JP2010024473A - Surface-treated steel sheet and method for producing the same - Google Patents
Surface-treated steel sheet and method for producing the same Download PDFInfo
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- JP2010024473A JP2010024473A JP2008184302A JP2008184302A JP2010024473A JP 2010024473 A JP2010024473 A JP 2010024473A JP 2008184302 A JP2008184302 A JP 2008184302A JP 2008184302 A JP2008184302 A JP 2008184302A JP 2010024473 A JP2010024473 A JP 2010024473A
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 101
- 239000010959 steel Substances 0.000 title claims abstract description 101
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 229920005989 resin Polymers 0.000 claims abstract description 35
- 239000011347 resin Substances 0.000 claims abstract description 35
- 238000005554 pickling Methods 0.000 claims abstract description 22
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 18
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 7
- 230000003287 optical effect Effects 0.000 claims description 6
- 239000000049 pigment Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 239000003822 epoxy resin Substances 0.000 claims description 5
- 229920000647 polyepoxide Polymers 0.000 claims description 5
- 230000003449 preventive effect Effects 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000005260 corrosion Methods 0.000 abstract description 24
- 230000007797 corrosion Effects 0.000 abstract description 24
- 238000007747 plating Methods 0.000 abstract description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 11
- 239000011701 zinc Substances 0.000 abstract description 11
- 229910052725 zinc Inorganic materials 0.000 abstract description 11
- 239000000243 solution Substances 0.000 abstract description 9
- 238000004458 analytical method Methods 0.000 abstract description 8
- 238000007654 immersion Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 20
- 239000010408 film Substances 0.000 description 16
- 238000011156 evaluation Methods 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 230000001681 protective effect Effects 0.000 description 5
- 239000011888 foil Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000010960 cold rolled steel Substances 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910001335 Galvanized steel Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000008397 galvanized steel Substances 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- FJMNNXLGOUYVHO-UHFFFAOYSA-N aluminum zinc Chemical compound [Al].[Zn] FJMNNXLGOUYVHO-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Chemical Treatment Of Metals (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
Description
本発明は、主に電気製品に用いられる表面処理鋼板であり、特に、亜鉛を含有するめっきを施すことなく、良好な耐食性を有することができる表面処理鋼板及びその製造方法に関するものである。 The present invention is a surface-treated steel sheet mainly used for electrical products, and particularly relates to a surface-treated steel sheet that can have good corrosion resistance without applying zinc-containing plating and a method for producing the same.
薄型テレビ用パネル等の電気製品に用いられるプレコート鋼板（塗装鋼板）としては、例えば特許文献１に開示されているように、鋼板の表面にめっき層を形成し、該めっき層上に、直接又は化成皮膜を介して、所定の樹脂を含有する皮膜を形成してなる塗装鋼板が挙げられる。特許文献１の塗装鋼板は、前記めっき層や樹脂被膜の作用によって、良好な耐食性を実現することができる。 As a pre-coated steel plate (painted steel plate) used for an electrical product such as a flat panel television, for example, as disclosed in Patent Document 1, a plated layer is formed on the surface of the steel plate, and directly or on the plated layer. A coated steel plate formed by forming a film containing a predetermined resin through a chemical conversion film is exemplified. The coated steel sheet of Patent Document 1 can achieve good corrosion resistance by the action of the plating layer and the resin film.
ここで、前記めっき層の種類としては、その用途によっても異なるが、良好な耐食性を有する点や、コストの点などから、亜鉛系のめっき層を設けた鋼板、例えば、溶融亜鉛めっき鋼板、電気亜鉛めっき鋼板、合金化溶融亜鉛めっき鋼板又はアルミニウム−亜鉛合金めっき鋼板等を用いるのが一般的である。しかしながら、かかる亜鉛系めっき層は、近年の亜鉛原料価格高騰のため、製品コストをアップさせるという点、及び鋼板リサイクルの際にできるだけ鋼板成分以外の元素を排除する必要があるという点から、前記鋼板表面に亜鉛めっき層を形成しない表面処理鋼板が望まれている。
前記亜鉛系めっき層を設けない鋼材として、例えば特許文献２に、鋼材を脱脂処理工程と、酸化処理によって前記鋼材の表面を凹凸化する工程と、変性ポリオレフィン樹脂をコーティングする工程によって製造される鋼材が挙げられる。
Here, the type of the plating layer varies depending on the application, but from the viewpoint of having good corrosion resistance and cost, a steel plate provided with a zinc-based plating layer, such as a hot dip galvanized steel plate, electric In general, a galvanized steel sheet, a galvannealed steel sheet, an aluminum-zinc alloy plated steel sheet, or the like is used. However, such a zinc-based plating layer increases the product cost due to the recent increase in the price of zinc raw materials, and it is necessary to eliminate elements other than steel plate components as much as possible when recycling steel plates. A surface-treated steel sheet that does not form a galvanized layer on the surface is desired.
As a steel material not provided with the zinc-based plating layer, for example, in Patent Document 2, a steel material manufactured by a degreasing treatment step of the steel material, a step of making the surface of the steel material uneven by an oxidation treatment, and a step of coating a modified polyolefin resin. Is mentioned.
しかしながら、特許文献２の鋼材のように、樹脂層（特許文献２では変性ポリオレフィン樹脂層）を厚く鋼材表面に形成することができるのであれば、一定の耐食性を有することは可能であるものの、家庭用電気製品等の場合は、十分な厚さの樹脂層を鋼板表面上に形成することはコストの点からも好ましくないことから、亜鉛系めっき層を形成しない限り、所望の耐食性を得ることができないと考えられている。
本発明の目的は、有機樹脂層の膜厚が薄い場合であっても、亜鉛系めっき層を形成することなく、良好な耐食性を備える表面処理鋼板及びその製造方法を提供することにある。 An object of the present invention is to provide a surface-treated steel sheet having good corrosion resistance and a method for producing the same without forming a zinc-based plating layer even when the organic resin layer is thin.
本発明者らは、上記の課題を解決するため検討を重ねた結果、素地鋼板として硝酸水溶液で酸洗処理した鋼板を用いて、その鋼板の酸洗処理面上に有機樹脂層を形成することで、前記酸洗処理の作用によって前記鋼板表面上に緻密な保護膜が形成されるため、有機樹脂層の膜厚が5μm以下と薄い場合であっても、鋼板表面に亜鉛系めっき層を形成することなく、良好な耐食性を備える表面処理鋼板が得られることを見出した。 As a result of repeated studies to solve the above problems, the present inventors use a steel plate that has been pickled with a nitric acid aqueous solution as a base steel plate, and form an organic resin layer on the pickled surface of the steel plate. Thus, a dense protective film is formed on the surface of the steel sheet by the action of the pickling treatment, so even if the organic resin layer has a thin film thickness of 5 μm or less, a zinc-based plating layer is formed on the surface of the steel sheet. It has been found that a surface-treated steel sheet having good corrosion resistance can be obtained without doing so.
本発明は、このような知見に基づきなされたもので、その要旨は以下の通りである。
（１）硝酸水溶液で酸洗処理した素地鋼板の少なくとも片面に、膜厚が5μm以下である有機樹脂層を形成したことを特徴とする表面処理鋼板。
The present invention has been made based on such findings, and the gist thereof is as follows.
(1) A surface-treated steel sheet in which an organic resin layer having a thickness of 5 μm or less is formed on at least one surface of a base steel sheet that has been pickled with an aqueous nitric acid solution.
（２）前記表面処理鋼板は、ＧＤＳ（グロー放電発光分光分析装置）を用いて前記素地鋼板の表面から深さ方向に分析し、所定のFe強度を得るまでに要する時間が、前記酸洗処理を施していない鋼板に対して、2〜10倍の範囲である上記（１）記載の表面処理鋼板。 (2) The surface-treated steel sheet is analyzed in the depth direction from the surface of the base steel sheet using a GDS (Glow Discharge Optical Emission Spectrometer), and the time required to obtain a predetermined Fe strength is determined by the pickling treatment. The surface-treated steel sheet according to (1), wherein the surface-treated steel sheet is in a range of 2 to 10 times that of the steel sheet not subjected to the treatment.
（３）前記所定のFe強度は4.5Vであり、その強度が得られるまでの時間が5〜30秒である上記（２）記載の表面処理鋼板。 (3) The surface-treated steel sheet according to (2), wherein the predetermined Fe strength is 4.5 V, and the time until the strength is obtained is 5 to 30 seconds.
（４）前記有機樹脂は、エポキシ系樹脂である上記（１）、（２）又は（３）記載の表面処理鋼板。 (4) The surface-treated steel sheet according to (1), (2) or (3), wherein the organic resin is an epoxy resin.
（５）前記有機樹脂層が、防錆顔料を含有する上記（１）〜（４）のいずれか１項記載の表面処理鋼板。 (5) The surface-treated steel sheet according to any one of (1) to (4), wherein the organic resin layer contains a rust preventive pigment.
（６）鋼板の少なくとも片面に対して、常温の5〜40mass％硝酸水溶液に30秒未満の間浸漬させる酸洗処理を施した後、水洗、乾燥させ、その後、鋼板の酸洗処理面に、有機樹脂を含有する塗料を塗布し、乾燥させて、有機樹脂層を形成することを特徴とする表面処理鋼板の製造方法。 (6) At least one side of the steel sheet is subjected to pickling treatment in which it is immersed in a 5 to 40 mass% nitric acid aqueous solution at room temperature for less than 30 seconds, and then washed with water and dried. A method for producing a surface-treated steel sheet, wherein an organic resin layer is formed by applying and drying a paint containing an organic resin.
（７）前記有機樹脂は、エポキシ系樹脂である上記（６）記載の表面処理鋼板の製造方法。 (7) The method for producing a surface-treated steel sheet according to (6), wherein the organic resin is an epoxy resin.
本発明によれば、有機樹脂層の膜厚が薄い場合であっても、亜鉛系めっき層を形成することなく、良好な耐食性を備える表面処理鋼板及びその製造方法を提供することが可能となった。 ADVANTAGE OF THE INVENTION According to this invention, even if it is a case where the film thickness of an organic resin layer is thin, it becomes possible to provide the surface treatment steel plate provided with favorable corrosion resistance, and its manufacturing method, without forming a zinc-type plating layer. It was.
以下、本発明の構成と限定理由を説明する。
本発明に従う表面処理鋼板は、硝酸水溶液で酸洗処理した素地鋼板の少なくとも片面に、膜厚が5μm以下の有機樹脂層を形成したことを特徴とする表面処理鋼板である。
Hereinafter, the configuration of the present invention and the reasons for limitation will be described.
The surface-treated steel sheet according to the present invention is a surface-treated steel sheet in which an organic resin layer having a thickness of 5 μm or less is formed on at least one surface of a base steel sheet that has been pickled with a nitric acid aqueous solution.
本発明の表面処理鋼板は、硝酸水溶液で酸洗処理を施した素地鋼板を用いることを特徴とする。硝酸水溶液で酸洗処理を施すことにより、素地鋼板表面に緻密な保護膜が形成される。さらに酸洗処理を施した表面上に、有機樹脂層を形成することにより、亜鉛系めっき層を形成することなく良好な耐食性を備えることが可能となる。また、基板である鋼板は、前記酸洗処理を施すことができる鋼板であれば特に限定はなく、用途に応じ適宜選択できる。 The surface-treated steel sheet of the present invention is characterized by using a base steel sheet that has been pickled with an aqueous nitric acid solution. By performing pickling treatment with an aqueous nitric acid solution, a dense protective film is formed on the surface of the base steel plate. Furthermore, by forming the organic resin layer on the surface subjected to pickling treatment, it becomes possible to provide good corrosion resistance without forming a zinc-based plating layer. Moreover, the steel plate which is a board | substrate will not be specifically limited if it is a steel plate which can perform the said pickling process, According to a use, it can select suitably.
なお、前記鋼板の酸洗処理表面は、常温の硝酸水溶液（5〜40mass％）に、前記鋼板を30秒未満の間浸漬させた後、水洗し、乾燥させることにより形成することができる。ここで、前記硝酸水溶液の濃度を5〜40mass％に限定したのは、濃度が5mass％未満の場合、鋼板表面上に前記緻密な保護膜が形成されにくいため、耐食性が低下し、一方、濃度が40mass％を超えると、前記鋼板が激しく反応するため、表面にムラ模様が発生し、外観を著しく低下させるためである。また、浸漬時間を30秒未満としたのは、30秒以上の場合、前記鋼板表面にムラ模様が発生し、外観を著しく低下させるからである。 The pickled surface of the steel sheet can be formed by immersing the steel sheet in an aqueous nitric acid solution (5 to 40 mass%) at room temperature for less than 30 seconds, and then washing and drying. Here, the concentration of the aqueous nitric acid solution is limited to 5 to 40 mass%. When the concentration is less than 5 mass%, the dense protective film is not easily formed on the surface of the steel sheet, so that the corrosion resistance is reduced. If the content exceeds 40 mass%, the steel sheet reacts violently, resulting in unevenness on the surface and significantly reducing the appearance. The reason why the immersion time is set to less than 30 seconds is that when the immersion time is 30 seconds or more, unevenness occurs on the surface of the steel sheet, and the appearance is remarkably deteriorated.
また、本発明の表面処理鋼板は、前記酸洗処理した素地鋼板の表面に、有機樹脂層を形成したものである。この有機樹脂層は、前記鋼板表面に、耐食性や、耐疵付き性、意匠性などを備えることができるように設けられる層であり、有機樹脂からなる層であれば特に限定されることはないが、前記鋼板の酸洗表面との相乗効果によって高い耐食性を得ることができる点から、エポキシ系樹脂を用いることが好ましい。 Moreover, the surface-treated steel sheet of the present invention is obtained by forming an organic resin layer on the surface of the pickled base steel sheet. This organic resin layer is a layer provided on the surface of the steel plate so as to be provided with corrosion resistance, scratch resistance, designability, and the like, and is not particularly limited as long as it is a layer made of an organic resin. However, it is preferable to use an epoxy resin from the viewpoint that high corrosion resistance can be obtained by a synergistic effect with the pickled surface of the steel sheet.
さらに、前記有機樹脂層の膜厚は5μm以下とする必要がある。膜厚が5μmを超えると、鋼板表面の電気抵抗が高くなるため、アース性が著しく低下し、さらに、製造コストが高騰するという問題が発生するためである。また、前述の有機樹脂層の効果を得るためには、膜厚は0.3μm以上とすることが好ましい。 Furthermore, the film thickness of the organic resin layer needs to be 5 μm or less. If the film thickness exceeds 5 μm, the electrical resistance on the surface of the steel sheet becomes high, so that the grounding property is remarkably lowered, and the manufacturing cost is increased. Further, in order to obtain the effect of the organic resin layer described above, the film thickness is preferably set to 0.3 μm or more.
なお、前記有機樹脂層は、前記素地鋼板の酸洗処理面に、前記有機樹脂を含有する塗料を塗布し、乾燥させることによって形成することができる。 In addition, the said organic resin layer can be formed by apply | coating the coating material containing the said organic resin to the pickling process surface of the said base steel plate, and making it dry.
また、前記有機樹脂層は、防錆顔料を含有することが好ましい。防錆顔料を含有すれば、さらに耐食性を向上させることができるためである。なお、前記防食顔料の種類は、特に限定はしないが、さらなる耐食性向上の点で、リンモリブデン酸アルミニウム、リン酸亜鉛又はトリポリリン酸アルミニウムを用いることがより好適である。 Moreover, it is preferable that the said organic resin layer contains a rust preventive pigment. This is because the corrosion resistance can be further improved by containing a rust preventive pigment. The type of the anticorrosive pigment is not particularly limited, but it is more preferable to use aluminum phosphomolybdate, zinc phosphate or aluminum tripolyphosphate from the viewpoint of further improving the corrosion resistance.
なお、本発明の表面処理鋼板は、ＧＤＳを用いて前記硝酸酸洗処理後の素地鋼板表面から深さ方向に分析し、所定のFe強度を得るまでに要する時間が、前記酸洗処理を施していない鋼板に対して、2〜10倍の範囲であることが好ましい。
ここで、前記ＧＤＳとは、グロー放電発光分光分析装置のことをいい、測定時間（秒）と光強度（Ｖ）との関係によって、表面からの所定の深さ位置にある各元素の濃度を知ることができるものである。そのため、ＧＤＳによる分析を行った場合、所定のFe強度を得るまでに要する時間が長ければ、その分、Feに到達するために要するエネルギーが必要となるということであるため、耐食性についても高くなる。また、所定のFe強度を得るまでに要する時間を2〜10倍の範囲としたのは、2倍未満の場合、前記保護膜がほとんど形成されないため、酸洗処理を施していない鋼板と比べて耐食性に大きな効果を奏することができないためであり、一方、10倍を超えると、耐食性については高くなるものの前記鋼板の表面にムラ模様が形成され、外観が著しく低下するためである。
The surface-treated steel sheet of the present invention is analyzed in the depth direction from the surface of the base steel sheet after the nitric acid pickling treatment using GDS, and the time required to obtain a predetermined Fe strength is subjected to the pickling treatment. It is preferable that it is in the range of 2 to 10 times with respect to the steel plate that is not.
Here, the GDS refers to a glow discharge optical emission spectrometer, and the concentration of each element at a predetermined depth from the surface is determined by the relationship between the measurement time (seconds) and the light intensity (V). It is something you can know. Therefore, when the analysis by GDS is performed, if the time required to obtain the predetermined Fe intensity is long, the energy required to reach Fe is required accordingly, so the corrosion resistance is also increased. . In addition, the time required to obtain the predetermined Fe strength is in the range of 2 to 10 times, because the protective film is hardly formed when less than 2 times, compared with a steel plate not subjected to pickling treatment This is because a great effect cannot be exerted on the corrosion resistance. On the other hand, if it exceeds 10 times, although the corrosion resistance is increased, unevenness is formed on the surface of the steel sheet, and the appearance is remarkably deteriorated.
図１は、ＧＤＳ（グロー放電発光分光分析装置）を用いて硝酸酸洗処理後の素地鋼板表面から深さ方向に分析した各原素（O、Ｃ及びFe）の強度（V）と分析時間（秒）との関係を示したグラフであり、(ａ)は20mass％の硝酸水溶液を用いて10秒間、酸洗処理を施した素地鋼板の分析結果を示したものであり、(ｂ)は酸洗処理を施していない冷延鋼板についての分析結果を示している。図１(ａ)に示すように、本発明の素地鋼板は、所定の酸洗を施していない鋼板（図１(ｂ)）に比べて、所定のFe強度（例えば5Ｖ）を得るまでに要する時間が３倍以上長いことがわかる。 Fig. 1 shows the strength (V) and analysis time of each element (O, C and Fe) analyzed in the depth direction from the surface of the base steel sheet after the nitric acid pickling treatment using a GDS (glow discharge optical emission spectrometer). (A) is a graph showing the analysis results of a base steel sheet that has been pickled for 10 seconds using a 20 mass% nitric acid aqueous solution, (b) The analysis result about the cold-rolled steel plate which has not performed the pickling process is shown. As shown to Fig.1 (a), the base steel plate of this invention is required until it obtains predetermined Fe intensity | strength (for example, 5V) compared with the steel plate (FIG.1 (b)) which has not performed the predetermined pickling. It can be seen that the time is more than three times longer.
また、前記所定のFe強度は4.5Vであり、その強度が得られるまでの時間が5〜30秒の範囲であることが好ましい。所定のFe強度を4.5Ｖとしたのは、目標強度が得られるまでの時間を読み取りやすいためであり、強度が得られるまでの時間を5〜30秒としたのは、5秒未満では、前記保護膜がほとんど形成されていないため十分な耐食性を備えることができず、30秒を超えると表面にムラ模様が形成され、外観が著しく低下するためである。 The predetermined Fe intensity is 4.5 V, and the time until the intensity is obtained is preferably in the range of 5 to 30 seconds. The reason why the predetermined Fe intensity is 4.5 V is because it is easy to read the time until the target intensity is obtained, and the time until the intensity is obtained is 5 to 30 seconds. This is because the protective film is hardly formed, so that sufficient corrosion resistance cannot be provided, and when it exceeds 30 seconds, an uneven pattern is formed on the surface and the appearance is remarkably deteriorated.
上述したところは、この発明の実施形態の一例を示したにすぎず、請求の範囲において種々の変更を加えることができる。 The above description is merely an example of the embodiment of the present invention, and various modifications can be made within the scope of the claims.
本発明の実施例について説明する。 Examples of the present invention will be described.
（実施例１〜１０及び比較例３〜５）
板厚0.8mmの冷延鋼板の片面に、前処理として、オルソ珪酸ソーダ（60g／L）添加のアルカリ脱脂液（液温：70℃）中で、対極をステンレス板として電流密度：5A／dm２ で30秒間の電解脱脂を施した後、水洗し、表１に示す条件の硝酸水溶液中に、所定時間（表１参照）浸漬させて酸洗した後、水洗、乾燥させた。
上記の酸洗処理後、有機樹脂及び必要に応じて防錆顔料を含有する所定の塗料を、前記硝酸酸洗処理した素地鋼板の表面に塗布し、乾燥させることにより、表１に示す構成の有機樹脂層を形成し、サンプルとなる表面処理鋼板を製造した。
なお、製造した各サンプルについて、ＧＤＳによって、前記素地鋼板の表面から深さ方向に分析し、所定のFe強度（4.5V）が得られるまでの時間（秒）を測定し、酸洗処理を施さない鋼板（比較例１）に対する割合を、表１に示す。
また、前記有機樹脂層の膜厚（μm）は、断面を光学顕微鏡又は電子顕微鏡を用い、１視野につき任意の３箇所の膜厚を測定し、少なくとも５視野で、合計１５箇所以上で測定した膜厚の平均値とする。
(Examples 1-10 and Comparative Examples 3-5)
On one side of a cold rolled steel sheet with a thickness of 0.8mm, as a pretreatment, in an alkaline degreasing solution (liquid temperature: 70 ° C) with sodium orthosilicate (60g / L), the counter electrode is a stainless steel plate, and the current density is 5A / dm. After performing electrolytic degreasing for 30 seconds in 2 , the sample was washed with water, immersed in a nitric acid solution under the conditions shown in Table 1 for a predetermined time (see Table 1), pickled, then washed with water and dried.
After the above pickling treatment, a predetermined paint containing an organic resin and, if necessary, a rust preventive pigment is applied to the surface of the nitric acid pickled base steel sheet and dried, so that the structure shown in Table 1 is obtained. An organic resin layer was formed, and a surface-treated steel sheet to be a sample was manufactured.
In addition, about each manufactured sample, it analyzes in the depth direction from the surface of the said base steel plate by GDS, measures time (second) until predetermined Fe intensity | strength (4.5V) is obtained, and pickles it Table 1 shows the ratio with respect to the steel plate without comparison (Comparative Example 1).
Moreover, the film thickness (micrometer) of the said organic resin layer measured the film thickness of arbitrary three places per field using an optical microscope or an electron microscope, and measured it at a total of 15 or more places by at least 5 fields of view. The average value of the film thickness.
（比較例１）
比較例１は、所定の酸洗処理を施さないこと以外は、実施例１と同様の条件によって、サンプルとなる表面処理鋼板を製造した。
(Comparative Example 1)
In Comparative Example 1, a surface-treated steel sheet as a sample was manufactured under the same conditions as in Example 1 except that the predetermined pickling treatment was not performed.
（比較例２）
比較例２は、実施例１と同様の鋼板に対して、実施例１と同様の前処理を施した後、水洗し、濃度が10mass％、温度が常温の塩酸水溶液中に、60秒間浸漬させて酸洗したこと以外は、実施例１と同様の条件によって、サンプルとなる表面処理鋼板を製造した。
(Comparative Example 2)
In Comparative Example 2, the same steel sheet as in Example 1 was subjected to the same pretreatment as in Example 1, then washed with water, and immersed in an aqueous hydrochloric acid solution having a concentration of 10 mass% and a temperature of room temperature for 60 seconds. A surface-treated steel sheet as a sample was manufactured under the same conditions as in Example 1 except that the sample was pickled.
以上のようにして得られた各表面処理鋼板のサンプルについて各種試験を行った。本実施例で行った試験の評価方法を以下に示す。 Various tests were performed on samples of the respective surface-treated steel sheets obtained as described above. The evaluation method of the test conducted in this example is shown below.
（評価方法）
（１）耐食性
実施例及び比較例の各サンプルについて、以下の耐食性評価を行った。具体的には、各サンプルに対して、１週間に２度の周期で、人工海塩を付着させて（付着量：10mg／m2）、絶対温度がほぼ一定となる乾燥環境（60℃、35%RH）と湿潤環境（40℃、95%RH）の乾湿繰り返しを移行時間１時間として、３時間ずつ保持し、２週間放置した後、各サンプルの表面の状態を観察し、以下の基準に従って評価した。評価結果を表２に示す。
○：赤錆発生面積率10%未満
×：赤錆発生面積率10%以上
さらに、実施例１、比較例１及び比較例２のサンプルについて、外観を撮影した写真を図２に示す。図２(ａ)が実施例１のサンプル、(ｂ)が比較例１のサンプル、(ｃ)が比較例２のサンプルについての写真である。
(Evaluation methods)
(1) Corrosion resistance The following corrosion resistance evaluation was performed about each sample of the Example and the comparative example. Specifically, for each sample, artificial sea salt is attached at a frequency of twice a week (attachment amount: 10 mg / m 2 ), and the dry environment (60 ° C, 35% RH) and wet environment (40 ° C, 95% RH) with a transition time of 1 hour, hold for 3 hours, leave it for 2 weeks, observe the surface condition of each sample, and Evaluated according to. The evaluation results are shown in Table 2.
○: Red rust generation area ratio less than 10% ×: Red rust generation area ratio 10% or more Further, photographs of the appearance of the samples of Example 1, Comparative Example 1 and Comparative Example 2 are shown in FIG. 2A is a photograph of the sample of Example 1, (b) is the sample of Comparative Example 1, and (c) is a photograph of the sample of Comparative Example 2. FIG.
（２）耐指紋性
実施例及び比較例の各サンプルについて、JIS K 2246：2007に規定される人工指紋液に、20℃雰囲気下で1分間浸漬し、浸漬前後の色差（ΔＥ）について、耐指紋性の評価をした。以下の評価基準に従って評価し、評価結果を表２に示す。
なお、ΔＥは、日本電気（株）社製カラーコンピュータで測定されるＬ値、ａ値、ｂ値を用いて、以下の計算式に従い算出したものである。
○：ΔＥ≦２
×：２＜ΔＥ
(2) Fingerprint resistance Each sample of the examples and comparative examples was immersed in an artificial fingerprint liquid defined in JIS K 2246: 2007 for 1 minute at 20 ° C, and the color difference (ΔE) before and after immersion was determined. The fingerprint property was evaluated. Evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in Table 2.
ΔE is calculated according to the following calculation formula using L value, a value, and b value measured by a color computer manufactured by NEC Corporation.
×: 2 <ΔE
（３）放熱性
実施例及び比較例の各サンプルについて、アクリル樹脂板（板厚２ｍｍ）で組立てた、筐体の内面（側面および底面）にアルミホイルを貼り、完全に被覆した。筐体の内部底面中央に設置したアルミ架台の上に底面より１０ｍｍの高さに位置するように、シリコンラバーヒーターをセットした。なお、各サンプルは、縦３００ｍｍ、横３００ｍｍの大きさに切り出して筐体の天板として用い、筐体の上面開口部（側面上端部）に設置されたパッキングに接するように載せ、密封した。下記のシース型白金抵抗温体とヒーターとの間の空間に、該ヒーターから該シース型白金抵抗測温体への直接輻射防止用アルミホイル（縦２００ｍｍ、横２００ｍｍ）を、シリコンラバーヒーターの直上、かつ、底面から３５ｍｍの定置に、底面と平行に設置し、その位置を維持できるようにアルミホイルの４角を針金で支えた。
そして、天板から鉛直下方向に３５ｍｍ離れ、かつ、アルミホイルから鉛直上方向に４０ｍｍ離れた筐体内部にシース型白金抵抗測温体（直径１．６ｍｍφ、長さ１５０ｍｍ）を筐体の側面から水平を保つように差込み、筐体内部の水平方向の中央部、天板から鉛直下方向に、３５ｍｍの付近の温度を測定できるようにした後、直流安定化電源から電圧を供給し、発熱させた（入力６５Ｖ×７０５ｍＡ＝４５．８Ｗ）。
筐体内部温度の変化をデータロガーに記録し、筐体の内部温度が定常状態に達したときの温度から天板の吸放熱性を判定した。評価基準を以下に示し、評価結果を表２に示す。
○：電気亜鉛めっき板に比べて温度低下が５℃以上
×：電気亜鉛めっき板に比べて温度低下が５℃未満
(3) Heat dissipation About each sample of an Example and a comparative example, the aluminum foil was affixed on the inner surface (side surface and bottom face) of the housing | casing assembled with the acrylic resin board (plate thickness 2mm), and was coat | covered completely. A silicon rubber heater was set on an aluminum frame installed at the center of the inner bottom surface of the housing so as to be positioned at a height of 10 mm from the bottom surface. Each sample was cut into a size of 300 mm in length and 300 mm in width, used as a top plate of the housing, and placed and sealed so as to be in contact with the packing installed at the upper surface opening (side upper end) of the housing. In the space between the sheath type platinum resistance thermometer and the heater below, an aluminum foil (200 mm long, 200 mm wide) for preventing direct radiation from the heater to the sheath type platinum resistance thermometer is directly above the silicon rubber heater. And it installed in parallel with the bottom face at a fixed position of 35 mm from the bottom face, and supported the four corners of the aluminum foil with a wire so that the position could be maintained.
Then, a sheath type platinum resistance thermometer (diameter: 1.6 mmφ, length: 150 mm) is placed on the side surface of the casing inside the casing, which is 35 mm away from the top plate vertically downward and 40 mm away from the aluminum foil vertically upward. It is inserted so as to maintain the horizontal position, and the temperature in the vicinity of 35 mm can be measured from the center in the horizontal direction inside the case and vertically downward from the top plate, and then a voltage is supplied from the DC stabilized power supply to generate heat. (Input 65 V × 705 mA = 45.8 W).
The change in the internal temperature of the case was recorded in a data logger, and the heat absorption / release performance of the top plate was determined from the temperature when the internal temperature of the case reached a steady state. The evaluation criteria are shown below, and the evaluation results are shown in Table 2.
○: Temperature drop is 5 ° C or higher compared to electrogalvanized plate ×: Temperature drop is less than 5 ° C compared to electrogalvanized plate
（４）外観
実施例及び比較例の各サンプルについて目視による外観の評価を行った。評価基準を以下に示し、評価結果を表２に示す。
○：外観にムラなし
×：外観にムラあり
(4) Appearance The appearance of each sample of Examples and Comparative Examples was visually evaluated. The evaluation criteria are shown below, and the evaluation results are shown in Table 2.
○: Uneven appearance ×: Uneven appearance
表２の結果から、実施例１〜１０の表面処理鋼板は、比較例１〜５の表面処理鋼板に比べ、いずれも良好な耐食性、耐指紋性、放熱性及び外観を有していることがわかる。また、図２(ａ)〜(ｃ)からも、実施例１の表面処理鋼板が、比較例１及び２の表面に比べて耐食性に優れていることが分かる。 From the results in Table 2, the surface-treated steel sheets of Examples 1 to 10 have better corrosion resistance, fingerprint resistance, heat dissipation and appearance than the surface-treated steel sheets of Comparative Examples 1 to 5. Recognize. 2A to 2C also show that the surface-treated steel sheet of Example 1 is superior to the surfaces of Comparative Examples 1 and 2 in corrosion resistance.
本発明によれば、有機樹脂層の膜厚が薄い場合であっても、亜鉛系めっき層を形成することなく、良好な耐食性を備える表面処理鋼板及びその製造方法を提供することが可能である。 ADVANTAGE OF THE INVENTION According to this invention, even if it is a case where the film thickness of an organic resin layer is thin, it is possible to provide the surface treatment steel plate provided with favorable corrosion resistance, and its manufacturing method, without forming a zinc plating layer. .
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