JP6643808B2 - Metal can manufacturing method - Google Patents
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本発明は、表面処理鋼板、金属容器、表面処理鋼板の製造方法、難錆性付与方法、すべり性改善方法、アブレーション防止方法、傷入り性改善方法、及び耐薬品性付与方法に関する。 The present invention relates to a surface-treated steel sheet, a metal container, a method for producing a surface-treated steel sheet, a method for imparting rust resistance, a method for improving slipperiness, a method for preventing ablation, a method for improving scratch resistance, and a method for imparting chemical resistance.
１８リッター缶をはじめとする金属容器には、ブリキ（以下、ＥＴともいう。）、ティンフリースチール（以下、ＴＦＳともいう。）、ティンニッケルスチール（以下、ＴＮＳともいう。）等の鋼板が使用されている。
ＥＴ、ＴＦＳ、ＴＮＳを用いた缶としては、無地板を製缶してなる無地缶や、鋼板の内外面に様々な塗料をコーティングして製缶してなる塗装缶が挙げられる。無地缶は、経時的な缶の錆を防止することは難しいという欠点がある。
Steel plates such as tin (hereinafter, also referred to as ET), tin-free steel (hereinafter, also referred to as TFS), and tin-nickel steel (hereinafter, also referred to as TNS) are used for metal containers such as 18-liter cans. Have been.
Examples of cans using ET, TFS, and TNS include plain cans made from a plain plate and painted cans made by coating various paints on the inner and outer surfaces of a steel plate. Solid cans have the disadvantage that it is difficult to prevent rust on the can over time.
また、缶の天板部分には持ち運びの為の手環や持ち手が溶接により取り付けられている。さらに、取り出し口にも金属加工した口金をカシメる事により取り付けられている。
塗装缶を製造する場合、溶接を可能にするために溶接部分は塗装を抜かなければならない。このような製缶上の制約の中、溶接部分の塗装抜き部分の錆を防止することは難しく、製缶時に補修ニスを塗る事で錆びの発生を防いでいる。
A hand ring and a handle for carrying are attached to the top plate of the can by welding. Furthermore, it is attached to the take-out port by caulking a metal-processed base.
When manufacturing painted cans, the welds must be unpainted to enable welding. Under such restrictions on can-making, it is difficult to prevent rust on the unpainted portion of the welded portion, and rust is prevented by applying a repair varnish during can-making.
耐食性と加工性を備え、耐食性付与を目的とした前処理やアフター塗装の省略が可能な表面処理鋼板として、特許文献１に記載の表面処理鋼板が提案されている。係る表面処理鋼板は、中和された酸基を有する重合体セグメントとポリシロキサンセグメントとが化学結合してなる複合樹脂のポリシロキサンセグメントと、炭素数１〜３のアルキルトリアルコキシシランの縮合物由来のポリシロキサンセグメントとが珪素−酸素結合を介して結合している複合樹脂を使用したものである。 A surface-treated steel sheet described in Patent Literature 1 has been proposed as a surface-treated steel sheet having corrosion resistance and workability and capable of omitting pretreatment and after-coating for the purpose of imparting corrosion resistance. Such a surface-treated steel sheet is derived from a condensate of a polysiloxane segment of a composite resin in which a polymer segment having a neutralized acid group and a polysiloxane segment are chemically bonded, and an alkyltrialkoxysilane having 1 to 3 carbon atoms. And a composite resin in which the polysiloxane segment is bonded via a silicon-oxygen bond.
更に、難錆性・すべり性・アブレーション（輸送等により鋼板表面に発生する黒点）・傷入り性・耐薬品性等の諸物性が改善された表面処理鋼板が求められている。
本発明は、上記事情に鑑みてなされたものであって、難錆性、すべり性、アブレーション（輸送等により鋼板表面に発生する黒点）、傷入り性、耐薬品性等の諸物性を改善させた鋼板、及びその製造方法を提供する。
また、本発明は、最終製品として、本発明の表面処理鋼板を用いた金属容器を提供する。
Further, there is a need for a surface-treated steel sheet having improved physical properties such as rust resistance, slip properties, ablation (black spots generated on the steel sheet surface due to transportation, etc.), scratch resistance, and chemical resistance.
The present invention has been made in view of the above circumstances, and improves various physical properties such as rust resistance, slip properties, ablation (black spots generated on the steel sheet surface due to transportation, etc.), scratching properties, and chemical resistance. And a method of manufacturing the same.
Further, the present invention provides a metal container using the surface-treated steel sheet of the present invention as a final product.
本発明者らは、本発明者らは、上記課題を解決すべく鋭意研究した結果、チタン酸化被膜により、難錆性・すべり性・アブレーション（輸送等により鋼板表面に発生する黒点）・傷入り性・耐薬品性等の諸物性の改善に成功し本発明を完成するに至った。 The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, the titanium oxide film has caused rust resistance, slippage, ablation (black spots generated on the steel sheet surface due to transportation, etc.), and scratches. The inventors succeeded in improving various properties such as properties and chemical resistance, and completed the present invention.
すなわち、本発明は、下記の特徴を有する表面処理鋼板、金属容器、表面処理鋼板の製造方法、難錆性付与方法、すべり性改善方法、アブレーション防止方法、傷入り性改善方法、及び耐薬品性付与方法を提供するものである。 That is, the present invention provides a surface-treated steel sheet, a metal container, a method for producing a surface-treated steel sheet, a method for imparting rust resistance, a method for improving slipperiness, a method for preventing ablation, a method for improving scratch resistance, and chemical resistance having the following characteristics. An application method is provided.
［１］鋼板又はめっき鋼板と、該鋼板又はめっきの少なくとも一方の面に形成されたチタン酸化被膜を備えたことを特徴とする表面処理鋼板。
［２］前記チタン酸化被膜は、下記式（１）で表される構造を有する前記［１］に記載の表面処理鋼板。
［３］前記［１］又は［２］に記載の表面処理鋼板を用いたことを特徴とする金属容器。
[1] A surface-treated steel sheet comprising: a steel sheet or a plated steel sheet; and a titanium oxide film formed on at least one surface of the steel sheet or the plated steel sheet.
[2] The surface-treated steel sheet according to [1], wherein the titanium oxide film has a structure represented by the following formula (1).
[3] A metal container using the surface-treated steel sheet according to [1] or [2].
［４］鋼板若しくはめっき鋼板又はこれらの加工品の表面に有機チタン化合物を付着させて、熱処理する表面処理工程を有することを特徴とする表面処理鋼板の製造方法。
［５］前記有機チタン化合物は、チタンアルコキシド、チタンキレート、及びチタンオリゴマーからなる群から選ばれる少なくとも一種である前記［４］に記載の表面処理鋼板の製造方法。
［６］前記表面処理工程は、めっき処理後に行われる前記［４］又は［５］に記載の表面処理鋼板の製造方法。
[4] A method for producing a surface-treated steel sheet, comprising a surface treatment step of applying an organotitanium compound to the surface of a steel sheet, a plated steel sheet, or a processed product thereof and performing a heat treatment.
[5] The method for producing a surface-treated steel sheet according to [4], wherein the organic titanium compound is at least one selected from the group consisting of titanium alkoxide, titanium chelate, and titanium oligomer.
[6] The method for producing a surface-treated steel sheet according to [4] or [5], wherein the surface treatment step is performed after plating.
［７］鋼板若しくはめっき鋼板又はこれらの加工品に難錆性を付与する方法であって、
鋼板若しくはめっき鋼板又はこれらの加工品の表面に有機チタン化合物を付着させて、熱処理する表面処理工程を有することを特徴とする難錆性付与方法。
［８］鋼板若しくはめっき鋼板又はこれらの加工品のすべり性を改善する方法であって、
鋼板若しくはめっき鋼板又はこれらの加工品の表面に有機チタン化合物を付着させて、熱処理する表面処理工程を有することを特徴とするすべり性改善方法。
［９］鋼板若しくはめっき鋼板又はこれらの加工品に生じるアブレーションの発生を防止する方法であって、
鋼板若しくはめっき鋼板又はこれらの加工品の表面に有機チタン化合物を付着させて、熱処理する表面処理工程を有することを特徴とするアブレーション防止方法。
［１０］鋼板若しくはめっき鋼板又はこれらの加工品の傷入り性を改善する方法であって、
鋼板若しくはめっき鋼板又はこれらの加工品の表面に有機チタン化合物を付着させて、熱処理する表面処理工程を有することを特徴とする傷入り性改善方法。
［１１］鋼板若しくはめっき鋼板又はこれらの加工品に耐薬品性を付与する方法であって、
鋼板若しくはめっき鋼板又はこれらの加工品の表面に有機チタン化合物を付着させて、熱処理する表面処理工程を有することを特徴とする耐薬品性付与方法。
[7] A method for imparting rust resistance to a steel sheet or a plated steel sheet or a processed product thereof,
A method for imparting rust resistance, comprising a surface treatment step of performing a heat treatment by attaching an organotitanium compound to the surface of a steel plate, a plated steel plate, or a processed product thereof.
[8] A method for improving the slip property of a steel sheet or a plated steel sheet or a processed product thereof,
A method for improving slipperiness, comprising a surface treatment step in which an organic titanium compound is adhered to the surface of a steel sheet, a plated steel sheet, or a processed product of these, and a heat treatment is performed.
[9] A method for preventing occurrence of ablation occurring in a steel plate or a plated steel plate or a processed product thereof,
An ablation prevention method, comprising a surface treatment step of performing a heat treatment by attaching an organic titanium compound to the surface of a steel plate, a plated steel plate, or a processed product thereof.
[10] A method for improving the scratch resistance of a steel sheet or a plated steel sheet or a processed product thereof,
A method for improving scratch resistance, comprising a surface treatment step of heat-treating a surface of a steel plate, a plated steel plate, or a processed product thereof by attaching an organic titanium compound.
[11] A method for imparting chemical resistance to a steel sheet or a plated steel sheet or a processed product thereof,
A method for imparting chemical resistance, comprising a surface treatment step of performing heat treatment by attaching an organic titanium compound to the surface of a steel sheet, a plated steel sheet, or a processed product of these.
本発明によれば、難錆性、すべり性、アブレーション（輸送等により鋼板表面に発生する黒点）、傷入り性、耐薬品性等の諸物性を改善させた鋼板、及びその製造方法、並びに、該鋼板を用いた金属容器を提供することができる。 According to the present invention, a steel sheet having improved physical properties such as rust resistance, slip properties, ablation (black spots generated on the steel sheet surface due to transportation, etc.), scratch resistance, chemical resistance, and a method for producing the same, and A metal container using the steel plate can be provided.
＜表面処理鋼板の製造方法＞
本発明の表面処理鋼板の製造方法は、鋼板若しくはめっき鋼板又はこれらの加工品の表面に有機チタン化合物を付着させて、熱処理する表面処理工程を有する。
本発明において、めっき鋼板としては、ＥＴ、ＴＦＳ、ＴＮＳ等が挙げられる。鋼板加工品又はめっき鋼板加工品としては、例えば、座金、口金等が挙げられる。
<Production method of surface-treated steel sheet>
The method for producing a surface-treated steel sheet according to the present invention includes a surface treatment step in which an organotitanium compound is attached to the surface of a steel sheet, a plated steel sheet, or a processed product of these, and heat-treated.
In the present invention, examples of the plated steel sheet include ET, TFS, and TNS. Examples of the processed steel sheet or plated steel sheet include a washer and a base.
ＥＴは、鋼／鉄−錫合金／錫めっき／クロム水和酸化物／油膜の層構成を有している。ＥＴの鋼を除く構成部分は、防錆効果があると考えられているが、鋼板を加工する事で鋼板表面にクラック等の傷が入る場合があり、係る場合、鉄は錫よりイオン化傾向が大きいため、容易に鉄が酸化され、錆が発生する。 ET has a layer structure of steel / iron-tin alloy / tin plating / chromium hydrated oxide / oil film. The components other than ET steel are considered to have a rust-preventive effect.However, processing steel plates may cause scratches such as cracks on the steel plate surface.In such cases, iron tends to ionize more than tin. Due to its large size, iron is easily oxidized and rust is generated.
ＴＦＳは、鋼／金属クロム／クロム水和酸化物／油膜の層構成を有している。ＴＦＳの鋼を除く構成部分は、防錆効果はあると考えられるが、鋼板を加工する事で鋼板表面にクラック等の傷が入り、錆が発生する。 TFS has a layer structure of steel / chromium metal / chromium hydrated oxide / oil film. Although the components of TFS other than steel are considered to have a rust-preventing effect, processing the steel plate causes scratches such as cracks on the surface of the steel plate and generates rust.
ＴＮＳは、鋼/ニッケル・錫メッキ/金属クロム/クロム水和酸化物／油膜の構成となっており、ＴＮＳの鋼を除く構成部分は、防錆効果はあると考えられるが、鋼板を加工する事で鋼板表面にクラック等の傷が入り、錆が発生する。 TNS is composed of steel / nickel / tin plating / chromium metal / chromium hydrated oxide / oil film. The components of TNS except for steel are considered to have a rust-preventive effect, but the steel plate is processed. As a result, scratches such as cracks are made on the steel sheet surface, and rust is generated.
このように、ＥＴ、ＴＦＳ、ＴＮＳとも加工等によりクラック等の傷が入ると、容易に錆が発生するため、鋼板のみでは錆の発生を抑える事が難しいため、容器化するに当たり鋼板の外面塗装やＰＥＴフィルムのラミネートを行うこととなる。
１８リッター缶の場合、ＥＴは無地缶が多いが、ＴＦＳ、ＴＮＳの場合、外面塗装を行うことにより、すべり性や傷入り性等の表面物性を改善しなければ製缶出来ない。外面塗装やラミネートを行う場合、溶接部分は塗装やラミネートを抜く必要があり、製缶時に溶接部分を補修ニスの吹付や部分塗装により補修している。
As described above, when ET, TFS, and TNS are all damaged due to cracks or the like due to processing or the like, rust is easily generated. Therefore, it is difficult to suppress rust with steel sheets alone. Or lamination of a PET film.
In the case of 18-liter cans, ETs are often plain cans, but in the case of TFS and TNS, cans cannot be made unless the surface properties such as slipping and scratching are improved by coating the outer surface. When performing exterior painting or laminating, it is necessary to remove the coating or laminate from the welded portion, and the welded portion is repaired by spraying a repair varnish or partial coating during can manufacturing.
容器には、持ち運びの為の手環が座金により天板に溶接され、持ち手が天板に直接溶接されている。また、注ぎ口には口金がはめ込まれており、これらの容器部品には多くの場合ＥＴが使用されている。前述した通りこれらの部品にも錆問題が発生するため、錆び発生の少ないアルミやステンレスを使った容器部品を使用するケースもある。また製缶時において補修ニスの塗装も行われている。 In the container, a hand ring for carrying is welded to the top plate by a washer, and a handle is directly welded to the top plate. The spout is fitted with a base, and ET is often used for these container parts. As described above, since rust problems occur in these parts, there are cases where container parts made of aluminum or stainless steel, which generate less rust, are used. Also, repair varnish is applied during can making.
後述するように、本発明の表面処理鋼板の製造方法によれば、難錆性を有し、表面処理工程後でも溶接可能であり、すべり性や耐スクラッチ性（傷入り性）に優れた表面処理鋼板を製造できる。 As described below, according to the method for producing a surface-treated steel sheet of the present invention, the surface has rust resistance, can be welded even after the surface treatment step, and has excellent slip resistance and scratch resistance (scratch resistance). Can produce treated steel sheets.
前記表面処理工程において、チタンアルコキシド、チタンキレート、及びチタンオリゴマーからなる群から選ばれる少なくとも一種の有機チタン化合物を、鋼板若しくはめっき鋼板又はこれらの加工品の表面に付着させ、熱処理することで、有機チタン化合物に加水分解や熱分解を生じさせ、鋼板若しくはめっき鋼板又はこれらの加工品の表面にチタン酸化被膜を生成させることが好ましい。 In the surface treatment step, at least one organic titanium compound selected from the group consisting of titanium alkoxide, titanium chelate, and titanium oligomer is attached to the surface of a steel plate or a plated steel plate or a processed product of these, and heat-treated to form an organic compound. It is preferable to cause hydrolysis or thermal decomposition of the titanium compound to generate a titanium oxide film on the surface of a steel plate, a plated steel plate, or a processed product thereof.
処理剤として使用可能な有機チタン化合物としては、チタンアルコキシド、チタンキレート、チタンオリゴマーが挙げられる。
チタンアルコキシドとしては、テトラアルコキシチタンが好ましく、テトライソプロピルチタネート、テトラノルマルブチルチタネート、テトラオクチルチタネート等が挙げられる。
チタンキレートとしては、前記テトラアルコキシチタンにキレート剤が配位したものが好ましく、溶剤系チタンキレートと水系チタンキレートが挙げられる。
溶剤系チタンキレートとしては、チタンアセチルアセトネート、チタンテトラアセチルアセトネート、チタンエチルアセトアセテート、リン酸チタン化合物、チタンオクチレングリコレート、チタンエチルアセトアセテートが挙げられる。
水系チタンキレートとしては、チタンラクテートアンモニウム塩、チタンラクテート、チタントリエタノールアミネート等が挙げられる。
チタンオリゴマーは、構成単位中にチタン原子を含む重合度が２以上のオリゴマーであり、前記テトラアルコキシチタン、又は前記チタンキレートを加水分解により縮合させたものが好ましく、ブチルチタネートダイマー等が挙げられる。
中でも、防錆効果が有機チタン化合物のチタン含有成分比率に比例する傾向がみられる点から、チタンアルコキシド、チタンアルコキシドを加水分解により縮合させたチタンオリゴマーが好ましい。水系としては、水系チタンキレートのチタンラクテートが好ましい。
Examples of the organotitanium compound that can be used as the treating agent include titanium alkoxide, titanium chelate, and titanium oligomer.
As the titanium alkoxide, tetraalkoxy titanium is preferable, and examples thereof include tetraisopropyl titanate, tetra-n-butyl titanate, and tetraoctyl titanate.
The titanium chelate is preferably one in which a chelating agent is coordinated to the tetraalkoxy titanium, and examples thereof include a solvent-based titanium chelate and an aqueous titanium chelate.
Examples of the solvent-based titanium chelate include titanium acetylacetonate, titanium tetraacetylacetonate, titanium ethyl acetoacetate, a titanium phosphate compound, titanium octylene glycolate, and titanium ethyl acetoacetate.
Examples of the aqueous titanium chelate include titanium lactate ammonium salt, titanium lactate, and titanium triethanol aminate.
The titanium oligomer is an oligomer containing a titanium atom in a constituent unit and having a degree of polymerization of 2 or more, and is preferably one obtained by condensing the above tetraalkoxy titanium or the above titanium chelate by hydrolysis, such as butyl titanate dimer.
Among them, titanium alkoxides and titanium oligomers obtained by condensing titanium alkoxides by hydrolysis are preferable because the rust prevention effect tends to be proportional to the titanium-containing component ratio of the organic titanium compound. As the aqueous system, titanium lactate of an aqueous titanium chelate is preferable.
有機チタン化合物の希釈溶媒としては、水、アルコール、エステル、ケトン、芳香族炭化水素、脂肪族炭化水素等が挙げられる。用いる有機チタン化合物により、溶解性が異なるため、適正な溶媒の選定が必要である。水系有機チタン化合物は水、溶剤系有機チタン化合物はアルコールを選定するのが作業環境面からみて好ましい。 Examples of the diluting solvent for the organic titanium compound include water, alcohols, esters, ketones, aromatic hydrocarbons, and aliphatic hydrocarbons. Since the solubility differs depending on the organic titanium compound used, it is necessary to select an appropriate solvent. It is preferable to select water as the water-based organic titanium compound and alcohol as the solvent-based organic titanium compound from the viewpoint of working environment.
前記表面処理工程において形成されるチタン酸化被膜の膜厚は、２０〜５００ｎｍが好ましく、２０〜２００ｎｍがより好ましく、２０〜５０ｎｍが特に好ましい。使用する有機チタン化合物に応じて最適な塗膜厚を決定しなければいけない。より緻密なチタン酸化被膜を形成させるためには、１回に付ける膜厚を抑え、塗布→熱処理を繰り返す重ね処理を行うことが好ましく、係る重ね処理により効果はさらに向上する。
既存鋼板の処理であれば金属板コーティング装置で塗装することが現実的であり、好ましくは１〜１０％、より好ましくは１〜５％の有機チタン化合物溶液をロールコーターで塗装し、オーブンで熱処理することが好ましい。
有機チタン化合物の希釈溶媒としては造膜性を考慮し選定する必要があるが、コーティングラインに見合う乾燥度合いのアルコール系溶媒が好ましい。
鋼板加工品であれば、様々な形状が考えられるため、浸漬方式が好ましい。更に、鋼板加工品は加工時にクラック等の傷が入りやすいため、浸漬法による重ね処理がより好ましい。有機チタン化合物に応じて最適な塗膜厚を得るため、１〜１０％の有機チタン溶液で処理することが好ましい。浸漬処理の場合は液切りを十分に行い、一次乾燥後または液切り後直ちに熱処理することが好ましい。
希釈溶媒としては、アルコール系が好ましいが、速乾アルコールだと乾燥時に蒸発潜熱が急速に奪われ、その結果としてブラッシング現象（白化）が起こるため、遅乾アルコールのブレンドにより乾燥の調整が必要である。
The thickness of the titanium oxide film formed in the surface treatment step is preferably 20 to 500 nm, more preferably 20 to 200 nm, and particularly preferably 20 to 50 nm. The optimum coating thickness must be determined according to the organic titanium compound used. In order to form a denser titanium oxide film, it is preferable to perform a stacking process in which the thickness applied at one time is suppressed and coating and heat treatment are repeated, and the effect is further improved by such a stacking process.
For the treatment of existing steel sheets, it is realistic to apply a metal plate coating apparatus, and preferably apply a 1 to 10%, more preferably 1 to 5% organic titanium compound solution with a roll coater and heat treat in an oven. Is preferred.
It is necessary to select a diluting solvent for the organotitanium compound in consideration of film forming properties, but an alcohol-based solvent having a drying degree suitable for the coating line is preferable.
If it is a steel plate processed product, various shapes can be considered, and therefore, the dipping method is preferable. Furthermore, since the processed steel sheet is liable to be damaged such as cracks during processing, the lapping treatment by the dipping method is more preferable. In order to obtain an optimum coating thickness according to the organic titanium compound, it is preferable to perform treatment with a 1 to 10% organic titanium solution. In the case of the immersion treatment, it is preferable that the liquid is sufficiently drained, and the heat treatment is performed immediately after the primary drying or the liquid draining.
As the diluting solvent, an alcohol solvent is preferable. However, since the latent heat of evaporation is rapidly taken away during drying when using a quick-drying alcohol, a brushing phenomenon (whitening) occurs as a result. is there.
有機チタン化合物の熱処理はチタン酸化被膜を生成する上で重要な要素である。有機チタン化合物は、熱処理により加水分解や熱分解が生じ、チタン酸化被膜を生成する。
処理温度は高いほど良いが、種々検討の結果、コーティング法・浸漬法ともに、１５０〜２２０℃が好ましく、１８０℃〜２００℃がより好ましい。
処理時間は長いほど良いが、種々検討の結果、コーティング法・浸漬法ともに、１〜１５分が好ましく、２〜１０分がより好ましい。
The heat treatment of the organic titanium compound is an important factor in forming a titanium oxide film. The organic titanium compound undergoes hydrolysis or thermal decomposition by heat treatment, and forms a titanium oxide film.
The higher the treatment temperature, the better, but as a result of various studies, both the coating method and the dipping method are preferably at 150 to 220 ° C, more preferably at 180 to 200 ° C.
The longer the treatment time, the better, but as a result of various studies, the coating method and the immersion method are preferably 1 to 15 minutes, more preferably 2 to 10 minutes.
前記表面処理工程において、有機チタン化合物からチタン酸化被膜を形成するプロセスを下記式（２）に示す。
鋼板製造時の化学処理の一つとして前記表面処理を行う場合は、ＥＴ、ＴＦＳ、ＴＮＳ共にめっき後の化学処理の一つとして有機チタン処理を行うことが好ましく、油膜処理の後に処理を行うことがより好ましい。
塗布方法は浸漬法、ロールコーティング法、吹付法等が挙げられる。製缶後の缶外面物性の向上を目的とする場合、容器外面に当たる片側にロールコーティング法又は吹付法にて膜厚２０〜２００ｎｍになるように処理を行うことが好ましい。熱処理は有機チタン処理後、鋼板の製品完成までの間に、２００℃、２〜１０分の加熱が特に好ましい。
When performing the surface treatment as one of the chemical treatments at the time of steel sheet production, it is preferable to perform an organic titanium treatment as one of the chemical treatments after plating for both ET, TFS, and TNS, and to perform the treatment after the oil film treatment. Is more preferred.
Examples of the application method include a dipping method, a roll coating method, and a spraying method. When the purpose is to improve the physical properties of the outer surface of the can after the can is made, it is preferable that one side corresponding to the outer surface of the container is treated by a roll coating method or a spraying method so as to have a thickness of 20 to 200 nm. The heat treatment is preferably performed at 200 ° C. for 2 to 10 minutes after the organic titanium treatment and before the product of the steel sheet is completed.
本発明の表面処理鋼板の製造方法により、表面処理された鋼板又はめっき鋼板は、その表面に極薄の強靭な被膜が生成され、以下に示す特長を有する。
（１） 本発明の表面処理鋼板の製造方法により得られた表面処理鋼板の外観は、表面処理前の鋼板又はめっき鋼板と同等であり、例えば、ＥＴやＴＦＳを表面処理した鋼板は無地である。
（２） 本発明の表面処理鋼板の製造方法により得られた表面処理鋼板は、溶接が可能であり、係る表面処理鋼板を缶製造に用いる場合、溶接部の表面処理を除く必要がない。
（３） 本発明の表面処理鋼板の製造方法により得られた表面処理鋼板は、従来の表面処理鋼板に比べ顕著な難錆性を有している。
（４） 本発明の表面処理鋼板の製造方法により得られた表面処理鋼板は、難錆性、アブレーションの改善、すべり性の向上、表面強度の向上（スクラッチ強度の向上）、耐薬品性向上等、表面物性が大幅に改善されている。これら諸物性の改善は、チタン酸化被膜の持つ優れた特性によるものと考えられ、難錆性についてはバリヤー防食及びチタンのイオン化傾向が鉄よりも大きい事による犠牲防食が働くためと考えられる。また、すべり性においては、低いほど好ましいが、実施例で後述するように、１２°〜１４°の角度のすべり性を有するものがより好ましい。
（５） 本発明の表面処理鋼板の製造方法により得られた表面処理鋼板を、缶のどの部分にも対応させることができる。例えばＥＴ、ＴＦＳにかかわらず全ての部分（胴板・天地板・口金・座金）に表面処理鋼板を用いる、又は錆の目立ちやすい天板と座金のみに表面処理鋼板を用いるなど、フレキシブルに対応する事ができる。
According to the method for producing a surface-treated steel sheet of the present invention, a surface-treated steel sheet or a plated steel sheet has an extremely thin and tough film formed on its surface, and has the following features.
(1) The appearance of a surface-treated steel sheet obtained by the method for producing a surface-treated steel sheet of the present invention is the same as that of a steel sheet or a plated steel sheet before surface treatment. For example, a steel sheet surface-treated with ET or TFS is plain. .
(2) The surface-treated steel sheet obtained by the method for producing a surface-treated steel sheet of the present invention can be welded, and when such a surface-treated steel sheet is used for manufacturing a can, there is no need to remove the surface treatment of the welded portion.
(3) The surface-treated steel sheet obtained by the method for producing a surface-treated steel sheet of the present invention has remarkable rust resistance as compared with the conventional surface-treated steel sheet.
(4) The surface-treated steel sheet obtained by the method for producing a surface-treated steel sheet of the present invention has improved rust resistance, improved abrasion, improved slipperiness, improved surface strength (improved scratch strength), improved chemical resistance, and the like. The surface properties have been greatly improved. It is considered that these improvements in physical properties are due to the excellent properties of the titanium oxide film, and the rust resistance is due to barrier corrosion protection and sacrificial corrosion protection due to the fact that titanium has a greater ionization tendency than iron. Further, in terms of the slip property, the lower the better, the more preferable is one having a slip property of an angle of 12 ° to 14 ° as described later in Examples.
(5) The surface-treated steel sheet obtained by the method for producing a surface-treated steel sheet of the present invention can be applied to any part of a can. For example, regardless of ET and TFS, flexible use is possible such as using a surface-treated steel plate for all parts (body plate, top plate, cap, and washer), or using only a surface-treated steel plate for the top plate and washer that are prone to rust. Can do things.
［表面処理鋼板］
本発明の表面処理鋼板は、鋼板又はめっき鋼板と、該鋼板又はめっき鋼板の少なくとも一方の面に形成されたチタン酸化被膜を備えている。鋼板又はめっき鋼板の両面にチタン酸化被膜が形成されてもよいが、金属容器等への用途の観点からは、片面に形成されることが好ましい。
本発明の表面処理鋼板におけるチタン酸化被膜の形成方法としては、特に限定されないが、上述した本発明の表面処理鋼板の製造方法を用いることが好ましい。
チタン酸化被膜は、下記式（１）で表される構造を有することが好ましい。
[Surface treated steel sheet]
The surface-treated steel sheet of the present invention includes a steel sheet or a plated steel sheet and a titanium oxide film formed on at least one surface of the steel sheet or the plated steel sheet. Although a titanium oxide film may be formed on both surfaces of the steel plate or the plated steel plate, it is preferably formed on one surface from the viewpoint of application to a metal container or the like.
The method for forming the titanium oxide film on the surface-treated steel sheet of the present invention is not particularly limited, but it is preferable to use the above-described method for producing a surface-treated steel sheet of the present invention.
The titanium oxide film preferably has a structure represented by the following formula (1).
本発明の表面処理鋼板は、本発明の鋼板の表面処理方法により得られた表面処理鋼板の特長と同様の特長を有する。 The surface-treated steel sheet of the present invention has the same features as those of the surface-treated steel sheet obtained by the method of surface treating a steel sheet of the present invention.
［金属容器］
本発明の金属容器は、上記本発明の表面処理鋼板を用いたものである。係る金属容器としては、特に限定されず、缶が挙げられる。缶としては、食缶、飲料缶、菓子缶、薬品缶、スプレー缶、ペール缶、１８Ｌ缶等が挙げられ、１８Ｌ缶が好ましい。
本発明の金属容器は、本発明の鋼板の表面処理方法により得られた表面処理鋼板の特長と同様の特長を有する。
[Metal container]
The metal container of the present invention uses the surface-treated steel sheet of the present invention. Such a metal container is not particularly limited, and includes a can. Examples of the can include a food can, a beverage can, a confectionery can, a chemical can, a spray can, a pail can, and an 18L can, and an 18L can is preferable.
The metal container of the present invention has the same features as those of the surface-treated steel sheet obtained by the method for treating the steel sheet of the present invention.
次に実施例を示して本発明をさらに詳細に説明するが、本発明は以下の実施例に限定されるものではない。 Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.
≪実施例１≫
［ＥＴ缶の有機チタン処理］
チタンアルコキシド系のブチルチタネートダイマー［（ｎ−Ｃ４Ｈ９Ｏ）３Ｔｉ−Ｏ−Ｔｉ（Ｏ−ｎ−Ｃ４Ｈ９）３］２部／ｎ−ブタノール ９８部からなる処理液を作製した。１８Ｌ缶用ＥＴ胴板及び天地板に、この処理液をロールコーター式のコーティングラインで塗布量（ｗｅｔ）が２０ｍｇ／１００ｃｍ２になるようにコーティングし、コーティングライン上で２００℃、１０分焼き付けた。
手環取付用座金については、同処理液にＥＴ座金を浸漬した。浸漬した座金を取り出した後、液切を十分に行い２００℃、１０分間、熱処理を行った。これらの処理材料を用いて実施例１のＥＴ缶を作製した。
<< Example 1 >>
[Organic titanium treatment of ET cans]
To prepare a treatment solution consisting of butyl titanate dimer of the titanium alkoxide [(n-C 4 H 9 O) 3 Ti-O-Ti (O-n-C 4 H 9) 3] 2 parts / n-butanol 98 parts . This treatment liquid was coated on an ET body plate and a top plate for an 18 L can by a roll coater type coating line so that the applied amount (wet) became 20 mg / 100 cm 2, and baked at 200 ° C. for 10 minutes on the coating line. .
The ET washer was immersed in the same treatment solution for the washer for attaching the ring. After taking out the immersed washer, it was sufficiently drained and heat-treated at 200 ° C. for 10 minutes. The ET can of Example 1 was manufactured using these processing materials.
≪実施例２≫
実施例１のＥＴ缶の溶接部（缶胴・手環部分）及び天地板巻締め部に補修ニスを塗り、実施例２のＥＴ缶を作製した。
<< Example 2 >>
A repair varnish was applied to the welded portion (can body / hand ring portion) and the top and bottom plate wound portion of the ET can of Example 1 to prepare an ET can of Example 2.
≪比較例１≫
有機チタン処理をしない以外は、実施例１と同様の方法で比較例１のＥＴ缶を作製した。
<< Comparative Example 1 >>
An ET can of Comparative Example 1 was produced in the same manner as in Example 1, except that the organic titanium treatment was not performed.
［錆比較試験１］
実施例１〜２のＥＴ缶、及び比較例１のＥＴ缶を屋外に１０日間（内、雨３日間）放置し、錆の発生を比較した。
錆が全く発生しなかったものを〇と評価し、錆の色が薄ら付着する程度に発生したものを△と評価し、錆が完全に生じているものを×と評価した。結果を表１に示す。各ＥＴ缶の各部分の写真を図１〜３に示す。
[Rust comparison test 1]
The ET cans of Examples 1 and 2 and the ET can of Comparative Example 1 were left outdoors for 10 days (including three days of rain), and the generation of rust was compared.
Those which did not generate rust at all were evaluated as Δ, those which were generated to such an extent that the color of the rust thinly adhered were evaluated as Δ, and those which completely generated rust were evaluated as ×. Table 1 shows the results. Photos of each part of each ET can are shown in FIGS.
図１〜３及び表１に示すように、比較例１のＥＴ缶には錆の発生が認められたのに対し、実施例１〜２のＥＴ缶には錆の発生が全く確認されなかった。 As shown in FIGS. 1 to 3 and Table 1, the occurrence of rust was observed in the ET can of Comparative Example 1, whereas no occurrence of rust was observed in the ET can of Examples 1 and 2. .
［錆比較試験２］
実施例１のＥＴ缶、及び比較例１のＥＴ缶を屋外に１０日間（内、雨３日間）放置し、錆の発生を比較した。
錆が全く発生しなかったものを◎と評価し、錆の色が薄ら付着する程度に発生したものを〇と評価し、錆の色が濃く付着する程度に発生したものを△と評価し、錆が完全に生じているものを×と評価した。結果を表２に示す。
[Rust comparison test 2]
The ET can of Example 1 and the ET can of Comparative Example 1 were left outdoors for 10 days (including three days of rain), and the generation of rust was compared.
If no rust was generated, it was evaluated as ◎, if the rust color was lightly adhered, it was evaluated as 〇, and if rust color was deeply adhered, it was evaluated as △. And those in which rust was completely formed were evaluated as x. Table 2 shows the results.
表２に示すように、実施例１のＥＴ缶は、比較例１のＥＴ缶に対して防錆効果を有していることが確認された。 As shown in Table 2, it was confirmed that the ET can of Example 1 had a rust preventive effect with respect to the ET can of Comparative Example 1.
［アブレーション試験］
水を充填した、実施例１及び比較例１のＥＴ缶を、振動試験機で６０分間振動させた後のアブレーションの発生の有無を確認した。結果を表３及び図４〜５に示す。
[Ablation test]
After the ET cans of Example 1 and Comparative Example 1 filled with water were vibrated for 60 minutes with a vibration tester, the occurrence of ablation was confirmed. The results are shown in Table 3 and FIGS.
表３及び図４〜５に示すように、比較例１のＥＴ缶の手環部分にはアブレーションの発生が認められたのに対し、実施例１のＥＴ缶の手環部分にはアブレーションの発生が認められなかった。 As shown in Table 3 and FIGS. 4 and 5, ablation occurred in the hand ring portion of the ET can of Comparative Example 1, whereas ablation occurred in the hand ring portion of the ET can of Example 1. Was not observed.
実施例１のＥＴ缶に用いられた表面処理鋼板（実施例１とする。）、及び比較例１のＥＴ缶に用いられた表面処理鋼板（比較例１とする。）について、以下の物性試験を行った。 The following physical property tests were performed on the surface-treated steel sheet used for the ET can of Example 1 (referred to as Example 1) and the surface-treated steel sheet used for the ET can of Comparative Example 1 (referred to as Comparative Example 1). Was done.
［すべり性］
実施例１の表面処理鋼板どうしを重ね合わせ、所定の角度に傾けて、摩擦係数を算出した。比較例１の表面処理鋼板についても同様にして摩擦係数を算出した。結果を表４に示す。実施例１の表面処理鋼板は、比較例１の表面処理鋼板よりもすべり性に優れていた。
[Slip property]
The surface-treated steel sheets of Example 1 were superposed on each other, tilted at a predetermined angle, and the friction coefficient was calculated. The coefficient of friction was similarly calculated for the surface-treated steel sheet of Comparative Example 1. Table 4 shows the results. The surface-treated steel sheet of Example 1 was superior to the surface-treated steel sheet of Comparative Example 1 in slipperiness.
［耐摩擦性］
実施例１の表面処理鋼板どうしを重ね合わせ、学振型耐摩擦試験器を用いて、所定の条件下（１ｋｇ/４ｃｍ２/１００往復）における、耐摩擦性を評価した。比較例１の表面処理鋼板についても同様にして耐摩擦性を評価した。結果を表４に示す。実施例１の表面処理鋼板は、比較例１の表面処理鋼板と同様に耐摩擦性に優れていた。
[Friction resistance]
Superposing the surface treated steel sheet to each other in Example 1, using a Gakushin-type abrasion tester, under a predetermined condition (1kg / 4cm 2/100 roundtrip) was evaluated rub resistance. The friction resistance of the surface-treated steel sheet of Comparative Example 1 was similarly evaluated. Table 4 shows the results. The surface-treated steel sheet of Example 1 was excellent in abrasion resistance similarly to the surface-treated steel sheet of Comparative Example 1.
［耐薬品性］
実施例１の表面処理鋼板に、５％硫酸銅溶液を滴下し、５分後の浸食度を評価した。侵食度合に応じて、××、×、△、〇、◎と評価した。結果を表４に示す。実施例１の表面処理鋼板は、比較例１の表面処理鋼板よりも耐薬品性に優れていた。
[chemical resistance]
A 5% copper sulfate solution was dropped on the surface-treated steel sheet of Example 1, and the erosion degree after 5 minutes was evaluated. Depending on the degree of erosion, the evaluation was XX, X, △, ◎, ◎. Table 4 shows the results. The surface-treated steel sheet of Example 1 had better chemical resistance than the surface-treated steel sheet of Comparative Example 1.
［耐溶剤性］
実施例１の表面処理鋼板に、アセトンラビングを１００往復行い、耐溶剤性を評価した。結果を表４に示す。実施例１の表面処理鋼板は、比較例１の表面処理鋼板よりも耐溶剤性に優れていた。
[Solvent resistance]
Acetone rubbing was performed 100 times on the surface-treated steel sheet of Example 1 to evaluate solvent resistance. Table 4 shows the results. The surface-treated steel sheet of Example 1 had better solvent resistance than the surface-treated steel sheet of Comparative Example 1.
≪実施例３≫
［ＴＦＳ缶の有機チタン処理］
チタンアルコキシド系のブチルチタネートダイマー［（ｎ−Ｃ４Ｈ９Ｏ）３Ｔｉ−Ｏ−Ｔｉ（Ｏ−ｎ−Ｃ４Ｈ９）３］２部／ｎ−ブタノール ９８部からなる処理液を作製した。１８Ｌ缶用ＴＦＳ胴板及び天地板に、この処理液をロールコーター式のコーティングラインで塗布量（ｗｅｔ）が２０ｍｇ／１００ｃｍ２になるようにコーティングし、コーティングライン上で２００℃、１０分間、熱処理を行った。
手環取付用座金については、同処理液にＥＴ座金を浸漬した。浸漬した座金を取り出した後、液切を十分に行い２００℃、１０分間、熱処理を行った。
Ｂ４０口金については、同処理液にＢ４０ＥＴ口金を浸漬した。口金を取り出した後、液切を十分に行い２００℃、１０分間、熱処理を行った。これらの処理材料を用いて実施例３のＴＦＳ缶を作製した。
Example 3
[Organic titanium treatment of TFS cans]
To prepare a treatment solution consisting of butyl titanate dimer of the titanium alkoxide [(n-C 4 H 9 O) 3 Ti-O-Ti (O-n-C 4 H 9) 3] 2 parts / n-butanol 98 parts . This treatment liquid was coated on a TFS body plate and a top plate for an 18 L can by a roll coater type coating line so that the applied amount (wet) became 20 mg / 100 cm 2 , and heat treated at 200 ° C. for 10 minutes on the coating line. Was done.
The ET washer was immersed in the same treatment solution for the washer for attaching the ring. After taking out the immersed washer, it was sufficiently drained and heat-treated at 200 ° C. for 10 minutes.
As for the B40 base, the B40ET base was immersed in the same processing solution. After removing the base, the solution was sufficiently drained and heat-treated at 200 ° C. for 10 minutes. The TFS can of Example 3 was manufactured using these processing materials.
≪実施例４≫
実施例３のＴＦＳ缶の溶接部（缶胴・手環部分）及び天地板巻締め部に補修ニスを塗り、実施例４のＥＴ缶を作製した。
Example 4
A repair varnish was applied to the welded portion (can body / hand ring portion) and the top and bottom plate tightening portion of the TFS can of Example 3 to prepare an ET can of Example 4.
≪比較例２≫
有機チタン処理をしない以外は、実施例３と同様の方法で比較例２のＴＦＳ缶を作製した。
<< Comparative Example 2 >>
A TFS can of Comparative Example 2 was produced in the same manner as in Example 3, except that the organic titanium treatment was not performed.
≪比較例３≫
有機チタン処理をしない以外は、実施例４と同様の方法で比較例３のＴＦＳ缶を作製した。
<< Comparative Example 3 >>
A TFS can of Comparative Example 3 was produced in the same manner as in Example 4 except that the organic titanium treatment was not performed.
［錆比較試験１］
実施例４のＴＦＳ缶、及び比較例３のＴＦＳ缶を屋外に１０日間（内、雨３日間）放置し、錆の発生を比較した。
錆が全く発生しなかったものを〇と評価し、錆の色が薄ら付着する程度に発生したものを△と評価し、錆が完全に生じているものを×と評価した。結果を表５に示す。各ＴＦＳ缶の各部分の写真を図６〜７に示す。
[Rust comparison test 1]
The TFS can of Example 4 and the TFS can of Comparative Example 3 were left outdoors for 10 days (including 3 days of rain), and the generation of rust was compared.
Those which did not generate rust at all were evaluated as Δ, those which were generated to such an extent that the color of the rust thinly adhered were evaluated as Δ, and those which completely generated rust were evaluated as ×. Table 5 shows the results. Photos of each part of each TFS can are shown in FIGS.
図６〜７及び表５に示すように、比較例３のＴＦＳ缶には錆の発生が認められたのに対し、実施例４のＴＦＳ缶には錆の発生が全く確認されなかった。 As shown in FIGS. 6 and 7 and Table 5, rust was observed in the TFS can of Comparative Example 3, whereas no rust was observed in the TFS can of Example 4.
［錆比較試験２］
実施例３のＴＦＳ缶、及び比較例２のＴＦＳ缶を屋外に１０日間（内、雨３日間）放置し、錆の発生を比較した。
錆が全く発生しなかったものを◎と評価し、錆の色が薄ら付着する程度に発生したものを〇と評価し、錆の色が濃く付着する程度に発生したものを△と評価し、錆が完全に生じているものを×と評価した。結果を表６に示す。
[Rust comparison test 2]
The TFS can of Example 3 and the TFS can of Comparative Example 2 were left outdoors for 10 days (including 3 days of rain), and the generation of rust was compared.
If no rust was generated, it was evaluated as ◎, if rust color faintly adhered, it was evaluated as 、, and if rust color was deeply adhered, it was evaluated as △. And those in which rust was completely formed were evaluated as x. Table 6 shows the results.
表６に示すように、実施例３のＴＦＳ缶は、比較例２のＴＦＳ缶に対して防錆効果を有していることが確認された。 As shown in Table 6, it was confirmed that the TFS can of Example 3 had a rust preventive effect with respect to the TFS can of Comparative Example 2.
［アブレーション試験］
水を充填した、実施例４及び比較例３のＴＦＳ缶を、振動試験機で６０分間振動させた後のアブレーションの発生の有無を確認した。結果を表７及び図６〜７に示す。
[Ablation test]
After the TFS cans of Example 4 and Comparative Example 3 filled with water were vibrated with a vibration tester for 60 minutes, the presence or absence of ablation was confirmed. The results are shown in Table 7 and FIGS.
表７及び図８〜９に示すように、比較例３のＴＦＳ缶の胴部にはアブレーションの発生が認められたのに対し、実施例４のＴＦＳ缶の胴部にはアブレーションの発生が認められなかった。 As shown in Table 7 and FIGS. 8 and 9, ablation occurred on the body of the TFS can of Comparative Example 3, whereas ablation occurred on the body of the TFS can of Example 4. I couldn't.
実施例３のＴＦＳ缶に用いられた表面処理鋼板（実施例３とする。）、及び比較例２〜３のＴＦＳ缶に用いられた表面処理鋼板（比較例２〜３とする。）について、以下の物性試験を行った。 Regarding the surface-treated steel sheet used for the TFS can of Example 3 (referred to as Example 3) and the surface-treated steel sheet used for the TFS can of Comparative Examples 2 and 3 (referred to as Comparative Examples 2 and 3), The following physical property test was performed.
［すべり性］
実施例３の表面処理鋼板どうしを重ね合わせ、所定の角度に傾けて、摩擦係数を算出した。比較例２、比較例３の表面処理鋼板についても同様にして摩擦係数を算出した。結果を表８に示す。実施例３の表面処理鋼板は、比較例２の表面処理鋼板よりもすべり性に優れていた。また、実施例３の表面処理鋼板は、比較例３の表面処理鋼板と同等のすべり性を有していた。
[Slip property]
The surface-treated steel sheets of Example 3 were superimposed on each other, tilted at a predetermined angle, and the friction coefficient was calculated. The friction coefficients of the surface-treated steel sheets of Comparative Examples 2 and 3 were calculated in the same manner. Table 8 shows the results. The surface-treated steel sheet of Example 3 was superior to the surface-treated steel sheet of Comparative Example 2 in slipperiness. Further, the surface-treated steel sheet of Example 3 had the same slip property as the surface-treated steel sheet of Comparative Example 3.
［耐摩擦性］
実施例３の表面処理鋼板どうしを重ね合わせ、学振型耐摩擦試験器を用いて、所定の条件下（１ｋｇ/４ｃｍ２/１００往復）における、耐摩擦性を評価した。比較例２、比較例３の表面処理鋼板についても同様にして耐摩擦性を評価した。結果を表８に示す。実施例３の表面処理鋼板は、比較例２〜３の表面処理鋼板よりも耐摩擦性に優れていた。
[Friction resistance]
Superposing the surface treated steel sheet to each other in the third embodiment, by using a Gakushin-type abrasion tester, under a predetermined condition (1kg / 4cm 2/100 roundtrip) was evaluated rub resistance. The friction resistance of the surface-treated steel sheets of Comparative Examples 2 and 3 was similarly evaluated. Table 8 shows the results. The surface-treated steel sheet of Example 3 was more excellent in friction resistance than the surface-treated steel sheets of Comparative Examples 2 and 3.
［耐薬品性］
実施例３、比較例２〜３の表面処理鋼板に、５％硫酸銅溶液を滴下し、５分後の浸食度を評価した。侵食度合に応じて、××、×、△、〇、◎と評価した。結果を表８に示す。実施例３の表面処理鋼板は、比較例２〜３の表面処理鋼板よりも耐薬品性に優れていた。
[chemical resistance]
A 5% copper sulfate solution was dropped on the surface-treated steel sheets of Example 3 and Comparative Examples 2 and 3, and the erosion degree after 5 minutes was evaluated. Depending on the degree of erosion, the evaluation was XX, X, △, ◎, ◎. Table 8 shows the results. The surface-treated steel sheet of Example 3 had better chemical resistance than the surface-treated steel sheets of Comparative Examples 2 and 3.
［耐溶剤性］
実施例３、比較例２〜３の表面処理鋼板に、アセトンラビングを１００往復行い、耐溶剤性を評価した。結果を表８に示す。実施例３の表面処理鋼板は、比較例２〜３の表面処理鋼板よりも耐溶剤性に優れていた。
[Solvent resistance]
Acetone rubbing was performed 100 times on the surface-treated steel sheets of Example 3 and Comparative Examples 2 and 3, and the solvent resistance was evaluated. Table 8 shows the results. The surface-treated steel sheet of Example 3 was more excellent in solvent resistance than the surface-treated steel sheets of Comparative Examples 2 and 3.
≪実施例５≫
［ＴＦＳ／ＴＮＳの有機チタン処理］
チタンアルコキシド系のブチルチタネートダイマー（ｎ−Ｃ４Ｈ９Ｏ）３Ｔｉ−Ｏ−Ｔｉ（Ｏ−ｎ−Ｃ４Ｈ９）３ ２部／ｎ−ブタノール ９８部からなる処理液を作製した。１８Ｌ缶用ＴＦＳ胴板及びＴＮＳ天地板に、この処理液をロールコーター式のコーティングラインで塗布量（ｗｅｔ）が２０ｍｇ／１００ｃｍ２になるようにコーティングし、コーティングライン上で２００℃、１０分焼き付けた。
手環取付用座金については、同処理液にＥＴ座金を浸漬した。浸漬した座金を取り出した後、液切を十分に行い２００℃、１０分間、熱処理を行った。
Ｂ４０口金については、同処理液にＢ４０ＥＴ口金を浸漬した。口金を取り出した後、液切を十分に行い２００℃、１０分間、熱処理を行った。これらの処理材料を用いて実施例５のＴＦＳ／ＴＮＳ缶を作製した。
Example 5
[Organic titanium treatment of TFS / TNS]
To prepare a treatment liquid comprising titanium alkoxide butyl titanate dimer (n-C 4 H 9 O ) 3 Ti-O-Ti (O-n-C 4 H 9) 3 2 parts / n-butanol 98 parts. This treatment liquid is coated on a TFS body plate for 18L cans and a TNS top and bottom plate by a roll coater type coating line so that an application amount (wet) becomes 20 mg / 100 cm 2, and baked at 200 ° C. for 10 minutes on the coating line. Was.
The ET washer was immersed in the same treatment solution for the washer for attaching the ring. After taking out the immersed washer, it was sufficiently drained and heat-treated at 200 ° C. for 10 minutes.
As for the B40 base, the B40ET base was immersed in the same processing solution. After removing the base, the solution was sufficiently drained and heat-treated at 200 ° C. for 10 minutes. A TFS / TNS can of Example 5 was manufactured using these processing materials.
≪比較例４≫
有機チタン処理をしない以外は、実施例５と同様の方法で比較例４のＴＦＳ／ＴＮＳ缶を作製した。
<< Comparative Example 4 >>
A TFS / TNS can of Comparative Example 4 was produced in the same manner as in Example 5, except that the organic titanium treatment was not performed.
［錆比較試験］
実施例５のＴＦＳ／ＴＮＳ缶、及び比較例４のＴＦＳ／ＴＮＳ缶を屋外に１０日間（内、雨３日間）放置し、錆の発生を比較した。
錆が全く発生しなかったものを◎と評価し、錆の色が薄ら付着する程度に発生したものを〇と評価し、錆の色が濃く付着する程度に発生したものを△と評価し、錆が完全に生じているものを×と評価した。結果を表９に示す。
[Rust comparison test]
The TFS / TNS can of Example 5 and the TFS / TNS can of Comparative Example 4 were left outdoors for 10 days (including 3 days of rain), and the generation of rust was compared.
If no rust was generated, it was evaluated as ◎, if the rust color was lightly adhered, it was evaluated as 〇, and if rust color was deeply adhered, it was evaluated as △. And those in which rust was completely formed were evaluated as x. Table 9 shows the results.
表９に示すように、実施例５のＴＦＳ／ＴＮＳ缶は、比較例４のＴＦＳ／ＴＮＳ缶に対して防錆効果を有していることが確認された。 As shown in Table 9, it was confirmed that the TFS / TNS can of Example 5 had a rust preventive effect with respect to the TFS / TNS can of Comparative Example 4.
［アブレーション試験］
水を充填した、実施例５及び比較例４のＥＴ缶を、振動試験機で６０分間振動させた後のアブレーションの発生の有無を確認した。結果を表１０に示す。
[Ablation test]
After the water-filled ET cans of Example 5 and Comparative Example 4 were vibrated for 60 minutes with a vibration tester, the occurrence of ablation was confirmed. Table 10 shows the results.
表１０に示すように、比較例４のＴＦＳ／ＴＮＳ缶の手環部分にはアブレーションの発生が認められたのに対し、実施例５のＴＦＳ／ＴＮＳ缶の手環部分にはアブレーションの発生が認められなかった。 As shown in Table 10, ablation occurred in the hand ring of the TFS / TNS can of Comparative Example 4, whereas ablation occurred in the hand ring of the TFS / TNS can of Example 5. I was not able to admit.
実施例５のＴＦＳ／ＴＮＳ缶に用いられた表面処理鋼板（ＴＮＳ）（実施例５とする。）、及び比較例４のＴＦＳ／ＴＮＳ缶に用いられた表面処理鋼板（ＴＮＳ）（比較例４とする。）について、以下の物性試験を行った。 The surface-treated steel sheet (TNS) used for the TFS / TNS can of Example 5 (referred to as Example 5) and the surface-treated steel sheet (TNS) used for the TFS / TNS can of Comparative Example 4 (Comparative Example 4) The following physical property test was conducted.
［すべり性］
実施例５の表面処理鋼板どうしを重ね合わせ、所定の角度に傾けて、摩擦係数を算出した。比較例４の表面処理鋼板についても同様にして摩擦係数を算出した。結果を表１１に示す。実施例５の表面処理鋼板は、比較例４の表面処理鋼板よりもすべり性に優れていた。
[Slip property]
The surface-treated steel sheets of Example 5 were superimposed on each other, tilted at a predetermined angle, and the friction coefficient was calculated. The coefficient of friction was similarly calculated for the surface-treated steel sheet of Comparative Example 4. Table 11 shows the results. The surface-treated steel sheet of Example 5 was superior to the surface-treated steel sheet of Comparative Example 4 in slipperiness.
［耐摩擦性］
実施例５の表面処理鋼板どうしを重ね合わせ、学振型耐摩擦試験器を用いて、所定の条件下（１ｋｇ/４ｃｍ２/１００往復）における、耐摩擦性を評価した。比較例４の表面処理鋼板についても同様にして耐摩擦性を評価した。結果を表１１に示す。実施例５の表面処理鋼板は、比較例４の表面処理鋼板よりもすべり性に優れていた。
[Friction resistance]
Superposing the surface treated steel sheet to each other in the fifth embodiment, by using a Gakushin-type abrasion tester, under a predetermined condition (1kg / 4cm 2/100 roundtrip) was evaluated rub resistance. The friction resistance of the surface-treated steel sheet of Comparative Example 4 was similarly evaluated. Table 11 shows the results. The surface-treated steel sheet of Example 5 was superior to the surface-treated steel sheet of Comparative Example 4 in slipperiness.
［耐薬品性］
実施例５の表面処理鋼板に、５％硫酸銅溶液を滴下し、５分後の浸食度を評価した。侵食度合に応じて、××、×、△、〇、◎と評価した。結果を表１１に示す。実施例４の表面処理鋼板は、比較例４の表面処理鋼板と同様に耐摩擦性に優れていた。
[chemical resistance]
A 5% copper sulfate solution was dropped on the surface-treated steel sheet of Example 5, and the erosion degree after 5 minutes was evaluated. Depending on the degree of erosion, the evaluation was XX, X, △, ◎, ◎. Table 11 shows the results. The surface-treated steel sheet of Example 4 was excellent in abrasion resistance similarly to the surface-treated steel sheet of Comparative Example 4.
［耐溶剤性］
実施例５の表面処理鋼板に、アセトンラビングを１００往復行い、耐溶剤性を評価した。結果を表１１に示す。実施例５の表面処理鋼板は、比較例４の表面処理鋼板と同様に耐摩擦性に優れていた。
[Solvent resistance]
Acetone rubbing was performed 100 times on the surface-treated steel sheet of Example 5 to evaluate solvent resistance. Table 11 shows the results. The surface-treated steel sheet of Example 5 was excellent in abrasion resistance similarly to the surface-treated steel sheet of Comparative Example 4.
１８リッター缶をはじめとする各種金属容器は、錆の発生や諸物性（すべり性、アブレーション等の耐摩擦性等）を改善するために、鋼板内外面へのコーティングニスの塗装、あるいは鋼板外面へのＰＥＴフィルムのラミネート等が行われている。
しかし、缶胴の溶接部や天板の手環溶接部においては、コーティングニスやＰＥＴフィルムを抜く必要があり、その部分は溶接のダメージと相まって錆が発生しやすいこともあり、製缶時においてこれらの溶接部（缶胴・手環部分）や鋼板加工でダメージのある天地板巻締め部には補修ニスを塗る必要があった。
この様な錆対策を行っても、例えば手環座金は無地ＥＴであるため座金裏側までは補修ニスが届かず、錆が発生する問題を抱えていた。
本発明によれば、（１）素材としての鋼板（２）現行の鋼板（３）鋼板加工品（座金・口金等）の全てにおいて最適な処理（コーティング法・浸漬法）が可能であり、且つそれらは溶接性を有しており、難錆性、すべり性、アブレーション、耐摩擦性、耐薬品性等の諸物性が向上する。これら諸物性の改善は、チタン酸化被膜の持つ優れた特性によるものと考えられ、難錆性についてはバリヤー防食及びチタンのイオン化傾向が鉄よりも大きい事による犠牲防食が働くためと考えられる。本発明により、従来の缶に比べ、格段に優れた性能を有する金属缶の提供が可能となった。
Various metal containers such as 18-liter cans are coated with a coating varnish on the inner and outer surfaces of the steel plate or on the outer surface of the steel plate in order to improve rust generation and various physical properties (such as slip resistance and abrasion resistance). And the like are being performed.
However, it is necessary to remove the coating varnish and PET film at the welded part of the can body and the hand ring welded part of the top plate, and that part may be easily rusted due to welding damage. It was necessary to apply a repair varnish to these welds (can body and hand ring) and the top and bottom plate wound parts damaged by steel plate processing.
Even if such a measure against rust is taken, for example, since the hand ring washer is a plain ET, the repair varnish does not reach the back side of the washer, and there is a problem that rust is generated.
According to the present invention, optimal processing (coating method / dipping method) is possible in all of (1) steel plate as a material (2) existing steel plate (3) processed steel plate (washer, die, etc.), and They have weldability and improve various properties such as rust resistance, slip properties, abrasion, friction resistance, chemical resistance and the like. It is considered that these improvements in physical properties are due to the excellent properties of the titanium oxide film, and the rust resistance is due to barrier corrosion protection and sacrificial corrosion protection due to the fact that titanium has a greater ionization tendency than iron. According to the present invention, it has become possible to provide a metal can having much better performance than a conventional can.
Claims (3)
鋼板加工品又はめっき鋼板加工品を、チタンアルコキシド、チタンキレート、及びチタンオリゴマーからなる群から選ばれる少なくとも一種の有機チタン化合物のアルコール溶液に浸漬して、処理温度１５０〜２２０℃で熱処理することにより、これらの加工品の表面にチタン酸化被膜を備えた表面処理鋼板加工品を得る工程と、
前記表面処理鋼板及び前記表面処理鋼板加工品を用いて金属缶を作製する工程と
を有する、金属缶の製造方法。 On the surface of the steel sheet or plated steel plate, a titanium alkoxide, a titanium chelate, and an alcohol solution of at least one organotitanium compound selected from the group consisting of titanium oligomer coated, by heat treatment at a treatment temperature 150 to 220 ° C., A step of obtaining a surface-treated steel sheet having a titanium oxide film on at least one surface of the steel sheet or plating;
By immersing the processed steel sheet or plated steel sheet in an alcohol solution of at least one organic titanium compound selected from the group consisting of titanium alkoxide, titanium chelate, and titanium oligomer, and performing a heat treatment at a processing temperature of 150 to 220 ° C. A step of obtaining a processed steel sheet having a titanium oxide film on the surface of these processed products;
The surface treated steel sheet and you have a a step of preparing a metal can with the surface treated steel sheet workpiece, the production method of metal cans.
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| JPS62272276A (en) * | 1986-05-21 | 1987-11-26 | Canon Inc | Production of electrophotographic sensitive body |
| JPH01149966A (en) * | 1987-12-07 | 1989-06-13 | Nisshin Steel Co Ltd | Manufacture of colored stainless steel sheet excellent in resistance to wear, heat, and fingerprint |
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| JP2001161533A (en) * | 1999-12-07 | 2001-06-19 | Myodo Metal Co Ltd | Container for kitchen/food and drink and its surface treating method |
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| JPWO2002061005A1 (en) * | 2001-01-30 | 2004-06-03 | 関西ペイント株式会社 | Coating agent for forming titanium oxide film, method for forming titanium oxide film, and metal substrate coated with titanium oxide film |
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