JPH01191772A - Production of plated steel sheet for can having excellent working corrosion resistance - Google Patents
Production of plated steel sheet for can having excellent working corrosion resistanceInfo
- Publication number
- JPH01191772A JPH01191772A JP1354988A JP1354988A JPH01191772A JP H01191772 A JPH01191772 A JP H01191772A JP 1354988 A JP1354988 A JP 1354988A JP 1354988 A JP1354988 A JP 1354988A JP H01191772 A JPH01191772 A JP H01191772A
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- plated
- plating
- amount
- corrosion resistance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 88
- 239000010959 steel Substances 0.000 title claims abstract description 88
- 238000005260 corrosion Methods 0.000 title claims abstract description 33
- 230000007797 corrosion Effects 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 239000011651 chromium Substances 0.000 claims abstract description 101
- 238000007747 plating Methods 0.000 claims abstract description 63
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000009792 diffusion process Methods 0.000 claims abstract description 31
- 230000001590 oxidative effect Effects 0.000 claims abstract description 18
- 229910052742 iron Inorganic materials 0.000 claims abstract description 16
- 229910020900 Sn-Fe Inorganic materials 0.000 claims abstract description 8
- 229910019314 Sn—Fe Inorganic materials 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims description 32
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 238000012545 processing Methods 0.000 claims description 17
- 229910052804 chromium Inorganic materials 0.000 claims description 16
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 abstract description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 abstract 1
- 229910000423 chromium oxide Inorganic materials 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 31
- 238000000034 method Methods 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 15
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 15
- 229910052718 tin Inorganic materials 0.000 description 13
- 238000005096 rolling process Methods 0.000 description 11
- 239000002344 surface layer Substances 0.000 description 11
- 238000010306 acid treatment Methods 0.000 description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000011282 treatment Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 229910052737 gold Inorganic materials 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000010960 cold rolled steel Substances 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- 239000005028 tinplate Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000005097 cold rolling Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical compound O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-UHFFFAOYSA-L 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- 150000004782 1-naphthols Chemical class 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 240000000560 Citrus x paradisi Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 101150018425 Cr1l gene Proteins 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910017091 Fe-Sn Inorganic materials 0.000 description 1
- 229910017142 Fe—Sn Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000010731 rolling oil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005496 tempering Methods 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
Landscapes
- Electroplating Methods And Accessories (AREA)
- Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は絞りしごき缶（Ｄｒａｗｎ ＆ Ｉｒｏｎｅｄ
Ｃａｎ 。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a Drawn & Ironed can.
Can.
ＤＩ缶）、絞り再絞り缶（Ｄｒａｗｎ ＆ Ｒｅｄｒａ
ｗｎ Ｃａｎ 。DI can), re-drawn can (Drawn & Redra)
wn Can.
ＤＲＤ缶入絞り缶および缶蓋など厳しい加工を受ける缶
用素材であるＳｎ系めっき鋼板、Ｃｒ系めっき鋼板の素
地鋼板として適した加工耐食性の優れた製缶用めっき素
地鋼板の製造方法に関する。This invention relates to a method for producing a plated base steel sheet for can making that has excellent process corrosion resistance and is suitable as a base steel plate for Sn-based plated steel sheets and Cr-based plated steel sheets, which are materials for cans that undergo severe processing such as DRD cans and can lids.
Ｓｎめっき鋼板、いわゆるぶりき、および金属Ｃｒとク
ロム水和酸化物の二層構造の皮膜で被覆された鋼板、い
わゆるナイン・フリー・スチール（以下ＴＦＳと略す）
は缶用素材として、広く使用されている。近年、製缶用
材料の分野にはアルミニウムなどの競合材料の進出が著
しく、安価で、かつ加工耐食性の優れた缶用表面処理鋼
板の開発が要望されている。製缶用表面処理鋼板を安価
Ｃ二する一方法として、めっき層を薄く、かつ緻密にす
ることが検討され、例えば薄Ｓｎめっき鋼板が溶接缶の
材料に使用されている。しかしながら、めっき層が薄い
ため、加工部などの耐食性は通常のぶりき、ＴＰ８より
劣り、加工の厳しい用途に使用するには、めっき素地鋼
板自体の耐食性を改良することが必要である。めっき素
地鋼板自体の耐食性を改良しようとする試みとして、製
鋼時にＣｒなどを添加する方法（特開昭６１−６２９３
．特開昭６１−１７７３７８、特開昭６１−２５３３７
７、特開昭６２−３０８９ など）、鋼板表面にＮｉめ
っきを施し、非酸化性雰囲気中で熱処理を行い、鋼板表
面にＮｉ拡散層を形成させる方法（特開昭５７−２００
５９２、特開昭６０−１５５６８５など）、鋼板表面に
Ｓｎめっきあるいは５ｎ−Ｎｉ合金めっきを施し、非酸
化性雰囲気中で熱処理を行い、鋼板表面にＳｎあるいは
ＳｎとＮｉの拡散層を形成させる方法（特開昭６０−５
８９４．特開昭６０−８９５９４ ）などが知られてい
る。Sn-plated steel sheets, so-called tinplate, and steel sheets coated with a two-layer film of metallic Cr and chromium hydrated oxide, so-called nine-free steel (hereinafter abbreviated as TFS).
is widely used as a material for cans. In recent years, competitive materials such as aluminum have made significant advances in the field of can-making materials, and there is a demand for the development of inexpensive, surface-treated steel sheets for cans that have excellent processing corrosion resistance. As a way to reduce the cost of surface-treated steel sheets for can manufacturing, making the plating layer thinner and denser has been studied, and for example, thin Sn-plated steel sheets are being used as materials for welded cans. However, because the plating layer is thin, the corrosion resistance of processed parts is inferior to that of ordinary tin plate, TP8, and in order to use it for applications that require severe processing, it is necessary to improve the corrosion resistance of the plated base steel sheet itself. In an attempt to improve the corrosion resistance of the plated base steel sheet itself, a method of adding Cr etc. during steel manufacturing (Japanese Patent Laid-Open No. 61-6293
．． JP-A-61-177378, JP-A-61-25337
7, Japanese Unexamined Patent Publication No. 62-3089, etc.), a method in which the surface of a steel plate is plated with Ni and heat treated in a non-oxidizing atmosphere to form a Ni diffusion layer on the surface of the steel sheet (Japanese Unexamined Patent Publication No. 57-200).
592, JP-A-60-155685, etc.), a method in which Sn plating or 5n-Ni alloy plating is applied to the surface of a steel sheet, heat treatment is performed in a non-oxidizing atmosphere, and a diffusion layer of Sn or Sn and Ni is formed on the surface of the steel sheet. (Unexamined Japanese Patent Publication No. 60-5
894. Japanese Unexamined Patent Publication No. 60-89594) is known.
確かＣ二、特開昭６２−３０８９などに示される製鋼時
にＣｒを添加する方法は鋼板自体の耐食性を著しく改良
する効果があるが、Ｃｒ添加による鋼板のコストアップ
だけでなく、熱開田延後の脱スケール性、Ｓｎなどのめ
っき性、製缶加工性などに種々の問題を生じ、安価な製
缶用めっき素地鋼板として適した素材といいがたい。ま
た特開昭５７−２００５９２など≦二示されるＮｉめり
きした鋼板を非酸化性雰囲気中で熱処理し、鋼板表面に
Ｎｉ拡散層を形成させる方法は未加工の場合の耐食性は
改良されるが、加工した場合、Ｎｉ拡散層にクラック□
が入る。このＮｉ拡散層は果汁などの飲料中で素地鉄よ
り電位が責であるため、このめっき素地鋼板を飲料缶用
材料に用いた場合、Ｎｉ拡散層のクラックから素地鉄の
腐食が促進され、孔食の危険性がある。したがって、こ
の方法によって得られためっき素地鋼板は製缶用めっき
鋼板の素地として満足できるものでない。さらに特開昭
６０−５８９４、特公昭６０−８９５９４に示されるＳ
ｎあるいはａｎ−Ｎｉ合金めつきした鋼板を非酸化性雰
囲気中で熱処理し、鋼板表面にＳｎあるいはＳｎとＮｉ
の拡散層を形成させる方法で得られためっき素地鋼板も
Ｎｉ拡散層を形成させためっき素地鋼板と同様（二飲料
中で素地鉄のカソードとして働き、これらの拡散層のク
ラックからの素地鉄の腐食が促進されるので、製缶用め
っき素地鋼板として十分なものでない。これらの問題点
を解決し、安価で、特に加工耐食性Ｃ一対して効果があ
り、かつ冷間圧延以降の工程において特別な問題点を生
じないめっき素地鋼板を開発することを目的として、種
々検討を重ねた結果、本発明に至ったものである。It is true that the method of adding Cr during steel manufacturing, as shown in C2 and JP-A-62-3089, has the effect of significantly improving the corrosion resistance of the steel sheet itself, but adding Cr not only increases the cost of the steel sheet, but also increases the This causes various problems in descaling properties, plating properties with Sn, etc., processability in can making, and it is difficult to say that this material is suitable as an inexpensive plated base steel sheet for can making. Furthermore, a method such as JP-A-57-200592 in which a Ni-plated steel plate is heat treated in a non-oxidizing atmosphere to form a Ni diffusion layer on the surface of the steel plate improves the corrosion resistance of the untreated steel plate, but When processed, cracks may occur in the Ni diffusion layer □
enters. This Ni diffusion layer has a higher potential than the base iron in drinks such as fruit juice, so when this plated base steel sheet is used as a material for beverage cans, corrosion of the base iron is accelerated from cracks in the Ni diffusion layer, and holes are formed. There is a food hazard. Therefore, the plated base steel sheet obtained by this method is not satisfactory as a base for plated steel sheets for can manufacturing. Furthermore, the S
A steel plate coated with an n- or an-Ni alloy is heat treated in a non-oxidizing atmosphere to coat the surface of the steel plate with Sn or Sn and Ni.
The plated base steel sheet obtained by the method of forming a diffusion layer is similar to the plated base steel sheet on which a Ni diffusion layer is formed. Because corrosion is accelerated, it is not sufficient as a plated base steel sheet for can manufacturing.We solved these problems, are inexpensive, are particularly effective in terms of processing corrosion resistance, and are particularly suitable for processes after cold rolling. The present invention was developed as a result of various studies aimed at developing a plated base steel sheet that does not cause such problems.
本発明は冷間圧延、電解クリーニング後の鋼板表面にＣ
ｒめっきを施し、さらにＳｎめっきを施した後、鉄の非
酸化性雰囲気中で熱処理を施し、鋼板の表面層にＣｒ
−ａｎ −ｒｅの三元系拡散層を形成させることによっ
て、加工後の耐食性の優れためっき素地鋼板を提供する
ことにある。In the present invention, carbon is added to the surface of the steel plate after cold rolling and electrolytic cleaning.
After R plating and further Sn plating, heat treatment is performed in a non-oxidizing iron atmosphere to add Cr to the surface layer of the steel sheet.
The object of the present invention is to provide a plated base steel sheet having excellent corrosion resistance after working by forming a ternary diffusion layer of -an-re.
以下、本発明の方法について具体的に説明する。The method of the present invention will be specifically explained below.
冷間圧延、電解クリーニング後の鋼板表面に金属Ｃｒ１
ｉ３〜１５０Ｉ！Ｉｇ／ｍ２のＣｒめっきを施し、ツイ
テ、その上層にＳｎ量２０〜５００■／ｍ２のａｎめっ
きを施した後、鉄の非酸化性雰囲気中で熱処理を施し、
鋼板の表面にめつきしたＳｎ量の９５％以上、およびめ
っきしたＣｒ量のＩ ＱＩ／ｍ２ｍ上を含み、かつＣｒ
／Ｓｎ＋Ｃｒの重量比が０．０２〜０．５０であるＣｒ
−ａｎ−Ｆｅ三元系拡散層を形成させるものである。Metal Cr1 on the steel plate surface after cold rolling and electrolytic cleaning
i3~150I! After applying Cr plating of Ig/m2, and applying ann plating on the upper layer of Sn content of 20 to 500 μ/m2, heat treatment is performed in an iron non-oxidizing atmosphere,
Includes 95% or more of the amount of Sn plated on the surface of the steel plate and the amount of Cr plated IQI/m2m, and Cr
Cr whose weight ratio of /Sn+Cr is 0.02 to 0.50
-an-Fe ternary diffusion layer is formed.
次に、本願発明の製缶用めっき素地鋼板の製造方法につ
いて説明する。最初（：、冷間圧延、電解クリーニング
後の鋼板表面Ｃ二Ｃｒめっきを施すが、Ｃｒめっきする
ための浴として適量の助剤を添加したクロム酸浴および
硫酸クロム浴が考えられるが、適量の助剤を添加したク
ロム酸浴が高速安定生産の点から・適している。このク
ロム酸浴には通常Ｃｒめっきに使用されているサージェ
ント浴をはじめＴＦＳの工業的な製造に使用されている
適量の硫酸とフッ素化合物を添加したクロム酸浴あるい
はフッ素化合物のみを添加したクロム酸浴が適している
。クロム酸濃度については特に限定する必要はないが、
金属Ｃｒの析出と同時に析出するクロム水和酸化物が多
いと、次工程のＳｎめっきに支障をきたすので、高濃度
クロム酸浴を用いることが好ましい。クロム酸濃度が１
００９／ｌ！以下の低濃度クロム酸浴を用いた場合、多
量のクロム水和酸化物が金属Ｃｒ上に析出するので、次
工程のＳｎめっき前に、用いたクロム酸浴中に浸漬し、
表面のクロム水和酸化物皮膜を溶解除去することが必要
である。溶解後の残存するクロム水和酸化物の量は理想
的には０であることが好ましいが、実用上クロム量とし
て５■／ｍ２以下であれば、次工程のＳｎめっきに支障
をきたすことはない。めっきされる金＠Ｃｒ量は３〜１
５０Ｉ！Ｉｇ／ｍ２の範囲がこのましいが、より好まし
くは５〜７０■／ｍ２である。金属Ｃｒ量が３ｒｎＱ／
ｍ２以下であると、１ ｍｇ／ｒｎ２以上ノＣｒヲ鋼板
表層に拡散させることは出来ず、本発明の目的とする加
工耐食性の優れためりき素地鋼板は得られない。金ｇｃ
ｒは非常に酸化されやすく、めっきされた金ｒＩＩ４Ｃ
ｒの一部は鉄の非酸化性雰囲気中での熱処理ミニよって
酸化Ｃｒになる。金属Ｃｒはこのように自己酸化して鉄
の酸化を防ぐとともに、鋼板中に含まれるＣの表面濃化
を防止する。また、溶接缶用鋼板のように、鋼板とＳｎ
層の間に態とＣｒを介在させて、大気中の加熱工程で酸
化Ｃｒの形成等によりＦｅ−Ｓｎ合金化をおさえ、溶接
性を改善させる方法があるが、この場合ａｎの均一性は
加熱によって著しく悪くなること、また、Ｓｎ 、！：
Ｆｅの合金化も疎外され、Ｓｎによる耐食性向上効果
は得られない。Next, a method for manufacturing a plated base steel sheet for can manufacturing according to the present invention will be explained. Initially (:, C2 Cr plating is applied to the steel plate surface after cold rolling and electrolytic cleaning. As a bath for Cr plating, a chromic acid bath or a chromium sulfate bath to which an appropriate amount of auxiliary agent is added can be considered. A chromic acid bath with additives added is suitable from the viewpoint of high-speed and stable production.This chromic acid bath includes the Sargent bath normally used for Cr plating and the appropriate amount used for industrial production of TFS. A chromic acid bath containing sulfuric acid and a fluorine compound, or a chromic acid bath containing only a fluorine compound is suitable.The chromic acid concentration does not need to be particularly limited;
If a large amount of chromium hydrated oxide precipitates at the same time as metal Cr, it will interfere with the next step of Sn plating, so it is preferable to use a high concentration chromic acid bath. Chromic acid concentration is 1
009/l! When using the following low concentration chromic acid bath, a large amount of chromium hydrated oxide will precipitate on the metal Cr, so before the next step of Sn plating, immerse it in the chromic acid bath used.
It is necessary to dissolve and remove the chromium hydrated oxide film on the surface. Ideally, the amount of chromium hydrated oxide remaining after dissolution is preferably 0, but in practice, if the amount of chromium is 5 μm/m2 or less, it will not interfere with the next step of Sn plating. do not have. The amount of gold @ Cr plated is 3 to 1
50I! The preferred range is Ig/m2, more preferably 5 to 70 g/m2. The amount of metal Cr is 3rnQ/
If it is less than 1 mg/rn2, Cr of 1 mg/rn2 or more cannot be diffused into the surface layer of the steel sheet, and it is impossible to obtain a plain steel sheet with excellent processing corrosion resistance, which is the object of the present invention. gold gc
r is very easily oxidized, plated gold rII4C
A part of r becomes oxidized Cr by heat treatment of iron in a non-oxidizing atmosphere. Metallic Cr self-oxidizes in this way and prevents iron from being oxidized, as well as preventing surface concentration of C contained in the steel sheet. Also, like steel plates for welded cans, steel plates and Sn
There is a method of interposing chromium and Cr between the layers to suppress Fe-Sn alloying by forming oxidized Cr in the heating process in the atmosphere and improve weldability, but in this case, the uniformity of an is Significantly worsened by Sn,! :
Alloying of Fe is also neglected, and the effect of improving corrosion resistance due to Sn cannot be obtained.
本願発明の目的は、ＣｒとＳｎを鋼板表面に拡散させる
ことが重要な要件であるが、そのために、酸化され易い
Ｃｒを最初にめっきし、後からＳｎめっきすることによ
ってＣｒの酸化をできるだけ押さえることを提案するも
のである。しかし、それでもＣｒ量が１５０■／ｍ２を
越えると酸化Ｃｒも増加し、後で行うＳｎめつき処理等
の前処理では十分に除去できなくなり、均一なａｎめり
き等が得られず、めつきによる耐食性向上効果を半減し
てしまう。さらに、金属Ｃｒ層上（二めっきされたＳｎ
と素地鉄との拡散反応も抑制し、めっき素地鋼板の耐食
性が改良されないので好ましくない。つぎに Ｃｒめっ
き後、施されるＳｎめっきには通常電気めっきぶりきの
製造に使用されている公知のＳｎめりき浴、例えばフェ
ロスタン浴、硫酸浴およびハロゲン浴などが用いられる
。鋼板上にＳｎめっきする場合と同様な条件でＳｎめっ
きを施すことができるが、金＠Ｃｒ上に析出したクロム
水和酸化物皮膜を除去し、かつ均一なａｎめっきを施す
ため（二、Ｓｎイオン濃度を通常のぶりきの製造の場合
に比較し、約１／３以下に稀釈し、Ｓｎのめっき効率を
低下させ、水素発生の多い浴を用いることが望ましい。The purpose of the present invention is to diffuse Cr and Sn onto the surface of the steel sheet. To this end, oxidation of Cr is suppressed as much as possible by first plating Cr, which is easily oxidized, and then plating Sn. This is what I propose. However, if the amount of Cr exceeds 150/m2, oxidized Cr will also increase, and it will not be possible to remove it sufficiently in pre-treatments such as Sn plating, which will be carried out later. This reduces the corrosion resistance improvement effect by half. Furthermore, on the metal Cr layer (double-plated Sn
This is not preferable because it also suppresses the diffusion reaction between the plated base steel and the corrosion resistance of the plated base steel sheet. Next, after Cr plating, Sn plating is performed using a known Sn plating bath that is normally used in the production of electroplated tin, such as a ferrostane bath, a sulfuric acid bath, and a halogen bath. Sn plating can be applied under the same conditions as Sn plating on a steel plate, but in order to remove the chromium hydrated oxide film deposited on gold@Cr and to apply uniform an plating (2. It is desirable to dilute the ion concentration to about 1/3 or less compared to the case of ordinary tinplate manufacturing, reduce the Sn plating efficiency, and use a bath that generates a large amount of hydrogen.
Ｃｒめっき後にめっきされたＳｎは鉄の非酸化性雰囲気
中での熱処理によって、鋼板表層と容易に拡散層を形成
する元素であるが、Ｓｎ量が２０■／ｒｎ２以下では本
発明の目的とする加工耐食性の優れためつき素地鋼板は
得られず、またＳｎめっき量が５００ ｍｇ／ｍ２以上
であると、鋼板表層に形成されるＣｒ −Ｓｎ −Ｆｅ
の三元系拡散層が脆くなり、加工耐食性が改良されない
。したがって、金属Ｃｒ層上にめっきされるＳｎ量は２
０〜５００ｍａ／ｍ２の範囲、より好ましくは５０〜２
００ｍｇ／ｍ２の範囲が本発明において適している。本
発明においては最初にＣｒめっきを施し、ついでＳｎめ
っきを施しているが、これは本発明の加工耐食性の優れ
ためっき素地鋼板を得るための必要条件である。Sn plated after Cr plating is an element that easily forms a diffusion layer with the steel plate surface layer by heat treatment in a non-oxidizing iron atmosphere, but if the Sn amount is less than 20 /rn2, it is an element that is not covered by the object of the present invention. A toughened base steel sheet with excellent processing corrosion resistance cannot be obtained, and if the amount of Sn plating is 500 mg/m2 or more, Cr-Sn-Fe formed on the surface layer of the steel sheet cannot be obtained.
The ternary diffusion layer becomes brittle and the processing corrosion resistance is not improved. Therefore, the amount of Sn plated on the metal Cr layer is 2
Range of 0 to 500 ma/m2, more preferably 50 to 2
A range of 00 mg/m2 is suitable in the present invention. In the present invention, Cr plating is first applied and then Sn plating is applied, which is a necessary condition for obtaining the plated base steel sheet of the present invention with excellent processing corrosion resistance.
すなわち、金属Ｃｒは鋼板表面と直接接触していないと
、熱処理時に鋼板表層中への拡散は非常にむずかしいの
で、Ｃｒめっきを最初に施すのである。That is, unless metal Cr is in direct contact with the surface of the steel sheet, it is very difficult for it to diffuse into the surface layer of the steel sheet during heat treatment, so Cr plating is applied first.
ついでめっきされるＳｎは熱処理時における金ｒｓ４ｃ
ｒの酸化を抑制し、金属Ｃｒの鋼板表層への拡散を助け
る効果をもっている。さらに素地鉄と拡散反応を起こし
、本発明の目的とする加工耐食性の改良に寄与している
。かりに、最初にＳｎめっきを施し、ついでＣｒめりき
を施した後、鉄の非酸化性雰囲気中で熱処理を行っても
、ａｎ−Ｆｅの三元系拡散層は形成されるが、金属Ｃｒ
はほとんど鋼板表層中シニ拡散されないので、加工耐食
性、Ｓｎなどのめっき性に優れためっき素地鋼板は得ら
れない。The Sn that is then plated is gold rs4c during heat treatment.
It has the effect of suppressing the oxidation of r and helping the diffusion of metal Cr into the surface layer of the steel sheet. Furthermore, it causes a diffusion reaction with the base iron, contributing to the improvement of processing corrosion resistance, which is the objective of the present invention. On the other hand, even if heat treatment is performed in a non-oxidizing iron atmosphere after first Sn plating and then Cr plating, a ternary an-Fe diffusion layer is formed, but metal Cr
is hardly diffused into the surface layer of the steel sheet, so it is not possible to obtain a plated base steel sheet with excellent processing corrosion resistance and plating properties for Sn, etc.
本発明の方法で得られるめつき素地鋼板は製缶用のぶり
きなどのめっき素地鋼板であり、優れた加工耐食性のは
かに、製缶性の良い機械的特性も兼ね備えていることが
必須の条件である。したがって、ぶりきおよびＴＦＳな
どの缶用鋼板の素地鋼板と同様な条件で熱処理を施すこ
とによって、鋼板表層にＣｒ −Ｓｎ −Ｆｅの三元系
拡散層を形成させることが本発明の前提である。すなわ
ち、たとえば水素６％、窒素９４％の鉄の非酸化性雰囲
気中で５２０〜７２０℃の温度で、１５〜３００００．
＋秒の熱処理を施すことによって、めっきしたａｎの９
５％以上、めっきしたＣｒの１ｍｇ／ｍ２以上を含み、
カッＣｒ／Ｓｎ＋Ｃｒの重量比が０．０２〜０．５０で
ある（：ｒ −Ｓｎ −ｒｅの三元系拡散層を形成させ
ることが本発明において不可欠である。すでに記した熱
処理条件では、めっきしたＳｎのほとんどは素地鉄と反
応し、５ｎ−Ｆｅの二元系拡散層を形成するが、金属Ｃ
ｒの５０％以上を鋼板中に拡散させることはむずかしく
、めっきした金属Ｃｒの約１５〜４０％が拡散される。The plated base steel sheet obtained by the method of the present invention is a plated base steel plate such as tin plate for can making, and it is essential that it has both excellent processing corrosion resistance and good mechanical properties for can manufacturing. This is the condition. Therefore, the premise of the present invention is to form a ternary diffusion layer of Cr-Sn-Fe on the surface layer of the steel sheet by heat-treating it under the same conditions as the base steel sheet for can steel sheets such as tinplate and TFS. . That is, for example, 15 to 30,000.
By applying heat treatment for + seconds, plated an 9
5% or more, containing 1mg/m2 or more of plated Cr,
The weight ratio of Cr/Sn+Cr is 0.02 to 0.50 (: It is essential in the present invention to form a ternary diffusion layer of r-Sn-re. Under the heat treatment conditions already described, plating Most of the Sn reacts with the base iron to form a binary diffusion layer of 5n-Fe, but the metal C
It is difficult to diffuse more than 50% of r into the steel sheet, and about 15 to 40% of the plated metal Cr is diffused.
したがって、鋼板表層中に拡散させようとするＣｒ量の
少なくとも２．５倍程度の金属Ｃｒを熱処理前にめっき
することが必要である。この熱処理によって形成される
Ｃｒ −Ｓｎ −Ｆｅの三元系拡散層において、Ｃｒ
／Ｓｎ ＋Ｃｒの重量比が０．０２以下であると、鋼板
中に拡散されたＣｒ量がＩ＋！１ｇ／ｍ２以上でも、本
発明の目的とする加工耐食性の優れためっき素地鋼板は
得られない。これは熱処理によって形成されるＣｒ −
ａｎ −Ｆｅの三元系拡散層中のＣｒ１ｌの僅かの増加
によっても、Ｓｎ量の著しい増加となり、この拡散層が
脆くなるためと考えられる。また、 Ｃｒ ／ Ｓｎ
＋Ｃｒの重量比を０．５０以上では、拡散層内のＣｒが
鋼板表面に露出した部分で酸化Ｃｒを形成するが、その
量が増加すること、また、すでに記した熱処理条件下に
おけるめっきした金属Ｃｒの拡散程度から考え、熱処理
前にめっきされる金属Ｃｒ量をＳｎ量に対して増加させ
る必要があり、その結果、金属Ｃｒはより酸化され熱処
理後拡散せずに残存した金属Ｃｒの酸化物が増加するこ
とにより、Ｓｎめっきなどの前処理として施される電解
クリーニングで十分除去されず、Ｓｎなどの均一めっき
性およびａｎなどの析出の電流効率を低下させる危険性
がある。したがって、本発明において、熱処理で形成さ
れるＣｒ −Ｓｎ −Ｆｅの三元系拡散層におけるＣｒ
／ Ｓｎ ＋ Ｃｒの重量比は重要な因子であり、０
．０２〜０．５０ｆ７）範囲が好ましく、０．０５〜０
．２０ （７）範囲がより好ましい。ぶりきなどの素地
銅板の熱処理条件では、本発明で限定した範囲のＳｎめ
っき量であれば、すでに記したようにほとんど素地鉄と
反応し、金属Ｓｎあるいは酸化Ｓｎとして残ることはな
いが、かりに残存すると、Ｓｎめっき、ＴＦＳ処理など
の前工程である調質田延時に支障をきたす恐れがあり、
あえてめっきしたＳｎ量の９５％ｊ２を上が熱処理で形
成されるＣｒ −Ｓｎ −Ｆｅの三元系拡散層に含まれ
るべきであると限定した。一方、本発明において、鋼板
表層中に拡散されるＣｒ量の下限は１ｒｎｇ／ｍ２に限
定したが、この下限は本発明の目的とする加工耐食性の
優れためっき素地鋼板を得るために必要な不可欠の因子
である。鋼板中に拡散されるＣｒ量がＩＩｌＩｇ／ｍ２
以下であると、たとえめっきしたＣｒ量が３ｍｇ／ｍ２
以上でも、得られためっき素地鋼板の加工耐食性は改良
されない。また、本発明の方法で得られためつき素地鋼
板は著しく耐食性が改良されるので、Ｓｎなどのめっき
を施すことなしに、無塗装で、あるいは塗装した後に缶
用材料に使用することも可能である。Therefore, it is necessary to plate metal Cr in an amount of at least 2.5 times the amount of Cr to be diffused into the surface layer of the steel sheet before heat treatment. In the Cr-Sn-Fe ternary diffusion layer formed by this heat treatment, Cr
/Sn + Cr weight ratio of 0.02 or less, the amount of Cr diffused into the steel sheet is I+! Even if it is 1 g/m2 or more, a plated base steel sheet with excellent processing corrosion resistance, which is the object of the present invention, cannot be obtained. This is Cr − formed by heat treatment.
This is thought to be because even a slight increase in Cr1l in the an -Fe ternary diffusion layer results in a significant increase in the amount of Sn, making this diffusion layer brittle. Also, Cr/Sn
When the weight ratio of +Cr is 0.50 or more, Cr in the diffusion layer forms Cr oxide on the exposed portion of the steel sheet surface, but the amount increases, and the plated metal under the heat treatment conditions described above also increases. Considering the degree of diffusion of Cr, it is necessary to increase the amount of metal Cr plated before heat treatment relative to the amount of Sn, and as a result, the metal Cr is more oxidized and the oxide of metal Cr that remains without being diffused after the heat treatment. Due to this increase, it may not be sufficiently removed by electrolytic cleaning performed as a pre-treatment for Sn plating, etc., and there is a risk that the uniform plating of Sn and the like and the current efficiency of precipitation of An and the like will be reduced. Therefore, in the present invention, Cr in the ternary diffusion layer of Cr-Sn-Fe formed by heat treatment
/Sn + Cr weight ratio is an important factor, 0
．． 02~0.50f7) range is preferable, 0.05~0
．． 20 (7) range is more preferable. Under the heat treatment conditions for base copper plates such as tinplate, if the amount of Sn plating is within the range specified in the present invention, as already mentioned, it will almost react with the base iron and will not remain as metal Sn or Sn oxide. If it remains, it may cause problems during tempering and rolling, which is a pre-process such as Sn plating and TFS treatment.
It was intentionally determined that 95% j2 of the plated Sn amount should be included in the ternary diffusion layer of Cr--Sn--Fe formed by heat treatment. On the other hand, in the present invention, the lower limit of the amount of Cr diffused into the surface layer of the steel sheet was limited to 1rng/m2, but this lower limit is indispensable to obtain a plated base steel sheet with excellent processing corrosion resistance, which is the objective of the present invention. This is the factor of The amount of Cr diffused into the steel plate is IIlIg/m2
If it is below, even if the amount of plated Cr is 3mg/m2
Even with the above, the processing corrosion resistance of the plated base steel sheet obtained is not improved. In addition, since the corrosion resistance of the dampened base steel sheet obtained by the method of the present invention is significantly improved, it can be used as a material for cans without being coated or after being coated with Sn or other plating. be.
（実施例）
以下、本発明の実施例を比較例と対比し具体的に説明す
る。(Example) Hereinafter, examples of the present invention will be specifically described in comparison with comparative examples.
実施例１
板厚０．２１ ｍｍの冷延鋼板を４′Ｋ）オルソケイ酸
ソーダ水溶液中で、温度９０℃、電流密度２０Ａ／ｄｍ
２、電解時間５秒の条件で、圧延油の脱脂処理を施し、
水洗後、（イ）に示す条件でＣｒめっきを施し、固液に
５秒浸漬した後水洗した。ついで、（ロ）に示す条件で
Ｓｎめっきを施し、水洗乾燥した。この試料を鉄の非酸
化性雰囲気（水素６％、窒素９４％）中で温度５２０〜
５６０℃で２０秒熱処理を施した。Example 1 A cold-rolled steel plate with a thickness of 0.21 mm was heated at a temperature of 90°C and a current density of 20 A/d in a 4'K) sodium orthosilicate aqueous solution.
2. Degrease the rolling oil under the conditions of electrolysis time of 5 seconds,
After washing with water, Cr plating was applied under the conditions shown in (a), immersed in a solid liquid for 5 seconds, and then washed with water. Then, Sn plating was applied under the conditions shown in (b), followed by washing with water and drying. This sample was heated to 520°C in a non-oxidizing iron atmosphere (6% hydrogen, 94% nitrogen).
Heat treatment was performed at 560°C for 20 seconds.
（イｌ Ｃｒめっき条件
浴組成
ＣｒＯ３１５０ｇｅｔ
ＮａＦ ５ ｇｅｌ：Ｈ２ＳＯ４０
，８ｇｅｔ
浴温度 ５５℃
陰極電流密度 ４０ Ａ／ｄｍ２金属Ｃｒ量
１０ｒ８７ｍ２残存クロム水和酸化物
１ｌ（Ｃｒとして）２■１ｍ２
（口ｌ ａｎめつき条件
浴組成
５ｎＳＯａ ２０ ａｌｌＨ２Ｓ０
２０ ｇ／Ｉ！エトキシ化α−ナフト
ール ５ ９／Ｉ！浴温度 ４５℃
陰極電流密度 ２５ Ａ／ｄｍ２ａｎめっき量
３０ ｍｇ／ｍ２実施例２
実施例１と同様の冷延鋼板を実施例１と同様の前処理を
施した後、実施例１の（イ）および（ロ）に示す条件で
、電解時間をかえてＣｒめっきおよびＳｎめっきを施し
、水洗乾燥した。ついで、実施例１と同じ非酸化性雰囲
気中で、温度６４０〜６８０℃で８時間箱型焼鈍炉を用
いて熱処理を施した。(I) Cr plating conditions Bath composition CrO3150get NaF5 gel:H2SO40
,8get Bath temperature 55℃ Cathode current density 40 A/dm2 Metal Cr amount
10r87m2 Residual chromium hydrated oxide 1l (as Cr) 2■1m2 (mouth l An plating condition Bath composition 5nSOa 20 allH2S0
20 g/I! Ethoxylated α-naphthol 5 9/I! Bath temperature: 45°C Cathode current density: 25 A/dm2an Coating amount: 30 mg/m2 Example 2 A cold-rolled steel sheet similar to that in Example 1 was pretreated in the same manner as in Example 1, and then subjected to (a) of Example 1. Cr plating and Sn plating were applied under the conditions shown in and (b) while changing the electrolysis time, followed by washing with water and drying. Then, heat treatment was performed in the same non-oxidizing atmosphere as in Example 1 at a temperature of 640 to 680° C. for 8 hours using a box-type annealing furnace.
金属Ｃｒ量 １２７１ｒＩＱ／ｍ２残存クロ
ム水和酸化物量（Ｃｒとして）３■／ｍ２
ａｎめっき量 ４１０ ｍｇ／ｍ２比較例１
実施例１と同様の冷延鋼板を実施例１と同様の前処理を
施し、水洗乾燥した。Metallic Cr amount 1271rIQ/m2 Residual chromium hydrated oxide amount (as Cr) 3/m2 An plating amount 410 mg/m2 Comparative Example 1 A cold rolled steel sheet similar to Example 1 was pretreated in the same manner as Example 1. , washed with water and dried.
比較例２
実施例１と同様の冷延鋼板を実施例１と同様の前処理を
施した後、実施例１の（イ）に示す条件で１５ｆＩＩｇ
／ｍ２のＣｒめっきを施した後、水洗乾燥した。ついで
、実施例１と同じ非酸化性雰囲気中で同様に熱処理を施
した。Comparative Example 2 A cold-rolled steel sheet similar to that in Example 1 was subjected to the same pretreatment as in Example 1, and then subjected to 15fIIg under the conditions shown in (a) of Example 1.
After applying Cr plating of /m2, it was washed with water and dried. Then, heat treatment was performed in the same non-oxidizing atmosphere as in Example 1.
比較例３
実施例１と同様の冷延鋼板を実施例１と同様の前処理を
施した後、実施例１の（ロ）に示す条件で１５０ Ｉｌ
）ｇ／ｍ２のＳｎめっきを施し、水洗乾燥した・ついで
、実施例１と同じ非酸化性雰囲気中で同様に熱処理を施
した。Comparative Example 3 A cold-rolled steel sheet similar to that in Example 1 was subjected to the same pretreatment as in Example 1, and then subjected to 150 Il under the conditions shown in (b) of Example 1.
)g/m2 Sn plating was applied, washed with water and dried.Then, heat treatment was performed in the same non-oxidizing atmosphere as in Example 1.
実施例３
実施例１と同様の冷延鋼板を実施例１と同様の前処理を
施した後、実施例１の（イ）および（ロ）に示す条件で
、それぞれ電解時間をかえてＣｒめっきおよびＳｎめっ
きを施、した後、水洗乾燥した。ついで、実施例１と同
じ非酸化性雰囲気中で、温度６２０〜６８０℃で３０秒
熱処理を施し、さらに２％の調質圧延を施した。その後
、（イ）に示す条件でＳｎめっきを施し、さらに加熱溶
融処理を施した後、５０℃の３％重クロム酸ソーダ溶液
で陰極電流密度１５Ａ／ｄｍ２で２秒電解し、水洗乾燥
した。Example 3 A cold-rolled steel sheet similar to that in Example 1 was subjected to the same pretreatment as in Example 1, and then Cr plating was performed under the conditions shown in (a) and (b) of Example 1, respectively, by changing the electrolysis time. After applying Sn plating, it was washed with water and dried. Then, in the same non-oxidizing atmosphere as in Example 1, heat treatment was performed at a temperature of 620 to 680°C for 30 seconds, and further temper rolling was performed by 2%. Thereafter, Sn plating was applied under the conditions shown in (a), and after further heating and melting treatment, electrolysis was performed for 2 seconds with a 3% sodium dichromate solution at 50° C. at a cathode current density of 15 A/dm 2 , followed by washing with water and drying.
Ｃｒ Ｉｔ） ？き量 ５０ ｍｇ／ｍ２残
存クロム水和酸化物量（Ｃｒとして）３■７ｍ２
ａｎめりき量 ２００ ＠／ｍ２（イ）熱処理
、調質圧延後のＳｎめっき条件浴組成
５ｎＳＯ４６０ａｌｌ
フェノールスルホン酸（硫酸として）
１５９／１
エトキシ化α−ナフトール ７９／１浴温度
４５℃
陰極電流密度 ２０ Ａ／ｄｍ２ａｎめっき貴
２．７９／ｍ２
比較例４
比較例１で得られた試料に２％の調質圧延を施した後、
実施例３の（イ）に示す条件でλ７９７ｍ２のＳｎめっ
きを施し、加熱溶融処理後、実施例３に示す条件で重ク
ロム酸処理を施し、水洗乾燥した。CrIt)? Amount 50 mg/m2 Amount of residual chromium hydrated oxide (as Cr) 3■7m2 An plating amount 200 @/m2 (a) Sn plating conditions after heat treatment and temper rolling Bath composition 5nSO460all Phenolsulfonic acid (as sulfuric acid) 159/1 Ethoxylated α-naphthol 79/1 Bath temperature
45°C Cathode current density 20 A/dm2an plating precious metal 2.79/m2 Comparative example 4 After subjecting the sample obtained in comparative example 1 to 2% temper rolling,
Sn plating of λ797m2 was applied under the conditions shown in (a) of Example 3, and after heating and melting treatment, dichromic acid treatment was performed under the conditions shown in Example 3, followed by washing with water and drying.
比較例５
比較例２で得られた試料に比較例４と同様に調質圧延、
ａｎめっき、加熱溶融処理および重クロム酸処理を施し
、水洗乾燥した。Comparative Example 5 The sample obtained in Comparative Example 2 was subjected to temper rolling and
An plating, heat melting treatment and dichromic acid treatment were performed, followed by washing with water and drying.
比較例６
比較例３で得られた試料に比較例４と同様Ｃ′−調質圧
延、Ｓｎめっき、加熱溶融処理および重クロム酸処理を
施し、水洗乾燥した。Comparative Example 6 The sample obtained in Comparative Example 3 was subjected to C'-temper rolling, Sn plating, heat melting treatment, and dichromic acid treatment in the same manner as in Comparative Example 4, followed by washing with water and drying.
実施例４
実施例１で得られた試料に２％の調質圧延を施した後、
（イ）に示す条件で電解クロム酸処理（ＴＦＳ処理）を
施し、水洗乾燥した。Example 4 After subjecting the sample obtained in Example 1 to 2% temper rolling,
Electrolytic chromic acid treatment (TFS treatment) was performed under the conditions shown in (a), followed by washing with water and drying.
（イ）熱処理、調質圧延後の電解クロム酸処理条件（Ｔ
Ｆ８処理条件）
浴組成
Ｃｒ０ａ ８０ ａｌｌ・ＮａＦ
４ ｇａｌｌ：Ｈ２８０ａ
０．５ ｇ／Ｊ浴温度 ４０’Ｃ
陰極電流密度 ４０ Ａ／ｄｍ２金ｒｔｓｃｒ
量 １０３ ＠／ｍ２クロム永和酸化物量（
Ｃｒとして）
１５■１ｍ２
比較例７
比較例１で得られた試料に２％の調質圧延を施し、実施
例４の（イ）に示す条件で電解クロム酸処理を施した後
、水洗乾燥した。(b) Heat treatment, electrolytic chromic acid treatment conditions after temper rolling (T
F8 treatment conditions) Bath composition Cr0a 80 all・NaF
4 gal:H280a
0.5 g/J Bath temperature 40'C Cathode current density 40 A/dm2 Gold rtscr
Amount 103 @/m2 Chromium Eiwa oxide amount (
(as Cr) 15 1 m2 Comparative Example 7 The sample obtained in Comparative Example 1 was subjected to 2% temper rolling, subjected to electrolytic chromic acid treatment under the conditions shown in (a) of Example 4, and then washed with water and dried. .
比較例８
比較例２で得られた試料に２％の調質圧延を施し、実施
例４の（イ）に示す条件で電解クロム酸処理を施した後
、水洗乾燥した。Comparative Example 8 The sample obtained in Comparative Example 2 was subjected to 2% temper rolling, subjected to electrolytic chromic acid treatment under the conditions shown in (a) of Example 4, and then washed with water and dried.
比較例９
比較例３で得られた試料に２％の調質圧延を施し、実施
例４の（イ）に示す条件で電解クロム酸処理を施した後
、水洗乾燥した。Comparative Example 9 The sample obtained in Comparative Example 3 was subjected to 2% temper rolling, subjected to electrolytic chromic acid treatment under the conditions shown in (a) of Example 4, and then washed with water and dried.
以上の方法で得られた鋼板のめっき皮膜組成を螢光Ｘ線
法で測定後、無塗装での耐錆性、耐食性および塗装後の
加工耐食性を次に示す方法で調査した。その結果を一括
して第１表に示す。After measuring the plating film composition of the steel plate obtained by the above method using a fluorescent X-ray method, the rust resistance and corrosion resistance without coating and the processing corrosion resistance after coating were investigated using the following methods. The results are summarized in Table 1.
（１） 熱処理によるＣｒおよびＳｎの鋼板中への拡
散量および率
二層めっきを施し、さらＣ＝鉄の非酸化性雰囲気中で熱
処理した試料の全Ｃｒ＠およびＳｎ量を螢光Ｘ線法で測
定後、室温の１規定ＮａＯＨ水溶液中で電流密度５ Ａ
／ｄｍ２の条件で陰極電解、陽極電解をそれぞれ３０秒
行い、鋼板表層の金ＩｇＣｒ、酸化Ｃｒ。(1) The amount and rate of diffusion of Cr and Sn into the steel sheet by heat treatment. The total amount of Cr and Sn in a sample that was subjected to two-layer plating and further heat treated in a non-oxidizing atmosphere where C=iron was measured using a fluorescent X-ray method. After measurement, the current density was 5 A in a 1N NaOH aqueous solution at room temperature.
Cathodic electrolysis and anodic electrolysis were performed for 30 seconds each under the conditions of /dm2 to remove gold IgCr and Cr oxide on the surface layer of the steel sheet.
金属Ｓｎ、酸化Ｓｎを溶解し、その後、再び螢光Ｘ線法
で残存Ｃｒ量および残存Ｓｎ量を測定した。この残存Ｇ
ｒｉｌｌおよび残存Ｓｎ量が熱処理で形成されたＣｒ
−Ｓｎ−Ｆｅの三元系拡散層中のＣｒ量およびＳｎ量と
した。After dissolving the metal Sn and Sn oxide, the amount of remaining Cr and the amount of remaining Sn were measured again using a fluorescent X-ray method. This residual G
rill and residual Sn amount formed by heat treatment.
-The amount of Cr and the amount of Sn in the ternary diffusion layer of Sn-Fe.
また、この処理前後のＳｎ量よりＳｎの拡散率を求めた
。Further, the diffusion rate of Sn was determined from the amount of Sn before and after this treatment.
（２） 塩水噴霧試験による無塗装での耐錆性ＪＩＳ
Ｚ２３７１ Ｃ従い、塩水噴霧試験機に無塗装の試料
を鉛直線から３０度の角度で立てかけ、３５℃の５％Ｎ
ａＣＪ水溶液を３時間噴霧し、錆の発生程度を１０段階
にわけ評価した。錆の発生なしを１０とし、発錆面積２
５〜５０％を１とした。(2) Rust resistance JIS without painting by salt spray test
According to Z2371C, an unpainted sample was placed in a salt spray tester at an angle of 30 degrees from the vertical line, and exposed to 5% N at 35°C.
The aCJ aqueous solution was sprayed for 3 hours, and the degree of rust generation was evaluated in 10 stages. No rust is defined as 10, rusted area is 2
5 to 50% was defined as 1.
（３） 屋内暴露試験による耐錆性
海岸付近の工場屋内６２４５度の角度で無塗装の試料を
立てかけ、１ケ月放置し、錆の発生程度を１０段階にわ
け評価した。錆の発生なしを１０とし、発錆面積２５〜
５０％を１とした。(3) Rust resistance by indoor exposure test An unpainted sample was propped up at an angle of 6245 degrees inside a factory near the coast, left for one month, and the degree of rust generation was evaluated on a 10-grade scale. No rust is defined as 10, and rust area is 25~
50% was set as 1.
（４）無塗装時の耐食性
２５℃の１００％グレープフルーツ溶液１００−に試験
面ｆｊｆ２０ｃｍ”の試料を１ケ月浸漬し、溶出Ｆｅ量
を原子吸光法で測定し、ｒＩＩＱｌｄｍ２・ｄａｙに換
算した。(4) Corrosion resistance when unpainted A sample with a test surface fjf 20cm'' was immersed in 100% grapefruit solution 100-25°C at 25°C for one month, and the amount of eluted Fe was measured by atomic absorption method and converted to rIIQldm2·day.
（５） 塗装加工後の耐食性
試料表面に６０■／ｍ２（乾燥重りのフェノール・エポ
キシ系塗料を塗布し、２１０℃で１０分キエアーした後
、エリキセン試験機を用い５ｍｍ張出し加工を施し、そ
の後、試験面積２０ｃｍ２の試料を２５℃のｏ、ａ ％
ＣＨａＣＯＯＨ水溶液１００−に２週間浸漬し、溶出
Ｆｅ量を原子吸光法で測定し、■／ｄｍ２・ｄａｙに換
算した。(5) Corrosion resistance after painting A phenol-epoxy paint with a dry weight of 60 μ/m2 (dry weight) was applied to the surface of the sample, and after being heated at 210°C for 10 minutes, a 5 mm overhang was applied using an Erichsen tester. A sample with a test area of 20 cm2 was heated to 25°C o, a%.
The sample was immersed in a CHaCOOH aqueous solution of 100 - for 2 weeks, and the amount of eluted Fe was measured by atomic absorption spectrometry and converted into ■/dm2·day.
本発明の方法で得られためっき素地鋼板は塗装後の加工
耐食性に優れ、かっａｎなどのめっき性にも優れている
ため、製缶用めっき素地鋼板として用いられるだけでな
く、そのまま缶用鋼板とじても用いることができ、産業
上きわめて有用なものである。The plated base steel sheet obtained by the method of the present invention has excellent processing corrosion resistance after painting and is also excellent in plating properties such as annealing, so it can be used not only as a plated base steel sheet for can manufacturing, but also as a steel sheet for cans as it is. It can be used even if it is closed, making it extremely useful industrially.
Claims (1)
＾２、クロム水和酸化物量がＣｒ量として５ｍｇ／ｍ＾
２以下であるＣｒめっきを施し、その上層にＳｎ量が２
０〜５００ｍｇ／ｍ＾２のＳｎめっきを施し、引き続き
鉄の非酸化性雰囲気中で熱処理を施し、形成されるＣｒ
−Ｓｎ−Ｆｅの三元系拡散層がめっきしたＳｎ量の９５
％以上、およびめっきした金属Ｃｒ量の１ｍｇ／ｍ＾２
以上を含み、かつ、Ｃｒ／Ｓｎ＋Ｃｒの重量比が０．０
２〜０．５０であることを特徴とする加工耐食性の優れ
た製缶用めっき素地鋼板の製造方法。The amount of metal Cr is 3 to 150 mg/m per side on the steel plate surface.
^2, the amount of chromium hydrated oxide is 5 mg/m^ as the amount of Cr
Cr plating with a Sn content of 2 or less is applied, and the upper layer has a Sn content of 2
0 to 500 mg/m^2 Sn plating is applied, followed by heat treatment in an iron non-oxidizing atmosphere, and the Cr formed
-The amount of Sn plated by the Sn-Fe ternary diffusion layer is 95
% or more, and the amount of plated metal Cr is 1mg/m^2
Contains the above, and the weight ratio of Cr/Sn+Cr is 0.0
2 to 0.50. A method for producing a plated base steel sheet for can making having excellent processing corrosion resistance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1354988A JPH01191772A (en) | 1988-01-26 | 1988-01-26 | Production of plated steel sheet for can having excellent working corrosion resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1354988A JPH01191772A (en) | 1988-01-26 | 1988-01-26 | Production of plated steel sheet for can having excellent working corrosion resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01191772A true JPH01191772A (en) | 1989-08-01 |
| JPH0510421B2 JPH0510421B2 (en) | 1993-02-09 |
Family
ID=11836242
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1354988A Granted JPH01191772A (en) | 1988-01-26 | 1988-01-26 | Production of plated steel sheet for can having excellent working corrosion resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01191772A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60190597A (en) * | 1984-03-09 | 1985-09-28 | Toyo Kohan Co Ltd | Surface treated steel sheet for welded can and its production |
| JPS61130500A (en) * | 1984-11-29 | 1986-06-18 | Kawasaki Steel Corp | Production of sn/cr two-layered plated steel plate |
| JPS63499A (en) * | 1986-06-20 | 1988-01-05 | Nippon Steel Corp | Surface treated steel sheet for vessel |
-
1988
- 1988-01-26 JP JP1354988A patent/JPH01191772A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60190597A (en) * | 1984-03-09 | 1985-09-28 | Toyo Kohan Co Ltd | Surface treated steel sheet for welded can and its production |
| JPS61130500A (en) * | 1984-11-29 | 1986-06-18 | Kawasaki Steel Corp | Production of sn/cr two-layered plated steel plate |
| JPS63499A (en) * | 1986-06-20 | 1988-01-05 | Nippon Steel Corp | Surface treated steel sheet for vessel |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0510421B2 (en) | 1993-02-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2143822B1 (en) | Plated steel sheet for cans and process for producing the same | |
| CA1102272A (en) | Heating thin tin-plated steel sheet to form alloy and electrolytically treating with chromate | |
| KR102150736B1 (en) | Coated substrate for packaging applications and a method for producing said coated substrate | |
| TWI477662B (en) | Method for production of tin plated steel sheet, tin plated steel sheet and chemical conversion treatment liquid | |
| JPH0328359A (en) | Production of hot-dip aluminized chromium-containing steel sheet | |
| JPH0649925B2 (en) | Method for producing plated base steel sheet with excellent corrosion resistance for can manufacturing | |
| JPS6136595B2 (en) | ||
| JPH01191772A (en) | Production of plated steel sheet for can having excellent working corrosion resistance | |
| JP2577246B2 (en) | Manufacturing method of surface-treated steel sheet for coating base with excellent processing corrosion resistance | |
| JP3261069B2 (en) | Surface-treated steel sheet, polyester resin-coated steel sheet having excellent content resistance, and method for producing the same | |
| JPH0826477B2 (en) | Manufacturing method of Sn-based multi-layered steel sheet with excellent paint adhesion | |
| JPS61124580A (en) | Production of solar heat absorption plate | |
| JPH03134147A (en) | Production of alloying hot dip galvanized steel sheet | |
| JPS6240396A (en) | Surface treated steel sheet for can having superior weldability and corrosion resistance | |
| JPS6366399B2 (en) | ||
| JPH0660387B2 (en) | Manufacturing method of surface-treated steel sheet for can manufacturing with excellent processing corrosion resistance | |
| JPS5938315B2 (en) | Manufacturing method of ultra-thin iron-tin alloy coated steel sheet | |
| JP3434927B2 (en) | Manufacturing method of steel plate for welding can with excellent paint appearance | |
| JP2000080499A (en) | Chemical treating method for nickel plated steel sheet | |
| JP3745457B2 (en) | Manufacturing method of steel sheet for welding can excellent in weldability, corrosion resistance, appearance and adhesion | |
| JPS6310238B2 (en) | ||
| JPS5989784A (en) | Manufacture of steel sheet for welded can with superior corrosion resistance after coating | |
| JPH0390593A (en) | Production of no-reflow tinplate excellent in rust resistance | |
| JPS62284086A (en) | Production of sn multilayer-coated steel sheet having excellent corrosion resistance, weldability, and coating performance | |
| JPH0971876A (en) | Steel sheet for welded can excellent in weldability, corrosion resistance, appearance and adhesion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |