JPH085160B2 - Polyester resin film laminated Sn plated steel sheet with excellent workability and corrosion resistance - Google Patents
Polyester resin film laminated Sn plated steel sheet with excellent workability and corrosion resistanceInfo
- Publication number
- JPH085160B2 JPH085160B2 JP31889589A JP31889589A JPH085160B2 JP H085160 B2 JPH085160 B2 JP H085160B2 JP 31889589 A JP31889589 A JP 31889589A JP 31889589 A JP31889589 A JP 31889589A JP H085160 B2 JPH085160 B2 JP H085160B2
- Authority
- JP
- Japan
- Prior art keywords
- resin film
- film
- amount
- steel sheet
- polyester resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229910000831 Steel Inorganic materials 0.000 title claims description 130
- 239000010959 steel Substances 0.000 title claims description 130
- 229920001225 polyester resin Polymers 0.000 title claims description 74
- 239000004645 polyester resin Substances 0.000 title claims description 74
- 230000007797 corrosion Effects 0.000 title claims description 15
- 238000005260 corrosion Methods 0.000 title claims description 15
- 239000013078 crystal Substances 0.000 claims description 100
- 238000007747 plating Methods 0.000 claims description 93
- 238000012545 processing Methods 0.000 claims description 71
- 229910052751 metal Inorganic materials 0.000 claims description 58
- 239000002184 metal Substances 0.000 claims description 58
- 230000008018 melting Effects 0.000 claims description 42
- 238000002844 melting Methods 0.000 claims description 42
- 238000010438 heat treatment Methods 0.000 claims description 36
- 229910045601 alloy Inorganic materials 0.000 claims description 19
- 239000000956 alloy Substances 0.000 claims description 19
- 238000010030 laminating Methods 0.000 claims description 17
- 229910017091 Fe-Sn Inorganic materials 0.000 claims description 15
- 229910017142 Fe—Sn Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000004070 electrodeposition Methods 0.000 claims description 5
- 229920005989 resin Polymers 0.000 description 85
- 239000011347 resin Substances 0.000 description 85
- 229920001634 Copolyester Polymers 0.000 description 82
- 238000000034 method Methods 0.000 description 49
- 238000011282 treatment Methods 0.000 description 33
- 230000000052 comparative effect Effects 0.000 description 21
- 238000005868 electrolysis reaction Methods 0.000 description 17
- 239000005028 tinplate Substances 0.000 description 17
- 230000000704 physical effect Effects 0.000 description 15
- 238000003475 lamination Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000002932 luster Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229920000098 polyolefin Polymers 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 238000007639 printing Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229910001128 Sn alloy Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 235000014171 carbonated beverage Nutrition 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 2
- 150000004782 1-naphthols Chemical class 0.000 description 2
- MMINFSMURORWKH-UHFFFAOYSA-N 3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical group O=C1OCCOC(=O)C2=CC=C1C=C2 MMINFSMURORWKH-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000012611 container material Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000011156 evaluation Methods 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
- 239000000155 melt Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229940044654 phenolsulfonic acid Drugs 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- ZVNPWFOVUDMGRP-UHFFFAOYSA-N 4-methylaminophenol sulfate Chemical compound OS(O)(=O)=O.CNC1=CC=C(O)C=C1.CNC1=CC=C(O)C=C1 ZVNPWFOVUDMGRP-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 101100096719 Arabidopsis thaliana SSL2 gene Proteins 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 101100366560 Panax ginseng SS10 gene Proteins 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910020900 Sn-Fe Inorganic materials 0.000 description 1
- 229910019314 Sn—Fe Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 238000003854 Surface Print Methods 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 239000001273 butane Substances 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 235000021443 coca cola Nutrition 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007739 conversion coating 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
- 230000003247 decreasing effect Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 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
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- FCJSHPDYVMKCHI-UHFFFAOYSA-N phenyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC=CC=C1 FCJSHPDYVMKCHI-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- -1 polytetramethylene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000005029 tin-free steel Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、加工密着性、加工耐食性の優れたポリエス
テル樹脂フイルム積層Snめっき鋼板に関するものであ
り、より詳細には、耐食性が要求され、かつ厳しい衝撃
加工あるいは、絞り加工が要求されるリベット加工を施
した缶蓋、数回の絞り加工を施した後ストレッチ加工を
施した背高缶に適したポリエステル樹脂フイルム積層Sn
めっき鋼板に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial application] The present invention relates to a polyester resin film laminated Sn-plated steel sheet excellent in processing adhesion and processing corrosion resistance, and more specifically, corrosion resistance is required, and Polyester resin film laminated Sn suitable for can lids that have been subjected to severe impact processing or rivet processing that requires drawing processing, and tall cans that have been drawn several times and then stretched
Regarding plated steel sheets.
従来、容器材料に用いられるぶりき、Cr水和酸化物層
を上層に、金属Cr層を下層にもつテインフリー スチー
ル（以下、TFS−CTと略す）、アルミニウムなどの金属
板は、一回あるいは複数回の塗装、焼付けを施された
後、加工されていた。塗装焼付け工程は、工程が煩雑で
あるばかりでなく、長時間の焼付けを必要としていた。
また、塗膜形成時に溶剤を排出するため、公害面からも
排出溶剤を特別な焼却炉に導き、焼却しなければならな
いという欠点を持っていた。最近、これらの欠点を解決
するために、熱可塑性樹脂フイルムを金属板に積層しよ
うとする試みが種々検討されている。一例として、ポリ
オレフインフイルムを金属板に積層したもの（特開昭53
−141786）、ポリエステルフイルムを接着材を用いるこ
となく金属板に積層したもの（特開昭60−47103）、二
軸延伸ポリエステルフイルムを接着剤を用いて金属板に
積層したもの（特公昭63−13829）、あるいは屈折率を
調整したポリエステル樹脂フイルムを使用して加工性の
改善をはかったものなど開示されている。Metal plates such as tin-free steel (hereinafter abbreviated as TFS-CT) and aluminum, which have been conventionally used for container materials, have a Cr hydrated oxide layer as an upper layer and a metal Cr layer as a lower layer, and are used once or It was processed after being painted and baked multiple times. The paint baking process is not only complicated, but also requires baking for a long time.
Further, since the solvent is discharged at the time of forming the coating film, there is a drawback in that the discharged solvent must be guided to a special incinerator and incinerated also in terms of pollution. Recently, in order to solve these drawbacks, various attempts have been made to stack a thermoplastic resin film on a metal plate. As an example, a laminate of a polyolefin film on a metal plate (Japanese Patent Laid-Open No. 53-53,049).
-141786), a polyester film laminated on a metal plate without using an adhesive (JP-A-60-47103), and a biaxially stretched polyester film laminated on a metal plate with an adhesive (Japanese Patent Publication No. 63- 13829), or a polyester resin film whose refractive index is adjusted to improve workability.
しかし、特開昭53−141786に開示されているポリオレ
フィンフイルムを積層した金属板を容器用材料として用
いた場合、ポリオレフィンフイルムは充填される内容物
に対してのバリヤー性が劣り、容易に腐食媒がポリオレ
フィンフイルムを透過し、金属板を腐食させやすいとい
う欠点を有している。また、ポリオレフインフイルムは
融点が100〜170℃の範囲にあるため、製缶工程で外面印
刷などの後の加熱工程（通常、170〜205℃）で、ポリオ
レフインフイルムは溶融状態になり、製缶工具に軟化接
着し、作業製を著しく低下させる危険性があり、容器用
材料に適した積層材料でない。However, when a metal plate laminated with a polyolefin film disclosed in JP-A-53-141786 is used as a material for a container, the polyolefin film has a poor barrier property with respect to the contents to be filled and is easily corroded. Has the drawback that it permeates the polyolefin film and easily corrodes the metal plate. In addition, since the polyolefin film has a melting point in the range of 100 to 170 ° C, the polyolefin film becomes a molten state in the heating step (usually 170 to 205 ° C) after outer surface printing in the can making process, and the can making tool It is not a laminated material suitable as a container material because it has a risk of softening and adhesion to, and significantly lowering workability.
特公昭60−47103,特公昭63−13829に開示されている
接着剤を用いることなしに、あるいは接着剤を用いてポ
リエステル樹脂フイルムを積層した金属板は、本発明で
要求される厳しい衝撃加工あるいは深絞り加工を施す
と、ポリエステル樹脂フイルムが剥離したり、ポリエス
テル樹脂フイルムにクラックが入り、その部分を起点と
して下地金属板の腐食が促進され、本発明の目的とする
厳しい加工用途に適した材料ではない。これらの欠点を
解決するため、特願昭63−75837（特開平１−249331,特
公平５−71035）に開示したように、少なくともエステ
ル反復単位の75〜99％がエチレンテレフタレート単位で
ある共重合ポリエステル樹脂フイルムを金属板に積層し
たものを開発した。しかしながら、特願昭63−75837に
おいて共重合ポリエステル樹脂フイルムが積層される金
属板にTFS−CTを使用した場合、数回の深絞り工程で得
られた深絞り缶に炭酸飲料などを充填し、室温で約１ケ
月貯蔵した時、加工部の共重合ポリエステル樹脂フイル
ムの微小クラックから孔食を起こすことが多い。これは
共重合ポリエステル樹脂フイルムの積層工程、深絞り工
程等におけるごみなどの混入に起因するものであり、こ
れらの工程を厳重に管理しなければならないという欠点
を有している。また通常の方法で製造されるSnめっき鋼
板、いわゆるぶりきを使用した場合、TFS−CTを使用し
た場合にみられる共重合ポリエステル樹脂フイルムの微
小クラック部からの孔食は、Snの耐食性によって著しく
減少する。しかし、通常のTFS−CTに積層する共重合ポ
リエステル樹脂フイルム（フイルムの面方向の屈折率1.
6000〜1.6600、フイルムの厚み方向の屈折率1.5000〜1.
5500）、及び積層条件でフイルムを積層した場合、数回
の深絞り加工後、さらにネックイン加工を施すと、共重
合ポリエステル樹脂フイルムが剥離する危険性がある。
すなわち、ぶりきはTFS−CTより共重合ポリエステル樹
脂フイルムの加工密着性が劣るため、共重合ポリエステ
ル樹脂フイルムの製膜時に形成された物性では、厳しい
加工を要求される用途に使用することは困難であった。Without using the adhesive disclosed in JP-B-60-47103, JP-B-63-13829, or a metal plate laminated with a polyester resin film using the adhesive, a severe impact processing required in the present invention or When subjected to deep drawing, the polyester resin film peels off or cracks occur in the polyester resin film, the corrosion of the underlying metal plate is promoted starting from that portion, and a material suitable for the severe processing purpose of the present invention is not. In order to solve these drawbacks, as disclosed in Japanese Patent Application No. 63-75837 (JP-A-1-249331, Japanese Patent Publication No. 5-71035), a copolymerization in which at least 75 to 99% of ester repeating units are ethylene terephthalate units. We developed a laminate of polyester resin film on a metal plate. However, when TFS-CT is used for the metal plate on which the copolyester resin film is laminated in Japanese Patent Application No. 63-75837, a deep-draw can obtained in several deep-drawing steps is filled with a carbonated beverage or the like, When stored for about 1 month at room temperature, pitting often occurs due to minute cracks in the copolyester resin film in the processed part. This is due to the inclusion of dust in the step of laminating the copolyester resin film, the deep drawing step, etc., and has a drawback that these steps must be strictly controlled. In addition, Sn-plated steel sheet produced by a normal method, when using so-called tinplate, pitting corrosion from the microcrack portion of the copolyester resin film found when using TFS-CT is significantly due to the corrosion resistance of Sn. Decrease. However, a copolyester resin film (a refractive index in the plane direction of the film of 1.
6000 to 1.6600, Refractive index in the thickness direction of the film 1.5000 to 1.
5500), and when the film is laminated under the laminating conditions, the copolyester resin film may be peeled off if the neck-in processing is performed after deep drawing several times.
In other words, tinplate is inferior to TFS-CT in processing cohesiveness of the copolyester resin film, so it is difficult to use it for applications that require severe processing because of the physical properties formed during film formation of the copolyester resin film. Met.
上記の問題点を解決すべく種々検討した結果、第一の
方法として、Snが鋼板表面に接着していない、すなわ
ち、第１図のａに示す通常のぶりきに対してｂに示すよ
うにSnの電析結晶の大きいSnめっきを施すことにより、
鋼板表面とSn層が離れた状態の部分を散在させ、ついで
電着したSnを加熱溶融せずに、金属Cr層、さらにその上
にCr水和酸化物層を必要量形成させた鋼板に、共重合ポ
リエステル樹脂フイルムを面方向の結晶配向を調整しな
がら積層する方法によって、また、第二の方法として、
通常の方法でめっきされたSnめっき鋼板のSnめっき量を
限定し、その上層に金属Cr層及びCr水和酸化物層を必要
量施し、かつ、その上に積層する共重合ポリエステル樹
脂フイルムの物性を厳しい加工に耐えるように、積層
時、あるいは積層後調整することによって、本発明の目
的である厳しい加工に耐え、かつ、加工後の耐食性の優
れたポリエステル樹脂フイルム積層Snめっき鋼板を得る
ことができた。As a result of various investigations to solve the above problems, as a first method, Sn is not adhered to the surface of the steel sheet, that is, as shown in b with respect to the normal tint shown in a of FIG. By applying Sn plating with large Sn electrodeposition crystals,
The steel sheet surface and the portion where the Sn layer is separated are scattered, and then the electrodeposited Sn is not heated and melted, but a metal Cr layer, and a steel sheet on which a necessary amount of a Cr hydrated oxide layer is formed thereon, By the method of laminating the copolyester resin film while adjusting the crystal orientation in the plane direction, and as the second method,
Limit the Sn plating amount of Sn-plated steel sheet plated by the usual method, apply the required amount of metal Cr layer and Cr hydrated oxide layer on the upper layer, and the physical properties of the copolymerized polyester resin film laminated on it To withstand severe processing, during lamination, or by adjusting after lamination, to withstand the severe processing that is the object of the present invention, and obtain a polyester resin film laminated Sn-plated steel sheet with excellent corrosion resistance after processing. did it.
以下、本発明の内容について詳細に説明する。 Hereinafter, the contents of the present invention will be described in detail.
本発明の請求項１の発明は、鋼板表面とSn層が直接接
着していない部分が散在するSnめっきを施すことが重要
な要件であり、また、本発明の特徴である。この表面処
理鋼板の特徴は、共重合ポリエステル樹脂フイルムとの
直接の加工密着性に対しては、最表層の金属CrとCr水和
酸化物層が受け持つが、Sn層と金属Cr等の加工密着性
は、Snの電析結晶を大きくして表面を粗くし、見掛け上
の接着面積の拡大とクサビ効果によって、また、鋼板と
Sn層との加工密着性は、ポリエステル樹脂フイルムを加
熱積層する際に形成されるFe−Sn合金層が破壊され易い
ので、合金層の形成しない面をつくり、この面が加工時
に加圧圧着され密着強度を維持することによって、ポリ
エステル樹脂フイルムとSnめっき鋼板との加工密着性の
改善をはかるものである。このため、鋼板表面とSn層が
直接接着していない面積の比率は本発明にとって重要な
因子である。電着したSnによる鋼板表面の未接着比率が
25％以下になると加工により、Fe−Sn合金層の破壊部が
増大し、結果的に厳しい加工に耐えうる限界を越え、フ
イルムの密着性は確保できなくなる。また、重なりあっ
て電析したSnの一つの結晶の直径が通常のぶりきのよう
に判別できないほど小さい場合や、Snめっき層の厚さが
１μｍ以下と薄いので、大きすぎると表面の平滑度が向
上し、ポリエステル樹脂フイルムの密着性に対する見掛
け上の接着面積の拡大、及びクサビ効果が期待できな
い。よって、電析Snの結晶の直径は0.2〜５μｍの範囲
が好ましく、より好ましくは0.3〜１μｍの範囲であ
る。また、効果の期待できる同結晶の占有率は60％以上
必要である。つぎに、電着されるSn量は1.0〜6.4g/m2、
より好ましくは1.4〜4.6g/m2の範囲である。本発明のSn
めっき処理は、ポリエステル樹脂フイルムの加熱圧着等
の加熱処理によってSn−Fe合金層の成長面積を少なくし
ているのが特徴であるが、Sn量が1.0g/m2以下と薄くな
ると、Fe−Sn合金層の成長する面は金属Cr層の近くまで
Fe−Sn合金層が成長し、その部位だけは加工密着性を悪
くする。また、加工等によるフイルムクラックからの孔
食を抑制するに足りる量のSnめっき量に達しえないた
め、耐孔食性が劣り好ましくない。Sn量が6.4g/m2以上
に厚くなると、Snめっき後の表面の平滑度が向上し、ポ
リエステル樹脂フイルムとの加工密着性が改善されな
い。また、経済的見地からもSnを増量することは好まし
くない。In the invention of claim 1 of the present invention, it is an important requirement to apply Sn plating in which there are scattered portions where the surface of the steel sheet and the Sn layer are not directly bonded, and it is a feature of the present invention. The characteristic of this surface-treated steel sheet is that the direct adhesion of the copolyester resin film is processed by the outermost metal Cr and Cr hydrate oxide layer, but the Sn layer and the metal Cr are processed and adhered. As for the property, the Sn electrodeposited crystal is enlarged to make the surface rough, and due to the expansion of the apparent adhesion area and the wedge effect,
Since the Fe-Sn alloy layer, which is formed when the polyester resin film is heated and laminated, is easily broken, the process adhesion with the Sn layer creates a surface on which the alloy layer is not formed, and this surface is pressed and pressed during processing. By maintaining the adhesion strength, the work adhesion between the polyester resin film and the Sn-plated steel sheet is improved. Therefore, the ratio of the area where the surface of the steel sheet and the Sn layer are not directly bonded is an important factor for the present invention. The unbonded ratio of the steel plate surface due to electrodeposited Sn is
When the content is 25% or less, the fractured portion of the Fe-Sn alloy layer increases due to the processing, and as a result, the limit that can withstand severe processing is exceeded, and the film adhesion cannot be secured. In addition, when the diameter of one Sn crystal deposited due to overlap is too small to be discerned as in ordinary tinplate, or the thickness of the Sn plating layer is as thin as 1 μm or less, the surface smoothness is too large. Of the polyester resin film, the apparent adhesion area to the adhesion of the polyester resin film and the wedge effect cannot be expected. Therefore, the diameter of the crystallized Sn crystal is preferably in the range of 0.2 to 5 μm, and more preferably in the range of 0.3 to 1 μm. In addition, the occupancy of the crystal, which is expected to be effective, must be 60% or more. Next, the amount of Sn to be electrodeposited is 1.0 to 6.4 g / m 2 ,
The range is more preferably 1.4 to 4.6 g / m 2 . Sn of the present invention
The plating process is characterized by reducing the growth area of the Sn-Fe alloy layer by heat treatment such as thermocompression bonding of a polyester resin film, but when the Sn amount becomes 1.0 g / m 2 or less, Fe- The growth surface of the Sn alloy layer is close to the metal Cr layer
The Fe-Sn alloy layer grows and only at that portion deteriorates the work adhesion. Further, since the Sn plating amount that is sufficient to suppress pitting corrosion from film cracks due to processing or the like cannot be reached, the pitting corrosion resistance is poor, which is not preferable. When the Sn amount becomes 6.4 g / m 2 or more, the smoothness of the surface after Sn plating is improved, and the processing adhesion with the polyester resin film is not improved. In addition, it is not preferable to increase the Sn content from the economical point of view.
つぎに、鋼板表面とSn層が直接接着しない部分をも
ち、かつ、電析Snの一つの結晶の直径が0.2〜５μｍに
なるSnめっき方法について示す。Snの電気めっきを行う
時、鋼板表面上のSnイオンの拡散層（＜100μｍ）に加
える電圧を小さくすると、Snの電析核が分散されてめっ
きされる。そのため、一般の電気めっき法によるSnめっ
きの場合は、光沢剤と言われる拡散層の電位差を大きく
するための分極剤を使用し、かつ、電解電圧を水の電気
分解によるH2ガスの発生しない範囲内で大きくして、鋼
板上の全面にSnの電析核を均一生成させて、金属光沢の
ある平滑なめっきを行う方法をとっている。この金属光
沢のある平滑なめっきができる範囲を一般に、電解電圧
と電解電流が正比例の関係があることから、適正電流密
度範囲という。ぶりきの製造の場合、常にこの適正電流
密度範囲で電気めっきできるように、めっき温度、めっ
き処理タンク数の切替え等で管理している。このぶりき
の製造条件に対し本発明の場合は、Snめっき条件におい
て、この適正電流密度範囲より低い電流密度でSnめっき
をすることで、第１図に示した特徴のあるSnの形態をし
た、Snめっき鋼板を製造することができる。前記したよ
うに、鋼板表面Snイオンの拡散層に加わる電圧を小さく
すると、Snの電析核がランダムに形成するが、さらに電
解を同じ条件で続けると、初期の電析核にSnの電析が集
中して起こり、Snの結晶が大きくなっていく、Snの結晶
が大きくなると隣の結晶と接合し、鋼板表面はSn層で覆
われてしまうが、初期にSnの電析核のないところは、鋼
板とSn層は完全に接着してない状態で残る。この状態で
Snの融点以下で加熱すると、Snの形態が変化しないの
で、Feの個体拡散によるFe−Sn合金の成長は初期にSnの
電析核が起きた所に限られてしまう。Fe−Sn合金層は加
工には破壊され易いが、この鋼板表面とSn層が直接接着
していない部分が加工によって密着し、結合して加工後
の密着性を維持する。なお、鋼板表面とSn層が直接接着
していないことを確認するには、Snめっき後、Snの融点
以下で加熱をし、NaOH水溶液中で金属Snだけを陽極電解
で溶かし、残留したFe−Sn合金層の成長面積をSnのＸ線
回析法で求めればよい。第２図は、浴組成（SnSO4;80g/
，フェノールスルホン酸;60g/，エトキシ化α−ナ
フトール;10g/）、ライン製造条件（浴温;50℃，ライ
ンスピード;300m/min,適正電流密度範囲;22〜36A/dm2）
の条件で、電流密度;30A/dm2で処理したぶりきと、本発
明の処理条件にある電流密度;11A/dm2で処理したSnめっ
き鋼板を210℃で加熱した時の、加熱時間に対するFe−S
n合金層の生成量を示したものである。この図からも、
適正電流密度範囲より低い電流密度で電解すると、Fe−
Sn合金層の成長が少なく、Fe−Sn合金層の成長する面積
がSn層の面積より小さくなっていることが判断できる。
また、本発明のSnめっき鋼板を実際のラインで製造する
場合の管理方法は簡単で、Snめっきの電解電流密度を下
げていくと、大きく成長したSnの結晶の乱反射によりSn
めっき鋼板全体が金属光沢から白く無金属光沢に変化す
るので、この白く無金属光沢の色調を維持するように管
理すればよい。Next, the Sn plating method will be described in which the surface of the steel sheet and the Sn layer do not directly adhere to each other and the diameter of one crystal of the deposited Sn is 0.2 to 5 μm. When performing Sn electroplating, if the voltage applied to the Sn ion diffusion layer (<100 μm) on the surface of the steel sheet is made small, Sn electrodeposition nuclei are dispersed and plated. Therefore, in the case of Sn plating by the general electroplating method, a polarizing agent for increasing the potential difference of the diffusion layer, which is called a brightening agent, is used, and the electrolysis voltage does not generate H 2 gas due to electrolysis of water. By increasing the size within the range, Sn electrodeposition nuclei are uniformly generated on the entire surface of the steel sheet, and smooth plating with metallic luster is performed. The range in which smooth plating with metallic luster is possible is generally called an appropriate current density range because the electrolysis voltage and the electrolysis current have a direct proportional relationship. In the manufacturing of tinplate, the plating temperature and the number of plating tanks are controlled so that electroplating can always be performed within this appropriate current density range. In the case of the present invention with respect to this tin plate manufacturing condition, Sn plating was carried out at a current density lower than the appropriate current density range under the Sn plating condition, whereby the characteristic Sn form shown in FIG. 1 was obtained. , Sn-plated steel sheet can be manufactured. As described above, when the voltage applied to the diffusion layer of the steel plate surface Sn ions is reduced, Sn electrodeposited nuclei are formed randomly, but if electrolysis is continued under the same conditions, the Sn electrodeposited on the initial electrodeposited nuclei. Occurs in a concentrated manner, the Sn crystal grows larger, and when the Sn crystal grows larger, it joins with the adjacent crystal and the steel sheet surface is covered with the Sn layer, but in the initial stage where there is no Sn deposition nucleus. Remains in the state where the steel sheet and the Sn layer are not completely bonded. In this state
When heated below the melting point of Sn, the morphology of Sn does not change, so the growth of the Fe-Sn alloy due to solid diffusion of Fe is limited to the place where the nuclei of electrodeposition of Sn occur in the initial stage. Although the Fe-Sn alloy layer is easily broken during processing, the surface of the steel sheet and the portion where the Sn layer is not directly adhered adhere to each other by processing, and bond to maintain the adhesion after processing. Incidentally, in order to confirm that the steel sheet surface and the Sn layer are not directly bonded, after Sn plating, heating below the melting point of Sn, only metallic Sn is dissolved by anodic electrolysis in a NaOH aqueous solution, and the residual Fe- The growth area of the Sn alloy layer may be determined by the Sn X-ray diffraction method. Fig. 2 shows the bath composition (SnSO 4 ; 80 g /
, Phenolsulfonic acid; 60g /, Ethoxylated α-naphthol; 10g /), Line manufacturing conditions (bath temperature; 50 ℃, line speed; 300m / min, appropriate current density range: 22 to 36A / dm 2 )
Under the conditions of current density; tinplate treated with 30 A / dm 2 and current density under the treatment conditions of the present invention; when Sn-plated steel sheet treated with 11 A / dm 2 was heated at 210 ° C., with respect to heating time Fe-S
It shows the amount of n-alloy layer produced. Also from this figure,
If electrolysis is performed at a current density lower than the appropriate current density range, Fe-
It can be judged that the growth of the Sn alloy layer is small and the growing area of the Fe—Sn alloy layer is smaller than the area of the Sn layer.
Further, the management method in the case of manufacturing the Sn-plated steel sheet of the present invention in an actual line is simple, and when the electrolytic current density of Sn plating is lowered, Sn is diffused due to the diffuse reflection of crystals of Sn that have grown greatly.
Since the entire plated steel sheet changes from metallic luster to white and non-metallic luster, it may be controlled so as to maintain the color tone of the white and non-metallic luster.
つぎに、Snめっき後、Snの上層に形成される金属Cr及
びCr水和酸化物層のめっき量範囲について示す。金属Cr
の量は16〜120mg/m2の範囲に、より好ましくは20〜100m
g/m2の範囲にコントロールすることが望ましい。一般の
溶接缶用低Snめっき鋼板は、耐食性にとって必要である
電解Crめっき処理層が、溶接性にとっては悪影響を与え
るので、金属Cr量とCr水和酸化物層量の総和で、Cr量と
して20mg/m2以内（金属Cr量＜15mg/m2）のものが市販さ
れている。しかし、この範囲のCr量は本発明の目的であ
る厳しい加工に対して、一般の共重合等したポリエステ
ル樹脂フイルムの加工密着性を十分に得ることはできな
い。本発明の表面処理鋼板は、ポリエステル樹脂フイル
ムとの密着性は、Snめっき鋼板の最表層にある金属Crと
Cr水和酸化物の層で維持しているので、金属Cr量が16mg
/m2以下では鋼板自体の露出が多く、フイルムとの十分
な密着性は得られない。しかし、金属Cr量が増加するに
つれて、加工時、積層されたポリエステル樹脂フイルム
に微細なクラックが入り易くなること、また、加工密着
性も金属Cr量が120mg/m2以上からはより改善されないの
で、金属Cr量を120mg/m2以上にすることは好ましくな
い。Next, the range of plating amounts of the metallic Cr and Cr hydrated oxide layers formed on the Sn upper layer after Sn plating will be described. Metal Cr
In the range of 16 to 120 mg / m 2 , more preferably 20 to 100 m
It is desirable to control in the range of g / m 2 . Low Sn-plated steel plates for general welding cans have an electrolytic Cr plating layer, which is necessary for corrosion resistance, which adversely affects weldability, so the sum of the amount of metallic Cr and the amount of Cr hydrated oxide layer is the Cr amount. Those with a content of 20 mg / m 2 or less (metal Cr content <15 mg / m 2 ) are commercially available. However, the Cr content in this range cannot sufficiently obtain the processing adhesiveness of a general polyester resin film subjected to copolymerization and the like for the severe processing which is the object of the present invention. The surface-treated steel sheet of the present invention, the adhesion with the polyester resin film, and the metal Cr in the outermost layer of the Sn-plated steel sheet
Since it is maintained in a layer of Cr hydrated oxide, the amount of metallic Cr is 16 mg.
If it is less than / m 2 , the steel sheet itself is exposed to a large extent and sufficient adhesion with the film cannot be obtained. However, as the amount of metal Cr increases, during processing, fine cracks are likely to occur in the laminated polyester resin film, and the processing adhesion is not further improved when the amount of metal Cr is 120 mg / m 2 or more. However, it is not preferable to set the amount of metallic Cr to 120 mg / m 2 or more.
つぎに、Cr水和酸化物の量は、Cr量として５〜30mg/m
2、より好ましくは７〜20mg/m2の範囲にすることが望ま
しい。水素結合基を持つCr水和酸化物は、有機被膜との
接着性に優れているので、最低、Cr量として5mg/m2は必
要である。これ以下のCr量ではCr水和酸化物層の均一性
が悪く、十分な密着性は得られない。しかし、Cr水和酸
化物の量がCr量として30mg/m2以上なると、ポリエステ
ル樹脂フイルムとの加工密着性がそれ以上向上せず、逆
にCr水和酸化物層が表面の美観を著しく損なうため好ま
しくない。Next, the amount of Cr hydrate oxide is 5 to 30 mg / m as the amount of Cr.
2 , more preferably in the range of 7 to 20 mg / m 2 . Since the hydrated Cr oxide having a hydrogen bonding group has excellent adhesion to the organic film, a minimum Cr amount of 5 mg / m 2 is required. If the amount of Cr is less than this, the uniformity of the Cr hydrated oxide layer is poor and sufficient adhesion cannot be obtained. However, when the amount of Cr hydrated oxide is 30 mg / m 2 or more as the amount of Cr, the process adhesion with the polyester resin film is not further improved, and on the contrary, the Cr hydrated oxide layer significantly impairs the appearance of the surface. Therefore, it is not preferable.
つぎに、本発明のSnめっき鋼板に金属Cr及びCr水和酸
化物を析出させる方法について示す。TFS−CTのように
鋼板上に金属Cr等を電析させる場合に比べ、Snめっき鋼
板のようにSnめっき層上に金属Cr等を電析させること
は、より困難である。Snめっき層に金属Crを電析させる
には、鋼板の場合よりCrイオンの拡散層に大きな電圧を
加える必要がある。電解電圧を大きくする方法として、
浴抵抗を上げて定電流電解するのが一般的である。すな
わち、CrO3の浴濃度をTFS−CT処理浴の1/3以下にし、電
解電流をTFS−CTの処理条件で電解すると、電解電圧は
大きくなり、金属CrがSnめっき層上に均一に析出する。
例えば、浴組織（CrO3;30g/,H2SO4;0.4g/）の浴
で、陰極電解電流密度30A/dm2以上の条件で、金属CrとC
r水和酸化物を同時に析出させることができる。Next, a method for depositing metal Cr and Cr hydrated oxide on the Sn-plated steel sheet of the present invention will be described. It is more difficult to deposit metal Cr or the like on the Sn plating layer as in the Sn-plated steel sheet, as compared with the case of depositing metal Cr or the like on the steel sheet as in TFS-CT. In order to deposit metal Cr on the Sn plating layer, it is necessary to apply a larger voltage to the Cr ion diffusion layer than in the case of a steel sheet. As a method of increasing the electrolysis voltage,
It is common to increase the bath resistance and carry out constant current electrolysis. That is, when the bath concentration of CrO 3 is set to 1/3 or less of that of the TFS-CT treatment bath, and the electrolysis current is electrolyzed under the treatment conditions of TFS-CT, the electrolysis voltage increases and the metal Cr is uniformly deposited on the Sn plating layer. To do.
For example, in a bath with a bath structure (CrO 3 ; 30g /, H 2 SO 4 ; 0.4g /), under conditions of cathode electrolysis current density 30A / dm 2 or more, metal Cr and C
The r-hydrated oxide can be simultaneously deposited.
つぎに、積層される共重合ポリエステル樹脂フイルム
は少なくともエステル反復単位の75〜99％がエチレンテ
レフタレート単位からなり、残りの１〜25％のエステル
反復単位は、フタル酸、イソフタル酸、テレフタル酸、
コハク酸、アゼライン酸、アジビン酸、セバチン酸、ド
デカンジオン酸、ジフェニルカルボン酸、2.6ナフタレ
ンジカルボン酸、1.4シクロヘキサンジカルボン酸、無
水トリメット酸の１種あるいは２種以上の酸成分と、エ
チレングリコール、1.4ブタンジオール、1.5ベンタンジ
オール、1.6ヘキサンジオール、プロピレングリコー
ル、ポリテトラメチレングリコール、トリメチレングリ
コール、トリエチレングリコール、ネオペンチルグリコ
ール、1.4シクロヘキサンジメタノール、トリメチロー
ルプロパン、ペンタエリスリトールの１種あるいは２種
以上の飽和多価アルコールの重縮合によって得られたポ
リエステル樹脂フイルムから軟化開始温度、結晶融解温
度、破断伸びによって選択されることが必要である。Next, at least 75 to 99% of the ester repeating units of the copolymerized polyester resin film to be laminated are ethylene terephthalate units, and the remaining 1 to 25% of the ester repeating units are phthalic acid, isophthalic acid, terephthalic acid,
One or more acid components of succinic acid, azelaic acid, adibic acid, sebacic acid, dodecanedioic acid, diphenylcarboxylic acid, 2.6 naphthalene dicarboxylic acid, 1.4 cyclohexanedicarboxylic acid, trimetic anhydride, and ethylene glycol, 1.4 butane Saturation of one or more of diol, 1.5-pentanediol, 1.6-hexanediol, propylene glycol, polytetramethylene glycol, trimethylene glycol, triethylene glycol, neopentyl glycol, 1.4 cyclohexanedimethanol, trimethylolpropane and pentaerythritol. It is necessary to select a polyester resin film obtained by polycondensation of a polyhydric alcohol according to the softening start temperature, the crystal melting temperature and the elongation at break.
この共重合ポリエステル樹脂フイルムは、樹脂を公知
の押出機によってフイルム成型され、未延伸共重合ポリ
エステル樹脂フイルムとしても本発明に供し得るが、フ
イルム成型後、縦横二方向に延伸した後、熱固定工程を
経たものの方が、フイルムのバリヤー性の点から好まし
い。成型された共重合ポリエステル樹脂フイルムを選択
するための第一の要因である軟化開始温度は170〜230℃
の範囲のものが好ましい。ここでいう軟化開始温度と
は、熱機械的分析装置（TMA100;セイコー電子工業
（株）製）を用いて、10℃／分の昇温速度で昇温した時
の針が共重合ポリエステル樹脂フイルムに侵入開始する
時の温度をいう。軟化開始温度が230℃以上になると、
共重合ポリエステル樹脂フイルムの加工性が低下し、深
絞り加工を施すとクラックが入りやすくなる。また、軟
化開始温度が170℃以下になると、製缶工程で缶外面に
施した印刷インクを焼き付ける温度が軟化開始温度より
高いため、積層された共重合ポリエステル樹脂フイルム
が軟化し、作業製を著しく低下させるので実用的でな
い。This copolymerized polyester resin film is formed into a film by a known extruder, and can be used in the present invention as an unstretched copolymerized polyester resin film. It is more preferable from the viewpoint of the barrier property of the film. The first factor for selecting a molded copolyester resin film is a softening start temperature of 170 to 230 ° C.
The range of is preferable. As used herein, the softening start temperature is a thermo-mechanical analyzer (TMA100; manufactured by Seiko Denshi Kogyo Co., Ltd.), and the needle when the temperature is raised at a heating rate of 10 ° C./min is a polyester resin film. The temperature at the start of invasion. When the softening start temperature reaches 230 ° C or higher,
The processability of the copolyester resin film decreases, and cracking tends to occur when deep drawing is performed. Further, when the softening start temperature is 170 ° C. or lower, the temperature at which the printing ink applied to the outer surface of the can in the can making process is higher than the softening start temperature, so that the laminated copolyester resin film is softened, and the working product is remarkably manufactured. It is not practical because it lowers.
共重合ポリエステル樹脂フイルムを選択するための第
二の要因は、共重合ポリエステル樹脂フイルムの結晶融
解温度であり、これは本発明において重要な因子の一つ
である。ここでいう結晶融解温度とは、示差走査熱量計
（SS10;セイコー電子工業（株）製）により、10℃／分
の昇温速度で昇温した時、吸熱ピークが認められるが、
その吸熱ピークの最大ピーク深さを示す温度でいう。The second factor for selecting the copolyester resin film is the crystal melting temperature of the copolyester resin film, which is one of the important factors in the present invention. The crystal melting temperature here means that an endothermic peak is observed by a differential scanning calorimeter (SS10; manufactured by Seiko Denshi Kogyo Co., Ltd.) when the temperature is raised at a heating rate of 10 ° C./min.
It is the temperature at which the maximum peak depth of the endothermic peak is shown.
本発明は共重合ポリエステル樹脂フイルムの結晶融解
温度が206〜238℃の範囲のものが使用できる。その理由
として、共重合ポリエステル樹脂フイルムをSnめっき鋼
板に加熱圧着によって積層する場合、Snが溶融すると、
Sn層上の金属Cr層等が破壊され、フイルムとSnめっき鋼
板との密着を悪くする。そのため、Snめっき層を持つ鋼
板にフイルムを積層する場合、その時の温度はSnの融点
以下で行うことが前提となる。フイルムの積層温度に関
してもう一つの問題は、ポリエステル樹脂フイルムは加
熱を受けると、結晶の配向が変化することである。第３
図は二軸延伸した共重合ポリエステル樹脂フイルムを鋼
板に積層した状態で、各温度で６分間加熱した時に変化
した面方向の結晶配向度をＸ線回折の値で示したもので
あるが、二軸延伸した共重合ポリエステル樹脂フイルム
は硝子転位温度を過ぎてから結晶融解温度の−10℃ま
で、面方向の結晶配向が増加する傾向を示す。本発明は
共重合ポリエステル樹脂フイルムの加工性に直接関係す
る面方向の結晶配向係数を0.100以下にしないとフイル
ムの加工強度が強過ぎて、厳しい加工に耐えられなくフ
イルムの剥離を生ずることがある。一般の共重合ポリエ
ステル樹脂フイルムが製膜時にもっている面方向の結晶
配向係数（＞0.100）では加工性に問題があり、フイル
ム積層時に面方向の結晶配向係数を下げる方向にしなけ
ればならない。このため、共重合ポリエステル樹脂フイ
ルムを積層する温度は、結晶融解温度の−10℃以内で積
層しなければならない。実際には面方向の結晶配向が増
加しない安全なフイルム積層温度として、結晶融解温度
の−６℃以内にすることが望ましく、したがって、共重
合ポリエステル樹脂フイルムの結晶融解温度の上限は23
8℃となる。また共重合ポリエステル樹脂フイルムの結
晶融解温度が206℃以下になると、製缶工程において、
共重合ポリエステル樹脂フイルムの上に印刷を施す際、
インク焼付け固定時の加熱（205℃以下）によってフイ
ルム自体が溶融し、使用に耐えなくなる。In the present invention, a copolymer polyester resin film having a crystal melting temperature in the range of 206 to 238 ° C. can be used. The reason is that when the copolyester resin film is laminated on the Sn-plated steel sheet by thermocompression bonding, when Sn melts,
The metal Cr layer and the like on the Sn layer are destroyed, and the adhesion between the film and the Sn-plated steel sheet deteriorates. Therefore, when laminating a film on a steel sheet having a Sn plating layer, it is premised that the temperature at that time is set to be equal to or lower than the melting point of Sn. Another problem with the film stacking temperature is that the polyester resin film changes its crystal orientation when heated. Third
The figure shows the degree of crystal orientation in the plane direction, which was changed by heating for 6 minutes at each temperature in the state where the biaxially stretched copolyester resin film was laminated on the steel plate, as a value of X-ray diffraction. The axially stretched copolyester resin film shows a tendency that the crystal orientation in the plane direction increases after the glass transition temperature is reached and until the crystal melting temperature is -10 ° C. The present invention, if the crystal orientation coefficient in the plane direction, which is directly related to the processability of the copolyester resin film, is set to 0.100 or less, the film processing strength is too strong, and the film may peel without being able to withstand severe processing. . The crystal orientation coefficient in the plane direction (> 0.100) that a general copolyester resin film has during film formation has a problem in workability, and the crystal orientation coefficient in the plane direction must be lowered when laminating the film. Therefore, the temperature at which the copolyester resin film is laminated must be within -10 ° C of the crystal melting temperature. Actually, it is desirable to set the safe film laminating temperature at which the crystal orientation in the plane direction does not increase within -6 ° C of the crystal melting temperature. Therefore, the upper limit of the crystal melting temperature of the copolyester resin film is 23
8 ℃. When the crystal melting temperature of the copolyester resin film becomes 206 ° C. or lower, in the can manufacturing process,
When printing on the copolyester resin film,
The film itself melts due to the heating (205 ° C or less) when the ink is baked and fixed, making it unusable.
共重合ポリエステル樹脂フイルムを選択するための第
三の要因は、フイルムの破断伸び範囲である。本発明で
使用する共重合ポリエステル樹脂フイルムの破断伸びは
150〜400％の範囲にあることが望ましい。ここで示す破
断伸びは通常の引張り試験機により、25℃の一定温度、
引張り速度100mm/分で引張り試験を行い求められる。特
に、共重合ポリエステル樹脂フイルムの破断伸びは縦、
横二方向だけでなく、フイルム面内の全方位においてこ
の範囲を満足することが好ましい。破断伸びが150％以
下でなると、共重合ポリエステル樹脂フイルムの加工性
が乏しくなり、深絞り加工、衝撃加工のような厳しい加
工を施すと、フイルムに延性がないため、クラックが入
りやすくなるので、好ましくない。また、破断伸びが40
0％以上になると、押出機からフイルムを成型する時、
フイルムに厚さむらが生じやすくなり、特に、二軸延伸
工程等で破断しやすくなり、実用的でない。The third factor for selecting the copolyester resin film is the breaking elongation range of the film. The breaking elongation of the copolyester resin film used in the present invention is
It is preferably in the range of 150 to 400%. The breaking elongation shown here is a constant tensile tester at a constant temperature of 25 ° C,
It can be obtained by conducting a tensile test at a pulling speed of 100 mm / min. In particular, the elongation at break of the copolyester resin film is
It is preferable to satisfy this range not only in the two lateral directions but also in all directions in the film plane. When the elongation at break is 150% or less, the processability of the copolyester resin film becomes poor, and when subjected to severe processing such as deep drawing and impact processing, the film has no ductility and cracks easily occur, Not preferable. Also, the breaking elongation is 40
When it exceeds 0%, when the film is molded from the extruder,
The thickness of the film is likely to be uneven, and the film tends to be broken particularly in a biaxial stretching process, which is not practical.
これらの要因で選択される共重合ポリエステル樹脂フ
イルムの厚さは５〜50μｍの範囲のものが適している。
厚さが５μｍ以下の共重合ポリエステル樹脂フイルムは
表面処理鋼板上に連続的かつ高速で積層することが難し
くなり、作業性を著しく低下させる。さらに厳しい加工
を施した後、優れた耐食性は得られず、本発明において
適していない。また、厚さが50μｍ以上になると、製缶
分野で広く使用されているエポキシ計樹脂塗料などと比
較して経済的でない。The thickness of the copolyester resin film selected by these factors is preferably in the range of 5 to 50 μm.
A copolyester resin film having a thickness of 5 μm or less becomes difficult to be laminated continuously and at high speed on the surface-treated steel sheet, and the workability is significantly deteriorated. After subjecting to more severe processing, excellent corrosion resistance is not obtained, which is not suitable in the present invention. Further, if the thickness is 50 μm or more, it is not economical as compared with epoxy meter resin paints widely used in the can manufacturing field.
つぎに、本発明の請求項２の発明について説明する。
通常のSnめっき鋼板であるぶりきは、共重合ポリエステ
ル樹脂フイルムを積層し加工した場合、そのままでは浅
い絞り缶程度の加工には耐えるが、本発明の目的とす
る、厳しい加工に耐える共重合ポリエステル樹脂フイル
ム積層Snめっき鋼板を得ることはできない。この原因と
して、３つの要因が考えられる。まず第一の要因は、加
熱等によって成長したFe−Sn合金層が加工時に破壊し易
いので、Sn量が少ない領域では、これを軽減する働きの
ある金属Snが不足し、加工時、Fe−Sn合金層面でのフイ
ルム剥離をおこす。第二の要因は、ぶりきの場合、Snの
酸化等を押えるために重クロム酸塩による化成処理を施
すがこの化成処理で形成された被膜は、被覆性が悪く共
重合ポリエステル樹脂フイルムとの十分な接着強度が得
られない。第三の要因は、ぶりきと共重合ポリエステル
樹脂フイルムの加工密着性に直接関係する問題で、共重
合を含むポリエステル樹脂フイルムを２軸延伸して製膜
する際、面方向に結晶配向を起こし、加工強度が高くな
ることである。この結晶配向はフイルム自体の強度を維
持するために必要であるが、ぶりきの場合はTFS−CTほ
どの密着力は得られず、厳しい加工を受けたとき、共重
合ポリエステル樹脂フイルムの加工強度に対して密着力
が勝てず、ぶりきと共重合ポリエステル樹脂フイルムの
剥離を生じてしまう。以上、これ等の要因によって、ぶ
りきと共重合ポリエステル樹脂フイルムを積層した鋼板
は、深絞り後、さらにネックイン加工をするような厳し
い加工応力を受ける缶用途には使用できなかった。Next, the invention of claim 2 of the present invention will be described.
Tinplate, which is an ordinary Sn-plated steel sheet, is a copolymerized polyester that withstands severe processing, which is the object of the present invention, even if it is processed by laminating and processing a copolyester resin film It is not possible to obtain a resin film laminated Sn plated steel sheet. There are three possible causes for this. The first factor is that the Fe-Sn alloy layer grown by heating or the like easily breaks during processing, so in a region with a small amount of Sn, there is a shortage of metal Sn that acts to reduce this, and during processing, Fe- Film peeling occurs on the Sn alloy layer surface. The second factor is that in the case of tinplate, chemical conversion treatment with dichromate is carried out to suppress oxidation of Sn, etc., but the coating formed by this chemical conversion treatment has poor coatability and copolyester resin film. Sufficient adhesive strength cannot be obtained. The third factor is a problem that is directly related to the tint and the processing adhesion of the copolyester resin film. When the polyester resin film containing the copolymer is biaxially stretched to form a film, crystal orientation occurs in the plane direction. That is, the processing strength is increased. This crystal orientation is necessary to maintain the strength of the film itself, but in the case of tinplate, the adhesion strength of TFS-CT is not obtained, and when subjected to severe processing, the processing strength of the copolyester resin film However, the adhesive strength cannot be achieved, and tink and peeling of the copolyester resin film occur. As described above, due to these factors, the steel sheet obtained by laminating tinplate and the copolyester resin film cannot be used for cans which are subjected to severe processing stress such as neck-in processing after deep drawing.
本発明の請求項２の発明はこれらの問題点を解決する
ために、Snめっき量、化成処理被膜の種類及び量を限定
し、かつ、共重合ポリエステル樹脂フイルムの製膜時か
らもっている物性を、フイルムを鋼板に積層後変化さ
せ、一定の物性範囲に調整することによって、ぶりきと
共重合ポリエステル樹脂フイルムを積層した鋼板が厳し
い加工を加えても、フイルムとの密着性が維持できるよ
うにしたものである。In order to solve these problems, the invention of claim 2 of the present invention limits the Sn plating amount, the type and amount of the chemical conversion coating, and has the physical properties that have been present during the film formation of the copolyester resin film. By changing the film after it is laminated on the steel sheet and adjusting it within a certain range of physical properties, it is possible to maintain the adhesion to the film even if the steel sheet laminated with tinplate and copolyester resin film is subjected to severe processing. It was done.
本発明の請求項２の発明において、Snめっきに対する
限定条件はつぎの通りである。本発明のSnめっき鋼板は
Snめっき条件がぶりきと同じであるため、製缶されるま
でフイルムの加熱積層や印刷の焼付け等、多くの熱処理
によって、３〜6g/m2のFe−Sn合金層が成長する。この
時、Fe−Sn合金層量の約３倍、すなわち、金属Snが1.4g
/m2以上残留するようにSnめっき量を確保しておけば、
厳しい加工をおこなった時、Snの流動性によってFe−Sn
合金層の凝集破壊を減少させる効果がある。しかし、Sn
めっき量が1.7g/m2以下になると熱処理後に金属Snが1.4
g/m2以上確保できず、厳しい加工によってFe−Sn合金層
の破壊が生じ、使用に耐えられない。また、Snめっき量
が7.4g/m2以上になると、金属Sn層が厚くなり、加工時
にSnの流動が増大し、共重合ポリエステル樹脂フイルム
が鋼板よりはみでて、いわゆるエナメルヘヤーと言われ
る髪の毛状のフイルムの脱落が生じやすくなる。以上、
Snめっき量は1.7〜7.4g/m2、好ましくは2.0〜6.4g/m2の
範囲にすることが望ましい。以上のSnめっき量範囲を外
れると、Snめっき後に施す化成処理及び積層後の共重合
ポリエステル樹脂フイルムの処理条件を最適条件に整え
ても、Fe−Sn合金層面での剥離によって、本発明の目的
を達成することはできなくなる。In the invention of claim 2 of the present invention, the limiting conditions for Sn plating are as follows. The Sn-plated steel sheet of the present invention is
Since the Sn plating conditions are the same as those for tin plating, 3 to 6 g / m 2 of Fe—Sn alloy layer grows by many heat treatments such as heat lamination of film and baking of printing until canned. At this time, about 3 times the amount of Fe-Sn alloy layer, that is, 1.4g of metallic Sn
If you secure the Sn plating amount so that / m 2 or more remains,
When subjected to severe processing, the flowability of Sn causes Fe-Sn
It has the effect of reducing the cohesive failure of the alloy layer. But Sn
When the plating amount is 1.7 g / m 2 or less, the metal Sn content is 1.4 after heat treatment.
Since g / m 2 or more cannot be secured, severe processing causes the Fe-Sn alloy layer to break, making it unusable for use. Also, when the Sn plating amount is 7.4 g / m 2 or more, the metal Sn layer becomes thicker, the flow of Sn increases during processing, and the copolyester resin film sticks out of the steel plate, resulting in a so-called enamel hair It is easy for the film to fall off. that's all,
The Sn plating amount is preferably 1.7 to 7.4 g / m 2 , and more preferably 2.0 to 6.4 g / m 2 . When out of the above Sn plating amount range, even if the treatment conditions of the chemical conversion treatment and the laminated polyester resin film after lamination are adjusted to the optimum conditions, the object of the present invention is by peeling at the Fe-Sn alloy layer surface. Can no longer be achieved.
Snめっきの条件としては、公知のぶりきの製造法、例
えば、フェロスタン浴あるいは、ハロゲン浴等を用い、
特別な条件設定の必要はなく、一般のぶりき製造条件で
めっきすればよい。As the Sn plating condition, a known tinplate manufacturing method, for example, a ferrostane bath or a halogen bath is used.
It is not necessary to set special conditions, and plating may be performed under general tint manufacturing conditions.
つぎに、本発明の請求項２の発明のSnめっき後に施す
化成処理条件について示す。Snめっき後の化成処理とし
てTFS−CTと同じ化成処理を施すが、そのときの被膜量
は、金属Cr量16〜100mg/m2、Cr水和酸化物の量はCrとし
て５〜20mg/m2の範囲にすることが好ましい。金属Cr量
の上限は、金属Crが増加するにしたがい共重合ポリエス
テル樹脂フイルムとの密着性は向上するが、Sn層上に金
属Crを析出させた場合には、金属Cr量が120mg/m2からは
逆に密着性は低下する現象がある。また、金属Cr量が増
加すると、それに比例してぶりきのもつ白色の光沢が失
われて黒色化する傾向を示すために、金属Cr量は100mg/
m2以内、より好ましくは、金属Cr量を60mg/m2程度にお
さえるのが望ましい。金属Cr量の下限については、金属
Cr量が16mg/m2以下で厳しい加工に耐えられる密着性は
得られず、好ましくは20mg/m2以上にすることが望まし
い。Cr水和酸化物の量は、本発明の請求項１の発明に記
載したものと同じ理由により、Cr水和酸化物量がCrとし
て5mg/m2以下では、厳しい加工に対して共重合ポリエス
テル樹脂フイルムと密着強度が得られない。また、Snめ
っき鋼板は白色の光沢を有しており、Cr水和酸化物層の
増加は汚れが目立ちやすく美観を損ねるため、Cr水和酸
化物の量をCrとして20mg/m2以上にすることは好ましく
ない。Next, chemical conversion treatment conditions to be applied after Sn plating according to the second aspect of the present invention will be shown. Although the same chemical conversion treatment as TFS-CT is performed as the chemical conversion treatment after Sn plating, the coating amount at that time is a metal Cr amount of 16 to 100 mg / m 2 , and the amount of Cr hydrate oxide is 5 to 20 mg / m as Cr. A range of 2 is preferable. The upper limit of the amount of metal Cr, the adhesion with the copolymer polyester resin film is improved as the metal Cr increases, when the metal Cr is deposited on the Sn layer, the amount of metal Cr is 120 mg / m 2. On the contrary, there is a phenomenon that the adhesiveness decreases. In addition, when the amount of metallic Cr increases, the white luster of tinplate tends to be lost in proportion to the increase in the amount of metallic Cr, so that the amount of metallic Cr is 100 mg /
It is desirable to keep the amount of metal Cr within m 2 , more preferably about 60 mg / m 2 . For the lower limit of the amount of metal Cr, see
If the Cr content is 16 mg / m 2 or less, the adhesion that can withstand severe processing cannot be obtained, and it is preferably 20 mg / m 2 or more. The amount of Cr hydrated oxide is the same as that described in the invention of claim 1 of the present invention. For the reason that the amount of Cr hydrated oxide is 5 mg / m 2 or less as Cr, the copolyester resin is difficult to process. The adhesion strength with the film cannot be obtained. Further, the Sn-plated steel sheet has a white luster, and an increase in the Cr hydrated oxide layer is liable to cause stains and impair the aesthetic appearance.Therefore, the amount of Cr hydrated oxide should be 20 mg / m 2 or more as Cr. Is not preferable.
金属Cr層及びCr水和酸化物層を形成させる方法は、本
発明の請求項１の発明と同じ方法ですればよい。The method for forming the metal Cr layer and the Cr hydrated oxide layer may be the same as the method of the first aspect of the present invention.
つぎに、本発明の請求項２の発明において最も重要な
要件である、Snめっき鋼板に積層後の共重合ポリエステ
ル樹脂フイルムの物性について示す。Next, the physical properties of the copolyester resin film after being laminated on the Sn-plated steel sheet, which is the most important requirement in the invention of claim 2 of the present invention, will be shown.
本発明はSnめっき鋼板であり、かつ、本発明の請求項
１の発明と同じ目的に使用するため、本発明に用いる共
重合ポリエステル樹脂フイルムは、本発明の請求項１の
発明に使用するフイルムと同じものを使用する。しか
し、本発明の請求項１の発明に使用する共重合ポリエス
テル樹脂フイルムをぶりきにそのまま使用し、厳しい加
工を行うと、鋼板とSnめっき層の間にFe−Sn合金層を有
しているので、製膜時の面方向の結晶配向による加工強
度が、フイルムとSnめっき鋼板の密着強度を越え剥離を
起こすことがある。本発明は、共重合ポリエステル樹脂
フイルムを鋼板上に積層した状態で引張り強度を下げて
も、フイルムの破断が起こりにくいことに着眼し、フイ
ルムの引張り強度を下げるため、フイルムの面方向の結
晶配向を少なくする処理を施すものである。しかし、フ
イルムの面方向の結晶配向を下げていくと加工強度は低
下し、結晶粒界でのすべりによって伸び易くなるが、無
配向にすると共重合ポリエステル樹脂フイルムがランダ
ムな球晶となり、加工はできてもフイルムにクラックが
入り易く、フイルム自体のバリアー性がなくなるので好
ましくない。したがって、共重合ポリエステル樹脂フイ
ルムの面方向の結晶配向度は、加工性と耐食性に適正な
範囲がある。ポリエステル樹脂フイルムの結晶配向度を
知る方法として、Ｘ線回折法によって測定する方法があ
るが、Ｘ線量の強度、装置感度によってピークカウント
数が異なるため、一般にはフイルムの屈折率より判断す
る。屈折率とポリエステル樹脂フイルムの結晶配向度の
間に相関があるので、この屈折率で本発明のフイルム積
層後の結晶配向度を示すと、面方向に対してどの部位に
おいても1.5850〜1.6100の範囲で、かつ、フイルムの厚
さ方向に対してどの部位においても1.5510〜1.5750の範
囲にし、そしてフイルムの面方向の結晶配向度に直接関
係する面配向係数を0.010〜0.049の範囲にすることで、
はじめて厳しい加工に耐える共重合ポリエステル樹脂フ
イルム積層Snめっき鋼板が得られる。ここで示した面方
向の結晶配向度の下限値は、加工後印刷あるいは加熱乾
燥等の加熱で、加工時に発生した微小クラックが再結合
し、共重合ポリエステル樹脂フイルムのバリアー性は、
もとの状態まで回復する限界の値である。Since the present invention is a Sn-plated steel sheet and is used for the same purpose as the invention of claim 1 of the present invention, the copolyester resin film used in the present invention is a film used in the invention of claim 1 of the present invention. Use the same as. However, when the copolyester resin film used in the invention of claim 1 of the present invention is used as it is for tinplate and subjected to severe processing, it has an Fe-Sn alloy layer between the steel plate and the Sn plating layer. Therefore, the processing strength due to the crystal orientation in the surface direction during film formation may exceed the adhesion strength between the film and the Sn-plated steel sheet and cause peeling. The present invention, even if the tensile strength is lowered in a state where the copolyester resin film is laminated on a steel sheet, the present invention focuses on the fact that breakage of the film is unlikely to occur, and in order to reduce the tensile strength of the film, the crystal orientation in the plane direction of the film The process of reducing the However, if the crystal orientation in the plane direction of the film is lowered, the processing strength decreases and it becomes easier to stretch due to slippage at the crystal grain boundaries, but if it is not oriented, the copolyester resin film becomes a random spherulite, and processing is Even if it is possible, the film tends to be cracked and the barrier property of the film itself is lost, which is not preferable. Therefore, the degree of crystal orientation in the plane direction of the copolyester resin film has an appropriate range for workability and corrosion resistance. There is a method of measuring the crystal orientation of the polyester resin film by an X-ray diffraction method, but since the peak count differs depending on the intensity of the X-ray dose and the sensitivity of the apparatus, it is generally judged from the refractive index of the film. Since there is a correlation between the refractive index and the crystal orientation of the polyester resin film, the crystal orientation after laminating the film of the present invention with this refractive index shows a range of 1.5850 to 1.6100 at any site with respect to the plane direction. And, in any part with respect to the thickness direction of the film in the range of 1.5510 to 1.5750, and by making the plane orientation coefficient directly related to the crystal orientation degree in the plane direction of the film in the range of 0.010 to 0.049,
For the first time, a copolyester resin film laminated Sn-plated steel sheet that can withstand severe processing can be obtained. The lower limit of the degree of crystal orientation in the plane direction shown here is heating such as printing or heat drying after processing, the microcracks generated during processing are recombined, and the barrier property of the copolyester resin film is
This is the limit value for recovering the original state.
共重合ポリエステル樹脂フイルムの加工性に関係する
面方向の結晶配向度は、屈折率より積層後の面方向の結
晶配向係数で判断されている場合が多い。しかし、この
面方向の結晶配向係数は元もと屈折率から求めたもの
で、フイルムの横及び縦方向の屈折率の平均値からフイ
ルムの厚み方向の屈折率を差し引いたものである。した
がって、フイルムの45゜方向、あるいは、135゜方向等
の結晶配向度の指標にはなっていない。しかし、絞り加
工等の製缶時には、あらゆる方向に加工を受けるため、
面方向の結晶配向係数に関与しない方向の屈折率も、本
発明は規制したものである。面内のどの部位において
も、面方向の屈折率が1.5850以下になると、無配向時の
屈折率（1.5800近傍）に近づき、面方向の結晶配向がほ
とんどなく、加工によって共重合ポリエステル樹脂フイ
ルムに腐食に関係するようなクラックが生じ易くなり、
このクラックは後の工程の加熱処理で再結合せずに残る
場合がある。面方向の屈折率が1.6100以上になると、フ
イルムの加工内部応力が強くなり、厳しい加工を受けた
場合、Snめっき鋼板とフイルムとの剥離が生じ易くな
る。また、厚み方向の屈折率は、面方向の結晶配向係数
を求めるのに使用され、フイルムの面方向の結晶配向度
に逆の要因として働く。この厚み方向の屈折率がどの部
位においても1.5510以下になると、共重合ポリエステル
樹脂フイルムの加工度が高くなり加工密着性が低下す
る。厚み方向の屈折率が1.5750以上になると、加工によ
ってフイルムにクラックが生じ易くなるので好ましくな
い。なお、ここで言うポリエステル樹脂フイルムの屈折
率は、アッペの屈折計を用い、接眼側に偏光板アナライ
ザーを取り付け、単色光Na−Ｄ線で、マウント液はヨウ
化メチレンを用いて25℃の温度下で測定した値である。The degree of crystal orientation in the plane direction, which is related to the processability of the copolyester resin film, is often determined by the crystal orientation coefficient in the plane direction after lamination rather than the refractive index. However, the crystal orientation coefficient in the plane direction is originally obtained from the refractive index, and is obtained by subtracting the refractive index in the thickness direction of the film from the average value of the refractive index in the horizontal and vertical directions of the film. Therefore, it is not an index of the crystal orientation degree in the 45 ° direction or the 135 ° direction of the film. However, when making cans such as drawing, processing is performed in all directions, so
The present invention also regulates the refractive index in the direction not related to the crystal orientation coefficient in the plane direction. When the refractive index in the surface direction becomes 1.5850 or less in any part of the surface, it approaches the refractive index in the non-oriented direction (near 1.5800), there is almost no crystal orientation in the surface direction, and the copolyester resin film corrodes due to processing. Is likely to cause cracks related to
This crack may remain without being recombined in the heat treatment of the subsequent step. If the in-plane refractive index is 1.6100 or more, the internal stress of the film during processing becomes strong, and when subjected to severe processing, peeling between the Sn-plated steel sheet and the film is likely to occur. Further, the refractive index in the thickness direction is used to determine the crystal orientation coefficient in the plane direction, and acts as an opposite factor to the crystal orientation degree in the plane direction of the film. When the refractive index in the thickness direction is 1.5510 or less at any part, the copolyester resin film has a high degree of processing and the processing adhesion is deteriorated. When the refractive index in the thickness direction is 1.5750 or more, cracking is likely to occur in the film due to processing, which is not preferable. In addition, the refractive index of the polyester resin film referred to here is a refractometer of Appe, a polarizing plate analyzer is attached to the eyepiece side, a monochromatic light Na-D line, and the mount solution is methylene iodide at a temperature of 25 ° C. It is the value measured below.
以上、屈折率を限定された範囲に設定しても面方向と
厚み方向の屈折率の組合わせによっては、フイルムの加
工可能な範囲を完全に抑えることはできない。すなわ
ち、面方向の結晶配向係数が加工密着性を維持できる範
囲を越える場合が生じる。例えば、確率的には非常に少
ないが、ある一点の面方向の屈折率が1.6100の時、同時
に厚み方向の屈折率が1.5510であったとすると、面方向
の結晶配向係数は0.059となる。しかし、ぶりきを下地
鋼板に使用した場合、面方向の結晶配向係数が0.049以
上を越えるとフイルムの加工応力が高く、厳しい加工を
した時に剥離し易くなる。この傾向を第４図に示した。
第４図は、絞り比;2.96の厳しい加工をした円筒缶側壁
部における共重合ポリエステル樹脂フイルムの剥離面積
比率を、面方向の結晶配向係数との関係で示したもので
ある。また、第４図に示す様に、面方向の結晶配向係数
が0.01以下になると加工性は良くなるが、しかし、共重
合ポリエステル樹脂フイルムにクラックが生じ易くな
り、かつ、後で印刷等の加熱処理で面方向の結晶配向が
増加せず、ポリエステル樹脂フイルムのバリアー性が向
上しなくなるので好ましくない。As described above, even if the refractive index is set in a limited range, the processable range of the film cannot be completely suppressed depending on the combination of the refractive indexes in the surface direction and the thickness direction. That is, the crystal orientation coefficient in the plane direction may exceed the range in which the work adhesion can be maintained. For example, if the refractive index of a certain point is 1.6100 and the refractive index in the thickness direction is 1.5510 at the same time, which is very small in probability, the crystal orientation coefficient in the surface direction is 0.059. However, when tin plate is used as a base steel sheet, if the crystal orientation coefficient in the plane direction exceeds 0.049 or more, the film processing stress is high, and the film tends to peel off when subjected to severe processing. This tendency is shown in FIG.
FIG. 4 shows the peeled area ratio of the copolyester resin film on the side wall of a cylindrical can that has been severely processed with a drawing ratio of 2.96, in relation to the crystal orientation coefficient in the plane direction. Further, as shown in FIG. 4, when the crystal orientation coefficient in the plane direction is 0.01 or less, the workability is improved, but cracks are likely to occur in the copolyester resin film, and after heating such as printing is performed. The treatment does not increase the crystal orientation in the plane direction and the barrier property of the polyester resin film is not improved, which is not preferable.
つぎに、製膜時の面方向の結晶配向を下げる方法につ
いて示す。面方向の結晶配向を下げる方法として、第３
図に示したように、ポリエステル樹脂フイルムの結晶融
解温度以下10℃以内から結晶配向が減少し、温度の上昇
につれて減少傾向が大きくなるので、フイルムの結晶融
解温度以上で短時間に積層する方法、あるいは積層後、
フイルムの結晶融解温度以下10℃以内の範囲で加熱処理
する方法をとる。しかし、前者はフイルムの結晶を無配
向にする危険性が高く、後者の方法の方が安全性が高
い。前者の場合、面方向の結晶配向係数を0.010以下に
しないで共重合ポリエステル樹脂フイルムを積層するに
は、フイルムを積層する前の鋼板の温度は、共重合ポリ
エステル樹脂フイルムの結晶融解温度以上から＋20℃以
内に加熱し、かつ、接着直後の温度が結晶融解温度以下
から−30℃以内になるように積層することが重要であ
る。そのためには、フイルムの温度、積層スピード、鋼
板の板厚を考慮してフイルム積層直後の温度が結晶融解
温度以下、−30℃以内に入るよう、鋼板の温度を結晶融
解温度以上から＋20℃以内の範囲で調整すればよい。し
かしこの方法の場合、鋼板の加熱温度がSn溶融温度（23
2℃）以下に限定されていることから、使用する共重合
ポリエステル樹脂フイルムの種類が限られる。後者の方
法は、安全で、かつ、簡単にフイルムの面方向の結晶配
向を調整することができる。フイルムの面方向の結晶配
向が下げられる限界温度は、共重合ポリエステル樹脂フ
イルムの結晶融解温度以下より−10℃以内の温度であ
り、この範囲で加熱することで、フイルムの面方向の結
晶配向を下げることが可能となる。実際には、結晶融解
温度以下から６℃以内の温度範囲で、４〜６分間加熱す
れば、共重合ポリエステル樹脂フイルム積層後の面方向
の結晶配向係数を、0.010〜0.049の範囲におさめること
ができる。この方法で厳守すべきことは、共重合ポリエ
ステル樹脂フイルムの結晶融解温度以下、−10℃を越え
る温度で決して加熱してはならない。すでに第３図で示
した通り、フイルムの結晶融解温度より−10℃以下で加
熱すると、時間と共にフイルムの面方向の結晶配向度が
増加し、加熱処理をする以前以上に加工によってフイル
ムがひどく剥離を起こしてしまう。例えば、共重合ポリ
エステル樹脂フイルムの結晶融解温度が235℃のフイル
ムを使用した場合、フイルムを積層後、210℃で６分間
加熱処理をすると、製膜時の面方向の結晶配向係数が1.
2〜1.5倍まで増加し、全く加工に耐えられなくなる。な
お、加熱の方法は別に限定しないが、熱風循環伝熱方
式、抵抗加熱方式、誘導加熱方式等使用できる。Next, a method for lowering the crystal orientation in the plane direction during film formation will be described. The third method is to reduce the crystal orientation in the plane direction.
As shown in the figure, the crystal orientation decreases from 10 ° C. or lower than the crystal melting temperature of the polyester resin film, and the decreasing tendency increases as the temperature rises.Therefore, a method of laminating in a short time above the crystal melting temperature of the film, Or after stacking,
Heat treatment is performed within the range of 10 ° C below the crystal melting temperature of the film. However, the former has a high risk of making the film crystals non-oriented, and the latter method is more safe. In the former case, in order to stack the copolyester resin film without setting the crystal orientation coefficient in the plane direction to 0.010 or less, the temperature of the steel sheet before laminating the film is +20 from the crystal melting temperature of the copolyester resin film or more. It is important to heat to within ℃, and to laminate so that the temperature immediately after bonding will be below the crystal melting temperature to within -30 ℃. In order to do so, the temperature of the steel sheet should be within + 20 ° C above the crystal melting temperature so that the temperature immediately after film lamination falls below -30 ° C below the crystal melting temperature, taking into consideration the film temperature, laminating speed, and plate thickness. You can adjust within the range. However, in this method, the heating temperature of the steel sheet is the Sn melting temperature (23
Since it is limited to 2 ° C) or less, the type of copolymer polyester resin film to be used is limited. The latter method is safe and can easily adjust the crystal orientation in the plane direction of the film. The critical temperature at which the crystal orientation in the plane direction of the film can be lowered is a temperature within −10 ° C. below the crystal melting temperature of the copolyester resin film, and by heating in this range, the crystal orientation in the plane direction of the film is It is possible to lower it. In practice, if the heating is carried out for 4 to 6 minutes in the temperature range from below the crystal melting temperature to within 6 ° C., the crystal orientation coefficient in the plane direction after laminating the copolyester resin film can be kept within the range of 0.010 to 0.049. it can. What must be strictly adhered to in this method is that the copolymer polyester resin film should never be heated to a temperature below the crystal melting temperature and above -10 ° C. As already shown in Fig. 3, when the film is heated below the crystal melting temperature of -10 ° C, the degree of crystal orientation in the plane direction of the film increases with time, and the film peels badly due to processing more than before the heat treatment. Will cause. For example, when a film having a crystal melting temperature of the copolyester resin film of 235 ° C. is used, when the films are laminated and then heat-treated at 210 ° C. for 6 minutes, the crystal orientation coefficient in the plane direction during film formation is 1.
It increases from 2 to 1.5 times, and can no longer withstand machining. The heating method is not particularly limited, but a hot air circulation heat transfer method, a resistance heating method, an induction heating method, or the like can be used.
つぎに、本発明において、フイルムと鋼板を接着する
には、２通りの方法がある。第一の方法は、鋼板に接す
る共重合ポリエステル樹脂フイルムを界面のみ溶融状態
にし、急冷することにより非晶質接合を行う方法であ
る。この方法は安価ではあるが、しかし、高湿度の雰囲
気に長時間保存すると、糸状錆が発生し易い欠点をもっ
ている。第二の方法は、分子内にエポキシ基、水酸基、
アミド基、エステル基、カルボキシル基、ウレタン基、
アクリル基、アミノ基の一種以上を含む重合組成物、例
えば、エポキシ樹脂、フェノール樹脂、ナイロン樹脂、
ポリエステル樹脂、ウレタン樹脂、アクリル樹脂、ユリ
ア樹脂を薄く塗布した共重合ポリエステル樹脂フイルム
を加熱したSnめっき鋼板に積層する方法である。この第
二の方法は、工程が増え、若干コストアップになるが、
長期保存に対して、糸状錆等の発生が少なく、品質的に
安定したものがえられる。また、共重合ポリエステル樹
脂フイルムの結晶融解温度以下の積層が可能で、繁用性
に優れ、本発明にとって有利な方法である。Next, in the present invention, there are two methods for adhering the film and the steel sheet. The first method is a method in which the copolyester resin film in contact with the steel sheet is melted only at the interface and is rapidly cooled to perform amorphous joining. Although this method is inexpensive, it has a drawback that if it is stored in a high-humidity atmosphere for a long time, filamentous rust easily occurs. The second method is epoxy group, hydroxyl group,
Amide group, ester group, carboxyl group, urethane group,
Acrylic group, a polymerization composition containing one or more amino groups, for example, epoxy resin, phenol resin, nylon resin,
It is a method of laminating a copolymerized polyester resin film thinly coated with polyester resin, urethane resin, acrylic resin, and urea resin on a heated Sn-plated steel sheet. This second method increases the number of steps and slightly increases the cost,
With long-term storage, there is little generation of filamentous rust and stable quality is obtained. Further, it is possible to stack the copolymer polyester resin film at a temperature not higher than the crystal melting temperature, which is excellent in versatility, which is an advantageous method for the present invention.
この第二の方法においては、重合組成物が該共重合ポ
リエステル樹脂フイルムの片面に薄く塗布されるが、そ
の方法として、ロールコートあるいはスプレー塗装可能
な溶液状態で塗布することが好ましく、塗布後、ドライ
ヤーオープンで乾燥し、タックフリーであることが好ま
しい。タックが大であると、フイルムの巻取り作業は可
能であるが、巻きほどく時、塗布した重合組成物が共重
合ポリエステル樹脂フイルムの他の片面に付着し、好ま
しくない。塗布した重合組成物の乾燥温度も重要で、乾
燥温度は60〜150℃の範囲が好ましい。乾燥温度が60℃
以下になると、溶剤離脱性が著しく低下し、重合体組成
物のタックが大きくなり実用的でない。また、150℃以
上になると、重合組成物の化学反応が乾燥工程中に著し
く進み、Snめっき鋼板へ重合組成物を塗布した共重合ポ
リエステル樹脂フイルムを積層した時、密着性が著しく
低下し、また、フイルムの形状がくずれやすくなるので
好ましくない。重合組成物を塗布する場合の溶剤として
は、水あるいは有機溶剤があげられるが、オーブンにお
ける乾燥性を考慮すると、低沸点溶剤の方が好ましい。
さらに、美観性を向上させるため、Snめっき鋼板との密
着性を阻害しない範囲で、顔料、染料を重合組成物に添
加配合してもよい。In this second method, the polymerization composition is thinly applied to one side of the copolyester resin film, but as a method, it is preferable to apply in a solution state capable of roll coating or spray coating. It is preferred that the dryer is open and dry, and that it is tack-free. When the tack is large, the film can be wound up, but when unwinding, the applied polymer composition adheres to the other side of the copolyester resin film, which is not preferable. The drying temperature of the applied polymerization composition is also important, and the drying temperature is preferably in the range of 60 to 150 ° C. Drying temperature is 60 ℃
When the amount is less than the above, the solvent releasability is remarkably lowered and the tackiness of the polymer composition is increased, which is not practical. Further, when the temperature is 150 ° C. or higher, the chemical reaction of the polymerization composition remarkably progresses during the drying step, and when the copolymerized polyester resin film coated with the polymerization composition is laminated on the Sn-plated steel sheet, the adhesiveness is remarkably reduced, and However, the shape of the film is likely to collapse, which is not preferable. The solvent for applying the polymerization composition may be water or an organic solvent, but a low boiling point solvent is preferable in view of the drying property in an oven.
Furthermore, in order to improve the aesthetic appearance, pigments and dyes may be added and blended with the polymerization composition as long as the adhesion to the Sn-plated steel sheet is not impaired.
重合組成物の塗布量は本発明において重要な因子の一
つであり、乾燥重量として、0.1〜5.0g/m2が好ましい。
塗布重量が0.1g/m2以下になるとすでに示した糸状錆の
防止効果が低下するばかりでなく、該ポリエステル樹脂
フイルムに均一に、かつ薄く塗布することがむずかし
い。また、塗布重量が5.0g/m2以上になると、得られた
共重合ポリエステル樹脂フイルム積層Snめっき鋼板に厳
しい加工を施した時、共重合ポリエステル樹脂フイルム
が剥離し、好ましくない。重合組成物をSnめっき鋼板に
塗布することも考えられるが、帯状のSnめっき鋼板は該
ポリエステル樹脂フイルムに比較し平坦性に劣るため、
連続的かつ均一に塗布することはむずかしい。The coating amount of the polymerization composition is one of the important factors in the present invention, and the dry weight is preferably 0.1 to 5.0 g / m 2 .
When the coating weight is 0.1 g / m 2 or less, not only the effect of preventing the thread-like rust as described above is deteriorated, but it is difficult to coat the polyester resin film uniformly and thinly. Further, if the coating weight is 5.0 g / m 2 or more, the copolymerized polyester resin film peels off when the obtained copolymerized polyester resin film laminated Sn-plated steel sheet is subjected to severe processing, which is not preferable. It is also conceivable to apply the polymerization composition to a Sn-plated steel sheet, but the strip-shaped Sn-plated steel sheet is inferior in flatness to the polyester resin film,
It is difficult to apply continuously and uniformly.
〔実施例〕 以下、本発明の実施例を比較例とともに示し、詳細に
説明する。[Examples] Hereinafter, examples of the present invention will be shown together with comparative examples, and will be described in detail.
本発明に使用した試料及びめっき前処理条件を下記に
示す。The samples used in the present invention and the pretreatment conditions for plating are shown below.
板厚0.21mm、T4−CA、Alキルド連鋳材の冷延鋼板を70
g/の水酸化ナトリウム溶液中で、10A/dm2、２秒間の
電解脱脂し、ついで100g/の硫酸溶液で２秒間浸漬し
て酸洗し、水洗した後、実験に供した。Cold-rolled steel sheet with a thickness of 0.21 mm, T4-CA, and Al-killed continuous cast material
It was electrolytically degreased at 10 A / dm 2 for 2 seconds in a g / sodium hydroxide solution, then immersed in a 100 g / sulfuric acid solution for 2 seconds, pickled, washed with water, and then subjected to an experiment.
１） 本発明の請求項１の発明 実施例 １ 前処理を施した試料を下記Snめっき条件でSnめっきを
行った。1) Invention of Claim 1 of the present invention Example 1 A sample subjected to pretreatment was Sn-plated under the following Sn-plating conditions.
（１） Snめっき処理条件 浴条件 SnSO4 80g/ フェノールスルホン酸（65％溶液） 60g/ エトキシ化αナフトールスルホン酸 10g/ 浴温 45℃ 電解電流密度 11A/dm2 流速 300m/分 Snめっき量 2.7g/m2 Snめっきを施した後、水洗後、金属Cr及びCr水和酸化
物層を形成させる電解CrO3処理を下記条件で行い、水洗
後、乾燥して供重合ポリエステル樹脂フイルム積層の下
地材とした。(1) Sn plating treatment conditions Bath conditions SnSO 4 80 g / phenol sulfonic acid (65% solution) 60 g / ethoxylated α-naphthol sulfonic acid 10 g / bath temperature 45 ° C Electrolytic current density 11 A / dm 2 Flow rate 300 m / min Sn plating amount 2.7 After applying g / m 2 Sn plating, after washing with water, electrolytic CrO 3 treatment to form a metal Cr and Cr hydrated oxide layer is performed under the following conditions, followed by washing with water and drying to provide a base for the polyester polymer film laminate It was made of wood.
（２） 電解CrO3処理条件 CrO3浴条件 CrO3 30g/ H2SO4 0.4g/ 浴温 50℃ 電解電流密度 40A/dm2 被膜量 金属Cr量 23mg/m2 Cr水和酸化物量（Crとして） 11mg/m2 上記表面処理鋼板の両面につぎに示す条件で処理され
た供重合ポリエステル樹脂フイルムを、つぎに示す条件
で連続的にフイルムを積層した。(2) Electrolytic CrO 3 treatment condition CrO 3 bath condition CrO 3 30g / H 2 SO 4 0.4g / bath temperature 50 ℃ Electrolytic current density 40A / dm 2 coating amount metal Cr amount 23mg / m 2 Cr hydrated oxide amount (Cr 11 mg / m 2 The surface-treated steel sheet was laminated on both sides with a polymerized polyester resin film treated under the following conditions, and the film was continuously laminated under the following conditions.
（３） 供重合ポリエステル樹脂フイルムの処理条件 二軸配向ポリエステル樹脂フイルム 25μｍ 結晶融解温度 230℃ 屈折率（面方向） 1.6498 （厚み方向） 1.5275 滑剤 平均粒径1.5μｍのSiO20.07重量％ 重合体組成物 組成 エポキシ樹脂80部とパラクレゾール20部 乾燥重量 0.25g/m2 鋼板加熱温度 228℃ 鋼板の加熱方法 ヒートロール 積層ロール シリコーンゴムロール 積層後の加熱処理 220℃、２分 実施例 ２ 前処理を施した鋼板を、実施例１の（１）に示す条件
でSnめっきを施し、実施例１の（２）に示す条件で、電
解CrO3処理を施した鋼板に、実施例１の（３）に示す条
件で共重合ポリエステル樹脂フイルムを積層した。(3) Treatment conditions for the polymerized polyester resin film Biaxially oriented polyester resin film 25 μm Crystal melting temperature 230 ° C. Refractive index (plane direction) 1.6498 (thickness direction) 1.5275 Lubricant SiO 2 0.07 wt% with an average particle size of 1.5 μm Polymer composition Material composition Epoxy resin 80 parts and para-cresol 20 parts Dry weight 0.25g / m 2 Steel plate heating temperature 228 ° C Steel plate heating method Heat roll Laminating roll Silicone rubber roll Heat treatment after laminating 220 ° C, 2 minutes Example 2 Pretreatment The obtained steel sheet was Sn-plated under the conditions shown in (1) of Example 1, and the electrolytic CrO 3 treatment was performed under the conditions shown in (2) of Example 1, and the steel plate of (3) of Example 1 was obtained. Copolymerized polyester resin films were laminated under the conditions shown.
なお、Snめっき量及び金属Cr量、Cr水和酸化物量を下
記に示す。The amount of Sn plating, the amount of metallic Cr, and the amount of hydrated Cr oxide are shown below.
Snめっき量 2.67g/m2 金属Cr量 92mg/m2 Cr水和酸化物量（Crとして） 16mg/m2 実施例 ３ 前処理を施した鋼板を、実施例１の（１）に示す条件
でSnめっきを施し、実施例１の（２）に示す条件で、電
解CrO3処理を施した鋼板に、実施例１の（３）共重合ポ
リエステル樹脂フイルムを積層した。Sn plating amount 2.67 g / m 2 Metal Cr amount 92 mg / m 2 Cr hydrated oxide amount (as Cr) 16 mg / m 2 Example 3 Pretreated steel plate was subjected to the conditions shown in (1) of Example 1. The (3) copolymerized polyester resin film of Example 1 was laminated on a steel plate which was Sn-plated and subjected to electrolytic CrO 3 treatment under the conditions shown in (2) of Example 1.
なお、Snめっき時の電解電流密度、Snめっき量及び金
属Cr量、Cr水和酸化物量を下記に示す。The electrolytic current density during Sn plating, the amount of Sn plating, the amount of metallic Cr, and the amount of Cr hydrate oxide are shown below.
電解電流密度 15A/dm2 Snめっき量 1.84g/m2 金属Cr量 52mg/m2 Cr水和酸化物量（Crとして） 13mg/m2 実施例 ４ 前処理を施した鋼板を、実施例１の（１）に示す条件
でSnめっきを施し、実施例１の（２）に示す条件で、電
解CrO3処理を施した鋼板に、実施例１の（３）に示す条
件で共重合ポリエステル樹脂フイルムを積層した。Electrolytic current density 15 A / dm 2 Sn Plating amount 1.84 g / m 2 Metal Cr amount 52 mg / m 2 Cr Hydrated oxide amount (as Cr) 13 mg / m 2 Example 4 The pretreated steel plate was A copolyester resin film was formed under the conditions shown in (3) of Example 1 on a steel plate that had been Sn-plated under the conditions shown in (1) and had been subjected to electrolytic CrO 3 treatment under the conditions shown in (2) of Example 1. Were laminated.
なお、Snめっき時の電解電流密度、Snめっき量及び金
属Cr量、Cr水和酸化物量を下記に示す。The electrolytic current density during Sn plating, the amount of Sn plating, the amount of metallic Cr, and the amount of Cr hydrate oxide are shown below.
電解電流密度 12A/dm2 Snめっき量 5.76g/m2 金属Cr量 57mg/m2 Cr水和酸化物量（Crとして） 15mg/m2 実施例 ５ 前処理を施した鋼板を、実施例１の（１）に示す条件
でSnめっきを施して、実施例１の（２）の示す条件で、
電解CrO3処理を施した鋼板に、実施例１の（３）に示す
条件で共重合ポリエステル樹脂フイルムを積層した。Electrolytic current density 12A / dm 2 Sn Plating amount 5.76g / m 2 Metallic Cr amount 57mg / m 2 Cr Hydrated oxide amount (as Cr) 15mg / m 2 Example 5 Sn plating was performed under the conditions shown in (1), and under the conditions shown in (2) of Example 1,
The copolyester resin film was laminated on the steel sheet subjected to electrolytic CrO 3 treatment under the conditions shown in (3) of Example 1.
なお、Snめっき時の電解電流密度、Snめっき量、金属
Cr量、Cr水和酸化物量及び使用した共重合ポリエステル
樹脂フイルムの物性を下記に示す。The electrolytic current density during Sn plating, Sn plating amount, metal
The Cr amount, Cr hydrated oxide amount, and the physical properties of the copolymerized polyester resin film used are shown below.
電解電流密度 11A/dm2 Snめっき量 2.73g/m2 金属Cr量 56mg/m2 Cr水和酸化物量（Crとして） 14mg/m2 二軸配向ポリエステル樹脂フイルム 25μｍ 結晶融解温度 216℃ 屈折率（面方向） 1.6360 （厚み方向） 1.5330 比較例 １ 比較例１はコントロールとして、通常のぶりき製造条
件で作成したものを示す。Electrolysis current density of 11A / dm 2 Sn coating weight 2.73 g / m 2 metal Cr content 56 mg / m (as Cr) 2 Cr hydrated oxide content 14 mg / m 2 biaxially oriented polyester resin film 25μm crystalline melting temperature 216 ° C. refractive index ( Surface direction) 1.6360 (Thickness direction) 1.5330 Comparative Example 1 Comparative Example 1 shows a sample prepared under normal tin plate manufacturing conditions as a control.
前処理を施した鋼板を、実施例１の（１）に示す条件
でSnめっきを施し、実施例１の（２）に示す条件で、電
解CrO3処理を施した鋼板に、実施例１の（３）に示す条
件で共重合ポリエステル樹脂フイルムを積層した。The pretreated steel sheet was Sn-plated under the conditions shown in (1) of Example 1, and the electrolytic CrO 3 treatment was applied to the steel plate obtained in Example 1 under the conditions shown in (2) of Example 1. Copolymerized polyester resin films were laminated under the conditions shown in (3).
なお、Snめっき時の電解電流密度、Snめっき量及び金
属Cr量、Cr水和酸化物量を下記に示す。The electrolytic current density during Sn plating, the amount of Sn plating, the amount of metallic Cr, and the amount of Cr hydrate oxide are shown below.
電解電流密度 30A/dm2 Snめっき量 2.76g/m2 金属Cr量 51mg/m2 Cr水和酸化物量（Crとして） 15mg/m2 比較例 ２ 比較例２として、Snめっき量、金属Cr量、Cr水和酸化
物量が本発明の請求項１の発明の範囲を外れたものを示
す。Electrolytic current density 30 A / dm 2 Sn plating amount 2.76 g / m 2 Metal Cr amount 51 mg / m 2 Cr hydrated oxide amount (as Cr) 15 mg / m 2 Comparative Example 2 As Comparative Example 2, Sn plating amount, metallic Cr amount , Cr hydrate oxide content is outside the scope of the invention of claim 1 of the present invention.
前処理を施した鋼板を、実施例１の（１）に示す条件
でSnめっきを施し、実施例１の（２）に示す条件で、電
解CrO3処理を施した鋼板に、実施例１の（３）の示す条
件で共重合ポリエステル樹脂フイルムを積層した。The pretreated steel sheet was Sn-plated under the conditions shown in (1) of Example 1, and the electrolytic CrO 3 treatment was applied to the steel plate obtained in Example 1 under the conditions shown in (2) of Example 1. The copolyester resin film was laminated under the condition (3).
なお、Snめっき量及び金属Cr量、Cr水和酸化物量を下
記に示す。The amount of Sn plating, the amount of metallic Cr, and the amount of hydrated Cr oxide are shown below.
Snめっき量 0.76g/m2 金属Cr量 11mg/m2 Cr水和酸化物量（Crとして） 5mg/m2 比較例 ３ 比較例３として、共重合ポリエステル樹脂フイルムの
結晶融解温度が本発明の請求項１の発明の範囲を外れた
ものを示す。Sn plating amount 0.76 g / m 2 metal Cr amount 11 mg / m 2 Cr hydrated oxide amount (as Cr) 5 mg / m 2 Comparative Example 3 As Comparative Example 3, the crystal melting temperature of the copolyester resin film is claimed in the present invention. Items outside the scope of the invention of Item 1 are shown.
前処理を施した鋼板を、実施例１の（１）に示す条件
でSnめっきを施し、実施例１の（２）に示す条件で、電
解CrO3処理を施した鋼板に、実施例１の（３）に示す条
件で共重合ポリエステル樹脂フイルムを積層した。The pretreated steel sheet was Sn-plated under the conditions shown in (1) of Example 1, and the electrolytic CrO 3 treatment was applied to the steel plate obtained in Example 1 under the conditions shown in (2) of Example 1. Copolymerized polyester resin films were laminated under the conditions shown in (3).
なお、Snめっき量、金属Cr量、Cr水和酸化物量及び使
用した共重合ポリエステル樹脂フイルムの物性を下記に
示す。The Sn plating amount, the metal Cr amount, the Cr hydrated oxide amount, and the physical properties of the used copolyester resin film are shown below.
Snめっき量 2.83g/m2 金属Cr量 56mg/m2 Cr水和酸化物量（Crとして） 14mg/m2 二軸配向ポリエステル樹脂フイルム 25μｍ 結晶融解温度 241℃ 屈折率（面方向） 1.6610 （厚み方向） 1.5250 比較例 ４ 比較例４は、TFS−CTを示す。Sn plating amount 2.83g / m 2 Metal Cr amount 56mg / m 2 Cr Hydrated oxide amount (as Cr) 14mg / m 2 Biaxially oriented polyester resin film 25μm Crystal melting temperature 241 ℃ Refractive index (plane direction) 1.6610 (thickness direction) ) 1.5250 Comparative Example 4 Comparative Example 4 shows TFS-CT.
前処理を施した鋼板に、下記に示す条件で電解CrO3処
理を施し、実施例１の（３）に示す条件で共重合ポリエ
ステル樹脂フイルムを積層した。The pretreated steel plate was subjected to electrolytic CrO 3 treatment under the conditions shown below, and a copolyester resin film was laminated under the conditions shown in (3) of Example 1.
（４） 電解CrO3処理条件 浴条件 CrO3 100g/ H2SO4 0.8g/ NaF 2.0g/ 浴温 50℃ 電解電流密度 40A/dm2 流速 300m/分 金属Cr量 102mg/m2 Cr水和酸化物量 17mg/m2 ２） 本発明の要求項２の発明 実施例６ 前処理を施した鋼板を、実施例１の（１）に示す条件
でSnめっきを施し、実施例１の（２）に示す条件で、電
解CrO3処理を施した鋼板に、実施例１の（３）に示す条
件で共重合ポリエステル樹脂フイルムを積層した。(4) Electrolytic CrO 3 treatment condition Bath condition CrO 3 100g / H 2 SO 4 0.8g / NaF 2.0g / bath temperature 50 ℃ Electrolytic current density 40A / dm 2 Flow rate 300m / min Metal Cr content 102mg / m 2 Cr hydration Oxide amount 17 mg / m 2 2) Invention of claim 2 of the present invention Example 6 A pre-treated steel sheet was Sn-plated under the conditions shown in (1) of Example 1 to give (2) of Example 1. Under the conditions shown in (1), the copolyester resin film was laminated on the steel plate subjected to electrolytic CrO 3 treatment under the conditions shown in (3) of Example 1.
なお、Snめっき時の電解電流密度、Snめっき量、金属
Cr量、Cr水和酸化物量及び使用した共重合ポリエステル
樹脂フイルムの物性及び鋼板加熱温度を下記に示す。The electrolytic current density during Sn plating, Sn plating amount, metal
The Cr amount, Cr hydrated oxide amount, physical properties of the used copolyester resin film and steel plate heating temperature are shown below.
電解電流密度 30A/dm2 Snめっき量 1.96g/m2 金属Cr量 25mg/m2 Cr水和酸化物量（Crとして） 12mg/m2 二軸配向ポリエステル樹脂フイルム 25μｍ 結晶融解温度 220℃ 屈折率（面方向） 1.6370 （厚み方向） 1.5242 破断伸び 210％ 積層前の鋼板温度 230℃ 実施例 ７ 前処理を施した鋼板を、実施例１の（１）に示す条件
でSnめっきを施し、実施例１の（２）に示す条件で、電
解CrO3処理を施した鋼板に、実施例１の（３）に示す条
件で共重合ポリエステル樹脂フイルムを積層した。Electrolytic current density 30A / dm 2 Sn Plating amount 1.96g / m 2 Metal Cr amount 25mg / m 2 Cr Hydrated oxide amount (as Cr) 12mg / m 2 Biaxially oriented polyester resin film 25μm Crystal melting temperature 220 ℃ Refractive index ( Plane direction) 1.6370 (Thickness direction) 1.5242 Elongation at break 210% Steel sheet temperature before lamination 230 ° C Example 7 The pretreated steel sheet was Sn-plated under the conditions shown in (1) of Example 1, and Example 1 Under the condition (2), the copolyester resin film was laminated on the steel plate subjected to the electrolytic CrO 3 treatment under the condition (3) of Example 1.
なお、Snめっき時の電解電流密度、Snめっき量、金属
Cr量、Cr水和酸化物量及び使用した共重合ポリエステル
樹脂フイルムの物性及び鋼板加熱温度を下記に示す。The electrolytic current density during Sn plating, Sn plating amount, metal
The Cr amount, Cr hydrated oxide amount, physical properties of the used copolyester resin film and steel plate heating temperature are shown below.
電解電流密度 30A/dm2 Snめっき量 2.86g/m2 金属Cr量 57mg/m2 Cr水和酸化物量（Crとして） 14mg/m2 二軸配向ポリエステル樹脂フイルム 25μｍ 結晶融解温度 220℃ 屈折率（面方向） 1.6370 （厚み方向） 1.5242 破断伸び 210％ 積層前の鋼板温度 230℃ 実施例８ 前処理を施した鋼板を、実施例１の（１）に示す条件
でSnめっきを施し、実施例１の（２）に示す条件で、電
解CrO3処理を施した鋼板に、実施例１の（３）に示す条
件で共重合ポリエステル樹脂フイルムを積層した。Electrolytic current density 30A / dm 2 Sn Plating amount 2.86g / m 2 Metal Cr amount 57mg / m 2 Cr Hydrated oxide amount (as Cr) 14mg / m 2 Biaxially oriented polyester resin film 25μm Crystal melting temperature 220 ℃ Refractive index ( Surface direction) 1.6370 (Thickness direction) 1.5242 Elongation at break 210% Steel plate temperature before lamination 230 ° C Example 8 The pretreated steel plate was Sn-plated under the conditions shown in (1) of Example 1, and Example 1 Under the condition (2), the copolyester resin film was laminated on the steel plate subjected to the electrolytic CrO 3 treatment under the condition (3) of Example 1.
なお、Snめっき時の電解電流密度、Snめっき量、金属
Cr量、Cr水和酸化物量及び使用した共重合ポリエステル
樹脂フイルムの物性及び鋼板加熱温度、フイルム面方向
の結晶配向調整条件を下記に示す。The electrolytic current density during Sn plating, Sn plating amount, metal
The Cr content, Cr hydrated oxide content, physical properties of the used copolyester resin film, steel plate heating temperature, and crystal orientation adjustment conditions in the film plane direction are shown below.
電解電流密度 30A/dm2 Snめっき量 2.76g/m2 金属Cr量 61mg/m2 Cr水和酸化物量（Crとして） 16mg/m2 二軸配向ポリエステル樹脂フイルム 25μｍ 結晶融解温度 230℃ 屈折率（面方向） 1.6545 （厚み方向） 1.5313 破断伸び 184％ 積層前の鋼板温度 230℃ 結晶配向調整条件 225℃×６分 実施例 ９ 前処理を施した鋼板を、実施例１の（１）に示す条件
でSnめっきを施し、実施例１の（２）に示す条件で、電
解CrO3処理を施した鋼板に、実施例１の（３）に示す条
件で共重合ポリエステル樹脂フイルムを積層した。Electrolysis current density of 30A / dm 2 Sn coating weight 2.76 g / m 2 metal Cr content 61 mg / m (as Cr) 2 Cr hydrated oxide content 16 mg / m 2 biaxially oriented polyester resin film 25μm crystalline melting temperature 230 ° C. refractive index ( Plane direction) 1.6545 (Thickness direction) 1.5313 Elongation at break 184% Steel sheet temperature before lamination 230 ° C Crystal orientation adjustment condition 225 ° C x 6 minutes Example 9 Pretreated steel sheet was subjected to the conditions shown in (1) of Example 1. The Sn-plated steel sheet and the electrolytic CrO 3 treatment under the conditions shown in (2) of Example 1 were laminated with the copolyester resin film under the conditions shown in (3) of Example 1.
なお、Snめっき時の電解電流密度、Snめっき量、金属
Cr量、Cr水和酸化物量及び使用した共重合ポリエステル
樹脂フイルムの物性及び鋼板加熱温度、フイルム面方向
の結晶配向調整条件を下記に示す。The electrolytic current density during Sn plating, Sn plating amount, metal
The Cr content, Cr hydrated oxide content, physical properties of the used copolyester resin film, steel plate heating temperature, and crystal orientation adjustment conditions in the film plane direction are shown below.
電解電流密度 30A/dm2 Snめっき量 4.62g/m2 金属Cr量 37mg/m2 Cr水和酸化物量（Crとして） 14mg/m2 二軸配向ポリエステル樹脂フイルム 25μｍ 結晶融解温度 236℃ 屈折率（面方向） 1.6590 （厚み方向） 1.5262 破断伸び 175％ 積層前の鋼板温度 230℃ 結晶配向調整条件 230℃×６分 比較例 ５ 比較例５として、共重合ポリエステル樹脂フイルムの
面方向の結晶配向を崩す処理を施していないものを示
す。Electrolysis current density of 30A / dm 2 Sn coating weight 4.62 g / m 2 metal Cr content 37 mg / m (as Cr) 2 Cr hydrated oxide content 14 mg / m 2 biaxially oriented polyester resin film 25μm crystalline melting temperature 236 ° C. refractive index ( Surface direction) 1.6590 (Thickness direction) 1.5262 Elongation at break 175% Steel sheet temperature before lamination 230 ° C Crystal orientation adjustment condition 230 ° C x 6 minutes Comparative Example 5 As Comparative Example 5, the crystal orientation in the in-plane direction of the copolyester resin film is destroyed. Those that have not been treated are shown.
前処理を施した鋼板を、実施例１の（１）に示す条件
でSnめっきを施し、実施例１の（２）に示す条件で、電
解CrO3処理を施した鋼板に、実施例１の（３）に示す条
件で共重合ポリエステル樹脂フイルムを積層した。The pretreated steel sheet was Sn-plated under the conditions shown in (1) of Example 1, and the electrolytic CrO 3 treatment was applied to the steel plate obtained in Example 1 under the conditions shown in (2) of Example 1. Copolymerized polyester resin films were laminated under the conditions shown in (3).
なお、Snめっき時電解電流密度、Snめっき量、金属Cr
量、Cr水和酸化物量及び使用した共重合ポリエステル樹
脂フイルムの物性及び鋼板加熱温度を下記に示す。In addition, electrolytic current density during Sn plating, Sn plating amount, metal Cr
The amount, the amount of Cr hydrated oxide, the physical properties of the copolyester resin film used, and the steel plate heating temperature are shown below.
電解電流密度 30A/dm2 Snめっき量 4.71g/m2 金属Cr量 36mg/m2 Cr水和酸化物量（Crとして） 14mg/m2 二軸配向ポリエステル樹脂フイルム 25μｍ 結晶融解温度 220℃ 屈折率（面方向） 1.6370 （厚み方向） 1.5242 破断伸び 210％ 積層前の鋼板温度 215℃ 比較例 ６ 比較例６として、配向調整温度が結晶融解温度以下、
−10℃以内より低い温度で処理したものを示す。Electrolysis current density of 30A / dm 2 Sn coating weight 4.71 g / m 2 (as Cr) metal Cr content 36 mg / m 2 Cr hydrated oxide content 14 mg / m 2 biaxially oriented polyester resin film 25μm crystalline melting temperature 220 ° C. refractive index ( Plane direction) 1.6370 (Thickness direction) 1.5242 Elongation at break 210% Steel plate temperature before lamination 215 ° C Comparative example 6 As Comparative example 6, the orientation adjustment temperature is below the crystal melting temperature,
Indicates that the sample was treated at a temperature lower than -10 ° C.
前処理を施した鋼板を、実施例１の（１）に示す条件
でSnめっきを施し、実施例１の（２）に示す条件で、電
解CrO3処理を施した鋼板に、実施例１の（３）に示す条
件で共重合ポリエステル樹脂フイルムを積層した。The pretreated steel sheet was Sn-plated under the conditions shown in (1) of Example 1, and the electrolytic CrO 3 treatment was applied to the steel plate obtained in Example 1 under the conditions shown in (2) of Example 1. Copolymerized polyester resin films were laminated under the conditions shown in (3).
なお、Snめっき時の電解電流密度、Snめっき量、金属
Cr量、Cr水和酸化物量及び使用した共重合ポリエステル
樹脂フイルムの物性及び鋼板加熱温度、フイルム面方向
の結晶配向調整条件を下記に示す。The electrolytic current density during Sn plating, Sn plating amount, metal
The Cr content, Cr hydrated oxide content, physical properties of the used copolyester resin film, steel plate heating temperature, and crystal orientation adjustment conditions in the film plane direction are shown below.
電解電流密度 30A/dm2 Snめっき量 2.72g/m2 金属Cr量 38mg/m2 Cr水和酸化物量（Crとして） 15mg/m2 二軸配向ポリエステル樹脂フイルム 25μｍ 結晶融解温度 220℃ 屈折率（面方向） 1.6370 （厚み方向） 1.5242 破断伸び 210％ 積層前の鋼板温度 210℃ 結晶配向調整条件 200℃×６分 比較例 ７ 比較例７として、Snめっき量が本発明の請求項２の発
明の範囲より少ないものを示す。Electrolytic current density 30A / dm 2 Sn Plating amount 2.72g / m 2 Metal Cr amount 38mg / m 2 Cr Hydrated oxide amount (as Cr) 15mg / m 2 Biaxially oriented polyester resin film 25μm Crystal melting temperature 220 ℃ Refractive index ( Plane direction) 1.6370 (Thickness direction) 1.5242 Elongation at break 210% Steel plate temperature before lamination 210 ° C Crystal orientation adjustment condition 200 ° C x 6 minutes Comparative example 7 As Comparative example 7, the Sn plating amount is the same as that of the invention of claim 2 of the present invention. Indicates less than the range.
前処理を施した鋼板を、実施例１の（１）に示す条件
でSnめっきを施し、実施例１の（２）に示す条件で、電
解CrO3処理を施した鋼板に、実施例１の（３）に示す条
件で共重合ポリエステル樹脂フイルムを積層した。The pretreated steel sheet was Sn-plated under the conditions shown in (1) of Example 1, and the electrolytic CrO 3 treatment was applied to the steel plate obtained in Example 1 under the conditions shown in (2) of Example 1. Copolymerized polyester resin films were laminated under the conditions shown in (3).
なお、Snめっき時の電解電流密度、Snめっき量、金属
Cr量、Cr水和酸化物量及び使用した共重合ポリエステル
樹脂フイルムの物性及び鋼板加熱温度、フイルム面方向
の結晶配向調整条件を下記に示す。The electrolytic current density during Sn plating, Sn plating amount, metal
The Cr content, Cr hydrated oxide content, physical properties of the used copolyester resin film, steel plate heating temperature, and crystal orientation adjustment conditions in the film plane direction are shown below.
電解電流密度 30A/dm2 Snめっき量 1.45g/m2 金属Cr量 41mg/m2 Cr水和酸化物量（Crとして） 15mg/m2 二軸配向ポリエステル樹脂フイルム 25μｍ 結晶融解温度 230℃ 屈折率（面方向） 1.6545 （厚み方向） 1.5313 破断伸び 184％ 積層前の鋼板温度 225℃ 結晶配向調整条件 225℃×６分 比較例 ８ 比較例８として、金属Cr量、Cr水和酸化物量が本発明
の請求項２の発明の範囲より少ないものを示す。Electrolytic current density 30A / dm 2 Sn Plating amount 1.45g / m 2 Metal Cr amount 41mg / m 2 Cr Hydrated oxide amount (as Cr) 15mg / m 2 Biaxially oriented polyester resin film 25μm Crystal melting temperature 230 ℃ Refractive index ( Plane direction) 1.6545 (Thickness direction) 1.5313 Elongation at break 184% Steel plate temperature before lamination 225 ° C Crystal orientation adjustment condition 225 ° C x 6 minutes Comparative example 8 As Comparative example 8, the amount of metallic Cr and the amount of Cr hydrated oxide are of the present invention. What is less than the scope of the invention of claim 2 is shown.
前処理を施した鋼板を、実施例１の（１）に示す条件
でSnめっきを施し、実施例１の（２）に示す条件で、電
解CrO3処理を施した鋼板に、実施例１の（３）に示す条
件で共重合ポリエステル樹脂フイルムを積層した。The pretreated steel sheet was Sn-plated under the conditions shown in (1) of Example 1, and the electrolytic CrO 3 treatment was applied to the steel plate obtained in Example 1 under the conditions shown in (2) of Example 1. Copolymerized polyester resin films were laminated under the conditions shown in (3).
なお、Snめっき時の電解電流密度、Snめっき量、金属
Cr量、Cr水和酸化物量及び使用した共重合ポリエステル
樹脂フイルムの物性及び鋼板加熱温度、フイルム面方向
の結晶配向調整条件を下記に示す。The electrolytic current density during Sn plating, Sn plating amount, metal
The Cr content, Cr hydrated oxide content, physical properties of the used copolyester resin film, steel plate heating temperature, and crystal orientation adjustment conditions in the film plane direction are shown below.
電解電流密度 30A/dm2 Snめっき量 2.86g/m2 金属Cr量 13mg/m2 Cr水和酸化物量（Crとして） 5mg/m2 二軸配向ポリエステル樹脂フイルム 25μｍ 結晶融解温度 230℃ 屈折率（面方向） 1.6545 （厚み方向） 1.5313 破断伸び 184％ 積層前の鋼板温度 230℃ 結晶配向調整条件 225℃×６分 比較例 ９ 比較例９として、TFS−CTを示す。Electrolytic current density 30A / dm 2 Sn Plating amount 2.86g / m 2 Metal Cr amount 13mg / m 2 Cr Hydrated oxide amount (as Cr) 5mg / m 2 Biaxially oriented polyester resin film 25μm Crystal melting temperature 230 ℃ Refractive index ( Plane direction) 1.6545 (Thickness direction) 1.5313 Elongation at break 184% Steel sheet temperature before lamination 230 ° C Crystal orientation adjustment condition 225 ° C x 6 minutes Comparative example 9 TFS-CT is shown as Comparative example 9.
前処理を施した鋼板に、比較例５の（４）に示す条件
で電解CrO3処理を施し、実施例１の（３）に示す条件で
共重合ポリエステル樹脂フイルムを積層した。なお、金
属Cr量及びCr水和酸化物量を下記に示す。The pretreated steel sheet was subjected to electrolytic CrO 3 treatment under the conditions shown in (4) of Comparative Example 5, and a copolymerized polyester resin film was laminated under the conditions shown in (3) of Example 1. The amounts of metallic Cr and hydrated Cr oxide are shown below.
金属Cr量 107mg/m2 Cr水和酸化物量（Crとして） 14mg/m2 得られた共重合ポリエステル樹脂フイルム積層Snめっ
き鋼板は、つぎに示す試験法で評価し、その結果を第１
表及び第２表に示した。Metal Cr amount 107 mg / m 2 Cr hydrated oxide amount (as Cr) 14 mg / m 2 The obtained copolyester resin film laminated Sn-plated steel sheet was evaluated by the following test method, and the result was
The results are shown in Tables and Table 2.
（１） 表面処理鋼板のめっき量測定 各実施例及び各比較例の鋼板表面のSnめっき量、金属
Cr量、Cr水和酸化物量の測定は公知の蛍光Ｘ線分析法よ
り測定した。(1) Measurement of plating amount on surface-treated steel plate Sn plating amount on surface of steel sheet of each Example and Comparative Example, metal
The Cr content and Cr hydrate oxide content were measured by a known fluorescent X-ray analysis method.
（２） Snめっき後の結晶粒及び占有率の測定 Snめっき後の鋼板の0.1cm×0.1cmの視野を、400倍の
偏光実体顕微鏡で観察し写真撮影をしたものについて、
結晶が0.2〜５μｍの範囲に入るものだけを黒く塗り、
画像解析装置で解析した。(2) Measurement of crystal grains and occupancy after Sn plating About the 0.1 cm x 0.1 cm field of view of the steel plate after Sn plating, and observing with a 400x polarizing stereomicroscope, a photograph was taken.
Only those crystals whose crystal size is within the range of 0.2-5 μm are painted black,
It was analyzed with an image analyzer.
（３） Snめっき層と鋼板の接触面積比率の測定 Snめっき後の鋼板をｎ数として10枚採取し、210℃×1
0分の空焼きを施した後、1N−NaOH溶液中で0.38Vの陽極
電解をし、金属Snを溶解後、走査型電子顕微鏡で倍率10
00倍のSn−Ｌα線EPMA分析を行い、合金層分布率を画像
解析装置で解析した。なお、Snめっき層は100％の被覆
率として行った。(3) Measurement of the contact area ratio between the Sn plating layer and the steel sheet Ten sheets of the Sn-plated steel sheet were sampled as the number of n and 210 ° C x 1
After baking for 0 minutes, 0.38 V anodic electrolysis was performed in a 1N-NaOH solution to dissolve metallic Sn, and a magnification of 10 was obtained with a scanning electron microscope.
00-fold Sn-Lα ray EPMA analysis was performed, and the alloy layer distribution ratio was analyzed by an image analyzer. The Sn plating layer was applied at a coverage of 100%.
（４） 電解法による深絞り製缶加工後のフイルム破壊
度の定量 市販の炭酸飲料２ピース缶（350ml缶）と同形の缶に
深絞り加工を行い、電解液（NaCl;1w％＋界面活性剤;0.
2w％）350mlを注入し、缶を直流整流器の（＋）に接続
し、（−）対極にステンレスの棒を使用して、電解電
圧;6.3Vで電解したときに流れた電流値でフイルムの破
壊度を示した。(4) Quantification of film destruction degree after deep drawing can processing by electrolytic method Deep drawing processing was performed on a can of the same shape as a commercially available carbonated beverage 2-piece can (350 ml can) and electrolytic solution (NaCl; 1w% + surface activity). Agent; 0.
2w%) 350ml was injected, the can was connected to the (+) of the DC rectifier, and the stainless steel rod was used for the (-) counter electrode. The degree of destruction was shown.
（５） 深絞り加工によるフイルム密着性 試料を直径158mmの円板に打ち抜き、絞り比2.92で円
筒状カップに絞り加工を施した。整形後の円筒状カップ
側面に発生したフイルム剥離状態、あるいはフイルムに
発生した割れの状態を下記に示すランクで、それぞれ３
段階に評価した。(5) Film adhesion by deep drawing A sample having a diameter of 158 mm was punched out and a cylindrical cup was drawn at a drawing ratio of 2.92. The film peeling state that occurred on the side surface of the cylindrical cup after shaping, or the state of cracks that occurred on the film was ranked as shown below in 3 ranks.
Graded.
評 価 剥離または割れの発生率（ｎ＝100） ○ ＝ ０％ △ ＝ 20％未満 × ＝ 20％以上 （６） 深絞り加工後ネックイン加工によるフイルム密
着性 上記（５）の加工試験後、剥離あるいは割れの発生し
なかった試料について、20％のネックイン加工を施し
た。加工後、ネックイン加工部に発生した剥離状態を、
（５）の項と同じ評価法で評価した。Evaluation Rate of peeling or cracking (n = 100) ○ = 0% △ = less than 20% × = 20% or more (6) Film adhesion by neck-in processing after deep drawing After the processing test of (5) above, A 20% neck-in process was performed on the sample in which no peeling or cracking occurred. After processing, remove the peeled state generated in the neck-in processing part,
It evaluated by the same evaluation method as the item of (5).
（７） 孔食缶発生試験 上記（５）の加工によって得られた円筒状のカップ50
缶に炭酸飲料のコカコーラを充填し、Al−EOを巻き締め
た後、37.5℃の恒温室で、３ケ月間貯蔵し、３ケ月貯蔵
後に発生した穿孔缶の発生率で示した。(7) Pitting canister generation test Cylindrical cup 50 obtained by the process of (5) above.
The cans were filled with Coca-Cola, a carbonated drink, and after tightening Al-EO, the cans were stored in a thermostatic chamber at 37.5 ° C. for 3 months, and the rate of occurrence of perforated cans after 3 months of storage was shown.
かくして得られたポリエステル樹脂フイルム積層Snめ
っき鋼板は、加工性に優れ、かつ、加工後の耐食性にも
優れるため、厳しい絞り加工及び絞り加工後ストレッチ
加工して製缶する缶に、腐食性の高い炭酸飲料を充填す
る容器用素材として広く適用できるものである。The polyester resin film laminated Sn-plated steel sheet thus obtained is excellent in workability, and also has excellent corrosion resistance after processing, so it is highly corrosive for cans made by severe drawing and stretching after drawing. It can be widely applied as a material for containers filled with carbonated drinks.
第１図のａは、一般のSnめっき鋼板（ぶりき）を示す断
面図、ｂは本発明の請求項１の発明のSnめっき後の状態
を示す断面図、第２図は、ａに示すぶりきと、ｂに示す
本発明の請求項１の発明のSnめっき鋼板を加熱処理した
後、Fe−Sn合金層の成長を示す図、第３図は、共重合ポ
リエステル樹脂フイルムを鋼板に積層後、加熱処理温度
によるフイルム面方向の結晶配向変化を示す図、第４図
は、絞り比2.96で絞り加工を施したときのポリエチレン
樹脂フイルムの剥離率と面方向の結晶配向係数の関係を
示す図である。 １……Sn、２……鋼板、 ３……接触面、４……非接触面。1A is a sectional view showing a general Sn-plated steel sheet (tinting), b is a sectional view showing a state after Sn plating according to the invention of claim 1 of the present invention, and FIG. 2 is shown in a. A diagram showing the growth of the Fe-Sn alloy layer after heat treatment of tin plate and the Sn-plated steel sheet of the invention of claim 1 shown in b, and FIG. 3 is a diagram showing that a copolyester resin film is laminated on a steel sheet. After that, a diagram showing a change in crystal orientation in the film surface direction depending on the heat treatment temperature, and FIG. 4 shows a relationship between the peeling rate of the polyethylene resin film and the crystal orientation coefficient in the surface direction when the film is drawn at a drawing ratio of 2.96. It is a figure. 1 ... Sn, 2 ... steel plate, 3 ... contact surface, 4 ... non-contact surface.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平１−136738（ＪＰ，Ａ) 特開 昭63−206481（ＪＰ，Ａ) 特開 平１−145137（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-1-136738 (JP, A) JP-A-63-206481 (JP, A) JP-A-1-145137 (JP, A)
Claims (2)
ポリエステル樹脂フイルム加熱積層後のFe−Sn合金層成
長面積がSnの電着面積の75％以下で、かつ、連なったSn
の一つの結晶の直径が0.2〜５μｍのものを60％以上含
むSnめっきを施した後、16〜120mg/m2の金属Cr層、その
上層にCr層として５〜30mg/m2のCr水和酸化物層を形成
させ、さらにその上層に、フイルムの結晶融解温度が20
6〜238℃であるポリエステル樹脂フイルムが被覆されて
いることを特徴とする加工性、加工耐食性の優れたポリ
エステル樹脂フイルム積層Snめっき鋼板。1. An amount of Sn on one surface of the steel sheet of 1.0 to 6.4 g / m 2 ,
The Fe-Sn alloy layer growth area after heating and laminating the polyester resin film is 75% or less of the electrodeposition area of Sn, and the continuous Sn
After the diameter of the single crystal was subjected to Sn plating, including those of 0.2 to 5 .mu.m 60% or more, 16~120mg / m 2 of metallic Cr layer, Cr water 5 to 30 mg / m 2 as Cr layer thereon A hydrated oxide layer is formed, and the crystal melting temperature of the film is 20
A polyester resin film-laminated Sn-plated steel sheet with excellent workability and corrosion resistance, characterized by being coated with a polyester resin film of 6 to 238 ° C.
のSnめっきを施した後、16〜100mg/m2の金属Cr層、その
上層にCr量として５〜20mg/m2のCr水和酸化物層を形成
させ、さらに上層にフイルムの結晶融解温度が206〜238
℃、フイルムの面内全ての部位における屈折率が1.5850
〜1.6100、フイルムの厚み方向の屈折率が1.5510〜1.57
50で、かつ、フイルムの面配向係数が0.010〜0.049であ
るポリエステル樹脂フイルムが被覆されていることを特
徴とする加工性、加工耐食性の優れたポリエステル樹脂
フイルム積層Snめっき鋼板。2. The amount of Sn on one surface of the steel sheet is 1.7 to 7.4 g / m 2 ,
After applying Sn plating of 16 to 100 mg / m 2 of metal Cr layer, Cr hydrate oxide layer of 5 to 20 mg / m 2 as Cr amount is formed on the upper layer, and the crystal melting temperature of the film is further formed on the upper layer. Is 206-238
℃, the refractive index of all parts of the film surface is 1.5850
~ 1.6100, the refractive index in the film thickness direction is 1.5510 ~ 1.57
A polyester resin film-laminated Sn-plated steel sheet having excellent processability and processing corrosion resistance, which is coated with a polyester resin film having a surface orientation coefficient of 50 and a film surface orientation coefficient of 0.010 to 0.049.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31889589A JPH085160B2 (en) | 1989-12-11 | 1989-12-11 | Polyester resin film laminated Sn plated steel sheet with excellent workability and corrosion resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31889589A JPH085160B2 (en) | 1989-12-11 | 1989-12-11 | Polyester resin film laminated Sn plated steel sheet with excellent workability and corrosion resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03180339A JPH03180339A (en) | 1991-08-06 |
| JPH085160B2 true JPH085160B2 (en) | 1996-01-24 |
Family
ID=18104166
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31889589A Expired - Fee Related JPH085160B2 (en) | 1989-12-11 | 1989-12-11 | Polyester resin film laminated Sn plated steel sheet with excellent workability and corrosion resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH085160B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4714974B2 (en) * | 2000-09-07 | 2011-07-06 | Ｊｆｅスチール株式会社 | Film laminated steel sheet |
-
1989
- 1989-12-11 JP JP31889589A patent/JPH085160B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03180339A (en) | 1991-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1337042C (en) | Polyester resin film laminated steel sheet for drawn and ironed can and method for production thereof | |
| JP4487651B2 (en) | Surface-treated metal material and surface treatment method thereof, resin-coated metal material, metal can, metal lid | |
| TW201217578A (en) | Steel sheet for container and method for manufacturing therefor | |
| JP3117727B2 (en) | Thermoplastic resin-coated aluminum alloy sheet, method for manufacturing the same, and manufacturing apparatus | |
| JP2012082515A (en) | Steel sheet for container and its manufacturing method | |
| JP4631111B2 (en) | Aluminum can materials, cans and can lids | |
| GB2234704A (en) | Method for producing steel sheet laminated with a polyester resin film | |
| JPH085160B2 (en) | Polyester resin film laminated Sn plated steel sheet with excellent workability and corrosion resistance | |
| CA2000356C (en) | Copolyester resin film laminated metal sheet and method for production thereof | |
| US5213903A (en) | Tin-plated steel sheet with a chromium bilayer and a copolyester resin laminate and method | |
| EP0415345B1 (en) | Composite steel sheet having high workability for drawn and ironed cans | |
| EP0664209A1 (en) | Metal sheet laminated with resin films | |
| JP2587302B2 (en) | Polyester resin film laminated surface treated steel sheet excellent in processing corrosion resistance and method for producing the same | |
| EP0747135B1 (en) | Drawn and wall-ironed can body having excellent corrosion resistance and flavor retention and production method thereof | |
| JP3034811B2 (en) | Thermoplastic polyester resin coated surface treated steel sheet and method for producing the same | |
| JP2515581B2 (en) | Polyester resin coated metal plate for ironing can | |
| GB2246319A (en) | Copolyester resin film laminated tin-plated steel sheet | |
| JP2790647B2 (en) | Composite coated steel sheet excellent in DI formability and method for producing the same | |
| JP3489167B2 (en) | Two-piece drawn ironing can with excellent corrosion resistance and flavor resistance, and method for producing the same | |
| JPH09123342A (en) | Manufacture of laminated steel plate, laminate steel plate and surface treating steel plate used therefor | |
| JP4872315B2 (en) | Surface-treated steel sheet and method for producing the same, resin-coated steel sheet, can and can lid | |
| JPH0225593A (en) | Production of taint-free steel sheet having uniform chromium oxidative film | |
| JPH0398844A (en) | Contracted or contracted-stroked can of laminated material and manufacture thereof | |
| JP2002299187A (en) | Thermoplastic resin-coated aluminum alloy board and method of manufacturing the same | |
| JP3029529B2 (en) | Polycarbonate resin coated metal plate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |