JP2003001760A - Resin-coated seamless can - Google Patents
Resin-coated seamless canInfo
- Publication number
- JP2003001760A JP2003001760A JP2001192047A JP2001192047A JP2003001760A JP 2003001760 A JP2003001760 A JP 2003001760A JP 2001192047 A JP2001192047 A JP 2001192047A JP 2001192047 A JP2001192047 A JP 2001192047A JP 2003001760 A JP2003001760 A JP 2003001760A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- coated
- polyester resin
- seamless
- layer
- 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
- 229920005989 resin Polymers 0.000 title claims abstract description 116
- 239000011347 resin Substances 0.000 title claims abstract description 116
- 229910052751 metal Inorganic materials 0.000 claims abstract description 110
- 239000002184 metal Substances 0.000 claims abstract description 110
- 229920001225 polyester resin Polymers 0.000 claims abstract description 108
- 239000004645 polyester resin Substances 0.000 claims abstract description 108
- 239000000758 substrate Substances 0.000 claims abstract description 42
- 238000010521 absorption reaction Methods 0.000 claims abstract description 17
- -1 polyethylene terephthalate Polymers 0.000 claims abstract description 17
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 14
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 14
- 239000010410 layer Substances 0.000 claims description 113
- 238000010409 ironing Methods 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 23
- 239000002344 surface layer Substances 0.000 claims description 17
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 14
- 238000005096 rolling process Methods 0.000 claims description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 claims description 6
- 230000007797 corrosion Effects 0.000 abstract description 29
- 238000005260 corrosion Methods 0.000 abstract description 29
- 239000010408 film Substances 0.000 description 42
- 239000000203 mixture Substances 0.000 description 29
- 238000012545 processing Methods 0.000 description 27
- 238000000576 coating method Methods 0.000 description 22
- 238000010438 heat treatment Methods 0.000 description 19
- 239000011248 coating agent Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 11
- 238000000465 moulding Methods 0.000 description 10
- 229910000831 Steel Inorganic materials 0.000 description 9
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 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 9
- 239000010959 steel Substances 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 7
- 239000000796 flavoring agent Substances 0.000 description 7
- 235000019634 flavors Nutrition 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 6
- 239000011651 chromium Substances 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 238000007765 extrusion coating Methods 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 229920005992 thermoplastic resin Polymers 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229910000838 Al alloy Inorganic materials 0.000 description 4
- 238000010306 acid treatment Methods 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 238000012805 post-processing Methods 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- 229920000298 Cellophane Polymers 0.000 description 3
- 229920001634 Copolyester Polymers 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 239000002335 surface treatment layer Substances 0.000 description 3
- 239000005029 tin-free steel Substances 0.000 description 3
- 239000005028 tinplate Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 238000009966 trimming Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003854 Surface Print Methods 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 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
- 238000003466 welding Methods 0.000 description 1
Landscapes
- Rigid Containers With Two Or More Constituent Elements (AREA)
- Details Of Rigid Or Semi-Rigid Containers (AREA)
- Laminated Bodies (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、樹脂被覆シームレ
ス缶に関するもので、より詳細には優れた耐食性、耐衝
撃性を有する樹脂被覆シームレス缶に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin-coated seamless can, and more particularly to a resin-coated seamless can having excellent corrosion resistance and impact resistance.
【０００２】[0002]
【従来の技術】従来、側面無継目缶（シームレス缶）と
しては、アルミニウム板、ブリキ板或いはティンフリー
スチール板等の金属素材を、絞りダイスとポンチとの間
で少なくとも一段の絞り加工に付して、側面に継ぎ目の
無い胴部と該胴部に継ぎ目無しに一体に接続された底部
から成る円筒状カップに形成し、次いで所望により、前
記胴部に、しごきポンチとダイスとの間でしごき加工を
加えて、胴部を薄肉化した缶体が知られている（絞り・
しごき加工）。また、前記しごき加工の代わりに、再絞
りダイスの曲率コーナ部で曲げ伸ばしによる薄肉化絞り
成形を行って側壁部を薄肉化することも既に知られてい
る（絞り・薄肉化絞り成形）。さらに、前記薄肉化絞り
加工時にしごき加工を加えて側壁部を薄肉化する薄肉化
絞り成形及びしごき加工も既に知られている（絞り・薄
肉化絞り成形及びしごき加工）。2. Description of the Related Art Conventionally, as a side seamless can (seamless can), a metal material such as an aluminum plate, a tin plate or a tin-free steel plate is subjected to at least one step of drawing between a drawing die and a punch. To form a cylindrical cup consisting of a side-seamless body and a bottom integrally connected to the body seamlessly, and then, if desired, squeezing between the ironing punch and the die on the body. A can body is known in which the body is thinned by processing (drawing /
Ironing process). Further, it is already known that, instead of the ironing, thinning of the side wall portion is performed by bending and stretching at the curvature corner of the redrawing die (drawing / thinning drawing). Further, thinning draw forming and ironing work in which ironing is applied at the time of the thinning drawing work to thin the side wall portion are already known (drawing / thinning draw forming and ironing work).
【０００３】また、側面無継目缶の有機樹脂被膜法とし
ては、一般的に広く使用されている成形後の缶に有機塗
料を施す方法の他に、成形前の金属素材に予め樹脂フィ
ルムをラミネートする方法が知られており、また、薄肉
化絞り成形による缶体の製造に際し、ポリエステル、ビ
ニルオルガノゾル、エポキシ、フェノール、アクリル等
の被覆金属板を用いることも知られている。As the organic resin coating method for side-surface seamless cans, in addition to the generally widely used method of applying an organic paint to a can after molding, a resin film is preliminarily laminated on a metal material before molding. It is also known to use a coated metal plate of polyester, vinyl organosol, epoxy, phenol, acrylic or the like in the production of a can body by thin-drawing.
【０００４】熱可塑性ポリエステルに代表される熱可塑
性樹脂フィルムの金属基材に対する被覆方式ついても、
非常に多くの提案がされており、例えば、二軸延伸フィ
ルムを直接、或いは接着用プライマー層を介して、金属
基板に熱接着により貼り合わせる方式（例えば特開平３
−１０１９３０号公報、特開平５−４２２９号公報、特
開平６−１７２５５６号公報）や、溶融樹脂を金属基体
に押し出しコートする方式（特開平１０−８６３０８号
公報）等が採用されている。Regarding the coating method of a thermoplastic resin film represented by thermoplastic polyester on a metal substrate,
A great number of proposals have been made, for example, a method in which a biaxially stretched film is bonded directly or via a bonding primer layer to a metal substrate by thermal bonding (see, for example, Japanese Unexamined Patent Application Publication No. Hei 3
No. 101930, JP-A-5-4229, and JP-A-6-172556), a method of extrusion coating a molten resin onto a metal substrate (JP-A-10-86308), and the like are employed.
【０００５】[0005]
【発明が解決しようとする課題】樹脂被覆金属板から、
絞り・しごき加工、絞り・薄肉化絞り成形、又は絞り・
薄肉化絞り成形及びしごき加工（以後これらの加工法を
絞り・薄肉化絞り成形及び／またはしごき加工という）
により成形されたシームレス缶においては、その加工程
度がコストダウンを図るために年々厳しいものとなって
おり、従来から一般に採用されている二軸延伸フィルム
を金属基体に熱接着で積層させた缶用樹脂被覆金属板で
は、厳しくなる苛酷な加工に追随することが難しくなっ
てきている。これに対し、金属基体に溶融樹脂を直接押
し出しコート、或いは、キャストフィルムをラミネート
した缶用樹脂被覆金属板は、前記樹脂が未配向の状態で
維持されるため、前記したような苛酷な加工に対する追
随性の許容度が大きいので、押し出しコート樹脂被覆金
属板が最近用いられるようになってきている。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
Drawing / ironing, drawing / thinning drawing, or drawing /
Thinning draw forming and ironing (hereinafter these processing methods are called drawing / thinning draw forming and / or ironing)
For seamless cans formed by, the degree of processing is becoming stricter year by year in order to reduce costs, and for cans in which a biaxially stretched film that has been commonly used in the past is laminated on a metal substrate by heat bonding. With resin-coated metal sheets, it has become difficult to follow the severe and severe processing. On the other hand, a resin coated metal plate for a can in which a molten resin is directly extrusion-coated on a metal substrate or a cast film is laminated, the resin is maintained in an unoriented state, so that the above-described severe processing against Extrusion-coated resin-coated metal sheets have recently been used because of their high degree of followability.
【０００６】これらの押し出しコート或いは、キャスト
フィルムをラミネートした熱可塑性樹脂被覆金属板は、
絞り成形により円筒状カップに成形され、次いで薄肉化
絞り成形及び／又はしごき加工によりハイトが高く、し
かも側壁が薄肉化されたシームレス缶に成形される。こ
のシームレス缶では、被覆樹脂層と金属基体との接着界
面の状態が、缶底部と缶胴部とで大きく相違している。
即ち、缶底部では、加工の程度が厳しくないため、前記
接着界面は実質上加工前の樹脂被覆金属板のままの形で
温存されており、一方、缶胴部では加工の程度が厳し
く、前記接着界面おける被覆樹脂層での加工による内部
応力が大きくなるため、前記接着界面において剥離や割
れ等の発生が認められる場合があり、金属基体表面の表
面処理層の有無に係わらずシームレス缶とした時の耐食
性、耐衝撃性を低下させていた。These extrusion-coated or cast film-laminated thermoplastic resin-coated metal plates are
It is formed into a cylindrical cup by drawing, and then formed into a seamless can having a high height and a thin side wall by drawing forming and / or ironing. In this seamless can, the state of the adhesive interface between the coating resin layer and the metal substrate is greatly different between the can bottom and the can body.
That is, since the degree of processing is not severe at the bottom of the can, the adhesive interface is substantially preserved in the form of the resin-coated metal plate before processing, while the degree of processing is severe at the body of the can. Since internal stress due to processing in the coating resin layer at the adhesive interface becomes large, peeling or cracking may be observed at the adhesive interface, and a seamless can was obtained regardless of the presence or absence of the surface treatment layer on the surface of the metal substrate. The corrosion resistance and impact resistance at that time were reduced.
【０００７】耐食性は、熱可塑性樹脂被覆金属板から成
るシームレス缶においては、一般にアンダー・フィルム
・コロージョン（ＵＦＣ）と呼ばれる被膜下腐食が進行
し易い。この腐食はフィルムによるカバレッジが見掛け
上安全であるにも係わらず、フィルム層の下の金属基板
に腐食が発生する現象であるが、これを防止することが
要求される。Corrosion resistance is liable to progress undercoat corrosion generally called under film corrosion (UFC) in a seamless can made of a thermoplastic resin-coated metal plate. This corrosion is a phenomenon in which the metal substrate below the film layer is corroded even though the coverage by the film is apparently safe, but it is required to prevent this.
【０００８】耐衝撃性は、実際の缶詰製品とした時の耐
デント性と呼ばれるものが有り、これは、缶詰製品を落
下して、或いは缶詰製品同士が相互に衝突して、缶詰製
品に打痕と呼ばれる凹みが生じた場合でも、被覆の密着
性、カバレッジが完全に保たれることが要求される。Impact resistance has what is called dent resistance when it is made into an actual canned product. This is because when the canned products are dropped or when the canned products collide with each other, the canned products are hit. Even if a dent called a mark is formed, it is required that the adhesion and coverage of the coating be completely maintained.
【０００９】従って、本発明の課題は、金属基体の表面
に熱可塑性樹脂を被覆した樹脂被覆金属板から成る樹脂
被覆シームレス缶において、耐食性、耐衝撃性に優れた
樹脂被覆シームレス缶を提供することである。Therefore, an object of the present invention is to provide a resin-coated seamless can which is excellent in corrosion resistance and impact resistance in a resin-coated seamless can made of a resin-coated metal plate having a surface of a metal substrate coated with a thermoplastic resin. Is.
【００１０】[0010]
【課題を解決するための手段】本発明の樹脂被覆シーム
レス缶は、金属基体の表面にポリエチレンテレフタレー
トを含有するポリエステル樹脂層を被覆した樹脂被覆金
属板から成る樹脂被覆シームレス缶において、下記式
（１）で表される缶胴部内面側のポリエステル樹脂層の
赤外二色比（Ｒ１）が、１．１以上であることを特徴と
する。
Ｒ１＝Ｉｗ(⊥)／Ｉｗ(‖)・・・（１）
但し、ここで、Ｉｗ(⊥)は、缶胴部での缶高さ方向に垂
直な偏光赤外線に対する９７３ｃｍ− １の赤外線吸収強
度であり、Ｉｗ(‖)は、缶胴部での缶高さ方向に平行な
偏光赤外線に対する９７３ｃｍ−１の赤外線吸収強度で
ある。前記構成により、金属基体表面の表面処理層と樹
脂層との密着性を高めることができ、シームレス缶の被
膜下の腐食（ＵＦＣ）を抑制し、また、被膜の耐衝撃性
（耐デント性）を高めるという作用が得られるという効
果を有する。前記樹脂被覆シームレス缶は、下記式
（２）で表される缶底部内面側のポリエステル樹脂層の
赤外二色比（Ｒ２）が、１．１以下であることが好まし
い。
Ｒ２＝ＩＢ(⊥)／ＩＢ(‖)・・・（２）
但し、ここで、ＩＢ(⊥)は、缶底部での金属基体圧延方
向に垂直な偏光赤外線に対する９７３ｃｍ−１の赤外線
吸収強度であり、ＩＢ(‖)は、缶底部での金属基体圧延
方向に平行な偏光赤外線に対する９７３ｃｍ−１の赤外
線吸収強度である。このため、前記樹脂被覆金属板は、
未配向のポリエステル樹脂層を金属基体に設けたもので
あることが望ましい。また、本発明の樹脂被覆シームレ
ス缶は、絞り・薄肉化絞り成形及び／またはしごき成形
により、缶胴部の厚みが缶底部の厚みの２０乃至８５％
となるように薄肉化されていることが好ましい。また、
本発明の樹脂被覆シームレス缶は、ポリエステル樹脂層
が２層から成り、表層（Ａ）がイソフタル酸含有量１５
モル％以下のポリエチレンテレフタレート／イソフタレ
ートから成り、下層（Ｂ）がイソフタル酸含有量８乃至
２５モル％のポリエチレンテレフタレート／イソフタレ
ートから成ることが好ましい。また、本発明の樹脂被覆
シームレス缶は、ポリエステル樹脂が固有粘度０．６ｄ
ｌ／ｇ以上であることが好ましい。さらに、本発明の樹
脂被覆シームレス缶は、缶胴部上部のポリエステル樹脂
層の密度法による結晶化度が２０乃至５５％の範囲であ
ることが好ましい。The resin-coated seamless can of the present invention is a resin-coated seamless can comprising a resin-coated metal plate in which a surface of a metal substrate is coated with a polyester resin layer containing polyethylene terephthalate. ), The infrared dichroic ratio (R1) of the polyester resin layer on the inner surface side of the can body is 1.1 or more. R1 = Iw (⊥) / Iw ( ||) (1) where, where, Iw (⊥) is, 973 cm for vertical polarization infrared to the can height direction at the can body - 1 of infrared absorption intensity And Iw (|) is the infrared absorption intensity of 973 cm −1 for polarized infrared rays parallel to the can height direction in the can body. With the above structure, the adhesion between the surface treatment layer on the surface of the metal substrate and the resin layer can be enhanced, corrosion under the coating (UFC) of the seamless can can be suppressed, and the impact resistance (dent resistance) of the coating can be suppressed. It has the effect of increasing the action of In the resin-coated seamless can, the infrared dichroic ratio (R2) of the polyester resin layer on the inner surface side of the can bottom portion represented by the following formula (2) is preferably 1.1 or less. R2 = IB (⊥) / IB (‖) (2) where IB (⊥) is the infrared absorption intensity of 973 cm −1 for polarized infrared rays perpendicular to the metal base rolling direction at the bottom of the can. Yes, IB (|) is the infrared absorption intensity of 973 cm −1 for polarized infrared rays parallel to the rolling direction of the metal substrate at the bottom of the can. Therefore, the resin-coated metal plate,
It is desirable to provide a non-oriented polyester resin layer on a metal substrate. Further, the resin-coated seamless can of the present invention has a thickness of the body of the can of 20 to 85% of a thickness of the bottom of the can obtained by drawing / thinning draw forming and / or ironing forming.
The thickness is preferably reduced so that Also,
The resin-coated seamless can of the present invention comprises two polyester resin layers, and the surface layer (A) has an isophthalic acid content of 15
Preferably, the lower layer (B) is composed of polyethylene terephthalate / isophthalate in an amount of not more than mol%, and the lower layer (B) is made of polyethylene terephthalate / isophthalate having an isophthalic acid content of 8 to 25 mol%. Further, in the resin-coated seamless can of the present invention, the polyester resin has an intrinsic viscosity of 0.6d.
It is preferably 1 / g or more. Further, in the resin-coated seamless can of the present invention, the crystallinity of the polyester resin layer on the upper part of the can body is preferably in the range of 20 to 55% by the density method.
【００１１】[0011]
【発明の実施の形態】［樹脂被覆シームレス缶］図１
は、本発明の樹脂被覆シームレス缶の一実施態様を示す
概略図である。図２は、本発明に用いる樹脂被覆金属板
の参考断面図である。図３は、本発明に用いる他の樹脂
被覆金属板の参考断面図である。図１〜図３において、
樹脂被覆シームレス缶１０は、樹脂被覆金属板１を、絞
り・薄肉化絞り成形及び／又はしごき加工することによ
り形成され、缶底部１１と缶胴部１２とから成ってい
る。本発明の樹脂被覆シームレス缶１０は、金属基体２
の表面にポリエチレンテレフタレートを含有するポリエ
ステル樹脂層３を被覆した樹脂被覆金属板１を、絞り・
薄肉化絞り成形及び／又はしごき加工して形成されたも
のである。DESCRIPTION OF THE PREFERRED EMBODIMENTS [Resin-coated seamless can] FIG.
FIG. 1 is a schematic view showing an embodiment of a resin-coated seamless can of the present invention. FIG. 2 is a reference sectional view of a resin-coated metal plate used in the present invention. FIG. 3 is a reference sectional view of another resin-coated metal plate used in the present invention. 1 to 3,
The resin-coated seamless can 10 is formed by drawing and thinning the resin-coated metal plate 1 and / or ironing it, and is composed of a can bottom 11 and a can body 12. The resin-coated seamless can 10 of the present invention includes a metal base 2
Squeeze the resin-coated metal plate 1 whose surface is coated with a polyester resin layer 3 containing polyethylene terephthalate
It is formed by thinning and forming and / or ironing.
【００１２】また、本発明の樹脂被覆シームレス缶１０
は、前記のポリエステル樹脂被覆金属板１をポンチとダ
イスの間で、有底カップ状に絞り、続いて曲げ伸ばし成
形による薄肉化絞り成形及び／又はしごき加工して形成
されたものである。前記薄肉化絞り成形及び／又はしご
き加工により、カップ側壁部は薄肉化加工され、成形さ
れた樹脂被覆シームレス缶１０の缶胴部１２の熱可塑性
樹脂層３は、少なくとも一軸方向に分子配向している。Also, the resin-coated seamless can 10 of the present invention.
Is formed by drawing the above-mentioned polyester resin-coated metal plate 1 between a punch and a die into a cup shape having a bottom, followed by thinning drawing by bending and stretching and / or ironing. The cup side wall is thinned by the thinning draw forming and / or ironing process, and the thermoplastic resin layer 3 of the formed can body 12 of the resin-coated seamless can 10 is molecularly oriented in at least one axial direction. There is.
【００１３】缶胴部１２の上端には、所望により形成さ
れるネック部１３と、ネック部１３を介して形成される
フランジ部１４とが形成されている。前記のようにして
形成された樹脂被覆シームレス缶１０は、缶胴部１２に
おけるポリエステル樹脂層３が少なくとも一軸方向に分
子配向された状態に維持されており、一方、缶底部１１
におけるポリエステル樹脂層３は無配向の状態に維持さ
れている点に特徴を有する。なお、本発明の樹脂被覆シ
ームレス缶１０は、金属基体２の両面にポリエステル樹
脂層３が被覆されているものであってもよい。この場合
は、図２に示すような断面構造の金属基体２の両面にポ
リエステル樹脂層３が被覆されている樹脂被覆金属板１
を、絞り・薄肉化絞り成形及び／又はしごき加工して形
成される。また、図３に示すような断面構造の内面ポリ
エステル樹脂層３上層に、さらに内表面層５が形成され
ているものであっても良い。このような内表面層５は樹
脂被覆シームレス缶１０の内面側に設けられており、例
えば、内容物中の香味成分に対して吸着性の少ない樹脂
などが好ましく用いられる。At the upper end of the can body portion 12, a neck portion 13 formed as desired and a flange portion 14 formed via the neck portion 13 are formed. In the resin-coated seamless can 10 formed as described above, the polyester resin layer 3 in the can body portion 12 is maintained in a state of being molecularly oriented in at least one axial direction, while the can bottom portion 11
The polyester resin layer 3 is characterized by being maintained in a non-oriented state. The resin-coated seamless can 10 of the present invention may be one in which both surfaces of the metal substrate 2 are coated with the polyester resin layer 3. In this case, a resin-coated metal plate 1 in which a polyester resin layer 3 is coated on both surfaces of a metal substrate 2 having a sectional structure as shown in FIG.
Is formed by drawing, thinning, and / or ironing. Further, the inner surface layer 5 may be further formed on the inner surface polyester resin layer 3 having the cross-sectional structure as shown in FIG. Such an inner surface layer 5 is provided on the inner surface side of the resin-coated seamless can 10, and for example, a resin having a low adsorptivity for the flavor component in the content is preferably used.
【００１４】［ポリエステル樹脂層］本発明の樹脂被覆
シームレス缶１０においては、缶胴部１２における内面
側のポリエステル樹脂層３の赤外二色比（Ｒ１）が１．
１以上であるという特徴を有する。赤外二色比（Ｒ１）
が、１．１未満では、形成されるシームレス缶に酸性内
容物を充填した際に被膜下腐食を生じるようになり、ま
た、金属基体との密着性及び耐デント性も低下するよう
になり、好ましくない。即ち、この点について説明する
と、前式（１）で定義される缶胴部内面側のポリエステ
ル樹脂層の赤外二色比（Ｒ１）は、缶胴部内面側のポリ
エステル樹脂層の缶高さ方向に垂直な偏光赤外線に対す
る９７３ｃｍ−１の赤外線吸収強度Ｉｗ(⊥)と、缶胴部
内面側のポリエステル樹脂層の缶高さ方向に平行な偏光
赤外線に対する９７３ｃｍ−１の赤外線吸収強度Ｉｗ
(‖)との比を示すものである。[Polyester Resin Layer] In the resin-coated seamless can 10 of the present invention, the infrared dichroic ratio (R1) of the polyester resin layer 3 on the inner surface side of the can body 12 is 1.
It is characterized by being 1 or more. Infrared dichroic ratio (R1)
However, if it is less than 1.1, undercoat corrosion will occur when the formed seamless can is filled with an acidic content, and the adhesion with the metal substrate and the dent resistance will also decrease. Not preferable. That is, to explain this point, the infrared dichroic ratio (R1) of the polyester resin layer on the inner surface side of the can body portion defined by the above equation (1) is the can height of the polyester resin layer on the inner surface side of the can body portion. Infrared absorption intensity Iw (⊥) of 973 cm −1 for polarized infrared light perpendicular to the direction and infrared absorption intensity Iw of 973 cm −1 for polarized infrared light parallel to the can height direction of the polyester resin layer on the inner surface of the can body.
It shows the ratio with (‖).
【００１５】本発明の樹脂被覆シームレス缶は、缶胴部
内面におけるポリエチレンテレフタレートを含有するポ
リエステル樹脂層が、缶胴部内面側のポリエステル樹脂
層の缶高さ方向に垂直な偏光赤外線に対する９７３ｃｍ
−１の赤外線吸収強度Ｉｗ(⊥)と、缶胴部内面側のポリ
エステル樹脂層の缶高さ方向に平行な偏光赤外線に対す
る９７３ｃｍ−１の赤外線吸収強度Ｉｗ(‖)との比（Ｒ
１）が１．１以上に維持されており、分子配向されてい
ることを特徴とする。このことにより、絞り・薄肉化絞
り成形及び／又はしごき加工によって、前記ポリエステ
ル樹脂層が缶高さ方向にある程度以上に分子配向し熱固
定されることによって、金属基体表面とポリエステル樹
脂層の接着界面におけるポリエステル樹脂層の加工の際
の内部応力等による密着性阻害要因が取り除かれ、耐食
性、耐衝撃性等を向上させることが可能となる。即ち、
被覆樹脂層と金属基体表面との接着界面における密着性
を高め、シームレス缶の被膜下腐食（ＵＦＣ）を抑制
し、また、被膜の耐衝撃性（耐デント性）を高めるとい
う作用効果が得られる。また、缶詰製品として保管した
時に、内容物のフレーバーが樹脂に吸着して、缶詰製品
を飲用、或いは食する際に開缶した時の味の変化を防止
するという作用効果がある。In the resin-coated seamless can of the present invention, the polyester resin layer containing polyethylene terephthalate on the inner surface of the can body is 973 cm against the polarized infrared rays perpendicular to the can height direction of the polyester resin layer on the inner surface of the can body.
-1 of the infrared absorption intensity Iw (⊥), the ratio of infrared absorption intensity of 973 cm -1 Iw (||) for polarization parallel infrared can height direction of the polyester resin layer of the can body inner surface side (R
1) is maintained at 1.1 or more, and is molecularly oriented. As a result, the polyester resin layer is molecularly oriented in the can height direction to a certain extent or more and heat-fixed by drawing / thinning draw forming and / or ironing process, so that the adhesive interface between the metal substrate surface and the polyester resin layer. In the processing of the polyester resin layer in 1), the factors that hinder the adhesion due to the internal stress and the like are removed, and it becomes possible to improve the corrosion resistance, the impact resistance, and the like. That is,
The adhesiveness between the coating resin layer and the surface of the metal substrate is enhanced, the undercoat corrosion (UFC) of the seamless can is suppressed, and the impact resistance (dent resistance) of the coating is enhanced. . Further, when stored as a canned product, the flavor of the content is adsorbed by the resin, and there is an effect that the change in taste when the canned product is opened when the canned product is drunk or eaten is prevented.
【００１６】また、本発明の樹脂被覆シームレス缶は、
缶底部の被覆樹脂層は未配向の状態であり、缶底部内面
におけるポリエチレンテレフタレートを含有するポリエ
ステル樹脂層が、缶底部での金属基体圧延方向に垂直な
偏光赤外線に対する９７３ｃｍ−１の赤外線吸収強度Ｉ
Ｂ(⊥)と、缶底部での金属基体圧延方向に平行な偏光赤
外線に対する９７３ｃｍ−１の赤外線吸収強度ＩＢ(‖)
との比（Ｒ２）は１．１以下であることが好ましい。缶
底部では、加工が厳しくないため、被覆した樹脂層の配
向状態を維持しており、缶底部の配向状態は、加工前の
被覆樹脂層の配向状態を示している。缶胴部の厳しい加
工に追随するには、加工前の被覆樹脂層の配向状態が未
配向状態である必要があり、高度に加工した樹脂被覆シ
ームレス缶を得るためには、加工前の被覆樹脂層の配向
状態を示す缶底部の配向が、実質的に未配向状態を示す
Ｒ２が１．１以下であることが必須である。また、缶底
部では、被覆樹脂層と金属基体表面との接着界面は、実
質上加工前の樹脂被覆金属板のままの形で温存されてい
るため両者の密着性は十分であり、耐食性、耐衝撃性等
を満足できる状態に保持される。The resin-coated seamless can of the present invention is
The coating resin layer on the bottom of the can is in an unoriented state, and the polyester resin layer containing polyethylene terephthalate on the inner surface of the bottom of the can is an infrared absorption intensity I of 973 cm −1 for polarized infrared rays perpendicular to the rolling direction of the metal substrate at the bottom of the can.
B (⊥) and infrared absorption intensity IB (‖) of 973 cm -1 against polarized infrared rays parallel to the rolling direction of the metal substrate at the bottom of the can
It is preferable that the ratio (R2) with is 1.1 or less. Since the processing is not severe at the bottom of the can, the orientation state of the coated resin layer is maintained, and the orientation of the bottom of the can indicates the orientation of the coating resin layer before processing. In order to follow the severe processing of the can body, it is necessary that the orientation state of the coating resin layer before processing is unoriented.To obtain a highly processed resin-coated seamless can, the coating resin before processing must be It is essential that the orientation of the bottom of the can, which indicates the orientation of the layer, is substantially unoriented and R2 is 1.1 or less. Also, at the bottom of the can, the adhesive interface between the coating resin layer and the surface of the metal substrate is preserved substantially in the form of the resin-coated metal plate before processing, so the adhesion between the two is sufficient, and the corrosion resistance and corrosion resistance It is maintained in a state where impact resistance and the like can be satisfied.
【００１７】前記樹脂被覆シームレス缶の赤外二色比
（Ｒ１）及び（Ｒ２）の特性の付与は、加工前の被覆ポ
リエステル樹脂の配向状態、シームレス缶成形条件、シ
ームレス缶成形後の熱処理等によって施すことができ
る。赤外二色比（Ｒ１）及び（Ｒ２）をコントロールす
るには、押し出しコート或いはキャストフィルムをラミ
ネートした実質上未配向のポリエステル樹脂被覆金属板
を用い、適切な温度条件下で、薄肉化絞り成形及び／又
はしごき加工でシームレスカップとした後、その缶胴部
の被覆樹脂層の前記加工による歪み（残留応力）を緩和
させると共に、分子配向を熱固定する熱処理が必要であ
る。The characteristics of the infrared dichroic ratios (R1) and (R2) of the resin-coated seamless can are imparted by the orientation state of the coated polyester resin before processing, seamless can molding conditions, heat treatment after seamless can molding, etc. Can be given. In order to control the infrared dichroic ratios (R1) and (R2), a substantially unoriented polyester resin-coated metal plate laminated with an extrusion coat or a cast film is used, and under appropriate temperature conditions, thinning drawing is performed. After forming a seamless cup by ironing and / or ironing, it is necessary to reduce the strain (residual stress) of the coating resin layer of the can body portion due to the above-mentioned processing and heat-treat the molecular orientation by heat.
【００１８】この熱処理は、樹脂被覆層のガラス転移点
（Ｔｇ）を基準にして、一般にＴｇ＋５０℃以上、特に
Ｔｇ＋１００乃至融点（Ｔｍ）−５℃の温度範囲で行う
のが好ましく、前記温度域よりも低温側では被覆ポリエ
ステル樹脂層の歪みの緩和が不十分となり、後加工性が
低下する傾向があり、一方、前記温度域よりも高温側で
は缶成形時に形成された分子配向が緩和されてしまう傾
向が大きくなり、缶胴部の耐食性が低下するという問題
が生ずるからである。尚、樹脂被覆層が２層以上の多層
の場合は、最下層の樹脂被覆層が前記温度範囲となるよ
うに熱処理を行うのが好ましい。この熱処理により、被
覆ポリエステル樹脂層の耐熱性が向上すると共に、金属
基体への密着性も向上し、更にネックイン加工やフラン
ジ加工等の後加工に対する加工性、或いは耐フレーバー
性も向上する。This heat treatment is preferably carried out in a temperature range of generally Tg + 50 ° C. or higher, especially Tg + 100 to melting point (Tm) −5 ° C., based on the glass transition point (Tg) of the resin coating layer. On the low temperature side, the strain of the coated polyester resin layer is insufficiently relaxed, and the post-processability tends to decrease, while on the high temperature side above the temperature range, the molecular orientation formed during can molding is relaxed. This is because the tendency tends to increase and the corrosion resistance of the body of the can decreases. When the resin coating layer is a multilayer having two or more layers, it is preferable to perform heat treatment so that the lowermost resin coating layer falls within the above temperature range. By this heat treatment, the heat resistance of the coated polyester resin layer is improved, the adhesion to the metal substrate is also improved, and the workability for post-processing such as neck-in processing and flange processing, or the flavor resistance is also improved.
【００１９】なお、ポリエステル樹脂の結晶化には、大
別して熱結晶化と配向結晶化があり、本発明の樹脂被覆
シームレス缶のポリエステル樹脂層は、前記の後者の結
晶化特性を主に持つことが特徴である。すなわち、缶胴
部上部のポリエステル樹脂層は、シームレス缶成形時に
高度に配向結晶化されるとともに、その後行う熱処理に
より、粗大なラメラ型結晶を生起することなく、耐熱
性、耐衝撃性及び耐腐食性に優れた特性を付与させるこ
とができる。前記熱処理操作は、シームレス缶成形時に
生じた缶耳部を切断するトリミングを行う前或いは後に
行う。The crystallization of the polyester resin is roughly classified into thermal crystallization and oriented crystallization, and the polyester resin layer of the resin-coated seamless can of the present invention mainly has the latter crystallization characteristics described above. Is a feature. That is, the polyester resin layer on the upper part of the can body is highly oriented and crystallized at the time of seamless can molding, and the subsequent heat treatment does not cause coarse lamella-type crystals, resulting in heat resistance, impact resistance and corrosion resistance. It is possible to impart excellent properties. The heat treatment operation is performed before or after trimming for cutting the can ear portion generated during seamless can molding.
【００２０】必要な熱処理時間は、缶成形時において缶
胴部の被覆ポリエステル樹脂層に形成される分子配向の
程度によっても相違するが、一般には短時間で十分であ
り、具体的には１乃至１０分間の間で行うことが好まし
い。尚、本発明においては、熱処理後のシームレス缶は
徐冷しても良いし、急冷しても良い。本発明の樹脂被覆
シームレス缶の缶内面側の缶胴部１２においては、加工
により分子配向が生じ、一方、缶底部１１では、加工の
程度が厳しくないため、缶底部の被覆樹脂層は未配向の
状態のままであり、金属基体２との接着界面は、実質上
そのままの形で温存されているのである。この結果、金
属基体表面の表面処理層が割れた場合でもポリエステル
樹脂層との密着性を高め、シームレス缶の被膜した腐食
（ＵＦＣ）を抑制し、また、被膜の耐衝撃性（耐デント
性）を高めるという作用効果が得られる。The required heat treatment time differs depending on the degree of molecular orientation formed in the coated polyester resin layer of the can body during can molding, but a short time is generally sufficient, and specifically 1 to 1 It is preferable to perform it for 10 minutes. In the present invention, the seamless can after heat treatment may be gradually cooled or rapidly cooled. In the can body portion 12 on the inner surface side of the can of the resin-coated seamless can of the present invention, molecular orientation occurs due to processing, while in the can bottom portion 11, since the degree of processing is not severe, the coating resin layer at the bottom portion of the can is unoriented. In this state, the adhesive interface with the metal substrate 2 is preserved in substantially the same state. As a result, even if the surface treatment layer on the surface of the metal substrate is cracked, the adhesion with the polyester resin layer is enhanced, corrosion (UFC) of the film coated on the seamless can is suppressed, and the film has impact resistance (dent resistance). It is possible to obtain the effect of increasing the.
【００２１】本発明の樹脂被覆シームレス缶１０は、絞
り成形し、続く曲げ伸ばしによる薄肉化絞り成形及び／
又はしごき加工により、缶胴部１２の厚みが缶底部１１
の厚みの２０乃至８５％、好ましくは４０乃至８０％の
厚みとなるように薄肉化されていることが好ましい。２
０％未満の厚みである場合は、缶胴部１２内面のポリエ
ステル樹脂層に十分な分子配向を付与させることができ
ないと考えられるからであり、８５％を超える厚みであ
る場合は実質的に薄肉化が達成できないからである。The resin-coated seamless can 10 of the present invention is formed by drawing, followed by bending and stretching to reduce the thickness and / or draw forming.
Or, by ironing, the thickness of the can body 12 becomes the bottom 11 of the can.
The thickness is preferably 20 to 85%, more preferably 40 to 80%. Two
This is because when the thickness is less than 0%, it is considered that sufficient molecular orientation cannot be imparted to the polyester resin layer on the inner surface of the can body portion 12, and when the thickness is more than 85%, it is substantially thin. This is because the realization cannot be achieved.
【００２２】本発明の絞り・薄肉化絞り成形及び／又は
しごき加工で形成される樹脂被覆シームレス缶１０の缶
胴部１２のポリエステル樹脂層３には、二種類の分子配
向が形成されている。第一のものは、絞り・薄肉化絞り
成形及び／又はしごき加工に際してポリエステル樹脂分
子が塑性流動に伴って缶軸（缶ハイト）方向に配向する
ものであり、これは繊維配向に近いものである。第二の
ものは、しごき加工特有のものであり、特許第２９７０
４５９号公報に記載されているように、ポリエステル分
子のベンゼン環面がフィルム面に平行に近い状態で配向
するものである。これらの分子配向は、いずれも樹脂被
覆シームレス缶の諸特性、特にデント性、耐食性の向上
に寄与する。Two types of molecular orientations are formed in the polyester resin layer 3 of the can body portion 12 of the resin-coated seamless can 10 formed by the drawing / thinning draw forming and / or ironing process of the present invention. The first one is that polyester resin molecules are oriented in the can axis (can height) direction due to plastic flow during drawing / thinning draw forming and / or ironing, which is close to fiber orientation. . The second one is peculiar to the ironing process, and is patent 2970.
As described in Japanese Patent No. 459, the benzene ring surface of the polyester molecule is oriented in a state of being substantially parallel to the film surface. All of these molecular orientations contribute to the improvement of various properties of the resin-coated seamless can, particularly dent property and corrosion resistance.
【００２３】本発明において、缶内面側の缶胴部におけ
るポリエチレンテレフタレートを主体とするポリエステ
ル樹脂層の赤外二色比（Ｒ１）が１．１以上になるよう
に熱処理することは既に述べたとおりであるが、熱処理
はまた、加工により残留する内部歪みを抑制する作用効
果を有する点でも行うことが好ましい。In the present invention, the heat treatment is carried out so that the infrared dichroic ratio (R1) of the polyester resin layer mainly composed of polyethylene terephthalate in the can body portion on the inner surface side of the can is 1.1 or more. However, the heat treatment is also preferably performed in terms of the effect of suppressing the internal strain remaining due to processing.
【００２４】次に、本発明の樹脂被覆シームレス缶に用
いられるポリエステル樹脂は、金属基体状に薄いフィル
ム層を形成するに足る分子量を有するべきであり、その
固有粘度（ＩＶ）は０．６ｄｌ／ｇ以上、特に０．６５
乃至１．４ｄｌ／ｇの範囲にあるものが望ましい。固有
粘度（ＩＶ）が０．６ｄｌ／ｇ未満であると、種々の熱
処理に耐える耐熱性、シームレス缶への成形加工、その
後の後加工に耐える加工性とを有していないからであ
り、また、前記数値範囲外のポリエステル樹脂は、十分
な機械的特性を有さず、腐食成分へのバリアー性、耐内
容物性に欠けるためである。なお、前記範囲内のポリエ
ステル樹脂は分子量が大きいため、半結晶化時間（τ）
が長く、後述する熱結晶化防止の点においても有用であ
る。Next, the polyester resin used for the resin-coated seamless can of the present invention should have a molecular weight sufficient to form a thin film layer on a metal substrate, and its intrinsic viscosity (IV) is 0.6 dl / g or more, especially 0.65
It is preferably in the range of 1.4 to 1.4 dl / g. When the intrinsic viscosity (IV) is less than 0.6 dl / g, it does not have heat resistance to withstand various heat treatments, processability for forming seamless cans, and processability for subsequent post-processing. This is because the polyester resin out of the above numerical range does not have sufficient mechanical properties and lacks barrier properties against corrosive components and content resistance. Since the polyester resin in the above range has a large molecular weight, the half-crystallization time (τ)
Is long and is also useful in terms of preventing thermal crystallization described later.
【００２５】本発明において、缶胴部におけるポリエス
テル樹脂層を少なくとも一軸方向に配向した状態に維持
するには、ポリエステル樹脂として分子配向可能な樹脂
を使用し、シームレス缶への加工も缶胴部の樹脂層に少
なくとも一軸方向の配向が残存するように行うのが良
い。In the present invention, in order to maintain the polyester resin layer in the body of the can in a state of being oriented at least uniaxially, a resin capable of molecular orientation is used as the polyester resin, and processing into a seamless can is also performed in the body of the can. It is preferable to carry out so that the orientation in the uniaxial direction remains in the resin layer.
【００２６】このため、金属基体の缶内面側に積層され
ているポリエステル樹脂層には、ポリエチレンテレフタ
レートやポリブチレンテレフタレート、更にはポリエチ
レンナフタレート等のホモポリエステルを使用すること
が好ましい。しかし、前記ポリエステル樹脂層の到達し
得る最高結晶化度を下げることが、熱結晶化防止、更に
は耐衝撃性や加工性の点で望ましい。このため、原料ポ
リエステル中にエチレンテレフタレート以外の共重合エ
ステル単位を導入することが好ましい。この共重合エス
テル単位の導入は、共重合を行うことで可能である。更
にポリマーブレンド、或いは多層とすることによっても
可能である。共重合ポリエステルでは、ホモポリエステ
ルに比してシームレス缶への成形時に生じる一軸配向を
緩和させる傾向がある。Therefore, it is preferable to use a homopolyester such as polyethylene terephthalate, polybutylene terephthalate, or polyethylene naphthalate for the polyester resin layer laminated on the inner surface side of the can of the metal substrate. However, it is desirable to reduce the maximum crystallinity that the polyester resin layer can reach in terms of thermal crystallization prevention, impact resistance and processability. Therefore, it is preferable to introduce a copolymerization ester unit other than ethylene terephthalate into the raw material polyester. This copolymerized ester unit can be introduced by copolymerization. It is also possible to use a polymer blend or a multilayer. Copolyesters tend to relax the uniaxial orientation that occurs during molding into seamless cans, as compared to homopolyesters.
【００２７】本発明に用いるポリエステル樹脂層は多層
の樹脂層から成っていても良く、この場合は、表層
（Ａ）がイソフタル酸含有量１５モル％以下のポリエチ
レンテレフタレート／イソフタレートから成り、下層
（Ｂ）がイソフタル酸含有量８乃至２５モル％のポリエ
チレンテレフタレート／イソフタレートであることが望
ましい。このような２層とすることにより、金属基体と
の密着性、高加工性、耐食性、耐衝撃性、耐フレーバー
吸着性等が付与される。The polyester resin layer used in the present invention may be composed of multiple resin layers. In this case, the surface layer (A) is composed of polyethylene terephthalate / isophthalate having an isophthalic acid content of 15 mol% or less, and the lower layer ( B) is preferably polyethylene terephthalate / isophthalate having an isophthalic acid content of 8 to 25 mol%. Adhesion to a metal substrate, high workability, corrosion resistance, impact resistance, flavor adsorption resistance, and the like are imparted by using such two layers.
【００２８】また、本発明の樹脂被覆シームレス缶は、
缶胴部上部のポリエステル樹脂層の、密度法による結晶
化度が２０乃至５５％の範囲にあることが好ましい。結
晶化度が２０％未満であると、金属基体との密着性、耐
食性、耐衝撃性が劣り、内容物のフレーバー成分の吸着
量が増える傾向にあり、シームレス缶として、好ましく
ない。一方、結晶化度が５５％を超えると、金属基体と
の密着性に劣り、また加工時にポリエステル樹脂層に割
れが入る可能性が大になるからである。密度法による結
晶化度（Ｘｃ）は、一般的に下記式（３）で表される。
Ｘｃ＝［ｄｃ（ｄ−ｄａ）］／［ｄ（ｄｃ−ｄａ）］×１００…（３）
（３）式中、ｄｃは完全結晶層の密度＝１．４５５ｇ／
ｃｍ３であり、ｄａは完全非晶層の密度＝１．３３５ｇ
／ｃｍ３であり、ｄは試料の密度（ｇ／ｃｍ３）であ
る。The resin-coated seamless can of the present invention is
It is preferable that the crystallinity of the polyester resin layer on the upper part of the can body is in the range of 20 to 55% by the density method. If the crystallinity is less than 20%, the adhesion to the metal substrate, the corrosion resistance, and the impact resistance are poor, and the amount of flavor components adsorbed in the content tends to increase, which is not preferable as a seamless can. On the other hand, if the crystallinity exceeds 55%, the adhesion to the metal substrate is poor, and the polyester resin layer is likely to crack during processing. The crystallinity (Xc) by the density method is generally represented by the following formula (3). Xc = [dc (d-da)] / [d (dc-da)] × 100 (3) In the formula (3), dc is the density of the perfect crystal layer = 1.455 g /
cm 3 , and da is the density of the completely amorphous layer = 1.335 g
/ Cm 3 and d is the density of the sample (g / cm 3 ).
【００２９】ポリエステル樹脂層には、それ自体公知の
樹脂用配合剤、例えば立体障害性フェノール類等の酸化
防止剤、非晶質シリカ等のアンチブロック剤、二酸化チ
タン（チタン白）等の顔料、各種帯電防止剤、滑剤等を
公知の処方に従って配合することができる。In the polyester resin layer, a compounding agent known per se, for example, antioxidants such as sterically hindered phenols, antiblocking agents such as amorphous silica, pigments such as titanium dioxide (titanium white), Various antistatic agents, lubricants and the like can be added according to a known formulation.
【００３０】［樹脂被覆金属板］次に、本発明の樹脂被
覆シームレス缶に用いられる樹脂被覆金属板について図
１〜図３を用いて説明する。本発明の樹脂被覆シームレ
ス缶１０に用いる樹脂被覆金属板１は、未配向のポリエ
ステル樹脂層３を金属基体２に積層したものである。未
配向のポリエステル樹脂層を用いる理由は、溶融樹脂の
押し出しコート法や未延伸フィルム（キャストフィル
ム）のラミネート法を用いることによって、少ない工程
数で、しかも安価に樹脂被覆金属板を製造できるためで
ある。更に、樹脂被覆金属板１上に形成されたポリエス
テル樹脂層３が未配向状態であるため、絞り・薄肉化絞
り成形及び／またはしごき加工性に優れており、缶胴部
１２を高度に薄肉化することができ、また、シームレス
缶１０のハイトを大きくすることも容易であるからであ
る。また、従来缶用途に用いられていた二軸延伸フィル
ムを用いないのは、加工が難しくコストアップにつなが
るという理由からである。[Resin-Coated Metal Plate] Next, the resin-coated metal plate used in the resin-coated seamless can of the present invention will be described with reference to FIGS. The resin-coated metal plate 1 used for the resin-coated seamless can 10 of the present invention is one in which a non-oriented polyester resin layer 3 is laminated on a metal substrate 2. The reason for using the non-oriented polyester resin layer is that a resin-coated metal plate can be manufactured at a low number of steps and at low cost by using a melt resin extrusion coating method or an unstretched film (cast film) laminating method. is there. Furthermore, since the polyester resin layer 3 formed on the resin-coated metal plate 1 is in an unoriented state, it is excellent in drawing / thinning draw forming and / or ironing workability, and the can body 12 is highly thinned. This is because the height of the seamless can 10 can be easily increased. In addition, the reason why the biaxially stretched film that has been conventionally used for cans is not used is that it is difficult to process and leads to cost increase.
【００３１】本発明に用いる樹脂被覆金属板１は、金属
基体２に分子配向可能なポリエステル樹脂層３を未延伸
の状態で熱接着させることにより製造される。即ち、シ
ームレス缶１０の缶胴部内面側のポリエステル樹脂層３
の赤外二色比（Ｒ１）を１．１以上に、また、缶底部内
面側のポリエステル樹脂層３の赤外二色比（Ｒ２）を
１．１以下にするためには、ポリエステル樹脂層３を実
質上未配向の状態でラミネートすることが重要となる。
以下、本発明に用いる金属基体２、ポリエステル樹脂層
３及び樹脂被覆金属板１について説明する。The resin-coated metal plate 1 used in the present invention is manufactured by thermally bonding the polyester resin layer 3 capable of molecular orientation to the metal substrate 2 in an unstretched state. That is, the polyester resin layer 3 on the inner surface side of the can body of the seamless can 10.
In order to make the infrared dichroic ratio (R1) of 1.1 or more and the infrared dichroic ratio (R2) of the polyester resin layer 3 on the inner surface side of the can bottom part 1.1 or less, It is important to laminate 3 in a substantially unoriented state.
The metal substrate 2, the polyester resin layer 3, and the resin-coated metal plate 1 used in the present invention will be described below.
【００３２】本発明に用いる樹脂被覆金属板１の断面構
造の一例を示す図２において、樹脂被覆金属板１は、金
属基体２と少なくとも缶内面側に位置するポリエステル
樹脂層３とからなっている。また、樹脂被覆金属板１に
は外面被膜４が形成されていることも好ましく、この外
面被膜４はポリエステル樹脂層３と同様のものであって
も良いし、また、通常の缶用塗料や樹脂フィルムであっ
ても良い。In FIG. 2 showing an example of the sectional structure of the resin-coated metal plate 1 used in the present invention, the resin-coated metal plate 1 comprises a metal substrate 2 and a polyester resin layer 3 located at least on the inner surface side of the can. . Further, it is also preferable that the resin-coated metal plate 1 is provided with an outer surface coating 4, and the outer surface coating 4 may be the same as the polyester resin layer 3, or may be an ordinary can paint or resin. It may be a film.
【００３３】樹脂被覆金属板の断面構造の他の例を示す
図３において、缶内面となる側のポリエステル樹脂層３
の上に内表面層５を設けることも好ましい。例えば、内
面表層が、内容物中の香味成分に対して吸着性の少な
い、テレフタル酸成分やイソフタル酸成分から誘導され
たポリエステル乃至コポリエステルであり、下層が、金
属基体に対する接着性に優れたイソフタル酸などの共重
合量の多いコポリエステルであることが好ましい。In FIG. 3 showing another example of the cross-sectional structure of the resin-coated metal plate, the polyester resin layer 3 on the inner surface of the can is shown.
It is also preferable to provide the inner surface layer 5 on the above. For example, the inner surface layer is a polyester or copolyester derived from a terephthalic acid component or an isophthalic acid component, which has low adsorptivity to the flavor component in the content, and the lower layer is an isophthalic compound excellent in adhesiveness to a metal substrate. A copolyester having a large copolymerization amount of an acid or the like is preferable.
【００３４】本発明に用いる樹脂被覆金属板１は、前記
ポリエステル樹脂層３を溶融状態で金属基体２上に押し
出しコートして、熱接着させることにより製造すること
ができる。また、別の製造方法としては、予め製膜され
たポリエステル樹脂の未延伸フィルム（キャストフィル
ム）を金属基体２上に熱接着させることによっても製造
することができる。本発明に使用するポリエステル樹脂
層３の厚みは、全体として２乃至６０μｍ、特に３乃至
４０μｍの範囲にあるのが金属の保護効果、加工性の点
で好ましい。また、必要に応じて、接着剤、接着用プラ
イマーを用いても良い。The resin-coated metal plate 1 used in the present invention can be produced by extrusion-coating the polyester resin layer 3 on the metal substrate 2 in a molten state and thermally adhering it. Further, as another manufacturing method, it can also be manufactured by thermally adhering an unstretched film (cast film) of a polyester resin formed in advance onto the metal substrate 2. The total thickness of the polyester resin layer 3 used in the present invention is preferably in the range of 2 to 60 μm, particularly 3 to 40 μm from the viewpoint of metal protection effect and workability. Moreover, you may use an adhesive agent and an adhesion primer as needed.
【００３５】［金属基体］金属基体としては、各種表面
処理鋼板やアルミニウム等の軽金属板を使用することが
できる。表面処理鋼板としては、冷圧延鋼板を焼鈍後二
次冷間圧延し、亜鉛メッキ、錫メッキ、ニッケルメッ
キ、ニッケル錫メッキ、電解クロム酸処理、クロム酸処
理等の表面処理の一種または二種以上行ったものを用い
ることができる。好適な表面処理鋼板の一例は、電解ク
ロム酸処理鋼板であり、特に１０乃至２００ｍｇ／ｍ２
の金属クロム層と、１乃至５０ｍｇ／ｍ２（金属換算）
のクロム酸化物層を備えたものであり、このものは、樹
脂被膜や塗膜などとの密着性に優れており、耐腐食性に
も優れている。表面処理鋼板の他の例は、０．５乃至１
１．２ｇ／ｍ２の錫メッキ量を有する硬質ブリキ板であ
る。このブリキ板の上層には、金属クロム換算で、クロ
ム量が１乃至３０ｍｇ／ｍ２ となるようなクロム酸処
理或いはクロム酸／リン酸処理が行われていることが望
ましい。更に、他の例としては、アルミニウムメッキ、
アルミニウム圧接等を施したアルミニウム被覆鋼板も用
いることができる。[Metal Base] As the metal base, various surface-treated steel plates and light metal plates such as aluminum can be used. As the surface-treated steel sheet, one or more kinds of surface treatment such as zinc-plated, tin-plated, nickel-plated, nickel-tin-plated, electrolytic chromic acid treatment, chromic acid treatment, etc. are obtained by annealing a cold-rolled steel sheet and then secondary cold rolling. What has been done can be used. An example of a suitable surface-treated steel sheet is an electrolytic chromic acid-treated steel sheet, particularly 10 to 200 mg / m 2
Metal chrome layer of 1 to 50 mg / m 2 (metal conversion)
Chrome oxide layer, which has excellent adhesion to resin coatings and coatings, and excellent corrosion resistance. Other examples of the surface-treated steel sheet are 0.5 to 1
A hard tin plate having a tin plating amount of 1.2 g / m 2 . It is desirable that the upper layer of this tin plate be treated with chromic acid or chromic acid / phosphoric acid so that the amount of chromium becomes 1 to 30 mg / m 2 in terms of metallic chromium. Furthermore, as another example, aluminum plating,
An aluminum-coated steel plate subjected to aluminum pressure welding or the like can also be used.
【００３６】軽金属板としては、アルミニウム板やアル
ミニウム合金板を使用することができる。耐食性と加工
性との点で優れるアルミニウム合金板は、Ｍｎ：０．２
乃至１．５重量％、Ｍｇ：０．８乃至５重量％、Ｚｎ：
０．２５乃至０．３重量％、及びＣｕ：０．１５乃至
０．２５重量％、残部がＡｌの組成を有するものが好ま
しい。これらの軽金属板の上層にも、金属クロム換算で
クロム量が２０乃至３００ｍｇ／ｍ２となるようなクロ
ム酸処理或いはクロム酸／リン酸処理が施されているこ
とが望ましい。軽金属板に対する表面処理は、水溶性フ
ェノール樹脂を併用して行うこともできる。As the light metal plate, an aluminum plate or an aluminum alloy plate can be used. An aluminum alloy plate having excellent corrosion resistance and workability has a Mn: 0.2.
To 1.5% by weight, Mg: 0.8 to 5% by weight, Zn:
It is preferable that the composition is 0.25 to 0.3% by weight, Cu: 0.15 to 0.25% by weight, and the balance is Al. The upper layer of these light metal plates is also preferably subjected to chromic acid treatment or chromic acid / phosphoric acid treatment so that the chromium amount becomes 20 to 300 mg / m 2 in terms of metal chromium. The surface treatment of the light metal plate can also be performed by using a water-soluble phenol resin in combination.
【００３７】金属基体の素板厚みは、金属の種類、シー
ムレス缶の用途或いはサイズによっても相違するが、一
般に０．１０乃至０．５０ｍｍの厚みを有するのが好ま
しく用いられる。中でも、表面処理鋼板の場合は、０．
１０乃至０．３０ｍｍの厚みのものが好ましく、また、
軽金属板の場合は、０．１５乃至０．４０ｍｍの厚みを
有するものが好ましい。The thickness of the base metal plate of the metal substrate varies depending on the type of metal, the use or size of the seamless can, but it is generally preferable to use a thickness of 0.10 to 0.50 mm. Above all, in the case of the surface-treated steel sheet, 0.
A thickness of 10 to 0.30 mm is preferable, and
In the case of a light metal plate, one having a thickness of 0.15 to 0.40 mm is preferable.
【００３８】[0038]
【実施例】本発明を、次の実施例を用いてさらに詳細に
説明する。表１には各実施例で用いた樹脂の組成を、表
２には各実施例の条件、評価等を示す。The present invention will be described in more detail with reference to the following examples. Table 1 shows the composition of the resin used in each example, and Table 2 shows the conditions and evaluations of each example.
【００３９】（実施例１）表１に示した組成Ｃのポリエ
ステル樹脂を、二軸押出機に投入し、Ｔダイを通して厚
さ２０μｍとなるように押し出して冷却ロールで冷却し
たフィルムを巻き取り、キャストフィルムとした。その
後、これらの作成したフィルムをアルミ合金板（板厚
０．２８ｍｍ、Ａ３００４材、クロム酸／リン酸表面処
理）の両面に熱ラミネートし、直ちに水冷することによ
りポリエステル樹脂被覆金属板を得た。この時のラミネ
ート前の金属板の温度は、ポリエステル樹脂の融点より
１５℃高く設定し、ラミネートロールの温度は１５０
℃、通板速度は４０ｍ／ｍｉｎ．でラミネートし樹脂被
覆金属板とした。Example 1 A polyester resin having the composition C shown in Table 1 was charged into a twin-screw extruder, extruded through a T-die to a thickness of 20 μm, and the film cooled with a cooling roll was wound up. It was a cast film. Then, the films thus prepared were heat laminated on both sides of an aluminum alloy plate (plate thickness 0.28 mm, A3004 material, chromic acid / phosphoric acid surface treatment), and immediately water-cooled to obtain a polyester resin-coated metal plate. The temperature of the metal plate before laminating at this time is set to be 15 ° C. higher than the melting point of the polyester resin, and the temperature of the laminating roll is 150 ° C.
C., the strip running speed is 40 m / min. Was laminated with to obtain a resin-coated metal plate.
【００４０】こうして作製したポリエステル樹脂被覆金
属板にワックス系潤滑剤を塗布し、直径１５２ｍｍの円
盤を打ち抜き、浅絞りカップを得た。次いで、この浅絞
りカップをしごき加工を行い、シームレスカップを得
た。このシームレスカップの諸特性は以下のとおりであ
った。
カップ径：６６ｍｍ
カップ高さ：１２７ｍｍ
素板に対する缶壁部の厚み：４５％
このシームレスカップを、常法に従ってドーミング成形
を行い、ポリエステル樹脂のＴｍ−１０℃、３分の熱処
理を行った後、カップを放冷後、開口端縁部のトリミン
グ加工、曲面印刷及び焼き付け乾燥、ネックイン加工、
フランジ加工等の後加工を行って、３５０ｃｃ用シーム
レス缶を得た。A wax type lubricant was applied to the polyester resin-coated metal plate thus produced, and a disk having a diameter of 152 mm was punched out to obtain a shallow-drawing cup. Then, this shallow drawn cup was subjected to ironing processing to obtain a seamless cup. The various characteristics of this seamless cup were as follows. Cup diameter: 66 mm Cup height: 127 mm Thickness of the can wall portion with respect to the base plate: 45% This seamless cup was subjected to doming molding according to a conventional method, and after heat-treating the polyester resin at Tm-10 ° C for 3 minutes, After cooling the cup, trimming of the opening edge, curved surface printing and baking drying, neck-in processing,
Post processing such as flanging was performed to obtain a 350 cc seamless can.
【００４１】（実施例２）表１に示す組成Ｄのポリエス
テル樹脂を用いた以外は、実施例１と同様の方法により
シームレス缶を得た。Example 2 A seamless can was obtained in the same manner as in Example 1 except that the polyester resin having the composition D shown in Table 1 was used.
【００４２】（実施例３）表１に示す組成Ｂのポリエス
テル樹脂を表層、組成Ｄのポリエステル樹脂を下層と
し、二台の二軸押出機に投入して、２層Ｔダイを通し
て、表層の厚さが５μｍ、下層の厚さが１５μｍの２層
となるように押し出したキャストフィルムを用いてラミ
ネート材を得た以外は、実施例１と同様の方法によりシ
ームレス缶を得た。(Example 3) The polyester resin having the composition B shown in Table 1 was used as a surface layer and the polyester resin having the composition D was used as a lower layer, and the mixture was put into two twin-screw extruders and passed through a two-layer T die to obtain the thickness of the surface layer. A seamless can was obtained by the same method as in Example 1 except that a laminate material was obtained by using a cast film extruded so that the thickness of the lower layer was 5 μm and the thickness of the lower layer was 15 μm.
【００４３】（実施例４）表１に示す組成Ａのポリエス
テル樹脂を表層、組成Ｃのポリエステル樹脂を下層とし
た以外は、実施例３と同様の方法によりシームレス缶を
得た。Example 4 A seamless can was obtained in the same manner as in Example 3 except that the polyester resin of composition A shown in Table 1 was used as the surface layer and the polyester resin of composition C was used as the lower layer.
【００４４】（実施例５）表１に示す組成Ｄのポリエス
テル樹脂を表層、組成Ｅのポリエステル樹脂を下層とし
たキャストフィルムを、ＴＦＳ鋼板（板厚０．１８ｍ
ｍ、金属クロム量１２０ｍｇ／ｍ２、クロム水和酸化物
量１５ｍｇ／ｍ２）の両面にラミネートした以外は、実
施例３と同様のラミネートを行った。Example 5 A cast film having a polyester resin of composition D shown in Table 1 as a surface layer and a polyester resin of composition E as a lower layer was formed into a TFS steel plate (sheet thickness 0.18 m).
m, the amount of metal chromium was 120 mg / m 2 , and the amount of hydrated chromium oxide was 15 mg / m 2 ), but the same lamination as in Example 3 was performed.
【００４５】こうして作製したポリエステル樹脂被覆金
属板にワックス系潤滑剤を塗布し、直径１６６ｍｍの円
盤を打ち抜き、浅絞りカップを得た。次いで、この浅絞
りカップを引き伸ばしによる薄肉化絞り加工・しごき加
工を行い、シームレスカップを得た。このシームレスカ
ップの諸特性は以下の通りであった。
カップ径：６６ｍｍ
カップ高さ：１２８ｍｍ
素板に対する缶壁部の厚み：６５％
このシームレスカップを、実施例１と同様の方法により
シームレス缶とした。A wax-type lubricant was applied to the polyester resin-coated metal plate thus produced, and a disk having a diameter of 166 mm was punched out to obtain a shallow drawn cup. Next, this shallow drawing cup was subjected to thinning drawing and ironing processing by stretching to obtain a seamless cup. The characteristics of this seamless cup were as follows. Cup diameter: 66 mm Cup height: 128 mm Thickness of the can wall portion with respect to the base plate: 65% This seamless cup was made into a seamless can by the same method as in Example 1.
【００４６】（実施例６）表１に示した組成Ｆのポリエ
ステル樹脂を、２５０℃に加熱したアルミ合金板（板厚
０．２８ｍｍ、Ａ３００４材、クロム酸／リン酸表面処
理）の両面側に、φ６５ｍｍの押出機から内外面側とし
てそれぞれ厚さが２０μｍとなるように同時押し出しコ
ートを行った後に冷却を行い、ポリエステル樹脂被覆金
属板を得た。こうして得られた樹脂被覆金属板を用い
て、実施例１と同様の方法によりシームレス缶を得た。Example 6 A polyester resin having the composition F shown in Table 1 was applied to both sides of an aluminum alloy plate (plate thickness 0.28 mm, A3004 material, chromic acid / phosphoric acid surface treatment) heated to 250 ° C. , A φ65 mm extruder was used to perform simultaneous extrusion coating on the inner and outer surfaces so that the thickness was 20 μm, and then cooling was performed to obtain a polyester resin-coated metal plate. Using the resin-coated metal plate thus obtained, a seamless can was obtained by the same method as in Example 1.
【００４７】（実施例７）表１に示した組成Ｇのポリエ
ステル樹脂を用いた以外は、実施例６と同様の方法によ
りシームレス缶を得た。(Example 7) A seamless can was obtained in the same manner as in Example 6 except that the polyester resin having the composition G shown in Table 1 was used.
【００４８】[0048]
【実施例８】表１に示す組成Ａのポリエステル樹脂を表
層、組成Ｅのポリエステル樹脂を下層とし、表層５μ
ｍ、下層１５μｍの２層になるように、二軸押出機及び
２層Ｔダイを用いて同時押し出しコートを行った以外
は、実施例６と同様の方法によりシームレス缶を得た。Example 8 A polyester resin having a composition A shown in Table 1 was used as a surface layer, and a polyester resin having a composition E was used as a lower layer.
A seamless can was obtained by the same method as in Example 6 except that simultaneous extrusion coating was carried out using a twin-screw extruder and a two-layer T die so that two layers of m and a lower layer of 15 μm were formed.
【００４９】（実施例９）表１に示す組成Ｄのポリエス
テル樹脂を表層、組成Ｃのポリエステル樹脂を下層とし
た以外は、実施例８と同様の方法によりシームレス缶を
得た。Example 9 A seamless can was obtained in the same manner as in Example 8 except that the polyester resin having the composition D shown in Table 1 was used as the surface layer and the polyester resin having the composition C was used as the lower layer.
【００５０】（比較例１）表１に示す組成Ａのポリエス
テル樹脂を用い表２に示した熱処理を施した以外は、実
施例１と同様の方法によりシームレス缶を得た。Comparative Example 1 A seamless can was obtained in the same manner as in Example 1 except that the polyester resin having the composition A shown in Table 1 was used and the heat treatment shown in Table 2 was performed.
【００５１】（比較例２）表１に示す組成Ｂのポリエス
テル樹脂を表層、組成Ｄのポリエステルを下層とし、表
２に示した熱処理を施した以外は、実施例１と同様の方
法によりシームレス缶を得た。Comparative Example 2 A seamless can was prepared in the same manner as in Example 1 except that the polyester resin having the composition B shown in Table 1 was used as the surface layer and the polyester having the composition D was used as the lower layer, and the heat treatment shown in Table 2 was performed. Got
【００５２】（比較例３）表１に示す組成Ａのポリエス
テル樹脂を用いたキャストフィルムを、ＴＦＳ鋼板（板
厚０．１８ｍｍ、金属クロム量１２０ｍｇ／ｍ２、クロ
ム水和酸化物量１５ｍｇ／ｍ２）にラミネートした以外
は、実施例１と同様の樹脂被覆金属板とした。この樹脂
金属板を用いて、実施例５と同様の薄肉化絞り加工・し
ごき加工及び表２に示した熱処理を行ってシームレスカ
ップとした。次いで、実施例１と同様の後加工を行って
シームレス缶を得た。Comparative Example 3 A cast film using the polyester resin having the composition A shown in Table 1 was used as a TFS steel plate (plate thickness 0.18 mm, metal chromium amount 120 mg / m 2 , chromium hydrate oxide amount 15 mg / m 2). The same resin-coated metal plate as in Example 1 except that the metal plate was laminated to (1). Using this resin metal plate, thinning, drawing and ironing as in Example 5 and the heat treatment shown in Table 2 were performed to obtain a seamless cup. Then, the same post-processing as in Example 1 was performed to obtain a seamless can.
【００５３】（比較例４）表１に示す組成Ｆのポリエス
テル樹脂を用い、シームレスカップの熱処理を行わなか
った以外は、比較例３と同様に樹脂被覆金属板を用いて
シームレス缶を得た。Comparative Example 4 A seamless can was obtained by using a resin-coated metal plate in the same manner as in Comparative Example 3 except that the polyester resin having the composition F shown in Table 1 was used and the heat treatment of the seamless cup was not performed.
【００５４】（比較例５）表１に示す組成Ｅのポリエス
テル樹脂を表層、組成Ｂのポリエステル樹脂を下層と
し、シームレスカップの熱処理を行わなかった以外は、
比較例３と同様にシームレス缶を得た。(Comparative Example 5) A polyester resin having a composition E shown in Table 1 was used as a surface layer and a polyester resin having a composition B was used as a lower layer, except that the heat treatment of the seamless cup was not performed.
A seamless can was obtained in the same manner as in Comparative Example 3.
【００５５】（比較例６）表１に示す組成Ａのポリエス
テル樹脂を用いてキャストフィルムとした後に、１００
℃で縦・横それぞれ３倍に延伸後、２３０℃で５秒間熱
処理して二軸延伸フィルムを作製し、用い、表２に示し
た熱処理を施した以外は、実施例１と同様の方法により
シームレス缶を得た。(Comparative Example 6) A polyester resin having the composition A shown in Table 1 was used to form a cast film, and then 100
The same method as in Example 1 was carried out except that the film was heat-treated at 230 ° C. for 5 seconds to prepare a biaxially-stretched film, and the heat treatment shown in Table 2 was performed after the film was stretched at a temperature of 3 ° C. in the lengthwise and transverse directions by 3 times. Got a seamless can.
【００５６】（比較例７）表１に示す組成Ｂのポリエス
テル樹脂を用い、表２に示した熱処理を施した以外は、
実施例６と同様の方法によりシームレス缶を得た。(Comparative Example 7) A polyester resin having the composition B shown in Table 1 was used, except that the heat treatment shown in Table 2 was performed.
A seamless can was obtained by the same method as in Example 6.
【００５７】（比較例８）表１に示す組成Ｅのポリエス
テル樹脂を表層、組成Ｄのポリエステル樹脂を下層とし
て、二軸押出機及び２層Ｔダイを用いて同時押し出しコ
ートを行い、表２に示した熱処理を施した以外は、実施
例６と同様の方法によりシームレス缶を得た。Comparative Example 8 A polyester resin of composition E shown in Table 1 was used as a surface layer and a polyester resin of composition D as a lower layer was subjected to simultaneous extrusion coating using a twin-screw extruder and a two-layer T die. A seamless can was obtained in the same manner as in Example 6 except that the heat treatment shown was applied.
【００５８】前記実施例及び比較例で作製した樹脂被覆
シームレス缶を、以下のような方法で評価した。The resin-coated seamless cans produced in the above Examples and Comparative Examples were evaluated by the following methods.
【００５９】［二色比測定］シームレス缶の缶底部から
７０ｍｍの位置の缶胴部を切り出し、金属を溶解して内
面樹脂層のフリーフィルムを単離した。その後少なくと
も２４時間真空乾燥を行った後、単離したフィルムの缶
高さ方向と垂直及び平行に偏光した赤外線の赤外吸収ス
ペクトルを測定し、得られた垂直及び平行の赤外吸収ス
ペクトルのチャートから、９７３ｃｍ−１のそれぞれの
吸光度Ｉw(⊥)とＩｗ(‖)を求め、缶胴部内面側のポリ
エステル樹脂層の赤外二色比Ｒ１を
Ｒ１＝Ｉw(⊥)／Ｉｗ(‖)・・・（１）
から計算し求めた。[Measurement of dichroic ratio] The can body portion at a position of 70 mm was cut out from the bottom portion of the seamless can, the metal was melted, and the free film of the inner surface resin layer was isolated. After vacuum drying for at least 24 hours, the infrared absorption spectrum of infrared rays polarized in the direction perpendicular to and parallel to the can height direction of the isolated film was measured, and the obtained chart of the vertical and parallel infrared absorption spectra was obtained. Then, the respective absorbances Iw (⊥) and Iw (‖) at 973 cm −1 are obtained, and the infrared dichroic ratio R1 of the polyester resin layer on the inner surface side of the can body is R1 = Iw (⊥) / Iw (‖).・ ・ Calculated from (1).
【００６０】同様に、缶底部を切り出し、金属を溶解し
て内面樹脂層のフリーフィルムを単離・乾燥を行い、缶
底部での金属基体圧延方向に垂直及び平行に偏光した赤
外線の赤外吸収スペクトルを測定し、得られた垂直及び
平行の赤外吸収スペクトルのチャートから、９７３ｃｍ
−１のそれぞれの吸光度ＩＢ(⊥)とＩＢ(‖)を求め、缶
胴部内面側のポリエステル樹脂層の赤外二色比Ｒ２を
Ｒ２＝ＩＢ(⊥)／ＩＢ(‖)・・・（２）
から計算し求めた。その結果を表２にまとめた。Similarly, the bottom of the can is cut out, the metal is melted, the free film of the inner surface resin layer is isolated and dried, and the infrared absorption of infrared rays polarized vertically and parallel to the rolling direction of the metal substrate at the bottom of the can. The spectrum was measured, and from the obtained chart of the vertical and parallel infrared absorption spectra, 973 cm
The respective absorbances IB (⊥) and IB (‖) of -1 are obtained, and the infrared dichroic ratio R2 of the polyester resin layer on the inner surface side of the can body is R2 = IB (⊥) / IB (‖) ... ( 2) Calculated from The results are summarized in Table 2.
【００６１】［結晶化度］シームレス缶の缶胴上部を切
り出し、金属を溶解してフリーフィルムを単離した。そ
の後少なくとも２４時間真空乾燥を行った後、試料の密
度を測定し、密度法により樹脂フィルムの結晶化度を計
算し表示した。[Crystallinity] The upper part of the can body of a seamless can was cut out and the metal was dissolved to isolate a free film. After vacuum drying for at least 24 hours, the density of the sample was measured, and the crystallinity of the resin film was calculated and displayed by the density method.
【００６２】［密着性評価］シームレス缶の缶胴上部内
面フィルムにカッターでクロスカットを入れ、その部分
にセロハンテープ（ニチバン社製：２４ｍｍ幅）を貼
り、そのセロハンテープを剥離した。評価は、セロハン
テープ剥離後のポリエステル樹脂被膜の剥離状態を目視
観察した。評価結果を表２に次の記号で示した。
○：フィルム剥離がなかった
×：フィルム剥離があった[Adhesion Evaluation] A cross cut was put on the inner surface film of the can body of the seamless can with a cutter, and cellophane tape (manufactured by Nichiban Co., Ltd .: 24 mm width) was attached to that portion, and the cellophane tape was peeled off. For the evaluation, the peeled state of the polyester resin coating after peeling the cellophane tape was visually observed. The evaluation results are shown in Table 2 with the following symbols. ○: There was no film peeling ×: There was film peeling
【００６３】［クロスカット評価］シームレス缶の缶胴
上部内面から３ｃｍ×３ｃｍを切り出し、カッターでク
ロスカットを入れた後、０．１％塩化ナトリウム水溶液
に浸し、５０℃で一週間経時した後、腐食状況を観察し
た。評価は、クロスカット部からのフィルム剥離の大き
さ及びフィルム下腐食の大きさで行った。評価結果を表
２に次の記号で示した。
○：１ｍｍ未満のフィルム剥離又はフィルム下腐食が見
られた
×：１ｍｍ以上のフィルム剥離又はフィルム下腐食が見
られたで示した。[Cross-Cut Evaluation] 3 cm × 3 cm was cut out from the inner surface of the upper part of the can body of a seamless can, the cross-cut was made with a cutter, the sample was dipped in a 0.1% sodium chloride aqueous solution, and after aging at 50 ° C. for one week, The corrosion condition was observed. The evaluation was carried out based on the size of film peeling from the cross-cut portion and the size of corrosion under the film. The evaluation results are shown in Table 2 with the following symbols. ◯: Film peeling or under-film corrosion of less than 1 mm was observed. ×: Film peeling or under-film corrosion of 1 mm or more was observed.
【００６４】［パック評価］コーラを充填した缶を横向
きに静置した後、５℃において金属板の圧延方向に対し
直角となる缶軸線上で、缶のネックイン加工部の缶底側
終点に、径６５．５ｍｍの球面を有する１ｋｇの重りを
４０ｍｍの高さから球面が当たるように落下させて衝撃
を与えた。その後、３７℃の温度で貯蔵試験を行い、一
年後の缶内面の状態を評価した。また、５０ｃｍの高さ
から正立落下させ、その後、３７℃の温度で貯蔵試験を
行い、一年後の缶内面の状態を観察した。特に缶ネック
部と缶底部の腐食を観察し表２に示した。[Pack evaluation] A can filled with cola was left to stand sideways, and then, at 5 ° C., on the can axis perpendicular to the rolling direction of the metal plate, at the end of the can bottom side of the can neck-in portion. A weight of 1 kg having a spherical surface having a diameter of 65.5 mm was dropped from a height of 40 mm so that the spherical surface hits, and shocked. Then, a storage test was performed at a temperature of 37 ° C. to evaluate the state of the inner surface of the can after one year. Further, the sample was dropped vertically from a height of 50 cm, and then a storage test was performed at a temperature of 37 ° C. to observe the state of the inner surface of the can after one year. In particular, corrosion of the can neck and the bottom of the can was observed and shown in Table 2.
【００６５】［レトルト処理評価］９５℃の蒸留水を充
填後、１３５℃３０分のレトルト処理を行い、室温に戻
して蒸留水を抜き取り、缶内面の腐食状態を観察した。
その結果を表２に示した。[Evaluation of Retort Treatment] After filling with distilled water at 95 ° C., retort treatment was performed at 135 ° C. for 30 minutes, the temperature was returned to room temperature, the distilled water was extracted, and the corrosion state of the inner surface of the can was observed.
The results are shown in Table 2.
【００６６】[0066]
【表１】 [Table 1]
【００６７】[0067]
【表２】 [Table 2]
【００６８】[0068]
【発明の効果】本発明の樹脂被覆シームレス缶は、缶胴
部内面側のポリエステル樹脂層の赤外二色比（Ｒ１）が
１．１以上なるように制御することにより、優れた、耐
腐食性、耐衝撃性、耐フレーバー性を有する。The resin-coated seamless can of the present invention has excellent corrosion resistance by controlling the infrared dichroic ratio (R1) of the polyester resin layer on the inner surface of the can body to be 1.1 or more. It has resistance, impact resistance, and flavor resistance.
【図１】本発明の樹脂被覆シームレス缶の参考図であ
る。FIG. 1 is a reference view of a resin-coated seamless can of the present invention.
【図２】本発明に用いる樹脂被覆金属板の参考断面図で
ある。FIG. 2 is a reference sectional view of a resin-coated metal plate used in the present invention.
【図３】本発明に用いるの他の樹脂被覆金属板の参考断
面図である。FIG. 3 is a reference cross-sectional view of another resin-coated metal plate used in the present invention.
１： 樹脂被覆金属板 ２： 金属基体 ３： 熱可塑性樹脂層（ポリエステル樹脂層） ４： 外面被膜 ５： 内表面層 １０： シームレス缶 １１： 缶底部 １２： 缶胴部 １３： ネック部 １４： フランジ部 1: Resin coated metal plate 2: Metal substrate 3: Thermoplastic resin layer (polyester resin layer) 4: Outer coating 5: Inner surface layer 10: Seamless can 11: Can bottom 12: Can body 13: Neck 14: Flange part
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 3E061 AA16 AB13 AC09 AD02 AD04 AD06 BA01 BB14 DA02 3E062 AA04 AB14 AC09 JA07 JB11 JC02 JD03 4F100 AB01A AK42B AK42K BA02 DA01 GB16 JA06B JA12B JB02 JD10B JK10 JL01 JN10B YY00B ─────────────────────────────────────────────────── ─── Continued front page F term (reference) 3E061 AA16 AB13 AC09 AD02 AD04 AD06 BA01 BB14 DA02 3E062 AA04 AB14 AC09 JA07 JB11 JC02 JD03 4F100 AB01A AK42B AK42K BA02 DA01 GB16 JA06B JA12B JB02 JD10B JK10 JL01 JN10B YY00B
Claims (7)
レートを含有するポリエステル樹脂層を被覆した樹脂被
覆金属板から成る樹脂被覆シームレス缶において、下記
式（１）で表される缶胴部内面側のポリエステル樹脂層
の赤外二色比（Ｒ１）が、１．１以上であることを特徴
とする樹脂被覆シームレス缶。 Ｒ１＝Ｉｗ(⊥)／Ｉｗ(‖)・・・（１） Ｉｗ(⊥)：缶胴部での缶高さ方向に垂直な偏光赤外線に
対する９７３ｃｍ−１の赤外線吸収強度 Ｉｗ(‖)：缶胴部での缶高さ方向に平行な偏光赤外線に
対する９７３ｃｍ−１の赤外線吸収強度1. A resin-coated seamless can comprising a resin-coated metal plate in which a surface of a metal substrate is coated with a polyester resin layer containing polyethylene terephthalate, wherein a polyester resin on the inner surface side of the can body represented by the following formula (1): Infrared dichroic ratio (R1) of the layer is 1.1 or more, a resin-coated seamless can. R1 = Iw (⊥) / Iw (‖) ・ ・ ・ (1) Iw (⊥): Infrared absorption intensity Iw (‖) of 973 cm −1 against polarized infrared light perpendicular to the can height direction in the can body. Infrared absorption intensity of 973 cm -1 for polarized infrared rays parallel to the can height direction at the body
ポリエステル樹脂層の赤外二色比（Ｒ２）が、１．１以
下であることを特徴とする請求項１に記載の樹脂被覆シ
ームレス缶。 Ｒ２＝ＩＢ(⊥)／ＩＢ(‖)・・・（２） ＩＢ(⊥)：缶底部での金属基体圧延方向に垂直な偏光赤
外線に対する９７３ｃｍ−１の赤外線吸収強度 ＩＢ(‖)：缶底部での金属基体圧延方向に平行な偏光赤
外線に対する９７３ｃｍ −１の赤外線吸収強度2. The inner surface of the bottom of the can represented by the following formula (2):
The infrared dichroic ratio (R2) of the polyester resin layer is 1.1 or less.
The resin-coated sheath according to claim 1, which is below.
Omeless can. R2 = IB (⊥) / IB (‖) ・ ・ ・ (2) IB (⊥): Polarized red perpendicular to the rolling direction of the metal base at the bottom of the can
973 cm for outside line-1Infrared absorption intensity IB (‖): Polarized red parallel to the rolling direction of the metal base at the bottom of the can
973 cm for outside line -1Infrared absorption intensity
ステル樹脂層を金属基体に設けたものであることを特徴
とする請求項１または２に記載の樹脂被覆シームレス
缶。3. The resin-coated seamless can according to claim 1, wherein the resin-coated metal plate is a metal substrate provided with a non-oriented polyester resin layer.
肉化絞り成形及び／またはしごき成形により、缶胴部の
厚みが缶底部の厚みの２０乃至８５％となるように薄肉
化されていることを特徴とする請求項１乃至３の何れか
に記載の樹脂被覆シームレス缶。4. The resin-coated seamless can is thinned by drawing / thinning drawing and / or ironing so that the thickness of the can body is 20 to 85% of the thickness of the can bottom. The resin-coated seamless can according to any one of claims 1 to 3.
り、表層（Ａ）がイソフタル酸含有量１５モル％以下の
ポリエチレンテレフタレート／イソフタレートから成
り、下層（Ｂ）がイソフタル酸含有量８乃至２５モル％
のポリエチレンテレフタレート／イソフタレートから成
ることを特徴とする請求項１乃至４の何れかに記載の樹
脂被覆シームレス缶。5. The polyester resin layer comprises two layers, the surface layer (A) comprises polyethylene terephthalate / isophthalate having an isophthalic acid content of 15 mol% or less, and the lower layer (B) comprises an isophthalic acid content of 8 to 25 mol. %
5. The resin-coated seamless can according to claim 1, which is made of polyethylene terephthalate / isophthalate.
エステル樹脂が、固有粘度０．６ｄｌ／ｇ以上であるこ
とを特徴とする請求項１乃至５の何れかに記載の樹脂被
覆シームレス缶。6. The resin-coated seamless can according to claim 1, wherein the polyester resin forming the polyester resin layer has an intrinsic viscosity of 0.6 dl / g or more.
法による結晶化度が、２０乃至５５％の範囲にあること
を特徴とする請求項１乃至６の何れかに記載の樹脂被覆
シームレス缶。7. The resin-coated seamless can according to claim 1, wherein the crystallinity of the polyester resin layer on the upper part of the can body is in the range of 20 to 55% by the density method. .
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001192047A JP4411802B2 (en) | 2001-06-25 | 2001-06-25 | Resin coated seamless can |
| TW091112740A TWI235128B (en) | 2001-06-25 | 2002-06-10 | Resin-coated seamless can |
| AU48818/02A AU785244B2 (en) | 2001-06-25 | 2002-06-17 | Resin-coated seamless can |
| EP02013930A EP1270201B1 (en) | 2001-06-25 | 2002-06-24 | Resin-coated seamless can |
| DE60227882T DE60227882D1 (en) | 2001-06-25 | 2002-06-24 | Resin coated seamless can |
| KR1020020035795A KR20030004047A (en) | 2001-06-25 | 2002-06-25 | Resin coated seamless can |
| US10/178,790 US20030039778A1 (en) | 2001-06-25 | 2002-06-25 | Resin-coated seamless can |
| US12/135,005 US8268422B2 (en) | 2001-06-25 | 2008-06-06 | Resin coated seamless can |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001192047A JP4411802B2 (en) | 2001-06-25 | 2001-06-25 | Resin coated seamless can |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2003001760A true JP2003001760A (en) | 2003-01-08 |
| JP4411802B2 JP4411802B2 (en) | 2010-02-10 |
Family
ID=19030558
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001192047A Expired - Lifetime JP4411802B2 (en) | 2001-06-25 | 2001-06-25 | Resin coated seamless can |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4411802B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006282195A (en) * | 2005-03-31 | 2006-10-19 | Toyo Seikan Kaisha Ltd | Resin-coated metal can and method for producing the same |
| JP2012110957A (en) * | 2010-11-26 | 2012-06-14 | Toyo Seikan Kaisha Ltd | Method for manufacturing square drawn can |
| WO2015068720A1 (en) * | 2013-11-06 | 2015-05-14 | 東洋製罐株式会社 | Resin-coated metal sheet and seamless can |
-
2001
- 2001-06-25 JP JP2001192047A patent/JP4411802B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006282195A (en) * | 2005-03-31 | 2006-10-19 | Toyo Seikan Kaisha Ltd | Resin-coated metal can and method for producing the same |
| JP2012110957A (en) * | 2010-11-26 | 2012-06-14 | Toyo Seikan Kaisha Ltd | Method for manufacturing square drawn can |
| WO2015068720A1 (en) * | 2013-11-06 | 2015-05-14 | 東洋製罐株式会社 | Resin-coated metal sheet and seamless can |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4411802B2 (en) | 2010-02-10 |
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