JP4349149B2 - Method for producing surface-treated steel sheet having excellent conductivity - Google Patents

Method for producing surface-treated steel sheet having excellent conductivity Download PDF

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JP4349149B2
JP4349149B2 JP2004049031A JP2004049031A JP4349149B2 JP 4349149 B2 JP4349149 B2 JP 4349149B2 JP 2004049031 A JP2004049031 A JP 2004049031A JP 2004049031 A JP2004049031 A JP 2004049031A JP 4349149 B2 JP4349149 B2 JP 4349149B2
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steel sheet
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treated steel
phosphoric acid
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JP2005238535A (en
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奉三 山下
輝雄 堀澤
茂 井上
武士 松田
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JFE Steel Corp
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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • C23C28/3225Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based layer
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer

Description

本発明は、導電性に優れる表面処理鋼板の製造方法に関する。   The present invention relates to a method for producing a surface-treated steel sheet having excellent conductivity.

家電製品用鋼板、建材用鋼板、自動車用鋼板等の用途に使用される亜鉛系めっき鋼板に対して、耐食性を向上させる目的で、その表面にクロメート処理を施すことが幅広く行われている。前記用途のうち、電気・電子機器などの用途に使用される亜鉛系めっき鋼板に対しては、加工した部品を抵抗溶接により接合したり、アースを取るといったことから、優れた導電性が要求される。   For the purpose of improving the corrosion resistance of zinc-based plated steel sheets used in applications such as steel sheets for home appliances, steel sheets for building materials, and steel sheets for automobiles, the chromate treatment is widely performed on the surfaces thereof. Among the above-mentioned applications, excellent conductivity is required for galvanized steel sheets used for applications such as electrical and electronic equipment because the processed parts are joined by resistance welding or grounded. The

クロメート処理液は6価クロムが含まれるため、従来から環境対策として、クロメート処理時の完全クローズドシステムによる排水処理の採用や、水洗工程を必要としない塗布型クロメート処理技術の開発が行われている。また、クロメート皮膜が微量に含有する6価クロムについても、クロム溶出を防止した有機複合被覆鋼板の開発、塗布型クロメート皮膜の難溶化の検討などが行われてきた。   Since the chromate treatment solution contains hexavalent chromium, the use of wastewater treatment with a completely closed system during chromate treatment and the development of coating-type chromate treatment technology that does not require a water-washing process have been conducted as environmental measures. . In addition, regarding hexavalent chromium contained in a minute amount in the chromate film, development of an organic composite coated steel sheet that prevents elution of chromium, and examination of poor coating-type chromate film have been carried out.

一方、環境対策面から、6価クロムを使用しないクロムフリー化成処理皮膜を形成した鋼板(クロムフリー鋼板)の開発が行われ、例えば、以下のような方法が提案されている。
(1)タンニン酸を用いる方法(例えば、特許文献1)
(2)エポキシ樹脂とアミノ樹脂とタンニン酸を混合した熱硬化性塗料を用いる方法(例えば、特許文献2)
(3)水系樹脂と多価フェノールカルボン酸の混合組成物を用いる方法(例えば、特許文献3)
(4)ヒドラジン誘導体水溶液をブリキまたは亜鉛鉄板の表面に塗布する表面処理方法(例えば、特許文献4)
(5)水酸基含有モノマーを共重合成分として含有する有機樹脂とリン酸、金属のリン酸系化合物からなる表面処理用組成物を用いる方法(例えば、特許文献5)
(6)下層に酸化物を含有するリン酸及び/又はリン酸化合物皮膜、その上層に樹脂皮膜からなる有機複合被覆を形成させる方法(例えば、特許文献6、特許文献7)
以下に先行技術文献情報について記載する。
特開昭51−71233号公報 特開昭63−90581号公報 特開平8−325760号公報 特公昭56−10386号公報 特開平9−208859号公報 特開2001−11645号公報 特開2001−11656号公報
On the other hand, from the viewpoint of environmental measures, a steel plate (chromium-free steel plate) formed with a chromium-free chemical conversion coating that does not use hexavalent chromium has been developed. For example, the following methods have been proposed.
(1) Method using tannic acid (for example, Patent Document 1)
(2) A method using a thermosetting paint in which an epoxy resin, an amino resin, and tannic acid are mixed (for example, Patent Document 2)
(3) A method using a mixed composition of an aqueous resin and a polyhydric phenol carboxylic acid (for example, Patent Document 3)
(4) Surface treatment method for applying an aqueous solution of hydrazine derivative to the surface of tinplate or zinc iron plate (for example, Patent Document 4)
(5) A method using a surface treatment composition comprising an organic resin containing a hydroxyl group-containing monomer as a copolymerization component, phosphoric acid, and a metal phosphate compound (for example, Patent Document 5)
(6) A method of forming an organic composite coating comprising a phosphoric acid and / or phosphoric acid compound film containing an oxide in the lower layer and a resin film on the upper layer (for example, Patent Document 6, Patent Document 7)
The prior art document information is described below.
JP-A-51-71233 JP-A 63-90581 JP-A-8-325760 Japanese Patent Publication No. 56-10386 Japanese Patent Laid-Open No. 9-208859 JP 2001-11645 A JP 2001-11656 A

しかし、前記(1)〜(6)には、導電性について全く記述されていない。化成処理皮膜の導電性は、表面に被覆する絶縁性皮膜の膜厚に依存するので、化成処理皮膜の膜厚を薄くすることで、導電性を良好にできる。しかし、化成処理皮膜の膜厚を薄くすると耐食性が低下するため、耐食性を低下させずに優れた導電性を有する表面処理鋼板を得ることは困難であった。   However, the above (1) to (6) do not describe conductivity at all. Since the electrical conductivity of the chemical conversion coating depends on the thickness of the insulating coating coated on the surface, the electrical conductivity can be improved by reducing the thickness of the chemical conversion coating. However, since the corrosion resistance is reduced when the chemical conversion film is thinned, it is difficult to obtain a surface-treated steel sheet having excellent conductivity without reducing the corrosion resistance.

本発明は、上記問題点を解決し、耐食性を低下させずに優れた導電性を得ることができる表面処理鋼板の製造方法を提供することを課題とする。   An object of the present invention is to solve the above problems and to provide a method for producing a surface-treated steel sheet capable of obtaining excellent conductivity without reducing corrosion resistance.

本発明者らは、上記課題を解決するために、調査・検討した結果、導電性はめっき原板の表面テクスチャーの影響を受けることが判明した。そこで、この点についてさらに検討した結果、本発明に至った。   As a result of investigation and examination in order to solve the above problems, the present inventors have found that the conductivity is affected by the surface texture of the original plating plate. As a result of further investigation on this point, the present invention has been achieved.

上記課題を解決する本発明の手段は以下の通りである。   Means of the present invention for solving the above problems are as follows.

第1発明は、亜鉛系めっき鋼板の表面に、有機および/または無機系皮膜を形成させる表面処理鋼板を製造するに際し、めっき原板として、カットオフ値0.8mmでの表面粗さRaが1.8〜3.2μmかつ、カットレベル±0.638μmでの粗さ曲線の平均線方向の長さ25.4mmあたりのピーク数であるPPIが195〜300の範囲内にある放電加工ロールで調質圧延した鋼板を使用することを特徴とする導電性に優れる表面処理鋼板の製造方法である。 In the first invention, when manufacturing a surface-treated steel sheet on which an organic and / or inorganic film is formed on the surface of a zinc-based plated steel sheet , the surface roughness Ra at a cutoff value of 0.8 mm is 1. Refining with EDM rolls with a PPI in the range of 195 to 300, which is the number of peaks per length of 25.4 mm in the average line direction of the roughness curve at 8 to 3.2 μm and cut level ± 0.638 μm It is a manufacturing method of the surface treatment steel plate excellent in electroconductivity characterized by using a rolled steel plate.

発明は、亜鉛系めっき鋼板の表面に、有機および/または無機系皮膜を形成させる表面処理鋼板を製造するに際し、めっき原板として、カットオフ値0.8mmでの表面粗さRaが1.8〜3.2μmかつ、カットレベル±0.638μmでの粗さ曲線の平均線方向の長さ25.4mmあたりのピーク数であるPPIが195〜300の範囲内にある圧延ロールで調質圧延した鋼板を使用することを特徴とする導電性に優れる表面処理鋼板の製造方法である。 In the second invention, when manufacturing a surface-treated steel sheet on which an organic and / or inorganic film is formed on the surface of a zinc-based plated steel sheet , the surface roughness Ra at a cutoff value of 0.8 mm is 1. Temper rolling with a rolling roll having a PPI in the range of 195 to 300, which is the number of peaks per length of 25.4 mm in the average line direction of the roughness curve at a cutting level of ± 0.638 μm at 8 to 3.2 μm It is a manufacturing method of the surface treatment steel plate excellent in electroconductivity characterized by using the made steel plate.

発明は、第1発明または第2発明において、前記有機および/または無機系皮膜は、クロムを含有しない有機および/または無機系皮膜であることを特徴とする導電性に優れる表面処理鋼板の製造方法である。 According to a third invention, in the first or second invention , the organic and / or inorganic coating is an organic and / or inorganic coating that does not contain chromium. It is a manufacturing method.

発明は、第1発明〜第発明において、前記クロムを含有しない有機および/または無機系皮膜は、下層に酸化物を含有するリン酸及び/又はリン酸化合物皮膜、その上層に樹脂皮膜からなる有機複合被覆を形成させた複層皮膜であることを特徴とする導電性に優れる表面処理鋼板の製造方法である。 According to a fourth aspect of the present invention, in the first to third aspects of the invention, the organic and / or inorganic film not containing chromium is a phosphoric acid and / or phosphoric acid compound film containing an oxide in the lower layer, and a resin film in the upper layer It is the manufacturing method of the surface-treated steel plate excellent in electroconductivity characterized by the multilayer film which formed the organic composite coating which consists of.

発明は、第1発明〜第発明において、前記亜鉛系めっき鋼板は、電気亜鉛系めっき鋼板であることを特徴とする導電性に優れる表面処理鋼板の製造方法である。 5th invention is the manufacturing method of the surface treatment steel plate which is excellent in electroconductivity characterized by the said zinc system plating steel plate in 1st invention- 4th invention being an electrogalvanization steel plate.

なお、本明細書で、放電加工ロールとは、放電加工法でダル加工されたロールである。表面粗さRaのカットオフ値は0.8mmである。PPIは、粗さ曲線の平均線方向の長さ25.4mmあたりのピーク数で、カットレベルは±0.638μmである。   In this specification, the electric discharge machining roll is a roll dulled by an electric discharge machining method. The cut-off value of the surface roughness Ra is 0.8 mm. PPI is the number of peaks per length of 25.4 mm in the average line direction of the roughness curve, and the cut level is ± 0.638 μm.

本発明によれば、膜厚を薄くしなくても導電性を向上させることができるので、耐食性を低下させることなく導電性に優れる表面処理鋼板を製造することができる。   According to the present invention, since the conductivity can be improved without reducing the film thickness, it is possible to produce a surface-treated steel sheet having excellent conductivity without reducing the corrosion resistance.

本発明によれば、亜鉛系めっき鋼板の表面にクロムを含有しない有機および/または無機系皮膜を形成させた表面処理鋼板に対しても、耐食性を低下させることなく優れた導電性を発現させることができる。   According to the present invention, excellent conductivity can be exhibited without reducing corrosion resistance even on a surface-treated steel sheet in which an organic and / or inorganic film not containing chromium is formed on the surface of a zinc-based plated steel sheet. Can do.

前記背景技術に記載した先行技術の中で、(6)に記載の下層に酸化物を含有するリン酸及び/又はリン酸化合物皮膜、その上層に樹脂皮膜からなる有機複合被覆を形成させる有機複合被覆鋼板は、従来のクロメート処理鋼板に充分代替出来る特性を有している。そこで、本発明者らは、電気亜鉛めっき鋼板の表面に、前記(6)に記載されている複層皮膜(有機複合皮膜)を形成させた表面処理鋼板について、耐食性を低下させることなく優れた導電性を得る方法につて種々検討した。 Among the prior art described in the background art, an organic composite in which an organic composite coating comprising a phosphoric acid and / or phosphoric acid compound film containing an oxide in the lower layer described in (6) and a resin film is formed on the upper layer. The coated steel sheet has characteristics that can sufficiently replace the conventional chromate-treated steel sheet. Therefore, the present inventors have excellent surface-treated steel sheets in which the multilayer coating (organic composite coating) described in (6) above is formed on the surface of the electrogalvanized steel sheet without reducing the corrosion resistance. various studies to have how to obtain conductivity.

前記電気亜鉛めっき鋼板の表面に前述の複層皮膜(有機複合皮膜)を形成させた表面処理鋼板は、冷間圧延鋼板に、焼鈍、調質圧延を施して製造されためっき原板に、電気亜鉛めっきを施し、しかる後その表面に複層皮膜を形成させて製造する。本発明者らは、前記製造工程において、調質圧延工程で使用した圧延ロールのダル加工法が、ショットブラスト法の場合と試験的に行った放電加工法の場合とで、複層皮膜を形成させた表面処理鋼板の導電性に差があることを知見した。そこで、この点についてさらに検討した結果、以下のことが明らかになった。   The surface-treated steel sheet in which the above-mentioned multilayer coating (organic composite film) is formed on the surface of the electrogalvanized steel sheet is obtained by subjecting a cold-rolled steel sheet to annealing and temper rolling. Plating is performed, and then a multilayer film is formed on the surface. In the manufacturing process, the inventors of the present invention formed a multilayer film when the dull processing method of the rolling roll used in the temper rolling step was a shot blasting method and a test electric discharge processing method. It was found that there was a difference in conductivity between the surface-treated steel sheets. As a result of further examination on this point, the following became clear.

(1)圧延ロールの表面テクスチャーの検討結果から、次のことがわかった。(i)圧延ロールの表面粗さRaが大きいと導電性が向上するが、耐食性は低下する。(ii)同一表面粗さRaでは、PPIが大きくなる程導電性が向上する。(iii)PPIが大きくなっても耐食性は変わらない。
(2)放電加工ロールとショットブラストロールを比べると、同じ表面粗さRaを付与すると放電加工ロールはショットブラストロールに比べて大きなPPI(高PPI)が得られる。このことから、調質圧延工程において、圧延ロールに放電加工ロールを使用することで、表面処理鋼板の耐食性を低下させずに導電性を向上できる。
(1) From the examination result of the surface texture of the rolling roll, the following was found. (I) When the surface roughness Ra of the rolling roll is large, the conductivity is improved, but the corrosion resistance is lowered. (Ii) With the same surface roughness Ra, the conductivity increases as the PPI increases. (Iii) Corrosion resistance does not change even if PPI increases.
(2) Comparing the electric discharge machining roll and the shot blast roll, if the same surface roughness Ra is applied, the electric discharge machining roll can obtain a larger PPI (high PPI) than the shot blast roll. For this reason, in the temper rolling process, by using an electric discharge machining roll as a rolling roll, the conductivity can be improved without reducing the corrosion resistance of the surface-treated steel sheet.

調質圧延工程で、放電加工ロールを用いて圧延することで表面処理鋼板の導電性が向上する理由は明確でないが、以下のように推測される。   The reason why the conductivity of the surface-treated steel sheet is improved by rolling using an electric discharge roll in the temper rolling process is not clear, but is presumed as follows.

調質圧延された鋼板(めっき原板)の表面テクスチャーは圧延ロールの表面テクスチャーと相関があり、皮膜形成後の表面テクスチャーはめっき原板の表面テクスチャーとある程度相関がある。調質圧延工程では、圧延ロールの表面粗さRa、PPIは、圧延された鋼板表面にある一定割合で転写される(一般的に、転写率と称される)。表面粗さRaとPPIでは転写率は異なるが、ショットブラストロールと放電加工ロールでは、転写率に差はない。同じ表面粗さRaの圧延ロールで圧延した場合、高PPIである放電加工ロールで圧延された鋼板はショットブラストロールで圧延された鋼板に比べて高PPIとなる。   The surface texture of the temper-rolled steel sheet (plating original sheet) has a correlation with the surface texture of the rolling roll, and the surface texture after film formation has a certain degree of correlation with the surface texture of the plating original sheet. In the temper rolling process, the surface roughness Ra and PPI of the rolling roll are transferred at a certain ratio on the surface of the rolled steel sheet (generally referred to as a transfer rate). The transfer rate is different between the surface roughness Ra and the PPI, but there is no difference in the transfer rate between the shot blast roll and the electric discharge machining roll. When rolled with a roll having the same surface roughness Ra, a steel sheet rolled with an electric discharge machining roll having a high PPI has a higher PPI than a steel sheet rolled with a shot blast roll.

PPIが異なるめっき原板の表面にめっき、有機および/又は無機皮膜を形成した表面処理鋼板の皮膜断面模式図を図1に示す。図1において、(a)はめっき原板が高PPI、(b)はめっき原板が低PPIの場合である。図1中、1は下地鋼板、2はめっき層、3はめっき層表面に形成された皮膜である。   FIG. 1 shows a schematic cross-sectional view of a surface-treated steel sheet in which a plated, organic and / or inorganic film is formed on the surface of a plating base plate having a different PPI. In FIG. 1, (a) is a case where the plating base plate is a high PPI, and (b) is a case where the plating base plate is a low PPI. In FIG. 1, 1 is a base steel plate, 2 is a plating layer, and 3 is a film formed on the surface of the plating layer.

下地鋼板1表面に凹凸があると、めっき層2表面もほぼそれに近い凹凸が形成され、この凹凸に起因して皮膜3の厚の分布が不均一になる。すなわち、下地鋼板1表面の凸部(粗さ曲線の山頂部分)では相対的に皮膜3の厚さが薄く、下地鋼板1表面の凹部(粗さ曲線に谷部部分)では相対的に皮膜3の厚さが厚くなる。皮膜の導電性は、凸部部分の皮膜の膜厚で決定されると考えられる。   If the surface of the underlying steel plate 1 has irregularities, the surface of the plating layer 2 is also substantially irregular, and the thickness distribution of the coating 3 becomes uneven due to the irregularities. That is, the thickness of the coating 3 is relatively thin at the convex portion (the peak portion of the roughness curve) on the surface of the base steel plate 1, and the coating 3 is relatively small at the concave portion (the valley portion on the roughness curve) of the surface of the base steel plate 1. The thickness of becomes thicker. It is considered that the conductivity of the film is determined by the film thickness of the film at the convex portion.

平均粗さRaが同程度の場合、高PPIのめっき原板の方が、低PPIのめっき原板に比べて、粗さ曲線の平均線方向においてカットレベルを超えるピーク数が多くなることから、(a)のめっき原板が高PPIの表面処理鋼板の凸部部分には、(b)のめっき原板が低PPIの表面処理鋼板の凸部部分に比べて、局部的に膜厚の薄い部分がより多く存在するようになり、その結果、皮膜の導電性が良好になると考えられる。   When the average roughness Ra is approximately the same, the number of peaks exceeding the cut level in the average line direction of the roughness curve is higher in the high PPI plating plate than in the low PPI plating plate. In the convex part of the surface-treated steel sheet with high PPI, the plating base plate of (b) has more locally thin parts than the convex part of the surface-treated steel plate with low plating temperature (b). As a result, it is considered that the conductivity of the film is improved.

一方、前記したように、平均皮膜厚とめっき原板の表面粗さRaが同程度であれば、高PPIのめっき原板を使用した表面処理鋼板の耐食性と低PPIのめっき原板を使用した表面処理鋼板の耐食性は同程度となる。したがって、表面粗さRaは変えないで、高PPIのめっき原板を使用することで、耐食性を低下させることなく、導電性を良好にできる。   On the other hand, as described above, if the average film thickness and the surface roughness Ra of the plating base plate are the same, the corrosion resistance of the surface-treated steel plate using the high PPI plating base plate and the surface-treated steel plate using the low PPI plating base plate Corrosion resistance is about the same. Therefore, the electrical conductivity can be improved without reducing the corrosion resistance by using a high PPI plating original plate without changing the surface roughness Ra.

以下、本発明についてさらに説明する。   The present invention will be further described below.

第1発明では、亜鉛系めっき鋼板の表面に、有機および/または無機系皮膜を形成させる表面処理鋼板を製造するに際し、めっき原板として、放電加工ロールで調質圧延した鋼板を使用する。すなわち、めっき原板として放電加工ロールで調質圧延した鋼板を使用し、この鋼板の表面に亜鉛系めっき、さらに有機及び/又は無機皮膜を形成させた表面処理鋼板は、めっき表面テクスチャーを高PPIにできることから、耐食性を劣化させずに優れた導電性が得られる。   In 1st invention, when manufacturing the surface treatment steel plate which forms an organic and / or inorganic type film on the surface of a zinc system plating steel plate, the steel plate which carried out the temper rolling with the electric discharge machining roll is used as a plating original plate. That is, a surface-treated steel sheet that uses a steel sheet that has been temper-rolled with an electric discharge machining roll as the plating base plate, and has a zinc-based plating and further an organic and / or inorganic coating formed on the surface of the steel sheet has a high plating surface texture. Therefore, excellent conductivity can be obtained without deteriorating the corrosion resistance.

耐食性と導電性の両方を良好にするには、調質圧延工程で使用する圧延ロールは、表面粗さRaが1.8〜3.2μmかつPPIが150〜300の範囲にあることが望ましい。表面粗さRaが1.8μm未満では、導電性が低下し、3.2μm超では、耐食性が低下する。PPIが150未満では、導電性を向上させる作用が不十分になり、300超では、ロールのダル摩耗粉異物がロール表面に付着して、「ダルハゲ」と呼ばれるロール疵が発生しやすくなる。   In order to improve both the corrosion resistance and the conductivity, it is desirable that the rolling roll used in the temper rolling process has a surface roughness Ra of 1.8 to 3.2 μm and a PPI of 150 to 300. When the surface roughness Ra is less than 1.8 μm, the conductivity is lowered, and when it exceeds 3.2 μm, the corrosion resistance is lowered. When the PPI is less than 150, the effect of improving the conductivity is insufficient, and when it exceeds 300, the dull wear powder foreign matter of the roll adheres to the roll surface, and roll wrinkles called “Dalhage” tend to occur.

調質圧延工程で使用する圧延ロールの表面粗さRaおよびPPIが前述の範囲内にあれば、圧延ロールのダル加工法は特に限定されない(第発明)が、現時点の技術では圧延ロールの表面粗さRaおよびPPIを前述の範囲に容易にできる放電加工法が有利である。放電加工法では電流の大きさと電流のオン−オフ時間を適宜条件に制御することで、圧延ロールの表面粗さRaおよびPPIを前述の範囲にできる。 If the surface roughness Ra and PPI of the rolling roll used in the temper rolling step are within the above-mentioned ranges, the dull processing method of the rolling roll is not particularly limited ( second invention), but the present technology has the surface of the rolling roll. An electric discharge machining method that can easily make the roughness Ra and PPI within the aforementioned ranges is advantageous. In the electric discharge machining method, the surface roughness Ra and PPI of the rolling roll can be set to the above-mentioned ranges by controlling the current magnitude and the current on / off time appropriately.

次に、本発明の表面処理鋼板の製造方法について説明する。表面粗さRaとPPIを前述の範囲内に調整した圧延ロールを準備し、この圧延ロールで鋼板を調質圧延し、めっき原板を製造する。次に、めっき工程で、前記で製造しためっき原板に亜鉛系めっきを施して、亜鉛系めっき鋼板を得る。次に、皮膜形成工程で、前記で得た亜鉛系めっき鋼板に、有機及び/または無機系皮膜成分を含む処理液を塗布した後、加熱乾燥して有機及び/または無機系皮膜を形成する。   Next, the manufacturing method of the surface treatment steel plate of this invention is demonstrated. A rolling roll whose surface roughness Ra and PPI are adjusted within the aforementioned ranges is prepared, and the steel sheet is temper-rolled with this rolling roll to produce a plating original sheet. Next, in the plating process, the plating base plate manufactured as described above is subjected to zinc-based plating to obtain a zinc-based plated steel sheet. Next, in the film forming step, a treatment liquid containing an organic and / or inorganic film component is applied to the galvanized steel sheet obtained above, and then dried by heating to form an organic and / or inorganic film.

本発明において、ベースとなる亜鉛系めっき鋼板としては、亜鉛めっき鋼板、Zn−Ni合金めっき鋼板、Zn−Fe合金めっき鋼板、Zn−Cr合金めっき鋼板、Zn−Mn合金めっき鋼板、Zn−Co合金めっき鋼板、Zn−Co−Cr合金めっき鋼板、Zn−Cr−Ni合金めっき鋼板、Zn−Cr−Fe合金めっき鋼板のめっき皮膜中に金属酸化物、ポリマーなどを分散した亜鉛系複合めっき鋼板(例えば、Zn−SiO分散めっき鋼板)などを用いることができる。また、上記のようなめっきのうち、同種又は異種のものを2層以上めっきした複層めっき鋼板を用いることもできる。めっき方法としては、電解法(水溶液中での電解又は非水溶媒中での電解)及び気相法のうち、実施可能ないずれの方法を採用することもできる。 In the present invention, the zinc-based plated steel sheet used as a base is a galvanized steel sheet, a Zn-Ni alloy-plated steel sheet, a Zn-Fe alloy-plated steel sheet, a Zn-Cr alloy-plated steel sheet, a Zn-Mn alloy-plated steel sheet, or a Zn-Co alloy. Galvanized steel sheet, Zn-Co-Cr alloy-plated steel sheet, Zn-Cr-Ni alloy-plated steel sheet, Zn-Cr-Fe alloy-plated steel sheet, zinc-based composite plated steel sheet in which metal oxide, polymer, etc. are dispersed (for example, , it can be used Zn-SiO 2 dispersion plating steel plate) and the like. Moreover, the multilayer plating steel plate which plated two or more layers of the same kind or different kind among the above plating can also be used. As a plating method, any feasible method can be adopted among an electrolytic method (electrolysis in an aqueous solution or electrolysis in a nonaqueous solvent) and a gas phase method.

亜鉛系めっき鋼板表面に形成させる有機および/または無機系皮膜は特に限定されない。前記皮膜は、クロメート処理皮膜であってもよい。   The organic and / or inorganic film formed on the surface of the galvanized steel sheet is not particularly limited. The film may be a chromate-treated film.

また、前記皮膜は、従来技術において導電性が十分に検討されていないクロムを含有しない有機および/または無機系皮膜であってもよい。先行技術の(6)に記載の下層に酸化物を含有するリン酸及び/又はリン酸化合物皮膜、その上層に樹脂皮膜からなる有機複合被覆を形成させた表面処理鋼板は、従来のクロメート処理鋼板に充分代替出来る特性を有している。従って、亜鉛系めっき鋼板表面に形成させる皮膜は、下層に酸化物を含有するリン酸及び/又はリン酸化合物皮膜、その上層に樹脂皮膜からなる有機複合被覆が好適である。   The film may be an organic and / or inorganic film that does not contain chromium, whose conductivity has not been sufficiently studied in the prior art. A surface-treated steel sheet in which an organic composite coating composed of a phosphoric acid and / or phosphoric acid compound film containing an oxide in the lower layer and a resin film is formed on the lower layer as described in (6) of the prior art is a conventional chromate-treated steel sheet It has the characteristics that can be sufficiently substituted. Accordingly, the film formed on the surface of the zinc-based plated steel sheet is preferably an organic composite coating comprising a phosphoric acid and / or phosphoric acid compound film containing an oxide in the lower layer and a resin film on the upper layer.

前記有機複合皮膜は、前記ベースとなる亜鉛系めっき鋼板に、リン酸及び/又はリン酸化合物を含有する処理液を塗布し、しかる後、乾燥加熱して、下層のリン酸含有皮膜を形成し、その上層に有機皮膜を形成する。   The organic composite film is formed by applying a treatment liquid containing phosphoric acid and / or a phosphoric acid compound to the base zinc-based plated steel sheet, and then drying and heating to form a lower phosphoric acid-containing film. An organic film is formed on the upper layer.

下層のリン酸含有皮膜の形成に用いるリン酸及び/又はリン酸化合物を含有する処理液は、(イ)リン酸及び/又はリン酸化合物を含み、または、さらに(ロ)酸化物微粒子と、(ハ)Mg、Ca、Sr、Ba、Mn、Al、Feの各金属イオン、前記金属のうちの少なくとも1種を含む水溶性イオン、前記金属のうちの少なくとも1種を含む化合物の中から選ばれる1種以上と、を含有する処理液である。   The treatment liquid containing phosphoric acid and / or a phosphoric acid compound used for forming the lower layer phosphoric acid-containing film contains (i) phosphoric acid and / or a phosphoric acid compound, or (b) oxide fine particles; (C) Selected from Mg, Ca, Sr, Ba, Mn, Al, Fe metal ions, water-soluble ions containing at least one of the metals, and compounds containing at least one of the metals And a treatment liquid containing at least one kind.

前記成分(イ)であるリン酸及び/又はリン酸化合物はとしては、オルトリン酸、ピロリン酸、トリポリリン酸などのポリリン酸、メタリン酸及びこれらの無機塩(例えば、第一リン酸アルミニウムなど)、亜リン酸、亜リン酸塩、次亜リン酸、次亜リン酸塩などのリン酸含有の化合物が、水溶液中で溶解した際に生じるアニオン、あるいは金属カチオンとの錯イオンとして存在している形態、遊離酸として存在している形態など全てを含み、本発明におけるリン酸成分の量は酸性水溶液中で存在するこれら全ての形態の合計をP換算として規定する。 Examples of the phosphoric acid and / or phosphoric acid compound as the component (a) include polyphosphoric acid such as orthophosphoric acid, pyrophosphoric acid, and tripolyphosphoric acid, metaphosphoric acid, and inorganic salts thereof (for example, primary aluminum phosphate), Compounds containing phosphoric acid such as phosphorous acid, phosphite, hypophosphorous acid, hypophosphite, etc. exist as complex ions with anions or metal cations generated when dissolved in aqueous solution The form and the form existing as a free acid are all included, and the amount of the phosphoric acid component in the present invention defines the sum of all these forms present in an acidic aqueous solution as P 2 O 5 equivalent.

処理液中でのリン酸及び/又はリン酸化合物の添加量はP換算で0.001〜6.0モル/L、好ましくは0.02〜1.0モル/L、さらに好ましくは0.1〜0.8モル/Lとする。リン酸及び/又はリン酸化合物の添加量が0.001モル/L未満では添加による効果が十分でなく、耐食性が劣る。一方、添加量が6.0モル/Lを超えると過剰のリン酸イオンが湿潤環境下においてめっき皮膜と反応し、腐食環境によってはめっき素地の腐食を促進し、変色やシミ状錆発生の要因となる。 The amount of phosphoric acid and / or phosphoric acid compound added in the treatment liquid is 0.001 to 6.0 mol / L, preferably 0.02 to 1.0 mol / L, more preferably in terms of P 2 O 5. 0.1 to 0.8 mol / L. If the addition amount of phosphoric acid and / or phosphoric acid compound is less than 0.001 mol / L, the effect of addition is not sufficient, and the corrosion resistance is poor. On the other hand, when the addition amount exceeds 6.0 mol / L, excess phosphate ions react with the plating film in a wet environment, and depending on the corrosive environment, the corrosion of the plating base is promoted, causing discoloration and spot-like rust. It becomes.

また、前記成分(イ)としては、耐食性の優れた複合酸化物を得ることができるため、リン酸アンモニウム塩を使用することも有効である。リン酸アンモニウム塩としては、第一リン酸アンモニウム、第二リン酸アンモニウムなどの1種又は2種以上を用いることが好ましい。   In addition, as the component (a), it is also effective to use an ammonium phosphate salt because a composite oxide having excellent corrosion resistance can be obtained. As an ammonium phosphate salt, it is preferable to use 1 type (s) or 2 or more types, such as primary ammonium phosphate and secondary ammonium phosphate.

前記成分(ロ)である酸化物微粒子としては、酸化ケイ素(SiO微粒子)が最も好ましい。この酸化ケイ素は酸性水溶液中で安定な水分散性のSiO微粒子であればよく、市販のシリカゾルや水分散性のケイ酸オリゴマーなどを用いることができる。但し、ヘキサフルオロケイ酸などのフッ化物は腐食性が強く、人体への影響も大きいため、作業環境への影響などの観点から使用しないことが望ましい。酸化物微粒子としては、上記の酸化ケイ素のほかに、酸化アルミニウム、酸化ジルコニウム、酸化チタン、酸化セリウム、酸化アンチモンなどのコロイド溶液、微粉末などを用いることもできる。 As the oxide fine particles as the component (b), silicon oxide (SiO 2 fine particles) is most preferable. The silicon oxide may be water-dispersible SiO 2 fine particles that are stable in an acidic aqueous solution, and commercially available silica sol, water-dispersible silicic acid oligomer, and the like can be used. However, since fluorides such as hexafluorosilicic acid are highly corrosive and have a great influence on the human body, it is desirable not to use them from the viewpoint of influence on the working environment. As the oxide fine particles, in addition to the above silicon oxide, colloidal solutions such as aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, and antimony oxide, and fine powders can also be used.

処理液中での、酸化物微粒子の添加量(酸化ケイ素の場合はSiO量としての添加量)は0.001〜3.0モル/L、好ましくは0.05〜1.0モル/L、さらに好ましくは0.1〜0.5モル/Lとする。酸化物微粒子の添加量が0.001モル/L未満では添加による効果が十分でなく、耐食性が劣る。一方、添加量が3.0モル/Lを超えると皮膜の耐水性が悪くなり、結果的に耐食性も劣化する。 The addition amount of oxide fine particles (addition amount as SiO 2 amount in the case of silicon oxide) in the treatment liquid is 0.001 to 3.0 mol / L, preferably 0.05 to 1.0 mol / L. More preferably, the content is 0.1 to 0.5 mol / L. When the addition amount of the oxide fine particles is less than 0.001 mol / L, the effect of the addition is not sufficient, and the corrosion resistance is inferior. On the other hand, when the addition amount exceeds 3.0 mol / L, the water resistance of the film is deteriorated, and as a result, the corrosion resistance is also deteriorated.

前記成分(ハ)であるMg、Ca、Sr、Ba、Mn、Al、Feの各金属イオン、前記金属のうちの少なくとも1種を含む水溶性イオン、前記金属のうちの少なくとも1種を含む化合物の中から選ばれる1種以上を処理液中に導入するには、前記金属のリン酸塩、硫酸塩、硝酸塩、塩化物などの1種又は2種以上を処理液中に添加すればよい。   The component (c), Mg, Ca, Sr, Ba, Mn, Al, Fe metal ions, water-soluble ions containing at least one of the metals, compounds containing at least one of the metals In order to introduce one or more selected from the above into the treatment liquid, one or more of the metal phosphates, sulfates, nitrates, chlorides, etc. may be added to the treatment liquid.

処理液中での上記添加成分(ハ)の添加量は、金属量換算の合計で0.001〜3.0モル/L、好ましくは0.01〜0.5モル/Lとする。これらの合計の添加量が0.001モル/L未満では添加による効果が十分に得られず、一方、添加量が3.0モル/Lを超えると、逆にこれらの成分が皮膜のネットワークを阻害するようになり、緻密な皮膜ができにくくなる。また、金属成分が皮膜から溶出しやすくなり、環境によっては外観が変色するなどの欠陥を生じる。   The addition amount of the additive component (c) in the treatment liquid is 0.001 to 3.0 mol / L, preferably 0.01 to 0.5 mol / L in terms of the total metal amount. If the total addition amount is less than 0.001 mol / L, the effect of addition cannot be sufficiently obtained. On the other hand, if the addition amount exceeds 3.0 mol / L, these components conversely cause a film network. It becomes difficult to form a dense film. In addition, the metal component tends to be eluted from the film, and defects such as discoloration of the appearance occur depending on the environment.

また、上記添加成分(ハ)において、Mg、Mnが顕著に耐食性を向上させる。なお、添加成分(ハ)のイオンを金属塩として供給するために、塩素イオン、硝酸イオン、硫酸イオン、酢酸イオン、ホウ酸イオンなどのアニオンが処理液中に添加されてもよい。   In the additive component (c), Mg and Mn remarkably improve the corrosion resistance. In order to supply the ions of the additive component (c) as a metal salt, anions such as chlorine ions, nitrate ions, sulfate ions, acetate ions, borate ions may be added to the treatment liquid.

上記添加成分(ハ)を含む処理液は、酸性水溶液である点が重要である。すなわち、処理液を酸性とすることにより亜鉛などのめっき成分が溶解しやすくなるため、化成処理皮膜とめっき界面に亜鉛などのめっき成分を含むリン酸化合物層が形成され、これにより両者の界面結合が強化される結果、耐食性に優れた皮膜になると推定される。   It is important that the treatment liquid containing the additive component (c) is an acidic aqueous solution. That is, since the plating component such as zinc is easily dissolved by making the treatment solution acidic, a phosphoric acid compound layer containing a plating component such as zinc is formed at the chemical conversion coating and the plating interface. As a result of strengthening, it is presumed that the film has excellent corrosion resistance.

処理液(水溶液)のpHは0.5〜5、好ましくは2〜4とすることが適当である。処理液がpH0.5未満では処理液の反応性が高くなり過ぎるため皮膜に微細な欠陥部が形成され、耐食性が低下する。一方、処理液がpH5を超えると処理液の反応性が低くなり、めっき皮膜と複合酸化物皮膜との界面の結合が不十分となり、この場合も耐食性が低下する。   The pH of the treatment liquid (aqueous solution) is 0.5-5, preferably 2-4. If the treatment liquid is less than pH 0.5, the reactivity of the treatment liquid becomes too high, so fine defects are formed in the film, and the corrosion resistance is lowered. On the other hand, when the treatment liquid exceeds pH 5, the reactivity of the treatment liquid becomes low, and the bonding at the interface between the plating film and the composite oxide film becomes insufficient. In this case, the corrosion resistance is also lowered.

本発明では、ベースとなるめっき鋼板に前記成分(イ)を含有する処理液、または成分(イ)、(ロ)及び(ハ)を含有する処理液を塗布し、しかる後、加熱乾燥して、めっき鋼板表面に第1層皮膜(下層)として、
(a)リン酸及び/又はリン酸化合物、
または、さらに、
(b)酸化物粒子と、
(c)Mg、Ca、Sr、Ba、Mn、Al、Feの中から選ばれる1種又は2種以上の金属(但し、化合物として含まれる場合を含む)と、を含有し、膜厚が0.005〜4μmのリン酸含有皮膜を形成する。
In the present invention, the treatment liquid containing the component (a) or the treatment liquid containing the components (a), (b) and (c) is applied to the base plated steel sheet, and then heated and dried. As a first layer coating (lower layer) on the surface of the plated steel plate,
(A) phosphoric acid and / or a phosphoric acid compound,
Or, in addition,
(B) oxide particles;
(C) one or two or more metals selected from Mg, Ca, Sr, Ba, Mn, Al, and Fe (including cases where they are included as compounds), and the film thickness is 0 A phosphoric acid-containing film of 0.005 to 4 μm is formed.

下層皮膜の膜厚を0.005〜4μmに限定したのは、膜厚が0.005μm未満では耐食性性が低下し、4μmを超えると溶性性などの導電性が低下するためである。膜厚は0.005〜3μmが好ましく、0.01〜2μがさらに好ましい。   The reason why the film thickness of the lower layer film is limited to 0.005 to 4 μm is that when the film thickness is less than 0.005 μm, the corrosion resistance decreases, and when it exceeds 4 μm, the conductivity such as solubility decreases. The film thickness is preferably 0.005 to 3 μm, and more preferably 0.01 to 2 μm.

なお、皮膜中でのリン酸、リン酸化合物の存在形態も特別な限定はなく、また、結晶若しくは非結晶であるか否かも問わない。また、皮膜中でのリン酸、リン酸化合物のイオン性、溶解度についても特別な制約はない。耐食性および溶接性などの観点から上記成分(a)の好ましい付着量はP量換算で0.01〜3000mg/m、より好ましくは0.1〜1000mg/m、さらに好ましくは1〜500mg/mである。 In addition, the presence form of phosphoric acid and phosphoric acid compound in the film is not particularly limited, and it may be crystalline or non-crystalline. There are no particular restrictions on the ionicity and solubility of phosphoric acid and phosphoric acid compounds in the film. Preferred coating weight 0.01~3000mg / m 2 with P 2 O 5 amount conversion from the viewpoint of the above components, such as corrosion resistance and weldability (a), more preferably 0.1 to 1000 mg / m 2, more preferably 1 it is a ~500mg / m 2.

耐食性および溶接性の観点から上記成分(b)の好ましい付着量は0.01〜3000mg/m、より好ましくは0.1〜1000mg/m、さらに好ましくは1〜500mg/mである。 Preferred coating weight of the corrosion resistance and weldability viewpoint from the component (b) 0.01~3000mg / m 2, more preferably 0.1 to 1000 mg / m 2, more preferably from 1-500 mg / m 2.

上記成分(c)である特定の金属成分(Mg、Ca、Sr、Ba、Mn、Al、Fe)が皮膜中で存在する形態は特に限定されず、金属として、あるいは酸化物、水酸化物、水和酸化物、リン酸化合物、配位化合物などのイオン性、溶解度などについても特に限定されない。   The form in which the specific metal component (Mg, Ca, Sr, Ba, Mn, Al, Fe) as the component (c) is present in the film is not particularly limited, and may be a metal or an oxide, hydroxide, There are no particular limitations on the ionicity, solubility, etc. of the hydrated oxide, phosphate compound, coordination compound, and the like.

耐食性および皮膜外観の低下防止の観点から上記成分(c)の好ましい付着量は金属量換算で0.01〜1000mg/m、より好ましくは0.1〜500mg/m、さらに好ましくは1〜100mg/mある。 Preferred adhesion amount of the components from the viewpoint of preventing deterioration in corrosion resistance and film appearance (c) is 0.01 to 1000 / m 2 by metal weight basis, more preferably 0.1 to 500 mg / m 2, more preferably 1 to there is 100mg / m 2.

本発明では、前記下層皮膜の上層に、膜厚が0.1〜5μmの有機皮膜を形成させる。上層の膜厚を0.1〜5μmに限定したのは、0.1μm未満では耐食性が不十分になり、5μmを超えると、導電性、加工性が低下するためである。   In the present invention, an organic film having a film thickness of 0.1 to 5 μm is formed on the upper layer of the lower film. The reason why the thickness of the upper layer is limited to 0.1 to 5 μm is that the corrosion resistance is insufficient when the thickness is less than 0.1 μm, and the conductivity and workability are deteriorated when the thickness exceeds 5 μm.

厚さ0.8mmの冷延鋼板を焼鈍後、ダル加工法、Ra、PPIの異なる圧延ロールを使用して調質圧延を施し、さらに硫酸亜鉛400g/l、硫酸ナトリウム50g/lを含み、pH2の硫酸酸性めっき浴で電気亜鉛めっき(めっき量(片面あたり):20g/m)を施して、亜鉛めっき鋼板を製造した。調質圧延で使用した圧延ロールの粗さ条件を表1に示す。 After annealing a cold-rolled steel sheet having a thickness of 0.8 mm, temper rolling was performed using rolling rolls having different dull processing methods, Ra, and PPI, and further including zinc sulfate 400 g / l, sodium sulfate 50 g / l, pH 2 Was subjected to electrogalvanizing (plating amount (per one side): 20 g / m 2 ) in a sulfuric acid acidic plating bath to produce a galvanized steel sheet. Table 1 shows the roughness conditions of the rolling rolls used in the temper rolling.

Figure 0004349149
Figure 0004349149

次に、上記で得た電気亜鉛めっき鋼板を、アルカリ脱脂処理、水洗乾燥し、次いでロール塗布装置を用いて、P換算で0.32モル/Lの第一リン酸、SiO換算で0.50モル/Lのコロイダルシリカ、及び0.16モル/LのMnを含有する処理液(pH=2.7)を塗布し、しかる後140℃で乾燥して、膜厚0.1μmのシリカ含有リン酸含有皮膜(第1層皮膜)を形成した。Mnは第一リン酸塩で供給した。次に、前記リン酸含有皮膜の上に、エポキシ系樹脂を含有する有機樹脂溶液を塗布し、140℃で焼き付け、膜厚0.6μmの有機樹脂皮膜を形成した。上記で得た有機複合被覆鋼板の導電性を以下のようにして評価した。 Next, the electrogalvanized steel sheet obtained above is subjected to alkaline degreasing treatment, washing with water and drying, and then using a roll coater, 0.32 mol / L of primary phosphoric acid in terms of P 2 O 5, in terms of SiO 2 Then, a treatment solution (pH = 2.7) containing 0.50 mol / L colloidal silica and 0.16 mol / L Mn was applied, and then dried at 140 ° C. to obtain a film thickness of 0.1 μm. A silica-containing phosphoric acid-containing film (first layer film) was formed. Mn was supplied as primary phosphate. Next, an organic resin solution containing an epoxy resin was applied onto the phosphoric acid-containing film and baked at 140 ° C. to form an organic resin film having a thickness of 0.6 μm. The conductivity of the organic composite coated steel sheet obtained above was evaluated as follows.

各サンプルについて、三菱油化製ロレスタAP、ASP端子を用い表面抵抗値を測定して評価した。表面抵抗値は8点測定し、表面抵抗値が最も高い測定値に基き、次のように評価した。
◎:10−4Ω以下
○:10−4Ω超、10Ω未満
×:10Ω以上。
About each sample, the surface resistance value was measured and evaluated using Lolesta AP and ASP terminal made from Mitsubishi Yuka. The surface resistance value was measured at 8 points and evaluated as follows based on the measured value having the highest surface resistance value.
◎: 10 −4 Ω or less ○: More than 10 −4 Ω, less than 10 7 Ω ×: 10 7 Ω or more.

評価結果を表1に併せて記載した。   The evaluation results are also shown in Table 1.

めっき原板として、表面粗さRa及びPPIが本発明範囲内にある放電加工ロールを使用して調質圧延した鋼板を使用した発明例の有機複合被覆鋼板は、導電性が良好である。   The organic composite coated steel sheet of the invention example using a steel sheet tempered and rolled using an electric discharge machining roll having surface roughness Ra and PPI within the scope of the present invention as the plating original sheet has good conductivity.

一方、めっき原板として、表面粗さRa及びPPIが本発明範囲外にあるショットブラストロールを使用して調質圧延した鋼板を使用した比較例の有機複合被覆鋼板は、導電性が劣る。   On the other hand, the organic composite-coated steel sheet of the comparative example using a steel sheet tempered and rolled using a shot blast roll having surface roughness Ra and PPI outside the scope of the present invention as the plating original sheet has poor conductivity.

本発明は、導電特性に優れる表面処理鋼板の製造方法として利用することができる。本発明法で製造された表面処理鋼板は、導電特性が要求される自動車、家電、建材用途、特に、電気・電子機器など、抵抗溶接により接合する必要のある用途や、アースをとる必要のある用途への使用に好適である。   The present invention can be used as a method for producing a surface-treated steel sheet having excellent conductive properties. The surface-treated steel sheet manufactured by the method of the present invention needs to be grounded for applications that require conductive properties, such as automobiles, home appliances, and building materials, in particular, electrical and electronic devices that need to be joined by resistance welding. Suitable for use in applications.

発明で製造される表面処理鋼板は、クロムを使用しない環境適応型表面処理鋼板が求められる用途に使用することができる。第発明で製造される表面処理鋼板は、従来のクロメート処理鋼板に充分代替出来る特性を有しているので、クロメート処理鋼板が使用される用途に対して、クロムを使用しない環境適応型表面処理鋼板として使用することができる。 The surface-treated steel sheet produced by the third invention can be used for applications requiring an environment-adaptive surface-treated steel sheet that does not use chromium. Since the surface-treated steel sheet manufactured in the fourth invention has characteristics that can be sufficiently substituted for the conventional chromate-treated steel sheet, the environment-adaptive surface treatment that does not use chromium for applications in which the chromate-treated steel sheet is used. It can be used as a steel plate.

PPIが異なるめっき原板の表面にめっき、その上に有機および/又は無機皮膜を形成した表面処理鋼板の皮膜断面模式図で、(a)はめっき原板が高PPI、(b)はめっき原板が低PPIの場合を示す。Fig. 2 is a schematic cross-sectional view of a surface-treated steel sheet in which an organic and / or inorganic film is formed on the surface of a plating base plate having a different PPI. (A) is a high PPI and (b) is a low plating base plate. The case of PPI is shown.

符号の説明Explanation of symbols

1 下地鋼板
2 めっき層
3 皮膜(有機及び/又は無機系皮膜)
DESCRIPTION OF SYMBOLS 1 Base steel plate 2 Plating layer 3 Film (organic and / or inorganic film)

Claims (5)

亜鉛系めっき鋼板の表面に、有機および/または無機系皮膜を形成させる表面処理鋼板を製造するに際し、めっき原板として、カットオフ値0.8mmでの表面粗さRaが1.8〜3.2μmかつ、カットレベル±0.638μmでの粗さ曲線の平均線方向の長さ25.4mmあたりのピーク数であるPPIが195〜300の範囲内にある放電加工ロールで調質圧延した鋼板を使用することを特徴とする導電性に優れる表面処理鋼板の製造方法。 When manufacturing a surface-treated steel sheet on which an organic and / or inorganic film is formed on the surface of a zinc-based plated steel sheet , the surface roughness Ra at a cutoff value of 0.8 mm is 1.8 to 3.2 μm as a plating original sheet. In addition, a steel sheet that has been temper- rolled with an electric discharge machining roll having a PPI in the range of 195 to 300, which is the number of peaks per length of 25.4 mm in the average line direction of the roughness curve at a cut level of ± 0.638 μm, is used. A method for producing a surface-treated steel sheet having excellent electrical conductivity. 亜鉛系めっき鋼板の表面に、有機および/または無機系皮膜を形成させる表面処理鋼板を製造するに際し、めっき原板として、カットオフ値0.8mmでの表面粗さRaが1.8〜3.2μmかつ、カットレベル±0.638μmでの粗さ曲線の平均線方向の長さ25.4mmあたりのピーク数であるPPIが195〜300の範囲内にある圧延ロールで調質圧延した鋼板を使用することを特徴とする導電性に優れる表面処理鋼板の製造方法。 When manufacturing a surface-treated steel sheet on which an organic and / or inorganic film is formed on the surface of a zinc-based plated steel sheet , the surface roughness Ra at a cutoff value of 0.8 mm is 1.8 to 3.2 μm as a plating original sheet. In addition , a steel sheet that has been temper- rolled with a rolling roll having a PPI in the range of 195 to 300, which is the number of peaks per length of 25.4 mm in the average line direction of the roughness curve at a cut level of ± 0.638 μm, is used. A method for producing a surface-treated steel sheet having excellent electrical conductivity. 前記有機および/または無機系皮膜は、クロムを含有しない有機および/または無機系皮膜であることを特徴とする請求項1または2記載の導電性に優れる表面処理鋼板の製造方法。 The method for producing a surface-treated steel sheet having excellent conductivity according to claim 1 or 2, wherein the organic and / or inorganic coating is an organic and / or inorganic coating that does not contain chromium. 前記クロムを含有しない有機および/または無機系皮膜は、下層に酸化物を含有するリン酸及び/又はリン酸化合物皮膜、その上層に樹脂皮膜からなる有機複合被覆を形成させた複層皮膜であることを特徴とする請求項1〜のうちのいずれかの項記載の導電性に優れる表面処理鋼板の製造方法。 The organic and / or inorganic film not containing chromium is a multilayer film in which an organic composite coating composed of a phosphoric acid and / or phosphoric acid compound film containing an oxide as a lower layer and a resin film as an upper layer is formed. The method for producing a surface-treated steel sheet having excellent conductivity according to any one of claims 1 to 3 . 前記亜鉛系めっき鋼板は、電気亜鉛系めっき鋼板であることを特徴とする請求項1〜のうちのいずれかの項記載の導電性に優れる表面処理鋼板の製造方法。 The method for producing a surface-treated steel sheet having excellent conductivity according to any one of claims 1 to 4 , wherein the zinc-based plated steel sheet is an electrogalvanized steel sheet.
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