WO2013051269A1 - Procédé de fabrication pour des feuilles d'acier à électroplacage au zinc - Google Patents

Procédé de fabrication pour des feuilles d'acier à électroplacage au zinc Download PDF

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Publication number
WO2013051269A1
WO2013051269A1 PCT/JP2012/006373 JP2012006373W WO2013051269A1 WO 2013051269 A1 WO2013051269 A1 WO 2013051269A1 JP 2012006373 W JP2012006373 W JP 2012006373W WO 2013051269 A1 WO2013051269 A1 WO 2013051269A1
Authority
WO
WIPO (PCT)
Prior art keywords
steel sheet
treatment
zinc
bath
whiteness
Prior art date
Application number
PCT/JP2012/006373
Other languages
English (en)
Japanese (ja)
Inventor
土本　和明
妹川　透
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 KR1020147010649A priority Critical patent/KR20140063868A/ko
Priority to CN201280048582.XA priority patent/CN103842559B/zh
Publication of WO2013051269A1 publication Critical patent/WO2013051269A1/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
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C25D5/46—Pretreatment of metallic surfaces to be electroplated of actinides

Definitions

  • the present invention relates to a method for producing an electrogalvanized steel sheet having high whiteness.
  • Chemically treated electrogalvanized steel sheets are used in a wide range of applications such as home appliances, automobiles, and building materials.
  • the demand for various chemical-treated electrogalvanized steel sheets used without coating has increased and has become an important field of application.
  • 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 Documents 1 to 4 are disclosed as techniques for improving whiteness by optimizing the conditions of electrogalvanizing treatment.
  • Patent Documents 1 and 2 disclose a method of manufacturing a galvanized steel sheet in which inorganic ions are added and electrolytically treated.
  • Patent Document 3 discloses a method for producing a galvanized steel sheet in which a carboxylic acid having two or more of glycine, aspartic acid, and carboxylic acid groups or a salt thereof is added to a plating bath, and the steel sheet is electrolytically treated.
  • Patent Document 4 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 Documents 1 and 2 have a drawback that the original properties of galvanization change, such as the eutectoid of an inorganic substance in the plating film and deterioration of the corrosion resistance of the plating film.
  • Patent Document 3 there is a problem that current efficiency is greatly reduced during electroplating, resulting in an increase in manufacturing cost.
  • patent document 4 it is excellent also in corrosion resistance, the original characteristic of galvanization does not change, and current efficiency does not fall greatly at the time of electroplating, and the problem of patent documents 1, 2, and 3 is solved.
  • Patent Document 4 when an electrogalvanizing bath is stirred for about 3 days, an organic compound having a 2-benzothiazolylthio group reacts in the plating bath, and the whitening effect is not stably exhibited. There's a problem.
  • an object of the present invention is to provide a method for producing an electrogalvanized steel sheet having high and stable whiteness.
  • the organic compound is adsorbed on the surface of the galvanizing during the electrolytic treatment, inhibits the crystal growth of the galvanizing, and promotes the generation of secondary crystals. Thereby, the crystal form of zinc is changed, and the depth of the unevenness of the galvanized crystal is reduced. For this reason, it is considered that light absorption in a deeply uneven portion is small, diffuse reflection light increases, and the appearance looks bright (whiteness is improved).
  • benzothiazole, 2-methylbenzothiazole, 2-aminobenzothiazole, and 2-benzothiazolone a stable and highly electrogalvanized steel sheet can be obtained. I also found out.
  • the present invention has been made based on the above findings, and the gist thereof is as follows.
  • [1] Cathodic electrolytic treatment of steel sheet in an electrogalvanizing bath containing 0.01 to 3 mass ppm of one or more of benzothiazole, 2-methylbenzothiazole, 2-aminobenzothiazole and 2-benzothiazolone A method for producing an electrogalvanized steel sheet.
  • an electrogalvanized steel sheet having high whiteness can be obtained stably. Further, there is no problem that other characteristics are greatly changed or current efficiency is greatly reduced. Also, not only after plating, but also for steel sheets that have been subjected to various chemical treatments (coating type, reaction type, electrolytic type) of chromate type or chromate-free type after electrogalvanizing treatment, and further resin coating treatment etc. An electrogalvanized steel sheet having whiteness and excellent surface appearance can be obtained.
  • the electrogalvanized steel sheet which is the subject of the present invention is an electrogalvanized steel sheet obtained by cathodic electrolysis 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 plating bath contains 0.01 to 3 mass ppm in total of one or more of the following benzothiazole, 2-methylbenzothiazole, 2-aminobenzothiazole, and 2-benzothiazolone. If the total amount of one or more of benzothiazole, 2-methylbenzothiazole, 2-aminobenzothiazole, and 2-benzothiazolone contained in the electrogalvanizing bath is less than 0.01 mass ppm, the effect of increasing whiteness is not good. It is enough. On the other hand, if it exceeds 3 mass ppm, stable whiteness cannot be obtained. In addition, current efficiency is greatly reduced. Preferably, it is 0.01 to 1.0 mass ppm.
  • the cathodic electrolysis treatment is not particularly limited except that the organic compound is contained in the concentration range in the electrogalvanizing bath.
  • the electrogalvanizing bath a sulfuric acid bath, a hydrochloric acid bath, or a mixture of both can be applied.
  • 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 electrogalvanizing bath may contain additives or impurities as conductivity aids such as sodium sulfate and potassium sulfate, and metal ions such as Fe, Ni, Pb, Sn and Co. good.
  • the relative flow velocity can be 0 to 4.0 m / sec.
  • the bath temperature is preferably 30 ° C. or higher considering the constant temperature retention.
  • the pH is not particularly specified, but is preferably 3.0 or less in view of the bath conductivity.
  • the total amount of plating deposited on one side is not particularly limited, but is usually 5 to 40 g / m 2 .
  • the current density is not particularly limited, but is usually 10 to 150 A / dm 2 .
  • electrogalvanizing treatment which is usually performed in the production of electrogalvanized steel sheet
  • Pickling treatment and water washing can be performed.
  • electrogalvanizing treatment cathodic electrolysis treatment
  • 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 or chromate-free treatment (coating type, reaction type, electrolytic type) is performed for the purpose of further improving various properties 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. For example, it is formed by a chromate-free chemical conversion treatment in which a heat-drying treatment with a steel plate temperature of 80 to 300 ° C. is performed without applying a chromate-free chemical conversion treatment solution and washing with water.
  • a method of applying a treatment liquid containing primary phosphoric acid, silica, Mn, Mg, V, Zr, Ti and the like with a bar coater and drying at 100 to 160 ° C. is used.
  • These chemical conversion treatment films may be a single layer or multiple layers, and in the case of multiple layers, a plurality of chemical conversion treatments may be performed sequentially.
  • the effect of this invention is exhibited to the maximum even with the electrogalvanized steel sheet subjected to such chemical conversion treatment.
  • the appearance greatly depends on the appearance after electrogalvanization (before chemical conversion treatment).
  • it will have high whiteness by using the electrogalvanized steel plate manufactured by the method of the present invention.
  • the electrogalvanized steel sheet produced by the production method of the present invention can form a single-layer or multi-layer coating film containing an organic resin on the surface of the chemical conversion coating 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.
  • a curing agent, a curing catalyst, a pigment, an additive, and the like can be added to the resin as necessary.
  • 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 having a thickness of 0.7 mm manufactured by a conventional method is subjected to a degreasing treatment with an alkali and a pickling treatment, and then electrolysis using the steel sheet as a cathode under the following conditions and the conditions shown in Table 1.
  • the treatment was carried out to produce an electrogalvanized steel sheet.
  • cathodic electrolysis was performed after stirring for 1 hour or after stirring for 3 days.
  • said cathode electrolysis process was implemented, without adding an organic compound in an electroplating bath.
  • the amount of zinc plating adhered per side was determined by dissolving zinc plating with dilute sulfuric acid, measuring the zinc concentration in the solution with an ICP (Inductively Coupled Plasma) mass spectrometer, and converting it to the amount of adhesion.
  • Electrolytic conditions Organic matter content, bath temperature, pH, current density: Electrogalvanizing bath shown in Table 1: Relative flow rate containing 1.5 mol / L of Zn 2+ ions: 1.5 m / s Electrode (anode): iridium oxide electrode The electrogalvanized steel sheet obtained above was measured and evaluated based on the following measurement method and evaluation criteria. The obtained results are also shown in Table 1.
  • the electrogalvanized steel sheet having a high L value that is, a high whiteness
  • the inventive examples were excellent in corrosion resistance, and the original characteristics of galvanization were not changed.
  • the current efficiency was not greatly reduced during electroplating.
  • the comparative example the L value is low.
  • the whiteness after stirring for 3 days was poor. This is because the thiol group (O-SH part) of 2-benzothiazolylthio group was oxidized to dimer (OSSO) and precipitated, that is, it reacted in the electrogalvanizing bath. This is because.
  • the electrogalvanized steel sheet of the present invention is excellent in surface appearance and can be used without any problems without being painted. Therefore, it can be used in a wide range of applications such as home appliances, automobiles, and building materials.

Landscapes

  • 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

L'invention concerne un procédé de fabrication de feuilles d'acier à électroplacage au zinc qui ont un degré élevé de blancheur, procédé suivant lequel des feuilles d'acier sont soumises à une électrolyse cathodique dans un bain d'électroplacage au zinc contenant 0,01-3 ppm en masse au total de 1 ou plus parmi le benzothiazole, le 2-méthylbenzothiazole, le 2-aminobenzothiazole et/ou la 2-benzothiazolone.
PCT/JP2012/006373 2011-10-04 2012-10-04 Procédé de fabrication pour des feuilles d'acier à électroplacage au zinc WO2013051269A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020147010649A KR20140063868A (ko) 2011-10-04 2012-10-04 전기 아연 도금 강판의 제조방법
CN201280048582.XA CN103842559B (zh) 2011-10-04 2012-10-04 电镀锌钢板的制造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011-219718 2011-10-04
JP2011219718A JP5834738B2 (ja) 2011-10-04 2011-10-04 電気亜鉛めっき鋼板の製造方法

Publications (1)

Publication Number Publication Date
WO2013051269A1 true WO2013051269A1 (fr) 2013-04-11

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Application Number Title Priority Date Filing Date
PCT/JP2012/006373 WO2013051269A1 (fr) 2011-10-04 2012-10-04 Procédé de fabrication pour des feuilles d'acier à électroplacage au zinc

Country Status (6)

Country Link
JP (1) JP5834738B2 (fr)
KR (1) KR20140063868A (fr)
CN (1) CN103842559B (fr)
MY (1) MY160990A (fr)
TW (1) TWI465612B (fr)
WO (1) WO2013051269A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160078289A (ko) 2014-12-24 2016-07-04 (주) 지오화인켐 금속 표면의 복층 도금 방법

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0959788A (ja) * 1995-06-14 1997-03-04 Kobe Steel Ltd 外観に優れた電気亜鉛めっき鋼板の製造方法
JP2003073882A (ja) * 2001-08-31 2003-03-12 Nippon Hyomen Kagaku Kk アルカリ性電気亜鉛めっき浴およびめっき方法
JP2004068153A (ja) * 2002-07-23 2004-03-04 Nippon Hyomen Kagaku Kk ジンケート浴亜鉛めっき方法
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

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3841982A (en) * 1972-04-17 1974-10-15 Oxy Metal Finishing Corp Method to improve the brightness of zinc from an alkaline zincate electrodeposition bath
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
JP2000054186A (ja) * 1998-07-31 2000-02-22 Nkk Corp 耐黒変性に優れ且つめっき皮膜の白色度と化成処理後の外観が良好な電気亜鉛めっき鋼板およびその製造方法
JP4862484B2 (ja) * 2006-05-16 2012-01-25 Ｊｆｅスチール株式会社 電気亜鉛めっき鋼板の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0959788A (ja) * 1995-06-14 1997-03-04 Kobe Steel Ltd 外観に優れた電気亜鉛めっき鋼板の製造方法
JP2003073882A (ja) * 2001-08-31 2003-03-12 Nippon Hyomen Kagaku Kk アルカリ性電気亜鉛めっき浴およびめっき方法
JP2004068153A (ja) * 2002-07-23 2004-03-04 Nippon Hyomen Kagaku Kk ジンケート浴亜鉛めっき方法
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

Also Published As

Publication number Publication date
CN103842559A (zh) 2014-06-04
CN103842559B (zh) 2016-11-09
TWI465612B (zh) 2014-12-21
MY160990A (en) 2017-03-31
JP5834738B2 (ja) 2015-12-24
KR20140063868A (ko) 2014-05-27
JP2013079421A (ja) 2013-05-02
TW201315842A (zh) 2013-04-16

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