability (handleability when fed to an extruder). Or it is preferable that they are 2 or more types.
ポリエステルフィルムへのワックスの配合方法は特に限定されない。即ち、ポリエステルとワックスを溶融混練して得たポリマーを用いてフィルムを作製する方法、ポリエステルとワックスとの混合物を用いてフィルムを作製する方法等を使用できる。また、ワックス以外の無機または有機粒子よりなる滑剤を併用してもかまわない。 The method for blending the wax into the polyester film is not particularly limited. That is, a method of producing a film using a polymer obtained by melt-kneading polyester and wax, a method of producing a film using a mixture of polyester and wax, and the like can be used. Also, a lubricant made of inorganic or organic particles other than wax may be used in combination.
本発明におけるポリエステルには、必要に応じて本発明の作用を阻害しない範囲内で、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。 In the polyester in the present invention, an antioxidant, a heat stabilizer, an ultraviolet absorber, a plasticizer, a pigment, an antistatic agent, a lubricant, a crystal nucleating agent, as long as the action of the present invention is not inhibited as necessary. A lubricant composed of inorganic or organic particles may be blended.
本発明におけるポリエステルフィルム（Ａ）の（ＩＩ）層を構成するポリエステルは、テレフタル酸残基が５０モル％以上であり炭素数１０以上の脂肪族ジカルボン酸が５〜５０モル％であることが必要である。炭素数１０以上の脂肪族ジカルボン酸としては、セバシン酸、エイコ酸、デカンジカルボン酸、ダイマー酸等が挙げられる。ダイマー酸とはオレイン酸等の高級不飽和脂肪酸の二量化反応によって得られ、通常不飽和結合を分子中に有するが、水素添加をして不飽和度を下げたものも使用できる。水素添加をした方が耐熱性や柔軟性が向上するためより好ましい。また、二量化反応の過程で直鎖分岐状構造、脂環構造、芳香環構造が生成されるが、これらの構造や量を特に限定するものではない。炭素数１０未満の脂肪族ジカルボン酸残基では耐衝撃性の付与が充分でないため好ましくない。炭素数１０以上の脂肪族ジカルボン酸残基が５モル％未満では耐衝撃性の付与が充分でないため好ましくない。逆に５０モル％を超えると耐衝撃性が飽和するばかりでなく、耐熱性が低下するため好ましくない。また、テレフタル酸残基が５０モル％未満では耐熱性が不足し、加工ポンチの離型性が悪くなるため好ましくない。ポリエステルフィルム（Ａ）の（ＩＩ）層を構成するポリエステルはテレフタル酸残基と炭素数１０以上の脂肪族ジカルボン酸残基が前記の範囲を満足していれば、これらの酸以外のジカルボン酸残基を含むことを特に限定するものではない。また、炭素数１０以上の脂肪族ジカルボン酸残基は１種類であってもよいし、２種類以上併用してもよい。また、ポリエステルフィルム（Ａ）の（ＩＩ）層を構成するポリエステルのグリコール残基を特に限定するものではなく、エチレングリコール、プロパンジオール、ブタ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の残基でよい。 The polyester constituting the (II) layer of the polyester film (A) in the present invention must have a terephthalic acid residue of 50 mol% or more and an aliphatic dicarboxylic acid having 10 or more carbon atoms of 5 to 50 mol%. It is. Examples of the aliphatic dicarboxylic acid having 10 or more carbon atoms include sebacic acid, eicoic acid, decanedicarboxylic acid, and dimer acid. Dimer acid is obtained by a dimerization reaction of a higher unsaturated fatty acid such as oleic acid, and usually has an unsaturated bond in the molecule, but it can also be used after hydrogenation to reduce the degree of unsaturation. Hydrogenation is more preferable because heat resistance and flexibility are improved. In addition, a linear branched structure, an alicyclic structure, and an aromatic ring structure are generated in the course of the dimerization reaction, but these structures and amounts are not particularly limited. Aliphatic dicarboxylic acid residues having less than 10 carbon atoms are not preferred because they do not provide sufficient impact resistance. If the aliphatic dicarboxylic acid residue having 10 or more carbon atoms is less than 5 mol%, it is not preferable because the impact resistance is not sufficient. On the other hand, if it exceeds 50 mol%, not only the impact resistance is saturated but also the heat resistance is lowered, which is not preferable. Further, if the terephthalic acid residue is less than 50 mol%, the heat resistance is insufficient, and the releasability of the processing punch is deteriorated, which is not preferable. If the terephthalic acid residue and the aliphatic dicarboxylic acid residue having 10 or more carbon atoms satisfy the above range, the polyester constituting the (II) layer of the polyester film (A) can be a residue of dicarboxylic acid other than these acids. Inclusion of a group is not particularly limited. Moreover, one type of aliphatic dicarboxylic acid residue having 10 or more carbon atoms may be used, or two or more types may be used in combination. In addition, the glycol residue of the polyester constituting the (II) layer of the polyester film (A) is not particularly limited, and aliphatic glycols such as ethylene glycol, propanediol, butanediol pentanediol, hexanediol, neopentyl glycol, etc. Or a residue of an alicyclic glycol such as cyclohexanedimethanol, or an aromatic glycol such as bisphenol A or bisphenol S.
本発明ではポリエステルを公知の１軸又は２軸押出機内で溶融させた後、Ｔダイから層状に押出した溶融樹脂膜を表面粗さ（Ｒａ）が０．２μｍ以上、４．０μｍ未満の冷却ロールで固化することが必要である。また、冷却ロールの表面形状はスパイラル状の溝に仕上げたもの、ダイヤカット状の溝に仕上げたもの、梨地状に仕上げたもの等が使用できるが、これらのうち、表面を梨地状に仕上げたロールが特に好ましい。 In the present invention, after the polyester is melted in a known single or twin screw extruder, a molten resin film extruded in a layer form from a T-die has a surface roughness (Ra) of 0.2 μm or more and less than 4.0 μm. It is necessary to solidify with. In addition, the surface shape of the cooling roll can be a spiral groove, a diamond cut groove, a satin finish, etc. Of these, the surface has a satin finish A roll is particularly preferred.
表面粗さが０．２μｍ未満の場合、高速（例えば、３０ｍ／分以上の速度）で溶融樹脂膜を冷却固化すると５０μｍを超える凹部が冷却ロールと接触するフィルム表面に無数に発生し、このフィルムを少なくとも縦方向に１軸延伸すると凹みが大きくなり、このフィルムを金属板にラミネートした場合、凹みに起因した気泡が存在したラミネート金属板となり、製缶時にこの気泡を起点として微細なフィルム破れが発生しやすい。逆にロール表面粗さが４．０μｍ以上の場合、梨地模様がフィルムに転写し、このフィルムを金属板にラミネートした場合、フィルムに斑状の外観不良が発生し、このフィルム面を缶外面側で使用した場合、商品価値が低下するため好ましくない。このとき、ロール表面粗さ（Ｒａ）は０．２μｍ以上、３．５μｍ以下が好ましく、２．５μｍ以下が更に好ましい。 When the surface roughness is less than 0.2 μm, when the molten resin film is cooled and solidified at a high speed (for example, a speed of 30 m / min or more), indentations exceeding 50 μm are generated innumerably on the film surface in contact with the cooling roll. When the film is stretched uniaxially at least in the longitudinal direction, the dents become large, and when this film is laminated to a metal plate, it becomes a laminated metal plate in which air bubbles resulting from the dents exist, and fine film tearing starts from the air bubbles during can making. Likely to happen. On the other hand, when the roll surface roughness is 4.0 μm or more, the satin pattern is transferred to the film, and when this film is laminated to a metal plate, a patchy appearance defect occurs on the film. When used, the commercial value is lowered, which is not preferable. At this time, the roll surface roughness (Ra) is preferably 0.2 μm or more and 3.5 μm or less, and more preferably 2.5 μm or less.
本発明ではポリエステルフィルムの表面粗さ（Ｒａ）が０．１μｍ以下であることが製缶性を確保し、得られた缶の商品価値を高めるために必要であるが、表面粗さ（Ｒａ）が０．０２〜０．１μｍであることが金属板とのラミネート性を確保するために（フィルムのブロッキングによる巻出し性の低下を制御するために）さらに好ましい。 In the present invention, it is necessary for the surface roughness (Ra) of the polyester film to be 0.1 μm or less in order to secure the can-making property and increase the commercial value of the resulting can, but the surface roughness (Ra) Is more preferably 0.02 to 0.1 μm in order to ensure laminating properties with the metal plate (in order to control a decrease in unwinding property due to blocking of the film).
冷却固化後の中央部の平均厚みは２５０μｍ以下であることが延伸性を良好にするため好ましい。 The average thickness of the central portion after cooling and solidification is preferably 250 μm or less in order to improve the stretchability.
本発明では溶融樹脂を冷却ロールに接触させる際、静電気で密着させる方法を採用することが好ましい。また、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。 In the present invention, it is preferable to adopt a method in which the molten resin is brought into close contact with static electricity when contacting the cooling roll. Moreover, the method of implementing independently the both ends and center part of layered resin is more preferable. Furthermore, when the molten resin contacts 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 accompanying flow by reducing the pressure on the opposite side.
本発明では冷却固化させた後、少なくとも縦方向に１軸延伸し、次いで得られた延伸フィルムの両端部を切断除去してポリエステルフィルムを得ることが必要である。縦延伸条件としては、フィルムを構成するポリエステルのガラス転移温度以上の温度で縦方向に１．３〜６．０倍延伸することが好ましい。縦延伸を実施した場合、フィルムの両端部を切断除去する際、フィルムが破断しにくく、かつ生産性を向上させることができる。また、フィルムの両端部を切断除去して、金属板にラミネートした場合、材料ロスが少なくて経済的に好ましい。 In the present invention, after cooling and solidifying, it is necessary to uniaxially stretch at least in the longitudinal direction, and then to cut and remove both ends of the obtained stretched film to obtain a polyester film. As longitudinal stretching conditions, it is preferable to stretch 1.3 to 6.0 times in the longitudinal direction at a temperature equal to or higher than the glass transition temperature of the polyester constituting the film. When longitudinal stretching is carried out, when the both ends of the film are cut and removed, the film is hardly broken and productivity can be improved. Further, when both ends of the film are cut and removed and laminated on a metal plate, there is little material loss, which is economically preferable.
さらにポリエステルフィルムの生産性を向上させるため、縦延伸後に横延伸を実施してもよい。また、必要に応じて緊張下で５０℃以上かつポリエステルの融点−２０℃の温度で１〜２０秒間熱処理してフィルムの延伸方向の熱収縮率をコントロールしてもよい。 Furthermore, in order to improve the productivity of the polyester film, transverse stretching may be performed after longitudinal stretching. If necessary, the heat shrinkage in the stretching direction of the film may be controlled by heat treatment for 1 to 20 seconds at a temperature of 50 ° C. or higher and a melting point of the polyester −20 ° C. under tension.
本発明では金属板として、鋼板、アルミニウム板、アルミニウム合金板が使用されるが、特に限定されるものではなく、鋼板は、通常製缶用鋼板として使用されているもの、具体的には絞り缶用、絞り・しごき缶用、蓋用のそれぞれの用途に用いられている鋼板が使用される。鋼板表面に施される表面処理も同様で、通称ＴＦＳ−ＣＴと呼ばれている電解クロム酸処理鋼板、Ｎｉめっき皮膜の上層に電解クロム酸処理を施した鋼板、等が使用される。 In the present invention, a steel plate, an aluminum plate, and an aluminum alloy plate are used as the metal plate. However, the metal plate is not particularly limited, and the steel plate is normally used as a steel plate for can manufacturing, specifically, a drawn can. Steel plates that are used in various applications such as squeezing, squeezing and ironing cans, and lids are used. The surface treatment applied to the surface of the steel plate is the same, and an electrolytic chromic acid-treated steel plate commonly referred to as TFS-CT, a steel plate with an electrolytic chromic acid treatment applied to the upper layer of the Ni plating film, and the like are used.
アルミニウム板やアルミニウム合金板も同様で、通常製缶用アルミニウム板として使用されているもの、具体的には絞り・しごき缶用、蓋用のそれぞれの用途に用いられているアルミニウム板が使用される。 The same applies to aluminum plates and aluminum alloy plates, which are usually used as aluminum plates for cans. Specifically, aluminum plates used for squeezing and ironing cans and lids are used. .
これらの金属板を加熱した後、ラミネートロールを使用してポリエステルフィルムを金属板の両面に同時ラミネートまたは逐次ラミネートする。加熱温度は、ポリエステルの融点−２０℃以上かつ融点＋１５０℃であるのが好ましい。引き続いてこのラミネート金属板を加熱した後、水冷および／または空冷してポリエステルフィルム被覆金属板を得る。加熱温度は、ポリエステルの融点＋１０℃以上かつ融点＋６０℃であるのが好ましい。 After these metal plates are heated, the polyester film is simultaneously or sequentially laminated on both surfaces of the metal plate using a laminating roll. The heating temperature is preferably a melting point of polyester of −20 ° C. or higher and a melting point of + 150 ° C. Subsequently, the laminated metal plate is heated and then cooled with water and / or air to obtain a polyester film-coated metal plate. The heating temperature is preferably the melting point of polyester + 10 ° C. or higher and the melting point + 60 ° C.
金属板の両面にラミネートする場合、ポリエステルフィルム（Ａ）同士やポリエステルフィルム（Ｂ）同士の組み合わせも可能であるが、それぞれのポリエステルフィルムの構成が異なるのが好ましい。勿論、ポリエステルフィルム（Ａ）および（Ｂ）を金属板の片面にのみラミネートすることは可能である。加熱温度は、ポリエステルの融点＋１０℃以上かつ融点＋６０℃であるのが好ましい。 When laminating on both surfaces of the metal plate, a combination of the polyester films (A) and the polyester films (B) is also possible, but it is preferable that the configurations of the respective polyester films are different. Of course, it is possible to laminate the polyester films (A) and (B) only on one side of the metal plate. The heating temperature is preferably the melting point of polyester + 10 ° C. or higher and the melting point + 60 ° C.
本発明では缶の内面側にはポリエステルフィルム（Ａ）を使用することは必須であるが、もう一方の缶の外面側にはポリエステル（Ｂ）を使用するのが、内容物を充填・密封した後に実施される温水殺菌処理で金属缶外面の外観不良（ポリエステルフィルムの白化）が発生しにくくなる点で好ましい。 In the present invention, it is essential to use the polyester film (A) on the inner surface side of the can, but the polyester (B) is used on the outer surface side of the other can to fill and seal the contents. The hot water sterilization process performed later is preferable in that the appearance defect of the outer surface of the metal can (whitening of the polyester film) hardly occurs.
以下、実施例をもとに本発明を説明する。 Hereinafter, the present invention will be described based on examples.
［評価方法］
（１）ポリエステルフィルムを構成するポリエステルの融点
ポリエステルフィルム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。
（２）ポリエステルを構成するポリエステルの極限粘度（ＩＶ）
オルトクロルフェノール中２５℃でウベローデ粘度管を用い測定した値（ｄｌ／ｇ）である。
（３）冷却ロールの表面粗さ（Ｒａ）
ＪＩＳ Ｂ０６０１（１９８２）にしたがって測定した。
（４）ポリエステルフィルムの表面粗さ（Ｒａ）
１０ｃｍ×１０ｃｍに切り出したフィルムを目視観察してキャスト時に冷却ロールに接したフィルム表面に５０μｍを超える凹みがないものを評価価値ありとして下記の方法で評価した。なお、２０回測定の平均値をもって表面粗さ（Ｒａ）とした。
ａ．測定装置：（株）小坂研究所製 ＥＴ−３０ＨＫ
ｂ．触針先端半径：０．５μｍ
ｃ．触針荷重：５ｍｇ
ｄ．測定長：１ｍｍ
ｅ．カットオフ値：０．０８ｍｍ
（５）ポリエステルフィルムを構成するポリエステルの重量平均分子量
１０ｍｇのポリエステルフィルムをクロロホルム／ＨＥＩＰ：９６／４（容量％）に溶解させ、ＳｈｏｄｅｘＧＰＣ２４Ｈの測定装置を用いて、４０℃・ＵＶ２５４ｎｍの条件で測定した。
（６）ポリエステル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）の一方の面にポリエステルフィルム（Ａ）を他の面にポリエステルフィルム（Ｂ）を同時にラミネートした後、２７５℃で加熱した後に水中で急冷してポリエステルフィルム被覆アルミニウム板を得た。
（７）缶内面樹脂と加工ポンチの離型性
実施例１〜６、比較例１〜７で得られたポリエステルフィルム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２５μｍのポリエステルフィルム（Ａ）が缶内面側となるようにして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８０缶／分の速度でしごき加工を実施し、３５０ｍｌサイズのシームレス缶を４００缶製缶し、最初の１０缶と最後の１０缶の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
（８）缶外面の耐かじり性（缶外面樹脂における縦方向のキズ）
実施例１〜６、比較例１〜７で得られたポリエステルフィルム被覆アルミニウム板から上記（７）と同様にして４００缶製缶し、最初の１０缶と最後の１０缶の成形した缶体胴壁部外面樹脂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
（９）耐衝撃性
実施例１〜６、比較例１〜７で得られたポリエステルフィルム被覆アルミニウム板から上記（７）と同様にして製缶して得た缶を２８０℃で４０秒加熱後水中で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
（１０）温水処理後の缶外面の白化程度
実施例１〜６、比較例１〜７で得られたポリエステルフィルム被覆アルミニウム板から上記（７）と同様にして製缶して得た缶を２７０℃で４０秒間加熱した後水中で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、水中で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見えない
（１１）共重合ポリエステルの組成比
サンプル約５ｍｇを重クロロホルムとトリフルオロ酢酸の混合溶液（９／１；体積比）０．７ｍｌに溶解し、１Ｈ−ＮＭＲ（ｖａｒｉａｎ製、ＵＮＩＴＹ５０）を使用して求めた。
積層フィルムを測定する場合は、金属と接していない面から順次削り出し、測定対象層のポリマー片をサンプルとして、同様の測定を実施する。
[Evaluation methods]
(1) Melting point of polyester constituting polyester film Using 10 mg of polyester film, a differential scanning calorimeter (DSC) in a nitrogen stream was used to generate an exothermic / endothermic curve (DSC curve) at a heating rate of 10 ° C / min. The peak temperature of the endothermic peak accompanying melting when measured was defined as the melting point Tm (° C.).
(2) Intrinsic viscosity of polyester constituting polyester (IV)
It is a value (dl / g) measured using an Ubbelohde viscosity tube at 25 ° C. in orthochlorophenol.
(3) Cooling roll surface roughness (Ra)
It measured according to JIS B0601 (1982).
(4) Surface roughness of the polyester film (Ra)
The film cut out to 10 cm × 10 cm was visually observed, and the film surface that was in contact with the cooling roll at the time of casting had no dent exceeding 50 μm and was evaluated by the following method as having an evaluation value. In addition, it was set as the surface roughness (Ra) with the average value of 20 times measurement.
a. Measuring device: ET-30HK manufactured by Kosaka Laboratory
b. Stitch tip radius: 0.5 μm
c. Stylus load: 5mg
d. Measurement length: 1mm
e. Cut-off value: 0.08mm
(5) Weight average molecular weight of polyester constituting polyester film 10 mg of polyester film was dissolved in chloroform / HEIP: 96/4 (volume%), and measured using a Shodex GPC24H measuring device at 40 ° C. and UV 254 nm. .
(6) Production method of polyester film-coated metal plate A polyester film (A) is applied to one surface of an aluminum alloy plate (3004 series alloy plate having a thickness of 0.26 mm) heated to 250 ° C., and a polyester film (B ) Were simultaneously laminated, heated at 275 ° C., and then rapidly cooled in water to obtain a polyester film-coated aluminum plate.
(7) Releasability between can inner surface resin and processing punches After applying a forming lubricant to the polyester film-coated aluminum plates obtained in Examples 1 to 6 and Comparative Examples 1 to 7, the plate temperature was 70 ° C. The drawing was carried out so that the 25 μm polyester film (A) was on the inner surface side of the can. Next, the temperature of the obtained cup was set to 40 ° C., and ironing was performed at a mold temperature of 80 ° C. at a speed of 80 cans / minute, and 400 cans of 350 ml-sized seamless cans were made. The degree of buckling occurring at the top of the 10 cans was visually observed. Evaluation criteria were set as follows, and ○ was evaluated as practical.
○: Buckling has not occurred in the can opening △: Buckling has occurred in about 1/3 of the circumference of the can opening x: Buckling has occurred in more than 1/3 of the circumference of the can opening (8) Anti-galling of the outer surface of the can Properties (longitudinal scratches on can outer surface resin)
400 cans were made from the polyester film-coated aluminum plates obtained in Examples 1 to 6 and Comparative Examples 1 to 7 in the same manner as in (7) above, and the first 10 cans and the last 10 cans were formed. The degree of occurrence of scratches on the wall outer surface resin was visually observed. Evaluation criteria were set as follows, and ○ was evaluated as practical.
○: Scratch not occurred Δ: Scratch occurred in about 1/3 of the outer surface ×: Severe scratch generated more than 1/3 of the outer surface (9) Impact resistance Polyesters obtained in Examples 1 to 6 and Comparative Examples 1 to 7 A 7 cm square sample is cut out from the center of the barrel wall of a can obtained by making a can from a film-coated aluminum plate in the same manner as in (7) above, heating 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 to the surface corresponding to the outer surface of the can of this sample to give an impact. Next, the sample was placed on a glass container filled with 7% dilute hydrochloric acid (with the convex portion of the sample immersed), and the corrosion state of the convex portion was visually observed after 3 days. Evaluation criteria were set as follows, and ○ was evaluated as practical.
○: Corrosion occurrence of convex portions X: Corrosion occurrence of convex portions (10) Degree of whitening of can outer surface after hot water treatment From the polyester film-coated aluminum plates obtained in Examples 1 to 6 and Comparative Examples 1 to 7 ( A can obtained in the same manner as in 7) was heated at 270 ° C. for 40 seconds, and then rapidly cooled in water. After immersing this sample in warm water at 80 ° C. for 10 minutes, the outer surface of the can obtained by quenching in water was visually observed. Evaluation criteria were set as follows, and ○ was evaluated as practical.
○: Whitening is inconspicuous Δ: Clearly whitened, but the color of the aluminum alloy plate is visible ×: The color of the aluminum alloy plate is not visible due to whitening (11) Composition ratio of copolymerized polyester About 5 mg of the sample is deuterated in chloroform And dissolved in 0.7 ml of a mixed solution of trifluoroacetic acid (9/1; volume ratio) and obtained using 1H-NMR (manufactured by varian, UNITY 50).
In the case of measuring a laminated film, the same measurement is performed using a polymer piece of a measurement target layer as a sample by sequentially cutting from a surface not in contact with a metal.
（１）、（３）〜（４）、（７）〜（１０）の測定・評価結果を表１−１、表１−２に示す。 The measurement and evaluation results of (1), (3) to (4), and (7) to (10) are shown in Table 1-1 and Table 1-2.
［実施例・比較例に用いたポリエステルとワックスの略号と内容］
（１）ＰＥＴ ：ポリエチレンテレフタレート（ＩＶ：０．７５、平均粒径１．５μｍの凝集シリカを２０００ｐｐｍ配合）
（２）ＰＢＴ ：ポリブチレンテレフタレート（ＩＶ：１．２０）
（３）ポリエステルＡ ：テレフタル酸／炭素数３６のダイマー酸（モル比９０／１０）とエチレングリコールとの共重合ポリエステル（ＩＶ：０．７３、平均粒径１．５μｍの凝集シリカを１０００ｐｐｍ配合）
（４）ポリエステルＢ ：テレフタル酸／炭素数３６のダイマー酸（モル比９５／５）とエチレングリコール／１，４ブタンジオール（モル比３０／７０）との共重合ポリエステル（ＩＶ：０．８５、平均粒径１．５μｖｍの凝集シリカを１０００ｐｐｍ配合）
（５）ポリエステルＣ ：テレフタル酸とエチレングリコール／ネオペンチルグリコール（モル％ ７０／３０）との共重合ポリエステル（ＩＶ：０．７２、平均粒径１．５μｍの凝集シリカを１０００ｐｐｍ配合）
（６）ワックス ：ポリエチレンワックス（三井化学社製、ハイワックスＮＬ
５００：商品名）
[Abbreviations and contents of polyester and wax used in Examples and Comparative Examples]
(1) PET: Polyethylene terephthalate (IV: 0.75, 2000 ppm of agglomerated silica having an average particle size of 1.5 μm)
(2) PBT: Polybutylene terephthalate (IV: 1.20)
(3) Polyester A: Copolyester of terephthalic acid / C36 dimer acid (molar ratio 90/10) and ethylene glycol (IV: 0.73, 1000 ppm of agglomerated silica having an average particle size of 1.5 μm)
(4) Polyester B: Copolyester of terephthalic acid / C36 dimer acid (molar ratio 95/5) and ethylene glycol / 1,4 butanediol (molar ratio 30/70) (IV: 0.85, (Containing 1000 ppm of agglomerated silica with an average particle size of 1.5 μvm)
(5) Polyester C: Copolyester of terephthalic acid and ethylene glycol / neopentyl glycol (mol% 70/30) (IV: 0.72, 1000 ppm of agglomerated silica having an average particle size of 1.5 μm)
(6) Wax: Polyethylene wax (manufactured by Mitsui Chemicals, high wax NL
500: Product name)
［実施例 １］
ポリエステルフィルム（Ａ）の（Ｉ）層を構成するポリエステルフィルムの原料ポリエステルとしてＰＥＴ／ＰＢＴ＝４０／６０（重量比）のポリエステル１００重量部にワックスを０．０５重量部配合した組成物を用い、（ＩＩ）層を構成するポリエステルフィルムの原料ポリエステルとしてポリエステルＡ単体を用い、それぞれを２７０℃で溶融させ、Ｔダイを用いて、表面粗さ（Ｒａ）が１μｍの梨地状の冷却ロール（周速５０ｍ／分）へ層状にキャストし、Ｔダイと冷却ロールとの間隔２ｃｍ、中央部と両端部は別々の装置で静電密着させ（中央部：４．５ｋＶ、両端部：６ｋＶの直流電源を印加）冷却固化させた後、予熱温度６５℃、延伸温度１００℃で縦方向に４倍延伸し（Ｉ）層と（ＩＩ）層とを積層して厚みが２５μｍ（（Ｉ）層厚み６μｍ、（ＩＩ）層厚み１３μｍ）のポリエステルフィルム（Ａ）を得た。ポリエステルフィルム（Ａ）の（ＩＩ）層中のダイマー酸の含有率は１０モル％であった。
また、ＰＥＴ／ＰＢＴ＝４０／６０（重量比）のポリエステル１００重量部にワックスを０．０５重量部配合した組成物を２８０℃で溶融させ、Ｔダイを用いて、表面粗さ（Ｒａ）が１μｍの梨地状の冷却ロール（周速５０ｍ／分）へ層状にキャストし、Ｔダイと冷却ロールとの間隔２ｃｍ、中央部と両端部は別々の装置で静電密着させ（中央部：４．５ｋＶ、両端部：６ｋＶの直流電源を印加）冷却固化させた後、予熱温度６５℃、延伸温度１００℃で縦方向に４倍延伸して厚みが１６μｍのポリエステルフィルム（Ｂ）を得た。
次いで、２５０℃に加熱した３００４系アルミニウム合金板（厚み０．２６ｍｍ）の片面に１６μｍのポリエステルフィルム（Ｂ）を圧着し、もう一方の面に２５μｍのポリエステルフィルム（Ａ）を圧着し２７５℃に加熱した後、水中で急冷してポリエステルフィルム被覆アルミニウム板を得た。
本実施例の方法は、製缶性に優れたポリエステルフィルム被覆金属板の製造方法であり、かつ内面フィルムは耐衝撃性に優れまた外面フィルムは耐温水白化性が優れた金属缶が得られる表面平滑性に優れた金属板被覆用ポリエステルフィルム、金属板被覆用ポリエステルフィルムの製造方法であり、ポリエステルフィルム被覆金属板の製造方法であるといえる。
[Example 1]
As a raw material polyester of the polyester film constituting the (I) layer of the polyester film (A), a composition in which 0.05 part by weight of a wax is blended with 100 parts by weight of polyester of PET / PBT = 40/60 (weight ratio), (II) Polyester A alone is used as a raw material polyester of the polyester film constituting the layer, each is melted at 270 ° C., and a T-die is used to form a satin-like cooling roll (surface speed) with a surface roughness (Ra) of 1 μm. 50m / min) in a layered manner, the distance between the T-die and the cooling roll is 2cm, and the central part and both ends are electrostatically adhered by separate devices (central part: 4.5kV, both ends: 6kV DC power supply) Application) After cooling and solidification, the film was stretched 4 times in the longitudinal direction at a preheating temperature of 65 ° C. and a stretching temperature of 100 ° C., and the (I) layer and the (II) layer were laminated to a thickness of 25 μm ((I A polyester film (A) having a layer thickness of 6 μm and (II) layer thickness of 13 μm) was obtained. The content of dimer acid in the (II) layer of the polyester film (A) was 10 mol%.
Also, a composition in which 0.05 part by weight of wax is blended with 100 parts by weight of polyester of PET / PBT = 40/60 (weight ratio) is melted at 280 ° C., and the surface roughness (Ra) is determined by using a T die. Casted in layers into a 1 μm satin-like cooling roll (peripheral speed 50 m / min), the distance between the T die and the cooling roll is 2 cm, and the center and both ends are electrostatically adhered by separate devices (center: 4. 5 kV, both ends: DC power supply of 6 kV applied) After cooling and solidification, the polyester film (B) having a thickness of 16 μm was obtained by stretching 4 times in the longitudinal direction at a preheating temperature of 65 ° C. and a stretching temperature of 100 ° C.
Next, a 16 μm polyester film (B) is pressure bonded to one side of a 3004 series aluminum alloy plate (thickness 0.26 mm) heated to 250 ° C., and a 25 μm polyester film (A) is pressure bonded to the other side to 275 ° C. After heating, it was quenched in water to obtain a polyester film-coated aluminum plate.
The method of this example is a method for producing a polyester film-coated metal plate having excellent canability, and the inner surface film is excellent in impact resistance and the outer surface film is a surface from which a metal can excellent in hot water whitening resistance can be obtained. It is a manufacturing method of a polyester film for covering a metal plate and a polyester film for covering a metal plate that is excellent in smoothness, and can be said to be a manufacturing method of a polyester film-covering metal plate.
［実施例 ２］
ポリエステルフィルム（Ａ）の（ＩＩ）層を構成するポリエステルフィルムの原料ポリエステルとしてポリエステルＢ単体を用いた以外は実施例１と同様にして厚みが２５μｍ（（Ｉ）層厚み６μｍ、（ＩＩ）層厚み１３μｍ）のポリエステルフィルム（Ａ）と１６μｍのポリエステルフィルム（Ｂ）を得た。ポリエステルフィルム（Ａ）の（ＩＩ）層中のダイマー酸の含有率は５モル％であった。
次いで、実施例１と同様にしてポリエステルフィルム被覆アルミニウム板を得た。
本実施例の方法は、製缶性に優れたポリエステルフィルム被覆金属板の製造方法であり、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表面平滑性に優れた金属板被覆用ポリエステルフィルム、金属板被覆用ポリエステルフィルムの製造方法であり、ポリエステルフィルム被覆金属板の製造方法であるといえる。
[Example 2]
The thickness is 25 μm ((I) layer thickness 6 μm, (II) layer thickness) except that polyester B alone is used as the raw material polyester of the polyester film constituting the (II) layer of the polyester film (A). 13 μm) polyester film (A) and 16 μm polyester film (B) were obtained. The content of dimer acid in the (II) layer of the polyester film (A) was 5 mol%.
Next, a polyester film-coated aluminum plate was obtained in the same manner as in Example 1.
The method of this example is a method for producing a polyester film-coated metal plate having excellent canability, and is a metal having excellent surface smoothness that provides a metal can having excellent impact resistance and resistance to warm water on the outer surface. It is a manufacturing method of a polyester film for covering a plate and a polyester film for covering a metal plate, and can be said to be a manufacturing method of a polyester film-covering metal plate.
［実施例 ３］
表面粗さ（Ｒａ）が０．５μｍの梨地状の冷却ロールを用いた以外は実施例１と同様にして厚みが２５μｍ（（Ｉ）層厚み６μｍ、（ＩＩ）層厚み１３μｍ）のポリエステルフィルム（Ａ）と１６μｍのポリエステルフィルム（Ｂ）を得た。ポリエステルフィルム（Ａ）の（ＩＩ）層中のダイマー酸の含有率は１０モル％であった。
次いで、実施例１と同様にしてポリエステルフィルム被覆アルミニウム板を得た。
本実施例の方法は、製缶性に優れたポリエステルフィルム被覆金属板の製造方法であり、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表面平滑性に優れた金属板被覆用ポリエステルフィルム、金属板被覆用ポリエステルフィルムの製造方法であり、ポリエステルフィルム被覆金属板の製造方法であるといえる。
[Example 3]
A polyester film having a thickness of 25 μm ((I) layer thickness 6 μm, (II) layer thickness 13 μm) in the same manner as in Example 1 except that a satin-like cooling roll having a surface roughness (Ra) of 0.5 μm was used. A) and a 16 μm polyester film (B) were obtained. The content of dimer acid in the (II) layer of the polyester film (A) was 10 mol%.
Next, a polyester film-coated aluminum plate was obtained in the same manner as in Example 1.
The method of this example is a method for producing a polyester film-coated metal plate having excellent canability, and is a metal having excellent surface smoothness that provides a metal can having excellent impact resistance and resistance to warm water on the outer surface. It is a manufacturing method of a polyester film for covering a plate and a polyester film for covering a metal plate, and can be said to be a manufacturing method of a polyester film-covering metal plate.
［実施例 ４］
表面粗さ（Ｒａ）が３．３μｍの梨地状の冷却ロールを用いた以外は実施例１と同様にして厚みが２５μｍ（（Ｉ）層厚み１２．５μｍ、（ＩＩ）層厚み１２．５μｍ）ポリエステルフィルム（Ａ）と１６μｍのポリエステルフィルム（Ｂ）を得た。ポリエステルフィルム（Ａ）の（ＩＩ）層中のダイマー酸の含有率は１０モル％であった。
次いで、実施例１と同様にしてポリエステルフィルム被覆アルミニウム板を得た。
本実施例の方法は、外観と製缶性に優れた金属板被覆用ポリエステルフィルム、金属板被覆用ポリエステルフィルムの製造方法であり、ポリエステルフィルム被覆金属板の製造方法であり、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表面平滑性に優れた金属板被覆用ポリエステルフィルム、金属板被覆用ポリエステルフィルムの製造方法であり、ポリエステルフィルム被覆金属板の製造方法であるといえる。
[Example 4]
The thickness was 25 μm ((I) layer thickness 12.5 μm, (II) layer thickness 12.5 μm) in the same manner as in Example 1 except that a satin-like cooling roll having a surface roughness (Ra) of 3.3 μm was used. A polyester film (A) and a 16 μm polyester film (B) were obtained. The content of dimer acid in the (II) layer of the polyester film (A) was 10 mol%.
Next, a polyester film-coated aluminum plate was obtained in the same manner as in Example 1.
The method of this example is a method for producing a polyester film for covering a metal plate, a polyester film for covering a metal plate, which is excellent in appearance and can-making properties, a method for producing a polyester film-covered metal plate, and having impact resistance. It is a method for producing a polyester film for covering a metal plate, a polyester film for covering a metal plate, and a method for producing a polyester film-covered metal plate, which is excellent in surface smoothness to obtain a metal can having excellent warm water whitening resistance on the outer surface. I can say that.
［実施例 ５］
実施例１と同様に冷却固化させた後、予熱温度６５℃、延伸温度１００℃で縦方向に３倍延伸し、ついで予熱温度６０℃、延伸温度１００℃で横方向に３倍延伸して厚みが２５μｍ（（Ｉ）層厚み６μｍ、（ＩＩ）層厚み１３μｍ）のポリエステルフィルム（Ａ）と１６μｍのポリエステルフィルム（Ｂ）を得た。ポリエステルフィルム（Ａ）の（ＩＩ）層中のダイマー酸の含有率は１０モル％であった。
次いで、実施例１と同様にしてポリエステルフィルム被覆アルミニウム板を得た。
本実施例の方法は、製缶性に優れたポリエステルフィルム被覆金属板の製造方法であり、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表面平滑性に優れた金属板被覆用ポリエステルフィルム、金属板被覆用ポリエステルフィルムの製造方法であり、ポリエステルフィルム被覆金属板の製造方法であるといえる。
[Example 5]
After cooling and solidifying in the same manner as in Example 1, the film was stretched three times in the machine direction at a preheating temperature of 65 ° C. and a stretching temperature of 100 ° C., and then stretched three times in the transverse direction at a preheating temperature of 60 ° C. and a stretching temperature of 100 ° C. Of 25 μm ((I) layer thickness 6 μm, (II) layer thickness 13 μm) were obtained as a polyester film (A) and a 16 μm polyester film (B). The content of dimer acid in the (II) layer of the polyester film (A) was 10 mol%.
Next, a polyester film-coated aluminum plate was obtained in the same manner as in Example 1.
The method of this example is a method for producing a polyester film-coated metal plate having excellent canability, and is a metal having excellent surface smoothness that provides a metal can having excellent impact resistance and resistance to warm water on the outer surface. It is a manufacturing method of a polyester film for covering a plate and a polyester film for covering a metal plate, and can be said to be a manufacturing method of a polyester film-covering metal plate.
［実施例 ６］
ポリエステルフィルム（Ａ）の（ＩＩ）層を構成するポリエステルフィルムの原料ポリエステルとしてポリエステルＡ４０重量部とポリエステルフィルム（Ａ）を得る前に切断除去した両端部を造粒して得たポリマー６０重量部とした以外は実施例１と同様にして厚みが２５μｍ（（Ｉ）層厚み６μｍ、（ＩＩ）層厚み１３μｍ）のポリエステルフィルム（Ａ）と１６μｍのポリエステルフィルム（Ｂ）を得た。ポリエステルフィルム（Ａ）の（ＩＩ）層中のダイマー酸の含有率は９モル％であった。
次いで、実施例１と同様にしてポリエステルフィルム被覆アルミニウム板を得た。
本実施例の方法は、製缶性に優れたポリエステルフィルム被覆金属板の製造方法であり、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表面平滑性に優れた金属板被覆用ポリエステルフィルム、金属板被覆用ポリエステルフィルムの製造方法であり、ポリエステルフィルム被覆金属板の製造方法であるといえる。
[Example 6]
60 parts by weight of a polymer obtained by granulating 40 parts by weight of polyester A as a raw material polyester of the polyester film constituting the (II) layer of the polyester film (A) and both ends cut and removed before obtaining the polyester film (A); A polyester film (A) having a thickness of 25 μm ((I) layer thickness of 6 μm, (II) layer thickness of 13 μm) and a 16 μm polyester film (B) were obtained in the same manner as in Example 1. The content of dimer acid in the (II) layer of the polyester film (A) was 9 mol%.
Next, a polyester film-coated aluminum plate was obtained in the same manner as in Example 1.
The method of this example is a method for producing a polyester film-coated metal plate having excellent canability, and is a metal having excellent surface smoothness that provides a metal can having excellent impact resistance and resistance to warm water on the outer surface. It is a manufacturing method of a polyester film for covering a plate and a polyester film for covering a metal plate, and can be said to be a manufacturing method of a polyester film-covering metal plate.
［比較例 １］
ポリエステルフィルム（Ａ）の（Ｉ）層を構成するポリエステルフィルムの原料ポリエステルとポリエステルフィルム（Ｂ）の原料ポリエステルとしてＰＥＴ／ＰＢＴ＝２０／８０（重量比）のポリエステルを用いた以外は実施例１と同様にして製膜しようとしたが、冷却ロール後でフィルムの両端部が割れることが多く、ポリエステルフィルムを安定して得られなかった。
この方法は、金属板被覆用ポリエステルフィルム、金属板被覆用ポリエステルフィルムの製造方法、ポリエステルフィルム被覆金属板の製造方法として好ましくない。
[Comparative Example 1]
Example 1 except that polyester of PET / PBT = 20/80 (weight ratio) was used as the raw material polyester of the polyester film constituting the (I) layer of the polyester film (A) and the raw material polyester of the polyester film (B). Although an attempt was made to form a film in the same manner, both ends of the film often cracked after the cooling roll, and the polyester film could not be stably obtained.
This method is not preferable as a polyester film for covering a metal plate, a method for producing a polyester film for covering a metal plate, and a method for producing a polyester film-covered metal plate.
［比較例 ２］
ポリエステルフィルム（Ａ）の（Ｉ）層を構成するポリエステルフィルムの原料ポリエステルとポリエステルフィルム（Ｂ）の原料としてＰＥＴ／ＰＢＴ＝７０／３０（重量比）のポリエステルを用いた以外は実施例１と同様にして厚みが２５μｍ（（Ｉ）層厚み６μｍ、（ＩＩ）層厚み１３μｍ）ポリエステルフィルム（Ａ）と１６μｍのポリエステルフィルム（Ｂ）を得た。ポリエステルフィルム（Ａ）の（ＩＩ）層中のダイマー酸の含有率は１０モル％であった。
次いで、実施例１と同様にしてポリエステルフィルム被覆アルミニウム板を得た。
この方法は、製缶性に優れたポリエステルフィルム被覆金属板の製造方法であり、かつ耐衝撃性に優れていたが、外面の耐温水白化性が劣り、金属板被覆用ポリエステルフィルム、金属板被覆用ポリエステルフィルム、金属板被覆用ポリエステルフィルムの製造方法、ポリエステルフィルム被覆金属板の製造方法として好ましくない。
[Comparative Example 2]
Same as Example 1 except that the polyester film raw material polyester constituting the (I) layer of the polyester film (A) and polyester of PET / PBT = 70/30 (weight ratio) were used as the raw material for the polyester film (B). Thus, a polyester film (A) having a thickness of 25 μm ((I) layer thickness 6 μm, (II) layer thickness 13 μm) and a polyester film (B) having a thickness of 16 μm were obtained. The content of dimer acid in the (II) layer of the polyester film (A) was 10 mol%.
Next, a polyester film-coated aluminum plate was obtained in the same manner as in Example 1.
This method is a method for producing a polyester film-coated metal plate with excellent canability and excellent impact resistance, but the outer surface is inferior in hot water whitening resistance. It is not preferable as a method for producing a polyester film for coating, a polyester film for coating a metal plate, and a method for producing a polyester film-coated metal plate.
［比較例 ３］
表面粗さ（Ｒａ）が０．０５μｍ以下の鏡面状の冷却ロールを用いた以外は実施例１と同様にして厚みが２５μｍ（（Ｉ）層厚み６μｍ、（ＩＩ）層厚み１３μｍ）のポリエステルフィルム（Ａ）と１６μｍのポリエステルフィルム（Ｂ）を得た。ポリエステルフィルム（Ａ）の（ＩＩ）層中のダイマー酸の含有率は１０モル％であった。
次いで、実施例１と同様にしてポリエステルフィルム被覆アルミニウム板を得た。
この方法は、ラミネート金属板の外観が悪く（気泡が発生しており）、製缶した際、内面側及び外面側で気泡を起点としたフィルム破れが発生し、金属板被覆用ポリエステルフィルム、金属板被覆用ポリエステルフィルム、金属板被覆用ポリエステルフィルムの製造方法、ポリエステルフィルム被覆金属板の製造方法として好ましくない。
[Comparative Example 3]
A polyester film having a thickness of 25 μm ((I) layer thickness 6 μm, (II) layer thickness 13 μm) in the same manner as in Example 1 except that a mirror-like cooling roll having a surface roughness (Ra) of 0.05 μm or less was used. (A) and a 16-micrometer polyester film (B) were obtained. The content of dimer acid in the (II) layer of the polyester film (A) was 10 mol%.
Next, a polyester film-coated aluminum plate was obtained in the same manner as in Example 1.
With this method, the appearance of the laminated metal plate is poor (bubbles are generated), and when the can is made, film breakage starting from the bubbles occurs on the inner surface side and the outer surface side, and the polyester film for covering the metal plate, the metal It is not preferable as a production method of a polyester film for coating a plate, a polyester film for coating a metal plate, or a production method of a polyester film-coated metal plate.
［比較例 ４］
表面粗さ（Ｒａ）が４．０μｍの梨地状の冷却ロールを用いた以外は実施例１と同様にして厚みが２５μｍ（（Ｉ）層厚み６μｍ、（ＩＩ）層厚み１３μｍ）のポリエステルフィルム（Ａ）と１６μｍのポリエステルフィルム（Ｂ）を得た。ポリエステルフィルム（Ａ）の（ＩＩ）層中のダイマー酸の含有率は１０モル％であった。
次いで、実施例１と同様にしてポリエステルフィルム被覆アルミニウム板を得た。
この方法は、ラミネート金属板の外観が悪く（梨地の跡型が斑状に広がり透明性が悪く）、得られた金属缶の外面側で跡型に起因したゾウリ状の斑が発生し、金属缶の商品価値が低下し、金属板被覆用ポリエステルフィルム、金属板被覆用ポリエステルフィルム、金属板被覆用ポリエステルフィルムの製造方法、ポリエステルフィルム被覆金属板の製造方法として好ましくない。
[Comparative Example 4]
A polyester film having a thickness of 25 μm ((I) layer thickness 6 μm, (II) layer thickness 13 μm) in the same manner as in Example 1 except that a satin-like cooling roll having a surface roughness (Ra) of 4.0 μm was used. A) and a 16 μm polyester film (B) were obtained. The content of dimer acid in the (II) layer of the polyester film (A) was 10 mol%.
Next, a polyester film-coated aluminum plate was obtained in the same manner as in Example 1.
In this method, the appearance of the laminated metal plate is poor (the satin trace is spread like a patch and the transparency is poor), and an elephant-like spot caused by the trace occurs on the outer surface side of the resulting metal can. This is not preferable as a polyester film for covering a metal plate, a polyester film for covering a metal plate, a method for producing a polyester film for covering a metal plate, and a method for producing a polyester film-covered metal plate.
［比較例 ５］
ポリエステルフィルム（Ａ）の（Ｉ）層および（ＩＩ）層原料としてポリエステルＡ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）のポリエステルフィルム（Ａ）と１６μｍのポリエステルフィルム（Ｂ）を得た。ポリエステルフィルム（Ａ）の（Ｉ）層および（ＩＩ）層中のダイマー酸の含有率は１０モル％であった。
次いで、実施例１と同様にしてポリエステルフィルム被覆アルミニウム板を得た。
この方法は外観に優れたポリエステルフィルム被覆金属板の製造方法であったが、ポリエステルフィルム被覆金属板（ラミネートアルミニウム板）を製缶した際、缶内面樹脂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、金属板被覆用ポリエステルフィルム、金属板被覆用ポリエステルフィルム、金属板被覆用ポリエステルフィルムの製造方法、ポリエステルフィルム被覆金属板の製造方法として好ましくない。
[Comparative Example 5]
A thickness of 25 μm ((I) layer thickness 12.5 μm, (II) layer thickness 12.) is the same as in Example 1 except that polyester A is used as the raw material (I) and (II) of the polyester film (A). 5 μm) polyester film (A) and 16 μm polyester film (B) were obtained. The content of dimer acid in the (I) layer and the (II) layer of the polyester film (A) was 10 mol%.
Next, a polyester film-coated aluminum plate was obtained in the same manner as in Example 1.
This method was a method for producing a polyester film-coated metal plate having an excellent appearance. However, when a polyester film-coated metal plate (laminated aluminum plate) was made, the inner resin of the can and the processing punch adhered to each other so that the entire opening of the can Buckling occurs around the circumference, which is not preferable as a polyester film for covering a metal plate, a polyester film for covering a metal plate, a method for producing a polyester film for covering a metal plate, and a method for producing a polyester film-covered metal plate.
［比較例 ６］
ポリエステルフィルム（Ａ）の（Ｉ）層を構成するポリエステルフィルムの原料ポリエステルとポリエステルフィルム（Ｂ）の原料ポリエステルとしてポリエステル（Ｃ）を用いた以外は実施例１と同様にして厚みが２５μｍ（（Ｉ）層厚み６μｍ、（ＩＩ）層厚み１３μｍ）のポリエステルフィルム（Ａ）と１６μｍのポリエステルフィルム（Ｂ）を得た。ポリエステルフィルム（Ａ）の（ＩＩ）層中のダイマー酸の含有率は１０モル％であった。
次いで、実施例１と同様にしてポリエステルフィルム被覆アルミニウム板を得た。
この方法は外観に優れたポリエステルフィルム被覆金属板の製造方法であったが、ポリエステルフィルム被覆金属板（ラミネートアルミニウム板）を製缶した際、缶内面樹脂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、さらに缶外面樹脂の全周にキズが発生し、金属板被覆用ポリエステルフィルム、金属板被覆用ポリエステルフィルム、金属板被覆用ポリエステルフィルムの製造方法、ポリエステルフィルム被覆金属板の製造方法として好ましくない。
[Comparative Example 6]
The thickness of the polyester film (A) is 25 μm ((I) except that the polyester (C) is used as the raw material polyester of the polyester film and the polyester film (B) constituting the (I) layer of the polyester film (A). ) Layer thickness 6 μm, (II) layer thickness 13 μm) polyester film (A) and 16 μm polyester film (B). The content of dimer acid in the (II) layer of the polyester film (A) was 10 mol%.
Next, a polyester film-coated aluminum plate was obtained in the same manner as in Example 1.
This method was a method for producing a polyester film-coated metal plate having an excellent appearance. However, when a polyester film-coated metal plate (laminated aluminum plate) was made, the inner resin of the can and the processing punch adhered to each other so that the entire opening of the can Buckling occurs around the circumference, and scratches are generated all around the outer surface of the can. Polyester film for metal plate coating, polyester film for metal plate coating, method for producing polyester film for metal plate coating, polyester film coated metal plate It is not preferable as a production method.
［比較例 ７］
ポリエステルフィルム（Ａ）の（Ｉ）層を構成するポリエステルフィルムの原料ポリエステルとポリエステルフィルム（Ｂ）の原料ポリエステルとしてＰＥＴ／ＰＢＴを用いた以外は実施例１と同様にして厚みが２５μｍ（（Ｉ）層厚み６μｍ、（ＩＩ）層厚み１３μｍ）のポリエステルフィルム（Ａ）と１６μｍのポリエステルフィルム（Ｂ）を得た。ポリエステルフィルム（Ａ）の（ＩＩ）層中のダイマー酸の含有率は１０モル％であった。
次いで、実施例１と同様にしてポリエステルフィルム被覆アルミニウム板を得た。
この方法は外観に優れたポリエステルフィルム被覆金属板の製造方法であったが、ポリエステルフィルム被覆金属板（ラミネートアルミニウム板）を製缶した際、缶内面樹脂と加工ポンチの離型性が悪く缶開口部の約１／３にわたって座屈が発生し、さらに缶外面樹脂の１／３にキズが発生したため製缶性が劣り、金属板被覆用ポリエステルフィルム、金属板被覆用ポリエステルフィルム、金属板被覆用ポリエステルフィルムの製造方法、ポリエステルフィルム被覆金属板の製造方法として好ましくない。
但し、製缶速度を３０缶／分にした場合の製缶性（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）は問題なかった。
[Comparative Example 7]
The thickness is 25 μm in the same manner as in Example 1 except that PET / PBT is used as the raw material polyester of the polyester film and the raw material polyester of the polyester film (B) constituting the (I) layer of the polyester film (A) ((I) A polyester film (A) having a layer thickness of 6 μm and a (II) layer thickness of 13 μm) and a polyester film (B) having a thickness of 16 μm were obtained. The content of dimer acid in the (II) layer of the polyester film (A) was 10 mol%.
Next, a polyester film-coated aluminum plate was obtained in the same manner as in Example 1.
This method was a method for producing a polyester film-coated metal sheet with an excellent appearance, but when a polyester film-coated metal sheet (laminated aluminum sheet) was made, the mold release of the can inner surface resin and processing punch was poor and the can opening Buckling occurred over about 1/3 of the area, and scratches occurred in 1/3 of the outer resin of the can, resulting in poor canability. Polyester film for metal plate coating, polyester film for metal plate coating, for metal plate coating It is not preferable as a method for producing a polyester film or a method for producing a polyester film-coated metal plate.
However, there was no problem in can-making performance (can releasability between can inner surface resin film and punch and occurrence of scratches on can outer surface resin film) when the can-making speed was 30 cans / minute.
注２）非晶性のため融解ピークなし。
注３）比較例７では製缶速度を３０缶／分に低下させた場合は加工ポンチの離型性、外面フィルムのキズ発生程度とも○であった。
※融点は、上段：ポリエステルフィルム（Ａ）の（Ｉ）層、中段：ポリエステルフィルム（Ａ）の（ＩＩ）層、下段：ポリエステルフィルム（Ｂ）。
Note 2) No melting peak due to amorphous nature.
Note 3) In Comparative Example 7, when the can-making speed was reduced to 30 cans / min, the mold release property of the processing punch and the degree of scratching of the outer film were good.
* Melting points: Upper: polyester film (A) (I) layer, middle: polyester film (A) (II) layer, lower: polyester film (B).
本発明のポリエステルフィルム被覆金属板の製造方法は材料ロスを少なくすることができるため、経済性に優れた製造方法であるばかりでなく、外観と製缶性（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）に優れたポリエステルフィルム被覆金属板が得られる製造方法である。さらに、本発明によって得られるポリエステルフィルム被覆金属板を製缶した場合、内容物を充填・密封した後に実施される温水殺菌処理で金属缶外面の外観不良（ポリエステルフィルムの白化）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フィルム被覆金属板の製造方法といえる。 Since the method for producing a polyester film-coated metal sheet of the present invention can reduce material loss, it is not only an economical production method, but also the appearance and can-making properties (particularly, can inner surface resin film and processing punch). This is a production method for obtaining a polyester film-coated metal plate excellent in mold release properties and scratch resistance of the outer resin film of the can. Furthermore, when the polyester film-coated metal plate obtained by the present invention can be made, poor appearance of the outer surface of the metal can (whitening of the polyester film) hardly occurs in the hot water sterilization performed after filling and sealing the contents, In addition, since the impact resistance is unlikely to decrease even when heating is performed assuming an external baking coating performed for the purpose of beautification after canning, it can be said to be an extremely useful method for producing a polyester film-coated metal sheet.
Claims (5)
表面粗さ（Ｒａ）が０．２μｍ以上、３．５μｍ以下の梨地状の冷却ロールに層状にキャストし、樹脂の両端部と中央部とを別々の静電気で独立密着させ、前記溶融樹脂膜を固化した後に少なくとも縦方向に１軸延伸することを特徴とする金属板被覆用ポリエステルフィルムの製造方法。 It is a manufacturing method of the polyester film for metal plate coating of Claim 1,
The surface roughness (Ra) is cast in a layer form on a satin-like cooling roll having a surface roughness (Ra) of 0.2 μm or more and 3.5 μm or less , and both ends and the center of the resin are independently brought into close contact with different static electricity, and the molten resin film is A method for producing a metal film-covering polyester film, wherein the metal film is uniaxially stretched at least in the longitudinal direction after solidification.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003379093A JP4258807B2 (en) | 2003-11-07 | 2003-11-07 | Polyester film for coating metal plate, method for producing the same, and method for producing polyester film-coated metal plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003379093A JP4258807B2 (en) | 2003-11-07 | 2003-11-07 | Polyester film for coating metal plate, method for producing the same, and method for producing polyester film-coated metal plate |
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| Publication Number | Publication Date |
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| JP2005138505A JP2005138505A (en) | 2005-06-02 |
| JP4258807B2 true JP4258807B2 (en) | 2009-04-30 |
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| PL3126136T3 (en) * | 2014-03-31 | 2020-10-19 | Tata Steel Ijmuiden B.V. | Polyester film having a multilayered structure for laminating to a metal substrate, metal substrate having such a polyester film and container having a component manufactured from this metal substrate |
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