JPH05269858A - Manufacture of resin coated steel plate excellent in processing adhesion - Google Patents
Manufacture of resin coated steel plate excellent in processing adhesionInfo
- Publication number
- JPH05269858A JPH05269858A JP10236092A JP10236092A JPH05269858A JP H05269858 A JPH05269858 A JP H05269858A JP 10236092 A JP10236092 A JP 10236092A JP 10236092 A JP10236092 A JP 10236092A JP H05269858 A JPH05269858 A JP H05269858A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- film
- steel sheet
- adhesion
- layer resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- 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、加工密着性に優れた樹
脂被覆鋼板の熱接着法による製造方法に関する。より詳
細には、多段圧着を行う加工密着性に優れた樹脂被覆鋼
板の製造方法に関するものであり、缶蓋（エンド）・イ
ージーオープンエンド（ＥＯＥ）・絞り缶・絞り再絞り
缶（ＤＲＤ缶）・ストレッチ加工を伴う絞り再絞り缶
（ＤＴＲ缶）・５ｇａｌ缶などの容器材料としての樹脂
フィルム被覆鋼板の熱接着法による製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a resin-coated steel sheet excellent in working adhesion by a heat bonding method. More specifically, the present invention relates to a method for producing a resin-coated steel sheet that is subjected to multi-step crimping and has excellent process adhesion, and can lid (end), easy open end (EOE), squeezed can, squeezed redrawn can (DRD can). The present invention relates to a method for producing a resin film-coated steel sheet as a container material such as a drawn and redrawn can (DTR can) and a 5 gal can accompanied by a stretch process by a heat bonding method.
【０００２】[0002]
【従来の技術】従来より、エンド・ＥＯＥ・絞り缶・５
ｇａｌ缶は、ブリキ板、電解クロム酸処理鋼板或いはア
ルミニウム板に一回あるいは複数回の塗装、焼付けを施
した後、加工されていた。このように塗装を施すこと
は、焼付け工程が煩雑であるばかりでなく、多大な焼付
け時間を必要としていた。また、塗膜形成時に多量の溶
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いう欠点を有してい
た。2. Description of the Related Art End, EOE, squeeze can, 5
Gal cans were processed after coating and baking a tin plate, an electrolytic chromic acid treated steel plate or an aluminum plate one or more times. Such coating not only complicates the baking process, but also requires a long baking time. Further, since a large amount of solvent is discharged when forming the coating film, there is a drawback in that the discharged solvent must be guided to a special incinerator and incinerated from the viewpoint of pollution.
【０００３】近年、これらの欠点を解決するためにポリ
エステルフィルム或いはポリプロピレンフィルムを金属
板に被覆したもの、あるいはその製造方法の提案がなさ
れている。特に、熱接着法は、少なくともラミネート時
には溶剤を全く使わない点、高速生産性の点で有利であ
る。In recent years, in order to solve these drawbacks, there has been proposed a product in which a polyester film or a polypropylene film is coated on a metal plate, or a manufacturing method thereof. In particular, the thermal bonding method is advantageous in that at least the solvent is not used at the time of laminating and the high-speed productivity is achieved.
【０００４】容器用樹脂積層鋼板の製造方法について
は、熱可塑性樹脂からなるフィルムを鋼板基質に対して
毎分１００ｍ以上の高速度で融着し、欠陥のないフィル
ム被覆鋼板を製造する方法（特開昭５１−１１４４８４
号公報）、単層のポリエステルフィルムを用いて、積層
時の鋼板温度を樹脂フィルムの融点Ｔｍ〜Ｔｍ＋１００
℃、ラミネートロールの表面温度を３０〜１８０℃とす
ることにより樹脂皮膜の配向結晶構造を残そうとするも
の（特開昭６１−１４９３４０号公報）がある。さら
に、２層構造のフィルムを使用した例が特開平１−１８
０３３６号公報に開示されている。Regarding a method for producing a resin laminated steel sheet for containers, a film made of a thermoplastic resin is fused to a steel sheet substrate at a high speed of 100 m / min or more to produce a defect-free film-coated steel sheet (special feature: Kai 51-114484
Gazette), using a single-layer polyester film, the steel plate temperature at the time of lamination is set to the melting point Tm to Tm + 100 of the resin film.
In some cases, the oriented crystal structure of the resin film is left by setting the surface temperature of the laminate roll to 30 to 180 ° C. (Japanese Patent Laid-Open No. 61-149340). Further, an example using a film having a two-layer structure is disclosed in JP-A-1-18.
It is disclosed in Japanese Patent No. 0336.
【０００５】[0005]
【発明が解決しようとする課題】ポリエステルやポリプ
ロピレン樹脂フィルムを熱接着法で積層した樹脂ラミネ
ート鋼板を容器材料として使用する場合には、缶体に内
容物を充填した後の皮膜の耐食性を確保するため、樹脂
皮膜に配向結晶構造を残すこと、さらにこの配向結晶構
造を残した皮膜が鋼板に十分な密着力をもって積層され
ていることが必要である。When a resin-laminated steel sheet obtained by laminating a polyester or polypropylene resin film by a heat-bonding method is used as a container material, the corrosion resistance of the film after filling the can body with the contents is ensured. Therefore, it is necessary to leave the oriented crystal structure in the resin film and to further laminate the film having the oriented crystal structure left on the steel sheet with sufficient adhesion.
【０００６】鋼板と樹脂皮膜との十分な密着力を確保す
るためには、樹脂フィルムを溶融させられる鋼板温度で
もって樹脂フィルムを鋼板にラミネートしなければなら
ないが、鋼板温度が高過ぎると樹脂皮膜全体の配向結晶
構造が破壊されてしまう。つまり、鋼板が有する熱によ
って樹脂の結晶を加熱溶融して非晶質として鋼板との密
着力を確保し、フィルムの厚み方向の一部では配向結晶
性を残すようにラミネートする必要がある。このため、
ラミネート時の鋼板温度の非常に厳しい管理が必要とな
っている。特に、帯状鋼板を用いて連続的に生産を行う
場合には、鋼板の幅方向での温度管理が極めて難しいこ
とから、生産性が悪く問題である。In order to secure a sufficient adhesion between the steel sheet and the resin film, the resin film must be laminated on the steel sheet at a steel sheet temperature at which the resin film can be melted. The entire oriented crystal structure is destroyed. That is, it is necessary to heat and melt the crystal of the resin by the heat of the steel sheet to make it amorphous so as to secure the adhesiveness with the steel sheet, and to laminate so as to leave the oriented crystallinity in a part of the thickness direction of the film. For this reason,
Very strict control of the steel plate temperature during lamination is required. In particular, in the case where continuous production is performed using a strip-shaped steel sheet, it is extremely difficult to control the temperature in the width direction of the steel sheet, resulting in poor productivity and a problem.
【０００７】本発明は上記実状に鑑みなされたもので、
樹脂フィルム皮膜の加工密着性を確保し、厳しい加工用
途に対しても使用できる樹脂フィルム被覆鋼板を製造す
るものである。The present invention has been made in view of the above situation,
It is intended to produce a resin film-coated steel sheet that secures the processing adhesiveness of the resin film coating and can be used even in severe processing applications.
【０００８】[0008]
【課題を解決するための手段】本発明の要旨は、以下の
通りである。The gist of the present invention is as follows.
【０００９】 下層樹脂の粘着開始温度（Ｔａｓ１）
に対し上層樹脂の粘着開始温度（Ｔａｓ２）が５℃以上
高く、かつ、上層樹脂の融点（Ｔｍ２）が下層樹脂の粘
着開始温度（Ｔａｓ１）よりも２０〜７０℃高い２層構
造の樹脂フィルムを用い、下層樹脂の粘着開始温度（Ｔ
ａｓ１）〜上層樹脂の融点（Ｔｍ２）の範囲内に加熱さ
れた鋼板の片面あるいは両面に第一回目の圧着を行い、
次いで下層樹脂の粘着開始温度（Ｔａｓ１）〜上層樹脂
の粘着開始温度（Ｔａｓ２）の範囲内の鋼板温度で第二
回目以降の圧着を行う多段圧着を特徴とする加工密着性
に優れた樹脂被覆鋼板の製造方法。Adhesion start temperature of the lower layer resin (Tas1)
On the other hand, a resin film having a two-layer structure in which the upper layer resin has a higher adhesion start temperature (Tas2) of 5 ° C. or more and the upper layer resin has a melting point (Tm2) that is 20 to 70 ° C. higher than the lower layer resin adhesion start temperature (Tas1). Used, the adhesion starting temperature (T
as1) to the melting point (Tm2) of the upper resin, the first pressure bonding is performed on one or both surfaces of the steel sheet heated.
Next, a resin-coated steel sheet having excellent work adhesion, which is characterized by multi-step pressure bonding in which the second and subsequent pressure bonding is performed at a steel plate temperature within the range of the adhesion starting temperature (Tas1) of the lower layer resin to the adhesion starting temperature (Tas2) of the upper layer resin. Manufacturing method.
【００１０】 該２層構造の樹脂フィルムの少なくと
も上層樹脂がポリエステル樹脂であることを特徴とする
前記の加工密着性に優れた樹脂被覆鋼板の製造方法。At least the upper layer resin of the two-layer structure resin film is a polyester resin, the method for producing a resin-coated steel sheet excellent in process adhesion as described above.
【００１１】 該２層構造の樹脂フィルムの少なくと
も上層樹脂がポリプロピレン樹脂であることを特徴とす
る前記の加工密着性に優れた樹脂被覆鋼板の製造方
法。The method for producing a resin-coated steel sheet having excellent process adhesion, characterized in that at least an upper layer resin of the two-layer structure resin film is a polypropylene resin.
【００１２】[0012]
【作用】本発明に用いる２層構造の樹脂フィルムは、下
層樹脂の粘着開始温度をＴａｓ１とし、上層樹脂の粘着
開始温度をＴａｓ２とし、上層樹脂の融点をＴｍ２とし
たとき、５℃≦Ｔａｓ２−Ｔａｓ１かつ２０℃≦Ｔｍ２
−Ｔａｓ１≦７０℃の要件を満たす。さらに、下層樹脂
の粘着開始温度（Ｔａｓ１）〜上層樹脂の融点（Ｔｍ
２）の範囲内に加熱された鋼板の片面あるいは両面に第
一回目の圧着を行い、下層樹脂の粘着開始温度（Ｔａｓ
１）〜上層樹脂の粘着開始温度（Ｔａｓ２）の範囲内の
鋼板温度で第二回目以降の圧着を行う多段圧着により樹
脂積層鋼板を製造する。この条件を満足していれば、鋼
板との十分な密着力を有し、かつ配向結晶性を有する皮
膜をもつラミネート鋼板を得ることができる。なお、こ
こで下層樹脂とは、鋼板との接着界面側の樹脂層を指
し、他の面側、即ちラミネート後に最表面となる側の樹
脂層を上層樹脂とする。The two-layer structure resin film used in the present invention has a lower layer resin adhesion starting temperature of Tas1, an upper layer resin adhesion starting temperature of Tas2, and an upper layer resin melting point of Tm2, 5 ° C. ≦ Tas2- Tas1 and 20 ° C. ≦ Tm2
Meets the requirement of −Tas1 ≦ 70 ° C. Furthermore, the adhesion starting temperature (Tas1) of the lower layer resin to the melting point (Tm of the upper layer resin
The first pressure bonding is applied to one side or both sides of the steel plate heated within the range of 2), and the adhesion start temperature (Tas
1) -A resin laminated steel plate is manufactured by multi-stage pressure bonding in which the second and subsequent pressure bondings are performed at a steel plate temperature within the range of the adhesion start temperature (Tas2) of the upper layer resin. If this condition is satisfied, it is possible to obtain a laminated steel sheet having a film having a sufficient adhesion to the steel sheet and having oriented crystallinity. Here, the lower layer resin refers to the resin layer on the adhesive interface side with the steel sheet, and the other surface side, that is, the resin layer on the outermost surface after laminating is the upper layer resin.
【００１３】なお、本発明における粘着開始温度とは、
鋼板上に樹脂フィルムを置き、１００ｇ／ｃｍ2 の圧力
を加えて鋼板を加熱したとき、フィルムが鋼板に融着す
る最低温度を記録することにより測定された温度であ
る。結晶性樹脂の場合、示差熱分析において、昇温速度
１０ｄｅｇ／ｍｉｎの測定条件で得られる結晶融解の吸
熱ピークの立ち上がりを示す部分の温度、即ち融解開始
温度が粘着開始温度とほぼ一致する。The sticking start temperature in the present invention means
It is a temperature measured by recording the lowest temperature at which the film is fused to the steel sheet when the resin film is placed on the steel sheet and the steel sheet is heated by applying a pressure of 100 g / cm 2 . In the case of a crystalline resin, the temperature of the part showing the rise of the endothermic peak of the crystal melting obtained under the measurement conditions of the temperature rising rate of 10 deg / min in the differential thermal analysis, that is, the melting start temperature is almost the same as the sticking start temperature.
【００１４】また、融点とは、示差熱分析において、昇
温速度１０ｄｅｇ／ｍｉｎの測定条件で得られる結晶融
解の吸熱ピークのピーク温度をいう。The melting point refers to a peak temperature of an endothermic peak of crystal melting obtained by a differential thermal analysis under a measurement condition of a heating rate of 10 deg / min.
【００１５】まず、多段で圧着を行う理由は、一回の圧
着だけでは樹脂フィルムと鋼板との十分な密着力が確保
できない場合が多いためである。特に、帯状鋼板に連続
的にラミネートを行う場合には、圧着ロールを用いて鋼
板にフィルムの圧着を行うが、生産性を上げるために通
板速度を高くする。通板速度が高くなると鋼板とフィル
ムを圧着している時間が短くなり、鋼板界面の樹脂フィ
ルムの分子が鋼板表面にしっかりと馴染む前に圧下力の
作用がなくなってしまうため、十分な密着力を確保でき
なくなる。したがって、第一回目の圧着後、鋼板が加熱
されている間に更に第二回目以降の圧着をすることで、
樹脂の分子を鋼板表面にしっかりと馴染ませることがで
き、密着力が確保できるようになる。First, the reason why the pressure bonding is performed in multiple stages is that it is often the case that sufficient adhesion between the resin film and the steel plate cannot be secured by only one pressure bonding. In particular, when laminating a strip-shaped steel sheet continuously, the film is pressure-bonded to the steel sheet using a pressure roll, but the sheet passing speed is increased to increase productivity. As the stripping speed increases, the time during which the steel sheet and the film are pressure bonded is shortened, and the molecules of the resin film at the steel sheet interface lose their action of the pressing force before they are firmly fitted to the steel sheet surface. It cannot be secured. Therefore, after the first crimping, by further crimping the second and subsequent times while the steel sheet is being heated,
Resin molecules can be made to fit onto the surface of the steel sheet firmly, and adhesion can be secured.
【００１６】圧着に用いるロールについては、少なくと
もフィルムの接触する側のロールはシリコンゴムあるい
はフッ素ゴムでライニングしたロールが望ましい。圧着
時間を稼ぐだけであれば、圧着ロールの材質の柔らかい
ものを用いてニップ幅を広く取るようにすることもでき
るが、高速では圧着ロールの偏心やラミネート皮膜のシ
ワ発生の原因となる。また、圧着ロールを大径化するこ
とも考えられる。しかしながら、圧着ロール温度が一定
になるのに時間がかかりラミネート鋼板の歩留まりが悪
くなることや、フィルムによってはシワや収縮が起こり
易い場合があるため好ましくない。As for the roll used for pressure bonding, it is desirable that at least the roll which is in contact with the film is lined with silicone rubber or fluororubber. If only the pressure-bonding time is needed, a soft material for the pressure-bonding roll can be used to widen the nip width, but at high speeds, it causes eccentricity of the pressure-bonding roll and wrinkles in the laminate film. It is also possible to increase the diameter of the pressure bonding roll. However, it is not preferable because it takes time for the pressure-bonding roll temperature to become constant, the yield of the laminated steel sheet is deteriorated, and wrinkles and shrinkage are likely to occur depending on the film.
【００１７】特に、絞り缶用ラミネート鋼板について
は、鋼板とラミネート皮膜との密着性は、密着ラミネー
ト鋼板状態での密着力をピール法にて測定した場合に皮
膜の破断が起こりピール強度が測定できない程に強固に
密着したレベルが少なくとも必要である。１２μｍのＰ
ＥＴフィルムでの破断強度がおおよそ２．１ｋｇ／１０
ｍｍであるから、これ以上の密着力が必要となる。In particular, in the case of a laminated steel sheet for drawn cans, the adhesion between the steel sheet and the laminate film is such that when the adhesion force in the state of the adhered laminated steel sheet is measured by the peel method, the film breaks and the peel strength cannot be measured. At least a level of firm adhesion is required. 12 μm P
Breaking strength of ET film is approximately 2.1kg / 10
Since it is mm, the adhesion force more than this is required.
【００１８】なお、ピール法とは、幅１０ｍｍ、１８０
°ピール剥離、引っ張り速度１００ｍｍ／ｍｉｎの条件
で測定するもので、試料の作成方法は、鋼板との密着力
を測定しようとする皮膜の積層された逆の面から、測定
しようとする皮膜に疵を付けることなく鋼板のみに切れ
込みをいれて鋼板のみを切断し、試料とする。The peel method is a width of 10 mm, 180
Measured under the conditions of peeling and pulling speed of 100 mm / min. The method of preparing the sample is to measure the adhesion force with the steel plate from the opposite surface of the laminated film to the surface of the film to be measured. Without cutting, make a cut only in the steel plate and cut only the steel plate to obtain a sample.
【００１９】さらに、ピール強度測定試験で膜破断を生
じるようなラミネート鋼板でも、製缶工程での絞り成形
を受けると皮膜の密着力は低下する。加工が厳しい場合
には、皮膜が容易に剥離することもある。実用上、表１
に示す条件で絞り成形を行った後の皮膜のピール強度値
は０．１ｋｇ／１０ｍｍ以上が必要である。Further, even with a laminated steel sheet which causes film breakage in the peel strength measurement test, the adhesion of the film decreases when it is subjected to drawing in the can making process. If the processing is severe, the film may easily peel off. Practically, Table 1
The peel strength value of the film after draw forming under the conditions shown in is required to be 0.1 kg / 10 mm or more.
【００２０】[0020]
【表１】 [Table 1]
【００２１】圧着を行う回数については、多段圧着を行
った場合の圧着回数と皮膜と鋼板との密着力との関係
は、４回以上の圧着ではほぼ一定の密着力となり効果が
飽和した。１回しか圧着しなかったものと２回圧着した
ものを比較すると、２回圧着で密着力は大きく向上した
が、２回と３回ではその差はあまり大きくなかった。実
用上は２回の圧着でも十分な密着力が確保できた。圧着
回数の効果が飽和すること、設備上幾つも圧着ロールを
設けることは設備コストの負担が大きくなることから、
３回以下にすることが望ましい。しかも、圧着線圧は１
０〜６０ｋｇ／ｃｍが望ましい。Regarding the number of times of crimping, the relationship between the number of times of crimping and the adhesive force between the film and the steel plate when performing multi-step crimping was almost constant when the pressure was applied four times or more, and the effect was saturated. Comparing the one that was crimped only once and the one that was crimped twice, the adhesion was significantly improved by the crimping twice, but the difference was not so large between the two and three times. Practically, sufficient adhesion could be secured even with two pressure bondings. Since the effect of the number of crimps is saturated, and the provision of several crimp rolls on the equipment increases the burden of equipment cost,
It is desirable that the number is 3 times or less. Moreover, the crimping line pressure is 1
0-60 kg / cm is desirable.
【００２２】次に、第１回目の圧着時の鋼板温度を、下
層樹脂の粘着開始温度（Ｔａｓ１）〜上層樹脂の融点
（Ｔｍ２）の範囲内とした理由は、下限の下層樹脂の粘
着開始温度（Ｔａｓ１）以下では樹脂が鋼板に粘着せ
ず、密着力が確保できないだけでなく、鋼板とフィルム
の間に空気巻き込みによる微細な気泡が残り、第２回目
以降の圧着でもこの気泡が消えなかったりしてシワ発生
の原因となる場合が多いためである。一方、上限の上層
樹脂の融点（Ｔｍ２）超の鋼板温度では、上層の配向結
晶が全て壊されてしまうためである。Next, the reason why the temperature of the steel plate during the first pressure bonding is set within the range of the adhesion start temperature (Tas1) of the lower layer resin to the melting point (Tm2) of the upper layer resin is the lower limit of the adhesion start temperature of the lower layer resin. Below (Tas1), the resin does not adhere to the steel plate and the adhesion cannot be secured, and fine air bubbles remain due to air entrapment between the steel plate and the film, and these air bubbles do not disappear even after the second and subsequent pressure bonding. This is because it often causes wrinkles. On the other hand, at a steel plate temperature above the upper limit of the melting point (Tm2) of the upper layer resin, all the oriented crystals of the upper layer are destroyed.
【００２３】更に、第２回目以降の圧着時の鋼板温度
を、下層樹脂の粘着開始温度（Ｔａｓ１）〜上層樹脂の
粘着開始温度（Ｔａｓ２）の範囲内としたのは、下限の
下層樹脂の粘着開始温度（Ｔａｓ１）以下では鋼板界面
の樹脂の分子鎖が動き難く、鋼板表面にうまく馴染んで
行かず、密着力に対して効果が現れないためである。一
方、上限の上層樹脂の融解開始温度（Ｔａｓ２）超で
は、上層樹脂が圧着ロールへ粘着してしまい、ラミネー
ト皮膜の外観が悪くなるためである。Further, the temperature of the steel sheet during the second and subsequent pressure bonding is set within the range of the adhesion start temperature (Tas1) of the lower layer resin to the adhesion start temperature (Tas2) of the upper layer resin, that is, the lower limit of the adhesion of the lower layer resin. This is because at the start temperature (Tas1) or lower, the molecular chains of the resin at the steel sheet interface are difficult to move, the resin does not fit well on the steel sheet surface, and the effect on the adhesion is not exhibited. On the other hand, above the upper limit of the melting start temperature (Tas2) of the upper layer resin, the upper layer resin adheres to the pressure bonding roll, and the appearance of the laminate film deteriorates.
【００２４】次に、本発明に用いる樹脂フィルムの特性
についてであるが、まず、本発明ではラミネートに用い
る樹脂フィルムを２層構造としたものに限定している。
この理由は、ラミネート後に形成される皮膜において、
上層樹脂層が配向結晶を有し、耐食性、機械的特性、耐
熱水性を有する層として、また、下層樹脂層が上層樹脂
層と鋼板との接着層として働くように機能分担を行うた
めである。このことにより、配向結晶構造を有する皮膜
が鋼板に十分な密着力をもって積層されているラミネー
ト鋼板を製造するラミネート条件、即ち圧着時の鋼板加
熱温度を広く設定できる。Next, regarding the characteristics of the resin film used in the present invention, first, in the present invention, the resin film used for lamination is limited to a two-layer structure.
The reason for this is that in the film formed after lamination,
This is because the upper resin layer has oriented crystals and functions as a layer having corrosion resistance, mechanical properties, and hot water resistance, and the lower resin layer functions as an adhesive layer between the upper resin layer and the steel sheet. This makes it possible to set a wide range of laminating conditions for producing a laminated steel sheet in which a film having an oriented crystal structure is laminated on the steel sheet with sufficient adhesion, that is, a steel sheet heating temperature during pressure bonding.
【００２５】上層樹脂の粘着開始温度（Ｔａｓ２）−下
層樹脂の粘着開始温度（Ｔａｓ１）が５℃未満では、第
２回以降の圧着の鋼板温度を５℃未満の範囲で制御しな
ければ密着力の確保と良好な外観との両立ができない。
好ましくは１０℃以上６０℃以下とする。If the adhesion start temperature (Tas2) of the upper layer resin minus the adhesion start temperature (Tas1) of the lower layer resin is lower than 5 ° C., the adhesive strength will be obtained unless the steel plate temperature for the second and subsequent pressure bonding is controlled within the range of lower than 5 ° C. It is not possible to achieve both good quality and good appearance.
It is preferably 10 ° C. or higher and 60 ° C. or lower.
【００２６】上層樹脂の融点（Ｔｍ２）−下層樹脂の粘
着開始温度（Ｔａｓ１）が２０℃未満では、第１回目の
圧着での鋼板温度範囲が狭くなり、ラミネート条件が厳
しくなる。特に、帯状鋼板を用いた連続生産の第１回目
の圧着において、非常に厳しい鋼板の温度管理を行って
も配向結晶構造を有しかつ十分に密着した皮膜を得るこ
とが非常に難しくなる。すなわち、鋼板の長手方向と鋼
板幅方向の両方向での温度のバラツキを非常に小さくす
る必要があり、このバラツキによってしばしば生産性が
低下してしまう。一方、前述したように、本発明で２層
構造の樹脂フィルムを用いるのはラミネート条件を広く
設定できるように機能を分担させるためであり、下層樹
脂は接着剤層として働けばよい。ラミネート条件を広く
設定することから言えば、上限値の７０℃で既に２層構
造とした効果は飽和する。７０℃を超すような下層を選
定した場合には、耐熱性が低下するという問題が生じ
る。すなわち、樹脂積層鋼板を加工後加熱を受ける工程
中の上層皮膜は十分熱的に耐え得る温度範囲において、
皮膜が収縮し、鋼板からの膜ズレを生じる。したがっ
て、接着層の粘着開始温度を必要以上に下げるとラミネ
ート材としての耐熱温度が下がってしまう。好ましく
は、３０〜６０℃とする。When the melting point (Tm2) of the upper layer resin-adhesion starting temperature (Tas1) of the lower layer resin is less than 20 ° C., the temperature range of the steel sheet in the first pressure bonding becomes narrow, and the laminating conditions become strict. In particular, in the first press-bonding of continuous production using a strip-shaped steel sheet, it becomes very difficult to obtain a film having an oriented crystal structure and being sufficiently adhered, even if very strictly controlling the temperature of the steel sheet. That is, it is necessary to make extremely small variations in temperature both in the longitudinal direction of the steel sheet and in the width direction of the steel sheet, and this variation often reduces productivity. On the other hand, as described above, the reason why the two-layer structure resin film is used in the present invention is to share the functions so that the laminating conditions can be widely set, and the lower layer resin may function as an adhesive layer. In terms of setting the laminating conditions to be wide, the effect of already forming the two-layer structure is saturated at the upper limit value of 70 ° C. If a lower layer having a temperature of more than 70 ° C. is selected, there is a problem that the heat resistance is lowered. That is, in the temperature range in which the upper layer coating during the step of receiving heating after processing the resin laminated steel sheet can sufficiently withstand heat,
The film shrinks, causing film deviation from the steel plate. Therefore, if the sticking start temperature of the adhesive layer is lowered more than necessary, the heat resistant temperature of the laminate material will be lowered. The temperature is preferably 30 to 60 ° C.
【００２７】樹脂フィルムの少なくとも上層をポリエス
テル樹脂とするのが好ましい理由は、ポリエステル樹脂
の基礎特性として、ポリエチレンやポリプロピレン等の
ポリオレフィン樹脂のようなオレフィン臭がないため、
フレーバー性が良好であるという優れた内容物特性を有
するからである。The reason why it is preferable to use at least the upper layer of the resin film as the polyester resin is that the basic characteristics of the polyester resin are that it does not have an olefin odor unlike polyolefin resins such as polyethylene and polypropylene.
This is because it has an excellent content property that the flavor property is good.
【００２８】本発明において上層に使用するポリエステ
ル樹脂は、フィルム分子鎖中に二重結合を含まない飽和
ポリエステル樹脂で、周知のように飽和多価カルボン酸
と飽和多価アルコールとの重合体である。飽和多価カル
ボン酸としては、テレフタル酸、フタル酸、イソフタル
酸、コハク酸、アゼライン酸、アジピン酸、セバチン
酸、ドデカンジオン酸、ジフェニルカルボン酸、２，６
ナフタレンジカルボン酸、１，４シクロヘキサンジカル
ボン酸、無水トリメッリト酸等のカルボン酸が、また、
飽和多価アルコールとしては、エチレングリコール、４
ブタンジオール、１，５ペンタンジオール、１，６ヘキ
サンジオール、プロピレングリコール、ポリテトラメチ
レングリコール、トリメチレングリコール、トリエチレ
ングリコール、ネオペンチルグリコール、１，４シクロ
ヘキサンジメタノール、トリメチロールプロパン、ペン
タエリスリトール等があり、これらのホモポリマー、コ
ポリマーの単体及びブレンドされたポリエステル樹脂を
使用する。The polyester resin used in the upper layer in the present invention is a saturated polyester resin containing no double bond in the film molecular chain and is a polymer of a saturated polycarboxylic acid and a saturated polyhydric alcohol as is well known. .. Saturated polycarboxylic acids include terephthalic acid, phthalic acid, isophthalic acid, succinic acid, azelaic acid, adipic acid, sebacic acid, dodecanedioic acid, diphenylcarboxylic acid, 2,6
Carboxylic acids such as naphthalene dicarboxylic acid, 1,4 cyclohexanedicarboxylic acid, trimellitic anhydride,
As the saturated polyhydric alcohol, ethylene glycol, 4
Butanediol, 1,5 pentanediol, 1,6 hexanediol, propylene glycol, polytetramethylene glycol, trimethylene glycol, triethylene glycol, neopentyl glycol, 1,4 cyclohexanedimethanol, trimethylolpropane, pentaerythritol, etc. Yes, these homopolymers, copolymers alone and blended polyester resins are used.
【００２９】また、上記ポリエステル樹脂に衝撃強度、
レトルト性等の改善を目的にポリアルキレングリコール
誘導体等を添加したものも使用できる。Further, the above polyester resin has impact strength,
The thing which added the polyalkylene glycol derivative etc. for the purpose of improving retort property etc. can also be used.
【００３０】また、フレーバー性の問われない内容物用
途に対しては、上層樹脂としてポリプロピレン樹脂の使
用が可能であり、この場合、ポリエチレンを配合した
り、密着性を改善するためにマレイン酸を配合した樹脂
を使用する。In addition, for the use of contents in which flavor property is not required, polypropylene resin can be used as the upper layer resin. In this case, maleic acid is added in order to blend polyethylene or improve adhesion. Use the compounded resin.
【００３１】ポリエステル、ポリプロピレンのいずれの
樹脂においても、必要に応じて酸化防止剤、熱安定剤、
紫外線吸収剤、帯電防止剤、着色剤などを添加すること
は差し支えない。In both polyester and polypropylene resins, an antioxidant, a heat stabilizer, and
There is no problem in adding an ultraviolet absorber, an antistatic agent, a coloring agent and the like.
【００３２】下層樹脂の組成については特に限定しない
が、上層樹脂に近い成分のものが望ましい。これは、樹
脂フィルムの製造において、寸法精度が良好で比較的低
コストな共押しだしによる二軸延伸法が採用できるため
である。また、上層樹脂と下層樹脂の層間密着力が大き
くなることも利点である。コスト的には不利となるが、
単層二軸延伸樹脂フィルムにエポキシ樹脂、不飽和ポリ
エステル、アルキッド樹脂、フェノール樹脂などの熱硬
化性樹脂を下層樹脂層となるよう塗布して作った２層構
造のフィルムを用いることも差し支えない。The composition of the lower layer resin is not particularly limited, but it is desirable that the composition of the lower layer resin is similar to that of the upper layer resin. This is because in the production of the resin film, the biaxial stretching method by co-extrusion with good dimensional accuracy and relatively low cost can be adopted. Another advantage is that the interlayer adhesion between the upper layer resin and the lower layer resin is increased. It's a cost disadvantage,
It is also possible to use a film having a two-layer structure formed by applying a thermosetting resin such as an epoxy resin, an unsaturated polyester, an alkyd resin, or a phenol resin to a lower layer resin layer on a single-layer biaxially stretched resin film.
【００３３】また、本発明に用いる樹脂フィルムの厚み
は、上層樹脂の厚みが５〜４５μｍ、下層樹脂の厚みが
０．１〜５μｍ、そしてフィルムの総厚みが７〜５０μ
ｍの範囲とする。The resin film used in the present invention has an upper layer resin thickness of 5 to 45 μm, a lower layer resin thickness of 0.1 to 5 μm, and a total film thickness of 7 to 50 μm.
The range is m.
【００３４】上層樹脂の厚みは耐食性の点から決めたも
ので、製缶工程におけるフィルム損傷による耐食性劣化
を想定し、十分な内容物保存性を確保するためには５μ
ｍ未満では不十分である。一方、上限の４５μｍを超え
ても耐食性の点での効果は飽和し、経済的に不利とな
る。したがって、上層樹脂の厚みは５〜４５μｍとする
必要があり、望ましくは１０〜３０μｍの範囲とする。The thickness of the upper layer resin is determined from the viewpoint of corrosion resistance. In order to secure sufficient content storability, it is assumed that corrosion resistance deterioration due to film damage in the can making process is assumed.
If it is less than m, it is insufficient. On the other hand, even if the upper limit of 45 μm is exceeded, the effect in terms of corrosion resistance is saturated, which is economically disadvantageous. Therefore, the thickness of the upper layer resin needs to be 5 to 45 μm, preferably 10 to 30 μm.
【００３５】フィルムの下層樹脂の厚みが下限値の０．
１μｍ未満では鋼板との十分な密着性が確保できず、一
方、上限の５μｍを超えても密着性の点では飽和し、逆
に加工試験の結果では皮膜剥離が起こることがある。The lower layer resin thickness of the film is 0.
If it is less than 1 μm, sufficient adhesion to the steel sheet cannot be secured, while if it exceeds the upper limit of 5 μm, it is saturated in terms of adhesion, and conversely, film peeling may occur as a result of the working test.
【００３６】フィルム総厚みは、上層樹脂の機能及び下
層樹脂の機能を勘案しつつ実験検討した結果によるもの
で、下限の７μｍ未満では耐食性が不十分であり、上限
の５０μ超では耐食性の点での効果が飽和し、経済的に
不利となる。したがって、フィルムの総厚みは７〜５０
μｍとする必要があり、望ましくは１２〜３３μｍの範
囲とする。The total thickness of the film is based on the results of experiments conducted while considering the function of the upper layer resin and the function of the lower layer resin. If the lower limit is less than 7 μm, the corrosion resistance is insufficient, and if it exceeds the upper limit of 50 μ, the corrosion resistance is low. The effect of is saturated and it becomes economically disadvantageous. Therefore, the total thickness of the film is 7-50.
The thickness is required to be in the range of 12 to 33 μm.
【００３７】本発明に使用する鋼板は、Ｓｎめっき・Ｎ
ｉめっき・Ｓｎ／Ｎｉめっきのそれぞれめっき層の上層
に化成処理を施しためっき鋼板及び電解クロム酸処理鋼
板である。電解クロム処理鋼板は通称ＴＦＳ（Ｔｉｎ
Ｆｒｅｅ Ｓｔｅｅｌ）と呼ばれているクロム・クロメ
ート処理鋼板で、付着量は金属クロムが３０〜１５０ｍ
ｇ／ｍ2 、水和酸化クロムが金属クロム換算で５〜２０
ｍｇ／ｍ2 である。Ｓｎめっき鋼板、Ｓｎ／Ｎｉめっき
鋼板、Ｎｉめっき鋼板の各々のめっき皮膜の上層に施す
化成処理は、前述したＴＦＳのようなクロム、クロメー
ト処理、及び従来からぶりきの化成処理として用いられ
ているＣＤＣ処理と呼ばれるクロメート処理等である。
容器は絞り等の加工が行われるため、鋼板と皮膜の密着
性が要求される。このため、鋼板の化成処理が重要とな
る。The steel sheet used in the present invention is Sn plating / N
These are a plated steel sheet and an electrolytic chromic acid treated steel sheet in which chemical conversion treatment is applied to the upper layer of each of the i-plated and Sn / Ni plated layers. Electrolytic chromium treated steel plate is commonly known as TFS (Tin
It is a chromium / chromate treated steel plate called Free Steel, and the adhesion amount is 30 to 150 m of chromium metal.
g / m 2 , hydrated chromium oxide is 5 to 20 in terms of metallic chromium
It is mg / m 2 . The chemical conversion treatment applied to the upper layer of the plating film of each of Sn-plated steel sheet, Sn / Ni-plated steel sheet, and Ni-plated steel sheet has been conventionally used as chromium, chromate treatment such as TFS described above, and tinplate chemical conversion treatment. It is a chromate treatment called CDC treatment.
Since processing such as drawing is performed on the container, the adhesion between the steel plate and the film is required. Therefore, the chemical conversion treatment of the steel sheet is important.
【００３８】本発明における板の加熱方法としては、加
熱した炉の中を通す方法、鋼板に通電して加熱する通電
加熱方法、誘導加熱方法、加熱されたロールに接触させ
て加熱する方法等が使用できる。Examples of the method for heating the plate in the present invention include a method of passing it through a heated furnace, an electric heating method of energizing and heating a steel sheet, an induction heating method, a method of heating by contacting a heated roll, and the like. Can be used.
【００３９】熱接着法でポリエステル或いはポリプロピ
レンを積層した鋼板を製造する場合、鋼板と皮膜の密着
性を確保するためには圧着後の冷却条件も重要となる。
ラミネート後ガラス転移点以下に急冷されないと、ラミ
ネートの加熱で溶融した鋼板界面の樹脂が再結晶化して
無配向結晶となり、密着性の低下をまねくことから、最
終圧着終了後、速やかに樹脂のガラス転移点以下に冷却
するのが良い。急冷の方法としては、水に浸漬して急冷
する方法、冷えた空気を吹き付けて急冷する方法、空気
と水を同時に吹きかけて急冷する方法、及びこれらの併
用等が採用できるが、いずれの方法を採用するにしろ、
冷却速度は十分に確保する必要がある。When manufacturing a steel sheet in which polyester or polypropylene is laminated by the heat-bonding method, the cooling condition after pressure bonding is also important in order to secure the adhesion between the steel sheet and the film.
If it is not rapidly cooled below the glass transition point after lamination, the resin at the steel sheet interface melted by the heating of the laminate will recrystallize and become non-oriented crystals, leading to a decrease in adhesion. It is better to cool below the transition point. As the method of quenching, a method of immersing in water and quenching, a method of quenching by blowing cold air, a method of simultaneously quenching by blowing air and water, and a combination thereof can be adopted, but either method can be adopted. Whether to adopt it,
It is necessary to secure a sufficient cooling rate.
【００４０】[0040]
【実施例】通電加熱方式で加熱したＴＦＳ（板厚０．２
０ｍｍ、テンパーＤＲ９、金属クロム８０ｍｇ／ｍ2 、
水和酸化クロム１５ｍｇ／ｍ2 ）の両面に、二軸延伸製
膜法で作った樹脂フィルムを一回ないし２回両面同時圧
着した後水中急冷する熱接着法で樹脂被覆鋼板を得た。
なお、実施例に用いた２層構造ポリエステルフィルムＡ
〜Ｅの諸特性を表２に、２層構造ポリプロピレンフィル
ムＦ〜Ｊの諸特性を表３に示す。ラミネート条件及びラ
ミネートで得られた皮膜の評価結果は表４〜７に示した
通りである。[Example] TFS (plate thickness 0.2
0 mm, temper DR9, metal chrome 80 mg / m 2 ,
A resin-coated steel sheet was obtained by a heat-bonding method in which a resin film made by a biaxially stretched film forming method was pressed simultaneously on both sides once or twice on both surfaces of hydrated chromium oxide (15 mg / m 2 ) and then rapidly cooled in water.
The two-layer structure polyester film A used in the examples
Tables 2 to 3 show various characteristics of E to E, and Table 3 shows various characteristics of the two-layer structure polypropylene films F to J. The laminating conditions and the evaluation results of the film obtained by laminating are as shown in Tables 4 to 7.
【００４１】[0041]
【表２】 [Table 2]
【００４２】[0042]
【表３】 [Table 3]
【００４３】[0043]
【表４】 [Table 4]
【００４４】[0044]
【表５】 [Table 5]
【００４５】[0045]
【表６】 [Table 6]
【００４６】[0046]
【表７】 [Table 7]
【００４７】得られた樹脂被覆鋼板を次のように評価し
た。The resin-coated steel sheet thus obtained was evaluated as follows.
【００４８】（１）外観 得られたラミネート鋼板の外観を○、×で評価した。(1) Appearance The appearance of the obtained laminated steel sheet was evaluated by O and X.
【００４９】（２）密着性 ピール試験を行い、膜破れしたものを○、しなかったも
のを×として評価した。なお、ピール試験条件は、幅１
０ｍｍ、角度１８０°、引っ張り速度１００ｍｍ／ｍｉ
ｎとした。(2) Adhesiveness A peel test was conducted, and the film breakage was evaluated as ◯, and the film breakage was evaluated as x. The peel test condition is a width of 1
0 mm, angle 180 °, pulling speed 100 mm / mi
n.
【００５０】（３）加工密着性 加工密着性は表８に示す条件の２段絞り後前記（２）の
密着性と同一のピール試験を行い、密着力を調べた。密
着力０．１ｋｇ／１０ｍｍ以上を○、０．１ｋｇ／１０
ｍｍ未満を×とした。(3) Processing adhesion The processing adhesion was examined after the two-stage drawing under the conditions shown in Table 8 and the same peel test as that of the above (2) was carried out to examine the adhesion. Adhesion of 0.1 kg / 10 mm or more is ○, 0.1 kg / 10
Less than mm was defined as x.
【００５１】[0051]
【表８】 [Table 8]
【００５２】（４）耐熱性 得られた最終再絞り缶を上層樹脂の融点（Ｔｍ２）−５
０℃の温度に１０分間加熱し、膜ズレの状況を肉眼で観
察し、膜ズレの状況を○、△、×の３段階に分けて評価
した。(4) Heat resistance The obtained final redrawing can was melted at the melting point (Tm2) -5 of the upper layer resin.
The film was heated to a temperature of 0 ° C. for 10 minutes, the condition of the film deviation was visually observed, and the condition of the film deviation was evaluated by classifying it into three grades of ◯, Δ and ×.
【００５３】（５）耐食性 得られた最終再絞り缶に３％酢酸水を充填し、５０℃で
３ヵ月貯蔵後開缶し、缶内面の腐食状況を肉眼で観察
し、腐食の状況を○、△、×の３段階に分けて評価し
た。(5) Corrosion resistance The obtained final re-squeezed can was filled with 3% acetic acid water, stored at 50 ° C. for 3 months and opened, and the inside of the can was visually observed for corrosion, and the corrosion was evaluated as ○. The evaluation was made in three grades, Δ, ×.
【００５４】[0054]
【発明の効果】本発明により製造された樹脂フィルム被
覆鋼板は加工密着性に優れ、かつ製缶後の耐食性が優れ
た絞り缶を安価に製造することができる。また、絞り缶
だけでなくエンド、イージーオープン蓋、５ｇａｌ缶そ
の他の容器用材料としても広く使用できる。さらに、建
材、家電、自動車等の用途でも使用可能な樹脂被覆鋼板
を得ることができる。EFFECTS OF THE INVENTION The steel sheet coated with the resin film produced according to the present invention can be manufactured at a low cost with excellent squeezing adhesion and excellent corrosion resistance after the can is manufactured. Further, it can be widely used not only as a squeeze can but also as a material for containers such as an end, an easy open lid, a 5gal can and the like. Further, it is possible to obtain a resin-coated steel sheet that can be used in applications such as building materials, home appliances, and automobiles.
Claims (3)
対し上層樹脂の粘着開始温度（Ｔａｓ２）が５℃以上高
く、かつ、上層樹脂の融点（Ｔｍ２）が下層樹脂の粘着
開始温度（Ｔａｓ１）よりも２０〜７０℃高い２層構造
の樹脂フィルムを用い、下層樹脂の粘着開始温度（Ｔａ
ｓ１）〜上層樹脂の融点（Ｔｍ２）の範囲内に加熱され
た鋼板の片面あるいは両面に第一回目の圧着を行い、次
いで下層樹脂の粘着開始温度（Ｔａｓ１）〜上層樹脂の
粘着開始温度（Ｔａｓ２）の範囲内の鋼板温度で第二回
目以降の圧着を行う多段圧着を特徴とする加工密着性に
優れた樹脂被覆鋼板の製造方法。1. The adhesion starting temperature (Tas2) of the upper layer resin is 5 ° C. or more higher than the adhesion starting temperature (Tas1) of the lower layer resin, and the melting point (Tm2) of the upper layer resin is the adhesion starting temperature (Tas1) of the lower layer resin. A resin film having a two-layer structure that is 20 to 70 ° C. higher than that of the lower layer resin is used.
s1) to the melting point (Tm2) of the upper layer resin, the first pressure bonding is performed on one side or both sides of the steel sheet heated, and then the adhesion starting temperature (Tas1) of the lower layer resin to the adhesion starting temperature (Tas2) of the upper layer resin. ) A method for producing a resin-coated steel sheet having excellent work adhesion, which is characterized by multi-step pressure bonding in which the second and subsequent pressure bondings are performed at a steel plate temperature within the range.
上層樹脂がポリエステル樹脂であることを特徴とする請
求項１記載の加工密着性に優れた樹脂被覆鋼板の製造方
法。2. The method for producing a resin-coated steel sheet having excellent work adhesion according to claim 1, wherein at least the upper layer resin of the two-layer structure resin film is a polyester resin.
上層樹脂がポリプロピレン樹脂であることを特徴とする
請求項１記載の加工密着性に優れた樹脂被覆鋼板の製造
方法。3. The method for producing a resin-coated steel sheet excellent in process adhesion according to claim 1, wherein at least an upper layer resin of the two-layer structure resin film is a polypropylene resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10236092A JP3125157B2 (en) | 1992-03-30 | 1992-03-30 | Manufacturing method of resin coated steel sheet with excellent processing adhesion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10236092A JP3125157B2 (en) | 1992-03-30 | 1992-03-30 | Manufacturing method of resin coated steel sheet with excellent processing adhesion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05269858A true JPH05269858A (en) | 1993-10-19 |
| JP3125157B2 JP3125157B2 (en) | 2001-01-15 |
Family
ID=14325299
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10236092A Expired - Fee Related JP3125157B2 (en) | 1992-03-30 | 1992-03-30 | Manufacturing method of resin coated steel sheet with excellent processing adhesion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3125157B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007045510A (en) * | 2005-08-12 | 2007-02-22 | Jfe Steel Kk | Laminated steel sheet for two-piece can, and two-piece laminated can |
| JP2012529389A (en) * | 2009-06-08 | 2012-11-22 | アルセロルミタル・インベステイガシオン・イ・デサロジヨ・エセ・エレ | Composite metal and polymer parts, especially in the automotive field |
-
1992
- 1992-03-30 JP JP10236092A patent/JP3125157B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007045510A (en) * | 2005-08-12 | 2007-02-22 | Jfe Steel Kk | Laminated steel sheet for two-piece can, and two-piece laminated can |
| JP2012529389A (en) * | 2009-06-08 | 2012-11-22 | アルセロルミタル・インベステイガシオン・イ・デサロジヨ・エセ・エレ | Composite metal and polymer parts, especially in the automotive field |
| KR101424324B1 (en) * | 2009-06-08 | 2014-08-06 | 아르셀러미탈 인베스티가시온 와이 데살롤로 에스엘 | Composite metal and polymer part, use in particular in the automotive field |
| US9950497B2 (en) | 2009-06-08 | 2018-04-24 | Arcelormittal Investigacion Y Desarrollo | Composite metal and polymer part |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3125157B2 (en) | 2001-01-15 |
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