JPH05200961A - Production of polyethylene resin coated metal plate excellent in hot water resistance - Google Patents
Production of polyethylene resin coated metal plate excellent in hot water resistanceInfo
- Publication number
- JPH05200961A JPH05200961A JP4035746A JP3574692A JPH05200961A JP H05200961 A JPH05200961 A JP H05200961A JP 4035746 A JP4035746 A JP 4035746A JP 3574692 A JP3574692 A JP 3574692A JP H05200961 A JPH05200961 A JP H05200961A
- Authority
- JP
- Japan
- Prior art keywords
- metal plate
- polyethylene resin
- film
- laminated
- resin film
- 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
- B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
- Lining Or Joining Of Plastics Or The Like (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、耐熱水性に優れた缶用
ポリエチレン樹脂被覆金属板の製造方法に関する。より
詳細には、特定の表面処理層を有した金属板の片面、あ
るいは両面に放射線照射を施したポリエチレン樹脂フイ
ルムを積層、急冷するか、あるいはポリエチレン樹脂層
を積層、急冷後、放射線照射を施す耐熱水性に優れた缶
用ポリエチレン樹脂被覆金属板の製造方法に関し、缶工
業分野で広く行われている高温での殺菌処理、例えばレ
トルト処理を必要とする用途に適した素材を提供するも
のである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyethylene resin-coated metal sheet for cans having excellent hot water resistance. More specifically, one side or both sides of a metal plate having a specific surface treatment layer is laminated with a polyethylene resin film irradiated with radiation and then rapidly cooled, or a polyethylene resin layer is laminated and rapidly cooled and then irradiated with radiation. The present invention relates to a method for producing a polyethylene resin-coated metal plate for cans having excellent hot water resistance, which provides a material suitable for applications requiring sterilization treatment at high temperature which is widely performed in the can industry field, for example, retort treatment. ..
【0002】[0002]
【従来の技術】食缶あるいは飲料缶に用いられる金属缶
用素材であるテインフリースチール(以下、TFSと略
す)およびアルミニウムなどの金属板には一回あるいは
複数回の塗装が施されていた。この塗装を施すことは、
塗料の焼き付け工程が煩雑であるばかりでなく、多大な
焼き付け時間を必要とし、さらに多量の溶剤を排出する
ため、公害面からも排出溶剤を特別の焼却炉に導き焼却
しなければならないと言う問題を有していた。これらの
問題を解決するため、熱可塑性樹脂フイルムを加熱した
金属板に積層する方法が数多く提案されている。例え
ば、ポリエチレン樹脂フイルムを上層がクロム水和酸化
物、下層が金属クロムの二層皮膜を有した鋼板、いわゆ
るTFSに熱融着させる方法(特開昭46ー6142
号)、ポリエステル樹脂フイルムを接着剤を用いること
なく金属板に積層する方法(特公昭60ー47103
号、特願平2ー6342号)、ポリエステル樹脂フイル
ムを特定の接着剤を用いて金属板に積層する方法(特公
昭63ー13829号)、二層ポリエステル樹脂フイル
ムと接着剤成分を含有する ポリオレフインフイルムを金
属板のそれぞれの面に同時に積層する方法(特表平2ー
501644号)などが開示されている。BACKGROUND OF THE INVENTION food cans or Te Lee emission-free steel is a metal can for materials used in beverage cans (hereinafter, referred to as TFS) and the metal plate such as aluminum is decorated with one or a plurality of times of coating It was To apply this painting,
Not only the paint baking process is complicated, but it also requires a long baking time and discharges a large amount of solvent, so the discharged solvent must be guided to a special incinerator and burned from the perspective of pollution. Had. In order to solve these problems, many methods of laminating a thermoplastic resin film on a heated metal plate have been proposed. For example, a method in which a polyethylene resin film is heat-sealed to a so-called TFS, which is a steel sheet having a double-layer coating of chromium hydrate oxide in the upper layer and metallic chromium in the lower layer (JP-A-46-6142).
No.), a method of laminating a polyester resin film on a metal plate without using an adhesive (Japanese Patent Publication No. 60-47103).
No. 2, Japanese Patent Application No. 2-6342), a method of laminating a polyester resin film on a metal plate using a specific adhesive (Japanese Patent Publication No. 63-13829), a two-layer polyester resin film and a polyolefin containing an adhesive component. and a method of the Lee Nfuirumu laminated simultaneously on each side of the metal plate (Kohyo 2-Patent 501 644) is disclosed.
【0003】特開昭46ー6142号に開示されている
方法で得られたポリエチレン樹脂フイルム積層TFSは
耐熱水性に劣り、缶体に成形後、食品内容物を充填し1
20〜130℃の温度の加圧水蒸気で殺菌処理(以下、
レトルト処理と略す)を施すと、缶外面の積層されたポ
リエチレン樹脂フイルムが溶融した状態で加圧水蒸気及
び熱水と接触するため、表面凹凸を有した不均一な表面
外観を呈し、商品価値を著しく損ねるので、レトルト処
理を施す缶用材料に適用することはできない。The polyethylene resin film-laminated TFS obtained by the method disclosed in JP-A-46-6142 is inferior in hot water resistance, and after being molded into a can, it is filled with food contents.
Sterilization treatment with pressurized steam at a temperature of 20 to 130 ° C (hereinafter,
When abbreviated as retort treatment), the laminated polyethylene resin film on the outer surface of the can comes into contact with pressurized steam and hot water in a molten state, resulting in a non-uniform surface appearance with surface irregularities and a remarkable commercial value. Therefore, it cannot be applied to the material for cans that are subjected to retort processing because it damages.
【0004】特公昭60ー47103号に開示されてい
る方法で得られたポリエステル樹脂被覆金属板は熱融着
により積層体を得る方法の一つであるが、缶体に成形
後、上記同様にレトルト処理を施すと、缶外面のポリエ
ステル樹脂層が斑点状に乳白色に変色し、著しく商品価
値を低下させるので、レトルト処理を施す缶用材料に用
いることはできない。特に、レトルト処理時に水蒸気が
均一に積層したポリエステル樹脂層にあたらないと、顕
著に斑点状に乳白化し、より好ましくない。この原因は
該ポリエステル樹脂フイルムの融点以上の温度で二軸配
向ポリエステル樹脂フイルムを金属板に積層するとき、
生成する無定形ポリエステル樹脂層の再結晶化によると
考えられている。特願平2ー6342号に開示された方
法は特公昭60ー47103号の方法で得られたポリエ
ステル樹脂被覆金属板の欠点であるレトルト処理時の積
層されたポリエステル樹脂層の乳白化を防止するため、
特定の共重合ポリエステル樹脂フイルムを該樹脂の融点
以下の温度で金属板に積層し、積層時に生成する無定形
ポリエステル樹脂層の量をできるだけ少なくし、無定形
ポリエステル樹脂の再結晶による乳白化を防止すること
を特徴としている。しかし、この特願平2ー6342号
で用いられる特定の物性をもつ共重合ポリエステル樹脂
フイルムは本発明で用いられるポリエチレン樹脂フイル
ムに比較し、高価であり、缶コストの低減の観点より好
ましくない。The polyester resin-coated metal plate obtained by the method disclosed in Japanese Examined Patent Publication No. 47103/1985 is one of the methods for obtaining a laminate by heat fusion. When the retort treatment is applied, the polyester resin layer on the outer surface of the can discolors into milky white spots, and the commercial value is remarkably reduced. Therefore, it cannot be used as a material for a can subjected to the retort treatment. In particular, when the polyester resin layer in which water vapor is evenly laminated does not reach the polyester resin layer during the retort treatment, it becomes more speckled and opalescent, which is not preferable. The reason for this is that when a biaxially oriented polyester resin film is laminated on a metal plate at a temperature above the melting point of the polyester resin film,
It is believed that this is due to recrystallization of the formed amorphous polyester resin layer. The method disclosed in Japanese Patent Application No. 2-6342 prevents opacification of a laminated polyester resin layer during retort treatment, which is a drawback of the polyester resin-coated metal sheet obtained by the method of Japanese Patent Publication No. 60-47103. For,
Laminate a specific copolyester resin film on a metal plate at a temperature lower than the melting point of the resin to minimize the amount of the amorphous polyester resin layer generated during lamination to prevent opacification due to recrystallization of the amorphous polyester resin. It is characterized by doing. However, the copolyester resin film having specific physical properties used in this Japanese Patent Application No. 2-6342 is more expensive than the polyethylene resin film used in the present invention, and is not preferable from the viewpoint of reduction in can cost.
【0005】特公昭63ー13829号に開示された方
法で得られたポリエステル樹脂被覆TFSは予め接着剤
を塗布された二軸配向ポリエステル樹脂フイルムを該フ
イルムの融点以下の温度で積層されたものであり、上記
特公昭60ー47103号の方法で得られたポリエステ
ル樹脂被覆金属板のような無定形ポリエステル樹脂層は
ほとんど形成されないので、レトルト処理を施しても、
表面が乳白化することはないが 、該ポリエステル樹脂
フイルムに接着剤を均一に薄く塗布、 乾燥することが
不可欠であり、そのため塗装装置、溶剤、乾燥用オーブ
ン、排出溶剤焼却装置などを必要とし、経済的な方法と
はいえず、缶用材料として好ましくない。The polyester resin-coated TFS obtained by the method disclosed in Japanese Examined Patent Publication No. 63-13829 is a biaxially oriented polyester resin film coated with an adhesive in advance and laminated at a temperature below the melting point of the film. However, since an amorphous polyester resin layer such as a polyester resin-coated metal plate obtained by the method of Japanese Patent Publication No. 60-47103 is hardly formed, even if a retort treatment is applied,
Although the surface does not become opalescent, it is essential that the polyester resin film be evenly and thinly coated with an adhesive and dried, which requires a coating device, solvent, drying oven, exhaust solvent incinerator, etc. It is not an economical method and is not preferable as a material for cans.
【0006】特表平2ー501644号に開示された方
法で得られた二層ポリエステル樹脂フイルム及び接着剤
成分を含むオレフィン樹脂フイルムで金属板のそれぞれ
の面を被覆した金属板は、二層ポリエステル樹脂フイル
ムを積層した金属面を缶外面として、上記同様にレトル
ト処理を施すと、特公昭60ー47103号の方法で得
られたポリエステル樹脂被覆金属板と同様に、下層の無
定形ポリエステル樹脂層が再結晶化し、表面が斑点状に
乳白色に変色する。また、接着剤成分を含むオレフィン
樹脂フイルムを積層した金属面を缶外面として用いた場
合、例えば、ポリエチレンを主体としたオレフィン樹脂
フイルムの場合、レトルト処理時に該フイルムが部分的
に溶融し、特開昭46ー6142号の方法で得られたポ
リエチレン樹脂被覆TFSの場合と同様に表面凹凸のあ
る不均一な表面外観を呈し、商品価値を損ねるので、レ
トルト処理を施す缶用材料に適していない。さらに、接
着剤成分をオレフィン樹脂フイルムに塗布する場合、前
記特公昭63ー13829号の方法で得られたポリエス
テル樹脂被覆TFSの場合と同様な欠点を有し、経済性
の優れた缶用材料でない 。また、 特表平2ー5016
44号に開示された方法は、特定温度に加熱された金属
板に前記二種類の樹脂フイルムを積層後、230〜27
0℃の温度で再加熱することを特徴としているが、高い
温度で再加熱されるため、積層された二層ポリエステル
樹脂フイルム及び接着剤成分を含むオレフィン樹脂層が
再溶融する危険性があり、表面外観の優れた樹脂フイル
ム被覆金属板が得られない可能性もある。また、積層ロ
ールの温度を考慮すればわざわざ経済性の劣る二層ポリ
エステル樹脂フイルムを使用する必要もなく単層のポリ
エステルフイルムで金属板に良好に積層可能であり、経
済性に劣ることは言うまでもない。このように特表平2
ー501644号に開示された方法は、製造工程、フイ
ルムの準備工程も煩雑であり、経済的な缶用材料の製造
方法とは言いがたい 。[0006] The two-layer polyester resin film obtained by the method disclosed in JP-A-2-501644 and the olefin resin film containing the adhesive component coated on each side of the metal plate are two-layer polyester. When the retort treatment is performed in the same manner as above with the metal surface laminated with the resin film as the outer surface of the can, the lower amorphous polyester resin layer is formed in the same manner as the polyester resin-coated metal plate obtained by the method of JP-B-60-47103. It recrystallizes, and the surface changes to milky white with spots. Further, when a metal surface laminated with an olefin resin film containing an adhesive component is used as an outer surface of a can, for example, in the case of an olefin resin film mainly containing polyethylene, the film is partially melted during retort treatment, As in the case of the polyethylene resin-coated TFS obtained by the method of JP-A-46-6142, it has a non-uniform surface appearance with surface irregularities and impairs the commercial value, so it is not suitable as a can material for retort treatment. Further, when an adhesive component is applied to an olefin resin film, it has the same drawbacks as the polyester resin-coated TFS obtained by the method of Japanese Patent Publication No. 63-13829, and it is not an economical can material. .. In addition, special table flat 2-5016
The method disclosed in No. 44 is a method of laminating two kinds of resin films on a metal plate heated to a specific temperature, and then 230-27.
It is characterized in that it is reheated at a temperature of 0 ° C., but since it is reheated at a high temperature, there is a risk that the laminated two-layer polyester resin film and the olefin resin layer containing the adhesive component are re-melted, It may not be possible to obtain a resin film-coated metal plate having an excellent surface appearance. Further, considering the temperature of the laminating roll, it is not necessary to use a two-layer polyester resin film, which is economically inferior, and a single-layer polyester film can be favorably laminated on a metal plate, which is not economical. .. Like this special table flat 2
The method disclosed in U.S. Pat. No. 5,011,644 is complicated in the manufacturing process and the film preparation process, and cannot be said to be an economical method for manufacturing a can material.
【0007】一方、電子線照射による樹脂特性の改良の
試みが数多くされている。例えば、ポリオレフィンフイ
ルムを、アクリル酸またはこれと放射線硬化性モノマー
の混合物を介して金属板表面に積層後、放射線を照射す
ることにより、優れた接着強度で両者を接合する方法
(特開昭63ー150330号)、金属板表面にポリオ
レフィンフイルムを特定の高分子接着剤によって接着
後、表面に電子線またはγ線を照射することにより、防
錆鋼板の表面硬度と耐熱性を向上させる方法(特開昭6
2ー156944号)、導体の外周に電子線照射で分解
する糸をらせん状に巻き、その外周に電子線照射架橋型
絶縁体を被覆して電子線を照射することにより、絶縁電
線のカッテングを容易にする方法(特開昭55ー126
48号)、などが開示されている。On the other hand, many attempts have been made to improve the resin properties by electron beam irradiation. For example, a method in which a polyolefin film is laminated on the surface of a metal plate through acrylic acid or a mixture of this and a radiation-curable monomer and then irradiated with radiation to bond the two with excellent adhesive strength (JP-A-63-63). No. 150330), a method of improving the surface hardness and heat resistance of a rust-preventing steel sheet by gluing a polyolefin film on the surface of a metal plate with a specific polymer adhesive and then irradiating the surface with an electron beam or γ-rays Sho 6
No. 2-156944), a thread that is decomposed by electron beam irradiation is spirally wound on the outer circumference of the conductor, and the outer circumference of the thread is covered with an electron beam irradiation cross-linking type insulator to irradiate the electron beam, so that the insulated wire is covered. Method for facilitating (Japanese Patent Application Laid-Open No. 55-126
48), etc. are disclosed.
【0008】特開昭63ー150330号及び特開昭6
2ー156944号に開示されている方法で得られた被
覆金属板はフイルムを金属板に積層するために接着剤を
介することが必須であり、経済性に劣り好ましくない。
また、本発明とは用途も目的も異なるものである。一
方、特開昭55ー12648号に開示されている方法
は、電子線照射技術が広く応用されている電線製造分野
での一技術となり得ると考えられるが、本発明とは形態
及び用途も異なることは当然であるばかりでなく、金属
とフイルム間の良好な密着力は確保し得ない。JP-A-63-150330 and JP-A-6-150330
The coated metal sheet obtained by the method disclosed in JP-A-2-156944 is not preferable because it is indispensable to interpose an adhesive for laminating the film on the metal sheet and the economy is poor.
Further, the present invention is different in use and purpose. On the other hand, the method disclosed in JP-A-55-12648 is considered to be one technique in the field of electric wire production to which the electron beam irradiation technique is widely applied, but the form and the application are different from the present invention. Not only that, but also good adhesion between the metal and the film cannot be ensured.
【0009】[0009]
【発明が解決しようとする課題】前記のように塗装に代
わる方法として開示された方法で得られた熱可塑性樹脂
被覆金属板には、レトルト処理時の表面の斑点状乳白化
だけでなく、経済性にも問題がある。また、電線分野に
広く応用されている電子線照射技術のみでは、金属板と
樹脂層との密着性が確保できない。本発明が解決しよう
としている課題は上記の問題を解決するとともに、缶用
材料として要求される耐食性、積層された樹脂フイルム
の加工密着性、特にレトルト処理時における積層された
熱可塑性樹脂フイルムの密着性も兼ね備えた缶用の熱可
塑性樹脂被覆金属板を熱融着により高速かつ連続的に製
造する方法を開発することにある。As described above, the thermoplastic resin-coated metal sheet obtained by the method disclosed as an alternative to painting has not only the mottled opalification on the surface at the time of retort treatment but also the economy. There is also a problem with sex. Further, the adhesion between the metal plate and the resin layer cannot be ensured only by the electron beam irradiation technique widely applied to the electric wire field. The problem to be solved by the present invention is to solve the above problems, corrosion resistance required as a material for cans, processing adhesion of laminated resin film, especially adhesion of laminated thermoplastic resin film during retort treatment. The object of the present invention is to develop a method for producing a thermoplastic resin-coated metal sheet for cans, which also has good properties, at high speed and continuously by heat fusion.
【0010】[0010]
【課題を解決するための手段】本発明は、上記の問題点
を解決するため、種々検討した結果、少なくともクロム
水和酸化物皮膜を有した金属板を熱可塑性樹脂フイルム
の中で安価なポリエチレン樹脂フイルムで積層する前、
あるいは、積層した後、放射線照射によりポリエチレン
樹脂の架橋反応を起こさせることによって、本発明の主
目的である缶体を成形し、内容物充填後のレトルト処理
で缶外面が斑点状に乳白化せず、かつレトルト処理時に
剥離しない優れた密着性を有す缶用ポリエチレン樹脂被
覆金属板が得られることを見いだしたものである。[Means for Solving the Problems] In order to solve the above-mentioned problems, the present invention has made various investigations and as a result, at least a metal plate having a hydrated chromium oxide film is used as an inexpensive polyethylene film in a thermoplastic resin film. Before stacking with resin film,
Alternatively, after stacking, a can body, which is the main object of the present invention, is formed by causing a crosslinking reaction of a polyethylene resin by irradiation with radiation, and the outer surface of the can is opalified in spots by retort treatment after filling the contents. It was found that a polyethylene resin-coated metal plate for cans, which does not peel off during retort treatment and has excellent adhesion, can be obtained.
【0011】以下、本発明について詳細に説明する。ま
ず、本発明で用いられるエチレン反復単位70〜100
モル%のポリエチレン樹脂(以下、ポリエチレン樹脂と
略す)には、一般的に包装材料として広く使用されてい
る低密度ポリエチレン、リニア低密度ポリエチレン、中
密度ポリエチレン、高密度ポリエチレンあるいはこれら
の混合物が適している。さらに、ナトリウム、カリウ
ム、亜鉛、マグネシウム、カルシウム、アルミニウム等
の金属イオンを含むメタクリル酸、アクリル酸、マレイ
ン酸などのα・β不飽和カルボン酸のイオン性塩である
アイオノマー等をブレンドしたり、マレイン酸、アクリ
ル酸などで変性したり、ポリプロピレンなどと共重合化
したポリエチレンも本発明で用いられるポリエチレン樹
脂として適用可能である。しかし、エチレン反復単位が
70モル%未満、すなわち上記のようなエチレン以外の
成分が70モル%を越えると、放射線照射によるポリエ
チレンの架橋反応が進まず、放射線照射の効果が得られ
なくなる可能性が高いばかりでなく、経済性の点からも
好ましくない。これらの成分が適量であればポリエチレ
ン樹脂層の金属板との密着性が改良されるが、ポリエチ
レン樹脂単独より経済性が低下するので、これらの成分
の量は経済性及びその効果を勘案し決定することが必要
で、その効果が充分得られれば、より少ない方が好まし
い 。該樹脂の特性としては、 ASTM D638によ
る試験法で測定した破断伸びが80%以上であることが
加工性の点から好ましい。The present invention will be described in detail below. First, the ethylene repeating unit 70-100 used in the present invention is used.
Suitable for mol% polyethylene resin (hereinafter abbreviated as polyethylene resin) is low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene or a mixture thereof which is generally widely used as a packaging material. There is. Further, it is possible to blend ionomer, which is an ionic salt of α / β unsaturated carboxylic acid such as methacrylic acid, acrylic acid, and maleic acid containing metal ions such as sodium, potassium, zinc, magnesium, calcium, and aluminum, and maleic acid. Polyethylene modified with acid, acrylic acid or the like or copolymerized with polypropylene or the like is also applicable as the polyethylene resin used in the present invention. However, if the ethylene repeating unit is less than 70 mol%, that is, if the above-mentioned components other than ethylene exceed 70 mol%, the crosslinking reaction of polyethylene due to irradiation does not proceed and the effect of irradiation may not be obtained. Not only is it expensive, but it is also not economical. Adequate amounts of these components improve the adhesion of the polyethylene resin layer to the metal plate, but since the economic efficiency is lower than that of the polyethylene resin alone, the amounts of these components are determined in consideration of economic efficiency and its effect. It is necessary to do so, and if the effect is sufficiently obtained, the smaller the amount is, the more preferable. From the viewpoint of workability, the resin preferably has a breaking elongation of 80% or more as measured by the test method according to ASTM D638.
【0012】本発明において、ポリエチレン樹脂で金属
板を被覆するには、ポリエチレン樹脂フイルムを加熱し
た金属板に連続的に積層する方法、公知の押し出し機よ
り押し出された溶融ポリエチレン樹脂を直接加熱した金
属板表面に連続的に積層する方法のいずれでも良い。金
属板に積層する前にポリエチレン樹脂に放射線を照射す
る方法においては、ポリエチレン樹脂フイルムを用いる
ことが本発明のポリエチレン樹脂被覆金属板を高速かつ
連続的に生産する上で好ましく、金属板にポリエチレン
樹脂を積層後に放射線照射する方法においては、上記の
いずれの方法でも良い。金属板に積層するポリエチレン
樹脂層の厚さは経済性、耐食性、加工密着性など缶用材
料に要求される特性を考慮すると、7〜250μmが好
ましい。厚さが7μm未満であると、耐食性の点から好
ましくない。また、金属板にフイルムの状態で積層する
場合、作業性を著しく低下させる危険性がある。 また
、厚さが250μmを越えると、経済性を低下させる
だけでなく、 加工密着性も低下し、缶用材料として好
ましくない。In the present invention, to coat a metal plate with a polyethylene resin, a method of continuously laminating a polyethylene resin film on a heated metal plate, a method of directly heating a molten polyethylene resin extruded by a known extruder to a metal heated Any method of continuously laminating on the plate surface may be used. In the method of irradiating polyethylene resin with radiation before laminating on a metal plate, it is preferable to use a polyethylene resin film for high-speed and continuous production of the polyethylene resin-coated metal plate of the present invention. Any of the above methods may be used in the method of irradiating with radiation after being laminated. The thickness of the polyethylene resin layer to be laminated on the metal plate is preferably 7 to 250 μm in consideration of properties required for can materials such as economy, corrosion resistance, and processing adhesion. If the thickness is less than 7 μm, it is not preferable in terms of corrosion resistance. Further, when the film is laminated on the metal plate, there is a risk of significantly lowering workability. On the other hand, if the thickness exceeds 250 μm, not only the economical efficiency is deteriorated but also the processing adhesion is deteriorated, which is not preferable as a can material.
【0013】次に、本発明において重要な条件である金
属板に積層する前のポリエチレン樹脂フイルムあるいは
積層後のポリエチレン樹脂層に照射される放射線の量は
放射線の照射線量の国際単位のキロクーロン/キログラ
ム(以下、Kc/Kgと略す) で表すと、1〜25Kc/Kgの
範囲が好ましく、より好ましい範囲が2〜20Kc/Kgで
ある。放射線照射量が1Kc/Kg未満であると 、ポリエチ
レン樹脂の架橋反応があまり進行していないので、レト
ルト処理時の耐熱水性は改良されず、レトルト処理によ
ってポリエチレン樹脂被覆金属板の外観は一部該樹脂層
が溶融され、表面凹凸の多い状態となり好ましくない。
また、 放射線照射量が25Kc/Kgを越えると、放射線照
射による効果の向上がほとんど認められず経済性が劣る
ばかりでなく、フイルム形状に悪影響を及ぼすので好ま
しくない。このポリエチレン樹脂への放射線照射量は金
属板へ積層する前のポリエチレン樹脂フイルムの場合と
金属板に積層後のポリエチレン樹脂層の場合と比較する
と、 両者の差は顕著でないが、ポリエチレン樹脂フイ
ルムを加熱された金属板に積層するときに放射線照射の
効果が多少減少する。したがって、金属板に積層する前
のポリエチレン樹脂フイルムにはやや多い放射線照射を
施すことが好ましい。 この放射線には電子線、γ線、
X線が含まれるが、単位時間当たりの放射線強度は本発
明のポリエチレン樹脂被覆金属板の生産速度、経済性を
考慮して決定されるべきであり、特に限定するものでな
い。Next, the amount of radiation applied to the polyethylene resin film before being laminated on the metal plate or the polyethylene resin layer after being laminated, which is an important condition in the present invention, is the international unit of irradiation dose of kilocoulomb / When expressed in kilograms (hereinafter abbreviated as Kc / Kg), the range of 1 to 25 Kc / Kg is preferable, and the more preferable range is 2 to 20 Kc / Kg. When the irradiation dose is less than 1 Kc / Kg, the cross-linking reaction of the polyethylene resin does not proceed so much, so the hot water resistance during retort treatment is not improved, and the appearance of the polyethylene resin-coated metal sheet is partially affected by the retort treatment. It is not preferable because the resin layer is melted and the surface has many irregularities.
Further, if the radiation dose exceeds 25 Kc / Kg, not only the improvement of the effect due to the radiation is not recognized but the economical efficiency is deteriorated, and the film shape is adversely affected, which is not preferable. The radiation dose to this polyethylene resin is not as remarkable as the polyethylene resin film before laminating on the metal plate and the polyethylene resin layer after laminating on the metal plate. The effect of radiation irradiation is slightly reduced when laminated on the metal plate. Therefore, it is preferable that the polyethylene resin film before being laminated on the metal plate is irradiated with a slightly large amount of radiation. This radiation includes electron rays, γ rays,
Although X-rays are included, the radiation intensity per unit time should be determined in consideration of the production rate and economic efficiency of the polyethylene resin-coated metal sheet of the present invention, and is not particularly limited.
【0014】また、本発明において用いられるポリエチ
レン樹脂フイルムの金属板面と接する面にはコロナ放
電、プラズマ処理、火炎処理などの表面酸化処理を施
し、濡れ指数で38〜54ダインとすることが金属板と
の加工密着性の観点から好ましい。 特に、金属板の加
熱温度が装置上、皮膜構成上制限される場合やクロム水
和酸化物皮膜で被覆した錫めっき鋼鈑、ニッケルめっき
鋼鈑等の場合、上記の表面酸化処理を施したポリエチレ
ン樹脂フイルムを用いることが好ましい。濡れ指数で3
8ダイン未満であると、表面酸化処理を施した効果は少
なく、また、濡れ指数で54ダインを越えた表面酸化処
理を施しても、その効果は向上せず、経済性ばかりでな
く、着色の危険性もあり、好ましくない。なお、ここで
いう濡れ指数はJIS K6768ー1977に従い測
定した値である。Further, the surface of the polyethylene resin film used in the present invention in contact with the metal plate surface is subjected to surface oxidation treatment such as corona discharge, plasma treatment, flame treatment, etc., so that the wetting index is 38 to 54 dynes. It is preferable from the viewpoint of processing adhesion to the plate. In particular, when the heating temperature of the metal plate is limited by the equipment or the film structure, or in the case of tin-plated steel sheet coated with a hydrated chromium oxide film, nickel-plated steel sheet, etc., the polyethylene subjected to the above surface oxidation treatment is used. It is preferable to use a resin film. Wetting index 3
If it is less than 8 dynes, the effect of the surface oxidation treatment is small, and even if the surface oxidization treatment having a wetting index of more than 54 dynes is applied, the effect is not improved, and not only the economical efficiency but also the coloring There is a risk and it is not preferable. The wetting index here is a value measured according to JIS K6768-1977.
【0015】両面に樹脂フイルムを積層する場合は、片
面ずつ積層しても良いし、また両面同時に積層しても良
い。 さらに、本発明において重要なポリエチレン樹脂
フイルムが積層される直前の金属板の温度は、積層フイ
ルムがポリエチレン樹脂フイルムだけの場合、ポリエチ
レン樹脂の融点(Tm1)〜Tm1+240℃の範囲にコン
トロールすることが必要である。また、片面にポリエチ
レン樹脂フイルム、他の面にポリエステル樹脂フイルム
を積層する場合、ポリエチレン樹脂フイルムが積層され
る直前の金属板の温度は、ポリエチレン樹脂の融点(T
m1)〜Tm1+240℃の範囲、ポリエステル樹脂フイル
ムが積層される直前の金属板の温度は、ポリエステル樹
脂の融点(Tm2)〜Tm2+160℃の範囲で、かつ、T
m1+240℃以下にコントロールすることが必要であ
る。金属板の温度がTm1未満であると、積層されるポリ
エチレン樹脂フイルムの金属板と接する面が溶融せず、
充分な密着性は得られない。さらに、ポリエステル樹脂
フイルムの積層時、ポリエステル樹脂フイルムが積層さ
れる直前の金属板の温度がTm2未満であると、積層され
るポリエステル樹脂フイルムの金属板と接する面が溶融
せず、充分な密着性は得られない。また 、 ポリエチレ
ン樹脂フイルムが積層される直前の金属板の温度がTm1
+240℃を越えると、たとえ、一対の積層ロールを充
分冷却していても積層されるポリエチレン樹脂フイルム
中の熱伝達が速く、最表層が著しく溶融され表面外観を
損なうだけでなく、積層ロールに付着するようになり、
生産性を阻害するので好ましくない。また、積層ロール
の温度は、フイルムのロールへの付着、被覆金属板の表
面外観等を考慮すると、積層フイルムの融点以下にする
ことが好ましい。さらに、ポリエステル樹脂の積層時、
ポリエステル樹脂フイルムが積層される直前の金属板の
温度がTm2+160℃を越えると、たとえ、一対の積層
ロールを充分冷却していても積層されるポリエスエテル
樹脂フイルム中の熱伝達が速く、最表層が著しく溶融さ
れ表面外観を損なうだけでなく、積層ロールに付着する
ようになり、生産性を阻害すること及び熱履歴が樹脂に
悪影響を与え、充分な耐食性が得られなくなるので好ま
しくない。さらに、腐食性の強い内容物を充填し、レト
ルト処理を施す缶用に用いられるポリエチレン樹脂被覆
金属板の製造においては、缶内面となる金属板の面はポ
リエチレン樹脂より内容物に対するバリアー性が優れる
二軸配向ポリエステル樹脂フイルムで積層し、缶外面と
なる金属板の面は積層前あるいは積層後に放射線照射を
施したポリエチレン樹脂層で積層することが好ましく、
この異種の樹脂フイルムを同時に金属板に積層する場合
には、金属板をポリエチレン樹脂フイルムが溶融し、か
つポリエステル樹脂フイルムの融点近傍の温度に加熱
し、さらに、一対の積層ロールの内、ポリエチレン樹脂
フイルムと接する積層ロールの温度はポリエチレン樹脂
フイルムの融点以下に、ポリエステル樹脂フイルムと接
する積層ロールの温度は該ポリエステル樹脂フイルムの
融点以下で、かつ無定形ポリエステル樹脂層の生成量を
考慮して決定することが本発明のポリエチレン樹脂被覆
金属板の連続生産において重要である。また、押し出し
機から押し出される溶融したポリエチレン樹脂を直接金
属板に連続的に積層する場合には、金属板の温度はポリ
エチレン樹脂の融点(Tm1 )ー50〜Tm1+200℃
の範囲にコントロールすることが必要である。金属板の
温度がTm1ー50℃未満 であると、 被膜表面形状が悪
くなる。また、金属板の温度がTm1+200℃を越えて
も密着性の向上は認められず経済性に劣り好ましくな
い。一方、ポリエチレン樹脂の溶融温度は、Tm1+20
〜Tm1+150℃の範囲が好ましい。 Tm1+20℃未
満ではフイルムの均一な成膜が困難で 、Tm1+150
℃を越えると経済性が劣るばかりでなく、ポリエチレン
の分解が進む恐れがあるので好ましくない。なお、ここ
で言う融点とは、 10℃/min.の加熱速度の示差走
査熱量計(DSC)の吸熱ピークから求めたものであ
り、吸熱ピークの最大深さを示す温度を言う。 樹脂が
二種以上の場合は、主体となる樹脂のピークより求め
る。When the resin film is laminated on both sides, it may be laminated on each side, or both sides may be laminated simultaneously. Further, the temperature of the metal plate immediately before the lamination of the polyethylene resin film, which is important in the present invention, must be controlled within the range of the melting point (Tm1) to Tm1 + 240 ° C. of the polyethylene resin when the laminated film is only the polyethylene resin film. Is. When a polyethylene resin film is laminated on one side and a polyester resin film is laminated on the other side, the temperature of the metal plate immediately before the polyethylene resin film is laminated is the melting point (T) of the polyethylene resin.
m1) to Tm1 + 240 ° C., the temperature of the metal plate immediately before the polyester resin film is laminated is in the range of the melting point of the polyester resin (Tm2) to Tm2 + 160 ° C., and T
It is necessary to control the temperature below m1 + 240 ° C. When the temperature of the metal plate is lower than Tm1, the surface of the laminated polyethylene resin film which is in contact with the metal plate does not melt,
Sufficient adhesion cannot be obtained. Further, when the temperature of the metal plate immediately before the polyester resin film is laminated is less than Tm2 during the lamination of the polyester resin film, the surface of the laminated polyester resin film which is in contact with the metal plate is not melted and sufficient adhesion is obtained. Can't get In addition, the temperature of the metal plate immediately before the polyethylene resin film is laminated is Tm1.
If the temperature exceeds + 240 ° C, even if the pair of laminating rolls are sufficiently cooled, the heat transfer in the laminated polyethylene resin film is fast, the outermost layer is notably melted and the surface appearance is impaired, and it also adheres to the laminating rolls. Comes to
It is not preferable because it hinders productivity. The temperature of the laminating roll is preferably not higher than the melting point of the laminating film in consideration of the adhesion of the film to the roll, the surface appearance of the coated metal plate and the like. Furthermore, when laminating polyester resin,
When the temperature of the metal plate just before the polyester resin film is laminated exceeds Tm2 + 160 ° C, even if the pair of laminating rolls are sufficiently cooled, the heat transfer in the laminated polyester resin film is fast and the outermost layer is remarkable. Not only is it melted and the surface appearance is impaired, but it also becomes attached to the laminating rolls, which hinders productivity and heat history adversely affects the resin, and sufficient corrosion resistance cannot be obtained. Furthermore, in the production of polyethylene resin-coated metal plates used for cans that are filled with highly corrosive contents and subjected to retort treatment, the metal plate surface that is the inner surface of the can has a barrier property against contents that is superior to polyethylene resin. Laminated with a biaxially oriented polyester resin film, the surface of the metal plate to be the outer surface of the can is preferably laminated with a polyethylene resin layer subjected to irradiation before or after lamination,
When laminating these different types of resin films on a metal plate at the same time, the metal plate is heated to a temperature near the melting point of the polyethylene resin film and the melting point of the polyester resin film. The temperature of the laminating roll in contact with the film is determined below the melting point of the polyethylene resin film, the temperature of the laminating roll in contact with the polyester resin film is below the melting point of the polyester resin film, and is determined considering the amount of formation of the amorphous polyester resin layer. What is important in continuous production of the polyethylene resin-coated metal sheet of the present invention. Further, when the molten polyethylene resin extruded from the extruder is directly laminated on the metal plate directly, the temperature of the metal plate is the melting point (Tm1) of the polyethylene resin-50 to Tm1 + 200 ° C.
It is necessary to control within the range. If the temperature of the metal plate is less than Tm1-50 ° C, the surface shape of the coating film becomes poor. Further, even if the temperature of the metal plate exceeds Tm1 + 200 ° C., no improvement in adhesion is observed and the economy is poor, which is not preferable. On the other hand, the melting temperature of polyethylene resin is Tm1 + 20
The range of to Tm1 + 150 ° C is preferred. If Tm1 + 20 ° C or less, it is difficult to form a uniform film.
If the temperature exceeds ℃, not only is the economy inferior, but also the decomposition of polyethylene may proceed, which is not preferable. The melting point mentioned here is obtained from the endothermic peak of a differential scanning calorimeter (DSC) at a heating rate of 10 ° C./min., And refers to the temperature indicating the maximum depth of the endothermic peak. When two or more resins are used, it is determined from the peak of the main resin.
【0016】金属板表面にポリエチレン樹脂層、あるい
はポリエステル樹脂層を形成後の冷却は重要な条件であ
り、フイルムが積層される直前の金属板の適正な温度範
囲以上の温度で加熱されてはならないことはもちろんの
こと、積層後6秒以内にフイルムの融点ー30℃の温度
に冷却されることが好ましい。あまりにもゆっくり冷却
すると、積層された樹脂層内に球晶が形成され、樹脂層
の加工性が低下するので好ましくなく急冷することが好
ましい。Cooling after forming the polyethylene resin layer or the polyester resin layer on the surface of the metal plate is an important condition, and must not be heated at a temperature higher than the proper temperature range of the metal plate immediately before the film is laminated. Needless to say, it is preferable that the film is cooled to a temperature of -30 ° C. within the melting point of the film within 6 seconds. If cooled too slowly, spherulites are formed in the laminated resin layers and the workability of the resin layers deteriorates.
【0017】本発明において、腐食性の強い内容物を充
填し、レトルト処理を施す缶体の内面となる金属板表面
に積層されるポリエステル樹脂フイルムには二軸配向ポ
リエステル樹脂フイルムを用いることが好ましく、厳し
い加工性が要求されない場合には、二軸配向ポリエチレ
ンテレフタレートフイルムで充分であるが、より厳しい
加工性が要求される場合、エチレンテレフタレートを主
体とした共重合ポリエステル樹脂フイルム、特にエチレ
ンイソフタレート、ブチレンテレフタレート、エチレン
セバケートなどとの共重合ポリエステル樹脂フイルムを
用いることが好ましい。構造的には金属板に積層する前
は二軸配向構造を有し、積層後においても、できるだけ
二軸配向構造が残存していることが耐内容物の観点から
好ましいが、二軸配向ポリエステル層と金属板との強固
な加工密着性を確保するため、その界面に無定形ポリエ
ステル樹脂層を生成させることが不可欠である。In the present invention, a biaxially oriented polyester resin film is preferably used as the polyester resin film laminated on the surface of the metal plate which is the inner surface of the can body which is filled with a highly corrosive content and is subjected to retort treatment. In the case where strict processability is not required, a biaxially oriented polyethylene terephthalate film is sufficient, but when stricter processability is required, a copolymerized polyester resin film mainly composed of ethylene terephthalate, particularly ethylene isophthalate, It is preferable to use a copolymerized polyester resin film with butylene terephthalate, ethylene sebacate or the like. Structurally, it has a biaxially oriented structure before being laminated on a metal plate, and it is preferable that the biaxially oriented structure remains as much as possible after laminating from the viewpoint of the content resistance. It is essential to form an amorphous polyester resin layer at the interface between the metal plate and the metal plate in order to secure strong processing adhesion.
【0018】次に、本発明において用いられる金属板は
積層されるポリエチレン樹脂層との優れた加工密着性を
確保するため、金属板の表層は少なくともクロムとして
5〜25mg/m2 のクロム水和酸化物皮膜を最上層に有す
ることが不可欠である。クロム水和酸化物皮膜の量が該
範囲外であると加工密着性が著しく低下するので好まし
くない。缶用材料として広く使用されている軟鋼板、ア
ルミニウム板、錫めっき鋼鈑、ニッケルめっき鋼鈑に電
解クロム酸処理を施し、クロム水和酸化物あるいは下層
が金属クロム、上層がクロム水和酸化物からなる二層皮
膜、いわゆるTFS皮膜を生成させた表面処理鋼板等が
本発明に適用可能であるが、耐食性など要求特性及び経
済性を考慮して適用することが必要である。なお、ここ
で言うクロム換算による値とは、一般的に行われている
方法によるもので、はじめに蛍光X線により試料のクロ
ム・カウントを計り、次に試料を100℃の7. 5Nの
NaOH溶液中に5分間浸漬して、クロム水和酸化物を
除去して、ふたたびクロム・カウントを計り、両者の差
から検量線によって求めたクロム量である。Next, the metal plate used in the present invention ensures excellent processing adhesion with the laminated polyethylene resin layer, so that the surface layer of the metal plate is at least 5 to 25 mg / m 2 of chromium hydrate. It is essential to have an oxide coating on the top layer. If the amount of the hydrated chromium oxide film is out of this range, the work adhesion is significantly deteriorated, which is not preferable. Electrolytic chromic acid treatment is applied to mild steel sheets, aluminum sheets, tin-plated steel sheets, and nickel-plated steel sheets, which are widely used as materials for cans, and chromium hydrate oxide or lower layer is metallic chromium, and upper layer is chromium hydrate oxide. A two-layer coating composed of a so-called TFS coating, such as a surface-treated steel sheet, is applicable to the present invention, but it is necessary to apply it in consideration of required properties such as corrosion resistance and economical efficiency. In addition, the value in terms of chromium referred to here is based on a commonly used method. First, the chromium count of the sample is measured by fluorescent X-ray, and then the sample is measured at 100 ° C. in 7.5N NaOH solution. It is the amount of chromium obtained by immersing in the inside for 5 minutes to remove the hydrated chromium oxide, again measuring the chromium count, and using the calibration curve from the difference between the two.
【0019】また、本発明における金属板の加熱方法と
して、公知の熱風循環伝熱方式、抵抗加熱方式、誘導加
熱方式、ヒートロール方式などがあげられ、これらの方
式を単独あるいは併用しても良い。Further, as a method for heating the metal plate in the present invention, there are known hot air circulation heat transfer method, resistance heating method, induction heating method, heat roll method and the like, and these methods may be used alone or in combination. ..
【0020】[0020]
【実施例】以下、本発明の実施例及び比較例について説
明する。EXAMPLES Examples and comparative examples of the present invention will be described below.
【0021】実施例1 両面にクロム酸処理皮膜(金属クロム量:120mg/
m2、 クロム水和酸化物量:クロムとして20mg/m2)を
有す帯状のTFS(板厚0・17mm、板巾250m
m、テンパー度DRー10)を誘導加熱ロールにより2
90℃に加熱し、その片面に低密度ポリエチレン樹脂フ
イルム(タマポリ(株)製、商品名:AJー1、厚さ4
0μm)を表面温度80℃の一対の積層ロールを用い
て、ライン速度60m/分で積層し、水中に急冷、乾燥
後、1・2Kc/Kgの電子線照射を施し、被覆金属板を得
た。Example 1 Chromic acid treated films on both sides (amount of metallic chromium: 120 mg /
m 2, hydrated chromium oxide content: strip TFS that having a 20 mg / m 2) as a chromium (thickness 0 · 17 mm, Itahaba 250m
m, temper degree DR-10) 2 by induction heating roll
It is heated to 90 ° C and a low-density polyethylene resin film (Tama Poly Co., Ltd., trade name: AJ-1, thickness 4) is provided on one side.
0 μm) was laminated at a line speed of 60 m / min using a pair of laminating rolls having a surface temperature of 80 ° C., rapidly cooled in water, dried, and irradiated with an electron beam of 1.2 Kc / Kg to obtain a coated metal plate. ..
【0022】実施例2 乾燥後、23Kc/Kgの電子線照射を施した他は、 実施例
1と同様にして被覆金属板を得た。Example 2 A coated metal plate was obtained in the same manner as in Example 1 except that after drying, irradiation with an electron beam of 23 Kc / Kg was performed.
【0023】実施例3 実施例1と同様な低密度ポリエチレン樹脂フイルムにコ
ロナ放電による表面酸化処理を施し、濡れ指数が38ダ
インの表面酸化処理フイルムとした。このフイルムの表
面酸化処理面を金属板積層面とし、これらのフイルムを
板厚0.21mm、板巾250mm、テンパーDRー10の
冷延鋼板に公知の方法で脱脂、酸洗を施した後、硫酸錫
80g/l、フェノールスルホン酸(65%水溶液)60g
/l、エトキシ化αナフトール0.06g/l の錫めっき浴
を用い、浴温度45℃、陰極電流密度20A/dm2の条件
で両面に1.5g/m2の錫めっきを施し、水洗後、無水ク
ロム酸50g/l、硫酸0.5g/l のクロム酸溶液を用
い、浴温度50℃、陰極電流密度40A/dm2 の条件で
両面にTFS皮膜(金属クロム量:95mg/m2、クロム
水和酸化物量:クロムとして、 13mg/m2)を形成さ
せ、湯洗、乾燥した錫めっき鋼板を200℃に加熱し、
該フイルムを積層する他は、実施例1と同様にして被覆
金属板を得た。Example 3 A low density polyethylene resin film similar to that of Example 1 was subjected to surface oxidation treatment by corona discharge to obtain a surface oxidation treatment film having a wetting index of 38 dynes. The surface oxidation-treated surface of this film was used as a metal plate laminating surface, and these films were degreased and pickled by a known method on a cold-rolled steel plate having a plate thickness of 0.21 mm, a plate width of 250 mm, and temper DR-10, Tin sulfate 80g / l, phenolsulfonic acid (65% aqueous solution) 60g
/ l, ethoxylated α-naphthol 0.06 g / l tin plating bath, 1.5 g / m 2 tin plating on both sides under conditions of bath temperature 45 ° C and cathode current density 20 A / dm 2 , and after washing with water , chromic anhydride 50 g / l, using a chromic acid solution of sulfuric acid 0.5 g / l, bath temperature 50 ° C., cathode current density 40A / dm TFS film on both sides with second condition (metallic chromium amount: 95 mg / m 2, Chromium hydrated oxide amount: 13 mg / m 2 ) was formed as chromium, and the tin-plated steel sheet washed with hot water and dried was heated to 200 ° C.,
A coated metal plate was obtained in the same manner as in Example 1 except that the films were laminated.
【0024】実施例4 濡れ指数が54ダインの表面酸化処理フイルムとした他
は、実施例3と同様にして被覆金属板を得た。Example 4 A coated metal plate was obtained in the same manner as in Example 3 except that the surface-oxidized film having a wetting index of 54 dynes was used.
【0025】実施例5 帯状のTFSのクロム水和酸化物量がクロムとして25
mg/m2 である他は、実施例1と同様にして被覆金属板を
得た。Example 5 The amount of chromium hydrated oxide of band-shaped TFS was 25 as chromium.
A coated metal plate was obtained in the same manner as in Example 1 except that the amount was mg / m 2 .
【0026】実施例6 帯状のTFSのクロム水和酸化物量がクロムとして5mg
/m2 である他は、実施例1と同様にして被覆金属板を得
た。Example 6 Chromium hydrated oxide of band-shaped TFS was 5 mg as chromium.
A coated metal plate was obtained in the same manner as in Example 1 except that / m 2 was used.
【0027】実施例7 実施例1と同様な帯状のTFSの片面に、リニアー低密
度ポリエチレン樹脂フイルム(タマポリ(株)製、商品
名:NBー1、厚さ40μm)を、他の片面に二軸配向
ポリエチレンテレフタレート樹脂フイルム(東レ(株)
製、ルミラーS10、厚さ25μm)を、一対の表面温
度の異なる積層ロール(ポリエチレン樹脂フイルムと接
する積層ロールの表面温度:80℃、ポリエチレンテレ
フタレート樹脂フイルムと接する積層ロールの表面温
度:120℃)を用いて、ライン速度60m/分で同時
に積層、急冷、乾燥した。その後ポリエチレン樹脂フイ
ルム被覆面に10Kc/Kg の電子線照射を施し、被覆金属
板を得た。Example 7 A linear low-density polyethylene resin film (manufactured by TamaPoly Co., Ltd., trade name: NB-1, thickness 40 μm) was applied to one side of a strip-shaped TFS similar to that used in Example 1 on the other side. Axial oriented polyethylene terephthalate resin film (Toray Industries, Inc.)
Lumirror S10 (thickness: 25 μm), and a pair of laminating rolls having different surface temperatures (surface temperature of laminating roll in contact with polyethylene resin film: 80 ° C., surface temperature of laminating roll in contact with polyethylene terephthalate resin film: 120 ° C.). At the same time, they were laminated at a line speed of 60 m / min, rapidly cooled and dried. Thereafter, the surface coated with the polyethylene resin film was irradiated with an electron beam of 10 Kc / Kg to obtain a coated metal plate.
【0028】実施例8 実施例1と同様な低密度ポリエチレン樹脂フイルムに1
0Kc/Kg の電子線照射を積層前に施したフイルムを実施
例1と同様な金属板及び条件で積層、急冷、乾燥し、そ
の後電子線照射を施すこと無く、被覆金属板を得た。Example 8 A low density polyethylene resin film similar to that of Example 1 was used.
The film which had been irradiated with an electron beam of 0 Kc / Kg before lamination was laminated, quenched and dried under the same metal plate and conditions as in Example 1, and then a coated metal plate was obtained without electron beam irradiation.
【0029】実施例9 実施例1と同様な帯状のTFSを高周波加熱により10
0℃に加熱し、その片面にライン速度60m/分で実施
例1のフイルムと同一組成の低密度ポリエチレン樹脂を
Tダイ押し出し機により溶融押し出し(溶融樹脂温度=
220℃、樹脂厚み=10μm)し、水中に急冷、乾燥
後、6Kc/Kgの電子線照射を施し、 被覆金属板を得た。Example 9 The same band-shaped TFS as in Example 1 was heated to 10 by high frequency heating.
It was heated to 0 ° C., and a low-density polyethylene resin having the same composition as that of the film of Example 1 was melt-extruded on one surface thereof at a line speed of 60 m / min by a T-die extruder (melt resin temperature =
220 ° C., resin thickness = 10 μm), quenched in water, dried, and then subjected to electron beam irradiation of 6 Kc / Kg to obtain a coated metal plate.
【0030】比較例1 実施例1と同様な帯状のTFSの片面に、実施例1と同
様なポリエチレン樹脂フイルムを実施例1と同様な条件
で積層、急冷、乾燥した後、電子線照射を施すこと無
く、被覆金属板を得た。Comparative Example 1 A polyethylene resin film similar to that used in Example 1 was laminated on one side of a strip-shaped TFS similar to that used in Example 1 under the same conditions as Example 1, quenched and dried, and then irradiated with an electron beam. Without a coated metal plate was obtained.
【0031】比較例2 実施例1と同様なポリエチレン樹脂フイルムを実施例1
と同様な条件で積層、急冷、乾燥した。その後、0・8K
c/Kgの電子線照射を施し、被覆金属板を得た。Comparative Example 2 A polyethylene resin film similar to that of Example 1 was used.
Laminated, quenched, and dried under the same conditions as. Then, 0 · 8K
An electron beam of c / Kg was applied to obtain a coated metal plate.
【0032】比較例3 28Kc/Kgの電子線照射を施した他は、 比較例2と同様
にして被覆金属板を得た。Comparative Example 3 A coated metal plate was obtained in the same manner as in Comparative Example 2 except that electron beam irradiation of 28 Kc / Kg was performed.
【0033】比較例4 実施例1と同様なポリエチレン樹脂フイルムにコロナ放
電処理による表面酸化処理を施し、濡れ指数35ダイン
の表面酸化処理フイルムとした。このフイルムを実施例
3と同様な金属板及び条件で積層、急冷、乾燥し、電子
線照射を施すこと無く、被覆金属板を得た。Comparative Example 4 The same polyethylene resin film as in Example 1 was subjected to surface oxidation treatment by corona discharge treatment to obtain a surface oxidation treatment film having a wetting index of 35 dynes. This film was laminated, quenched and dried under the same metal plate and conditions as in Example 3, and a coated metal plate was obtained without electron beam irradiation.
【0034】比較例5 クロム水和酸化物皮膜量がクロムとして3mg/m2 である
帯状のTFSである他は実施例1と同様にして作成し、
被覆金属板を得た。Comparative Example 5 The procedure of Example 1 was repeated except that the amount of chromium hydrate oxide film was a band-shaped TFS having a chromium content of 3 mg / m 2 .
A coated metal plate was obtained.
【0035】比較例6 クロム水和酸化物皮膜量がクロムとして28mg/m2 であ
る帯状のTFSである他は実施例1と同様にして作成
し、被覆金属板を得た。Comparative Example 6 A coated metal plate was obtained in the same manner as in Example 1 except that it was a band-shaped TFS having a chromium hydrate oxide coating amount of 28 mg / m 2 as chromium.
【0036】実施例1〜9および比較例1〜6にて作成
した試料の特性を次ぎに示す方法で評価した。 (1)ポリエチレン樹脂層の加工密着性 試料を直径80mmの円板に打ち抜き、ポリエチレン樹
脂被覆面を外面として、絞り比2・0で深絞り加工を施
し、 深絞りカップの側面のポリエチレン樹脂層の剥離
程度を肉眼で評価し、剥離なしを5、ほぼ全面剥離を1
とし、5段階で表示した。(4以上が特性良好) (2)耐レトルト性 (1)の方法で得られた円筒状の深絞りカップをレトル
ト釜に入れ、130℃の加圧水蒸気で30分処理し、該
カップの側面のポリエチレン樹脂層の剥離程度を肉眼で
評価し、(1)の場合と同様に5段階で表示するととも
に、表面外観の変化を肉眼で観察し、変化なしを5、顕
著な変化ありを1とし、5段階で表示した。(4以上が
特性良好) (3)耐衝撃加工性 JIS Kー6744(1977)の折り曲げ性試験法
により、ポリエチレン樹脂被覆面が外面となるように、
2mmの半径を有す軸で折り曲げた。この折り曲げた試
料の内側に、板厚0・34mmの鋼板を挿入し、 2kg
の荷重を50cmの高さから落下させ、加工部のポリエ
チレン樹脂層のクラックの有無を顕微鏡で観察し、全く
クラックがない状態を5、無数にクラックがある状態を
1とし、5段階で表示した。(4以上が特性良好)The characteristics of the samples prepared in Examples 1 to 9 and Comparative Examples 1 to 6 were evaluated by the methods described below. (1) punching processability adhesion samples polyethylene resin layer into a circular plate having a diameter of 80 mm, a polyethylene resin-coated surface as the outer surface, draw ratio deep-drawn in 2-0, the side surfaces of the deep drawn cup of a polyethylene resin layer The degree of peeling was evaluated with the naked eye, 5 without peeling and 1 with almost all peeling.
And displayed in 5 steps. (4 or more is good characteristic) (2) Retort resistance The cylindrical deep-drawing cup obtained by the method of (1) is put in a retort kettle and treated with pressurized steam at 130 ° C for 30 minutes to The degree of peeling of the polyethylene resin layer was evaluated with the naked eye, and displayed in 5 levels as in the case of (1), and the change in the surface appearance was observed with the naked eye. It is displayed in five levels. (4 or more is good in characteristics) (3) Impact processing resistance According to the bending property test method of JIS K-6744 (1977), the polyethylene resin coated surface becomes the outer surface,
It was folded on an axis with a radius of 2 mm. On the inside of the bent sample, insert the steel sheet having a thickness of 0 · 34 mm, 2 kg
Was dropped from a height of 50 cm, and the presence or absence of cracks in the polyethylene resin layer of the processed portion was observed with a microscope. .. (4 or more are good characteristics)
【0037】[0037]
【表1】 [Table 1]
【0038】[0038]
【表2】 [Table 2]
【0039】[0039]
【発明の効果】以上、表1及び表2に示すように、本発
明によれば、加工密着性、耐衝撃加工性、レトルト処理
後のポリエチレン樹脂層の密着性に優れ、高温の加圧水
蒸気によるレトルト処理を施しても表面外観が良好で、
経済性にも優れた缶用材料が提供できる。特に、本発明
品はポリエチレン樹脂被覆面を外面となるように缶体に
成形後、内容物を充填し、レトルト処理が施される缶用
材料として適している。缶蓋、絞り缶、王冠、キャップ
類など広く適用可能である。なお、缶体の内面となる金
属板表面は充填する内容物に対する耐食性がポリエチレ
ン樹脂層より優れた二軸配向ポリエステル樹脂フイルム
で被覆することにより、本発明の方法によるポリエチレ
ン樹脂被覆金属板の缶用材料としての用途をさらに拡大
できる。As described above, according to the present invention, as shown in Tables 1 and 2, the processing adhesion, the impact resistance, and the adhesion of the polyethylene resin layer after the retort treatment are excellent. The surface appearance is good even after retort treatment,
It is possible to provide a material for a can that is also highly economical. In particular, the product of the present invention is suitable as a material for a can, which is formed by molding a can so that the polyethylene resin-coated surface is the outer surface, filling the contents, and then performing a retort treatment. Widely applicable to can lids, squeezed cans, crowns, caps, etc. The inner surface of the can body is coated with a biaxially oriented polyester resin film, which has better corrosion resistance to the contents to be filled than the polyethylene resin layer, so that the polyethylene resin-coated metal plate for a can according to the method of the present invention can be used. The application as a material can be further expanded.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 FI 技術表示箇所 B29L 9:00 4F C08L 23:06 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location B29L 9:00 4F C08L 23:06
Claims (5)
水和酸化物皮膜を有した金属板を積層フイルムの融点
(Tm1)〜Tm1+240℃に加熱し、その片面あるいは
両面に1〜25キロクーロン/キログラムの放射線照射
を施したエチレン反復単位70〜100モル%のポリエ
チレン樹脂フイルムを熱融着により積層し、急冷するこ
とを特徴とする耐熱水性に優れたポリエチレン樹脂被覆
金属板の製造方法。1. A metal plate having a hydrated chromium oxide film of 5 to 25 mg / m 2 as chromium is heated to a melting point (Tm1) to Tm1 + 240 ° C. of a laminated film and 1 to 25 kg on one side or both sides thereof. A method for producing a polyethylene resin-coated metal sheet excellent in hot water resistance, which comprises laminating a polyethylene resin film having ethylene repeating units of 70 to 100 mol% irradiated with coulomb / kg of radiation by heat fusion and then rapidly cooling.
水和酸化物皮膜を有した金属板を、積層フイルムの融点
(Tm1)〜Tm1+240℃に加熱し、その片面あるいは
両面にエチレン反復単位70〜100モル%のポリエチ
レン樹脂フイルムを積層し、急冷後、さらに1〜25キ
ロクーロン/キログラムの放射線照射を施すことを特徴
とする耐熱水性に優れたポリエチレン樹脂被覆金属板の
製造方法。2. A metal plate having, as chromium, a hydrated chromium oxide film of 5 to 25 mg / m 2 is heated to a melting point (Tm1) to Tm1 + 240 ° C. of a laminated film, and an ethylene repeating unit is provided on one or both sides thereof. A method for producing a polyethylene resin-coated metal sheet excellent in hot water resistance, comprising laminating 70 to 100 mol% of a polyethylene resin film, quenching, and further irradiating with radiation of 1 to 25 kilocoulombs / kilogram.
水和酸化物皮膜を有した金属板を、ポリエチレンの融点
(Tm1)−50〜Tm1+200℃に加熱し、その片面あ
るいは両面にTm1〜Tm1+150℃の温度の溶融したエ
チレン反復単位70〜100モル%のポリエチレン樹脂
を押し出し積層し、急冷後、さらに1〜25キロクーロ
ン/キログラムの放射線照射を施すことを特徴とする耐
熱水性に優れたポリエチレン樹脂被覆金属板の製造方
法。3. As chromium, a metal plate having a hydrated chromium oxide film of 5 to 25 mg / m 2 is heated to a melting point (Tm1) of polyethylene of −50 to Tm1 + 200 ° C., and Tm1 to Tm1 to both sides thereof are heated. Polyethylene excellent in hot water resistance, characterized by extruding and laminating a polyethylene resin containing 70 to 100 mol% of a repeating ethylene unit at a temperature of Tm1 + 150 ° C, quenching, and then irradiating with radiation of 1 to 25 kilocoulombs / kilogram. A method for producing a resin-coated metal plate.
ポリエチレン樹脂フイルムが濡れ指数38〜54ダイン
の表面酸化処理が施されたことを特徴とする請求項1ま
たは2の耐熱水性に優れたポリエチレン樹脂被覆金属板
の製造方法。4. A polyethylene resin film having excellent hot water resistance according to claim 1 or 2, wherein a polyethylene resin film having an ethylene repeating unit of 70 to 100 mol% is subjected to surface oxidation treatment with a wetting index of 38 to 54 dynes. A method for manufacturing a coated metal plate.
ポリエチレン樹脂層を積層し、他の片面はポリエステル
樹脂フイルムを該ポリエステル樹脂の融点(Tm2)〜T
m2+160℃に加熱された金属板に積層することを特徴
とする請求項1、2または3の耐熱水性に優れたポリエ
チレン樹脂被覆金属板の製造方法。5. A polyethylene resin layer according to claim 1, 2 or 3 is laminated on one surface of the metal plate, and a polyester resin film is laminated on the other surface of the metal plate, the melting point (Tm2) to T of the polyester resin.
The method for producing a polyethylene resin-coated metal plate excellent in hot water resistance according to claim 1, wherein the metal plate is laminated on a metal plate heated to m2 + 160 ° C.
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4035746A JP2835386B2 (en) | 1992-01-28 | 1992-01-28 | Method for producing polyethylene resin-coated metal sheet excellent in hot water resistance |
US07/898,469 US5234516A (en) | 1992-01-28 | 1992-06-15 | Method for production of a polyethylene laminated metal sheet |
CA002071590A CA2071590A1 (en) | 1992-01-28 | 1992-06-18 | A method for production of a polyethylene laminated metal sheet |
FR9207966A FR2692835B1 (en) | 1992-01-28 | 1992-06-29 | PROCESS FOR PRODUCING A METAL SHEET LAMINATED WITH POLYETHYLENE. |
GB9214155A GB2268441B (en) | 1992-01-28 | 1992-07-02 | A method for production of a polyethylene laminated metal sheet |
DE4222464A DE4222464A1 (en) | 1992-01-28 | 1992-07-08 | Process for producing a metal sheet laminated with polyethylene |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4035746A JP2835386B2 (en) | 1992-01-28 | 1992-01-28 | Method for producing polyethylene resin-coated metal sheet excellent in hot water resistance |
CA002071590A CA2071590A1 (en) | 1992-01-28 | 1992-06-18 | A method for production of a polyethylene laminated metal sheet |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP08293199A Division JP3075994B2 (en) | 1996-10-16 | 1996-10-16 | Method for manufacturing resin-coated metal sheet for can and can manufactured using the metal sheet |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH05200961A true JPH05200961A (en) | 1993-08-10 |
JP2835386B2 JP2835386B2 (en) | 1998-12-14 |
Family
ID=25675238
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP4035746A Expired - Fee Related JP2835386B2 (en) | 1992-01-28 | 1992-01-28 | Method for producing polyethylene resin-coated metal sheet excellent in hot water resistance |
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Country | Link |
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JP (1) | JP2835386B2 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6723441B1 (en) | 1999-09-22 | 2004-04-20 | Nkk Corporation | Resin film laminated metal sheet for can and method for fabricating the same |
WO2005016631A1 (en) * | 2003-08-18 | 2005-02-24 | Nippon Steel Corporation | Laminated metal sheet and process for producing the same |
US7198856B2 (en) | 2001-03-14 | 2007-04-03 | Jfe Steel Corporation | Film-laminated metal sheet for container |
JP2013107325A (en) * | 2011-11-22 | 2013-06-06 | Fujimori Kogyo Co Ltd | Method of joining metal and polyolefin resin and laminate |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6471734A (en) * | 1987-09-12 | 1989-03-16 | Nisshin Steel Co Ltd | Manufacture of polyorefin resin laminated steel sheet |
-
1992
- 1992-01-28 JP JP4035746A patent/JP2835386B2/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6471734A (en) * | 1987-09-12 | 1989-03-16 | Nisshin Steel Co Ltd | Manufacture of polyorefin resin laminated steel sheet |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6723441B1 (en) | 1999-09-22 | 2004-04-20 | Nkk Corporation | Resin film laminated metal sheet for can and method for fabricating the same |
US7198856B2 (en) | 2001-03-14 | 2007-04-03 | Jfe Steel Corporation | Film-laminated metal sheet for container |
US7435465B2 (en) | 2001-03-14 | 2008-10-14 | Jfe Steel Corporation | Film-laminated metal sheet for container |
WO2005016631A1 (en) * | 2003-08-18 | 2005-02-24 | Nippon Steel Corporation | Laminated metal sheet and process for producing the same |
US8551281B2 (en) | 2003-08-18 | 2013-10-08 | Nippon Steel & Sumitomo Metal Corporation | Laminated metal sheet and method of production of same |
JP2013107325A (en) * | 2011-11-22 | 2013-06-06 | Fujimori Kogyo Co Ltd | Method of joining metal and polyolefin resin and laminate |
Also Published As
Publication number | Publication date |
---|---|
JP2835386B2 (en) | 1998-12-14 |
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