JPH06320669A - Resin-coated metal plate for thin and deeply drawn can - Google Patents
Resin-coated metal plate for thin and deeply drawn canInfo
- Publication number
- JPH06320669A JPH06320669A JP2418199A JP41819990A JPH06320669A JP H06320669 A JPH06320669 A JP H06320669A JP 2418199 A JP2418199 A JP 2418199A JP 41819990 A JP41819990 A JP 41819990A JP H06320669 A JPH06320669 A JP H06320669A
- Authority
- JP
- Japan
- Prior art keywords
- polyester resin
- metal plate
- resin layer
- layer
- coated
- 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.)
- Granted
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 134
- 239000002184 metal Substances 0.000 title claims abstract description 134
- 229920005989 resin Polymers 0.000 title claims abstract description 36
- 239000011347 resin Substances 0.000 title claims abstract description 36
- 229920001225 polyester resin Polymers 0.000 claims abstract description 228
- 239000004645 polyester resin Substances 0.000 claims abstract description 228
- 239000010410 layer Substances 0.000 claims abstract description 186
- 239000012790 adhesive layer Substances 0.000 claims abstract description 9
- 238000002844 melting Methods 0.000 claims description 31
- 230000008018 melting Effects 0.000 claims description 31
- 239000000049 pigment Substances 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 abstract description 27
- 230000007797 corrosion Effects 0.000 abstract description 27
- 238000012545 processing Methods 0.000 abstract description 18
- 239000000853 adhesive Substances 0.000 abstract description 11
- 230000001070 adhesive effect Effects 0.000 abstract description 11
- 239000000203 mixture Substances 0.000 abstract description 9
- 239000003822 epoxy resin Substances 0.000 abstract description 5
- 229920000647 polyepoxide Polymers 0.000 abstract description 5
- 238000000034 method Methods 0.000 description 74
- 239000005029 tin-free steel Substances 0.000 description 47
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 46
- 229910000831 Steel Inorganic materials 0.000 description 34
- 239000010959 steel Substances 0.000 description 34
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 32
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 28
- 238000000465 moulding Methods 0.000 description 26
- 229910052782 aluminium Inorganic materials 0.000 description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 18
- 229920001634 Copolyester Polymers 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 16
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- -1 polyethylene terephthalate Polymers 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 13
- 229910052804 chromium Inorganic materials 0.000 description 12
- 239000011651 chromium Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 239000003973 paint Substances 0.000 description 12
- 229920000728 polyester Polymers 0.000 description 12
- 150000002148 esters Chemical class 0.000 description 9
- 238000010030 laminating Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 238000003475 lamination Methods 0.000 description 8
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 8
- 239000002344 surface layer Substances 0.000 description 7
- 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 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 6
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 6
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 6
- 239000010687 lubricating oil Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000011135 tin Substances 0.000 description 6
- 229910052718 tin Inorganic materials 0.000 description 6
- 239000005028 tinplate Substances 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 230000037303 wrinkles Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 3
- 238000010306 acid treatment Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910000423 chromium oxide Inorganic materials 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000012937 correction Methods 0.000 description 3
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 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 2
- 229910018134 Al-Mg Inorganic materials 0.000 description 2
- 229910018467 Al—Mg Inorganic materials 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000009998 heat setting Methods 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- FCJSHPDYVMKCHI-UHFFFAOYSA-N phenyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC=CC=C1 FCJSHPDYVMKCHI-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229940043375 1,5-pentanediol Drugs 0.000 description 1
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、薄肉化深絞り缶用樹脂
被覆金属板に関するものであり、さらに詳しくは最表層
と金属板と相接している層の面配向係数が異なるポリエ
ステル樹脂層で被覆された薄肉化深絞り缶用樹脂被覆金
属板に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin-coated metal plate for a thin-walled deep drawing can, and more specifically, a polyester resin layer having different surface orientation coefficients between the outermost layer and the layer in contact with the metal plate. The present invention relates to a resin-coated metal plate for use in a thin-walled deep-drawing can coated with.
【０００２】[0002]
【従来の技術】従来から、食缶あるいは飲料缶には、缶
胴、缶蓋、底蓋の三つの部分からなる３ピース缶と缶胴
と底蓋が一体となった缶体、缶蓋の二つの部分からなる
２ピース缶が用いられている。この３ピース缶の缶胴に
は一回あるいは数回の塗装を施したぶりき、電解クロム
酸処理鋼板（一般にティンフリースチールと呼ばれ、以
下ＴＦＳと略す）が使用され、接合にははんだ付け、ナ
イロンによる接着、あるいは抵抗溶接をする方法が使用
されている。このように塗装を施すことは、焼付工程が
煩雑であるばかりでなく、焼付けのため長時間の加熱が
必要である。また、焼付工程で塗料中の多量の溶剤成分
が排出されるため、公害面から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もってい
た。また、２ピース缶には絞り缶、絞り再絞り缶（Ｄｒ
ａｗｎ ａｎｄ ｒｅｄｒａｗｎ ｃａｎ、ＤＲＤ
缶）、絞りしごき缶（Ｄｒａｗｎ ａｎｄ Ｉｒｏｎｅ
ｄ Ｃａｎ、ＤＩ缶）があるが、絞り缶、ＤＲＤ缶のよ
うな比較的絞り比の小さい缶には上記の３ピース缶用の
材料と同様に塗装を施したぶりきまたはＴＦＳが使用さ
れている。 そのため上記同様に工程面および環境汚染
の面から問題がある。また絞り缶、ＤＩ缶にはぶりきお
よびアルミニウムが使用されているが、ＤＩ缶の製造に
は成形時に潤滑油を用い、成形加工後、この潤滑油を洗
浄で除去し、乾燥後、缶の内外面に塗装が施される。こ
のＤＩ缶の製造工程は公害面から潤滑油の処理、塗料焼
き付け時における塗料中から揮散される溶剤成分の処理
などに問題がある。近年、塗装を施したＴＦＳを絞り加
工後、ストレッチ加工を施す薄肉化深絞り缶の製造技術
が開発され、その材料として塗装したＴＦＳが検討され
てきた。しかし塗装したＴＦＳはこのような厳しい加工
を施した時、塗膜に無数のクラックが入り、いまだに特
性良好な薄肉化深絞り缶は実用化されていない。2. Description of the Related Art Conventionally, a food or beverage can has a three-piece can consisting of a can body, a can lid, and a bottom lid, a can body in which the can body and the bottom lid are integrated, and a can lid. A two-piece can consisting of two parts is used. The tin barrel of this three-piece can is coated with tinplate once or several times, and electrolytic chromic acid treated steel plate (generally called tin-free steel, abbreviated as TFS hereafter) is used, and soldering is used for joining. Adhesion with nylon, or resistance welding is used. Such coating not only complicates the baking process, but also requires heating for a long time for baking. Further, since a large amount of solvent component in the paint is discharged in the baking process, there is a drawback that the discharged solvent must be guided to a special incinerator and incinerated from the viewpoint of pollution. Two-piece cans are squeezed cans and squeezed re-squeezed cans (Dr.
aw and red draw can, DRD
Cans, squeezed ironed cans (Drawn and Iron)
d Can, DI can), but cans with a relatively small drawing ratio, such as squeezed cans and DRD cans, are coated with tinplate or TFS as with the materials for the above-mentioned three-piece cans. There is. Therefore, similar to the above, there are problems in terms of process and environmental pollution. Although tin and aluminum are used for squeezing cans and DI cans, lubricating oil is used at the time of molding for the manufacture of DI cans. After molding, this lubricating oil is removed by washing, and after drying, The inner and outer surfaces are painted. In the manufacturing process of this DI can, there are problems in terms of pollution, such as the treatment of lubricating oil and the treatment of solvent components that are volatilized from the paint during baking of the paint. In recent years, a manufacturing technology for a thin-walled deep-drawing can in which a coated TFS is drawn and then stretched is developed, and the painted TFS has been studied as a material thereof. However, when the coated TFS undergoes such severe processing, numerous cracks are formed in the coating film, and a thin-walled deep-drawing can having good characteristics has not yet been put to practical use.
【０００３】この薄肉化深絞り缶の製造技術はＤＩ缶の
製造技術に比較し、例えば、製造設備がコンパクトで設
備費が安い、設備設置面積が小さい、運転人員の削減が
可能である、プレコート材の使用が可能であり、公害対
策が不要であり、ぶりきより安価なＴＦＳの使用が可能
であるなど多くの利点をもっているが、塗料をプレコー
トしたＴＦＳを薄肉化深絞り缶へ適用した場合、加工後
の耐食性が不十分であるため、いまだに広く普及してい
ない。一方、塗装に代わる方法として、ポリエステル樹
脂フィルムを接着剤を使用せずに金属板に積層する方法
（特公昭６０−４７１０３号）およびエポキシ樹脂とそ
の硬化剤などからなる重合組成物などを予め塗布したポ
リエステル樹脂フィルムを金属板に積層する方法（特公
昭６３−１３８２９号、特開平１−２４９３３１号、特
願平１−１５４５２３号）が開発されている。特公昭６
３−１３８２９号の方法で得られたポリエステル樹脂被
覆鋼板はエポキシ系の重合組成物を介して二軸延伸ポリ
エチレンテレフタレートフィルムで鋼板表面を被覆した
鋼板であり、ポリエチレンテレフタレートフィルムの加
工性がつぎに記す共重合ポリエステル樹脂フィルムの加
工性より劣り、比較的加工程度が小さい絞り缶、ＤＲＤ
缶、缶蓋用には使用可能であるが、さらに厳しい加工性
が要求される薄肉化深絞り缶用には使用できない。その
理由はこのような厳しい加工を施すと、ポリエステル樹
脂フィルムが剥離したり、フィルムに無数のクラックが
入るためであり、腐食性の強い内容物を充填することが
できない。また、特開平１−２４９３３１号の方法で得
られたポリエステル樹脂被覆金属板は積層される共重合
ポリエステル樹脂フィルムの軟化開始温度、結晶融解温
度、破断伸びを限定したものであり、また特願平１−１
５４５２３号の方法で得られるポリエステル樹脂被覆金
属板は積層される共重合ポリエステル樹脂フィルムの面
内の屈折率および結晶融解温度を限定したものである。
これらの方法で用いられるフィルムは特公昭６３−１３
８２９号で用いられるフィルムより加工性は優れている
が、薄肉化深絞り缶用に適用した場合、積層されたフィ
ルムが金属表面より剥離することがある。これは金属表
面と相接しているポリエステル樹脂層の面配向係数およ
び最表層のポリエステル樹脂層の面配向係数を調整され
ないため、成形加工性および金属板表面との密着性、特
に、薄肉化深絞り缶のような厳しい成形加工後の密着性
が劣ることによる。The manufacturing technology of this thin-walled deep-drawing can is compared with the manufacturing technology of DI can, for example, the manufacturing equipment is compact and the equipment cost is low, the equipment installation area is small, and the number of operating personnel can be reduced. It has many advantages such as the ability to use materials, no pollution measures required, and the use of cheaper TFS than tinplate, but when applying TFS pre-coated with paint to thin-walled deep-drawing cans. However, the corrosion resistance after processing is insufficient, so that it is not widely used yet. On the other hand, as an alternative to painting, a method of laminating a polyester resin film on a metal plate without using an adhesive (Japanese Patent Publication No. 60-47103) and a polymer composition composed of an epoxy resin and its curing agent, etc. are applied beforehand. A method of laminating the above polyester resin film on a metal plate (Japanese Patent Publication No. 63-13829, Japanese Patent Application Laid-Open No. 1-249331, Japanese Patent Application No. 1-154523) has been developed. Tokusho Sho 6
The polyester resin-coated steel sheet obtained by the method of 3-13829 is a steel sheet whose steel sheet surface is coated with a biaxially stretched polyethylene terephthalate film through an epoxy-based polymerization composition, and the workability of the polyethylene terephthalate film is described below. DRD, which is inferior to the processability of the copolyester resin film and has a relatively small processability
Although it can be used for cans and can lids, it cannot be used for thin-walled deep-drawing cans that require more severe workability. The reason for this is that if such a severe process is applied, the polyester resin film peels off or countless cracks are formed in the film, and it is not possible to fill the contents with strong corrosiveness. Further, the polyester resin-coated metal plate obtained by the method of JP-A-1-249331 limits the softening start temperature, crystal melting temperature, and elongation at break of the copolymerized polyester resin film to be laminated. 1-1
The polyester resin-coated metal plate obtained by the method of No. 54523 has a limited in-plane refractive index and crystal melting temperature of the copolymerized polyester resin film to be laminated.
Films used in these methods are disclosed in JP-B-63-13.
Although it has better processability than the film used in No. 829, when applied to a thin-walled deep drawing can, the laminated film may peel off from the metal surface. This is because the surface orientation coefficient of the polyester resin layer that is in contact with the metal surface and the surface orientation coefficient of the outermost polyester resin layer are not adjusted, so that the moldability and the adhesion to the metal plate surface, especially the thinning depth This is due to the poor adhesion after severe forming such as a squeeze can.
【０００４】[0004]
【発明が解決しようとする課題】このように従来の製缶
技術に比較し、薄肉化深絞り缶の製造技術は多くの利点
をもっているが、この薄肉化深絞り缶に適した材料がな
い。本発明は薄肉化深絞り缶に適した優れた加工性、お
よび加工耐食性を兼ね備えた樹脂被覆金属板を開発する
ことにある。As described above, the manufacturing technique of the thin-walled deep-drawing can has many advantages as compared with the conventional can-making technology, but there is no material suitable for the thin-walled deep-drawing can. The present invention is to develop a resin-coated metal plate suitable for a thin-walled deep-drawing can and having excellent workability and corrosion resistance.
【０００５】[0005]
【課題を解決するための手段】本発明は、種々検討の結
果、金属板の片面あるいは両面上に接着剤を介して、ま
たは介さずに金属板と相接しているポリエステル樹脂層
の面配向係数（ｎ１）を０以上、０．１０以下、最表層
のポリエステル樹脂層の面配向係数（ｎ２）を０．０１
以上、０．１５以下で、好ましくは、ｎ２≧ｎ１である
ポリエステル樹脂層を金属板上に形成することによっ
て、厳しい加工性および加工耐食性が要求される薄肉化
深絞り缶用に適したポリエステル樹脂被覆金属板を得る
ことができる。DISCLOSURE OF THE INVENTION As a result of various studies, the present invention has revealed that the surface orientation of a polyester resin layer which is in contact with a metal plate on one side or both sides of the metal plate with or without an adhesive. The coefficient (n 1 ) is 0 or more and 0.10 or less, and the surface orientation coefficient (n 2 ) of the outermost polyester resin layer is 0.01.
As described above, by forming the polyester resin layer of 0.15 or less, preferably n 2 ≧ n 1 on the metal plate, it is suitable for a thin-walled deep-drawing can requiring severe workability and work corrosion resistance. A polyester resin-coated metal plate can be obtained.
【０００６】以下、本発明の内容について詳細に説明す
る。まず、本発明に用いられるポリエステル樹脂フィル
ムは、少なくともポリエステル樹脂層のなかに配向部分
があることが重要である。ポリエステル樹脂の組成とし
てはエステル反復単位の７５〜９５％がエチレンテレフ
タレート単位からなり、残りの５〜２５％のエステル反
復単位がエチレンテレフタレート単位以外のエステル単
位からなることが好ましい。テレフタル酸以外の酸成分
としては、フタル酸、イソフタル酸、コハク酸、アゼラ
イン酸、アジピン酸、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種以上の酸成分が挙げられ、エチ
レングリコール以外のアルコール成分としては、１，４
ブタンジオール、１，５ペンタンジオンジオール、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
和多価アルコールが挙げられる。エチレンテレフタレー
ト単位以外のエステル単位は、酸成分およびアルコール
成分の何れか一方あるいは両方がテレフタル酸以外の酸
成分およびエチレングリコール以外の多価アルコールで
あれば良く、上述した酸成分および多価アルコール成分
を用いて共重合ポリエステルを得ることができる。この
ような共重合ポリエステル樹脂は共重合成分からなるポ
リエステルをエチレンテレフタレート樹脂にブレンド
後、溶融し、分配反応により共重合化する方法により得
ることも可能である。これらの共重合ポリエステル樹脂
は公知の押出機によりフィルム成形後、縦横二方向に延
伸し、熱固定することによって製造される。また、融点
がことなる二種以上のポリエステル樹脂を共押出しする
ことによって、多層化することも可能である。フィルム
成形後、延伸を施さない未延伸フィルムは製缶工具との
摩擦係数が高くなり、極端に製缶性が低下するととも
に、内容物に対するバリヤー性も劣ってくるため、本発
明において最表層を構成するポリエステル樹脂層は配向
されていることが必須である。ある場合には、フィルム
成形時に必要に応じて、安定剤、酸化防止剤、帯電防止
剤、顔料、滑剤、腐食防止剤などのような添加剤を加え
ても本発明に支障をきたすことはない。The contents of the present invention will be described in detail below. First, it is important that the polyester resin film used in the present invention has an oriented portion at least in the polyester resin layer. As for the composition of the polyester resin, it is preferable that 75 to 95% of the ester repeating units consist of ethylene terephthalate units and the remaining 5 to 25% of the ester repeating units consist of ester units other than ethylene terephthalate units. Acid components other than terephthalic acid include phthalic acid, isophthalic acid, succinic acid, azelaic acid, adipic acid, sebacic acid, dodecanedioic acid,
Diphenylcarboxylic acid, 2,6 naphthalenedicarboxylic acid, 1,4 cyclohexanedicarboxylic acid, and one or more kinds of acid components such as trimetic anhydride can be mentioned. Examples of alcohol components other than ethylene glycol include 1,4
Butanediol, 1,5 Pentanedionediol, 1,
6 Hexanediol, propylene glycol, polytetramethylene glycol, trimethylene glycol, triethylene glycol, neopentyl glycol, 1,4
One or more saturated polyhydric alcohols such as cyclohexanedimethanol, trimethylolpropane and pentaerythritol may be mentioned. The ester unit other than the ethylene terephthalate unit may be any one or both of the acid component and the alcohol component as long as it is an acid component other than terephthalic acid and a polyhydric alcohol other than ethylene glycol. It can be used to obtain a copolyester. Such a copolymerized polyester resin can also be obtained by a method in which a polyester comprising a copolymerization component is blended with an ethylene terephthalate resin, melted, and copolymerized by a partition reaction. These copolyester resins are produced by forming a film by a known extruder, stretching the film in two directions of length and width, and heat setting. It is also possible to form a multilayer by coextruding two or more kinds of polyester resins having different melting points. After film formation, an unstretched film that has not been stretched has a high coefficient of friction with a can making tool, and extremely lowers can forming properties, and also has poor barrier properties with respect to the contents. It is essential that the constituent polyester resin layer is oriented. In some cases, addition of additives such as stabilizers, antioxidants, antistatic agents, pigments, lubricants, corrosion inhibitors, etc., as necessary during film formation does not hinder the present invention. .
【０００７】また、本発明において使用されるポリエス
テル樹脂フィルムの厚さは特に限定するものでないが、
５〜５０μｍが好ましい。厚さが５μｍ以下になると、
ラミネート作業性が著しく低下するとともに、十分な加
工耐食性が得られない。また、厚さが５０μｍ以上にな
ると、製缶用材料に広く使用されているエポキシ系樹脂
塗料などと比較し経済的でない。The thickness of the polyester resin film used in the present invention is not particularly limited,
It is preferably 5 to 50 μm. When the thickness is 5 μm or less,
Laminating workability is significantly reduced, and sufficient processing corrosion resistance cannot be obtained. Further, when the thickness is 50 μm or more, it is not economical as compared with the epoxy resin paint widely used as a material for a can.
【０００８】本発明において重要な要因であるポリエス
テル樹脂被覆鋼板の金属板と相接しているポリエステル
樹脂層および最表層のポリエステル樹脂層の面配向係数
は次ぎに示す方法で求められる。すなわち、得られたポ
リエステル樹脂被覆鋼板を塩酸に浸漬し、金属板表面を
化学的に溶解させ、ポリエステル樹脂フィルムのみを剥
離し、そのフィルムの表面側および金属との接触面側の
それぞれの縦方向、横方向および厚さ方向の屈折率をア
ッベの屈折率計で測定し、次式から求める。 面配向係数−（Ａ＋Ｂ）／２−Ｃ Ａ：縦方向のポリエステル樹脂層の屈折率 Ｂ：横方向のポリエステル樹脂層の屈折率 Ｃ：厚さ方向のポリエステル樹脂層の屈折率 この方法で求められた金属面と接しているポリエステル
樹脂層の面配向係数が０．１０以上であると、薄肉化深
絞り缶に加工した時、ポリエステル樹脂層が金属板表面
から容易に剥離する。この面配向係数が０．１０以下で
あれば、ポリエステル樹脂層は剥離しにくいが、より好
ましくは０．０５以下が必要である。上記の方法で測定
される屈折率は樹脂層の最表層から深さ５μｍ程度の樹
脂層の平均的な値であり、その値より求められる金属板
と相接しているポリエステル樹脂層の面配向係数は金属
板表面と本当に接している層の面配向係数が０、すなわ
ち、無配向ポリエステル層であっても、深さ方向５μｍ
以内に配向ポリエステル層が存在すれば、０以上とな
る。本発明において金属板表面と相接しているポリエス
テル樹脂層の面配向係数を０以上、０．１０以下とした
はこのようなことを考慮した結果であり、金属板表面と
相接しているポリエステル樹脂層の面配向係数が０であ
ることは、詳しくいえば、金属板表面と相接しているポ
リエステル樹脂層の５μｍが０、すなわち無配向ポリエ
ステル樹脂層であることを意味している。最表層のポリ
エステル樹脂層の面配向係数が０．０１以下であると、
前述したように絞り工程にいて、しわ押え工具、ポンチ
などの製缶工具との摩擦係数が高くなりすぎ、加工が均
一に行われなくなり、ポリエステル樹脂層および金属層
に著しい肌荒れを生じ好ましくない。また、ポリエステ
ル樹脂層自体の内容物に対するバリヤー性が著しく劣
り、腐食性の強い内容物を充填後、長期間保存した場
合、金属板表面が腐食されるので好ましくない。最表層
のポリエステル樹脂層の面配向係数が０．１５以上であ
ると、たとえ金属板表面と相接しているポリエステル樹
脂層の面配向係数が０．１０以下でも、薄肉化深絞り缶
へ加工した時、上層のポリエステル樹脂層に無数のクラ
ックが入り、缶として実用に供し得なくなる。すなわ
ち、薄肉化深絞り缶に加工する時、最表層のポリエステ
ル樹脂層は缶を製造する時の作業性および缶の特性（内
容物保存性、耐きず付き性など）を考慮した上で決定さ
れるべきで、最表層を構成するポリエステル樹脂層の面
配向係数としては０．０１〜０．１５の範囲にあること
が必要である。一方、厳しい絞り加工、ストレッチ加
工、ネッキング加工などを施しても、ポリエステル樹脂
層が金属板より剥離することなく追従させるためには、
金属板と相接しているポリエステル樹脂層の配向パラメ
ーターは特に重要であり、面配向係数として０以上、
０．１０以下であることが必要である。最表層のポリエ
ステル樹脂層および金属板表面と相接しているポリエス
テル樹脂層の面配向係数が前述の範囲に入っていれば特
に問題ないが、このようなポリエステル樹脂被覆金属板
を安定して製造するには、最表層のポリエステル樹脂層
の面配向係数を金属板と相接するポリエステル樹脂層の
面配向係数より大にすることが好ましい。The plane orientation coefficients of the polyester resin layer in contact with the metal plate of the polyester resin-coated steel sheet and the polyester resin layer of the outermost layer, which are important factors in the present invention, are determined by the following method. That is, the obtained polyester resin-coated steel sheet is immersed in hydrochloric acid, the surface of the metal plate is chemically dissolved, only the polyester resin film is peeled off, and the longitudinal direction of the surface side of the film and the contact surface side with the metal The refractive index in the lateral direction and the thickness direction is measured by Abbe's refractometer and calculated from the following formula. Plane orientation coefficient- (A + B) / 2-C A: Refractive index of polyester resin layer in longitudinal direction B: Refractive index of polyester resin layer in lateral direction C: Refractive index of polyester resin layer in thickness direction Determined by this method When the polyester resin layer in contact with the metal surface has a surface orientation coefficient of 0.10 or more, the polyester resin layer is easily peeled from the surface of the metal plate when processed into a thin-walled deep-drawn can. When the surface orientation coefficient is 0.10 or less, the polyester resin layer is difficult to peel off, but more preferably 0.05 or less. The refractive index measured by the above method is an average value of the resin layer having a depth of about 5 μm from the outermost layer of the resin layer, and the surface orientation of the polyester resin layer in contact with the metal plate obtained from the value As for the coefficient, the plane orientation coefficient of the layer that is actually in contact with the surface of the metal plate is 0, that is, even in the non-oriented polyester layer, the depth direction is 5 μm.
If the oriented polyester layer is present within, the value is 0 or more. In the present invention, the plane orientation coefficient of the polyester resin layer which is in contact with the surface of the metal plate is set to 0 or more and 0.10 or less, which is a result of considering such a fact, and the surface orientation coefficient is in contact with the surface of the metal plate. Specifically, the fact that the plane orientation coefficient of the polyester resin layer is 0 means that 5 μm of the polyester resin layer in contact with the surface of the metal plate is 0, that is, it is a non-oriented polyester resin layer. When the surface orientation coefficient of the outermost polyester resin layer is 0.01 or less,
As described above, in the drawing step, the coefficient of friction with a wrinkle pressing tool, a punch or the like can-making tool becomes too high, processing is not performed uniformly, and the polyester resin layer and the metal layer are notably roughened, which is not preferable. Further, the barrier property of the polyester resin layer itself to the contents is remarkably inferior, and when the contents having strong corrosiveness are filled and stored for a long period of time, the surface of the metal plate is corroded, which is not preferable. If the surface orientation coefficient of the outermost polyester resin layer is 0.15 or more, even if the surface orientation coefficient of the polyester resin layer in contact with the metal plate surface is 0.10 or less, it can be processed into a thin-walled deep-drawn can. When this happens, countless cracks are formed in the upper polyester resin layer, making it unusable as a can. That is, when processing into a thin-walled deep-drawn can, the outermost polyester resin layer is determined after considering workability in manufacturing the can and characteristics of the can (content preservation, scratch resistance, etc.). The surface orientation coefficient of the polyester resin layer forming the outermost layer should be in the range of 0.01 to 0.15. On the other hand, in order to follow the polyester resin layer without peeling from the metal plate even if subjected to severe drawing, stretching, necking, etc.,
The orientation parameter of the polyester resin layer in contact with the metal plate is particularly important, and the plane orientation coefficient is 0 or more,
It should be 0.10 or less. There is no particular problem as long as the plane orientation coefficient of the outermost polyester resin layer and the polyester resin layer in contact with the surface of the metal plate is within the above range, but such a polyester resin-coated metal plate can be stably produced. In order to achieve this, the surface orientation coefficient of the outermost polyester resin layer is preferably larger than the surface orientation coefficient of the polyester resin layer in contact with the metal plate.
【０００９】つぎに、金属板とポリエステル樹脂層の間
に接着剤層が介在する場合について説明する。接着剤層
が介在せず、かつ本発明で限定した範囲の面配向係数の
ポリエステル樹脂層で被覆された金属板はすでに記した
ように優れた加工性、加工耐食性、耐きず付き性を有し
ているが、より腐食性の強い内容物と接触すると、ポリ
エステル樹脂層を通して金属板表面が腐食され、ポリエ
ステル樹脂層が金属板より剥離する場合がある。金属板
とポリエステル樹脂層の間に介在する接着剤層はこのよ
うな場合における金属板表面の腐食およびポリエステル
樹脂層の剥離を防止するのに効果的である。接着剤には
公知のものも使用可能であるが、エポキシ基を分子内に
有する重合組成物がより好ましく、ポリエステル樹脂フ
ィルムの金属板と接する面に塗布、乾燥しても、あるい
は金属板表面に塗布、乾燥してもよく、その塗布方法は
特に規制するものでない。Next, the case where the adhesive layer is interposed between the metal plate and the polyester resin layer will be described. A metal plate without an adhesive layer and covered with a polyester resin layer having a plane orientation coefficient within the range limited by the present invention has excellent workability, work corrosion resistance, and scratch resistance as described above. However, when contacted with a more corrosive content, the surface of the metal plate may be corroded through the polyester resin layer, and the polyester resin layer may peel off from the metal plate. The adhesive layer interposed between the metal plate and the polyester resin layer is effective in preventing corrosion of the metal plate surface and peeling of the polyester resin layer in such a case. Known adhesives may be used as the adhesive, but a polymerization composition having an epoxy group in the molecule is more preferable, and the adhesive is applied to the surface of the polyester resin film in contact with the metal plate or dried, or on the metal plate surface. It may be applied and dried, and the application method is not particularly limited.
【００１０】本発明のポリエステル樹脂被覆鋼板を得る
には例えば次ぎに示す方法がある。すなわち、面配向係
数０．１０〜０．１５の二軸延伸ポリエステル樹脂フィ
ルムをその融点前後に加熱した金属板にラミネートし、
金属表面と接触するポリエステル樹脂面の一部あるいは
全部を溶融させ、金属板と接しているポリエステル樹脂
層の面配向係数を０以上、０．１０以下に調整する方
法、金属板に積層されるポリエステル樹脂フィルムのそ
れぞれの最表層が融点を１９０〜２３０℃のポリエステ
ル樹脂と融点２１０〜２５０℃で構成される少なくとも
二層以上からなるポリエステル樹脂フィルムを融点の低
いポリエステル樹脂面をその融点前後に加熱した金属板
に積層する方法などがある。一般にポリエステル樹脂フ
ィルムはその融点前後の温度に加熱された金属板に積層
されるため、積層後のポリエステル樹脂フィルムの金属
板側の面配向係数は積層前のフィルムの面配向係数より
低下する。また、金属板の加熱温度、ラミネートロール
の温度が高く、冷却までの時間が短いほど積層後のフィ
ルムの面配向係数は低下する。特に、加熱された金属板
から積層されるポリエステル樹脂フィルムに熱が伝達さ
れるため、金属板と相接しているポリエステル樹脂層の
面配向係数が最も小さく、金属板表面と離れるにしたが
って、積層されたポリエステル樹脂層の面配向係数は大
になり、最表層のポリエステル樹脂層の面配向係数が最
も大になる。すなわち、積層されたポリエステル樹脂層
の面配向係数は自然に傾斜が形成されていると考えられ
る。To obtain the polyester resin-coated steel sheet of the present invention, there is, for example, the following method. That is, a biaxially stretched polyester resin film having a plane orientation coefficient of 0.10 to 0.15 is laminated on a metal plate heated around its melting point,
A method of melting part or all of the polyester resin surface in contact with the metal surface to adjust the plane orientation coefficient of the polyester resin layer in contact with the metal plate to 0 or more and 0.10 or less, polyester laminated on the metal plate The outermost layer of each of the resin films is a polyester resin film having a melting point of 190 to 230 ° C. and at least two layers having a melting point of 210 to 250 ° C. A polyester resin film having a low melting point is heated around the melting point. There is a method of laminating on a metal plate. Generally, a polyester resin film is laminated on a metal plate heated to a temperature around its melting point, so that the plane orientation coefficient on the metal plate side of the polyester resin film after lamination is lower than the plane orientation coefficient of the film before lamination. Further, the higher the heating temperature of the metal plate and the temperature of the laminating roll and the shorter the time until cooling, the lower the plane orientation coefficient of the film after lamination. In particular, since heat is transferred from the heated metal plate to the laminated polyester resin film, the polyester resin layer that is in contact with the metal plate has the smallest plane orientation coefficient, and as the distance from the surface of the metal plate increases, the lamination increases. The polyester resin layer thus obtained has a large surface orientation coefficient, and the outermost polyester resin layer has the largest surface orientation coefficient. That is, it is considered that the plane orientation coefficient of the laminated polyester resin layers is naturally inclined.
【００１１】つぎに、本発明において用いられる金属板
としては、シート状および帯状の鋼板およびアルミニウ
ム板の表層にクロム水和酸化物皮膜を有することが積層
されるポリエステル樹脂フィルムとの優れた密着性を確
保するために有用である。特に下層が金属クロム、上層
がクロム水和酸化物の二層構造をもつＴＦＳが好まし
く、さらに鋼板表面に錫、ニッケル、亜鉛、アルミニウ
ムなどの１種あるいは２種以上の複層めっき、合金めっ
きを施し、その上層に上記の二層構造をもつＴＦＳ皮膜
あるいはクロム水和酸化物皮膜を形成させたもの、ある
いはアルミニウムに電解クロム酸処理、浸漬クロム酸処
理を施し、表層にクロム水和酸化物皮膜を形成させたも
のなどが用いられる。表層のクロム水和酸化物皮膜の量
がクロムとして３ｍｇ／ｍ２以下あるいは５０ｍｇ／ｍ
２以上であると、積層されたポリエステル樹脂層との密
着性、とくに加工後の密着性が低下する。したがって、
クロム水和酸化物皮膜の量はクロムとして３〜５０ｍｇ
／ｍ２の範囲が好ましく、より好ましくは７〜２５ｍｇ
／ｍ２である。金属クロム量は特に限定する必要はない
が、加工後の耐食性、ポリエステル樹脂層の密着性の観
点より、１０〜２００ｍｇ／ｍ２の範囲にあることがよ
り好ましい。Next, as the metal plate used in the present invention, a sheet-shaped or strip-shaped steel plate and an aluminum plate having a chromium hydrate oxide film on the surface layer have excellent adhesion to a polyester resin film to be laminated. Is useful to secure. In particular, TFS having a two-layer structure in which the lower layer is metallic chromium and the upper layer is chromium hydrated oxide is preferable, and one or more multi-layer plating or alloy plating of tin, nickel, zinc, aluminum or the like is further applied to the steel plate surface. The above-mentioned two-layered TFS film or chrome hydrate oxide film is formed on the upper layer, or aluminum is subjected to electrolytic chromic acid treatment or immersion chromic acid treatment, and the surface layer is a chrome hydrate oxide film. What is formed is used. The amount of chromium hydrate oxide film on the surface layer is 3 mg / m 2 or less as chromium or 50 mg / m
When it is 2 or more, the adhesiveness to the laminated polyester resin layer, especially the adhesiveness after processing is deteriorated. Therefore,
The amount of chromium hydrate oxide film is 3 to 50 mg as chromium.
/ M 2 range is preferred, more preferably 7-25 mg
/ M 2 . The amount of metallic chromium is not particularly limited, but is preferably in the range of 10 to 200 mg / m 2 from the viewpoint of corrosion resistance after processing and adhesion of the polyester resin layer.
【００１２】金属板を加熱する方法都市手は、公知の熱
風循環伝熱方式、抵抗加熱方式、誘導加熱方式、ヒート
ロール方式などがあげられ、これらの方式を単独あるい
は併用してもよい。Methods for heating a metal plate In the city area, known hot air circulation heat transfer methods, resistance heating methods, induction heating methods, heat roll methods, etc. may be mentioned, and these methods may be used alone or in combination.
【００１３】[0013]
実施例１ 板厚０．１７ｍｍ、テンパー度ＤＲ−１０のＴＦＳ（金
属クロム量１１０ｍｇ／ｍ２、クロム水和酸化物皮膜中
のクロム量１４ｍｇ／ｍ２）の両面に、イソフタル酸１
２モル％、テレフタル酸８８モル％、エチレングリコー
ル１００モル％の重合で得られた二軸配向共重合ポリエ
ステル樹脂フィルム（面配向係数０．１２５、厚さ２０
μｍ、融点２３０℃）を２３５℃の温度で積層した。得
られたポリエステル樹脂被覆鋼板を詳細な説明の中で示
した方法で、鋼板と相接していたポリエステル樹脂層お
よび最表層のポリエステル樹脂層の面配向係数を求めた
後、下記に示す加工条件で薄肉化深絞り缶を得た。さら
に、常法の手段により、ドーミング、ネッキング、フラ
ンジング加工を施した。 〔成形条件〕 Ａ．絞り工程 ブランク径：１８７ｍｍ 絞り比：１．５０ Ｂ．再絞り工程 第１次再絞り比：１．２９ 第２次再絞り比：１．２４ 第３次再絞り比：１．２０ 再絞り工程のダイスのコーナー部の曲率半径：０．４ｍ
ｍ 再絞り工程のしわ押え荷重：６０００ｋｇ Ｃ．缶胴部の平均薄肉化率 成形前のポリエステル樹脂被覆鋼板の厚さに対し−２０
％Example 1 Isophthalic acid 1 was formed on both surfaces of a TFS having a plate thickness of 0.17 mm and a temper degree of DR-10 (amount of metallic chromium of 110 mg / m 2 and an amount of chromium in a hydrated chromium oxide film of 14 mg / m 2 ).
Biaxially oriented copolymerized polyester resin film obtained by polymerization of 2 mol%, terephthalic acid 88 mol% and ethylene glycol 100 mol% (plane orientation coefficient 0.125, thickness 20
μm, melting point 230 ° C.) was laminated at a temperature of 235 ° C. The obtained polyester resin-coated steel sheet was obtained by the method shown in the detailed description, after determining the plane orientation coefficient of the polyester resin layer and the outermost polyester resin layer that were in contact with the steel sheet, and then the processing conditions shown below. Thus, a thin-walled deep-drawing can was obtained. Further, doming, necking, and flanging were performed by a conventional method. [Molding conditions] A. Drawing process Blank diameter: 187 mm Drawing ratio: 1.50 B. Redrawing process Primary redrawing ratio: 1.29 Secondary redrawing ratio: 1.24 Third redrawing ratio: 1.20 Curvature radius of corner of die in redrawing process: 0.4 m
Wrinkle holding load in redrawing process: 6000 kg C.I. The average thinning rate of the body of the can -20 against the thickness of the polyester resin-coated steel sheet before forming
%
【００１４】実施例２ 実施例１に示したＴＦＳの両面にイソフタル酸１２モル
％、テレフタル酸８８モル％、エチレングリコール１０
０モル％の重合で得られたポリエステル樹脂とイソフタ
ル酸１８モル％、テレフタル酸８２モル％、エチレング
リコール１００モル％の重合で得られたポリエステル樹
脂からなる二層二軸配向共重合ポリエステル樹脂フィル
ム（イソフタル酸１２モル％含むポリエステル樹脂層の
厚さ１５μｍ、融点２３０℃、面配向係数０．１２２、
イソフタル酸１８モル％含むポリエステル樹脂層の厚さ
５μｍ、融点２１４℃、面配向係数０．０８）をイソフ
タル酸１８モル％含むポリエステル樹脂層側がＴＦＳ面
と相接するように、２２８℃で積層した。得られたポリ
エステル樹脂被覆鋼板のＴＦＳ面と相接する層および最
表層のポリエステル樹脂層の面配向係数を求めた後、実
施例１と同様な条件で成形加工を施した。Example 2 Isophthalic acid 12 mol%, terephthalic acid 88 mol%, ethylene glycol 10 on both sides of the TFS shown in Example 1.
A two-layer biaxially oriented copolymerized polyester resin film comprising a polyester resin obtained by polymerization of 0 mol% and a polyester resin obtained by polymerization of 18 mol% of isophthalic acid, 82 mol% of terephthalic acid and 100 mol% of ethylene glycol ( Polyester resin layer containing 12 mol% of isophthalic acid having a thickness of 15 μm, melting point of 230 ° C., plane orientation coefficient of 0.122,
A polyester resin layer containing 18 mol% of isophthalic acid having a thickness of 5 μm, a melting point of 214 ° C. and a plane orientation coefficient of 0.08) was laminated at 228 ° C. so that the polyester resin layer side containing 18 mol% of isophthalic acid was in contact with the TFS surface. . After obtaining the plane orientation coefficients of the layer contacting the TFS surface and the outermost polyester resin layer of the obtained polyester resin-coated steel sheet, molding was performed under the same conditions as in Example 1.
【００１５】実施例３ 実施例１に示したＴＦＳの片面に実施例１で用いた二軸
配向共重合ポリエステル樹脂フィルムを、他の片面に酸
化チタン１２重量％含むイソフタル酸１２モル％、テレ
フタル酸８８モル％、エチレングリコール１００モル％
の重合で得られた白色共重合ポリエステル樹脂フィルム
（厚さ２０μｍ）を２５０℃で積層した。得られたポリ
エステル樹脂被覆鋼板のＴＦＳ面と相接する層および最
表層のポリエステル樹脂層の面配向係数を求めた後、白
色共重合ポリエステル樹脂フィルム被覆面が缶外面とな
るように、実施例１と同様な条件で成形加工を施した。
ただし白色共重合ポリエステルフィルムの面配向係数は
求めることができないので省略した。Example 3 The biaxially oriented copolyester resin film used in Example 1 was used on one side of the TFS shown in Example 1, and 12 mol% of isophthalic acid containing 12% by weight of titanium oxide and terephthalic acid on the other side. 88 mol%, ethylene glycol 100 mol%
The white copolyester resin film (thickness 20 μm) obtained by the above polymerization was laminated at 250 ° C. The surface orientation coefficients of the layer contacting the TFS surface and the outermost polyester resin layer of the obtained polyester resin-coated steel sheet were determined, and then the white copolyester resin film-coated surface was used as the outer surface of Example 1 so that Molding was performed under the same conditions as in.
However, since the plane orientation coefficient of the white copolyester film cannot be obtained, it is omitted.
【００１６】実施例４ 実施例１に示したＴＦＳの両面に予めエポキシーフェノ
ール系塗料を０．５ｇ／ｍ２塗布し、１５０℃で予備乾
燥させた後、実施例１に示したポリエステル樹脂フィル
ムを２４５℃で積層した。得られたポリエステル樹脂被
覆鋼板のＴＦＳ面および最表層のポリエステル樹脂層の
面配向係数を求めた後、実施例１と同様な条件で成形加
工を施した。Example 4 0.5 g / m 2 of an epoxy-phenolic coating material was previously applied to both surfaces of the TFS shown in Example 1 and pre-dried at 150 ° C., and then the polyester resin film shown in Example 1 was applied. Laminated at 245 ° C. After the plane orientation coefficients of the TFS surface and the outermost polyester resin layer of the obtained polyester resin-coated steel sheet were determined, the molding process was performed under the same conditions as in Example 1.
【００１７】実施例５ 予めエポキシーフェノール系塗料を０．３ｇ／ｍ２を塗
布し、１２０℃で乾燥させたセバチン酸１５モル％、テ
レフタル酸８５モル％、エチレングリコール１００モル
％の重合で得られた二軸配向共重合ポリエステル樹脂フ
ィルム（厚さ１５μｍ、融点２２３℃、面配向係数０．
０９９）を板厚０．３０ｍｍのアルミ板（Ａｌ−Ｍｇ合
金系）の片面のみに２２０℃で積層した。得られたポリ
エステル樹脂被覆アルミ板の他の片面にはビニルオルガ
ノゾル塗料を乾燥厚さで１０ｇ／ｍ２になるように塗布
し、２００℃で１０分間加熱した。得られたポリエステ
ル樹脂被覆アルミ板のアルミ表面と相接する層および最
表層のポリエステル樹脂層の面配向係数を求めた後、ポ
リエステル樹脂フィルム被覆面が缶内面となるように、
再絞り工程の成形条件を下記のように変更した以外は実
施例１と同様な条件で成形加工を施した。 〔再絞り工程の実施例１と異なる条件〕 再絞り工程のダイスのコーナー部の曲率半径：０．４ｍ
ｍ 再絞り工程のしわ押え荷重：２０００ｋｇExample 5 Obtained by polymerizing 15 mol% of sebacic acid, 85 mol% of terephthalic acid and 100 mol% of ethylene glycol, which was previously coated with 0.3 g / m 2 of an epoxy-phenolic paint and dried at 120 ° C. Biaxially oriented copolyester resin film (thickness 15 μm, melting point 223 ° C., plane orientation coefficient 0.
099) was laminated at 220 ° C. on only one surface of an aluminum plate (Al—Mg alloy system) having a plate thickness of 0.30 mm. The other surface of the obtained polyester resin-coated aluminum plate was coated with a vinyl organosol paint so that the dry thickness would be 10 g / m 2, and heated at 200 ° C. for 10 minutes. After determining the plane orientation coefficient of the layer and the outermost polyester resin layer that are in contact with the aluminum surface of the obtained polyester resin-coated aluminum plate, the polyester resin film coated surface is the inner surface of the can,
Molding was performed under the same conditions as in Example 1 except that the molding conditions in the redrawing process were changed as follows. [Conditions Different from Example 1 of Redrawing Step] Curvature Radius of Corner of Die in Redrawing Step: 0.4 m
m Wrinkle holding load in redrawing process: 2000kg
【００１８】比較例１ 実施例１に示したＴＦＳの両面に二軸配向ポリエチレン
テレフタレートフィルム（厚さ２５μｍ、融点２６０
℃、面配向係数０．１６５）を２８０℃で積層した。得
られたポリエステル樹脂被覆鋼板のＴＦＳ面と相接する
層および最表層のポリエステル樹脂層の面配向係数を求
めた後、実施例１と同様な条件で成形加工を施した。Comparative Example 1 Biaxially oriented polyethylene terephthalate film (thickness: 25 μm, melting point: 260) on both sides of the TFS shown in Example 1.
And a plane orientation coefficient of 0.165) were laminated at 280 ° C. After obtaining the plane orientation coefficients of the layer contacting the TFS surface and the outermost polyester resin layer of the obtained polyester resin-coated steel sheet, molding was performed under the same conditions as in Example 1.
【００１９】比較例２ 実施例１に示したＴＦＳの両面に実施例１に用いたポリ
エステルもち樹脂フィルムを２１０℃で積層した。得ら
れたポリエステル樹脂鋼板のＴＦＳ面と相接する層およ
び最表層のポリエステル樹脂層の面配向係数を求めた
後、実施例１と同様な条件で成形加工を施した。Comparative Example 2 The polyester glutinous resin film used in Example 1 was laminated on both surfaces of the TFS shown in Example 1 at 210 ° C. After obtaining the plane orientation coefficients of the layer contacting the TFS surface and the outermost polyester resin layer of the obtained polyester resin steel sheet, molding was performed under the same conditions as in Example 1.
【００２０】比較例３ 実施例１に示したＴＦＳの両面に実施例１に示したポリ
エステル樹脂フィルムを３０５℃で積層した。得られた
ポリエステル樹脂被覆鋼板のＴＦＳ面と相接する層およ
び最表層のポリエステル樹脂層の面配向係数を求めた
後、実施例１と同様な条件で成形加工を施した。Comparative Example 3 The polyester resin film shown in Example 1 was laminated on both sides of the TFS shown in Example 1 at 305 ° C. After obtaining the plane orientation coefficients of the layer contacting the TFS surface and the outermost polyester resin layer of the obtained polyester resin-coated steel sheet, molding was performed under the same conditions as in Example 1.
【００２１】実施例１〜５および比較例１〜３で得られ
たポリエステル被覆鋼板およびアルミ板の成形加工工程
におけるポリエステル樹脂フィルムの割れおよび剥離状
況を肉眼で観察するとともに、得られた２ピース缶体の
特性を次に示す方法で評価した。その結果を表１および
表２に示した。 （１）缶体内面の金属表面の露出度 得られた薄肉化深絞り缶に３％食塩水を充填し、缶体に
６．５Ｖの直流電圧を印加し、流れる電流値で金属表面
の露出度を評価した。 （２）耐熱水性 得られた薄肉化深絞り缶をレトルト釜に入れ、１２５℃
の水蒸気で３０分間熱水処理を施し、フランジ加工部よ
りのポリエステル樹脂フィルムの剥離状況を肉眼で評価
した。 （３）耐熱性 第３次再絞り工程を終えた絞り缶を、外面印刷の焼き付
けを想定した温度、すなわち、２００℃で５分間加熱処
理を施した後、缶胴部のポリエステル樹脂フィルムの変
色、割れ、剥離状況を肉眼で評価した。 （４）耐食性 得られた薄肉化深絞り缶に３％酢酸水を充填し、５０℃
で３ヶ月貯蔵後、開缶し、缶内面の腐食状況を、肉眼で
観察し、腐食なしを５点とし、４点、３点、２点、１点
になるにつれて腐食程度が大になるように５段階にわけ
て評価した。Two-piece cans obtained by visually observing the cracking and peeling conditions of the polyester resin film in the molding process of the polyester-coated steel plates and aluminum plates obtained in Examples 1 to 5 and Comparative Examples 1 to 3 The characteristics of the body were evaluated by the following methods. The results are shown in Tables 1 and 2. (1) Exposed degree of metal surface on the inside of the can The obtained thin-walled deep-drawn can was filled with 3% saline solution, a direct current voltage of 6.5 V was applied to the can, and the metal surface was exposed by the flowing current value. The degree was evaluated. (2) Hot water resistance Place the obtained thin-walled deep-drawing can in a retort kettle at 125 ° C.
Was subjected to hot water treatment for 30 minutes, and the state of peeling of the polyester resin film from the flanged portion was visually evaluated. (3) Heat resistance The squeezed can that has undergone the third redrawing process is subjected to heat treatment for 5 minutes at a temperature assumed for external printing, that is, 200 ° C, and then the discoloration of the polyester resin film on the can body The state of cracking and peeling was visually evaluated. (4) Corrosion resistance The obtained thin-walled deep drawing can was filled with 3% acetic acid water and heated to 50 ° C.
After storage for 3 months, open the can and observe the corrosion state of the inner surface of the can with the naked eye, and set 5 points for no corrosion to 4 points, 3 points, 2 points, 1 point so that the degree of corrosion increases The evaluation was divided into 5 stages.
【００２２】[0022]
【表１】 [Table 1]
【００２３】[0023]
【表２】 [Table 2]
【００２４】[0024]
【発明の効果】以上説明したように、本発明の薄肉化深
絞り缶用ポリエステル樹脂被覆金属板は加工性および加
工耐食性に優れた材料であり、従来の缶体に比較し、種
々の利点をもつ薄肉化深絞り缶用に用いられるだけでな
く、絞り缶、缶蓋、イージーオープン可能な缶蓋、王
冠、キャップ類など容器用材料としても、広く適用でき
る。As described above, the polyester resin-coated metal sheet for a thin-walled deep-drawn can of the present invention is a material excellent in workability and work corrosion resistance, and has various advantages as compared with the conventional can body. Not only is it used for thin-walled deep-drawing cans, but it can also be widely applied as a material for containers such as drawn cans, can lids, can lids that can be easily opened, crowns, and caps.
【手続補正書】[Procedure amendment]
【提出日】平成４年１０月２６日[Submission date] October 26, 1992
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】全文[Correction target item name] Full text
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【書類名】 明細書[Document name] Statement
【発明の名称】 薄肉化深絞り缶用樹脂被覆金属板[Title of Invention] Resin-coated metal plate for thin-walled deep-drawing can
【特許請求の範囲】[Claims]
【発明の詳細な説明】Detailed Description of the Invention
【０００１】[0001]
【産業上の利用分野】本発明は、薄肉化深絞り缶用樹脂
被覆金属板に関するものであり、さらに詳しくは最表層
と金属板と相接している層の面配向係数が異なるポリエ
ステル樹脂層で被覆された薄肉化深絞り缶用樹脂被覆金
属板に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin-coated metal plate for a thin-walled deep drawing can, and more specifically, a polyester resin layer having different surface orientation coefficients between the outermost layer and the layer in contact with the metal plate. The present invention relates to a resin-coated metal plate for use in a thin-walled deep-drawing can coated with.
【０００２】[0002]
【従来の技術】従来から、食缶あるいは飲料缶には、缶
胴、缶蓋、底蓋の三つの部分からなる３ピース缶と缶胴
と底蓋が一体となった缶体、缶蓋の二つの部分からなる
２ピース缶が用いられている。この３ピース缶の缶胴に
は一回あるいは数回の塗装を施したぶりき、電解クロム
酸処理鋼板（一般にティンフリースチールと呼ばれ、以
下ＴＦＳと略す）が使用され、接合にははんだ付け、ナ
イロンによる接着、あるいは抵抗溶接をする方法が採用
されている。このように塗装を施すことは、焼付工程が
煩雑であるばかりでなく、焼付けのため長時間の加熱が
必要である。また、焼付工程で塗料巾の多量の溶剤成分
が排出されるため、公害面から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もってい
る。また、２ピース缶には絞り缶、絞り再絞り缶（Ｄｒ
ａｗｎ ａｎｄ Ｒｅｄｒａｗｎ Ｃａｎ、ＤＲＤ
缶）、絞りしごき缶（Ｄｒａｗｎ ａｎｄ Ｉｒｏｎｅ
ｄ Ｃａｎ、ＤＩ缶）があるが、絞り缶、ＤＲＤ缶のよ
うな比較的絞り比の小さい缶には上記の３ピース缶用の
材料と同様に塗装を施したぶりきまたはＴＦＳが使用さ
れている。そのため上記同様に工程面および環境汚染の
面から問題がある。また絞り缶、ＤＩ缶にはぶりきおよ
びアルミニウムが使用されているが、ＤＩ缶の製造には
成形時に潤滑油を用い、成形加工後、この潤滑油を洗浄
で除去し、乾燥後、缶の内外面に塗装が施される。この
ＤＩ缶の製造工程は公害面から潤滑油の処理、塗料焼付
け時における塗料中から気化する溶剤成分の処理などに
問題がある。近年、塗装を施したＴＦＳを絞り加工後、
ストレッチ加工を施す薄肉化深絞り缶の製造技術が開発
され、その材料として塗装したＴＦＳが検討されてき
た。しかし、塗装したＴＦＳはこのような厳しい加工を
施した時、塗膜に無数のクラックが入り、いまだに特性
良好な薄肉化深絞り缶は実用化されていない。2. Description of the Related Art Conventionally, a food or beverage can has a three-piece can consisting of a can body, a can lid, and a bottom lid, a can body in which the can body and the bottom lid are integrated, and a can lid. A two-piece can consisting of two parts is used. The tin barrel of this three-piece can is coated with tinplate once or several times, and electrolytic chromic acid treated steel plate (generally called tin-free steel, abbreviated as TFS hereafter) is used, and soldering is used for joining. , it has been adopted a method of bonding or resistance welding with a nylon. Such coating not only complicates the baking process, but also requires heating for a long time for baking. Further, since a large amount of the solvent component having a paint width is discharged in the baking step, there is a drawback that the discharged solvent must be guided to a special incinerator and burned from the viewpoint of pollution. Two-piece cans are squeezed cans and squeezed re-squeezed cans (Dr.
awn and R edrawn C an, DRD
Cans, squeezed ironed cans (Drawn and Iron)
d Can, DI can), but cans with a relatively small drawing ratio, such as squeezed cans and DRD cans, are coated with tinplate or TFS as with the materials for the above-mentioned three-piece cans. There is. Therefore, similar to the above, there are problems in terms of process and environmental pollution. Although tin and aluminum are used for squeezing cans and DI cans, lubricating oil is used at the time of molding for the manufacture of DI cans. After molding, this lubricating oil is removed by washing, and after drying, The inner and outer surfaces are painted. In the manufacturing process of this DI can, there are problems in terms of pollution, such as the treatment of lubricating oil and the treatment of solvent components that are vaporized from the paint during baking of the paint. In recent years, after drawing coated TFS,
A manufacturing technology for a thin-walled deep-drawn can that is stretched has been developed, and coated TFS has been studied as a material for the can. However, when the coated TFS is subjected to such severe processing, countless cracks are formed in the coating film, and a thin-walled deep-drawing can having good characteristics has not yet been put into practical use.
【０００３】この薄肉化深絞り缶の製造技術はＤＩ缶の
製造技術に比較し、例えば、製造設備がコンパクトで設
備費が安い、設備設置面積が小さい、運転人員の削減が
可能である、プレコート材の使用が可能であり、公害対
策が不要であり、ぶりきより安価なＴＦＳの使用が可能
であるなど多くの利点をもっているが、塗料をプレコー
トしたＴＦＳを薄肉化深絞り缶へ適用した場合、加工後
の耐食性が不十分であるため、いまだに広く普及してい
ない。一方、塗装に代わる方法として、ポリエステル樹
脂フィルムを接着剤を使用せずに金属板に積層する方法
（特公昭６０−４７１０３号）およびエポキシ樹脂とそ
の硬化剤などからなる重合組成物などを予め塗布したポ
リエステル樹脂フィルムを金属板に積層する方法（特公
昭６３−１３８２９号、特開平１−２４９３３１号、特
願平１−１５４５２３号）が開発されている。特公昭６
３−１３８２９号の方法で得られたポリエステル樹脂被
覆鋼板はエポキシ系の重合組成物を介して二軸延伸ポリ
エチレンテレフタレートフィルムで鋼板表面を被覆した
鋼板であり、ポリエチレンテレフタレートフィルムの加
工性がつぎに記す共重合ポリエステル樹脂フイルムの加
工性より劣り、比較的加工程度が小さい絞り缶、ＤＲＤ
缶、缶蓋用には使用可能であるが、さらに厳しい加工性
が要求される薄肉化深絞り缶用には使用できない。その
理由はこのような厳しい加工を施すと、ポリエステル樹
脂フィルムが剥離したり、フィルムに無数のクラックが
入るためであり、腐食性の強い内容物を充填することが
できない。また、特開平１−２４９３３１号の方法で得
られたポリエステル樹脂被覆金属板は積層される共重合
ポリエステル樹脂フィルムの軟化開始温度、結晶融解温
度、破断伸びを限定したものであり、また特願平１−１
５４５２３号の方法で得られたポリエステル樹脂被覆金
属板は積層される共重合ポリエステル樹脂フィルムの面
内の屈折率および結晶融解温度を限定したものである。
これらの方法で用いられるフィルムは特公昭６３−１３
８２９号で用いられるフィルムより加工性は優れている
が、薄肉化深絞り缶用に適用した場合、積層されたフィ
ルムが金属板表面より剥離することがある。これは金属
板表面と相接しているポリエステル樹脂層の面配向係数
および最表層のポリエステル樹脂層の面配向係数が調整
されないため、成形加工性および金属板表面との密着
性、特に、薄肉化深絞り缶のような厳しい成形加工後の
密着性が劣ることによる。The manufacturing technology of this thin-walled deep-drawing can is compared with the manufacturing technology of DI can, for example, the manufacturing equipment is compact and the equipment cost is low, the equipment installation area is small, and the number of operating personnel can be reduced. It has many advantages such as the ability to use materials, no pollution measures required, and the use of cheaper TFS than tinplate, but when applying TFS pre-coated with paint to thin-walled deep-drawing cans. However, the corrosion resistance after processing is insufficient, so that it is not widely used yet. On the other hand, as an alternative to painting, a method of laminating a polyester resin film on a metal plate without using an adhesive (Japanese Patent Publication No. 60-47103) and a polymer composition composed of an epoxy resin and its curing agent, etc. are applied beforehand. A method of laminating the above polyester resin film on a metal plate (Japanese Patent Publication No. 63-13829, Japanese Patent Application Laid-Open No. 1-249331, Japanese Patent Application No. 1-154523) has been developed. Tokusho Sho 6
The polyester resin-coated steel sheet obtained by the method of 3-13829 is a steel sheet whose steel sheet surface is coated with a biaxially stretched polyethylene terephthalate film through an epoxy-based polymerization composition, and the workability of the polyethylene terephthalate film is described below. DRD, which is inferior to the processability of copolyester resin film and has a relatively small degree of processing
Although it can be used for cans and can lids, it cannot be used for thin-walled deep-drawing cans that require more severe workability. The reason for this is that if such a severe process is applied, the polyester resin film peels off or countless cracks are formed in the film, and it is not possible to fill the contents with strong corrosiveness. Further, the polyester resin-coated metal plate obtained by the method of JP-A-1-249331 limits the softening start temperature, crystal melting temperature, and elongation at break of the copolymerized polyester resin film to be laminated. 1-1
The polyester resin-coated metal plate obtained by the method of No. 54523 has limited in-plane refractive index and crystal melting temperature of the copolymerized polyester resin film to be laminated.
Films used in these methods are disclosed in JP-B-63-13.
Although it has better processability than the film used in No. 829, when applied to a thin-walled deep drawing can, the laminated film may peel off from the surface of the metal plate . This is metal
Since the plane orientation coefficient and surface orientation coefficient of the outermost layer of the polyester resin layer of the polyester resin layer in contact with the plate surface phase is not adjusted, adhesion between the molding processability and the surface of the metal plate, in particular, thin deep drawn cans Due to poor adhesion after severe molding.
【０００４】[0004]
【発明が解決しようとする課題】このように従来の製缶
技術に比較し、薄肉化深絞り缶の製造技術は多くの利点
をもっているが、この薄肉化深絞り缶に適した材料がな
い。本発明は薄肉化深絞り缶に適した優れた加工性およ
び加工耐食性を兼ね備えた樹脂被覆金属板を開発するこ
とにある。As described above, the manufacturing technique of the thin-walled deep-drawing can has many advantages as compared with the conventional can-making technology, but there is no material suitable for the thin-walled deep-drawing can. The present invention is to develop a resin-coated metal plate suitable for a thin-walled deep-drawing can and having excellent workability and work corrosion resistance.
【０００５】[0005]
【課題を解決するための手段】本発明は、種々検討の結
果、金属板の片面あるいは両面上に接着剤を介して、ま
たは介さずに金属板と相接しているポリエステル樹脂層
の面配向係数（ｎ１）を０以上、０．１０以下、最表層
のポリエステル樹脂層の面配向係数（ｎ２）を０．０１
以上、０．１５以下で、好ましくは、ｎ２≧ｎ１である
ポリエステル樹脂層を金属板上に形成することによっ
て、厳しい加工性および加工耐食性が要求される薄肉化
深絞り缶用に適したポリエステル樹脂被覆金属板を得る
ことができる。DISCLOSURE OF THE INVENTION As a result of various studies, the present invention has revealed that the surface orientation of a polyester resin layer which is in contact with a metal plate on one side or both sides of the metal plate with or without an adhesive. The coefficient (n 1 ) is 0 or more and 0.10 or less, and the surface orientation coefficient (n 2 ) of the outermost polyester resin layer is 0.01.
As described above, by forming the polyester resin layer of 0.15 or less, preferably n 2 ≧ n 1 on the metal plate, it is suitable for a thin-walled deep-drawing can requiring severe workability and work corrosion resistance. A polyester resin-coated metal plate can be obtained.
【０００６】以下、本発明の内容について詳細に説明す
る。まず、本発明に用いられるポリエステル樹脂フィル
ムは、少なくともポリエステル樹脂層のなかに配向部分
があることが重要である。ポリエステル樹脂の組成とし
てはエステル反復単位の７５〜９５％がエチレンテレフ
タレート単位からなり、残りの５〜２５％のエステル反
復単位がエチレンテレフタレート単位以外のエステル単
位からなることが好ましい。テレフタル酸以外の酸成分
としては、フタル酸、イソフタル酸、コハク酸、アゼラ
イン酸、アジピン酸、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種以上の酸成分が挙げられ、エチ
レングリコール以外のアルコール成分としては、１，４
ブタンジオール、１，５ペンタンジオール、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
ルコールが挙げられる。エチレンテレフタレート単位以
外のエステル単位は、酸成分およびアルコール成分の何
れか一方あるいは両方がテレフタル酸以外の酸成分およ
びエチレングリコール以外の多価アルコールであれば良
く、上述した酸成分および多価アルコール成分を用いて
共重合ポリエステルを得ることができる。このような共
重合ポリエステル樹脂は共重合成分からなるポリエステ
ルをポリエチレンテレフタレート樹脂にブレンド後、溶
融し、分配反応により共重合化する方法により得ること
も可能である。これらの共重合ポリエステル樹脂は公知
の押出機によりフィルム成形後、縦横二方向に延伸し、
熱固定することによって製造される。また、融点が異な
る２種以上のポリエステル樹脂を共押出しすることによ
って、多層化することも可能である。フィルム成形後、
延伸を施さない未延伸フィルムは製缶工具との摩擦係数
が高くなり、極端に製缶性が低下するとともに、内容物
に対するバリヤー性も劣ってくるため、本発明において
最表層を構成するポリエステル樹脂層は配向されている
ことが必須である。ある場合には、フィルム成形時に必
要に応じて、安定剤、酸化防止剤、帯電防止剤、顔料、
滑剤、腐食防止剤などのような添加剤を加えても本発明
に支障をきたすことはない。The contents of the present invention will be described in detail below. First, it is important that the polyester resin film used in the present invention has an oriented portion at least in the polyester resin layer. As for the composition of the polyester resin, it is preferable that 75 to 95% of the ester repeating units consist of ethylene terephthalate units and the remaining 5 to 25% of the ester repeating units consist of ester units other than ethylene terephthalate units. Acid components other than terephthalic acid include phthalic acid, isophthalic acid, succinic acid, azelaic acid, adipic acid, sebacic acid, dodecanedioic acid,
Diphenylcarboxylic acid, 2,6 naphthalenedicarboxylic acid, 1,4 cyclohexanedicarboxylic acid, and one or more kinds of acid components such as trimetic anhydride can be mentioned. Examples of alcohol components other than ethylene glycol include 1,4
1 of butanediol, 1,5 pentanediol , 1,6 hexanediol, propylene glycol, polytetramethylene glycol, trimethylene glycol, triethylene glycol, neopentyl glycol, 1,4 cyclohexanedimethanol, trimethylolpropane, pentaerythritol 1 type or 2 or more types of saturated polyhydric alcohols. The ester unit other than the ethylene terephthalate unit may be any one or both of the acid component and the alcohol component as long as it is an acid component other than terephthalic acid and a polyhydric alcohol other than ethylene glycol. It can be used to obtain a copolyester. After blending such copolyester resin a polyester composed of a copolymerization component poly ethylene terephthalate resin, melted, it is possible to obtain by a method of copolymerization by the distribution reaction. These copolymerized polyester resins are formed into a film by a known extruder, and then stretched in two directions of length and width,
Manufactured by heat setting. It is also possible to form a multilayer by coextruding two or more polyester resins having different melting points. After film formation,
An unstretched film that has not been stretched has a high coefficient of friction with a can-making tool and extremely lowers can-making properties, and also has poor barrier properties with respect to the contents. It is essential that the layers are oriented. In some cases, stabilizers, antioxidants, antistatic agents, pigments,
The addition of additives such as lubricants and corrosion inhibitors does not hinder the present invention.
【０００７】また、本発明において使用されるポリエス
テル樹脂フィルムの厚さは特に限定するものでないが、
５〜５０μｍが好ましい。厚さが５μｍ以下になると、
ラミネート作業性が著しく低下するとともに、十分な加
工耐食性が得られない。また、厚さが５０μｍ以上にな
ると、製缶用材料に広く使用されているエポキシ系樹脂
塗料などと比較し経済的でない。The thickness of the polyester resin film used in the present invention is not particularly limited,
It is preferably 5 to 50 μm. When the thickness is 5 μm or less,
Laminating workability is significantly reduced, and sufficient processing corrosion resistance cannot be obtained. Further, when the thickness is 50 μm or more, it is not economical as compared with the epoxy resin paint widely used as a material for a can.
【０００８】本発明において重要な要因であるポリエス
テル樹脂被覆金属板の金属板と相接しているポリエステ
ル樹脂層および最表層のポリエステル樹脂層の面配向係
数は次ぎに示す方法で求められる。すなわち、得られた
ポリエステル樹脂被覆金属板を塩酸に浸漬し、金属板表
面を化学的に溶解させ、ポリエステル樹脂フィルムのみ
を剥離し、そのフィルムの表面側および金属板との接触
面側のそれぞれの縦方向、横方向および厚さ方向の屈折
率をアッベの屈折率計で測定し、次式から求める。 面配向係数−（Ａ＋Ｂ）／Ｃ−２ Ａ：縦方向のポリエステル樹脂層の屈折率 Ｂ：横方向のポリエステル樹脂層の屈折率 Ｃ：厚さ方向のポリエステル樹脂層の屈折率 この方法で求められた金属板面と接しているポリエステ
ル樹脂層の面配向係数が０．１０以上であると、薄肉化
深絞り缶に加工した時、ポリエステル樹脂層が金属板表
面から容易に剥離する。この面配向係数が０．１０以下
であれば、ポリエステル樹脂層は剥離しにくいが、より
好ましくは０．０５以下が必要である。上記の方法で測
定される屈折率は樹脂層の最表層から深さ５μｍ程度の
樹脂層の平均的な値であり、その値より求められる金属
板と相接しているポリエステル樹脂層の面配向係数は金
属板表面と本当に接している層の面配向係数が０、すな
わち、無配向ポリエステル層であっても、深さ方向５μ
ｍ以内に配向ポリエステル層が存在すれば、０以上とな
る。本発明において金属板表面と相接しているポリエス
テル樹脂層の面配向係数を０以上、０．１０以下とした
のはこのようなことを考慮した結果であり、金属板表面
と相接しているポリエステル樹脂層の面配向係数が０で
あることは、詳しくいえば、金属板表面と相接している
ポリエステル樹脂層の５μｍが０、すなわち無配向ポリ
エステル樹脂層であることを意味している。最表層のポ
リエステル樹脂層の面配向係数が０．０１以下である
と、前述したように絞り工程において、しわ押え工具、
ポンチなどの製缶工具との摩擦係数が高くなりすぎ、加
工が均一に行われなくなり、ポリエステル樹脂層および
金属層に著しい肌荒れを生じ好ましくない。また、ポリ
エステル樹脂層自体の内容物に対するバリヤー性が著し
く劣り、腐食性の強い内容物を充填後、長期間保存した
場合、金属板表面が腐食されるので好ましくない。最表
層のポリエステル樹脂層の面配向係数が０．１５以上で
あると、たとえ金属板表面と相接しているポリエステル
樹脂層の面配向係数が０．１０以下でも、薄肉化深絞り
缶へ加工した時、上層のポリエステル樹脂層に無数のク
ラックが入り、缶として実用に供し得なくなる。すなわ
ち、薄肉化深絞り缶に加工する時、最表層のポリエステ
ル樹脂層は缶を製造する時の作業性および缶の特性（内
容物保存性、耐きず付き性など）を考慮した上で決定さ
れるべきで、最表層を構成するポリエステル樹脂層の面
配向係数としては０．０１〜０．１５の範囲にあること
が必要である。一方、厳しい絞り加工、ストレッチ加
工、ネッキング加工などを施しても、ポリエステル樹脂
層が金属板より剥離することなく追従させるためには、
金属板と相接しているポリエステル樹脂層の配向パラメ
ーターは特に重要であり、面配向係数として０以上、
０．１０以下であることが必要である。最表層のポリエ
ステル樹脂層および金属板表面と相接しているポリエス
テル樹脂層の面配向係数が前述の範囲に入っていれば特
に問題ないが、このようなポリエステル樹脂被覆金属板
を安定して製造するには、最表層のポリエステル樹脂層
の面配向係数を金属板と相接するポリエステル樹脂層の
面配向係数より大にすることが好ましい。The plane orientation coefficients of the polyester resin layer which is in contact with the metal plate of the polyester resin-coated metal plate and the polyester resin layer of the outermost layer, which are important factors in the present invention, are determined by the following method. That is, the obtained polyester resin-coated metal plate is immersed in hydrochloric acid, the surface of the metal plate is chemically dissolved, only the polyester resin film is peeled off, and the surface side of the film and the contact surface side with the metal plate are respectively removed. The refractive index in the longitudinal direction, the lateral direction and the thickness direction is measured by Abbe's refractometer, and is calculated from the following formula. Surface orientation coefficient- (A + B) / C-2 A: Refractive index of the polyester resin layer in the longitudinal direction B: Refractive index of the polyester resin layer in the lateral direction C: Refractive index of the polyester resin layer in the thickness direction Determined by this method When the polyester resin layer in contact with the metal plate surface has a plane orientation coefficient of 0.10 or more, the polyester resin layer is easily peeled off from the metal plate surface when processed into a thin-walled deep drawing can. When the surface orientation coefficient is 0.10 or less, the polyester resin layer is difficult to peel off, but more preferably 0.05 or less. The refractive index measured by the above method is an average value of the resin layer having a depth of about 5 μm from the outermost layer of the resin layer, and the surface orientation of the polyester resin layer in contact with the metal plate obtained from the value As for the coefficient, the plane orientation coefficient of the layer that is actually in contact with the surface of the metal plate is 0, that is, even if it is a non-oriented polyester layer, the depth direction is 5 μm.
If the oriented polyester layer exists within m, the value is 0 or more. In the present invention, the plane orientation coefficient of the polyester resin layer in contact with the surface of the metal plate is set to 0 or more and 0.10 or less.
The is a result of considering such things, polyesters that plane orientation coefficient of the polyester resin layer in contact with the metal plate surface phase is 0, that is speaking in detail, the surface of the metal plate and the phase contact 5 μm of the resin layer is 0, which means that it is a non-oriented polyester resin layer. When plane orientation coefficient of the outermost surface layer of the polyester resin layer is 0.01 or less, and have contact to the process diaphragm as described above, blank holder tools,
The coefficient of friction with a can making tool such as a punch becomes too high, processing cannot be performed uniformly, and the polyester resin layer and the metal layer are significantly roughened, which is not preferable. Further, the barrier property of the polyester resin layer itself to the contents is remarkably inferior, and when the contents having strong corrosiveness are filled and stored for a long period of time, the surface of the metal plate is corroded, which is not preferable. If the surface orientation coefficient of the outermost polyester resin layer is 0.15 or more, even if the surface orientation coefficient of the polyester resin layer in contact with the metal plate surface is 0.10 or less, it can be processed into a thin-walled deep-drawn can. When this happens, countless cracks are formed in the upper polyester resin layer, making it unusable as a can. That is, when processing into a thin-walled deep-drawn can, the outermost polyester resin layer is determined after considering workability in manufacturing the can and characteristics of the can (content preservation, scratch resistance, etc.). The surface orientation coefficient of the polyester resin layer forming the outermost layer should be in the range of 0.01 to 0.15. On the other hand, in order to follow the polyester resin layer without peeling from the metal plate even if subjected to severe drawing, stretching, necking, etc.,
The orientation parameter of the polyester resin layer in contact with the metal plate is particularly important, and the plane orientation coefficient is 0 or more,
It should be 0.10 or less. There is no particular problem as long as the plane orientation coefficient of the outermost polyester resin layer and the polyester resin layer in contact with the surface of the metal plate is within the above range, but such a polyester resin-coated metal plate can be stably produced. In order to achieve this, the surface orientation coefficient of the outermost polyester resin layer is preferably larger than the surface orientation coefficient of the polyester resin layer in contact with the metal plate.
【０００９】つぎに、金属板とポリエステル樹脂層の間
に接着剤層が介在する場合について説明する。接着剤層
が介在せず、かつ本発明で限定した範囲の面配向係数の
ポリエステル樹脂層で被覆された金属板はすでに記した
ように優れた加工性、加工耐食性、耐きず付き性を有し
ているが、より腐食性の強い内容物と接触すると、ポリ
エステル樹脂層を通して金属板表面が腐食され、ポリエ
ステル樹脂層が金属板より剥離する場合がある。金属板
とポリエステル樹脂層の間に介在する接着剤層はこのよ
うな場合における金属板表面の腐食およびポリエステル
樹脂層の剥離を防止するのに効果的である。接着剤には
公知のものも使用可能であるが、エポキシ基を分子内に
有する重合組成物がより好ましく、ポリエステル樹脂フ
ィルムの金属板と接する面に塗布、乾燥しても、あるい
は金属板表面に塗布、乾燥してもよく、その塗布方法は
特に規制するものでない。Next, the case where the adhesive layer is interposed between the metal plate and the polyester resin layer will be described. A metal plate without an adhesive layer and covered with a polyester resin layer having a plane orientation coefficient within the range limited by the present invention has excellent workability, work corrosion resistance, and scratch resistance as described above. However, when contacted with a more corrosive content, the surface of the metal plate may be corroded through the polyester resin layer, and the polyester resin layer may peel off from the metal plate. The adhesive layer interposed between the metal plate and the polyester resin layer is effective in preventing corrosion of the metal plate surface and peeling of the polyester resin layer in such a case. Known adhesives may be used as the adhesive, but a polymerization composition having an epoxy group in the molecule is more preferable, and the adhesive is applied to the surface of the polyester resin film in contact with the metal plate or dried, or on the metal plate surface. It may be applied and dried, and the application method is not particularly limited.
【００１０】本発明のポリエステル樹脂被覆金属板を得
るには例えば次ぎに示す方法がある。すなわち、面配向
係数０．１０〜０．１５の二軸延伸ポリエステル樹脂フ
ィルムをその融点前後に加熱した金属板にラミネート
し、金属板表面と接触するポリエステル樹脂面の一部あ
るいは全部を溶融させ、金属板と接しているポリエステ
ル樹脂層の面配向係数を０以上、０．１０以下に調整す
る方法、融点１９０〜２３０℃および融点２１０〜２５
０℃の少なくとも二層以上のポリエステル樹脂層から構
成されるポリエステル樹脂フィルムを、融点の低いポリ
エステル樹脂の融点前後の温度に加熱した金属板に、融
点の低いポリエステル樹脂層面が金属板に相接するよう
に、積層する方法などがある。一般にポリエステル樹脂
フイルムはその融点前後の温度に加熱された金属板に積
層されるため、積層後のポリエステル樹脂フィルムの金
属板側の面配向係数は積層前のフィルムの面配向係数よ
り低下する。また、金属板の加熱温度、ラミネートロー
ルの温度が高く、冷却までの時間が短いほど、積層後の
フィルムの面配向係数は低下する。特に、加熱された金
属板から積層されるポリエステル樹脂フィルムに熱が伝
達されるため、金属板と相接しているポリエステル樹脂
層の面配向係数が最も小さく、金属板表面と離れるにし
たがって、積層されたポリエステル樹脂層の面配向係数
は大になり、最表層のポリエステル樹脂層の面配向係数
が最も大になる。すなわち、積層されたポリエステル樹
脂層の面配向係数は自然に傾斜が形成されていると考え
られる。To obtain the polyester resin-coated metal plate of the present invention, there is, for example, the following method. That is, a biaxially stretched polyester resin film having a plane orientation coefficient of 0.10 to 0.15 is laminated on a metal plate heated before and after its melting point, and a part or all of the polyester resin surface in contact with the metal plate surface is melted, Method for adjusting the plane orientation coefficient of the polyester resin layer in contact with the metal plate to 0 or more and 0.10 or less, melting point 190 to 230 ° C. and melting point 210 to 25
Constructed from at least two polyester resin layers at 0 ° C
The polyester resin film formed is
Melt on a metal plate heated to a temperature around the melting point of the ester resin.
Make sure that the polyester resin layer surface with a low point touches the metal plate.
There are methods such as stacking. In general, since the polyester resin film is laminated on a metal plate heated to a temperature around its melting point, the plane orientation coefficient on the metal plate side of the polyester resin film after lamination is lower than the plane orientation coefficient of the film before lamination. The heating temperature of the metal plate, the temperature of the laminating rolls is high, the shorter the time until cooling, plane orientation coefficient of the film after lamination is reduced. In particular, since heat is transferred from the heated metal plate to the laminated polyester resin film, the polyester resin layer that is in contact with the metal plate has the smallest plane orientation coefficient, and as the distance from the surface of the metal plate increases, the lamination increases. The polyester resin layer thus obtained has a large surface orientation coefficient, and the outermost polyester resin layer has the largest surface orientation coefficient. That is, it is considered that the plane orientation coefficient of the laminated polyester resin layers is naturally inclined.
【００１１】つぎに、本発明において用いられる金属板
としては、シート状および帯状の鋼板およびアルミニウ
ム板の表層にクロム水和酸化物皮膜を有することが積層
されるポリエステル樹脂フィルムとの優れた密着性を確
保するために有用である。特に下層が金属クロム、上層
がクロム水和酸化物の二層構造の皮膜で被覆されたＴＦ
Ｓが好ましく、さらに鋼板表面に錫、ニッケル、亜鉛、
アルミニウムなどの１種あるいは２種以上の複層めっ
き、合金めっきを施し、その上層に上記の二層構造をも
つＴＦＳ皮膜あるいはクロム水和酸化物皮膜を形成させ
たもの、あるいはアルミニウムに電解クロム酸処理、浸
漬クロム酸処理を施し、表層にクロム水和酸化物皮膜を
形成させたものなどが用いられる。表層のクロム水和酸
化物皮膜の量がクロムとして３ｍｇ／ｍ２以下あるいは
５０ｍｇ／ｍ２以上であると、積層されたポリエステル
樹脂層との密着性、特に加工後の密着性が低下する。し
たがって、クロム水和酸化物皮膜の量はクロムとして３
〜５０ｍｇ／ｍ２の範囲が好ましく、より好ましくは７
〜２５ｍｇ／ｍ２である。金属クロム量は特に限定する
必要はないが、加工後の耐食性、ポリエステル樹脂層の
密着性の観点より、１０〜２００ｍｇ／ｍ２の範囲にあ
ることが好ましい。Next, as the metal plate used in the present invention, a sheet-shaped or strip-shaped steel plate and an aluminum plate having a chromium hydrate oxide film on the surface layer have excellent adhesion to a polyester resin film to be laminated. Is useful to secure. In particular , TF coated with a double-layered film of lower layer of metallic chromium and upper layer of hydrated chromium oxide
S is preferable, and tin, nickel, zinc, and
One or two or more types of multi-layer plating or alloy plating of aluminum and the like, on which a TFS film or chromium hydrate oxide film having the above-mentioned two-layer structure is formed, or electrolytic chromic acid on aluminum What has been subjected to a treatment and a dipping chromic acid treatment to form a chromium hydrate oxide film on the surface layer is used. When the amount of the surface layer of hydrated chromium oxide coating is at 3 mg / m 2 or less or 50 mg / m 2 or more as chromium, adhesion between the laminated polyester resin layer, the adhesiveness after processing, especially decreases. Therefore, the amount of chromium hydrate oxide film is 3 as chromium.
To 50 mg / m 2 is preferable, and more preferably 7
~ 25 mg / m < 2 >. The amount of metallic chromium is not particularly limited, but it is preferably in the range of 10 to 200 mg / m 2 from the viewpoint of corrosion resistance after processing and adhesion of the polyester resin layer.
【００１２】金属板を加熱する方法としては、公知の熱
風循環伝熱方式、抵抗加熱方式、誘導加熱方式、ヒート
ロール方式などがあげられ、これらの方式を単独あるい
は併用してもよい。As a method for heating the metal plate, there are known hot air circulation heat transfer method, resistance heating method, induction heating method, heat roll method and the like, and these methods may be used alone or in combination.
【００１３】[0013]
【実施例】 実施例１ 板厚０．１７ｍｍ、テンパー度ＤＲ−１０のＴＦＳ（金
属クロム量１１０ｍｇ／ｍ２、クロム水和酸化物皮膜中
のクロム量１４ｍｇ／ｍ２）の両面に、イソフタル酸１
２モル％、テレフタル酸８８モル％、エチレングリコー
ル１００モル％の重合で得られた二軸配向共重合ポリエ
ステル樹脂フィルム（面配向係数０．１２５、厚さ２０
μｍ、融点２３０℃）を２３５℃の温度で積層した。得
られたポリエステル樹脂被覆鋼板を詳細な説明の中で示
した方法で、鋼板と相接しているポリエステル樹脂層お
よび最表層のポリエステル樹脂層の面配向係数を求めた
後、下記に示す加工条件で薄肉化深絞り缶を得た。さら
に、常法の手段により、ドーミング、ネッキング、フラ
ンジング加工を施した。 〔成形条件〕Ａ．絞り工程 ブランク径：１８７ｍｍ 絞り比：１．５０ Ｂ．再絞り工程 第一次再絞り比：１．２９ 第二次再絞り比：１．２４ 第三次再絞り比：１．２０ 再絞り工程のダイスのコーナー部の曲率半径：０．４ｍ
ｍ 再絞り工程のしわ押え荷重：６０００ｋｇ Ｃ．缶胴部の平均薄肉化率 成形前のポリエステル樹脂被覆鋼板の厚さに対し−２０
％Example 1 Isophthalic acid was applied to both surfaces of a TFS having a plate thickness of 0.17 mm and a temper degree of DR-10 (amount of chromium metal: 110 mg / m 2 , amount of chromium in a chromium hydrate oxide film: 14 mg / m 2 ). 1
Biaxially oriented copolymerized polyester resin film obtained by polymerization of 2 mol%, terephthalic acid 88 mol% and ethylene glycol 100 mol% (plane orientation coefficient 0.125, thickness 20
μm, melting point 230 ° C.) was laminated at a temperature of 235 ° C. The obtained polyester resin-coated steel sheet was obtained by the method shown in the detailed description, after obtaining the plane orientation coefficient of the polyester resin layer and the outermost polyester resin layer in contact with the steel sheet, and then the processing conditions shown below. Thus, a thin-walled deep-drawing can was obtained. Further, doming, necking, and flanging were performed by a conventional method. [Molding conditions] A. Drawing process Blank diameter: 187 mm Drawing ratio: 1.50 B. Redrawing process Primary redrawing ratio: 1.29 Secondary redrawing ratio: 1.24 Third redrawing ratio: 1.20 Curvature radius of corner of die in redrawing process: 0.4 m
Wrinkle holding load in redrawing process: 6000 kg C.I. The average thinning rate of the body of the can -20 against the thickness of the polyester resin-coated steel sheet before forming
%
【００１４】実施例２ 実施例１に示したＴＦＳの両面にイソフタル酸１２モル
％、テレフタル酸８８モル％、エチレングリコール１０
０モル％の重合で得られたポリエステル樹脂とイソフタ
ル酸１８モル％、テレフタル酸８２モル％、エチレング
リコール１００モル％の重合で得られたポリエステル樹
脂からなる二層二軸配向共重合ポリエステル樹脂フィル
ム（イソフタル酸１２モル％含むポリエステル樹脂層の
厚さ１５μｍ、融点２３０℃、面配向係数０．１２２、
イソフタル酸１８モル％含むポリエステル樹脂層の厚さ
５μｍ、融点２１４℃、面配向係数０．０８）をイソフ
タル酸１８モル％含むポリエステル樹脂層側がＴＦＳ面
と相接するように、２２８℃で積層した。得られたポリ
エステル樹脂被覆鋼板のＴＦＳ面と相接する層および最
表層のポリエステル樹脂層の面配向係数を求めた後、実
施例１と同様な条件で成形加工を施した。Example 2 Isophthalic acid 12 mol%, terephthalic acid 88 mol%, ethylene glycol 10 on both sides of the TFS shown in Example 1.
A two-layer biaxially oriented copolymerized polyester resin film comprising a polyester resin obtained by polymerization of 0 mol% and a polyester resin obtained by polymerization of 18 mol% of isophthalic acid, 82 mol% of terephthalic acid and 100 mol% of ethylene glycol ( Polyester resin layer containing 12 mol% of isophthalic acid having a thickness of 15 μm, melting point of 230 ° C., plane orientation coefficient of 0.122,
A polyester resin layer containing 18 mol% of isophthalic acid having a thickness of 5 μm, a melting point of 214 ° C. and a plane orientation coefficient of 0.08) was laminated at 228 ° C. so that the polyester resin layer side containing 18 mol% of isophthalic acid was in contact with the TFS surface. . After obtaining the plane orientation coefficients of the layer contacting the TFS surface and the outermost polyester resin layer of the obtained polyester resin-coated steel sheet, molding was performed under the same conditions as in Example 1.
【００１５】実施例３ 実施例１に示したＴＦＳの片面に実施例１で用いた二軸
配向共重合ポリエステル樹脂フィルムを、他の片面に酸
化チタン１２重量％含むイソフタル酸１２モル％、テレ
フタル酸８８モル％、エチレングリコール１００モル％
の重合で得られた白色共重合ポリエステル樹脂フィルム
（厚さ２０μｍ）を２５０℃で積層した。得られたポリ
エステル樹脂被覆鋼板のＴＦＳ面と相接する層および最
表層のポリエステル樹脂層の面配向係数を求めた後、自
色共重合ポリエステル樹脂フィルム被覆面が缶外面とな
るように、実施例１と同様な条件で成形加工を施した。
ただし、白色共重合ポリエステル樹脂フィルムの面配向
係数は求めることができないので省略した。Example 3 The biaxially oriented copolyester resin film used in Example 1 was used on one side of the TFS shown in Example 1, and 12 mol% of isophthalic acid containing 12% by weight of titanium oxide and terephthalic acid on the other side. 88 mol%, ethylene glycol 100 mol%
The white copolyester resin film (thickness 20 μm) obtained by the above polymerization was laminated at 250 ° C. After the plane orientation coefficients of the layer contacting the TFS surface of the obtained polyester resin-coated steel sheet and the polyester resin layer of the outermost layer were determined, the self-colored copolyester resin film coated surface was the outer surface of the can. Molding was performed under the same conditions as in 1.
However, since the plane orientation coefficient of the white copolyester resin film cannot be obtained, it is omitted.
【００１６】実施例４ 実施例１に示したＴＦＳの両面に予めエポキシ−フェノ
ール系塗料を０．５ｇ／ｍ２塗布し、１５０℃で予備乾
燥させた後、実施例１に示したポリエステル樹脂フィル
ムを２４５℃で積層した。得られたポリエステル樹脂被
覆鋼板のＴＦＳ面および最表層のポリエステル樹脂層の
面配向係数を求めた後、実施例１と同様な条件で成形加
工を施した。Example 4 0.5 g / m 2 of an epoxy-phenolic coating material was previously applied to both surfaces of the TFS shown in Example 1, pre-dried at 150 ° C., and then the polyester resin film shown in Example 1 was used. Were laminated at 245 ° C. After the plane orientation coefficients of the TFS surface and the outermost polyester resin layer of the obtained polyester resin-coated steel sheet were determined, the molding process was performed under the same conditions as in Example 1.
【００１７】実施例５ 予めエポキシ−フェノール系塗料を０．３ｇ／ｍ２塗布
し、１２０℃で乾燥させたセバチン酸１５モル％、テレ
フタル酸８５モル％、エチレングリコール１００モル％
の重合で得られた二軸配向共重合ポリエステル樹脂フィ
ルム（厚さ１５μｍ、融点２２３℃、面配向係数０．０
９９）を、板厚０．３０ｍｍのアルミ板（Ａｌ−Ｍｇ合
金系）の片面のみに２２０℃で積層した。得られたポリ
エステル樹脂被覆アルミ板の他の片面に、ビニルオルガ
ノゾル塗料を乾燥厚さで１０ｇ／ｍ２になるように塗布
し、２００℃で１０分間加熱した。得られたポリエステ
ル樹脂被覆アルミ板のアルミ表面と相接する層および最
表層のポリエステル樹脂層の面配向係数を求めた後、ポ
リエステル樹脂フィルム被覆面が缶内面となるように、
再絞り工程の成形条件を下記のように変更した以外は実
施例１と同様な条件で成形加工を施した。 〔再絞り工程の実施例１と異なる条件〕 再絞り工程のダイスのコーナー部の曲率半径：０．４ｍ
ｍ 再絞り工程のしわ押え荷重：２０００ｋｇExample 5 Epoxy-phenol based coating composition 0.3 g / m 2 was previously applied and dried at 120 ° C. 15 mol% sebacic acid, 85 mol% terephthalic acid, 100 mol% ethylene glycol.
Biaxially oriented copolyester resin film obtained by the polymerization of (thickness 15 μm, melting point 223 ° C., plane orientation coefficient 0.0
99) was laminated at 220 ° C. only on one surface of an aluminum plate (Al—Mg alloy system) having a plate thickness of 0.30 mm. The other surface of the obtained polyester resin-coated aluminum plate was coated with a vinylorganosol coating so that the dry thickness was 10 g / m 2, and heated at 200 ° C. for 10 minutes. After determining the plane orientation coefficient of the layer and the outermost polyester resin layer that are in contact with the aluminum surface of the obtained polyester resin-coated aluminum plate, the polyester resin film coated surface is the inner surface of the can,
Molding was performed under the same conditions as in Example 1 except that the molding conditions in the redrawing process were changed as follows. [Conditions Different from Example 1 of Redrawing Step] Curvature Radius of Corner of Die in Redrawing Step: 0.4 m
m Wrinkle holding load in redrawing process: 2000kg
【００１８】比較例１ 実施例１に示したＴＦＳの両面に二軸配向ポリエチレン
テレフタレートフィルム（厚さ２５μｍ、融点２６０
℃、面配向係数０．１６５）を２８０℃で積層した。得
られたポリエステル樹脂被覆鋼板のＴＦＳ面と相接する
層および最表層のポリエステル樹脂層の面配向係数を求
めた後、実施例１と同様な条件で成形加工を施した。Comparative Example 1 Biaxially oriented polyethylene terephthalate film (thickness: 25 μm, melting point: 260) on both sides of the TFS shown in Example 1.
And a plane orientation coefficient of 0.165) were laminated at 280 ° C. After obtaining the plane orientation coefficients of the layer contacting the TFS surface and the outermost polyester resin layer of the obtained polyester resin-coated steel sheet, molding was performed under the same conditions as in Example 1.
【００１９】比較例２ 実施例１に示したＴＦＳの両面に実施例１に用いたポリ
エステル樹脂フィルムを２１０℃で積層した。得られた
ポリエステル樹脂被覆鋼板のＴＦＳ面と相接する層およ
び最表層のポリエステル樹脂層の面配向係数を求めた
後、実施例１と同様な条件で成形加工を施した。Comparative Example 2 The polyester resin film used in Example 1 was laminated on both surfaces of the TFS shown in Example 1 at 210 ° C. After obtaining the plane orientation coefficients of the layer contacting the TFS surface and the outermost polyester resin layer of the obtained polyester resin- coated steel sheet, molding was performed under the same conditions as in Example 1.
【００２０】比較例３ 実施例３に示したＴＦＳの両面に実施例１に示したポリ
エステル樹脂フィルムを３０５℃で積層した。得られた
ポリエステル樹脂被覆鋼板のＴＦＳ面と相接する層およ
び最表層のポリエステル樹脂層の面配向係数を求めた
後、実施例１と同様な条件で成形加工を施した。Comparative Example 3 The polyester resin film shown in Example 1 was laminated on both sides of the TFS shown in Example 3 at 305 ° C. After obtaining the plane orientation coefficients of the layer contacting the TFS surface and the outermost polyester resin layer of the obtained polyester resin-coated steel sheet, molding was performed under the same conditions as in Example 1.
【００２１】実施例１〜５および比較例１〜３で得られ
たポリエステル樹脂被覆鋼板およびアルミ板の成形加工
工程におけるポリエステル樹脂フィルムの割れおよび剥
離状況を肉眼で観察するとともに、得られた２ピース缶
体の特性を次に示す方法で評価した。その結果を表１お
よび表２に示した。 （１）缶体内面の金属表面の露出度 得られた薄肉化深絞り缶に３％食塩水を充填し、缶体に
６．５Ｖの直流電圧を印加し、流れる電流値で金属表面
の露出度を評価した。 （２）耐熱水性 得られた薄肉化深絞り缶をレトルト釜に入れ、１２５℃
の水蒸気で３０分間熱水処理を施し、フランジ加工部よ
りのポリエステル樹脂フィルムの剥離状況を肉眼で評価
した。 （３）耐熱性 第３次再絞り工程を終えた絞り缶を、外面印刷の焼き付
けを想定した温度、すなわち、２００℃で５分間熱処理
を施した後、缶胴部のポリエステル樹脂フィルムの変
色、割れ、剥離状況を肉眼で評価した。 （４）耐食性 得られた薄肉化深絞り缶に３％酢酸水を充填し、５０℃
で３ヶ月貯蔵後、開缶し、缶内面の腐食状況を肉眼で観
察し、腐食なしを５点とし、４点、３点、２点、１点に
なるにつれて腐食程度が大になるように５段階にわけて
評価した。The polyester resin- coated steel sheets obtained in Examples 1 to 5 and Comparative Examples 1 to 3 and the aluminum plate were visually observed for cracking and peeling of the polyester resin film in the molding process, and the obtained two pieces were obtained. The characteristics of the cans were evaluated by the following methods. The results are shown in Tables 1 and 2. (1) Exposed degree of metal surface on the inside of the can The obtained thin-walled deep-drawn can was filled with 3% saline solution, a direct current voltage of 6.5 V was applied to the can, and the metal surface was exposed by the flowing current value. The degree was evaluated. (2) Hot water resistance Place the obtained thin-walled deep-drawing can in a retort kettle at 125 ° C.
Was subjected to hot water treatment for 30 minutes, and the state of peeling of the polyester resin film from the flanged portion was visually evaluated. (3) Heat resistance The drawn can that has undergone the third redrawing process is subjected to heat treatment at a temperature assuming baking for external printing, that is, at 200 ° C. for 5 minutes, and then the discoloration of the polyester resin film on the body of the can, The state of cracking and peeling was visually evaluated. (4) Corrosion resistance The obtained thin-walled deep drawing can was filled with 3% acetic acid water and heated to 50 ° C.
After storage for 3 months, open the can and visually observe the corrosion condition on the inner surface of the can. Set 5 points for no corrosion, 4 points, 3 points, 2 points, 1 point so that the degree of corrosion increases The evaluation was divided into 5 stages.
【００２２】[0022]
【表１】 [Table 1]
【００２３】[0023]
【表２】 [Table 2]
【００２４】[0024]
【発明の効果】以上説明したように、本発明の薄肉化深
絞り缶用ポリエステル樹脂被覆金属板は加工性および加
工耐食性に優れた材料であり、従来の缶体に比較し、種
々の利点をもち、薄肉化深絞り缶用に用いられるだけで
なく、絞り缶、缶蓋、イージーオープン可能な缶蓋、王
冠、キャップ類など容器用としても広く適用できる。As described above, the polyester resin-coated metal sheet for a thin-walled deep-drawn can of the present invention is a material excellent in workability and work corrosion resistance, and has various advantages as compared with the conventional can body. also Chi, not only used for thin deep drawn can, drawn can, can lid, can be applied widely as containers such as easy-open can can lids, crown, caps.
Claims (5)
ル樹脂で被覆された金属板において、金属板と相接して
いるポリエステル樹脂層の面配向係数をｎ１とし、最表
層のポリエステル樹脂層の面配向係数をｎ２とした時、
ｎ１が０以上で、０．１０以下、ｎ２が０．０１以上
で、０．１５以下であることを特徴とする薄肉化深絞り
缶用樹脂被覆金属板。1. In a metal plate in which both sides or one side of a metal plate is coated with a polyester resin, the plane orientation coefficient of the polyester resin layer in contact with the metal plate is n 1, and the plane of the outermost polyester resin layer is set. When the orientation coefficient is n 2 ,
n 1 is 0 or more and 0.10 or less, and n 2 is 0.01 or more and 0.15 or less, and a resin-coated metal plate for a thin-walled deep drawing can.
項１記載の薄肉化深絞り缶用樹脂被覆金属板。2. The resin-coated metal plate for a thin-walled deep-drawing can according to claim 1 , wherein n 2 ≧ n 1 .
層の融点が１９０〜２３０℃、最表層を構成するポリエ
ステル樹脂層の融点が２１０〜２５０℃であることを特
徴とする請求項１記載の薄肉化深絞り缶用樹脂被覆金属
板。3. The polyester resin layer in contact with the metal plate has a melting point of 190 to 230 ° C. and the polyester resin layer constituting the outermost layer has a melting point of 210 to 250 ° C. Resin-coated metal plate for thin-walled deep-drawing cans.
テル樹脂層で被覆され、他の片面は融点が１９０〜２５
０℃で、着色顔料を２〜２０重量部含有するポリエステ
ル樹脂層で被覆されていることを特徴とする薄肉化深絞
り缶用樹脂被覆金属板。4. One side of the metal plate is coated with the polyester resin layer according to claim 1, and the other side has a melting point of 190 to 25.
A resin-coated metal plate for a thin-walled deep drawing can, which is coated with a polyester resin layer containing 2 to 20 parts by weight of a color pigment at 0 ° C.
ポリエステル樹脂層の間に接着剤層が介在することを特
徴とする請求項１、２、３または４記載の薄肉化深絞り
缶用樹脂被覆金属板。5. The thinned deep-drawing can according to claim 1, wherein an adhesive layer is provided between the metal plate and the polyester resin layer on both sides or one side of the metal plate. Resin coated metal plate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2418199A JP2532002B2 (en) | 1990-12-26 | 1990-12-26 | Resin coated metal plate for thin-walled deep drawing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2418199A JP2532002B2 (en) | 1990-12-26 | 1990-12-26 | Resin coated metal plate for thin-walled deep drawing |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7337658A Division JP2934182B2 (en) | 1995-12-04 | 1995-12-04 | Resin coated metal plate for thinned deep drawn cans |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06320669A true JPH06320669A (en) | 1994-11-22 |
| JP2532002B2 JP2532002B2 (en) | 1996-09-11 |
Family
ID=18526111
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2418199A Expired - Lifetime JP2532002B2 (en) | 1990-12-26 | 1990-12-26 | Resin coated metal plate for thin-walled deep drawing |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2532002B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997037845A1 (en) * | 1996-04-10 | 1997-10-16 | Toyo Kohan Co., Ltd. | Polyethylene terephthalate resin-coated metal plate of high processability |
| WO2000000400A1 (en) | 1998-06-26 | 2000-01-06 | Ishida Co., Ltd. | Composite container |
| JP2002536209A (en) * | 1999-02-02 | 2002-10-29 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Polymer film containing heat-sealable layer and substrate layer |
| US7063889B2 (en) | 2001-11-27 | 2006-06-20 | Jfe Steel Corporation | Resin film and manufacturing method for the same, and resin laminated metal sheet using said resin film and manufacturing method for the same |
| JP2006168122A (en) * | 2004-12-15 | 2006-06-29 | Jfe Steel Kk | Laminated steel sheet with excellent scratch resistance and sliding property and can body using the same |
| JP2007105948A (en) * | 2005-10-12 | 2007-04-26 | Toray Ind Inc | Polyester film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01192546A (en) * | 1988-01-28 | 1989-08-02 | Nippon Steel Corp | Laminated steel plate having two-layer film structure and preparation thereof |
| JPH02501640A (en) * | 1987-10-15 | 1990-06-07 | シーエムビー パッケイジング（ユーケー） リミテド | laminated metal sheets |
-
1990
- 1990-12-26 JP JP2418199A patent/JP2532002B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02501640A (en) * | 1987-10-15 | 1990-06-07 | シーエムビー パッケイジング（ユーケー） リミテド | laminated metal sheets |
| JPH01192546A (en) * | 1988-01-28 | 1989-08-02 | Nippon Steel Corp | Laminated steel plate having two-layer film structure and preparation thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997037845A1 (en) * | 1996-04-10 | 1997-10-16 | Toyo Kohan Co., Ltd. | Polyethylene terephthalate resin-coated metal plate of high processability |
| US6270874B1 (en) | 1996-04-10 | 2001-08-07 | Toyo Kohan Co., Ltd. | Polyethylene terephthalate resin-coated metal plate of high processability |
| WO2000000400A1 (en) | 1998-06-26 | 2000-01-06 | Ishida Co., Ltd. | Composite container |
| JP2002536209A (en) * | 1999-02-02 | 2002-10-29 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Polymer film containing heat-sealable layer and substrate layer |
| US7063889B2 (en) | 2001-11-27 | 2006-06-20 | Jfe Steel Corporation | Resin film and manufacturing method for the same, and resin laminated metal sheet using said resin film and manufacturing method for the same |
| US7273653B2 (en) | 2001-11-27 | 2007-09-25 | Jfe Steel Corporation | Resin film and manufacturing method for the same, and resin laminated metal sheet using said resin film and manufacturing method for the same |
| JP2006168122A (en) * | 2004-12-15 | 2006-06-29 | Jfe Steel Kk | Laminated steel sheet with excellent scratch resistance and sliding property and can body using the same |
| JP2007105948A (en) * | 2005-10-12 | 2007-04-26 | Toray Ind Inc | Polyester film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2532002B2 (en) | 1996-09-11 |
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