JPH02263632A - Laminated steel plate for can with excellent preserving property of content - Google Patents
Laminated steel plate for can with excellent preserving property of contentInfo
- Publication number
- JPH02263632A JPH02263632A JP8546989A JP8546989A JPH02263632A JP H02263632 A JPH02263632 A JP H02263632A JP 8546989 A JP8546989 A JP 8546989A JP 8546989 A JP8546989 A JP 8546989A JP H02263632 A JPH02263632 A JP H02263632A
- Authority
- JP
- Japan
- Prior art keywords
- steel plate
- resin
- film
- laminated
- cans
- 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.)
- Pending
Links
- 229910000576 Laminated steel Inorganic materials 0.000 title claims description 19
- 239000001301 oxygen Substances 0.000 claims abstract description 56
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 56
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229920005989 resin Polymers 0.000 claims abstract description 47
- 239000011347 resin Substances 0.000 claims abstract description 47
- 239000010419 fine particle Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 17
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 16
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 10
- 230000035699 permeability Effects 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 229920000620 organic polymer Polymers 0.000 claims abstract description 6
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 16
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 15
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 15
- 238000007747 plating Methods 0.000 claims description 13
- -1 polyethylene Polymers 0.000 claims description 7
- 229920000306 polymethylpentene Polymers 0.000 claims description 7
- 239000011116 polymethylpentene Substances 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 239000011859 microparticle Substances 0.000 claims description 4
- 239000005062 Polybutadiene Substances 0.000 claims description 3
- 229920002857 polybutadiene Polymers 0.000 claims description 3
- 239000002313 adhesive film Substances 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 abstract description 40
- 239000010959 steel Substances 0.000 abstract description 40
- 239000002245 particle Substances 0.000 abstract description 12
- 239000000796 flavoring agent Substances 0.000 abstract description 7
- 235000019634 flavors Nutrition 0.000 abstract description 7
- 238000010030 laminating Methods 0.000 abstract description 5
- 239000004925 Acrylic resin Substances 0.000 abstract description 2
- 229920000178 Acrylic resin Polymers 0.000 abstract description 2
- 239000004677 Nylon Substances 0.000 abstract description 2
- 239000003822 epoxy resin Substances 0.000 abstract description 2
- 229920001778 nylon Polymers 0.000 abstract description 2
- 229920000647 polyepoxide Polymers 0.000 abstract description 2
- 229920001225 polyester resin Polymers 0.000 abstract description 2
- 239000004645 polyester resin Substances 0.000 abstract description 2
- 229920005672 polyolefin resin Polymers 0.000 abstract description 2
- 229920005749 polyurethane resin Polymers 0.000 abstract description 2
- 230000002000 scavenging effect Effects 0.000 description 17
- 239000003973 paint Substances 0.000 description 12
- 239000000853 adhesive Substances 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000004593 Epoxy Substances 0.000 description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 229920001187 thermosetting polymer Polymers 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 5
- 235000013405 beer Nutrition 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000009503 electrostatic coating Methods 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 230000001953 sensory effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 3
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 235000014171 carbonated beverage Nutrition 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 235000006694 eating habits Nutrition 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 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 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000000192 social effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000005029 tin-free steel Substances 0.000 description 1
- 239000005028 tinplate 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
Landscapes
- Laminated Bodies (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野］
本発明は、ビール、炭酸飲料、ジュース或は一般食品等
として充填・保存するための金属容器（缶）に関するも
ので、更に詳しくは、内容物の変敗を防止し充填した状
態に保存しつる金属容器を提供しようとするものである
。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a metal container (can) for filling and storing beer, carbonated drinks, juice, general foods, etc. The purpose is to provide a metal container that can prevent things from deteriorating and store them in a filled state.
〔従来の技術Ｊ
金属容器用の鉄材料としては、鋼板にＳｎめっきを施し
た”ぶりき”或は電解クロム酸処理鋼板である”ティン
フリースチール（ＴＦＳ）”が良く知られており、溶接
缶、接着缶、ＤＩ缶（絞りとしごき加工により成形され
た缶）用素材として広く用いられている。[Conventional technology J] As iron materials for metal containers, "tinplate", which is a steel plate with Sn plating, and "tin-free steel (TFS)", which is an electrolytic chromic acid treated steel plate, are well known. It is widely used as a material for cans, adhesive cans, and DI cans (cans formed by drawing and ironing).
これらの素材は、製缶加工の前或は製缶加工の後に、５
〜１５μｍ程度の厚みの有機塗料を塗装し用いられるの
が一般的で、有機塗料としはエポキシ系塗料、エポキシ
フェノール系塗料、エポキシエステル系塗料、ビニル系
塗料等が用いられている。These materials are processed before or after the can manufacturing process.
It is common to use an organic paint with a thickness of about 15 μm, and examples of organic paints include epoxy paints, epoxyphenol paints, epoxy ester paints, and vinyl paints.
そして、金属容器の内容物に対する耐食性は、主として
この有機塗膜によって保持されているが、内容物を新鮮
で充填した状態に積極的に維持する機能はない。Corrosion resistance for the contents of the metal container is primarily maintained by this organic coating, but it does not actively maintain the contents fresh and full.
金属容器（缶）に内容物が充填される場合。When filling metal containers (cans) with contents.
内容物自身或はヘッドスペースに酸素が含まれており、
従って、酸素は缶内には不可避的に持ち込まれることに
なる。The contents themselves or the headspace contain oxygen,
Therefore, oxygen will inevitably be brought into the can.
周知のように、この酸素は各種の飲料或は食物を変敗さ
せる原因となる物質であり、出来るだけ缶内に存在させ
ないことが肝要である。As is well known, this oxygen is a substance that causes various beverages and foods to spoil, and it is important to prevent its presence in cans as much as possible.
従来の缶体では、不可避的に持ち込まれる酸素を除去す
る有効な方法が無く、経時と共に内容物の”味”風味”
の低下は避けられない状況であった。With conventional cans, there is no effective way to remove the oxygen that is inevitably brought in, and the taste of the contents deteriorates over time.
The decline was unavoidable.
勿論、この”味”風味゛の低下、及び缶内腐食の点から
、缶内ヘッドスペースの酸素低減には十分配慮がなされ
てはいる。Of course, due consideration has been given to reducing the amount of oxygen in the head space within the can in order to reduce the "taste" and corrosion within the can.
しかし、積極的に缶内の残存酸素を除去し、内容物の”
味”風味”を保持する有効な技術は前述したように無（
、こうした技術の出現が待望されていた。However, by actively removing the remaining oxygen in the can,
As mentioned above, there is no effective technology for retaining taste (flavor).
The advent of such technology has been long awaited.
〔発明が解決しようとする課題］
本発明はこうした実情に鑑みなされたもので１缶内に不
可避的に持ち込まれる酸素を速やかに除去することで、
内用物の変改を防ぎ”味° “風味°の低下を起こさず
、長期にわたり内容物の鮮度を保ちうる缶用鋼板を提供
するものである。[Problems to be Solved by the Invention] The present invention was created in view of these circumstances, and by quickly removing the oxygen that is inevitably brought into a can,
To provide a steel plate for cans that prevents tampering of internally-used products, prevents deterioration of taste, and maintains the freshness of the contents for a long period of time.
本発明は、製缶後に缶内面側となる鋼板表面に、缶内の
酸素を速やかに除去可能な皮膜を積層させたラミ七−ト
鋼板である。即ちその要旨とするところは、
（１）鋼板の表面に５〜５０μ−の微粒子を散在させ、
その上層に酸素透過性の優れた厚み１５〜１００μ−の
熱可塑性樹脂フィルムを、熱接（法により積層した缶用
ラミネート鋼板
（２）製缶後に缶内面側となる鋼板の表面に、５〜５０
μ■の微粒子の表面をヒドロキシエチルセルロース樹脂
３０〜８０％、ポリビニルアルコール２０〜７０％の混
合樹脂で被覆した微粒子を散在させ、その上層に酸素透
過性の優れた厚み１５〜１００μ−の熱可塑性樹脂フィ
ルムを、熱接着法により積層させたことを特徴とする内
容物保存性に優れた缶用ラミネート鋼板
（３）微粒子が有機ポリマーの微粉末である（１）又は
（２）に記載の内容物保存性に優れた缶用ラミネート鋼
板
（４）積層させる樹脂フィルムがポリエチレン。The present invention is a laminated steel sheet in which a film capable of quickly removing oxygen within the can is laminated on the surface of the steel sheet that becomes the inner surface of the can after can manufacturing. In other words, the gist is as follows: (1) Fine particles of 5 to 50μ are scattered on the surface of the steel plate,
A thermoplastic resin film with a thickness of 15 to 100 μm with excellent oxygen permeability is applied as an upper layer to the surface of the steel plate that will become the inner side of the can after can manufacturing. 50
The surface of microparticles of μ■ is coated with a mixed resin of 30-80% hydroxyethyl cellulose resin and 20-70% polyvinyl alcohol, and the upper layer is a thermoplastic resin with a thickness of 15-100μ that has excellent oxygen permeability. A laminated steel plate for cans with excellent content preservation properties characterized by laminating films by a thermal bonding method (3) The content according to (1) or (2), wherein the fine particles are organic polymer fine powders. Laminated steel plate for cans with excellent storage stability (4) The resin film to be laminated is polyethylene.
ポリブタジェン、ポリメチルペンテンのいずれかの自己
接着性を有するフィルムである（１）又は（２）に記載
の内容物保存性に優れたラミネート鋼板
（５）鋼板の缶外面となる片面には、Ｓｎめっき。The laminated steel plate with excellent content preservation properties according to (1) or (2), which is a self-adhesive film made of either polybutadiene or polymethylpentene (5) One side of the steel plate, which is the outer surface of the can, is coated with Sn. Plating.
Ｃｒめっき、Ｎｌめっきのいずれかの皮膜を有するもの
である、（１）又は（２）に記載の内容物保存性に優れ
た缶用ラミネート鋼板
である。The laminated steel sheet for cans having an excellent content preservation property according to (1) or (2), which has a film of either Cr plating or Nl plating.
以下、本発明の構成・作用について説明する。Hereinafter, the structure and operation of the present invention will be explained.
本発明の主要構成要件は、第１に鋼板の表面に５〜５０
μ閣の微粒子を散在させることにあり、第２は続いて酸
素透過性の良い、厚み１５〜１００μ園の熱可塑性樹脂
フィルムを熱接着法により積層することにある。The main constituent elements of the present invention are: firstly, the surface of the steel plate has a 5-50%
The second step is to scatter microparticles of microorganisms, and the second step is to laminate a thermoplastic resin film with a thickness of 15 to 100 μm, which has good oxygen permeability, by a thermal bonding method.
最初に第１の要件である、鋼板の表面に散在させる微粒
子について述べる。First, the first requirement, the fine particles to be scattered on the surface of the steel sheet, will be described.
本発明において、不可避的に缶内に持ち込まれる酸素の
透過を促進し、更には透過してきた酸素の消費速度を大
きくし、内容物中の酸素をいかに減少させる（内容物中
の酸素を取るを言う意味で以下「脱酸素」と呼ぶ）か、
即ち脱酸素をいかに短期間に行うかが重要な点となって
いる。In the present invention, the permeation of oxygen that is unavoidably brought into the can is promoted, and the consumption rate of the permeated oxygen is increased, and the oxygen in the contents is reduced (how to remove oxygen from the contents). (hereinafter referred to as "deoxygenation"),
That is, the important point is how to perform deoxidation in a short period of time.
缶内に持ち込まれた酸素は、熱可塑性樹脂フィルムを透
過したのち、鋼板表面と反応して消費されるわけである
が、従って脱酸素能は、フィルム厚によって違うが、基
本的には使用する樹脂への依存性が大きい、とは言え、
透過してきたものが消費されなければ、透過は進行しな
い。The oxygen brought into the can passes through the thermoplastic resin film and is consumed by reacting with the surface of the steel plate.Therefore, the oxygen removal ability varies depending on the film thickness, but basically the Although it is highly dependent on resin,
If the things that have passed through are not consumed, the penetration will not proceed.
発明者らは、この点に着目し検討した結果、鋼板と積層
させたフィルムの間に適度な隙間を形成させることで、
鋼板表面での反応が促進され、脱酸素能が向上すること
を見いだし、本発明に至ったものである。The inventors focused on this point and studied it, and found that by forming an appropriate gap between the steel plate and the laminated film,
It was discovered that the reaction on the surface of the steel sheet is promoted and the deoxidizing ability is improved, leading to the present invention.
適度な隙間を形成させることで、鋼板表面での反応が促
進される理由は明らかになっていないが、おそらく、酸
素及び水の透過が隙間部の方が他の部分より大きいため
、酸素濃淡電池が容易に形成されるためと推定される。It is not clear why the reaction on the surface of the steel sheet is promoted by forming an appropriate gap, but it is probably because oxygen and water permeate through the gap more than in other areas. This is presumed to be because it is easily formed.
この適度な隙間を形成させる役目を微粒子が担うわけで
あるが、５０μｍを超すと隙間が大きくなり過ぎ脱酸素
能は向上するが、フィルムと鋼板との接着面積が減少す
るため接着力が低下し、加工性が劣ってくるので好まし
くない。Fine particles play the role of forming this appropriate gap, but if the gap exceeds 50 μm, the gap becomes too large and the oxygen scavenging ability improves, but the adhesion strength decreases because the bonding area between the film and the steel plate decreases. , which is not preferable because the processability deteriorates.
一方、５μｍ以下では逆にフィルムと鋼板の間に隙間が
生じなくなり、接着力は向上するが、脱酸素能は低下す
る。微粒子のサイズ５〜５０μ−と特定したのはこうし
た脱酸素能とフィルムの接着力のバランスの点からであ
る。On the other hand, if the thickness is less than 5 μm, no gap will be formed between the film and the steel plate, and the adhesive strength will be improved, but the oxygen scavenging ability will be reduced. The reason why the size of the fine particles was specified as 5 to 50 μm was because of the balance between the oxygen scavenging ability and the adhesive strength of the film.
勿論、脱酸素能と接着性は、以下に述べる微粒子の表面
被覆樹脂や、分散状態が併せて関係を有していることは
言うまでもないことである。Of course, it goes without saying that the oxygen scavenging ability and adhesiveness are also related to the surface coating resin of the fine particles and the dispersion state described below.
本発明においては、鋼板表面に散在させる微粒子は有機
ポリマーの微粉末で、例えば、ポリエチレン樹脂、ポリ
スチレン樹脂等のポリオレフィン樹脂の微粉末、エボシ
キ樹脂の微粉末、ナイロンの微粉末、ポリエステル樹脂
の微粉末、アクリル樹脂の微粉末、ポリウレタン樹脂の
微粉末、フッ素樹脂の微粉末等が適用出来る。In the present invention, the fine particles to be scattered on the surface of the steel plate are fine powders of organic polymers, such as fine powders of polyolefin resins such as polyethylene resin and polystyrene resin, fine powders of epoxy resin, fine powders of nylon, and fine powders of polyester resins. , acrylic resin fine powder, polyurethane resin fine powder, fluororesin fine powder, etc. can be applied.
次に、微粒子の表面を被覆する樹脂について述べる。Next, the resin that coats the surface of the fine particles will be described.
本発明では、微粒子の表面をヒドロキシエチルセルロー
ス樹脂３０〜８０％、ポリビニルアルコール樹脂２０〜
７０％の樹脂で被覆した微粒子を適用することで、脱酸
素能は更に向上する。In the present invention, the surface of the fine particles is made of 30 to 80% hydroxyethyl cellulose resin and 20 to 80% polyvinyl alcohol resin.
The oxygen scavenging ability is further improved by applying 70% resin coated microparticles.
脱酸素を速やかに行うためには、鋼板とフィルムの間に
適度な隙間を形成させた方が有利であることは前述した
通りである。As mentioned above, it is advantageous to form an appropriate gap between the steel plate and the film in order to quickly remove oxygen.
しかし、脱酸素を更に効率的に行う、即ちフィルムを透
過してきた酸素と鋼板との反応を速めるには、水が存在
していた方が良いことは言うまでもない。この水を適度
に存在させ鋼板との反応を速めるのが、ヒドロキシエチ
ルセルロース樹脂３０〜８０％、ポリビニルアルコール
樹脂２０〜７０％の樹脂である。However, it goes without saying that it is better for water to be present in order to more efficiently deoxidize, that is, to speed up the reaction between the oxygen that has passed through the film and the steel sheet. A resin composed of 30 to 80% hydroxyethyl cellulose resin and 20 to 70% polyvinyl alcohol resin is used to speed up the reaction with the steel plate by making an appropriate amount of water exist.
ヒドロキシエチルセルロース樹脂とポリビニルアルコー
ル樹脂の混合割合は以下の理由から設定されたものであ
る。The mixing ratio of hydroxyethyl cellulose resin and polyvinyl alcohol resin was determined for the following reasons.
ヒドロキシエチルセルロース樹脂が３０％未満、ポリビ
ニルアルコール樹脂７０％超では、脱酸素能に対し、被
覆効果はほとんど見られない。When the hydroxyethyl cellulose resin is less than 30% and the polyvinyl alcohol resin is more than 70%, there is almost no coating effect on the oxygen scavenging ability.
一方、ヒドロキシエチルセルロース樹脂が８０％超、ポ
リビニルアルコール樹脂２０％未満では、水の存在が過
剰となり内容物充填以前に機能を失ったり、積層させた
フィルムの密暮性が低下してくることが起こる。On the other hand, if the hydroxyethyl cellulose resin is more than 80% and the polyvinyl alcohol resin is less than 20%, the presence of water will be excessive and the function will be lost before the contents are filled, and the tightness of the laminated film will decrease. .
このように、脱酸素機能とフィルムの密着性を兼備させ
るには、ヒドロキシエチルセルロ−ス樹脂３０〜８０％
、ポリビニルアルコール樹脂２０〜７０％の混合樹脂が
必要で、好ましくはヒドロキシエチルセルロース樹脂４
０〜７５％、ポリビニルアルコール樹脂２５〜５０％で
ある。In this way, in order to have both oxygen scavenging function and film adhesion, hydroxyethyl cellulose resin should be 30 to 80%
, a mixed resin of 20 to 70% polyvinyl alcohol resin is required, preferably hydroxyethyl cellulose resin 4
0 to 75%, polyvinyl alcohol resin 25 to 50%.
微粒子の表面をヒドロキシエチルセルロース樹脂とポリ
ビニルアルコール樹脂の混合樹脂で被覆したものを用い
る場合には、微粒子の大きさと分散状態には一層の配慮
が必要である。When using fine particles whose surfaces are coated with a mixed resin of hydroxyethyl cellulose resin and polyvinyl alcohol resin, further consideration must be given to the size and dispersion state of the fine particles.
以上述べた微粒子のサイズや微粒子の表面を被覆する樹
脂に関することは、次に述べる鋼板の表面に散在させる
、と言うことと無関係ではない。即ち、鋼板表面へ散在
させた量によって、脱酸素能及びフィルムの密着性に影
響を及ぼすからである。The above-mentioned matters regarding the size of the fine particles and the resin coating the surface of the fine particles are not unrelated to the fact that they are scattered on the surface of a steel plate, which will be described next. That is, the amount scattered on the steel plate surface affects the oxygen scavenging ability and the adhesion of the film.
前述したように、フィルムを透過してきた酸素は鋼板表
面で反応して消費されるわけだが、この反応する箇所は
、存在する微粒子の近傍であり、脱酸素能からは微粒子
の存在を十分に確保する必要がある。一方、フィルムの
鋼板との密着力は有機ポリマーの粉末自体には自己接着
性を有しておらず、又、適用した粉末と積層させたフィ
ルムとの間の接着性の問題などから、主に微粒子の存在
しない箇所で保持されるため、加工性の点からは微粒子
の存在しない箇所を十分に確保する必要がある。As mentioned above, the oxygen that has passed through the film reacts and is consumed on the surface of the steel sheet, but this reaction occurs near the existing fine particles, and the oxygen scavenging ability ensures that the presence of fine particles is sufficient. There is a need to. On the other hand, the adhesion of the film to the steel plate is mainly due to the fact that the organic polymer powder itself does not have self-adhesive properties, and there are problems with the adhesion between the applied powder and the laminated film. Since it is held in areas where fine particles are not present, it is necessary to secure sufficient areas where fine particles are not present from the viewpoint of workability.
従って、脱酸素能とフィルム密着性は基本的には相反す
る機能である。Therefore, oxygen scavenging ability and film adhesion are basically contradictory functions.
この点のバランスを確保するのが、微粒子の量と分散状
態であり、量的には鋼板上の面積率として１０〜２０％
が好ましく、例えば１０μｍ程度の微粒子では約１０〜
２０万個／ ｃ ｒｔ？程度である。The key to ensuring a balance in this regard is the amount and dispersion state of fine particles, and in terms of quantity, the area ratio on the steel plate is 10 to 20%.
is preferable, for example, for fine particles of about 10 μm, about 10 to
200,000 pieces/crt? That's about it.
又、分散状態は、当然特定の箇所に固まらないようにす
る必要があることは言うまでもない。Furthermore, it goes without saying that the dispersed state needs to be prevented from consolidating in a specific location.
この、特定の箇所に固まらないようにする手段としては
、流動浸漬法、静電塗布法等があるが、量及び分散状態
の管理と言う点からは、静電塗布法が好適である。Methods for preventing the composition from clumping in specific locations include fluidized dipping, electrostatic coating, etc., but electrostatic coating is preferred from the standpoint of controlling the amount and dispersion state.
次に積層させる熱可塑性樹脂フィルム及び積層させる手
段について述べる。Next, the thermoplastic resin films to be laminated and the means for laminating them will be described.
積層させる熱可塑性樹脂フィルムは、ポリエチレン、ポ
リブタジェン、ポリメチルペンテン等の酸素透過性の良
いフィルムである。The thermoplastic resin film to be laminated is a film with good oxygen permeability such as polyethylene, polybutadiene, polymethylpentene, or the like.
缶内に持ち込まれた酸素はフィルムを透過して鋼板表面
に到達することになるため、フィルム厚は出来るだけ薄
いほうが好ましいが、薄すぎると、フィルム自体のピン
ホールの発生や、或は腐食生成物の内容物への移行等の
問題があり、又、厚すぎると酸素の透過速度が遅（なり
脱酸素能は低下するばかりでなく、コスト的にも不利と
なる。そこで適度な厚みを選定する必要があるわけで、
本発明でフィルム厚を１５〜１００μｍに限定した理由
は以上の通りである。Oxygen brought into the can will pass through the film and reach the surface of the steel plate, so it is preferable that the film be as thin as possible, but if it is too thin, pinholes may form in the film itself, or corrosion may occur. There are problems such as migration to the contents of the product, and if it is too thick, the oxygen permeation rate will be slow (this will not only reduce the oxygen removal ability but also be disadvantageous in terms of cost. Therefore, choose an appropriate thickness. Therefore, it is necessary to
The reason why the film thickness is limited to 15 to 100 μm in the present invention is as described above.
本発明では、これらのフィルムの積層方法としては、積
層させるフィルムに自己接着性を保有させ、予め加熱さ
れた鋼板上に熱圧着することによって積層する熱接着法
が適用される。In the present invention, as a method for laminating these films, a thermal adhesion method is applied in which the films to be laminated have self-adhesive properties and are laminated by thermocompression bonding onto a preheated steel plate.
積層させるフィルムには自己接着性を有するもので、フ
タル酸、無水フタル酸等で変性するなど、通常行われて
る方法で製造したものである。The film to be laminated has self-adhesive properties and is manufactured by a commonly used method such as modification with phthalic acid, phthalic anhydride, or the like.
なお、本発明では、例えば二層フィルムで鋼板に積層さ
せる方にだけ自己接着性を保有させたもの等が適用され
る。In the present invention, for example, a two-layer film in which only the side to be laminated to the steel plate has self-adhesive properties is applied.
熱接着法に限定した理由は、接着剤塗布法では、接着剤
中の有機溶剤による有機ポリマー粉末の溶解や膨潤した
りすること、又、ヒドロキシエチルセルロース樹脂とポ
リビニルアルコール樹脂の混合樹脂の被覆層の溶解が起
こったりして目的のものが得られない場合があるが、熱
接着法ではこのようなことは起こらないためである。又
、生産性も熱接着の方が良く有利である。The reason why we chose to use the thermal bonding method is that in the adhesive coating method, the organic polymer powder may dissolve or swell due to the organic solvent in the adhesive, and the coating layer of a mixed resin of hydroxyethyl cellulose resin and polyvinyl alcohol resin may This is because melting may occur and the desired product may not be obtained, but this does not occur with the thermal bonding method. In addition, thermal bonding is more advantageous in terms of productivity.
熱接着法では、熱と圧着により微粒子が変形しないよう
に留意する必要があり、熱的に安定なもの、例えば超高
分子量ポリエチレン等の粒子を用いた方が良い、更に熱
接着法を採用する場合、積層するフィルムを溶融させる
か否かは、目的とする脱酸素能の点からは大きな問題と
はならないことを述べてお（。In the thermal bonding method, care must be taken to prevent the particles from deforming due to heat and pressure bonding, and it is better to use particles that are thermally stable, such as ultra-high molecular weight polyethylene. In this case, it is stated that whether or not the films to be laminated are melted or not is not a big problem from the viewpoint of the desired oxygen scavenging ability.
以上、缶内面についての構成及び機能について説明した
が、次に缶外面について説明する。The structure and function of the inner surface of the can have been explained above, and next, the outer surface of the can will be explained.
本発明においては、缶外面については特に限定するもの
ではないが、Ｓｎめっき、 Ｃｒめっき。In the present invention, the outer surface of the can is not particularly limited, but may be Sn plating or Cr plating.
Ｎｉめつき等の現在容器用鋼板として実用されている皮
膜が適用できる。Coatings currently in practical use as steel plates for containers, such as Ni plating, can be applied.
いずれのめっきの場合も、塗装性を向上させるためにク
ロメート処理が施される場合が多いことを付言しておく
。It should be noted that in the case of any plating, chromate treatment is often applied to improve paintability.
これらのめっき皮膜は、理想的にはフィルムを積層させ
た後めっきされるのが望ましい。Ideally, these plating films should be plated after laminating the films.
この理由はＮ１めっき皮膜を除いて、フィルム下にＳｎ
皮膜、 Ｃｒ皮膜、クロメート処理皮膜が多く存在する
と酸素の消費反応を低下させる原因となり、望ましい結
果が得られないことがあるためである。The reason for this is that, except for the N1 plating film, there is Sn under the film.
This is because if a large amount of the film, Cr film, or chromate-treated film is present, the oxygen consumption reaction may be reduced, and desired results may not be obtained.
従って、工程上缶外面のめっきを先に行う必要がある場
合は、缶内面に当たる鋼板表面には非めっきとなるよう
な手段を講じるか、必要に応じては表面研削等の手段を
講じることが望ましい。Therefore, if it is necessary to plate the outer surface of the can first due to the process, it is necessary to take measures to ensure that the surface of the steel plate that is the inner surface of the can is not plated, or to take measures such as surface grinding as necessary. desirable.
以上、本発明の構成９作用について説明したが、本発明
を実施することにより缶内の酸素を早期に除去し、内容
物の鮮度、保存性を向上できるなど、酸素を嫌う内容物
用の容器として。As above, the structure 9 of the present invention has been explained. By carrying out the present invention, oxygen in the can can be quickly removed, and the freshness and preservation of the contents can be improved. As.
主として缶体の蓋部分への適用が可能である。It can be mainly applied to the lid of a can.
〔実施例Ｊ 以下、実施例で本発明の効果を具体的に示す。[Example J Hereinafter, the effects of the present invention will be specifically shown in Examples.
実施例−１
板厚０．２２ｍｍの薄鋼板の片面に、静電塗布により平
均粒径が１０μｌ、３０μ−１５０μｌの高分子量ポリ
エチレン粉末を面積率で約１０％程度散在させた後、そ
れぞれの鋼板を２３０℃に予熱し、２０μｔｍ 、５０
μｍ 、８０μｍの膜厚のポリメチルペンテンフィルム
を熱接着法により積層した。Example 1 High molecular weight polyethylene powder with an average particle size of 10 μl and 30 μl to 150 μl was scattered on one side of a thin steel plate with a thickness of 0.22 mm by electrostatic coating at an area ratio of about 10%, and then each steel plate was coated. Preheat to 230℃, 20 μtm, 50
A polymethylpentene film having a thickness of 80 μm was laminated by a thermal bonding method.
その際、ポリメチルペンテンフィルムは二層構造のもの
で、鋼板に積層させる側は酸変性した自己接着能を有す
るものを用いた。At that time, the polymethylpentene film had a two-layer structure, and the side to be laminated to the steel plate was acid-modified and had self-adhesive ability.
こうして得たフィルム積層鋼板から、フィルム面が缶内
面になるように製蓋加工で蓋を製造した。A lid was manufactured from the film-laminated steel plate thus obtained by lid-making processing so that the film surface was on the inside of the can.
又、缶胴としては従来製品（内油に熱硬化性エポキシ系
塗料を塗装したぶりきの溶接缶）を用い缶を作った。更
にこの缶に、内容物としてビールを充填後、２０℃で１
ケ月間貯蔵後の溶存酸素量を測定し、脱酸素能を求めた
。The can body was made using a conventional product (a welded tin can with inner oil coated with thermosetting epoxy paint). Furthermore, after filling this can with beer as contents, it was heated at 20℃ for 1 hour.
After storage for several months, the amount of dissolved oxygen was measured and the oxygen scavenging ability was determined.
なお、比較として、蓋、胴共にぶりきに熱硬化性エポキ
シ系塗料を塗装した缶を用いて、同様に脱酸素能を求め
た。結果を第１表に示す。For comparison, the oxygen scavenging ability was determined in the same manner using a can whose lid and body were tin coated with thermosetting epoxy paint. The results are shown in Table 1.
第１表
第１表から分かるように、本発明で得られるラミネート
鋼板を蓋とした缶は従来製品の塗装ぶりきの缶に比べ、
内容物の脱酸素能は高い値を示している。Table 1 As can be seen from Table 1, the cans with lids made of laminated steel plates obtained by the present invention have a lower
The oxygen scavenging ability of the contents is high.
又、鉄溶出は問題な（、味・フレーバー等の官能テスト
では比較例の従来製品に比べ、格段に優れたレベルであ
った。In addition, iron elution is a problem (and in sensory tests such as taste and flavor, it was at a much superior level compared to the conventional product of the comparative example.
実施例−２
板厚０．２２ｍｍの薄鋼板の片面に、静電塗布により平
均粒径が１０μｍ、３０μｍ、 ５０Ｂｍの超高分子量
ポリエチレン粒子にヒドロキシエチルセルロース樹脂５
０％とポリビニルアルコール樹脂５０％の混合樹脂、ヒ
ドロキシエチルセルロース樹脂７０％とポリビニルアル
コール樹脂３０％の混合樹脂を被覆した粒子を面積率約
１０％程度敗在させた後、実施例１の手順に従ってフィ
ルム厚５０μｍのポリメチルペンテンフィルムを熱接着
した。Example 2 On one side of a thin steel plate with a thickness of 0.22 mm, ultra-high molecular weight polyethylene particles with average particle diameters of 10 μm, 30 μm, and 50 Bm were coated with hydroxyethyl cellulose resin 5 by electrostatic coating.
After coating particles coated with a mixed resin of 0% and 50% polyvinyl alcohol resin and a mixed resin of 70% hydroxyethyl cellulose resin and 30% polyvinyl alcohol resin at an area ratio of about 10%, a film was prepared according to the procedure of Example 1. A 50 μm thick polymethylpentene film was thermally bonded.
こうして得たフィルム積層鋼板から、フィルム面が缶内
面になるように製蓋加工で蓋を製造した。A lid was manufactured from the film-laminated steel plate thus obtained by lid-making processing so that the film surface was on the inside of the can.
又、缶胴としては従来製品（内面に熱硬化性エポキシ系
塗料を塗装したぶりきの溶接缶）を用い缶を作った。更
にこの缶に、内容物としてビールを充填後、２０℃で１
ケ月間貯蔵後の溶存酸素量を測定し、脱酸素率を求めた
。In addition, cans were made using a conventional product (a welded tin can coated with thermosetting epoxy paint on the inside) for the can body. Furthermore, after filling this can with beer as contents, it was heated at 20℃ for 1 hour.
After storage for several months, the amount of dissolved oxygen was measured and the oxygen removal rate was determined.
なお、比較として、実施例１で用いた蓋、胴共にぶりき
に熱硬化性エポキシ系塗料を塗装した缶を用いて、同様
に脱酸素率を求めた。結果を第２表に示す。For comparison, the deoxidation rate was determined in the same manner using the can used in Example 1, in which both the lid and the barrel were tin coated with a thermosetting epoxy paint. The results are shown in Table 2.
第２表
ＨＥＣ：ヒドロキシエチルセルロース樹脂Ｐｖ＾：ポリ
ビニルアルコール樹脂
第２表から分かるように、本発明で得られるラミネート
鋼板を蓋とした缶は、従来製品の塗装ぶりきの缶に比べ
、内容物の脱酸素率は高い値を示している。Table 2 HEC: Hydroxyethyl cellulose resin Pv^: Polyvinyl alcohol resin As can be seen from Table 2, the cans with lids made of laminated steel plates obtained by the present invention have a lower content than conventional painted tin cans. The deoxidation rate shows a high value.
又、鉄溶出は問題なく、味・フレーバー等の官能テスト
では比較例の従来製品に比べ、格段に優れたレベルであ
った。In addition, there was no problem with iron elution, and in sensory tests such as taste and flavor, it was at a much superior level compared to the conventional product of the comparative example.
実施例−３
付着量５．８ｇ／ｒｒｒの片面Ｓｎめっき鋼板の非めっ
き面側に、静電塗布により平均粒径が１０μｍの超高分
子量ポリエチレン粒子にヒドロキシエチルセルロース樹
脂５０％とポリビニルアルコール樹脂５０％の混合樹脂
を被覆した粒子を面積率で約１０％程度敗在させた後、
実施例１の手順に従って５０μ履の膜厚のポリメチルペ
ンテンフィルムを熱接着した。Example 3 Ultra-high molecular weight polyethylene particles with an average particle size of 10 μm, 50% hydroxyethyl cellulose resin and 50% polyvinyl alcohol resin were electrostatically applied to the non-plated side of a single-sided Sn-plated steel sheet with a coating weight of 5.8 g/rrr. After dissolving the particles coated with the mixed resin by about 10% in terms of area ratio,
A polymethylpentene film having a thickness of 50 μm was thermally bonded according to the procedure of Example 1.
こうして得たフィルム積層鋼板から、フィルム面が缶内
面になるように製蓋加工で蓋を製造した。A lid was manufactured from the film-laminated steel plate thus obtained by lid-making processing so that the film surface was on the inside of the can.
又、缶胴としては従来製品（内面に熱硬化性エポキシ系
塗料を塗装したぶりきの溶接缶）を用い缶を作った。更
にこの缶に、内容物としてビールを充填後、２０℃で１
ケ月間貯蔵後の溶存酸素量を測定し、脱酸素率を求めた
。In addition, cans were made using a conventional product (a welded tin can coated with thermosetting epoxy paint on the inside) for the can body. Furthermore, after filling this can with beer as contents, it was heated at 20℃ for 1 hour.
After storage for several months, the amount of dissolved oxygen was measured and the oxygen removal rate was determined.
なお、比較として、実施例１で用いた蓋、胴共にぶりき
に熱硬化性エポキシ系塗料を塗装した缶を用いて、同様
に脱酸素率を求めた。For comparison, the deoxidation rate was determined in the same manner using the can used in Example 1, in which both the lid and the barrel were tin coated with a thermosetting epoxy paint.
結果は脱酸率能４７％で、非めっき鋼板に比べ若干劣る
が、従来製品の缶の脱酸素率Ｏ〜２％より高い値を示し
た。The result was a deoxidation efficiency of 47%, which was slightly inferior to non-coated steel sheets, but higher than the deoxidation efficiency of conventional cans of 0~2%.
又、鉄溶出は全（問題なく、味・フレーバー等の官能テ
ストでは従来製品より優れていた。In addition, there was no problem with iron elution, and it was superior to conventional products in sensory tests such as taste and flavor.
実施例−４
板厚０．２２＋＋＋ｍの薄鋼板の片面に、静電塗布によ
り平均粒径が３０μｍ、のポリプロピレン粒子を面積率
で約１０％程度敢在させた後、該鋼板を１５０℃に予熱
し膜厚５０μｍの自己接着性ポリエチレンフィルムを熱
接着し積層した。Example-4 Polypropylene particles with an average particle size of 30 μm were applied on one side of a thin steel plate with a thickness of 0.22+++m at an area ratio of about 10%, and then the steel plate was preheated to 150°C. A self-adhesive polyethylene film having a thickness of 50 μm was thermally bonded and laminated.
こうして得たフィルム積層鋼板を、実施例１の手順に従
って缶の製造、脱酸素能の評価を行った。The film-laminated steel plate thus obtained was manufactured into a can according to the procedure of Example 1, and its oxygen scavenging ability was evaluated.
なお、比較には実施例１と同様従来製造の塗装ぶりき缶
を用いた。For comparison, similarly to Example 1, conventionally manufactured painted tin cans were used.
結果は、ポリエチレンフィルム積層鋼板から得た蓋を用
いた缶は脱酸素能が３３％と、従来の缶の０〜２％に比
べ優れた性能を示した。The results showed that the cans with lids made of polyethylene film-laminated steel sheets had an oxygen scavenging capacity of 33%, which was superior to the 0-2% of conventional cans.
又、鉄溶出は全（問題な（、味・フレーバー等の官能テ
ストでは従来製品より優れていた。In addition, iron elution was problematic, and it was superior to conventional products in sensory tests such as taste and flavor.
尚、脱酸素能とは、一定時間経過後の酸素量において、
第１図に示した数値ａとｂを用いて１６次式より算出さ
れるものである。In addition, oxygen scavenging ability refers to the amount of oxygen after a certain period of time.
It is calculated from the 16th equation using the numerical values a and b shown in FIG.
脱酸素率（％）＝ （ａ／ｂ）ｘｌｏｏ〔発明の効果〕
以上説明したように、本発明を実施することにより、缶
内に不可避的に持ち込まれる酸素を速やかに除去し、内
用物の”味“風味”等の低下を起こさず、長期にわたり
内用物の鮮度を保持することが可能となる。Oxygen removal rate (%) = (a/b) It becomes possible to maintain the freshness of internal medicines for a long period of time without causing any deterioration in their taste or flavor.
従って食生活の高度化に十分応えることができ、経済的
１社会的効果は大きいものがある。Therefore, it can fully respond to the increasing sophistication of dietary habits, and has great economic and social effects.
４、4,
第１図は、 ビール缶の貯蔵期間と缶内の溶存 酸素濃度との関係を示す図である。 他４名 第 図 貯蔵期間（日） Figure 1 shows Storage period of beer cans and dissolution inside the cans It is a figure showing the relationship with oxygen concentration. 4 others No. figure Storage period (days)
Claims (1)
ｍの微粒子を散在させ、その上層に酸素透過性の優れた
厚み１５〜１００μｍの熱可塑性樹脂フィルムを、熱接
着法により積層させたことを特徴とする内容物保存性に
優れた缶用ラミネート鋼板 ２ 製缶後に缶内面側となる鋼板の表面に、５〜５０μ
ｍの微粒子の表面をヒドロキシエチルセルロース樹脂３
０〜８０％、ポリビニルアルコール樹脂２０〜７０％の
混合樹脂で被覆した微粒子を散在させ、その上層に酸素
透過性の優れた厚み１５〜１００μｍの熱可塑性樹脂フ
ィルムを、熱接着法により積層させたことを特徴とする
内容物保存性に優れた缶用ラミネート鋼板 ３ 微粒子が有機ポリマーの微粉末である、請求項１又
は２に記載の内容物保存性に優れた缶用ラミネート鋼板 ４ 積層させる樹脂フィルムがポリエチレン、ポリブタ
ジエン、ポリメチルペンテンのいずれかの自己接着性を
有するフィルムである、請求項１又は２に記載の内容物
保存性に優れたラミネート鋼板 ５ 鋼板の缶外面となる片面には、Ｓｎめっき、Ｃｒめ
っき、Ｎｉめっきのいずれかの皮膜を有するものである
、請求項１又は２に記載の内容物保存性に優れた缶用ラ
ミネート鋼板[Claims] 1. After can manufacturing, a 5 to 50μ
A laminated steel sheet for cans with excellent content storage stability, characterized by having microparticles of 500 m thick interspersed therein and a thermoplastic resin film with a thickness of 15 to 100 μm with excellent oxygen permeability laminated on the upper layer by a thermal bonding method. 2. After can manufacturing, a 5 to 50μ
The surface of the fine particles of m is coated with hydroxyethyl cellulose resin 3
Fine particles coated with a mixed resin of 0 to 80% polyvinyl alcohol resin and 20 to 70% polyvinyl alcohol resin were scattered, and a thermoplastic resin film with a thickness of 15 to 100 μm with excellent oxygen permeability was laminated on the upper layer by a thermal bonding method. A laminated steel plate for cans with excellent content preservability, characterized in that: 3 A laminated steel plate for cans with excellent content preservability according to claim 1 or 2, wherein the fine particles are fine powders of an organic polymer; A laminated steel plate for cans with excellent content preservability; The laminated steel plate 5 with excellent content storage stability according to claim 1 or 2, wherein the film is a self-adhesive film made of polyethylene, polybutadiene, or polymethylpentene. The laminated steel sheet for cans with excellent content preservation properties according to claim 1 or 2, which has a film of Sn plating, Cr plating, or Ni plating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8546989A JPH02263632A (en) | 1989-04-04 | 1989-04-04 | Laminated steel plate for can with excellent preserving property of content |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8546989A JPH02263632A (en) | 1989-04-04 | 1989-04-04 | Laminated steel plate for can with excellent preserving property of content |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02263632A true JPH02263632A (en) | 1990-10-26 |
Family
ID=13859754
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8546989A Pending JPH02263632A (en) | 1989-04-04 | 1989-04-04 | Laminated steel plate for can with excellent preserving property of content |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02263632A (en) |
-
1989
- 1989-04-04 JP JP8546989A patent/JPH02263632A/en active Pending
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