WO2013051268A1 - Procédé de production d'une tôle d'acier électrozinguée - Google Patents

Procédé de production d'une tôle d'acier électrozinguée Download PDF

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Publication number
WO2013051268A1
WO2013051268A1 PCT/JP2012/006372 JP2012006372W WO2013051268A1 WO 2013051268 A1 WO2013051268 A1 WO 2013051268A1 JP 2012006372 W JP2012006372 W JP 2012006372W WO 2013051268 A1 WO2013051268 A1 WO 2013051268A1
Authority
WO
WIPO (PCT)
Prior art keywords
zinc
steel sheet
electrogalvanizing
treatment
total
Prior art date
Application number
PCT/JP2012/006372
Other languages
English (en)
Japanese (ja)
Inventor
妹川　透
土本　和明
松崎　晃
Original Assignee
Ｊｆｅスチール株式会社
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Ｊｆｅスチール株式会社 filed Critical Ｊｆｅスチール株式会社
Priority to CN201280048572.6A priority Critical patent/CN103842558B/zh
Priority to KR1020167025454A priority patent/KR20160113312A/ko
Priority to KR1020147010648A priority patent/KR20140064995A/ko
Publication of WO2013051268A1 publication Critical patent/WO2013051268A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/22—Electroplating: Baths therefor from solutions of zinc
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel

Definitions

  • the present invention relates to a method for producing a high whiteness electrogalvanized steel sheet.
  • Electro-galvanized steel sheets are used in a wide range of applications such as home appliances, automobiles, and building materials.
  • the demand for various types of chemically treated electrogalvanized steel sheets used for home appliances that are used without coating is increasing, which is an important application field.
  • it since it is used without coating, it is required to have an excellent surface appearance.
  • As a condition of excellent surface appearance in addition to no surface defects such as unevenness, whiteness is high.
  • the external appearance after various chemical conversion treatments is greatly influenced by the external appearance of the galvanization before chemical conversion treatment, it is calculated
  • Patent Document 1 is cited as a technique for improving whiteness by optimizing electrogalvanizing conditions.
  • Patent Document 1 discloses a method for producing a galvanized steel sheet in which an organic compound having a 2-benzothiazolylthio group is added to a plating bath, and the steel sheet is subjected to cathodic electrolytic treatment.
  • Patent Document 1 the current efficiency slightly decreases by adding an organic compound having a 2-benzothiazolylthio group to the electroplating bath. Therefore, the amount of electricity for obtaining a predetermined plating amount increases, the power cost increases, and as a result, the manufacturing cost of the electrogalvanized steel sheet increases.
  • an object of the present invention is to provide a method for producing an electrogalvanized steel sheet that suppresses a decrease in current efficiency and has high whiteness.
  • the inventors of the present invention have made extensive studies to obtain a galvanized steel sheet having high whiteness.
  • the steel sheet is subjected to cathode electrolytic treatment in an electrogalvanizing bath containing a total of 0.01 to 3 mass ppm of one or more organic compounds having a 2-benzothiazolylthio group without deteriorating the corrosion resistance.
  • the inventors found that an electrogalvanized steel sheet having high whiteness can be obtained without causing glossing, and filed an application as Patent Document 1.
  • Patent Document 1 As described above, the current efficiency decreases, and as a result, the manufacturing cost of the electrogalvanized steel sheet increases.
  • the amount of plating adhesion in the electrogalvanizing treatment of a) above is 90% of the total plating layer, and the amount of plating adhesion in the electrogalvanizing treatment of b) is 10% of the entire plating layer. It was investigated whether the production of electrogalvanized steel sheet is most effective in terms of suppressing the decrease in current efficiency and having high whiteness.
  • Electroplating conditions Relative flow velocity 1.5m / s, current density: 100A / dm 2
  • Electro-galvanizing treatment conditions of a) above Plating bath Acidic bath of sulfuric acid (pH 2.0, temperature 50 ° C) with 1.5 mol / l of Zn 2+ ions that does not contain organic compounds with 2-benzothiazolylthio group
  • Electro-galvanizing treatment conditions in (a) above: Plating bath: Zn 2+ ion 1.5 mol / l sulfuric acid acid bath (pH 2.0, temperature 50 ° C) containing 0.5 mass ppm of sodium salt of 2-mercaptobenzothiazole The experimental results obtained above are shown in Table 1.
  • the present invention has been made based on the above findings, and the gist thereof is as follows.
  • One or more organic compounds with 2-benzothiazolylthio group are subjected to electrogalvanizing treatment in an electrogalvanizing bath with a total of less than 0.01 mass ppm, and then 2-benzothiazolylthio Electrogalvanizing is performed in an electrogalvanizing bath containing a total of 0.01 to 3 mass ppm of one or more organic compounds having a group, so that the amount deposited is 1 to 50% of the total plating layer.
  • a method for producing an electrogalvanized steel sheet [2] The method for producing an electrogalvanized steel sheet according to [1], wherein the organic compound having a 2-benzothiazolylthio group is 2-mercaptobenzothiazole or a salt of 2-mercaptobenzothiazole.
  • the present invention by appropriately controlling the concentration of an organic compound having a 2-benzothiazolylthio group, it is possible to produce an electrogalvanized steel sheet having high whiteness without greatly reducing current efficiency. . And as a result, the chemical conversion treatment electrogalvanized steel plate excellent in the surface external appearance will be obtained.
  • the electrogalvanized steel sheet that is the subject of the present invention is a steel sheet obtained by electrogalvanizing using an acidic bath. From the balance of performance (corrosion resistance, workability, whiteness, etc.) and operation, the preferable range of the zinc content in the plating film is 98 mass% or more.
  • the electrogalvanizing treatment in the electrogalvanizing treatment, is performed in an electrogalvanizing bath in which one or more organic compounds having a 2-benzothiazolylthio group are less than 0.01 mass% ppm.
  • the amount of adhesion in an electrogalvanizing bath containing one or more organic compounds with 2-benzothiazolylthio group in a total of 0.01 to 3 mass ppm is 1 to 50% of the total plating layer.
  • Electrogalvanization treatment is performed so as to be. That is, the electrogalvanizing process is performed in two steps.
  • one or more organic compounds having a 2-benzothiazolylthio group are electrogalvanized by electrolytic treatment using a steel plate as a cathode in an electrogalvanizing bath with a total of less than 0.01 mass ppm. Processing is performed (hereinafter abbreviated as the first step).
  • the coating amount is 1 to 50% of the total plating layer in an electrogalvanizing bath containing one or more organic compounds having 2-benzothiazolylthio group in a total of 0.01 to 3 mass ppm.
  • electrogalvanizing treatment is performed by electrolytic treatment using the steel plate as a cathode (hereinafter abbreviated as the second step).
  • the total amount of one or more organic compounds having a 2-benzothiazolylthio group shown below in the plating bath is less than 0.01 mass ppm.
  • the current efficiency is lowered.
  • the zinc adhesion amount in the first step exceeds 50% with respect to the entire plating layer, the ratio of the zinc adhesion amount in the second step with low current efficiency will not be too high, leading to a decrease in current efficiency. Absent.
  • the zinc adhesion amount in the first step is less than 99% with respect to the entire plating layer, the ratio of the zinc adhesion amount in the second step is not too low, and sufficient whiteness can be obtained. Therefore, in the first step, it is preferable to perform the electrogalvanizing treatment so that the zinc adhesion amount is more than 50% and less than 99% of the entire plating layer.
  • the plating bath contains a total of 0.01 to 3 mass ppm of one or more organic compounds having the 2-benzothiazolylthio group shown above.
  • the organic compound having a 2-benzothiazolylthio group is less than 0.01 mass ppm or exceeds 3 mass ppm, sufficient whiteness cannot be obtained.
  • the zinc adhesion amount in the second step is less than 1% with respect to the entire plating layer, sufficient whiteness cannot be obtained.
  • the electrogalvanizing treatment is performed so that the zinc adhesion amount is 1 to 50% of the entire plating layer.
  • the organic compound having a 2-benzothiazolylthio group it is preferable to use the following 2-mercaptobenzothiazole or a salt of 2-mercaptobenzothiazole.
  • the whiteness can be increased more effectively.
  • the salt of 2-mercaptobenzothiazole include Na salt, K salt, Zn salt and Cu salt.
  • the electrogalvanizing treatment is not particularly limited except that the organic compound is contained in the concentration range in the electroplating bath and the above-described two-stage treatment is performed.
  • a sulfuric acid acidic bath, a hydrochloric acid acidic bath, or a mixture of both can be applied as the electroplating bath.
  • the zinc content in the electrogalvanizing bath is preferably 1.0 mol / L or more as ZnSO 4 . If it is 1.0 mol / L or more, sufficiently high whiteness can be obtained.
  • the electroplating bath may contain additives or impurities as conductivity aids such as sodium sulfate and potassium sulfate, metal ions such as Fe, Ni, Pb, Sn, and Co. .
  • the electroplating bath conditions are not particularly limited.
  • the bath temperature may be 30 to 70 ° C.
  • the pH may be 0.5 to 4.5
  • the relative flow rate may be 0 to 4.0 m / sec.
  • the electrolytic current density is not particularly limited, but may be, for example, 10 to 150 A / dm 2 .
  • the amount of electrogalvanized adhesion is not particularly limited, but is usually about 5 to 40 g / m 2 per side in total for the first step and the second step.
  • degreasing treatment and water washing for cleaning the steel plate surface, and further pickling for activating the steel plate surface are preferred.
  • Treatment and water washing are performed, and following these pretreatments, an electrogalvanizing treatment is performed.
  • the degreasing treatment and the water washing method are not particularly limited. Conventional methods can be used.
  • various acids such as sulfuric acid, hydrochloric acid, nitric acid, and mixtures thereof can be used. Of these, sulfuric acid, hydrochloric acid, or a mixture thereof is desirable.
  • the concentration of the acid is not particularly specified, but it is preferably about 1 to 20 mass% in consideration of the ability to remove the oxide film and the prevention of rough skin by peracid washing.
  • the pickling treatment liquid may contain an antifoaming agent, a pickling accelerator, a pickling inhibitor, and the like.
  • chromate treatment or chromate-free treatment is performed for the purpose of further improving various performances such as corrosion resistance, scratch resistance, and workability. Furthermore, a resin coating process etc. can also be implemented on it.
  • the type of the chemical conversion coating is not particularly limited, and a known method can be used.
  • the effect of this invention is acquired also about the steel plate which performed these processes.
  • the appearance of the chemical conversion treated steel sheet subjected to these treatments greatly depends on the appearance after electrogalvanizing (before chemical conversion treatment) when used without coating. Therefore, when using the steel plate after such a chemical conversion treatment without coating, it has high whiteness by using the electrogalvanized steel plate produced by the method of the present invention.
  • the electrogalvanized steel sheet of the present invention can form a chemical conversion film, and further, a single layer or a multilayer film containing an organic resin, depending on the application.
  • the coating film include a polyester resin coating film, an epoxy resin coating film, an acrylic resin coating film, a urethane resin coating film, and a fluorine resin coating film.
  • an epoxy-modified polyester resin coating film in which a part of the resin is modified with another resin can be applied.
  • curing agent, a hardening catalyst, a pigment, other additives, etc. can be added to the said resin as needed.
  • the coating method for forming the coating film is not particularly defined, examples of the coating method include roll coater coating, curtain flow coating, and spray coating. After coating a paint containing an organic resin, the coating film can be formed by heating and drying by means of hot air drying, infrared heating, induction heating or the like.
  • the manufacturing method of the said surface treatment steel plate is an example, and is not limited to this.
  • a cold rolled steel sheet with a thickness of 0.7 mm manufactured by a conventional method is degreased with alkali, washed with water, then pickled, washed with water, and then in the following conditions and in Tables 2 and 3 Electrogalvanization was performed using the steel sheet as the cathode at the types and concentrations of the organic compounds shown. In addition, about some things, the metal-plating process was implemented without adding an organic compound in an electroplating bath.
  • the amount of zinc plating deposited on one side was determined by dissolving zinc plating with dilute hydrochloric acid, measuring the zinc concentration in the solution with an ICP (Inductively Coupled Plasma) mass spectrometer, and converting it to the amount deposited.
  • Electrolytic conditions Organic substance content, current density: plating bath shown in Table 2: Acidic acid bath containing Zn 2+ ions 1.5 mol / l Bath temperature: 50 ° C pH: 2.0 Relative flow velocity: 1.5m / s
  • the electrogalvanized steel sheet of the present invention has an excellent surface appearance and can be used without any problem without being painted. Therefore, it can be used in a wide range of applications such as home appliances, automobiles, and building materials.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Abstract

La présente invention se rapporte à un procédé de production d'une tôle d'acier électrozinguée qui présente un degré élevé de blancheur et qui limite les diminutions de l'efficacité du courant électrique. Un procédé d'électrozinguage est effectué dans un bain d'électrozinguage qui contient une quantité totale d'un ou plusieurs composés organiques comprenant un groupe de 2-(benzothiazolyl)thio inférieure à 0,01 ppm en masse. Ensuite, un procédé d'électrozinguage est effectué dans un bain d'électrozinguage qui contient une quantité totale d'un ou plusieurs composés organiques comprenant un groupe de 2-(benzothiazolyl)thio de 0,01 à 3 ppm en masse de telle sorte que la quantité de zinc déposée constitue 1 à 50 % de toute la couche de placage.
PCT/JP2012/006372 2011-10-04 2012-10-04 Procédé de production d'une tôle d'acier électrozinguée WO2013051268A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201280048572.6A CN103842558B (zh) 2011-10-04 2012-10-04 电镀锌钢板的制造方法
KR1020167025454A KR20160113312A (ko) 2011-10-04 2012-10-04 전기 아연 도금 강판의 제조 방법
KR1020147010648A KR20140064995A (ko) 2011-10-04 2012-10-04 전기 아연 도금 강판의 제조 방법

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011219719A JP2013079422A (ja) 2011-10-04 2011-10-04 電気亜鉛めっき鋼板の製造方法
JP2011-219719 2011-10-04

Publications (1)

Publication Number Publication Date
WO2013051268A1 true WO2013051268A1 (fr) 2013-04-11

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Application Number Title Priority Date Filing Date
PCT/JP2012/006372 WO2013051268A1 (fr) 2011-10-04 2012-10-04 Procédé de production d'une tôle d'acier électrozinguée

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JP (1) JP2013079422A (fr)
KR (2) KR20160113312A (fr)
CN (1) CN103842558B (fr)
TW (1) TWI461575B (fr)
WO (1) WO2013051268A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016094640A (ja) * 2014-11-13 2016-05-26 Ｊｆｅスチール株式会社 電気亜鉛めっき鋼板の製造方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102403649B1 (ko) 2019-12-20 2022-05-30 주식회사 포스코 백색도가 우수한 전기아연도금강판 및 그 제조방법

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05222572A (ja) * 1992-02-13 1993-08-31 Nkk Corp ２つのめっき層を有する、耐黒変性に優れた電気亜鉛めっき鋼板
JPH07278881A (ja) * 1994-04-15 1995-10-24 Nippon Steel Corp 表面外観に優れた電気亜鉛めっき鋼板の製造方法
JP2007297646A (ja) * 2006-03-22 2007-11-15 Jfe Steel Kk 電気亜鉛めっき鋼板の製造方法
JP2012193419A (ja) * 2011-03-17 2012-10-11 Jfe Steel Corp 化成処理鋼板の製造方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3233784B2 (ja) * 1994-08-01 2001-11-26 日本鋼管株式会社 優れた外観を有する電気亜鉛めっき鋼板

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05222572A (ja) * 1992-02-13 1993-08-31 Nkk Corp ２つのめっき層を有する、耐黒変性に優れた電気亜鉛めっき鋼板
JPH07278881A (ja) * 1994-04-15 1995-10-24 Nippon Steel Corp 表面外観に優れた電気亜鉛めっき鋼板の製造方法
JP2007297646A (ja) * 2006-03-22 2007-11-15 Jfe Steel Kk 電気亜鉛めっき鋼板の製造方法
JP2012193419A (ja) * 2011-03-17 2012-10-11 Jfe Steel Corp 化成処理鋼板の製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016094640A (ja) * 2014-11-13 2016-05-26 Ｊｆｅスチール株式会社 電気亜鉛めっき鋼板の製造方法

Also Published As

Publication number Publication date
KR20140064995A (ko) 2014-05-28
CN103842558A (zh) 2014-06-04
TW201315843A (zh) 2013-04-16
CN103842558B (zh) 2016-10-12
TWI461575B (zh) 2014-11-21
JP2013079422A (ja) 2013-05-02
KR20160113312A (ko) 2016-09-28

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