JP2014128814A - Manufacturing method of steel plate excellent in chemical convertibility and corrosion resistance after coating - Google Patents

Manufacturing method of steel plate excellent in chemical convertibility and corrosion resistance after coating Download PDF

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JP2014128814A
JP2014128814A JP2012286789A JP2012286789A JP2014128814A JP 2014128814 A JP2014128814 A JP 2014128814A JP 2012286789 A JP2012286789 A JP 2012286789A JP 2012286789 A JP2012286789 A JP 2012286789A JP 2014128814 A JP2014128814 A JP 2014128814A
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steel plate
grinding
steel sheet
coating
treatment
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Shoki Fujita
昇輝 藤田
Junichi Tateno
純一 舘野
Yoshihiko Ono
義彦 小野
Shinji Otsuka
真司 大塚
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JFE Steel Corp
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Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of a high strength steel plate excellent in a chemical convertibility and a corrosion resistance after coating by eliminating a Si-containing oxide layer on a surface of the steel plate after the continuous annealing of a Si-containing high strength steel plate.SOLUTION: A surface grinding process including a grinding using an elastic grind stone is carried out after the continuous annealing of a steel plate containing 0.5 mass% of Si or more, an acid cleaning is carried out, and then a temper rolling is carried out. The surface grinding process is carried out so that the maximum height roughness Rz in a plate width direction after the surface grinding process is 3.0 μm or less. The temper rolling is carried out so that a ratio (LRa/CRa) of arithmetic average roughness (LRa) of the steel plate in a rolling direction to arithmetic average roughness (CRa) in a plate width direction after the temper rolling is 0.5 or more and 1.3 or less.

Description

本発明は、化成処理性及び塗装後耐食性に優れた高Si含有鋼板の製造方法に関するものである。   The present invention relates to a method for producing a high Si-containing steel sheet having excellent chemical conversion properties and post-coating corrosion resistance.

近年、地球環境の保全という観点から自動車の燃費改善が求められている。また、衝突時における乗員保護の観点から自動車の安全性向上も要求されている。このため、自動車の車体には軽量化と高強度化が必要とされ、最近では、自動車部品の薄肉化と高強度化が積極的に行われている。   In recent years, improvement in fuel efficiency of automobiles has been demanded from the viewpoint of conservation of the global environment. There is also a demand for improving the safety of automobiles from the viewpoint of occupant protection in the event of a collision. For this reason, it is necessary to reduce the weight and strength of automobile bodies, and recently, automobile parts have been actively reduced in thickness and strength.

一方、自動車部品の多くは鋼板をプレス成形して製造されることから、鋼板には高いプレス成形性、特に高い強度と高い延性、すなわち優れた強度−延性バランスが強く求められる。高い延性を有する高強度冷延鋼板には、強化元素としてSiが多量に含有される場合が多く、焼鈍時にSiの酸化物が鋼板表面に形成される。   On the other hand, since many automobile parts are manufactured by press-forming steel sheets, the steel sheets are strongly required to have high press formability, particularly high strength and high ductility, that is, excellent strength-ductility balance. A high strength cold-rolled steel sheet having high ductility often contains a large amount of Si as a strengthening element, and an Si oxide is formed on the steel sheet surface during annealing.

そのため、こうしたSi含有量の多い高強度冷延鋼板は、次工程にて化成処理を行ったとしても、化成結晶を均一かつ微細に形成させることができず、部分的に欠損した表面状態となる。このような化成処理不良の鋼板表面では、電着塗装等の塗装を施したとしても、密着性の良好な塗膜が得られないばかりでなく、塗装後の耐食性が劣化することになる。   Therefore, such a high-strength cold-rolled steel sheet with a high Si content cannot be formed uniformly and finely even if chemical conversion treatment is performed in the next step, resulting in a partially deficient surface state. . On such a steel sheet surface with poor chemical conversion treatment, even if electrodeposition coating or the like is applied, not only a coating film with good adhesion can be obtained, but also the corrosion resistance after coating deteriorates.

これまで、このような課題を解決すべく様々な技術が提案されており、例えば、特許文献1には、Siを0.5質量%以上含有する高張力鋼板を連続焼鈍後に表面研削処理と酸洗処理を行い、鋼帯表面に生成したSi含有酸化物層を除去して化成処理性に優れた鋼板を製造する方法が開示されている。   Until now, various techniques have been proposed to solve such problems. For example, Patent Document 1 discloses that a high-tensile steel sheet containing 0.5 mass% or more of Si is subjected to surface grinding treatment and acid treatment after continuous annealing. A method for producing a steel sheet excellent in chemical conversion treatment by removing the Si-containing oxide layer formed on the steel strip surface by performing a washing treatment is disclosed.

特開2012−6128号公報JP 2012-6128 A

しかしながら、0.5質量%以上ものSiを含有する高張力鋼板に連続焼鈍を施すと、非常に強固でかつ厚いSi含有酸化物層が鋼板表面に形成される。このような非常に強固でかつ厚いSi含有酸化物層を除去するために、連続焼鈍炉出側において表面研削を行う際は、重研削が必要となる。   However, when continuous annealing is performed on a high-strength steel sheet containing 0.5 mass% or more of Si, a very strong and thick Si-containing oxide layer is formed on the steel sheet surface. In order to remove such a very strong and thick Si-containing oxide layer, heavy grinding is required when performing surface grinding on the exit side of the continuous annealing furnace.

表面研削では研削方向に研削目が残存し、上記のような重研削を施された鋼板表面は、鋼板幅方向に鋭い凹凸が残存してしまう。このような鋭い凹凸が残存した表面状態の鋼板に電着塗装を施すと、塗装の剥離が生じた場合に鋼板表面の鋭い凹凸を起点として剥離が拡大し、塗装後耐食性が大きく低下してしまう懸念があった。   In surface grinding, grinding marks remain in the grinding direction, and sharp irregularities remain in the steel plate width direction on the steel plate surface subjected to heavy grinding as described above. When electrodeposition coating is applied to a steel sheet with such sharp irregularities remaining on the surface, when the peeling of the coating occurs, the peeling is enlarged starting from the sharp irregularities on the surface of the steel sheet, and the corrosion resistance after painting is greatly reduced. There was concern.

そこで、本発明は0.5質量%以上のSiを含有する高張力鋼板について、連続焼鈍後の鋼板表面に存在するSi含有酸化物層を除去して化成処理性を高めると共に、電着塗装後の塗装剥離が起こりにくい塗装後耐食性にも優れる高張力鋼板を製造することを目的とする。   Therefore, the present invention removes the Si-containing oxide layer present on the surface of the steel sheet after the continuous annealing to improve the chemical conversion treatment for the high-tensile steel sheet containing 0.5% by mass or more of Si, and after electrodeposition coating. An object of the present invention is to produce a high-strength steel sheet that is excellent in post-coating corrosion resistance, in which coating peeling is unlikely to occur.

本発明者は、上記課題を解決し、化成処理性及び塗装後耐食性に優れた高張力鋼板を効率よく製造する方法について検討を重ね、以下のような知見を得た。   The present inventor has solved the above-mentioned problems and repeatedly studied on a method for efficiently producing a high-tensile steel sheet excellent in chemical conversion property and post-coating corrosion resistance, and obtained the following knowledge.

すなわち、表面研削後の表面テクスチャーと塗装後耐食性の関係について検討した結果、重研削後の表面の凹凸が塗装後耐食性に大きく影響すること、表面研削後の鋼板表面の最大高さ粗さRzをある程度小さくした上で、酸洗後に施す調質圧延によって鋼板長手方向(圧延方向)と鋼板幅方向(板幅方向)における表面粗さの異方性を低減させると、塗装後耐食性を改善できることを見出した。   That is, as a result of examining the relationship between the surface texture after surface grinding and the corrosion resistance after painting, the surface roughness after heavy grinding greatly affects the corrosion resistance after painting, and the maximum height roughness Rz of the steel sheet surface after surface grinding is After reducing the surface roughness anisotropy in the steel plate longitudinal direction (rolling direction) and steel plate width direction (plate width direction) by temper rolling after pickling after reducing to some extent, the corrosion resistance after coating can be improved. I found it.

本発明は、上記した知見に基づきなされたもので、以下を要旨とするものである。   The present invention has been made on the basis of the above-described findings, and has the following gist.

[1]Siを0.5質量%以上含有する鋼板を連続焼鈍した後に、弾性砥石を用いた研削を含む表面研削処理を行い、次いで酸洗処理を行った後、調質圧延を行うに際し、前記表面研削処理後の鋼板の板幅方向の最大高さ粗さRzが3.0μm以下となるように表面研削処理し、さらに調質圧延後の鋼板の圧延方向の算術平均粗さと板幅方向の算術平均粗さが下記の式(1)を満足するように調質圧延することを特徴とする化成処理性及び塗装後耐食性に優れた鋼板の製造方法;
0.5≦LRa/CRa≦1.3・・・(1)
ただし、式(1)中のLRaは調質圧延後の鋼板の圧延方向の算術平均粗さRa(μm)を、CRaは調質圧延後の鋼板の板幅方向の算術平均粗さRa(μm)を表す。
[1] After continuously annealing a steel sheet containing 0.5% by mass or more of Si, after performing surface grinding treatment including grinding using an elastic grindstone, and then performing pickling treatment, temper rolling is performed. Surface grinding treatment is performed so that the maximum height roughness Rz in the plate width direction of the steel plate after the surface grinding treatment is 3.0 μm or less, and the arithmetic average roughness and the plate width direction in the rolling direction of the steel plate after temper rolling A method for producing a steel sheet excellent in chemical conversion treatment and corrosion resistance after coating, characterized by temper rolling so that the arithmetic average roughness of the above satisfies the following formula (1):
0.5 ≦ LRa / CRa ≦ 1.3 (1)
However, LRa in Formula (1) is the arithmetic average roughness Ra (μm) in the rolling direction of the steel sheet after temper rolling, and CRa is the arithmetic average roughness Ra (μm) in the sheet width direction of the steel sheet after temper rolling. ).

[2]前記表面研削処理は、鋼板両面を研削する上下1対の研削体を2対以上用いて行うことを特徴とする前記[1]に記載の化成処理性及び塗装後耐食性に優れた鋼板の製造方法。   [2] The surface grinding treatment is performed by using two or more pairs of upper and lower grinding bodies that grind both sides of the steel plate, and the steel plate having excellent chemical conversion property and post-coating corrosion resistance according to the above [1] Manufacturing method.

本発明により、良好な化成処理性と塗装後耐食性を確保した、Siを0.5質量%以上含有する高張力鋼板を製造できるようになった。本発明により製造した鋼板は、薄肉化と高強度化が求められる自動車部品等に好適である。   According to the present invention, it has become possible to produce a high-tensile steel sheet containing 0.5% by mass or more of Si that ensures good chemical conversion properties and post-coating corrosion resistance. The steel sheet produced according to the present invention is suitable for automobile parts and the like that are required to be thin and have high strength.

本発明の鋼板の製造方法が適用される製造設備の一例を模式的に示す図である。It is a figure which shows typically an example of the manufacturing equipment with which the manufacturing method of the steel plate of this invention is applied.

以下、本発明を実施するための形態の一例を説明する。
本発明の鋼板の製造方法においては、Siを0.5質量%以上含有する鋼板を用いる。鋼板のSi含有量が0.5質量%未満では、焼鈍時に鋼板表層に形成されるSi含有酸化物層が僅かであり、特別な前処理を施さなくても十分な化成処理性が確保されるため、Si含有量が0.5質量%以上の鋼板を対象とする。鋼板のSi含有量の上限は特に規定しないが、鋼板中のSi含有量が3質量%を超えると鋼板の加工性が劣化する傾向があるため、Si含有量は3質量%以下が望ましい。
Hereinafter, an example of an embodiment for carrying out the present invention will be described.
In the method for producing a steel plate of the present invention, a steel plate containing 0.5 mass% or more of Si is used. When the Si content of the steel sheet is less than 0.5% by mass, the Si-containing oxide layer formed on the surface layer of the steel sheet during annealing is slight, and sufficient chemical conversion treatment performance is ensured without special pretreatment. For this reason, steel sheets having a Si content of 0.5 mass% or more are targeted. The upper limit of the Si content of the steel sheet is not particularly specified, but if the Si content in the steel sheet exceeds 3% by mass, the workability of the steel sheet tends to deteriorate, so the Si content is desirably 3% by mass or less.

他の成分については、C、Mn、P、S、sol.Al、Cr、Mo、Ti、Nb等が適量添加された鋼板であっても、本発明の効果が損なわれることはない。   About another component, even if it is the steel plate to which C, Mn, P, S, sol.Al, Cr, Mo, Ti, Nb etc. were added in an appropriate quantity, the effect of this invention is not impaired.

本発明の製造方法により製造する鋼板は、たとえば日本鉄鋼連盟規格(JFS A2001-2008年)に記載の自動車用冷間圧延鋼板及び鋼帯、日本工業規格(JIS G3135−2006年)に記載の自動車用加工性冷間圧延高張力鋼板及び鋼帯に記載の鋼板において、Si含有量が0.5質量%以上の普通鋼高張力鋼板などであり、本発明により製造する鋼板の引張強度は、概ね390MPa以上である。   Steel sheets produced by the production method of the present invention are, for example, cold rolled steel sheets and steel strips for automobiles described in the Japan Iron and Steel Federation Standard (JFS A2001-2008), automobiles described in Japanese Industrial Standards (JIS G3135-2006). In the steel sheet described in the workability cold-rolled high-tensile steel sheet and steel strip, it is a plain steel high-tensile steel sheet having a Si content of 0.5% by mass or more, and the tensile strength of the steel sheet produced by the present invention is approximately It is 390 MPa or more.

また、本発明の製造方法に用いる鋼板、すなわち連続焼鈍に供する鋼板は、例えばSiを0.5質量%以上含有する鋼を、熱間圧延し、次いで冷間圧延して得たSi含有量が0.5質量%以上の鋼板(冷延鋼板)である。   Moreover, the steel content used for the manufacturing method of this invention, ie, the steel plate which uses for continuous annealing, for example, the Si content obtained by hot-rolling the steel containing 0.5 mass% or more of Si, and then cold-rolling. It is a steel plate (cold rolled steel plate) of 0.5 mass% or more.

図1は、本発明に係る鋼板の製造方法が適用される鋼板の製造設備の一例を示す概略構成図であり、連続焼鈍炉を含む連続処理ラインを示している。ここで、1は鋼板、2は連続焼鈍炉、3は表面研削装置、4は水切り装置、5は酸洗設備、6は調質圧延機、7はコイラーである。また、表面研削装置3において、31は弾性砥石ロール、32は鋼板を支えるバックアップロール、33は砥粒入りブラシロールであり、本実施形態において表面研削処理は、弾性砥石ロールによる研削(弾性砥石による研削)と砥粒入りブラシロールによる研削により行う。
図1に示す連続処理ラインでは、鋼板1は、図中の矢印方向に通板され、連続焼鈍炉2で連続焼鈍された後、表面研削装置3で表面研削処理され、水切り装置4を経て酸洗設備5で酸洗処理され、引き続き調質圧延機6で調質圧延された後、コイラー7でコイル形状に巻き取られる。
FIG. 1 is a schematic configuration diagram illustrating an example of a steel plate manufacturing facility to which a steel plate manufacturing method according to the present invention is applied, and shows a continuous processing line including a continuous annealing furnace. Here, 1 is a steel plate, 2 is a continuous annealing furnace, 3 is a surface grinding device, 4 is a draining device, 5 is a pickling facility, 6 is a temper rolling mill, and 7 is a coiler. Moreover, in the surface grinding apparatus 3, 31 is an elastic grindstone roll, 32 is a backup roll that supports a steel plate, and 33 is a brush roll containing abrasive grains. In this embodiment, the surface grinding treatment is performed by grinding with an elastic grindstone roll (with an elastic grindstone). Grinding) and grinding with a brush roll containing abrasive grains.
In the continuous processing line shown in FIG. 1, the steel plate 1 is passed in the direction of the arrow in the figure, and after being continuously annealed in the continuous annealing furnace 2, the surface is ground by the surface grinding device 3, and passes through the water draining device 4. After being pickled in the washing equipment 5 and subsequently temper-rolled by the temper rolling mill 6, it is wound into a coil shape by the coiler 7.

本実施形態では、上記したように、表面研削装置3で鋼板表面を研削(機械的研削)した後、酸洗設備5で酸洗処理(化学的研削)する。機械的研削の後に化学的研削である酸洗処理を行うことで、機械的研削では除去されない表層酸化物が残っても、その表層酸化物は機械的研削により剥離強度が低下しているため酸洗で除去しやすくなる。従って、表層酸化物を効率よく除去でき、部分的に酸化物が残存しない全面にわたって均一な処理後鋼板面を得ることができる。   In this embodiment, as described above, the steel plate surface is ground (mechanical grinding) by the surface grinding device 3 and then pickled (chemically ground) by the pickling equipment 5. By performing pickling treatment that is chemical grinding after mechanical grinding, even if surface oxide that cannot be removed by mechanical grinding remains, the peel strength of the surface oxide is reduced by mechanical grinding. Easy to remove by washing. Therefore, the surface layer oxide can be efficiently removed, and a uniform post-treated steel sheet surface can be obtained over the entire surface where no oxide remains partially.

ここで、本発明で行う表面研削処理には、弾性砥石を用いる必要がある。これは、弾性砥石は他の研削体に比べて、弾性率が高く、曲折することがないため、Siを含むような高強度材料に対しても重研削が可能なためである。   Here, it is necessary to use an elastic grindstone for the surface grinding process performed in the present invention. This is because the elastic grindstone has a higher elastic modulus than other grinding bodies and does not bend, so that heavy grinding is possible even for a high-strength material containing Si.

弾性砥石ロール31にて行う研削処理は、図1に示すように鋼板を挟んで弾性砥石ロール31と対向するバックアップロール32にて、鋼板を支えながら研削処理を行うものであり、鋼板の表面側(上面側)および鋼板の裏面側(下面側)を研削する各1つの弾性砥石ロールをもって、上下一対の弾性砥石ロール31が構成される。なお、ここで弾性砥石ロール、バックアップロールは、共に円形形状であるが、図1では、他のロールと区別するため、略多角形形状に図示している。   As shown in FIG. 1, the grinding process performed by the elastic grindstone roll 31 is performed by supporting the steel sheet with the backup roll 32 facing the elastic grindstone roll 31 with the steel sheet sandwiched between them. A pair of upper and lower elastic grindstone rolls 31 is formed with one elastic grindstone roll for grinding the (upper surface side) and the back surface side (lower surface side) of the steel plate. In addition, although both an elastic grindstone roll and a backup roll are circular shape here, in order to distinguish with another roll in FIG. 1, it has illustrated in the substantially polygonal shape.

また、表面研削処理は、上記したような弾性砥石を用いる研削処理を含み、複数パスによる表面研削(機械的研削)を行う、すなわち上下1対の研削体を2対以上用いて行うことが好ましい。図1に示す実施形態では、上下1対の研削体を2対有する、すなわち上下1対の弾性砥石ロール31および上下1対の砥粒入りブラシロール33を有する表面研削装置3により表面研削処理を行う。   Further, the surface grinding process includes a grinding process using an elastic grindstone as described above, and it is preferable to perform surface grinding (mechanical grinding) by a plurality of passes, that is, using two or more pairs of upper and lower grinding bodies. . In the embodiment shown in FIG. 1, the surface grinding process is performed by the surface grinding apparatus 3 having two pairs of upper and lower pairs of grinding bodies, that is, one pair of upper and lower elastic grindstone rolls 31 and one pair of upper and lower pairs of abrasive rolls 33. Do.

機械的な表面研削では鋼板表面の凸部が優先的に研削されるため、上下1対の研削体を2対以上用いて、複数パスによる表面研削を行う、すなわち鋼板の表面、裏面を各々複数回研削することで、重研削に伴う鋭い凹凸を滑らかにすることができ、研削目を滑らかにすることで鋼板長手方向と鋼板幅方向での表面粗さの差が小さくなり、異方性が一層改善される。複数パスにより表面研削を行う場合の具体的な研削条件としては、後段パスの研削体に用いる砥粒を前段パスよりも細かくする、つまり後段パス研削体に用いる砥粒番手を前段パスよりも大きくする、あるいは後段パスの研削体の弾性率を前段パスよりも小さくすることが、重研削に伴う鋭い凹凸を滑らかにする上で好ましい。   In mechanical surface grinding, the convex part on the steel sheet surface is preferentially ground, so two or more pairs of upper and lower grinding bodies are used for surface grinding by multiple passes, that is, the steel sheet has a plurality of front and back surfaces. By round grinding, sharp irregularities associated with heavy grinding can be smoothed, and by smoothing the ground, the difference in surface roughness between the steel plate longitudinal direction and the steel plate width direction is reduced, and anisotropy is reduced. It is further improved. Specific grinding conditions when performing surface grinding with multiple passes include making the abrasive grains used in the grinding body of the subsequent pass finer than the preceding pass, that is, increasing the grain count used in the post-pass grinding body than the preceding pass. It is preferable to make the elastic modulus of the grinding body in the subsequent stage pass smaller than that in the previous stage in order to smooth the sharp unevenness caused by heavy grinding.

図1の実施形態では、研削体として弾性砥石ロールとこの弾性砥石ロールよりも弾性率が小さい砥粒入りナイロンブラシロールを組み合わせて構成し、弾性率の異なる研削体を用いているが、これに限定されるものではなく、例えば、砥粒入りナイロンブラシロールに代えて、研磨布紙を用いた研磨布紙ロール(ベルトコンベア状)やワイヤブラシを用いたワイヤブラシロール等も適用することができる。また、弾性砥石ロールや砥粒入りナイロンブラシロール等の砥粒番号は、JIS−R6001規格の砥粒番号で♯80〜♯1200であることが好ましく、より好ましくは♯220〜♯800である。また、研削体の回転数は600〜1500rpmとすることが好ましい。
なお、図1の表面研削装置3は、上下1対の研削体を2対備えているが、これに限定されるものではなく、上下1対の弾性砥石ロール(研削体)を1対としてもよく、設備の設置スペースを確保できれば上下1対の研削体を3対以上設けてもよい。
In the embodiment of FIG. 1, an abrasive wheel roll and a nylon brush roll containing abrasive grains having a smaller elastic modulus than that of the elastic wheel roll are used as a grinding body, and a grinding body having a different elastic modulus is used. For example, instead of the nylon brush roll containing abrasive grains, an abrasive cloth roll (a belt conveyor) using abrasive cloth, a wire brush roll using a wire brush, or the like can be applied. . In addition, the abrasive grain number of an elastic grinding wheel roll or nylon brush roll containing abrasive grains is preferably JIS-R6001 standard abrasive grain number # 80 to # 1200, more preferably # 220 to # 800. Moreover, it is preferable that the rotation speed of a grinding body shall be 600-1500 rpm.
The surface grinding apparatus 3 in FIG. 1 includes two pairs of upper and lower pairs of grinding bodies. However, the present invention is not limited to this, and the pair of upper and lower elastic grindstone rolls (grinding bodies) may be a pair. Of course, three or more pairs of upper and lower grinding bodies may be provided as long as the installation space for the equipment can be secured.

ここで、上記したような表面研削処理を行った後、酸洗に供する鋼板の表面粗さについて、板幅方向の最大高さ粗さRzを3.0μm以下とする必要がある。なおここで、RzはJIS B 0601(2001)で規定される粗さ曲線の最大高さ粗さRzである。板幅方向の最大高さ粗さRzが3.0μmを超えると、調質圧延後の鋼板の圧延方向の算術平均粗さRaと鋼板の板幅方向の算術平均粗さRaが前記式(1)を満足するようにしても、鋭い凹凸溝が残存してしまうことがあるため、鋭い凹凸溝を起点とした塗装剥離が進行しやすく、塗装後耐食性を低下させやすくなる。
また、表面研削処理を行った後の鋼板の板幅方向の最大高さ粗さRzを3.0μm以下とするには、表面研削処理において、鋭い研削溝が鋼板に付与されないように、特に、初期研削パスでの砥粒番手を大きくして細かい砥粒を用いればよい。好ましくは砥粒番号#220〜#800とすることでRzを3.0μm以下にすることができる。
Here, after performing the above-described surface grinding treatment, it is necessary to set the maximum height roughness Rz in the sheet width direction to 3.0 μm or less for the surface roughness of the steel sheet to be pickled. Here, Rz is the maximum height roughness Rz of the roughness curve defined by JIS B 0601 (2001). When the maximum height roughness Rz in the sheet width direction exceeds 3.0 μm, the arithmetic average roughness Ra in the rolling direction of the steel sheet after temper rolling and the arithmetic average roughness Ra in the sheet width direction of the steel sheet are expressed by the above formula (1 However, since the sharp concavo-convex groove may remain, coating peeling starting from the sharp concavo-convex groove is likely to proceed, and the corrosion resistance after coating is likely to be lowered.
Further, in order to set the maximum height roughness Rz in the plate width direction of the steel plate after the surface grinding treatment to 3.0 μm or less, in the surface grinding treatment, in particular, a sharp grinding groove is not given to the steel plate. What is necessary is just to use a fine abrasive grain by enlarging the grain number in the initial grinding pass. Preferably, Rz can be 3.0 μm or less by setting the abrasive grain numbers # 220 to # 800.

鋼板1は表面研削装置3で表面研削処理(機械的研削)を行った後、水切り装置4において、表面研削の際に使用され鋼板表面に付着したクーラントを除去する。この水切り装置4の水切り手段に特別な制限はなく、例えば、リンガーロール、乾燥ドライヤーなどを用いることができる。   The steel plate 1 is subjected to a surface grinding process (mechanical grinding) with the surface grinding device 3, and then the water draining device 4 removes the coolant used in the surface grinding and adhered to the steel plate surface. There is no special restriction | limiting in the draining means of this drainer 4, For example, a ringer roll, a drying dryer, etc. can be used.

次いで、鋼板1を酸洗設備5に通すことにより酸洗処理(化学的研削)を行う。この酸洗処理では、機械的研削により表層酸化物が除去されて露出した母材と残存する表層酸化物との境界に酸が浸透し、残存する表層酸化物が剥離除去される。酸洗設備5に用いる酸洗液としては、濃度が5体積%以上の塩酸又は硫酸溶液、或いは硝塩酸溶液(例えば、5体積%以上の硝酸と0.5体積%以上の塩酸を混合させた溶液)などが好ましく、また酸洗処理は5秒間以上、より好ましくは8秒間以上行うことが望ましい。   Next, pickling treatment (chemical grinding) is performed by passing the steel plate 1 through the pickling equipment 5. In this pickling treatment, the surface layer oxide is removed by mechanical grinding, the acid penetrates the boundary between the exposed base material and the remaining surface oxide, and the remaining surface oxide is peeled and removed. As the pickling solution used in the pickling equipment 5, hydrochloric acid or sulfuric acid solution having a concentration of 5% by volume or more, or nitric acid hydrochloric acid solution (for example, 5% by volume or more nitric acid and 0.5% by volume or more hydrochloric acid were mixed). Solution) and the like, and the pickling treatment is desirably performed for 5 seconds or longer, more preferably for 8 seconds or longer.

ここで、表面研削装置3による表面研削処理(機械的研削)と酸洗設備5における酸洗処理(化学的研削)による鋼板質量の減少量の合計は4.0g/m以上であることが好ましい。鋼板質量の減少量の合計が4.0g/m未満では、表層酸化物が鋼板全面に亘って均一に除去されず、化成処理した場合に化成結晶が欠損した表面状態となるおそれがある。鋼板質量の減少量の合計の上限は特に規定しないが、鋼板質量の減少量が30.0g/mを超えると材料歩留が悪化する上、作業能率も悪くなる傾向があるため、鋼板質量の減少量の合計は30.0g/m以下とすることが望ましい。 Here, the sum total of the reduction | decrease amount of the steel plate mass by the surface grinding process (mechanical grinding) by the surface grinding apparatus 3 and the pickling process (chemical grinding) in the pickling equipment 5 shall be 4.0 g / m < 2 > or more. preferable. When the total amount of reduction in the steel sheet mass is less than 4.0 g / m 2 , the surface layer oxide is not uniformly removed over the entire surface of the steel sheet, and there is a possibility that the surface state in which the conversion crystals are lost when the conversion treatment is performed. The upper limit of the total amount of reduction in the steel sheet mass is not particularly specified, but if the amount of reduction in the steel sheet mass exceeds 30.0 g / m 2 , the material yield tends to deteriorate and the work efficiency tends to deteriorate. The total amount of decrease is preferably 30.0 g / m 2 or less.

酸洗処理(化学的研削)を行った鋼板1は、上記したような表面研削処理(機械的研削)および酸洗処理(化学的研削)を行ったSiを0.5質量%以上含有する鋼板の表面テクスチャーが、下記式(1)を満足するように調質圧延機6にて調質圧延が行われる。なお、式(1)中のLRaは調質圧延後の鋼板の圧延方向(長手方向)の算術平均粗さRa(μm)を、CRaは調質圧延後の鋼板の板幅方向の算術平均粗さRa(μm)を表す。また、本発明において算術平均粗さRaは、JIS B 0601(2001)で規定された算術平均粗さRaである。
0.5≦LRa/CRa≦1.3・・・・・(1)
A steel plate 1 subjected to pickling treatment (chemical grinding) is a steel plate containing 0.5% by mass or more of Si subjected to surface grinding treatment (mechanical grinding) and pickling treatment (chemical grinding) as described above. The temper rolling is performed in the temper rolling mill 6 so that the surface texture of the slab satisfies the following formula (1). In addition, LRa in Formula (1) is arithmetic average roughness Ra (micrometer) of the rolling direction (longitudinal direction) of the steel plate after temper rolling, CRa is arithmetic average roughness of the steel plate width direction after temper rolling. Ra (μm). In the present invention, the arithmetic average roughness Ra is an arithmetic average roughness Ra defined by JIS B 0601 (2001).
0.5 ≦ LRa / CRa ≦ 1.3 (1)

上記したように、表面研削(機械的研削)により重研削を施された鋼板表面は、鋼板圧延方向(鋼板長手方向)に凹凸溝が存在してしまい、その後酸洗処理(化学的研削)を行っても、このような凹凸溝は鋼板表面に残存したままとなり、電着塗装を行うと、このような凹凸溝を起点とした塗装剥離が進行しやすくなり、塗装後耐食性が劣化する。このため、調質圧延により、上記式(1)を満足する範囲となるように、表面研削処理および酸洗処理を施した後の鋼板表面テクスチャーを調質圧延により調整する。   As described above, the steel plate surface that has been subjected to heavy grinding by surface grinding (mechanical grinding) has uneven grooves in the steel plate rolling direction (longitudinal direction of the steel plate), and then pickling treatment (chemical grinding). Even if it is performed, such uneven grooves remain on the surface of the steel sheet, and when electrodeposition coating is performed, peeling of the coating starting from such uneven grooves tends to proceed, and the corrosion resistance after coating deteriorates. For this reason, the surface texture of the steel sheet after the surface grinding treatment and the pickling treatment is adjusted by temper rolling so that the above-described formula (1) is satisfied by temper rolling.

本実施形態では、表面研削によって生じる研削筋に起因した鋼板長手方向の連続した凹凸溝を、調質圧延ロールの凹凸で分断することで、連続した凹凸溝を起点とした塗装剥離が防止される。   In the present embodiment, by separating the continuous uneven grooves in the longitudinal direction of the steel sheet due to the grinding lines generated by surface grinding with the unevenness of the temper rolling roll, coating peeling starting from the continuous uneven grooves is prevented. .

ここで、調質圧延後における鋼板長手方向の算術平均粗さLRa(μm)と鋼板幅方向の算術平均粗さCRaの比(LRa/CRa)が前記式(1)の範囲から外れると、すなわち表面粗さの異方性が大きくなると、上記したように鋼板長手方向あるいは鋼板幅方向に連続した凹凸溝が存在することとなり、電着塗装を行うと、このような凹凸溝を起点とした塗装剥離が進行しやすくなり、塗装後耐食性が劣化する。このため、本発明では、調質圧延後における鋼板長手方向の算術平均粗さLRa(μm)と鋼板幅方向の算術平均粗さCRaの比(LRa/CRa)が前記式(1)を満足する範囲、すなわち0.5〜1.3の範囲とする。   Here, when the ratio (LRa / CRa) of the arithmetic average roughness LRa (μm) in the longitudinal direction of the steel sheet after the temper rolling and the arithmetic average roughness CRa in the width direction of the steel sheet is out of the range of the formula (1), If the anisotropy of the surface roughness is increased, there will be continuous concave and convex grooves in the longitudinal direction of the steel sheet or the width direction of the steel sheet as described above, and when electrodeposition coating is performed, coating with such uneven grooves as the starting point Peeling tends to proceed and the corrosion resistance after coating deteriorates. For this reason, in the present invention, the ratio (LRa / CRa) of the arithmetic average roughness LRa (μm) in the longitudinal direction of the steel sheet and the arithmetic average roughness CRa in the width direction of the steel sheet after temper rolling satisfies the above formula (1). The range is 0.5 to 1.3.

なお、通常の調質圧延に用いられるロールは0.5〜3.0μmRa未満であるが、上記したような鋼板表面テクスチャーを調整するため、調質圧延に用いられるロールの表面粗さ(算術平均粗さ)は3.0〜8.0μmRaの範囲であることが望ましい。前記範囲以外の表面粗さでは調質圧延による表面テクスチャーの作りこみが困難となるおそれがある。   In addition, although the roll used for normal temper rolling is less than 0.5-3.0 micrometers Ra, in order to adjust the above steel plate surface texture, the surface roughness (arithmetic average) of the roll used for temper rolling The roughness is desirably in the range of 3.0 to 8.0 μmRa. If the surface roughness is outside the above range, it may be difficult to create a surface texture by temper rolling.

また、このような調質圧延により、鋼板長手方向の算術平均粗さLRa(μm)と鋼板幅方向の算術平均粗さCRaの比(LRa/CRa)を上記した式(1)の範囲とするには、例えばロールの粗さを変更する、あるいは調質圧延時の単位幅荷重を変えて鋼板の伸び率を調整することにより達成できる。   Moreover, by such temper rolling, the ratio (LRa / CRa) of the arithmetic average roughness LRa (μm) in the longitudinal direction of the steel sheet and the arithmetic average roughness CRa in the width direction of the steel sheet is made the range of the above-described formula (1). For example, this can be achieved by changing the roughness of the roll or adjusting the elongation of the steel sheet by changing the unit width load during temper rolling.

以上示した本発明の鋼板の製造方法を用いることにより、高Si含有鋼板であっても焼鈍で生ずる表層酸化物を完全に除去し、鋼板表面の全面に亘って良好な化成被膜を形成させることが可能となる。また、表面粗さの異方性に起因した塗装後耐食性の劣化を生じない高張力鋼板を得ることができる。   By using the method for producing a steel sheet according to the present invention as described above, even if it is a high Si content steel sheet, the surface layer oxide generated by annealing is completely removed, and a good chemical conversion film is formed over the entire surface of the steel sheet surface. Is possible. Further, it is possible to obtain a high-tensile steel plate that does not cause deterioration in post-coating corrosion resistance due to anisotropy of the surface roughness.

表1に示すSi含有量が0.5〜1.5質量%の鋼を熱間圧延及び冷間圧延し、得られた鋼板(板厚1.2mm、板幅950mm)を、図1に示す製造設備を用い、連続焼鈍(ラインスピード:100mpm)した後、表層酸化物の除去を目的とした表面研削処理(機械的研削)を施し、表面研削処理した直後の鋼板に対して水切り装置(リンガーロール)で水切り処理(乾燥処理)を施し、次いで酸洗処理と調質圧延を実施した。   The steel sheet (sheet thickness 1.2 mm, sheet width 950 mm) obtained by hot-rolling and cold-rolling steel having a Si content of 0.5 to 1.5% by mass shown in Table 1 is shown in FIG. After continuous annealing (line speed: 100 mpm) using a production facility, surface grinding treatment (mechanical grinding) is performed for the purpose of removing surface oxides, and a water draining device (Ringer) is applied to the steel plate immediately after the surface grinding treatment. A draining treatment (drying treatment) was performed with a roll, and then pickling treatment and temper rolling were performed.

ここで表面研削処理は、回転式研削体としてJIS−R6001規格の砥粒番号♯220の弾性砥石ロール(ヤング率:137.2MPa(=14kgf/mm))と♯100の砥粒入りブラシロール(ヤング率:19.6MPa(=2kgf/mm))を用い、回転方向はアップカット(鋼板搬送方向とは逆の回転)とした。なお、弾性砥石ロールで研削する際に鋼板を保持するバックアップロールは、鋼製ロールを用いた。また、各ロールの回転数はブラシロールが1200rpm、弾性砥石ロールが800rpmとした。 In this case, the surface grinding treatment is carried out as an abrasive grindstone roll of abrasive grain number # 220 of JIS-R6001 standard (Young's modulus: 137.2 MPa (= 14 kgf / mm 2 )) and a brush roll containing # 100 abrasive grains. (Young's modulus: 19.6 MPa (= 2 kgf / mm 2 )) was used, and the rotation direction was upcut (rotation opposite to the steel plate conveyance direction). In addition, the steel roll was used for the backup roll which hold | maintains a steel plate when grinding with an elastic grindstone roll. The rotation speed of each roll was 1200 rpm for the brush roll and 800 rpm for the elastic grindstone roll.

酸洗処理は、60℃、酸濃度10体積%の硫酸浴を使用し、酸洗時間は10秒とした。表面研削及び酸洗処理を施したことによる鋼板質量の減少量は13〜15g/mであった。 In the pickling treatment, a sulfuric acid bath having an acid concentration of 10% by volume at 60 ° C. was used, and the pickling time was 10 seconds. The amount of reduction in the mass of the steel sheet due to the surface grinding and pickling treatment was 13 to 15 g / m 2 .

なお、製造された鋼板について、表面研削処理と酸洗処理による質量の減少量を、次のようにして求めた。各実施例に対応した同一鋼種でかつ熱間圧延〜連続焼鈍までは同一製造条件としたコイルを2つ準備し、一方のコイルを各実施例で用い、上記のように表面研削処理、酸洗処理を行った。他方のコイルについては表面研削と酸洗処理をしない鋼板を製造した。両方のコイルの長手方向のT部(先端部)、M部(中間部)、B部(尾端部)から一定面積(200mm×200mm角)の鋼板を切り出して質量を測定し、それらを切り出した面積で除して両者の差を算出することにより、表面研削処理及び酸洗処理による鋼板質量の減少量を求め、T部、M部、B部での計算値の平均を鋼板質量の減少量とした。   In addition, about the manufactured steel plate, the reduction | decrease amount of the mass by a surface grinding process and a pickling process was calculated | required as follows. Prepare two coils of the same steel type corresponding to each example and the same manufacturing conditions from hot rolling to continuous annealing. One coil is used in each example, and surface grinding treatment and pickling are performed as described above. Processed. For the other coil, a steel plate without surface grinding and pickling treatment was produced. Cut out steel sheets of a certain area (200mm x 200mm square) from the T part (tip part), M part (intermediate part), and B part (tail end part) in the longitudinal direction of both coils, measure the mass, and cut them out By calculating the difference between the two by dividing the area, the amount of reduction in the steel plate mass by surface grinding and pickling treatment is obtained, and the average of the calculated values in the T, M, and B parts is reduced in the steel plate mass. The amount.

また、研削条件(研削負荷(A/mm))、調質圧延の条件(ワークロールの表面粗さ(WR粗さ)、伸長率)を表1に示す。ここで、研削負荷とは、弾性砥石ロールを回転させるモータの負荷である。   Table 1 shows grinding conditions (grinding load (A / mm)) and temper rolling conditions (work roll surface roughness (WR roughness), elongation rate). Here, the grinding load is a load of a motor that rotates the elastic grindstone roll.

上記した表面研削処理後で酸洗処理前の鋼板から試験片を採取して、鋼板の板幅方向(C方向)についてJIS B 0601(2001)で規定された最大高さ粗さRzを測定した。結果を表1に示す。
また、上記調質圧延後の鋼板から試験片を採取し、鋼板の圧延方向(L方向)、鋼板の板幅方向(C方向)のそれぞれについてJIS B 0601(2001)で規定された算術平均粗さRaを測定し、L方向のRa(μm)とC方向のRa(μm)の比(L方向Ra/C方向Ra)を求めた。結果を表1に示す。なお上記Rz、Raの測定にあたり、測定長さを4.0mm、カットオフ値を0.8mmとした。
A test piece was collected from the steel plate after the surface grinding treatment and before the pickling treatment, and the maximum height roughness Rz defined in JIS B 0601 (2001) was measured in the plate width direction (C direction) of the steel plate. . The results are shown in Table 1.
Moreover, a test piece is taken from the steel sheet after the temper rolling, and the arithmetic average roughness specified in JIS B 0601 (2001) for each of the rolling direction (L direction) of the steel sheet and the width direction (C direction) of the steel sheet. The thickness Ra was measured, and the ratio of the Ra (μm) in the L direction to the Ra (μm) in the C direction (L direction Ra / C direction Ra) was determined. The results are shown in Table 1. In measuring Rz and Ra, the measurement length was 4.0 mm and the cut-off value was 0.8 mm.

なお、得られた鋼板について、JIS5号引張試験片を用いてJIS Z2241に準拠して求めた材質は、引張強度(TS)が980MPa、伸び(EL)が14%であった。   In addition, about the obtained steel plate, the tensile strength (TS) was 980 Mpa and elongation (EL) was 14% about the material calculated | required based on JISZ2241 using the JIS5 tension test piece.

さらに、上記調質圧延後の鋼板から試験片を採取し、下記の方法により、化成処理性、塗装後耐食性を評価した。結果を表1に示す。   Furthermore, a test piece was collected from the steel sheet after the temper rolling, and the chemical conversion treatment property and the corrosion resistance after coating were evaluated by the following methods. The results are shown in Table 1.

化成処理性
製造された鋼板に対して、脱脂、水洗、表面調整を順次施した後、化成処理薬剤(日本ペイント社製サーフダインSD2800)を用いて化成処理(液温:43℃、浸漬時間120sec)を行い、その表面を走査型電子顕微鏡にて倍率500倍で5視野観察し、面積率95%以上の均一な化成結晶が5視野全てにおいて生成しているものを○(良好)とし、面積率5%超えの隙間が1視野でも認められた場合は×(不良)として評価した。
Chemical conversion treatment After the steel plate manufactured was subjected to degreasing, water washing, and surface adjustment in sequence, chemical conversion treatment (liquid temperature: 43 ° C., immersion time 120 sec) using a chemical conversion treatment agent (Surfdyne SD2800 manufactured by Nippon Paint Co., Ltd.) ), And the surface is observed with a scanning electron microscope at 5 magnifications at 500 magnifications, and a uniform chemical crystal having an area ratio of 95% or more is generated in all 5 visual fields is marked as ◯ (good). When a gap exceeding 5% was observed even in one field of view, it was evaluated as x (defect).

塗装後耐食性
化成処理薬剤(日本ペイント社製サーフダインSD2800)を用いて化成処理(化成処理皮膜の付着量:2.0〜2.5g/m)を行った後、日本ペイント社製の電着塗料PN−150Gを用いて電着塗装(目標膜厚:25μm)を行った。電着塗装後の試験片について、下記のように塩温水浸漬試験(SDT)を行い、塗装後耐食性を評価した。
塩温水浸漬試験(SDT)は、上記した電着塗装を施した試験片に、カッターでクロスカット疵(クロス角60°)を付与し、55℃の5%NaCl溶液に240hr浸漬後、試験片を取り出し、水洗、乾燥後に、クロスカット疵部についてセロハンテープによるテープ剥離を行った。そしてテープ剥離後、クロスカット疵部から鋼板長手方向及び幅方向に進展した剥離幅を測定し、各方向の最大剥離幅を指標として塗装後耐食性を評価した。ここで、L方向最大塗装剥離幅およびC方向最大塗装剥離幅ともにクロスカット疵部からの最大剥離幅が2.6mm以下の場合に○(良好)と判断し、最大剥離幅が2.6mm超えの場合に、×(不良)と判断した。
After coating, a chemical treatment (Surfdyne SD2800 manufactured by Nippon Paint Co., Ltd.) was used for chemical conversion treatment (adhesion amount of chemical conversion coating: 2.0 to 2.5 g / m 2 ). Electrodeposition coating (target film thickness: 25 μm) was performed using the coating material PN-150G. About the test piece after electrodeposition coating, the salt warm water immersion test (SDT) was done as follows, and the corrosion resistance after coating was evaluated.
In the salt warm water immersion test (SDT), the above-mentioned electrodeposition-coated test piece was provided with a cross-cut wrinkle (cross angle 60 °) with a cutter, immersed in a 55% 5% NaCl solution for 240 hours, and then the test piece. Was taken out, washed with water and dried, and then the tape was peeled off with a cellophane tape on the crosscut collar. And after tape peeling, the peeling width which developed in the steel plate longitudinal direction and the width direction from the crosscut collar was measured, and the corrosion resistance after coating was evaluated using the maximum peeling width in each direction as an index. Here, when the maximum peel width from the crosscut collar is 2.6 mm or less for both the maximum paint peel width in the L direction and the maximum paint peel width in the C direction, it is judged as “good” and the maximum peel width exceeds 2.6 mm. In this case, it was judged as x (defect).

Figure 2014128814
Figure 2014128814

表1に示すように、比較例である及びNo.4は表面研削に伴う表面粗さの異方性が改善しておらず、L、C方向のいずれかにおいて最大塗装剥離幅が基準よりも大きく、塗装後耐食性が低下していることが判る。また、比較例であるNo.5に示すように、表面研削処理後のC方向のRzが3.0μmを超えてしまうと、調質圧延でL、C方向の表面粗さ異方性を改善しても、塗装後耐食性が低下していることが判る。これに対して本発明例(No.1〜3)では、L、C方向共に最大塗装剥離幅が小さく、塗装剥離が抑制されており、化成処理性だけでなく、塗装後耐食性に優れた高張力鋼板が得られることが判る。   As shown in Table 1, it is a comparative example and No. No. 4 shows that the anisotropy of the surface roughness accompanying the surface grinding is not improved, the maximum coating peeling width is larger than the standard in either the L or C direction, and the corrosion resistance after coating is reduced. Moreover, No. which is a comparative example. As shown in FIG. 5, when the Rz in the C direction after the surface grinding treatment exceeds 3.0 μm, the corrosion resistance after coating is improved even if the surface roughness anisotropy in the L and C directions is improved by temper rolling. It turns out that it has fallen. On the other hand, in the present invention examples (No. 1 to 3), the maximum coating peeling width is small in both the L and C directions, and the coating peeling is suppressed, and not only the chemical conversion processability but also the high corrosion resistance after coating is high. It can be seen that a tensile steel plate is obtained.

1 鋼板
2 連続焼鈍炉
3 表面研削装置
4 水切り装置
5 酸洗設備
6 調質圧延機
7 コイラー
31 弾性砥石ロール
32 バックアップロール
33 砥粒入りブラシロール
DESCRIPTION OF SYMBOLS 1 Steel plate 2 Continuous annealing furnace 3 Surface grinding apparatus 4 Draining apparatus 5 Pickling equipment 6 Temper rolling mill 7 Coiler 31 Elastic grindstone roll 32 Backup roll 33 Brush roll containing abrasive grains

Claims (2)

Siを0.5質量%以上含有する鋼板を連続焼鈍した後に、弾性砥石を用いた研削を含む表面研削処理を行い、次いで酸洗処理を行った後、調質圧延を行うに際し、前記表面研削処理後の鋼板の板幅方向の最大高さ粗さRzが3.0μm以下となるように表面研削処理し、さらに調質圧延後の鋼板の圧延方向の算術平均粗さと板幅方向の算術平均粗さが下記の式(1)を満足するように調質圧延することを特徴とする化成処理性及び塗装後耐食性に優れた鋼板の製造方法;
0.5≦LRa/CRa≦1.3・・・(1)
ただし、式(1)中のLRaは調質圧延後の鋼板の圧延方向の算術平均粗さRa(μm)を、CRaは調質圧延後の鋼板の板幅方向の算術平均粗さRa(μm)を表す。
After continuous annealing of a steel sheet containing 0.5% by mass or more of Si, surface grinding treatment including grinding using an elastic grindstone is performed, and then after pickling treatment, the surface grinding is performed in the temper rolling. Surface grinding treatment is performed so that the maximum height roughness Rz in the sheet width direction of the steel sheet after treatment is 3.0 μm or less, and the arithmetic average roughness in the rolling direction of the steel sheet after temper rolling and the arithmetic average in the sheet width direction A method for producing a steel sheet excellent in chemical conversion treatment and corrosion resistance after coating, characterized by temper rolling so that the roughness satisfies the following formula (1);
0.5 ≦ LRa / CRa ≦ 1.3 (1)
However, LRa in Formula (1) is the arithmetic average roughness Ra (μm) in the rolling direction of the steel sheet after temper rolling, and CRa is the arithmetic average roughness Ra (μm) in the sheet width direction of the steel sheet after temper rolling. ).
前記表面研削処理は、鋼板両面を研削する上下1対の研削体を2対以上用いて行うことを特徴とする請求項1に記載の化成処理性及び塗装後耐食性に優れた鋼板の製造方法。   The said surface grinding process is performed using 2 or more pairs of upper and lower grinding bodies which grind both surfaces of a steel plate, The manufacturing method of the steel plate excellent in chemical conversion treatment property and corrosion resistance after coating of Claim 1 characterized by the above-mentioned.
JP2012286789A 2012-12-28 2012-12-28 Manufacturing method of steel plate excellent in chemical convertibility and corrosion resistance after coating Pending JP2014128814A (en)

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