JP6839474B2 - Manufacturing method of galvanized steel sheet - Google Patents
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- JP6839474B2 JP6839474B2 JP2016177807A JP2016177807A JP6839474B2 JP 6839474 B2 JP6839474 B2 JP 6839474B2 JP 2016177807 A JP2016177807 A JP 2016177807A JP 2016177807 A JP2016177807 A JP 2016177807A JP 6839474 B2 JP6839474 B2 JP 6839474B2
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- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 229910001335 Galvanized steel Inorganic materials 0.000 title claims description 19
- 239000008397 galvanized steel Substances 0.000 title claims description 19
- 229910001410 inorganic ion Inorganic materials 0.000 claims description 33
- 238000007747 plating Methods 0.000 claims description 32
- 239000011701 zinc Substances 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 8
- 238000005554 pickling Methods 0.000 claims description 8
- 238000005238 degreasing Methods 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 description 51
- 239000004480 active ingredient Substances 0.000 description 45
- 230000007547 defect Effects 0.000 description 31
- 229910000831 Steel Inorganic materials 0.000 description 30
- 239000010959 steel Substances 0.000 description 30
- 239000010410 layer Substances 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 23
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- 230000002950 deficient Effects 0.000 description 11
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- 238000005259 measurement Methods 0.000 description 6
- 238000005246 galvanizing Methods 0.000 description 5
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- 239000007864 aqueous solution Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000655 Killed steel Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
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- 239000011247 coating layer Substances 0.000 description 2
- 229910021476 group 6 element Inorganic materials 0.000 description 2
- 229910021474 group 7 element Inorganic materials 0.000 description 2
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- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
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- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- 238000002441 X-ray diffraction Methods 0.000 description 1
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- 229910045601 alloy Inorganic materials 0.000 description 1
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- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 229910052798 chalcogen Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
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- 229920000554 ionomer Polymers 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
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- GZNAASVAJNXPPW-UHFFFAOYSA-M tin(4+) chloride dihydrate Chemical compound O.O.[Cl-].[Sn+4] GZNAASVAJNXPPW-UHFFFAOYSA-M 0.000 description 1
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 description 1
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Substances O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 1
Description
本発明は、亜鉛めっき鋼板の製造方法に関し、特に原板の欠陥などに由来する外観不良を改善する亜鉛めっき鋼板の製造方法に関する。 The present invention relates to a method for producing a galvanized steel sheet, and more particularly to a method for producing a galvanized steel sheet for improving appearance defects caused by defects in the original plate.
表面処理がなされた鋼板は、従来から様々な用途に使用されている。その中でも亜鉛めっき鋼板は、耐久性や経済性に優れるとともに保護皮膜作用と犠牲防食作用を併せ持つため、表面処理鋼板の中でも高いシェアを占めている。
かような亜鉛めっき鋼板は、溶融亜鉛めっき鋼板と電気亜鉛めっき鋼板に大別されるが、特に電気亜鉛めっき鋼板は白色度を調整して美麗な外観を呈することから、各種ケースやカバー、パネルなどの意匠用途としても用いられている。
Surface-treated steel sheets have been used for various purposes. Among them, galvanized steel sheets have excellent durability and economy, and also have a protective film action and a sacrificial anticorrosion action, so they occupy a high share among surface-treated steel sheets.
Such galvanized steel sheets are roughly classified into hot-dip galvanized steel sheets and electrogalvanized steel sheets. In particular, electrogalvanized steel sheets have a beautiful appearance by adjusting the whiteness, so various cases, covers, and panels are used. It is also used for design purposes such as.
一方で、例えば原板に欠陥などが存在する場合、亜鉛めっき処理後の外観に不良が生じることがある。
これに対して特許文献１では、白色度の低下を抑制しつつめっき原板の表面欠陥に起因するムラを抑制するため、鋼板上に析出量が０．１ｍｇ／ｍ２ 以上１０ｍｇ／ｍ２未満のＳｎ析出層、電気亜鉛めっき層、析出量が合わせて０．０５ｍｇ／ｍ２以上５ｍｇ／ｍ２以下の金属Ｎｉまたは金属Ｃｏのいずれか一方または両方からなる析出層、クロメート処理層を順次形成する技術が提案されている。
On the other hand, for example, if there is a defect in the original plate, the appearance after the galvanizing treatment may be defective.
On the other hand, in Patent Document 1, in order to suppress the decrease in whiteness and the unevenness caused by the surface defects of the plating original plate, the amount of precipitation on the steel sheet is 0.1 mg / m 2 or more and less than 10 mg / m 2. A Sn precipitation layer, an electrozinc plating layer, a precipitation layer composed of one or both of metal Ni and metal Co having a precipitation amount of 0.05 mg / m 2 or more and 5 mg / m 2 or less, and a chromate-treated layer are sequentially formed. Technology has been proposed.
更に特許文献２によれば、めっき層全体としての外観が均一で美麗な電気亜鉛めっき鋼板および該鋼板を効率よく製造するため、亜鉛結晶の（００２）面と（１０３）面の配向指数を特定の関係にするとともに、素地鋼板表面にＣｏ，Ｎｉ，Ｃｒ，Ｉｎ，Ｓｎ，Ｓｂ，ＴｌおよびＰｂよりなる群から選択される少なくとも１種の金属元素が総量として０．００５〜５２０ｍｇ／ｍ２の付着量で下地層として形成する技術が提案されている。 Further, according to Patent Document 2, in order to efficiently produce an electrogalvanized steel sheet having a uniform and beautiful appearance as a whole plating layer and the steel sheet, the orientation indexes of the (002) plane and the (103) plane of the zinc crystal are specified. The total amount of at least one metal element selected from the group consisting of Co, Ni, Cr, In, Sn, Sb, Tl and Pb is 0.005 to 520 mg / m 2 on the surface of the base steel sheet. A technique for forming a base layer by the amount of adhesion has been proposed.
しかしながら特に特許文献１にも言及されているとおり、原板の表面欠陥に起因して亜鉛めっき処理後の外観に不良個所が生じる課題は未だ解消されてはいない。また、特許文献１ではクロメート処理が前提の技術であって限定的な手法であることは否めない。
原板の表面欠陥としては、目視可能な物理的な欠陥と目視で視認できない欠陥が存在する。とくに後者の場合には、亜鉛めっき皮膜としての特性は全く問題がないにも関わらず外観が不良であるため結果として製品として採用できないという不都合が生じてしまう。
However, as particularly referred to in Patent Document 1, the problem that defective parts appear in the appearance after the galvanizing treatment due to the surface defects of the original plate has not been solved yet. Further, in Patent Document 1, it cannot be denied that chromate treatment is a premised technique and is a limited technique.
As the surface defects of the original plate, there are physical defects that can be visually recognized and defects that cannot be visually recognized. In particular, in the latter case, although there is no problem with the characteristics of the galvanized film, the appearance is poor, and as a result, there is a disadvantage that the product cannot be used.
こうした背景の下、発明者らは鋭意検討した結果、次に示すメカニズムによって亜鉛めっき処理後の外観に不良個所が発生すると推定した。
すなわち、まず原板表面の欠陥は鋼中の介在物や鋼成分の濃化部位等に起因して生じ、亜鉛めっきを施した場合にはこの欠陥部のみ部分的に結晶配向が乱れた状態で成膜される。
すると、この部分的に乱れた結晶配向が光学的な差異を生み出し、これが目視外観上の欠陥として認知されることになる。
これに対して原板の表面を事前に検査したとしても、原板の状態では物理的な凹凸が生成されたり汚染物が付着したりして欠陥となっているわけではなく、外観上で正常部と欠陥部を見分けることは困難である。
Against this background, as a result of diligent studies, the inventors presumed that the following mechanism would cause defective parts in the appearance after galvanizing.
That is, first, defects on the surface of the original plate are caused by inclusions in the steel, concentrated parts of the steel component, etc., and when galvanized, only these defective parts are formed in a state where the crystal orientation is partially disturbed. Be filmed.
Then, this partially disordered crystal orientation creates an optical difference, which is perceived as a visual defect.
On the other hand, even if the surface of the original plate is inspected in advance, it does not mean that physical irregularities are generated or contaminants adhere to the original plate, which is not a defect. It is difficult to distinguish the defective part.
本発明は、かような課題を解決することを鑑みてなされたものであり、原板の表面における不可視的な欠陥に起因する外観不良を抑制できる亜鉛めっき鋼板の製造方法を提供することを目的とする。 The present invention has been made in view of solving such a problem, and an object of the present invention is to provide a method for manufacturing a galvanized steel sheet capable of suppressing appearance defects due to invisible defects on the surface of the original plate. To do.
上記課題を解決するため、本発明の一実施形態にかかる亜鉛めっき鋼板の製造方法は、（１）原板を脱脂および酸洗する第１工程と、前記第１工程の後、Ｓｂ３＋ 又はＭｏ６＋の無機イオンを１０〜５０００ｍｇ／Ｌの濃度で含有してｐＨが３〜５である処理液に、前記原板を浸漬する第２工程と、前記第２工程の後、亜鉛めっき浴を用いて前記原板にＺｎめっき層を形成する第３工程と、を有することことを特徴とする。 In order to solve the above problems, the method for producing a zinc-plated steel sheet according to an embodiment of the present invention comprises (1) a first step of degreasing and pickling the original plate, and after the first step, Sb 3+ or Mo 6+. The original plate is immersed in a treatment liquid containing 10 to 5000 mg / L of the above inorganic ions and having a pH of 3 to 5, and after the second step, the zinc plating bath is used. It is characterized by having a third step of forming a Zn plating layer on the original plate.
なお上記（１）の亜鉛めっき鋼板の製造方法においては、（２）前記第２工程によって前記原板の表面に前記無機イオンがアイランド状に付着し、前記無機イオンが点在する前記原板の表面に亜鉛めっき皮膜が形成されることが好ましい。
また、上記（１）又は（２）の亜鉛めっき鋼板の製造方法においては、（３）前記処理液の温度は１０℃〜６０℃に維持されることが好ましい。
In the method for producing a galvanized steel sheet according to (1), (2) the inorganic ions adhere to the surface of the original plate in an island shape by the second step, and the inorganic ions are scattered on the surface of the original plate. It is preferable that a galvanized film is formed.
Further, in the method for producing a galvanized steel sheet according to (1) or (2), it is preferable that the temperature of (3) the treatment liquid is maintained at 10 ° C. to 60 ° C.
また、上記（１）〜（３）のいずれかに記載の亜鉛めっき鋼板の製造方法においては、（４）前記第２工程における前記無機イオンが、前記Ｓｂ ３＋ である場合に当該Ｓｂ ３＋ が１０〜５００ｍｇ／Ｌの濃度、前記Ｂｉ ３＋ である場合に当該Ｂｉ ３＋ が２０〜１０００ｍｇ／Ｌの濃度、で前記処理液に含有されることが好ましい。
また、上記（１）〜（４）のいずれかに記載の亜鉛めっき鋼板の製造方法においては、（５）前記第３工程において電気亜鉛めっきが用いられることが好ましい。
また、上記（５）に記載の亜鉛めっき鋼板の製造方法においては、（６）前記電気亜鉛めっきは、電流密度が５〜６０Ａ／ｄｍ ２ 、めっき付着量が５〜３０ｇ／ｍ ２ のめっき条件で行われることが好ましい。
Further, in the method for producing a galvanized steel sheet according to any one of (1) to (3) above, (4) when the inorganic ion in the second step is Sb 3+ , the Sb 3+ is 10. concentration to 500 mg / L, the concentration of the Bi 3+ is 20~1000mg / L in the case of Bi 3+, in is preferably contained in the processing solution.
Further, in the method for producing a galvanized steel sheet according to any one of (1) to (4) above, it is preferable that electrogalvanizing is used in (5) the third step.
Further, in the method for producing a galvanized steel sheet according to (5) above, (6) the electrogalvanized plating has a current density of 5 to 60 A / dm 2 and a plating adhesion amount of 5 to 30 g / m 2 . It is preferable that this is done in.
本発明によれば、鋼板の原板表面における光学的な差異を抑制でき、これにより原板の欠陥に由来する外観不良を抑制することが可能となる。 According to the present invention, it is possible to suppress the optical difference on the surface of the original plate of the steel sheet, and thereby it is possible to suppress the appearance defect caused by the defect of the original plate.
以下、本発明を実施するための実施形態について説明する。
≪第１実施形態≫
図１に示されるように、本実施形態に係る表面処理鋼板（亜鉛めっき鋼板）ＳＳは、原板１と、この原板１上に形成される表面処理層とを少なくとも含んで構成されている。表面処理層は、Ｚｎめっき層２と、このＺｎめっき層２上に形成される有機樹脂層３を含んで構成されている。
そして本実施形態に係る表面処理鋼板の製造方法は、原板を脱脂および酸洗する第１工程と、前記第１工程の後、第１４族元素および第１５族元素のうちの少なくとも１つの無機イオンを１０〜５０００ｍｇ／Ｌの濃度で含有する処理液に前記原板を浸漬する第２工程と、前記第２工程の後に前記原板を亜鉛めっき浴に浸漬する第３工程と、を有することを特徴としている。
Hereinafter, embodiments for carrying out the present invention will be described.
<< First Embodiment >>
As shown in FIG. 1, the surface-treated steel sheet (galvanized steel sheet) SS according to the present embodiment includes at least the original plate 1 and the surface-treated layer formed on the original plate 1. The surface treatment layer is composed of a Zn plating layer 2 and an organic resin layer 3 formed on the Zn plating layer 2.
The method for producing a surface-treated steel sheet according to the present embodiment includes a first step of degreasing and pickling the original sheet, and after the first step, at least one inorganic ion of Group 14 and Group 15 elements. It is characterized by having a second step of immersing the original plate in a treatment liquid containing a concentration of 10 to 5000 mg / L, and a third step of immersing the original plate in a galvanizing bath after the second step. There is.
次に図２を参照しながら、本実施形態の表面処理鋼板の製造方法について詳述する。
表面処理鋼板ＳＳを製造する際には、基材となる原板１を準備する。この原板１は、例えば０．０５ｍｍ〜１．６ｍｍ程度の金属板であり、例えば鉄または鋼板などの合金などが用いられる。なお、本実施形態との金属板としては、０．０５〜１．２０ｍｍ程度の厚さの普通鋼冷延鋼板が好ましい。冷延鋼板の中でも低炭素または炭素量０．０１質量％未満の極低炭素アルミキルド鋼板が、加工性などの観点から好ましく基板として使用される。
Next, the method for manufacturing the surface-treated steel sheet of the present embodiment will be described in detail with reference to FIG.
When manufacturing the surface-treated steel sheet SS, the original plate 1 as a base material is prepared. The original plate 1 is, for example, a metal plate having a size of about 0.05 mm to 1.6 mm, and for example, an alloy such as iron or a steel plate is used. As the metal plate with the present embodiment, an ordinary steel cold-rolled steel plate having a thickness of about 0.05 to 1.20 mm is preferable. Among the cold-rolled steel sheets, a low-carbon or ultra-low carbon aluminum killed steel sheet having a carbon content of less than 0.01% by mass is preferably used as a substrate from the viewpoint of workability and the like.
そしてこの原板１に対し、まずアルカリ脱脂して洗浄する処理を行う（ステップ１）。
なおアルカリ脱脂に使用するアルカリとしては、例えば、水酸化ナトリウムなどの強エッチングタイプのアルカリが挙げられる。また、弱アルカリ系や界面活性剤を配合したものを用いてもよい。
Then, the original plate 1 is first subjected to a process of alkaline degreasing and cleaning (step 1).
Examples of the alkali used for alkaline degreasing include strong etching type alkalis such as sodium hydroxide. Further, a weak alkaline type or a mixture containing a surfactant may be used.
ステップ１でアルカリ脱脂を終えた後、原板１に対して酸洗を行う（ステップ２）。
なお酸洗としては種々の公知の手法を用いてよく、例えば硫酸水溶液への浸漬による酸洗が適用可能である。原板１が酸洗処理されることで、原板１の表面に付着したスケール（酸化膜）が除去される。なお酸洗処理液としては上記硫酸水溶液に限定されず、原板１の種類に応じて酸の種類や液の濃度、あるいは温度などを適宜決定してもよい。
また、ステップ１やステップ２の後で、水などを用いてリンス処理（水洗）してもよい。
After the alkaline degreasing is completed in step 1, the original plate 1 is pickled (step 2).
As the pickling, various known methods may be used, and for example, pickling by immersing in an aqueous sulfuric acid solution can be applied. By pickling the original plate 1, the scale (oxide film) adhering to the surface of the original plate 1 is removed. The pickling treatment liquid is not limited to the above-mentioned sulfuric acid aqueous solution, and the type of acid, the concentration of the liquid, the temperature, and the like may be appropriately determined according to the type of the original plate 1.
Further, after step 1 and step 2, rinsing treatment (washing with water) may be performed with water or the like.
ステップ２で酸洗を終えた後、無機イオンを含有する前処理浴へ原板１を浸漬する処理を行う（ステップ３）。
この前処理浴に含有される無機イオンは、周期表中の第１４族元素および第１５族元素のうちの少なくとも１つの無機イオンである。なお、本実施形態では、以下の表１に示す無機イオンがより好ましい。
After pickling in step 2, the original plate 1 is immersed in a pretreatment bath containing inorganic ions (step 3).
The inorganic ions contained in this pretreatment bath are at least one inorganic ion among the Group 14 and Group 15 elements in the periodic table. In this embodiment, the inorganic ions shown in Table 1 below are more preferable.
すなわち表１に示すとおり、前処理浴に含有される無機イオンがＳｎ２＋の場合、その濃度は、１０〜５０００ｍｇ／Ｌであり、より好ましくは２０〜１０００、さらに好ましくは１００〜５００ｍｇ／Ｌである。
また、前処理浴に含有される無機イオンがＢｉ３＋の場合、その濃度は、１０〜５０００ｍｇ／Ｌであり、より好ましくは２０〜１０００、さらに好ましくは１００〜５００ｍｇ／Ｌである。
また、前処理浴に含有される無機イオンがＳｂ３＋の場合、その濃度は、１０〜５０００ｍｇ／Ｌであり、より好ましくは１０〜５００、さらに好ましくは１５〜３７０ｍｇ／Ｌである。
That is, as shown in Table 1, when the inorganic ions contained in the pretreatment bath are Sn 2+ , the concentration thereof is 10 to 5000 mg / L, more preferably 20 to 1000, and further preferably 100 to 500 mg / L. is there.
When the inorganic ions contained in the pretreatment bath are Bi 3+ , the concentration thereof is 10 to 5000 mg / L, more preferably 20 to 1000, and even more preferably 100 to 500 mg / L.
When the inorganic ions contained in the pretreatment bath are Sb 3+ , the concentration thereof is 10 to 5000 mg / L, more preferably 10 to 500, and even more preferably 15 to 370 mg / L.
なお表１に具体的な数値で示した材料の他にも、半導体となり得る第１４族元素、第１５族元素および第１６族元素のいずれかを適用することができ、この場合には実験やシミュレーションなどで具体的な元素や最適な濃度などを決定してもよい。
また、前処理浴における浴温は、１０℃〜６０℃であって、特に好ましくは２０℃〜４５℃である。６０℃を超える温度では費用対効果で新たな効果を期待できず不経済であり、一方で１０℃を下回ると無機イオンが定着し難くなるからである。
In addition to the materials shown in the specific numerical values in Table 1, any of Group 14 elements, Group 15 elements, and Group 16 elements that can be semiconductors can be applied. Specific elements, optimum concentrations, etc. may be determined by simulation or the like.
The bath temperature in the pretreatment bath is 10 ° C. to 60 ° C., particularly preferably 20 ° C. to 45 ° C. This is because if the temperature exceeds 60 ° C, new effects cannot be expected cost-effectively and it is uneconomical, while if the temperature is lower than 10 ° C, it becomes difficult for inorganic ions to settle.
また、前処理浴におけるｐＨは、例えば１〜６、好ましくは３〜５であることが好ましい。
また、かような前処理浴に原板１を浸漬する浸漬時間は、１〜６０秒であって、好ましくは２秒〜３０秒がよく、更に量産性も考慮すると２〜５秒が好ましい。６０秒以上では意図しない汚染が発生したり生産性が著しく低下してしまい、一方で１秒以下では無機イオンが定着し難いからである。
なお、上記した前処理浴に関しては、適宜、公知の安定剤や緩衝剤、あるいはｐＨ調整剤などを添加してもよい。
The pH in the pretreatment bath is preferably, for example, 1 to 6, preferably 3 to 5.
The immersion time for immersing the original plate 1 in such a pretreatment bath is preferably 1 to 60 seconds, preferably 2 to 30 seconds, and more preferably 2 to 5 seconds in consideration of mass productivity. This is because unintended contamination occurs or productivity is significantly reduced in 60 seconds or more, while inorganic ions are difficult to settle in 1 second or less.
As for the above-mentioned pretreatment bath, a known stabilizer, buffer, pH adjuster or the like may be added as appropriate.
ここで図３を用いて第１実施形態における前処理の特徴を詳細に説明する。
まず図３の左側には、後述するＺｎめっきが原板１に施された後の表面処理鋼板ＳＳにおける光学顕微鏡を用いた表面観察写真を示す。
同図から明らかなとおり、領域（ａ）で囲った部位（欠陥部）には筋状の欠陥が確認できる一方で、かような欠陥は正常な領域である領域（ｂ）で囲った部位（正常部）では見られない。
Here, the features of the pretreatment in the first embodiment will be described in detail with reference to FIG.
First, on the left side of FIG. 3, a surface observation photograph of the surface-treated steel sheet SS after the Zn plating described later is applied to the original plate 1 using an optical microscope is shown.
As is clear from the figure, a streak-like defect can be confirmed in the portion (defect portion) surrounded by the region (a), while such a defect is found in the region (b) surrounded by the normal region (b). It is not seen in the normal part).
この領域（ａ）および領域（ｂ）に対してＸ線回折法によるＺｎめっきの結晶配向性を測定した結果が、図３の右側に示されている。
このように、筋状の欠陥が確認された領域（ａ）では、領域（ｂ）に比して、（０００２）面の優先配向が崩れており、（1 0 -1 1）面や（1 0 -1 2）面など他の面の強度が相対的に増加していることが判明した。
なお、この領域（ａ）では部分的に乱れた結晶配向が光学的な差異を生じさせ、これにより、Ｚｎめっきとしての特性は変わらないものの目視外観上の不良となってしまう。
The results of measuring the crystal orientation of Zn plating by the X-ray diffraction method with respect to the region (a) and the region (b) are shown on the right side of FIG.
As described above, in the region (a) where the streaky defects are confirmed, the preferential orientation of the (0002) plane is broken as compared with the region (b), and the (10 -11) plane and the (1) plane and (1) 0 -1 2) It was found that the strength of other surfaces such as the surface increased relatively.
In this region (a), the partially disordered crystal orientation causes an optical difference, which causes a defect in the visual appearance although the characteristics as Zn plating do not change.
このような知見の下、本実施形態では、例えば表１で示した材料に代表される第１４族元素又は第１５族元素の無機イオンを含有する前処理浴に事前に浸漬する。これにより、原板１表面には、上記した無機イオンが均一な層としてではなく離散的（アイランド状）に吸着するものと推定される。換言すれば、上記した無機イオンの原板１への付着量が皮膜として十分に定量検出可能な量未満となっており、この原板１の表面には上記した無機イオンによる均一な層は形成されていない。したがって、かような状態では、原板１の表面に点在する無機イオンが核となり、後述するＺｎめっき層が原板１上に形成されていくと考えられる。 Based on such knowledge, in the present embodiment, for example, the materials are pre-immersed in a pretreatment bath containing inorganic ions of Group 14 elements or Group 15 elements represented by the materials shown in Table 1. As a result, it is presumed that the above-mentioned inorganic ions are adsorbed on the surface of the original plate 1 discretely (island-like) rather than as a uniform layer. In other words, the amount of the above-mentioned inorganic ions attached to the original plate 1 is less than the amount that can be sufficiently quantitatively detected as a film, and a uniform layer of the above-mentioned inorganic ions is formed on the surface of the original plate 1. Absent. Therefore, in such a state, it is considered that the inorganic ions scattered on the surface of the original plate 1 become nuclei and the Zn plating layer described later is formed on the original plate 1.
このように前処理浴への原板１の浸漬により、Ｚｎめっき全体の（０００２）面の優先配向を低下させて白色度を下げ、上記した欠陥部と正常部との配向差を小さくさせる。
したがって欠陥部と正常部とで色差が小さくなり、上述した目視外観上の不良を抑制されることが可能となっている。
By immersing the original plate 1 in the pretreatment bath in this way, the preferential orientation of the (0002) surface of the entire Zn plating is lowered to lower the whiteness, and the orientation difference between the above-mentioned defective portion and the normal portion is reduced.
Therefore, the color difference between the defective portion and the normal portion becomes small, and it is possible to suppress the above-mentioned defects in visual appearance.
図２に戻り、本実施形態の表面処理鋼板の製造方法について説明を継続する。
ステップ３で前処理浴に原板１を浸漬した後は、Ｚｎめっき層２を原板１上に形成する（ステップ４）。なおステップ３の後で水などを用いてリンス処理（水洗）を行った後に、ステップ４へ移行してもよい。
また、ステップ４で用いるＺｎめっき浴としては、例えば以下の条件を適用してもよい。
［Ｚｎめっき条件］
浴組成 ＺｎＳＯ４・７Ｈ２Ｏ：１５０〜３００ｇ／Ｌ
Ｎａ２ＳＯ４：２０〜１００ｇ／Ｌ
浴温 ：３０〜６０ ℃
電流密度 ：５〜６０ Ａ／ｄｍ２
めっき付着量 ：５〜３０ｇ／ｍ２
Returning to FIG. 2, the description of the method for manufacturing the surface-treated steel sheet of the present embodiment will be continued.
After immersing the original plate 1 in the pretreatment bath in step 3, the Zn plating layer 2 is formed on the original plate 1 (step 4). After step 3, rinsing treatment (washing with water) with water or the like may be performed, and then the process may proceed to step 4.
Further, as the Zn plating bath used in step 4, for example, the following conditions may be applied.
[Zn plating conditions]
Bath composition ZnSO4.7H2O: 150-300 g / L
Na2SO4: 20-100 g / L
Bath temperature: 30-60 ° C
Current density: 5 to 60 A / dm 2
Plating adhesion amount: 5 to 30 g / m 2
ステップ４でＺｎめっき層２が原板１に形成された後、このＺｎめっき層２上に有機樹脂層３を形成することができる（ステップ５）。なお、このステップ５は必須ではなく、適宜省略してもよい。
この有機樹脂層３は、例えばコーティング層として、透明性の高い樹脂（シリカゾルを含有した水系ウレタン樹脂、水系アクリル樹脂、水系エポキシ樹脂など）などを適用できる。また、このようなコーティング層を介して、またはＺｎめっき層２上に直接、種々の公知の塗料などが適用可能である。例えば熱可塑性樹脂としては、ポリエチレン、ポリプロピレン、エチレン−プロピレン共重合体、エチレン−酢酸ビニル共重合体、エチレン−アクリルエステル共重合体、アイオノマー等のオレフィン系樹脂フィルム、ポリエチレンテレフタレートやポリブチレンテレフタレート等のポリエステルフィルム、ポリ塩化ビニルフィルムやポリ塩化ビニリデンフィルム等の未延伸フィルム又は二軸延伸したフィルム、又はナイロン６、ナイロン６，６、ナイロン１１、ナイロン１２等のポリアミドフィルムなどを用いることができる。その中でも、イソフタル酸を共重合化してなる無配向のポリエチレンテレフタレートが特に好ましい。また、このような有機樹脂層７を構成するための有機材料は、単独で用いてもよく、異なる有機材料をブレンドして用いてもよい。また複数の有機樹脂層からなる多層構成であってもよい。熱硬化性樹脂としては、エポキシ−フェノール樹脂、ポリエステル樹脂等を用いることができる。
After the Zn plating layer 2 is formed on the original plate 1 in step 4, the organic resin layer 3 can be formed on the Zn plating layer 2 (step 5). Note that this step 5 is not essential and may be omitted as appropriate.
As the coating layer, for example, a highly transparent resin (water-based urethane resin containing silica sol, water-based acrylic resin, water-based epoxy resin, etc.) can be applied to the organic resin layer 3. Further, various known paints and the like can be applied through such a coating layer or directly on the Zn plating layer 2. For example, the thermoplastic resin includes polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic ester copolymer, olefin resin film such as ionomer, polyethylene terephthalate, polybutylene terephthalate and the like. An unstretched film such as a polyester film, a polyvinyl chloride film or a polyvinylidene chloride film, a biaxially stretched film, or a polyamide film such as nylon 6, nylon 6, 6, nylon 11, or nylon 12 can be used. Among them, non-oriented polyethylene terephthalate obtained by copolymerizing isophthalic acid is particularly preferable. Further, the organic material for forming such an organic resin layer 7 may be used alone or may be used by blending different organic materials. Further, it may have a multi-layer structure composed of a plurality of organic resin layers. As the thermosetting resin, an epoxy-phenol resin, a polyester resin or the like can be used.
上記した実施形態は、本発明の趣旨を逸脱しない範囲で種々の変形が可能である。以下、本発明の第２実施形態について説明する。なお、第２実施形態においては、既述の構成と同じ機能・作用を奏するものは同じ参照番号を付し、その説明は適宜省略する。
≪第２実施形態≫
上記した第１実施形態では、ステップ３の前処理浴に含有される無機イオンは表１に示される有効成分であったが、本第２実施形態では以下の表２に示す無機イオンを用いている。
The above-described embodiment can be modified in various ways without departing from the spirit of the present invention. Hereinafter, the second embodiment of the present invention will be described. In the second embodiment, those having the same functions and functions as those described above are given the same reference numbers, and the description thereof will be omitted as appropriate.
<< Second Embodiment >>
In the first embodiment described above, the inorganic ions contained in the pretreatment bath in step 3 were the active ingredients shown in Table 1, but in the second embodiment, the inorganic ions shown in Table 2 below are used. There is.
本実施形態では、例えば表２で示した材料に代表される遷移金属、とくに第６族元素又は第７族元素のうちいずれかの元素の無機イオンを含有する前処理浴に事前に浸漬する。これにより、Ｚｎめっきの結晶配向面を、（０００２）面に優先配向させる。すなわち、欠陥部の結晶配向を正常部の結晶配向に近づけ、これにより（０００２）面の結晶配向の乱れによる目視外観上の不良を抑制されることが可能となっている。
このように、上記した第１実施形態では欠陥部と正常部との配向差を小さくさせることを主眼に置いたのに対し、本実施形態では欠陥部の結晶配向を正常部の結晶配向に近づけることに主眼を置いていることに特徴がある。
In the present embodiment, for example, the transition metal represented by the material shown in Table 2 is pre-immersed in a pretreatment bath containing inorganic ions of any of Group 6 elements or Group 7 elements. As a result, the crystal orientation plane of Zn plating is preferentially oriented to the (0002) plane. That is, the crystal orientation of the defective portion is brought closer to the crystal orientation of the normal portion, which makes it possible to suppress defects in the visual appearance due to the disorder of the crystal orientation of the (0002) plane.
As described above, in the first embodiment described above, the main purpose is to reduce the orientation difference between the defective portion and the normal portion, whereas in the present embodiment, the crystal orientation of the defective portion is brought closer to the crystal orientation of the normal portion. It is characterized by focusing on it.
なお本実施形態でも、第１実施形態と同様に、前処理浴に浸漬した後の原板１の表面には、上記した無機イオンがアイランド状に付着しているものと推測される。
換言すれば、上記した無機イオンの原板１への付着量が皮膜として十分に定量検出可能な量未満となっており、この原板１の表面には上記した無機イオンによる均一な層は形成されていない。したがって、かような状態では、原板１の表面に点在する無機イオンが核となり、後述するＺｎめっき層が原板１上に形成されていくと考えられる。
In this embodiment as well, it is presumed that the above-mentioned inorganic ions are attached in an island shape on the surface of the original plate 1 after being immersed in the pretreatment bath, as in the first embodiment.
In other words, the amount of the above-mentioned inorganic ions attached to the original plate 1 is less than the amount that can be sufficiently quantitatively detected as a film, and a uniform layer of the above-mentioned inorganic ions is formed on the surface of the original plate 1. Absent. Therefore, in such a state, it is considered that the inorganic ions scattered on the surface of the original plate 1 become nuclei and the Zn plating layer described later is formed on the original plate 1.
また、表２に示すとおり、前処理浴に含有される無機イオンの濃度は、Ｍｏ酸アンモニウムの場合は１０〜５０００ｍｇ／Ｌであり、より好ましくは２０〜５０００、さらに好ましくは２０〜１００ｍｇ／Ｌである。一方で塩化Ｍｎの場合には１０〜５０００ｍｇ／Ｌであり、より好ましくは２０〜５０００、さらに好ましくは２０〜１００ｍｇ／Ｌである。
なお表２に具体的な数値で示した材料の他にも、他の遷移金属、より好ましくは第６族元素又は第７族元素のいずれかを適用することができ、この場合には実験やシミュレーションなどで具体的な元素や最適な濃度などを決定してもよい。
また、第２実施形態における前処理浴の浴温は、１０℃〜６０℃であって、特に好ましくは２０℃〜４５℃である。
また、かような前処理浴に原板１を浸漬する浸漬時間は、１秒〜６０秒であって、生産性を考慮すると好ましくは２秒〜５秒がよい。
Further, as shown in Table 2, the concentration of inorganic ions contained in the pretreatment bath is 10 to 5000 mg / L in the case of ammonium Moate, more preferably 20 to 5000, and further preferably 20 to 100 mg / L. Is. On the other hand, in the case of Mn chloride, it is 10 to 5000 mg / L, more preferably 20 to 5000, and even more preferably 20 to 100 mg / L.
In addition to the materials shown in the specific numerical values in Table 2, other transition metals, more preferably either Group 6 elements or Group 7 elements, can be applied. Specific elements, optimum concentrations, etc. may be determined by simulation or the like.
The bath temperature of the pretreatment bath in the second embodiment is 10 ° C. to 60 ° C., particularly preferably 20 ° C. to 45 ° C.
The immersion time for immersing the original plate 1 in such a pretreatment bath is 1 second to 60 seconds, preferably 2 seconds to 5 seconds in consideration of productivity.
≪実施例≫
以下に、実施例を挙げて本発明について、より具体的に説明する。
＜実施例１＞
厚さ０．２２５ｍｍの低炭素アルミキルド鋼の冷延鋼板を原板として用いた。まず、この鋼板をアルカリ水溶液中で電解脱脂して水洗いを行い、更に硫酸水溶液による酸洗と水洗いを行った後に、以下の条件で規定された前処理浴に浸漬した。
［前処理浴条件］
浴の主成分：イオン交換水にＭｏ酸アンモニウム四水和物を溶かして建浴
有効成分であるＭｏ６＋の濃度：２０ｍｇ／Ｌ
浴温：２５℃
浸漬時間：２秒
ｐＨ：建浴した状態の実測値で３．５〜４．５（中心ｐＨ値：４．１）
<< Example >>
Hereinafter, the present invention will be described in more detail with reference to examples.
<Example 1>
A cold-rolled steel plate of low-carbon aluminum killed steel having a thickness of 0.225 mm was used as the original plate. First, this steel sheet was electrolytically degreased in an alkaline aqueous solution and washed with water, and then pickled and washed with a sulfuric acid aqueous solution, and then immersed in a pretreatment bath specified under the following conditions.
[Pretreatment bath conditions]
Main component of bath: Concentration of Mo 6+ , which is the active ingredient of the bath, by dissolving ammonium moate tetrahydrate in ion-exchanged water: 20 mg / L
Bath temperature: 25 ° C
Immersion time: 2 seconds pH: 3.5 to 4.5 measured value in the state of standing bath (center pH value: 4.1)
その後、以下の条件で規定されたＺｎめっき浴を用いてＺｎめっき層を鋼板上に形成した。
［Ｚｎめっき条件］
浴組成 ＺｎＳＯ４・７Ｈ２Ｏ：２２０ｇ／Ｌ
Ｎａ２ＳＯ４：５０ｇ／Ｌ
浴温 ：４５℃
電流密度 ：２０ Ａ／ｄｍ２
ｐＨ：１．０〜２．０（中心ｐＨ値：１．５）
めっき付着量 ：２０ｇ／ｍ２
Then, a Zn plating layer was formed on the steel sheet using a Zn plating bath specified under the following conditions.
[Zn plating conditions]
Bath composition ZnSO 4 · 7H 2 O: 220g / L
Na2SO 4 : 50g / L
Bath temperature: 45 ° C
Current density: 20 A / dm 2
pH: 1.0 to 2.0 (center pH value: 1.5)
Plating adhesion amount: 20 g / m 2
以上により得られた表面処理鋼板ＳＳに対し光学顕微鏡を用いて表面観察写真を取得し、この表面処理鋼板ＳＳの表面における目視外観上の欠陥の有無を検査した。
［目視外観上の欠陥に関する評価指標］
３：筋状の領域が目視で確認されない
２：薄い筋状の領域が目視で確認された
１：濃い筋状の領域（欠陥）が目視で確認された
評価に際し、目視外観上の欠陥が発見されない３点について実用適性があると判断した。
この実施例１に用いた仕様とその評価結果を以下の表３に示す。
A surface observation photograph of the surface-treated steel sheet SS obtained as described above was obtained using an optical microscope, and the presence or absence of defects in the visual appearance on the surface of the surface-treated steel sheet SS was inspected.
[Evaluation index for visual defects]
3: Streaks are not visually confirmed 2: Thin streaks are visually confirmed 1: Dark streaks (defects) are visually confirmed Defects in visual appearance are found during evaluation It was judged that there is practical suitability for the three points that are not done.
The specifications used in Example 1 and the evaluation results thereof are shown in Table 3 below.
＜実施例２＞
有効成分であるＭｏ６＋の濃度を１００ｍｇ／Ｌとし、中心ｐＨ値：４．６とした以外は、実施例１と同様に行った。
<Example 2>
The same procedure as in Example 1 was carried out except that the concentration of Mo 6+ , which is an active ingredient, was set to 100 mg / L and the central pH value was set to 4.6.
＜実施例３＞
有効成分であるＭｏ６＋の濃度を５０００ｍｇ／Ｌとし、中心ｐＨ値：５．３とした以外は、実施例１と同様に行った。
<Example 3>
The same procedure as in Example 1 was carried out except that the concentration of Mo 6+ , which is an active ingredient, was set to 5000 mg / L and the central pH value was set to 5.3.
＜実施例４＞
前処理浴の主成分を塩化マンガン四水和物とし、有効成分であるＭｎ２＋の濃度を２０ｍｇ／Ｌとし、中心ｐＨ値：５．５とした以外は、実施例１と同様に行った。
<Example 4>
The same procedure as in Example 1 was carried out except that the main component of the pretreatment bath was manganese chloride tetrahydrate, the concentration of Mn 2+ as an active ingredient was 20 mg / L, and the central pH value was 5.5.
＜実施例５＞
有効成分であるＭｎ２＋の濃度を１００ｍｇ／Ｌとした以外は、実施例４と同様に行った。
<Example 5>
The same procedure as in Example 4 was carried out except that the concentration of Mn 2+ , which is an active ingredient, was set to 100 mg / L.
＜実施例６＞
有効成分であるＭｎ２＋の濃度を５０００ｍｇ／Ｌとし、中心ｐＨ値：５．３とした以外は、実施例４と同様に行った。
<Example 6>
The same procedure as in Example 4 was carried out except that the concentration of Mn 2+ , which is an active ingredient, was set to 5000 mg / L and the central pH value was set to 5.3.
＜実施例７＞
有効成分であるＭｎ２＋の濃度を１００００ｍｇ／Ｌとし、ｐＨ値を未測定とした以外は、実施例４と同様に行った。
<Example 7>
The same procedure as in Example 4 was carried out except that the concentration of Mn 2+ , which is an active ingredient, was set to 10000 mg / L and the pH value was not measured.
＜実施例８＞
前処理浴の主成分を塩化すず（ＩＩ）二水和物とし、有効成分であるＳｎ２＋の濃度を２０ｍｇ／Ｌとし、中心ｐＨ値：３．７とした以外は、実施例１と同様に行った。
<Example 8>
The same as in Example 1 except that the main component of the pretreatment bath was tin (II) chloride dihydrate, the concentration of the active ingredient Sn 2+ was 20 mg / L, and the central pH value was 3.7. went.
＜実施例９＞
有効成分であるＳｎ２＋の濃度を１００ｍｇ／Ｌとし、中心ｐＨ値：３．２とした以外は、実施例８と同様に行った。
<Example 9>
The same procedure as in Example 8 was carried out except that the concentration of Sn 2+ , which is an active ingredient, was set to 100 mg / L and the central pH value was set to 3.2.
＜実施例１０＞
有効成分であるＳｎ２＋の濃度を１０００ｍｇ／Ｌとし、中心ｐＨ値：２．５とした以外は、実施例８と同様に行った。
<Example 10>
The same procedure as in Example 8 was carried out except that the concentration of Sn 2+ , which is an active ingredient, was 1000 mg / L and the central pH value was 2.5.
＜実施例１１＞
有効成分であるＳｎ２＋の濃度を１００００ｍｇ／Ｌとし、中心ｐＨ値：１．９とした以外は、実施例８と同様に行った。
<Example 11>
The same procedure as in Example 8 was carried out except that the concentration of Sn 2+ , which is an active ingredient, was set to 10000 mg / L and the central pH value was set to 1.9.
＜実施例１２＞
前処理浴の主成分を硫酸すず（ＩＩ）とし、有効成分であるＳｎ２＋の濃度を５０００ｍｇ／Ｌとし、ｐＨ値を未測定とした以外は、実施例８と同様に行った。
<Example 12>
The same procedure as in Example 8 was carried out except that the main component of the pretreatment bath was tin sulfate (II), the concentration of Sn 2+ as an active ingredient was 5000 mg / L, and the pH value was not measured.
＜実施例１３＞
有効成分であるＳｎ２＋の濃度を１００００ｍｇ／Ｌとした以外は、実施例１２と同様に行った。
<Example 13>
The same procedure as in Example 12 was carried out except that the concentration of Sn 2+ , which is an active ingredient, was set to 10000 mg / L.
＜実施例１４＞
前処理浴の主成分を硝酸ビスマス（ＩＩＩ）五水和物とし、有効成分であるＢｉ３＋の濃度を２０ｍｇ／Ｌとし、ｐＨ値を未測定とした以外は、実施例１と同様に行った。
<Example 14>
The same procedure as in Example 1 was carried out except that the main component of the pretreatment bath was bismuth nitrate (III) pentahydrate, the concentration of the active ingredient Bi 3+ was 20 mg / L, and the pH value was not measured. ..
＜実施例１５＞
有効成分であるＢｉ３＋の濃度を１００ｍｇ／Ｌとした以外は、実施例１４と同様に行った。
<Example 15>
The same procedure as in Example 14 was carried out except that the concentration of Bi 3+ , which is an active ingredient, was set to 100 mg / L.
＜実施例１６＞
有効成分であるＢｉ３＋の濃度を５０００ｍｇ／Ｌとした以外は、実施例１４と同様に行った。
<Example 16>
The same procedure as in Example 14 was carried out except that the concentration of Bi 3+ , which is an active ingredient, was set to 5000 mg / L.
＜実施例１７＞
前処理浴の主成分を酒石酸アンチモニルカリウムとし、有効成分であるＳｂ３＋の濃度を１０ｍｇ／Ｌとし、中心ｐＨ値：２．１とした以外は、実施例１と同様に行った。
<Example 17>
The same procedure as in Example 1 was carried out except that the main component of the pretreatment bath was antimonyl potassium tartrate, the concentration of the active ingredient Sb 3+ was 10 mg / L, and the central pH value was 2.1.
＜実施例１８＞
有効成分であるＳｂ３＋の濃度を１５ｍｇ／Ｌとした以外は、実施例１７と同様に行った。
<Example 18>
The same procedure as in Example 17 was carried out except that the concentration of Sb 3+ , which is an active ingredient, was set to 15 mg / L.
＜実施例１９＞
有効成分であるＳｂ３＋の濃度を３７０ｍｇ／Ｌとし、中心ｐＨ値：１．１とした以外は、実施例１７と同様に行った。
<Example 19>
The same procedure as in Example 17 was carried out except that the concentration of the active ingredient Sb 3+ was set to 370 mg / L and the central pH value was set to 1.1.
＜実施例２０＞
有効成分であるＳｂ３＋の濃度を１８５０ｍｇ／Ｌとし、中心ｐＨ値：１．３とした以外は、実施例１７と同様に行った。
<Example 20>
The same procedure as in Example 17 was carried out except that the concentration of the active ingredient Sb 3+ was 1850 mg / L and the central pH value was 1.3.
＜実施例２１＞
有効成分であるＳｂ３＋の濃度を５０００ｍｇ／Ｌとし、ｐＨ値を未測定とした以外は、実施例１５と同様に行った。
<Example 21>
The same procedure as in Example 15 was carried out except that the concentration of the active ingredient Sb 3+ was set to 5000 mg / L and the pH value was not measured.
＜比較例１＞
有効成分であるＭｏ６＋の濃度を２ｍｇ／Ｌとし、中心ｐＨ値：４．３とした以外は、実施例１と同様に行った。
<Comparative example 1>
The same procedure as in Example 1 was carried out except that the concentration of Mo 6+ , which is an active ingredient, was set to 2 mg / L and the central pH value was set to 4.3.
＜比較例２＞
有効成分であるＭｏ６＋の濃度を１０ｍｇ／Ｌとし、中心ｐＨ値：４．２とした以外は、実施例１と同様に行った。
<Comparative example 2>
The same procedure as in Example 1 was carried out except that the concentration of Mo 6+ , which is an active ingredient, was set to 10 mg / L and the central pH value was set to 4.2.
＜比較例３＞
有効成分であるＭｏ６＋の濃度を１００００ｍｇ／Ｌとし、ｐＨ値を未測定とした以外は、実施例１と同様に行った。
<Comparative example 3>
The same procedure as in Example 1 was carried out except that the concentration of Mo 6+ , which is an active ingredient, was set to 10000 mg / L and the pH value was not measured.
＜比較例４＞
有効成分であるＭｎ２＋の濃度を２ｍｇ／Ｌとした以外は、実施例４と同様に行った。
<Comparative example 4>
The same procedure as in Example 4 was carried out except that the concentration of Mn 2+ , which is an active ingredient, was set to 2 mg / L.
＜比較例５＞
有効成分であるＭｎ２＋の濃度を１０ｍｇ／Ｌとした以外は、実施例４と同様に行った。
<Comparative example 5>
The same procedure as in Example 4 was carried out except that the concentration of Mn 2+ , which is an active ingredient, was set to 10 mg / L.
＜比較例６＞
有効成分であるＳｎ２＋の濃度を２ｍｇ／Ｌとし、中心ｐＨ値：４．５とした以外は、実施例８と同様に行った。
<Comparative Example 6>
The same procedure as in Example 8 was carried out except that the concentration of Sn 2+ , which is an active ingredient, was set to 2 mg / L and the central pH value was set to 4.5.
＜比較例７＞
有効成分であるＳｎ２＋の濃度を１０ｍｇ／Ｌとし、中心ｐＨ値：３．９とした以外は、実施例８と同様に行った。
<Comparative Example 7>
The same procedure as in Example 8 was carried out except that the concentration of Sn 2+ , which is an active ingredient, was set to 10 mg / L and the central pH value was set to 3.9.
＜比較例８＞
前処理浴の主成分を硫酸バナジル溶液とし、有効成分であるＶ４＋（ＶＯ２＋）の濃度を２０ｍｇ／Ｌとし、ｐＨ値を未測定とした以外は、実施例１と同様に行った。
<Comparative Example 8>
The same procedure as in Example 1 was carried out except that the main component of the pretreatment bath was a vanadyl sulfate solution, the concentration of the active ingredient V 4+ (VO 2+ ) was 20 mg / L, and the pH value was not measured.
＜比較例９＞
前処理浴の主成分を硫酸バナジル溶液とし、有効成分であるＶ４＋（ＶＯ２＋）の濃度を１００ｍｇ／Ｌとし、ｐＨ値を未測定とした以外は、実施例１と同様に行った。
<Comparative Example 9>
The same procedure as in Example 1 was carried out except that the main component of the pretreatment bath was a vanadyl sulfate solution, the concentration of the active ingredient V 4+ (VO 2+ ) was 100 mg / L, and the pH value was not measured.
＜比較例１０＞
前処理浴の主成分を硫酸アルミニウムとし、有効成分であるＡｌ３＋の濃度を２０ｍｇ／Ｌとし、ｐＨ値を未測定とした以外は、実施例１と同様に行った。
<Comparative Example 10>
The same procedure as in Example 1 was carried out except that the main component of the pretreatment bath was aluminum sulfate, the concentration of the active ingredient Al 3+ was 20 mg / L, and the pH value was not measured.
＜比較例１１＞
有効成分であるＡｌ３＋の濃度を１００ｍｇ／Ｌとした以外は、比較例１０と同様に行った。
<Comparative Example 11>
The same procedure as in Comparative Example 10 was carried out except that the concentration of Al 3+, which is an active ingredient, was set to 100 mg / L.
＜比較例１２＞
前処理浴の主成分をチオシアン酸アンモニウムとし、有効成分であるＳＣＮ−とＮＨ４ ＋の濃度を２００ｍｇ／Ｌとし、ｐＨ値を未測定とした以外は、実施例１と同様に行った。
<Comparative Example 12>
The main component of the pre-treatment bath with ammonium thiocyanate, SCN as an active ingredient - a NH 4 + concentration in the 200 mg / L, except that the non-measured pH value was performed in the same manner as in Example 1.
＜比較例１３＞
前処理浴の主成分をＰＥＧ（ポリエチレングリコール）＃１５４０とし、有効成分であるＰＥＧの濃度を２００ｍｇ／Ｌとし、ｐＨ値を未測定とした以外は、実施例１と同様に行った。
<Comparative Example 13>
The same procedure as in Example 1 was carried out except that the main component of the pretreatment bath was PEG (polyethylene glycol) # 1540, the concentration of PEG as an active ingredient was 200 mg / L, and the pH value was not measured.
＜比較例１４＞
前処理浴の主成分を酒石酸アンチモニルカリウムとし、有効成分であるＳｂ３＋の濃度を５ｍｇ／Ｌとし、中心ｐＨ値：２．１とした以外は、実施例１と同様に行った。
<Comparative Example 14>
The same procedure as in Example 1 was carried out except that the main component of the pretreatment bath was antimonyl potassium tartrate, the concentration of the active ingredient Sb 3+ was 5 mg / L, and the central pH value was 2.1.
以上説明した各実施例及び比較例に関する各種仕様値及び評価結果を表３に示す。 Table 3 shows various specification values and evaluation results for each of the above-described Examples and Comparative Examples.
各実施例では、表面処理鋼板ＳＳの表面における筋状の欠陥が確認されず、亜鉛めっきの特性は維持しつつ外観上の優れた美観を奏することが可能となっている。
一方で比較例においては、筋状の欠陥が確認されてしまい、亜鉛めっきの特性は変わらないものの目視外観上の欠陥が発現される結果となった。
In each example, streaky defects on the surface of the surface-treated steel sheet SS were not confirmed, and it was possible to achieve an excellent appearance while maintaining the characteristics of galvanization.
On the other hand, in the comparative example, streaky defects were confirmed, and although the characteristics of galvanization did not change, the result was that defects in the visual appearance were exhibited.
さらに発明者らは、得られた表面処理鋼板ＳＳに対し、目視以外の欠陥抑制効果の評価方法として、白色度を計測してその評価を行うとともにＸＲＤ（Ｘ線回折装置）によるピーク比を計測してその評価も行った。このうち、ＸＲＤに関する評価については、ＸＲＤのピーク積分強度及び強度比とＺｎ（1 0 -1 1）面への配向変更の効果に着目した。
なおＸＲＤの具体的な測定条件としては、次の仕様とした。
・ターゲット：Ｃｕ
・測定方法：集中法（θ/2θ法）
・管電圧：４０ｋＶ
・管電流：４０〜２００ｍＡ
Furthermore, the inventors measure and evaluate the whiteness of the obtained surface-treated steel sheet SS as a method for evaluating the defect suppressing effect other than visual inspection, and also measure the peak ratio by XRD (X-ray diffractometer). And the evaluation was also done. Of these, for the evaluation of XRD, we focused on the peak integrated intensity and intensity ratio of XRD and the effect of changing the orientation to the Zn (10-11) plane.
The specific measurement conditions for XRD are as follows.
・ Target: Cu
・ Measurement method: Concentration method (θ / 2θ method)
・ Tube voltage: 40kV
・ Tube current: 40-200mA
白色度計測およびＸＲＤ計測による評価項目については、任意の実施例（１、２、４〜７、９〜１２、１７〜２０）と各比較例についてそれぞれ行った。
この白色度計測およびＸＲＤ計測による評価結果を表４に示す。
Regarding the evaluation items by whiteness measurement and XRD measurement, arbitrary examples (1, 2, 4 to 7, 9 to 12, 17 to 20) and each comparative example were performed respectively.
Table 4 shows the evaluation results by the whiteness measurement and the XRD measurement.
表４からも明らかなとおり、実施例９〜１２、１７〜２０では非欠陥部のＺｎ（０００２）面の配向が著しく小さくなっており、これは前処理浴の有効成分である元素（Ｓｂ及びＳｎであり、Ｂｉも同様の傾向を示す）による（０００２）面の配向抑制効果であると推察できる。 As is clear from Table 4, in Examples 9 to 12 and 17 to 20, the orientation of the Zn (0002) plane of the non-defect portion is remarkably small, which is the element (Sb and Sb) which is the active ingredient of the pretreatment bath. It can be inferred that it is Sn and Bi also shows the same tendency), which is the effect of suppressing the orientation of the (0002) plane.
さらに、酒石酸アンチモニルカリウムを用いた上記実施例１７〜２１および比較例１４に対し、前処理浴の浴温とｐＨを上記と異なる値に設定して下記のとおり実験および評価を行った。 Further, with respect to Examples 17 to 21 and Comparative Example 14 using antimonyl potassium tartrate, the bath temperature and pH of the pretreatment bath were set to different values from the above, and experiments and evaluations were carried out as follows.
＜実施例２２＞
前処理浴の主成分を酒石酸アンチモニルカリウムとし、有効成分であるＳｂ３＋の濃度を１０ｍｇ／Ｌとし、浴温を２４℃とし、中心ｐＨ値：４．０とした以外は、実施例１と同様に行った。
<Example 22>
Example 1 except that the main component of the pretreatment bath was antimonyl potassium tartrate, the concentration of the active ingredient Sb 3+ was 10 mg / L, the bath temperature was 24 ° C, and the central pH value was 4.0. It was done in the same way.
＜実施例２３＞
有効成分であるＳｂ３＋の濃度を２０ｍｇ／Ｌとし、中心ｐＨ値：４．１とした以外は、実施例２２と同様に行った。
<Example 23>
The same procedure as in Example 22 was carried out except that the concentration of the active ingredient Sb 3+ was 20 mg / L and the central pH value was 4.1.
＜実施例２４＞
有効成分であるＳｂ３＋の濃度を３５．７ｍｇ／Ｌとし、中心ｐＨ値：４．２とした以外は、実施例２２と同様に行った。
<Example 24>
The same procedure as in Example 22 was carried out except that the concentration of the active ingredient Sb 3+ was 35.7 mg / L and the central pH value was 4.2.
＜実施例２５＞
有効成分であるＳｂ３＋の濃度を１００ｍｇ／Ｌとし、中心ｐＨ値：４．３とした以外は、実施例２２と同様に行った。
<Example 25>
The same procedure as in Example 22 was carried out except that the concentration of the active ingredient Sb 3+ was 100 mg / L and the central pH value was 4.3.
＜実施例２６＞
有効成分であるＳｂ３＋の濃度を５００ｍｇ／Ｌとし、中心ｐＨ値：４．３とした以外は、実施例２２と同様に行った。
<Example 26>
The same procedure as in Example 22 was carried out except that the concentration of the active ingredient Sb 3+ was set to 500 mg / L and the central pH value was set to 4.3.
＜実施例２７＞
有効成分であるＳｂ３＋の濃度を２０００ｍｇ／Ｌとし、中心ｐＨ値：４．２とした以外は、実施例２２と同様に行った。
<Example 27>
The same procedure as in Example 22 was carried out except that the concentration of the active ingredient Sb 3+ was 2000 mg / L and the central pH value was 4.2.
＜比較例１５＞
有効成分であるＳｂ３＋の濃度を５ｍｇ／Ｌとし、中心ｐＨ値：３．８とした以外は、実施例２２と同様に行った。
<Comparative Example 15>
The same procedure as in Example 22 was carried out except that the concentration of the active ingredient Sb 3+ was set to 5 mg / L and the central pH value was set to 3.8.
以上の実施例２２〜２７及び比較例１５における各種仕様値およびその評価結果を表５に示す。さらに、これらの実施例および比較例に対して行ったＸＲＤ計測による評価結果については表６に示す。 Table 5 shows various specification values and their evaluation results in Examples 22 to 27 and Comparative Example 15 described above. Furthermore, Table 6 shows the evaluation results by XRD measurement performed on these Examples and Comparative Examples.
なお、上記で説明した実施例および比較例においては、原板を前処理浴に浸漬したことによって各有効成分が原板表面にどの程度付着しているかを定量することは困難である。しかしながら例えばＧＤＳ（グロー放電発光分光分析装置）を用いた観察を実施することにより、前処理浴への浸せき時間と共にごく僅かながら原板表面に元素が吸着もしくは析出していることが分かる。
表７に、前処理浴へ浸漬する前の原板と前処理浴へ１０秒浸漬した後の原板におけるＧＤＳ観察による表面の元素分析結果を示す。
In the examples and comparative examples described above, it is difficult to quantify how much each active ingredient adheres to the surface of the original plate by immersing the original plate in the pretreatment bath. However, by carrying out observations using, for example, a GDS (Glow Discharge Emission Spectroscopy), it can be seen that elements are adsorbed or precipitated on the surface of the original plate with a slight amount of immersion time in the pretreatment bath.
Table 7 shows the results of elemental analysis of the surface of the original plate before being immersed in the pretreatment bath and the original plate after being immersed in the pretreatment bath for 10 seconds by GDS observation.
なお上記した実施形態と各実施例は、本発明の趣旨を逸脱しない範囲で種々の変形が可能である。
また、上記した前処理浴における無機イオンの濃度は１０〜５０００ｍｇ／Ｌである必要は必ずしもなく、含有される無機イオンの種類により上限または下限を適宜変化させてもよく、さらには前処理浴のｐＨに応じて上限または下限を変化させてもよい。例えば上記した適用材料が塩化Ｍｎの場合には、濃度範囲における上限は１００００ｍｇ／Ｌとなる。
The above-described embodiments and examples can be modified in various ways without departing from the spirit of the present invention.
The concentration of inorganic ions in the above-mentioned pretreatment bath does not necessarily have to be 10 to 5000 mg / L, and the upper or lower limit may be appropriately changed depending on the type of inorganic ions contained in the pretreatment bath. The upper or lower limit may be changed depending on the pH. For example, when the above-mentioned applicable material is Mn chloride, the upper limit in the concentration range is 10000 mg / L.
以上説明したように、本発明の表面処理鋼板の製造方法は、亜鉛めっきの特性と外観上の美観を同時に達成することが可能であり、広い分野の産業への適用が可能である。 As described above, the method for producing a surface-treated steel sheet of the present invention can simultaneously achieve the characteristics of galvanizing and the aesthetic appearance, and can be applied to a wide range of industries.
１ 原板
２ Ｚｎめっき層
３ 有機樹脂層
ＳＳ 表面処理鋼板
1 Original plate 2 Zn plating layer 3 Organic resin layer SS Surface-treated steel sheet
Claims (6)
前記第１工程の後、Ｓｂ３＋ 又はＭｏ６＋の無機イオンを１０〜５０００ｍｇ／Ｌの濃度で含有してｐＨが３〜５である処理液に、前記原板を浸漬する第２工程と、
前記第２工程の後、亜鉛めっき浴を用いて前記原板にＺｎめっき層を形成する第３工程と、
を有することを特徴とする亜鉛めっき鋼板の製造方法。 The first step of degreasing and pickling the original plate,
After the first step, the second step of immersing the original plate in a treatment liquid containing Sb 3+ or Mo 6+ inorganic ions at a concentration of 10 to 5000 mg / L and having a pH of 3 to 5
After the second step, a third step of forming a Zn plating layer on the original plate using a zinc plating bath, and
A method for producing a galvanized steel sheet, which comprises.
前記無機イオンが点在する前記原板の表面に亜鉛めっき皮膜が形成される請求項１に記載の亜鉛めっき鋼板の製造方法。 In the second step, the inorganic ions adhere to the surface of the original plate in an island shape.
The method for producing a galvanized steel sheet according to claim 1, wherein a galvanized film is formed on the surface of the original plate in which the inorganic ions are scattered.
前記Ｓｂ３＋である場合に当該Ｓｂ３＋が１０〜５００ｍｇ／Ｌの濃度、
で前記処理液に含有される請求項１に記載の亜鉛めっき鋼板の製造方法。 The inorganic ions in the second step
When the Sb 3+ is , the concentration of the Sb 3+ is 10 to 500 mg / L.
The method for producing a galvanized steel sheet according to claim 1, which is contained in the treatment liquid.
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