JP2006255687A - Production method of surface treated object - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To stably generate the required amount of a film in generating the film on the surface of an object to be treated by applying a water soluble treating liquid to the object to be treated and utilizing the chemical reaction of the object to be treated and the water soluble treating liquid. <P>SOLUTION: In the method for manufacturing the water soluble treating liquid of generating the film on the surface of the object to be treated by applying the water soluble treating liquid to the object to be treated and generating the film on the surface of the object to be treated by the chemical reaction of the object to be treated and the water soluble treating liquid, the treating liquid of the previously known concentration of the component of the treating liquid is applied to the object to be treated, and the moisture content in the treating liquid is measured and the amount of the treating liquid to be applied to the object to be treated is controlled by the measured value of the moisture content. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、被処理物に水溶性処理液を塗布し、被処理物と水溶性処理液との化学反応により、被処理物表面に皮膜を生成させる表面処理物の製造方法において、所定の皮膜量を安定して得る技術に関するものである。   The present invention relates to a method for producing a surface-treated product in which a water-soluble treatment liquid is applied to a treatment object, and a film is formed on the surface of the treatment object by a chemical reaction between the treatment object and the water-soluble treatment liquid. The present invention relates to a technique for stably obtaining a quantity.

例えば、鉄鋼、半導体、ディスプレーなどの製品分野では厚さ数１０〜数１００ｎｍの表層皮膜が製品特性の支配因子になっている場合がある。鉄鋼製品分野でこのような表層の極薄膜が関係する製品特性の一つにプレス成形性がある。自動車や家電製品に使用される鋼板には、近年、高耐食性の観点から亜鉛系のめっきが施される場合が多いが、亜鉛系めっき鋼板をプレス加工して難成形部品を製造する場合、加工の厳しい部位で鋼板のプレス割れが起こりやすいという問題がある。この亜鉛系めっき鋼板のプレス成形性をプレス時に高粘度の潤滑油を使用することで改善する方法が知られているが、この方法では脱脂工程を強化しないと化成処理や塗装などの後工程でムラが発生するという問題がある。   For example, in the field of products such as steel, semiconductors, and displays, a surface layer film having a thickness of several tens to several hundreds of nm may be a dominant factor of product characteristics. One of the product characteristics related to such a super-thin film in the steel product field is press formability. In recent years, steel plates used in automobiles and home appliances are often plated with zinc from the viewpoint of high corrosion resistance. However, when manufacturing difficult-to-form parts by pressing zinc-based plated steel, There is a problem that press cracking of the steel sheet is likely to occur at a severe part. A method is known to improve the press formability of this zinc-based plated steel sheet by using a high-viscosity lubricant during pressing. There is a problem that unevenness occurs.

このような後工程での懸念が少ない方法として、めっき層の表面にプレス成形時の摺動特性に優れる酸化物皮膜を形成させる方法が知られている。例えば、特許文献１〜３には、亜鉛系めっき鋼板の表面に電解処理、浸漬処理、塗布酸化処理、または加熱処理を施すことにより、亜鉛酸化物を主体とする酸化膜を形成させて溶接性または加工性を向上させる技術が開示されている。特許文献４には、亜鉛系めっき鋼板の表面にリン酸ナトリウム５〜６０ｇ／Ｌを含みｐＨ２〜６の水溶液にめっき鋼板を浸漬するか、電解処理を行うか、または、上記水溶液を塗布することにより、リン酸化物を主体とする酸化膜を形成して、プレス成形性及び化成処理性を向上させる技術が開示されている。特許文献５には、亜鉛系めっき鋼板の表面に電解処理、浸漬処理、塗布処理、塗布酸化処理、または加熱処理により、Ｎｉ酸化物を生成させることにより、プレス成形性および化成処理性を向上させる技術が開示されている。   As a method with less concern in such post-processes, a method is known in which an oxide film having excellent sliding characteristics during press molding is formed on the surface of a plating layer. For example, in Patent Documents 1 to 3, the surface of a zinc-based plated steel sheet is subjected to electrolytic treatment, dipping treatment, coating oxidation treatment, or heat treatment to form an oxide film mainly composed of zinc oxide and weldability. Or the technique which improves workability is disclosed. In Patent Document 4, the surface of the zinc-based plated steel sheet is immersed in an aqueous solution containing 5 to 60 g / L of sodium phosphate and having a pH of 2 to 6, or is subjected to electrolytic treatment, or the above aqueous solution is applied. Discloses a technique for improving the press formability and chemical conversion property by forming an oxide film mainly composed of phosphorous oxide. In Patent Document 5, the surface of a zinc-based plated steel sheet is improved in press formability and chemical conversion treatment by generating Ni oxide by electrolytic treatment, dipping treatment, coating treatment, coating oxidation treatment, or heat treatment. Technology is disclosed.

このような処理では、酸化物量が重要であり、めっき表面に所要の酸化物量を安定して生成させる必要がある。酸化物を生成させる手法として、鋼板と水溶性処理液との化学反応により、鋼板表面に酸化物を生成させる処理がある。この処理においては、酸化物の生成量は、反応速度、反応時間によって決定される。   In such treatment, the amount of oxide is important, and it is necessary to stably generate the required amount of oxide on the plating surface. As a method of generating an oxide, there is a process of generating an oxide on the surface of a steel sheet by a chemical reaction between the steel sheet and a water-soluble treatment liquid. In this treatment, the amount of oxide produced is determined by the reaction rate and reaction time.

水溶性処理液の塗布方法として、処理液をロールコーターで一定量塗布したり、処理液を塗布後、ロールで絞ったり、ガスワイピングノズルから加圧気体を吹き付けてガスワイピングするなどによって、処理液を一定量にする塗布した後鋼板と水溶性処理液との化学反応により、鋼板表面に酸化物を生成させる処理方式がある。この方式では、鋼板表面に酸化物を生成させた後、未反応の水溶性処理液を水洗除去して所要の酸化物を生成させる。反応時間は、処理液が鋼板と接触している時間に支配される。反応速度は、処理液温度、処理液濃度等に支配される。通常のプロセスラインは、鋼板サイズに対応して鋼板走行速度が変わることが多く、これに起因して皮膜生成量が変動する。処理液温度、処理液濃度を調整することで皮膜生成量を制御することが可能であるが、これらの条件変更は応答性に劣るため、皮膜生成量の変動が大きくなるという問題がある。   As a method for applying the water-soluble processing liquid, a predetermined amount of the processing liquid is applied by a roll coater, the processing liquid is applied, and then squeezed by a roll, or a gas wiping is performed by blowing a pressurized gas from a gas wiping nozzle. There is a treatment method in which an oxide is generated on the surface of the steel sheet by chemical reaction between the steel sheet and the water-soluble treatment liquid after coating to a certain amount. In this method, after an oxide is generated on the surface of the steel sheet, an unreacted water-soluble treatment solution is removed by washing to generate a required oxide. The reaction time is governed by the time during which the treatment liquid is in contact with the steel plate. The reaction rate is governed by the processing solution temperature, the processing solution concentration, and the like. In a normal process line, the steel plate traveling speed often changes corresponding to the steel plate size, and the film generation amount varies due to this. Although it is possible to control the film formation amount by adjusting the treatment liquid temperature and the treatment liquid concentration, there is a problem that fluctuations in the film formation amount become large because these changes in conditions are inferior in responsiveness.

鋼板上の皮膜厚を測定する方法が種々知られている。例えば、蛍光Ｘ線分析法（以下ＸＲＦ法と略記）がある。このＸＲＦ法はＸ線を皮膜が形成された鋼板に照射し、皮膜成分の元素から発生する蛍光Ｘ線強度を測定することで皮膜厚さを測定する方法である。この方法は、Ｚｎ、Ｎｉ、Ｃｒなどの重元素と呼ばれる原子番号の大きな元素には比較的簡単に適用できるが、軽元素と呼ばれる原子番号の小さな、特に水溶液の構成元素であるＨ、Ｏなどは、以下の理由で適用が困難である。
（１）軽元素の蛍光Ｘ線発生効率は、重元素に比べると桁違いに小さいため、前述の処理液量測定には適用できない。
（２）軽元素の蛍光Ｘ線波長は大気による吸収が大きく、高真空中での測定が必須であり、製造ラインにこのような高真空を保つことは無理である。 Various methods for measuring the film thickness on a steel plate are known. For example, there is a fluorescent X-ray analysis method (hereinafter abbreviated as XRF method). This XRF method is a method of measuring the thickness of a film by irradiating a steel sheet on which a film is formed with X-rays and measuring the intensity of fluorescent X-rays generated from the elements of the film components. This method can be applied relatively easily to elements with a large atomic number called heavy elements such as Zn, Ni, Cr, etc., but has a small atomic number called a light element, particularly H, O, which are constituent elements of aqueous solutions. Is difficult to apply for the following reasons.
(1) Since the fluorescent X-ray generation efficiency of light elements is orders of magnitude smaller than that of heavy elements, it cannot be applied to the above-described treatment liquid amount measurement.
(2) The fluorescence X-ray wavelength of light elements is greatly absorbed by the atmosphere, and measurement in a high vacuum is essential, and it is impossible to maintain such a high vacuum in the production line.

このような欠点を補うことを目的として、Ｘ線技術を応用した技術がある。しかしながら、Ｘ線技術を利用する方法は、処理液が数分間も保持され、かつ処理液量が多い場合には適用できるが、処理液の保持時間が短い場合あるいは処理液が微量の場合には適用することはできない。   For the purpose of compensating for such drawbacks, there is a technique that applies X-ray technology. However, the method using the X-ray technique can be applied when the treatment liquid is held for several minutes and the amount of the treatment liquid is large, but when the retention time of the treatment liquid is short or when the treatment liquid is a very small amount. It cannot be applied.

鋼板上の皮膜を測定する方法としては、Ｘ線技術以外にも、光干渉法を用いた技術、超音波を用いた技術が提案されている。しかし、光干渉法による技術は、下地表面が凸凹を有する場合、綺麗な干渉が得られないため、また超音波法による技術は超音波探触子を試料に接触する必要があるため、これらの技術は、走行中の鋼板表面で被処理物と水溶性処理液との化学反応により被処理物表面に皮膜を生成させる処理における処理液量測定には適用できない。   As a method for measuring a film on a steel plate, a technique using an optical interference method and a technique using an ultrasonic wave have been proposed in addition to the X-ray technique. However, since the optical interferometry technique cannot provide clean interference when the underlying surface has irregularities, and the ultrasonic interferometry technique requires the ultrasonic probe to be in contact with the sample. The technique cannot be applied to the measurement of the amount of processing liquid in a process of generating a film on the surface of the object to be processed by a chemical reaction between the object to be processed and the water-soluble processing liquid on the surface of the traveling steel plate.

また、処理液が水溶液または水溶液に分散物が分散した溶液の場合、フィルター式赤外吸収方式によって水分量を測定する技術がある。この手法は、近赤外領域での特定波長の光が水に吸収されることを利用した分析方法である。つまり、赤外光を被測定物に照射し、該被測定物から反射した光を、水に吸収される波長の光を通過するフィルターおよび水に吸収されない波長の光を通過するフィルターを通し、通過した光の強度を測定することによって水による光の吸収量を計測し水分量を分析する手法である。この手法は、応答性に優れ、容易な装置構成で実現できることから、多くの製造プロセスで使用されている（例えば特許文献６〜１０参照）。これらは、製造プロセスにおける水分そのものを測定するもの、または、特許文献１０が対象とする電磁鋼板絶縁皮膜のように塗料を加熱乾燥して水溶液等を除去することで処理液中の加熱残分からなる皮膜を形成するプロセスを対象とするもので、走行中の鋼板表面で被処理物と水溶性処理液との化学反応により被処理物表面に皮膜を生成させる処理方法を対象とするものはない。
特開昭５３−６０３３２号公報 特開平２−１９０４８３号公報 特開２００４−３００４号公報 特開平４−８８１９６号公報 特開平３−１９１０９３号公報 特開平３−１１５８３８号公報 特開２００４−２０１９２号公報 特開２００３−１５６４３７号公報 特開平４−４８９６７号公報 特開平３−１７７５７８号公報 In addition, when the treatment liquid is an aqueous solution or a solution in which a dispersion is dispersed in an aqueous solution, there is a technique for measuring the water content by a filter-type infrared absorption method. This method is an analysis method using the fact that light of a specific wavelength in the near infrared region is absorbed by water. In other words, infrared light is irradiated onto the object to be measured, and the light reflected from the object to be measured is passed through a filter that passes light having a wavelength that is absorbed by water and a filter that passes light having a wavelength that is not absorbed by water. This is a technique for measuring the amount of light absorbed by water by measuring the intensity of light passing therethrough and analyzing the amount of water. Since this method is excellent in responsiveness and can be realized with an easy apparatus configuration, it is used in many manufacturing processes (see, for example, Patent Documents 6 to 10). These consist of heating residues in the treatment liquid by measuring the moisture itself in the manufacturing process, or by removing the aqueous solution by heating and drying the paint as in the magnetic steel sheet insulation film targeted by Patent Document 10. There is no target for a process for forming a film on the surface of a steel plate during traveling, and a method for generating a film on the surface of the object to be processed by a chemical reaction between the object to be processed and a water-soluble treatment liquid.
JP-A-53-60332 Japanese Patent Laid-Open No. 2-190483 JP 2004-3004 A JP-A-4-88196 Japanese Patent Laid-Open No. 3-191093 Japanese Patent Laid-Open No. 3-115538 JP 2004-20192 A JP 2003-156437 A JP-A-4-48967 JP-A-3-177578

以上のように、前述の先行技術には、本願が目的とする水溶性処理液を塗布し、鋼板と水溶性処理液との化学反応により、鋼板表面に皮膜を生成させる処理を対象とし、この処理における皮膜生成量の変動を低減させる技術は存在しない。   As described above, the above-described prior art is applied to a process in which a water-soluble treatment liquid intended by the present application is applied, and a film is formed on the steel sheet surface by a chemical reaction between the steel sheet and the water-soluble treatment liquid. There is no technique for reducing fluctuations in the amount of film produced during processing.

また、製品特性を鋼板板幅方向で均一とするためには、皮膜生成量は鋼板幅方向の変動が少ないことが好ましい。前述の先行技術には、鋼板幅方向での皮膜を均一に生成させることを考慮した技術はない。   Moreover, in order to make product characteristics uniform in the width direction of the steel sheet, it is preferable that the amount of film formation has little fluctuation in the width direction of the steel sheet. The above-mentioned prior art does not include a technique that takes into account the uniform generation of a film in the width direction of the steel sheet.

本発明の課題は、前述の問題点を考慮し、被処理物に水溶性処理液を塗布し、被処理物と水溶性処理液との化学反応により、被処理物表面に皮膜を生成させる際に、安定して所要の皮膜量を生成でき、また被処理物が帯状体である場合、その幅方向の皮膜生成量を均一にできる表面処理物の製造方法を提供することである。   The object of the present invention is to apply the water-soluble treatment liquid to the object to be treated in consideration of the above-mentioned problems, and to generate a film on the surface of the object to be treated by the chemical reaction between the object to be treated and the water-soluble treatment liquid. In addition, it is to provide a method for producing a surface-treated product that can stably produce a required amount of film and that can uniformly produce a film in the width direction when the object to be treated is a strip.

被処理物に水溶性処理液を塗布し、被処理物と水溶性処理液との化学反応により被処理物表面に皮膜を生成させる処理では、処理液濃度、処理液温度、処理時間などを制御することで皮膜生成量が制御されている。本発明者らは、被処理物と水溶性処理液との化学反応により被処理物表面に皮膜を生成させる処理を行ったところ、鋼板上の処理液量と生成する皮膜量の間によい対応関係があることを見出した。本発明はこの知見に基くものである。   In the process of applying a water-soluble treatment liquid to the object to be processed and forming a film on the surface of the object by chemical reaction between the object to be treated and the water-soluble treatment liquid, the concentration of the treatment liquid, the treatment liquid temperature, the treatment time, etc. are controlled. By doing so, the amount of film formation is controlled. When the present inventors performed a treatment for generating a film on the surface of the object to be processed by a chemical reaction between the object to be processed and the water-soluble processing liquid, a good correspondence between the amount of the processing liquid on the steel sheet and the amount of the film to be generated I found that there is a relationship. The present invention is based on this finding.

上記課題を解決する本発明の手段は次のとおりである。   Means of the present invention for solving the above-mentioned problems are as follows.

第１発明は、被処理物に水溶性処理液を塗布し、被処理物と水溶性処理液との化学反応により被処理物表面に皮膜を生成させる表面処理物の製造方法において、被処理物に予め処理液の成分濃度が既知の処理液を塗布し、該処理物上の処理液中の水分量を計測し、水分量の計測値によって被処理物に塗布する処理液量を制御することを特徴とする表面処理物の製造方法である。   The first invention is a method for producing a surface-treated product, in which a water-soluble treatment liquid is applied to the workpiece, and a film is formed on the surface of the workpiece by a chemical reaction between the workpiece and the water-soluble treatment liquid. First, a treatment liquid having a known component concentration of the treatment liquid is applied, the amount of water in the treatment liquid on the treatment object is measured, and the amount of treatment liquid applied to the object to be treated is controlled by the measured value of the moisture amount. Is a method for producing a surface-treated product.

第２発明は、第１発明において、連続的に走行する被処理物に塗布した水溶性処理液の塗布量、被処理物の走行速度および被処理物表面に生成する皮膜量との関係を求めて、この関係及び被処理物上の処理液中の水分量の計測値に基いて被処理物に塗布する処理液量を制御することを特徴とする表面処理物の製造方法である。   According to a second invention, in the first invention, the relationship between the coating amount of the water-soluble treatment liquid applied to the workpiece to be continuously run, the running speed of the workpiece, and the coating amount generated on the workpiece surface is obtained. Thus, the surface treatment product manufacturing method is characterized in that the amount of the treatment liquid applied to the treatment object is controlled based on this relationship and the measured value of the amount of water in the treatment solution on the treatment object.

第３発明は、第１または第２発明において、処理液の塗布を絞りロールで行い、処理液量の制御を絞りロールの押付圧制御によって行うことを特徴とする表面処理物の製造方法である。   A third invention is a method for producing a surface-treated product according to the first or second invention, wherein the treatment liquid is applied by a squeeze roll, and the amount of the treatment liquid is controlled by pressing pressure control of the squeeze roll. .

第４発明は、第１〜第３発明において、被処理物が帯状体であり、該帯状体の幅方向の複数点の処理液の水分量を各々計測し、水分量の計測値によって帯状体幅方向の塗布液量を制御することを特徴とする表面処理物の製造方法である。   According to a fourth invention, in the first to third inventions, the object to be processed is a belt-like body, and the moisture content of the treatment liquid at a plurality of points in the width direction of the belt-like body is measured. It is a manufacturing method of the surface treatment thing characterized by controlling the amount of coating liquids of the width direction.

第５発明は、第１〜第４発明において、フィルター型赤外吸収方式の装置によって処理液の水分量を計測することを特徴とする表面処理物の製造方法である。   5th invention is the manufacturing method of the surface treatment thing characterized by measuring the moisture content of a process liquid with the apparatus of a filter type infrared absorption system in 1st-4th invention.

第６発明は、第１〜第５発明において、被処理物が金属帯であることを特徴とする表面処理物の製造方法である。   A sixth invention is a method for producing a surface-treated product according to any one of the first to fifth inventions, wherein the workpiece is a metal strip.

第７発明は、第６発明において、金属帯が亜鉛めっき鋼板であり、その表面に生成させる皮膜が亜鉛系酸化物であることを特徴とする表面処理物の製造方である法。   A seventh invention is a method for producing a surface-treated product according to the sixth invention, wherein the metal strip is a galvanized steel sheet, and the coating formed on the surface thereof is a zinc-based oxide.

本発明によれば、被処理物表面の処理液の水分量をオンライン分析し、その結果に基き、塗布する処理液量を制御することで、皮膜生成量の変動を低減し、所要皮膜量を有する表面処理鋼板を安定製造できる。   According to the present invention, the moisture content of the treatment liquid on the surface of the object to be treated is analyzed online, and based on the result, by controlling the amount of the treatment liquid to be applied, the fluctuation of the film formation amount is reduced, and the required film amount is reduced. The surface-treated steel sheet can be stably manufactured.

前記したとおり、被処理物に水溶性処理液を塗布し、被処理物と水溶性処理液との化学反応により被処理物表面に皮膜を生成させる処理では、処理液濃度、処理液温度、処理時間などを制御することで皮膜生成量が制御されていた。そのため、制御の応答性に劣る問題があった。   As described above, in the process of applying a water-soluble treatment liquid to a treatment object and generating a film on the treatment object surface by a chemical reaction between the treatment object and the water-soluble treatment liquid, the treatment solution concentration, treatment solution temperature, treatment The amount of film formation was controlled by controlling time and the like. Therefore, there is a problem that the control response is inferior.

本発明者らは、被処理物と水溶性処理液との化学反応により被処理物表面に皮膜を生成させる処理をロール塗布で行ったところ、鋼板上の処理液の塗布量と生成する皮膜量の間によい対応関係があることを見出した。塗布した処理液を加熱乾燥させて皮膜を形成する、いわゆる塗布型皮膜形成処理においては、処理液の塗布量と生成する皮膜量の間によい対応関係（比例関係）があることは知られていたが、被処理物と水溶性処理液との化学反応により被処理物表面に皮膜を生成させる処理において、前述のような関係のあることは本発明者らが初めて見出した事項である。本発明はこの知見に基くものである。   When the present inventors performed a roll coating process to generate a film on the surface of the object to be processed by a chemical reaction between the object to be processed and the water-soluble processing liquid, the coating amount of the processing liquid on the steel sheet and the amount of the film to be generated I found a good correspondence between the two. It is known that there is a good correspondence (proportional relationship) between the amount of coating of the treatment liquid and the amount of film produced in the so-called coating-type film forming process in which the coating liquid is heated and dried to form a film. However, the present inventors have found for the first time that the above-mentioned relationship exists in the treatment for forming a film on the surface of the object to be treated by the chemical reaction between the object to be treated and the water-soluble treatment liquid. The present invention is based on this finding.

以下、合金化溶融亜鉛めっき鋼板に、絞りロールでめっき皮膜と水溶性処理液との化学反応により、亜鉛系酸化物を生成させる表面改質用の水溶性処理液である酢酸ナトリウム２０ｇ／リットルを添加したｐＨ：２．０、液温：５０℃の硫酸酸性水溶液を塗布し、めっき表面にめっき皮膜と水溶性処理液との化学反応により亜鉛系酸化物からなる皮膜を形成する反応を生じている際中に、鋼板表面の処理液量を測定した実験結果を例に挙げて、本発明の実施の形態を具体的に説明する。   Hereinafter, 20 g / liter of sodium acetate, which is a water-soluble treatment liquid for surface modification that generates a zinc-based oxide by a chemical reaction between a plating film and a water-soluble treatment liquid with a squeezing roll, is applied to an alloyed hot-dip galvanized steel sheet. Added pH: 2.0, liquid temperature: 50 ° C sulfuric acid aqueous solution was applied, and a reaction of forming a zinc oxide film was formed on the plating surface by a chemical reaction between the plating film and the water-soluble treatment liquid. The embodiment of the present invention will be specifically described with reference to an experimental result of measuring the amount of the treatment liquid on the surface of the steel sheet as an example.

図１は、処理液量測定実験を説明する模式図である。図１（ａ）に示すように、処理液４が保持された処理液槽７に合金化溶融亜鉛めっき鋼板６を浸漬する。次いで、合金化溶融亜鉛めっき鋼板６を取り出し、ただちに図１（ｂ）に示すように、絞りロール５を通過させ、通板直後の合金化溶融亜鉛めっき鋼板６表面の処理液量を水分計１によって計測した。水分計は、フィルター型赤外吸収方式の水分計測装置を使用した（以下、この水分計測装置を、「赤外水分計」、または単に「水分計」と記載する。）。絞りロール５のロールギャップＡを３段階（広、中、狭）に変化させることで塗布する処理液量を３水準（厚、中、薄）変化させた。   FIG. 1 is a schematic diagram for explaining a treatment liquid amount measurement experiment. As shown in FIG. 1A, an alloyed hot-dip galvanized steel sheet 6 is immersed in a treatment liquid tank 7 in which the treatment liquid 4 is held. Next, the galvannealed steel sheet 6 is taken out and immediately passed through a squeeze roll 5, as shown in FIG. 1 (b). Measured by. As the moisture meter, a filter type infrared absorption type moisture measuring device was used (hereinafter, this moisture measuring device is referred to as “infrared moisture meter” or simply “moisture meter”). By changing the roll gap A of the squeezing roll 5 in three steps (wide, medium, and narrow), the amount of treatment liquid to be applied was changed by three levels (thickness, medium, and thin).

ロールギャップと赤外水分計による計測値の関係を図２に示す。図２より明らかなように、赤外水分計の計測値は、ロールギャップ設定値の３段階に対応して変化していることがわかる。ロールギャップを狭くすれば、鋼板上に存在する処理液は絞りロールによってより絞られるために、鋼板表面の処理液量が減少し、逆にロールギャップを広くすると処理液量は増加する。従って、赤外水分計の計測値は、絞りロール通過後に鋼板の表面に存在する処理液量に応じて変化していることがわかる。   The relationship between the roll gap and the measured value by the infrared moisture meter is shown in FIG. As can be seen from FIG. 2, the measured value of the infrared moisture meter changes corresponding to the three stages of the roll gap set value. If the roll gap is narrowed, the treatment liquid present on the steel sheet is further squeezed by the squeeze roll, so that the amount of the treatment liquid on the surface of the steel sheet decreases, and conversely, if the roll gap is widened, the treatment liquid amount increases. Therefore, it can be seen that the measured value of the infrared moisture meter changes in accordance with the amount of treatment liquid present on the surface of the steel sheet after passing through the squeeze roll.

さらに、赤外水分計による測定結果と、実水分量の関係を調べた。具体的には、精密電子天秤に板厚０．８ｍｍ×４０ｍｍφの合金化溶融亜鉛めっき鋼板試料を設置し、該鋼板上の全面に所定量の処理溶液をピペットで塗布し、該試料全面の水分量を赤外水分計で測定した。処理溶液の膜厚は、電子天秤で得られた重量から換算した。処理溶液の膜厚と水分計の計測値の関係を図３に示す。処理液の膜厚が０〜４０μｍの間で両者に良い対応関係があり、処理溶液の膜厚を赤外水分計で精度良く測定できることがわかる。   Furthermore, the relationship between the measurement result by the infrared moisture meter and the actual moisture content was examined. Specifically, an alloyed hot-dip galvanized steel sheet sample with a plate thickness of 0.8 mm × 40 mmφ is placed on a precision electronic balance, and a predetermined amount of treatment solution is applied to the entire surface of the steel sheet with a pipette. The amount was measured with an infrared moisture meter. The film thickness of the treatment solution was converted from the weight obtained with an electronic balance. The relationship between the film thickness of the treatment solution and the measured value of the moisture meter is shown in FIG. It can be seen that there is a good correspondence between the treatment liquid film thicknesses of 0 to 40 μm and the film thickness of the treatment solution can be accurately measured with an infrared moisture meter.

そこで、図１の実験装置を用いて、合金化溶融亜鉛めっき鋼板に同一通板速度でロールギャップを変えて前述の表面改質用処理液を塗布し、めっき表面にめっき皮膜と水溶性処理液との化学反応により、亜鉛系酸化物を生成させた後、水洗乾燥を行う実験を行い、絞りロール直後の鋼板表面の処理液の水分量と水洗乾燥後の酸化物の膜厚を調査した。水分量は赤外水分計で測定し、酸化膜厚はＸＲＦ法で測定した。調査結果を図４に示す。図４より処理液の水分量と酸化膜厚の間によい対応関係があることがわかる。   Therefore, by using the experimental apparatus shown in FIG. 1, the above-described surface modification treatment liquid is applied to the galvannealed steel sheet while changing the roll gap at the same sheet feeding speed, and the plating film and the water-soluble treatment liquid are applied to the plating surface. After the zinc oxide was generated by the chemical reaction, an experiment in which washing with water and drying was performed was performed, and the moisture content of the treatment liquid on the steel sheet surface immediately after the drawing roll and the film thickness of the oxide after washing and drying were investigated. The moisture content was measured with an infrared moisture meter, and the oxide film thickness was measured with the XRF method. The survey results are shown in FIG. It can be seen from FIG. 4 that there is a good correspondence between the water content of the treatment liquid and the oxide film thickness.

酸化物生成量は、反応時間によっても変わる。そこで、図１の実験装置で、合金化溶融亜鉛めっき鋼板に、通板速度及びロールギャップを変えて前述の表面改質用処理液を塗布した後水洗乾燥を行う実験を行い、絞りロール直後の鋼板表面の処理液の水分量、反応時間、及び水洗乾燥後における酸化物膜厚を調査した。反応時間は、絞りロール通過後水洗までの時間である。図５は、この調査で得られた絞りロール出側における処理液の水分量、反応時間及び生成した酸化膜厚の関係を示す。   The amount of oxide produced also varies depending on the reaction time. Therefore, in the experimental apparatus shown in FIG. 1, an experiment was performed in which the above-described surface modification treatment liquid was applied to the alloyed hot-dip galvanized steel sheet while changing the sheet passing speed and the roll gap, followed by washing and drying. The water content of the treatment liquid on the steel sheet surface, the reaction time, and the oxide film thickness after washing and drying were investigated. The reaction time is the time from squeezing rolls to washing with water. FIG. 5 shows the relationship between the moisture content of the treatment liquid on the outlet side of the squeeze roll, the reaction time, and the generated oxide film thickness obtained in this investigation.

以上の結果から、めっき表面に生成する酸化膜厚は、塗布された処理液の水分量（水分計による水分計測値）及び反応時間との間によい対応関係があること、また塗布された処理液の水分量は絞りロールのロールギャップとよい対応関係があることがわかる。この関係を用いて、ロールギャップを設定し、また塗布された処理液の水分量を計測し、計測結果に基いてロールギャップを調整することで、鋼板表面に所要の膜厚の酸化物を安定生成させることができる。   From the above results, the oxide film thickness generated on the plating surface has a good correspondence between the moisture content of the applied treatment liquid (moisture measurement value by the moisture meter) and the reaction time, and the applied treatment. It can be seen that the water content of the liquid has a good correspondence with the roll gap of the squeeze roll. Using this relationship, the roll gap is set, the moisture content of the applied processing solution is measured, and the roll gap is adjusted based on the measurement results, thereby stabilizing the oxide with the required film thickness on the steel sheet surface. Can be generated.

反応時間は、鋼板通板速度に対応して決まる。図５から、生成させる酸化膜厚の基準値（Ｍｓ）、及び鋼板通板速度Ｌｓに対応する反応時間ｔｓに基いて、塗布する処理液の水分量の設定値Ｗｓを決定し、また、図２から前記水分量の設定値Ｗｓに対応する絞りロールのロールギャップＧｓを決定する。ロールギャップの調整は絞りロールの圧下力を調整して行う。また、図２から、ロールギャップを変えたときのロールギャップの変化量ΔＧに対する塗布される処理液の水分量変化（水分計での水分計測値の変化量）ΔＷの関係を求めておく。ΔＷは図２の特性曲線の勾配から求められる。   The reaction time is determined according to the steel plate passing speed. From FIG. 5, the set value Ws of the moisture amount of the treatment liquid to be applied is determined based on the reference value (Ms) of the oxide film thickness to be generated and the reaction time ts corresponding to the steel plate passing speed Ls. 2 determines a roll gap Gs of the squeezing roll corresponding to the set value Ws of the moisture amount. The roll gap is adjusted by adjusting the rolling force of the squeeze roll. Further, from FIG. 2, the relationship of the change in the amount of moisture in the applied processing liquid to the amount of change ΔG in the roll gap when the roll gap is changed (the amount of change in the moisture measurement value in the moisture meter) ΔW is obtained. ΔW is obtained from the slope of the characteristic curve in FIG.

鋼板通板速度をＬｓ、ロールギャップをＧｓに設定して処理液を塗布し、塗布した処理液の水分量Ｗｍを水分計で計測する。計測水分量Ｗｍと設定水分量Ｗｓに差がある場合、その差を解消するようにロールギャップを調整する。例えば、計測水分量Ｗｍと設定水分量Ｗｓの差がΔＷｍである場合、ロールギャップ調整量ΔＧｍを、ΔＧｍ＝（Ｗｍ−Ｗｓ）×ΔＧ／ΔＷに基き演算して求め、前記で求めたΔＧに基き、ロールギャップをＧｓからＧｓ＋ΔＧｍへ調整する。ロールギャップの調整は応答性に優れるので、処理液の塗布量を所要の塗布量に迅速に調整でき、それによって、所要膜厚の酸化物を安定製造できる。   The steel plate passing speed is set to Ls, the roll gap is set to Gs, the treatment liquid is applied, and the moisture content Wm of the applied treatment liquid is measured with a moisture meter. When there is a difference between the measured water amount Wm and the set water amount Ws, the roll gap is adjusted so as to eliminate the difference. For example, when the difference between the measured water amount Wm and the set water amount Ws is ΔWm, the roll gap adjustment amount ΔGm is calculated based on ΔGm = (Wm−Ws) × ΔG / ΔW, and the ΔG obtained above is calculated. Based on this, the roll gap is adjusted from Gs to Gs + ΔGm. Since adjustment of the roll gap is excellent in responsiveness, the coating amount of the treatment liquid can be quickly adjusted to a required coating amount, and thereby an oxide having a required film thickness can be stably produced.

ここで、水分計の設定値Ｗｓは、酸化膜厚の目標値Ｍｏに対応する水分計の指示値Ｗｏを採用することで生成する酸化膜厚の変動を小さくすることができる。   Here, the set value Ws of the moisture meter can reduce the fluctuation of the oxide film thickness generated by adopting the instruction value Wo of the moisture meter corresponding to the target value Mo of the oxide film thickness.

また、酸化膜厚に目標範囲Ｍｍｉｎ〜Ｍｍａｘを設け、水分計の設定値Ｗｓとして下限値Ｍｍｉｎ、上限値Ｍｍａｘの各々に対応する水分計の指示値Ｗｍｉｎ、Ｗｍａｘを採用し、水分計の計測値がＷｍｉｎを下回った場合、水分計の計測値がＷｍｉｎ以上になるようにロールギャップを調整し、水分計の計測値がＷｍａｘを上回った場合、水分計の計測値がＷｍａｘ以下になるようにロールギャップを調整することもできる。   Further, target ranges Mmin to Mmax are provided for the oxide film thickness, and the moisture meter indication values Wmin and Wmax corresponding to the lower limit value Mmin and the upper limit value Mmax are adopted as the setting value Ws of the moisture meter. The roll gap is adjusted so that the measured value of the moisture meter is greater than or equal to Wmin when the water content is less than Wmin, and the roll is adjusted so that the measured value of the moisture meter is less than or equal to Wmax when the measured value of the moisture meter exceeds Wmax. The gap can also be adjusted.

特許文献１０は、いわゆる塗布型皮膜形成処理を対象とするもので、形成される皮膜厚は塗布される塗料中の水分量に比例する。塗布された塗料の水分量をｘ、形成される皮膜厚をｙとすると、両者は概ね、ｙ＝ａｘで関係づけられる。塗料は原板の電磁鋼帯と反応することがなく、また通板速度が変化しても形成される皮膜厚は同じである。これに対して、本発明は、図４に示されるように、処理液の水分量と生成する皮膜量は比例関係がなく、また皮膜生成量は、反応時間、すなわち通板速度の影響を受ける。したがって、本願発明における製膜メカニズムと特許文献１０の製膜メカニズムは本質的に異なる。したがって、特許文献１０等に、塗料中の水分量を計測し、その結果に基づいて、塗料の塗布量を制御することが記載されていたとしても、処理液の塗布量、反応時間（通板速度）によって皮膜生成量が異なる本発明の表面処理鋼板の製造方法において、安定して所要の皮膜量を生成させる観点から、塗布された処理液中の水分量を計測し、水分量の計測値によって鋼板に塗布する処理液量を制御することは想到されない。   Patent Document 10 is directed to a so-called coating-type film forming process, and the film thickness to be formed is proportional to the amount of water in the coating material to be applied. If the moisture content of the applied paint is x and the thickness of the coating film to be formed is y, they are generally related by y = ax. The coating does not react with the electromagnetic steel strip of the original plate, and the formed film thickness is the same even if the plate passing speed is changed. On the other hand, according to the present invention, as shown in FIG. 4, the amount of water in the treatment liquid and the amount of film produced are not proportional, and the amount of film produced is affected by the reaction time, that is, the plate passing speed. . Therefore, the film forming mechanism in the present invention and the film forming mechanism of Patent Document 10 are essentially different. Therefore, even if Patent Document 10 and the like describe that the amount of moisture in the coating material is measured and the coating amount of the coating material is controlled based on the result, the coating amount of the treatment liquid, the reaction time (through plate) In the method for producing a surface-treated steel sheet according to the present invention in which the amount of film produced varies depending on the speed), from the viewpoint of stably producing the required amount of film, the amount of water in the applied treatment liquid is measured, and the measured value of the amount of water Thus, it is not conceivable to control the amount of the treatment liquid applied to the steel sheet.

皮膜生成量は鋼板幅方向で均一であることが好ましい。鋼板幅方向の処理液の水分量分布を均一にすることで、鋼板幅方向の皮膜生成量の分布を均一にできる。赤外水分計を鋼板幅方向に走査させて鋼板幅方向の複数位置の処理液水分量を計測することで、鋼板幅方向の水分の分布状況を知ることができる。例えば、幅方向両端部近傍部分及び幅方向中央の３点の処理液水分量を計測することで、鋼板幅方向の水分の分布状況を知ることができる。また、絞りロールの圧下力を幅方向両側で独立に調整可能とし、絞りロール両側の圧下力の差と、それに対応する幅方向両端部近傍部分の水分量の差との関係を求めておくことにより、測定した幅方向両端部近傍部分の水分量の差に基いて、その差を解消するように絞りロールの圧下力を調整することで、鋼板幅方向の皮膜生成量の分布を均一にできる。   The amount of film formation is preferably uniform in the width direction of the steel sheet. By making the moisture content distribution of the treatment liquid in the steel plate width direction uniform, the distribution of the film formation amount in the steel plate width direction can be made uniform. By measuring the moisture content of the treatment liquid at a plurality of positions in the steel plate width direction by scanning the infrared moisture meter in the steel plate width direction, it is possible to know the moisture distribution in the steel plate width direction. For example, it is possible to know the distribution of moisture in the width direction of the steel sheet by measuring the amount of water in the treatment liquid at three points near the both ends in the width direction and in the center in the width direction. In addition, the reduction force of the squeeze roll can be adjusted independently on both sides in the width direction, and the relationship between the difference in the reduction force on both sides of the squeeze roll and the difference in the water content in the vicinity of both ends in the width direction should be determined. Thus, based on the difference in the moisture content in the vicinity of both ends in the width direction, the distribution of the amount of film formed in the steel sheet width direction can be made uniform by adjusting the rolling force of the squeeze roll so as to eliminate the difference. .

本発明が対象とする処理液は前述の処理液に限定されない。成分組成が既知である処理液について、塗布された処理液の水分量（すなわち水分計による計測値）、反応時間及び酸化物生成量の関係を調査して求め、この関係を用いることで、前記と同様にして処理液を塗布することで、鋼板表面に所要の膜厚の皮膜を安定生成させることができる。   The treatment liquid targeted by the present invention is not limited to the aforementioned treatment liquid. About the processing liquid having a known component composition, the water amount of the applied processing liquid (that is, a measured value by a moisture meter), the relationship between the reaction time and the amount of oxide generated is investigated and obtained, and by using this relationship, By applying the treatment liquid in the same manner as described above, a film having a required film thickness can be stably generated on the steel sheet surface.

以下、本発明を実施例により具体的に説明する。図６は本実施例に使用した処理ラインの要部を示す概略図である。   Hereinafter, the present invention will be specifically described by way of examples. FIG. 6 is a schematic view showing the main part of the processing line used in this embodiment.

合金化溶融亜鉛めっき鋼板６は、酢酸ナトリウム２０ｇ／リットルを添加したｐＨ：２．０、液温：５０℃の硫酸酸性水溶液（以下、処理溶液と記す）４が保持された処理溶液槽７に保持された処理溶液４内に侵入し、出口に配置された絞りロール５を通過させることで、亜鉛めっき鋼板６表面に所定量の処理溶液が塗布される。さらに、鋼板６は、所定距離走行後、洗浄溶液８が保たれた洗浄槽９、乾燥装置１０に順次通板される。絞りロール５から洗浄槽９の間で、亜鉛めっき鋼板６表面は、付着している処理溶液４との化学反応によって酸化物層が生成されて表面改質される。洗浄槽９で洗浄されることで、処理液との反応は終了し、乾燥装置１０で乾燥して所要の表面改質皮膜が形成される。ロールギャップ制御装置３によって、絞りロール５は、操作側、駆動側のロールギャップを独立に制御することが可能である。   The alloyed hot-dip galvanized steel sheet 6 is placed in a treatment solution tank 7 in which a sulfuric acid aqueous solution (hereinafter referred to as a treatment solution) 4 having a pH of 2.0 and a liquid temperature of 50 ° C. to which 20 g / liter of sodium acetate has been added is held. A predetermined amount of the treatment solution is applied to the surface of the galvanized steel sheet 6 by entering the retained treatment solution 4 and passing through the squeezing roll 5 disposed at the outlet. Further, after traveling a predetermined distance, the steel plate 6 is sequentially passed through a cleaning tank 9 and a drying device 10 in which the cleaning solution 8 is maintained. Between the squeezing roll 5 and the cleaning tank 9, the surface of the galvanized steel sheet 6 is surface-modified by a chemical reaction with the treatment solution 4 adhering thereto. By washing in the washing tank 9, the reaction with the treatment liquid is completed, and the desired surface modification film is formed by drying with the drying device 10. With the roll gap control device 3, the squeezing roll 5 can independently control the roll gap on the operation side and the drive side.

演算装置２には、赤外水分計１で計測する水分量の計測値、鋼板走行速度と洗浄槽９、乾燥装置１０で水洗乾燥後の皮膜生成量の関係、絞りロール５の圧下力と処理液の水分量の関係、及び絞りロール５の両側の圧下力差に対応する幅方向処理液量分布の不均一の程度（幅方向両端部近傍部分の水分量の差）の関係が、各々入力されている。   The computing device 2 includes a measured value of the moisture content measured by the infrared moisture meter 1, the relationship between the steel plate traveling speed and the cleaning tank 9, the amount of film formed after washing and drying by the drying device 10, the rolling force and processing of the squeeze roll 5. The relationship between the water content of the liquid and the non-uniform degree of the liquid distribution in the width direction corresponding to the rolling force difference between the sides of the squeeze roll 5 (the difference in the water content in the vicinity of both ends in the width direction) is input. Has been.

赤外水分計１は板幅方向トラバース装置（図示せず）によって板幅方向に走査させながら合金化溶融亜鉛めっき鋼板６上の水分量を計測できるようにした。演算装置２は、鋼板６の長手方向とともに板幅方向での水分量の計測結果とその平均値と、予め設定している水分量との較差からロールギャップの設定値を演算できるようにした。   The infrared moisture meter 1 can measure the moisture content on the alloyed hot-dip galvanized steel sheet 6 while being scanned in the sheet width direction by a sheet width direction traverse device (not shown). The calculation device 2 can calculate the set value of the roll gap from the difference between the measurement result of the moisture content in the sheet width direction as well as the longitudinal direction of the steel plate 6 and the average value thereof and the preset moisture content.

本発明法では、前記処理において、赤外水分計１によって反応中の処理液の水分量を計測する。計測された処理液の水分量が予め設定された設定値と異なる場合、演算装置２は、絞りロールで塗布する処理液の水分量を設定値に近づけるように、ロールギャップ制御装置３に指令を出す。ロールギャップ制御装置３は、該指令によって絞りロール５のロールギャップを制御する。   In the method of the present invention, in the treatment, the moisture content of the treatment liquid during the reaction is measured by the infrared moisture meter 1. When the measured moisture content of the processing liquid is different from a preset value, the calculation device 2 issues a command to the roll gap control device 3 so that the moisture content of the processing liquid applied by the squeeze roll approaches the set value. put out. The roll gap control device 3 controls the roll gap of the squeezing roll 5 according to the command.

本発明法で製造したコイルから鋼板の長手方向および板幅方向で試料を採取し、酸化膜厚を評価した。全５コイルの長手方向３点、板幅方向３点の計４５点の試料を採取し、その表裏面について調査した。従来法では、絞りロールのロールギャップは、予め押し付け圧を変化させて製造した製品の酸化膜厚を求めておき、所定の酸化膜厚が得られた押し付け圧となるように調整し、製造したコイルについて本発明法と同様の調査を行った。その結果、従来法では、目標範囲を外れるものが１３．３％発生したが、本発明法では目標範囲を外れるものは発生しなかった。   Samples were taken from the coil produced by the method of the present invention in the longitudinal direction and the width direction of the steel plate, and the oxide film thickness was evaluated. A total of 45 samples of 3 points in the longitudinal direction and 3 points in the plate width direction of all 5 coils were collected, and the front and back surfaces thereof were investigated. In the conventional method, the roll gap of the squeezing roll was previously prepared by obtaining the oxide film thickness of the product manufactured by changing the pressing pressure, and adjusting the pressure to obtain a predetermined oxide film thickness. The coil was examined in the same manner as the method of the present invention. As a result, in the conventional method, 13.3% occurred outside the target range, but in the method of the present invention, nothing out of the target range occurred.

実施例１では、鋼板走行速度と処理液の水分量の関係、絞りロール５の圧下力と幅方向の処理液膜量の均一性の関係について予めその関係を求めておいたが、これに限定されるものではなく、処理液膜量を変化させる因子については、それぞれの因子と処理液膜量の関係を求めておけばよい。   In Example 1, the relationship between the travel speed of the steel sheet and the moisture content of the treatment liquid and the relationship between the rolling force of the squeeze roll 5 and the uniformity of the treatment liquid film amount in the width direction were obtained in advance, but this is limited to this. However, for the factors that change the amount of the processing liquid film, the relationship between each factor and the amount of the processing liquid film may be obtained.

例えば、鋼板の幅が変化すると絞りロールの押し付け線圧が変化するために、処理液膜量が変化する。また、鋼板走行速度は、絞りロールからの処理液持ち出し量を変えることが考えられる。   For example, when the width of the steel plate changes, the pressing linear pressure of the squeezing roll changes, so that the amount of the processing liquid film changes. Further, it is conceivable that the traveling speed of the steel plate changes the amount of the processing liquid taken out from the squeeze roll.

図７は、図６に示した処理ラインにおいて予め求めた鋼板幅と処理液量の関係を示す。図７において、横軸（鋼板幅比）は、設備能力の最大鋼板幅に対する処理される鋼板幅の比率（％）である。鋼板幅比１００％は設備能力の最大鋼板幅に対応する。図７より、鋼板幅比が７５％を超えると処理液膜量が増加していくことから、鋼板幅比が７５％を超える鋼板では絞りロールの押し付け圧力を増加させることで処理液膜量が増加するのを防止できる。   FIG. 7 shows the relationship between the steel plate width and the amount of processing liquid obtained in advance in the processing line shown in FIG. In FIG. 7, the horizontal axis (steel plate width ratio) is the ratio (%) of the processed steel plate width to the maximum steel plate width of the equipment capacity. The steel plate width ratio of 100% corresponds to the maximum steel plate width of the equipment capacity. From FIG. 7, since the amount of the treatment liquid film increases when the steel plate width ratio exceeds 75%, the amount of the treatment liquid film is increased by increasing the pressing pressure of the squeeze roll in the steel plate with the steel plate width ratio exceeding 75%. The increase can be prevented.

また、鋼板走行速度に比例して処理液膜量が増加することがわかった。従って、この場合は、鋼板速度に比例して絞りロール押し付け圧力を増減させればよいことになる。例えば鋼板走行速度を増加する場合は、絞りロール押し付け圧力を増加させる。   Moreover, it turned out that the amount of process liquid films increases in proportion to the steel plate traveling speed. Therefore, in this case, the squeeze roll pressing pressure may be increased or decreased in proportion to the steel plate speed. For example, when the steel plate traveling speed is increased, the squeeze roll pressing pressure is increased.

以上の関係を予め求めておけば、処理される鋼板幅、鋼板走行速度が変わっても、前記で求めた関係を用いて、処理される鋼板幅、鋼板走行速度に応じて、処理液膜量を目標液膜量にするのに適した絞りロールの押し付け圧力の設定値を決定でき、この設定値を用いて処理をすることで、鋼板表面に形成される酸化膜厚の目標酸化膜厚に対するばらつきを低減することが可能になる。   If the above relationship is obtained in advance, even if the steel plate width to be processed and the steel plate traveling speed are changed, the amount of the processing liquid film is determined according to the steel plate width to be processed and the steel plate traveling speed by using the relationship obtained above. The setting value of the pressing pressure of the squeezing roll suitable for setting the target liquid film amount can be determined, and by processing using this set value, the oxide film thickness formed on the steel sheet surface with respect to the target oxide film thickness Variations can be reduced.

以上の関係を用いて処理を行いて一ヶ月間に製造されたコイルから、各コイル毎に試料を切り出して酸化膜厚を測定したところ、従来法では目標酸化膜厚に対するばらつきが±３０％以内であったものを本発明法では±１０％以内に低減することができた。   When the oxide film thickness was measured by cutting out a sample for each coil from the coil manufactured for one month by processing using the above relationship, the variation with respect to the target oxide film thickness was within ± 30% in the conventional method. Can be reduced within ± 10% by the method of the present invention.

なお、処理液膜量を変化させる因子として、鋼板走行速度、鋼板幅について説明したが、これに限定されるものではなく、必要に応じて、例えば、鋼板厚、鋼板粗度、鋼板温度などの因子と処理液膜量の関係を求めておけばよい。   In addition, although the steel plate traveling speed and the steel plate width have been described as factors for changing the amount of the processing liquid film, the present invention is not limited to this, and as necessary, for example, the steel plate thickness, the steel plate roughness, the steel plate temperature, etc. What is necessary is just to obtain | require the relationship between a factor and the amount of process liquid films.

本発明は、連続走行する被処理物に水溶性処理液を塗布し、被処理物と水溶性処理液との化学反応により、被処理物表面に皮膜を生成させる表面処理物の製造方法として利用することができる。   INDUSTRIAL APPLICABILITY The present invention is used as a method for producing a surface-treated product in which a water-soluble treatment liquid is applied to a continuously running workpiece, and a film is formed on the surface of the workpiece by a chemical reaction between the workpiece and the water-soluble treatment liquid. can do.

処理液量測定実験を説明する模式図である。It is a schematic diagram explaining a processing liquid quantity measurement experiment. ロールギャップと赤外水分計の水分計測値の関係を示す図である。It is a figure which shows the relationship between a roll gap and the moisture measurement value of an infrared moisture meter. 処理溶液の膜厚と水分計の水分計測値の関係を示す図である。It is a figure which shows the relationship between the film thickness of a process solution, and the moisture measurement value of a moisture meter. 水分計で計測された水分量と酸化膜厚の関係を示す図である。It is a figure which shows the relationship between the moisture content measured with the moisture meter, and the oxide film thickness. 絞りロール出側の処理液の水分量、反応時間及び生成した酸化膜厚の関係を示す図である。It is a figure which shows the relationship of the moisture content of the process liquid of a squeeze roll exit side, reaction time, and the produced | generated oxide film thickness. 本実施例に使用した処理ラインの要部を示す概略図である。It is the schematic which shows the principal part of the processing line used for the present Example. 本実施例に使用した処理ラインにおける板幅と処理液膜量の関係を示す図である。It is a figure which shows the relationship between the board width in the processing line used for the present Example, and the amount of process liquid films.

符号の説明Explanation of symbols

１ 赤外水分計
２ 演算装置
３ ロールギャップ制御装置
４ 処理液
５ 絞りロール
６ 合金化溶融亜鉛めっき鋼板
７ 処理液槽
８ 洗浄溶液（洗浄水）
９ 洗浄槽
１０ 乾燥装置 DESCRIPTION OF SYMBOLS 1 Infrared moisture meter 2 Computation apparatus 3 Roll gap control apparatus 4 Processing liquid 5 Drawing roll 6 Alloying hot dip galvanized steel sheet 7 Processing liquid tank 8 Cleaning solution (cleaning water)
9 Washing tank 10 Drying device

Claims (7)

被処理物に水溶性処理液を塗布し、被処理物と水溶性処理液との化学反応により被処理物表面に皮膜を生成させる表面処理物の製造方法において、被処理物に予め処理液の成分濃度が既知の処理液を塗布し、該処理物上の処理液中の水分量を計測し、水分量の計測値によって被処理物に塗布する処理液量を制御することを特徴とする表面処理物の製造方法。   In a method for producing a surface-treated product in which a water-soluble treatment liquid is applied to a workpiece and a film is formed on the surface of the workpiece by a chemical reaction between the workpiece and the water-soluble treatment liquid, the treatment liquid is previously applied to the workpiece. A surface characterized by applying a treatment liquid having a known component concentration, measuring the amount of water in the treatment liquid on the treatment object, and controlling the amount of treatment liquid to be applied to the object to be treated according to the measured value of the moisture amount Processed product manufacturing method. 連続的に走行する被処理物に塗布した水溶性処理液の塗布量、被処理物の走行速度および被処理物表面に生成する皮膜量との関係を求めて、この関係及び被処理物上の処理液中の水分量の計測値に基いて被処理物に塗布する処理液量を制御することを特徴とする請求項１に記載の表面処理物の製造方法。   The relationship between the coating amount of the water-soluble treatment liquid applied to the workpiece to be continuously run, the running speed of the workpiece, and the amount of film formed on the workpiece surface is obtained. 2. The method for producing a surface-treated product according to claim 1, wherein the amount of the treatment liquid applied to the object to be treated is controlled based on a measured value of the amount of water in the treatment liquid. 処理液の塗布を絞りロールで行い、処理液量の制御を絞りロールの押付圧制御によって行なうことを特徴とする請求項１または２に記載の表面処理物の製造方法。   The method for producing a surface-treated product according to claim 1 or 2, wherein the treatment liquid is applied by a squeeze roll, and the amount of the treatment liquid is controlled by pressing pressure control of the squeeze roll. 被処理物が帯状体であり、該帯状体の幅方向の複数点の処理液の水分量を各々計測し、水分量の計測値によって帯状体幅方向の塗布液量を制御することを特徴とする請求項１〜３のうちのいずれかの項に記載の表面処理物の製造方法。   The object to be processed is a band-shaped body, the water amounts of the treatment liquid at a plurality of points in the width direction of the band-shaped body are respectively measured, and the coating liquid amount in the band-shaped body width direction is controlled by the measured value of the water amount. The method for producing a surface-treated product according to any one of claims 1 to 3. フィルター型赤外吸収方式の装置によって処理液の水分量を計測することを特徴とする請求項１〜４のうちのいずれかの項に記載の表面処理物の製造方法。   The method for producing a surface-treated product according to any one of claims 1 to 4, wherein the moisture content of the treatment liquid is measured by a filter-type infrared absorption type apparatus. 被処理物が金属帯であることを特徴とする請求項１〜５のうちのいずれかの項に記載の表面処理物の製造方法。   The method for producing a surface-treated product according to any one of claims 1 to 5, wherein the workpiece is a metal strip. 金属帯が亜鉛めっき鋼板であり、その表面に生成させる皮膜が亜鉛系酸化物であることを特徴とする請求項６に記載の表面処理物の製造方法。
The method for producing a surface-treated product according to claim 6, wherein the metal strip is a galvanized steel sheet, and the coating film formed on the surface thereof is a zinc-based oxide.

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