WO2013051269A1 - Production method for zinc-electroplated steel sheets - Google Patents
Production method for zinc-electroplated steel sheets Download PDFInfo
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- 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
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- WIPO (PCT)
- Prior art keywords
- steel sheet
- treatment
- zinc
- bath
- whiteness
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- 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
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- 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.
Abstract
Provided is a production method for zinc-electroplated steel sheets which have a high degree of whiteness, wherein steel sheets are subjected to cathodic electrolysis in a zinc-electroplating bath containing 0.01-3mass ppm in total of 1 or more of benzothiazole, 2-methylbenzothiazole, 2-aminobenzothiazole, and/or 2-benzothiazolone.
Description
本発明は、高い白色度を有する電気亜鉛めっき鋼板の製造方法に関するものである。
The present invention relates to a method for producing an electrogalvanized steel sheet having high whiteness.
化成処理電気亜鉛めっき鋼板は家電製品、自動車、建材等の広範な用途で使用されている。中でも、近年、無塗装で使用される各種化成処理電気亜鉛めっき鋼板の需要が増大しており、重要な用途分野となっている。この用途では無塗装で使用されるために表面外観に優れることが要求される。優れた表面外観の条件としては、ムラ等の表面欠陥が無いことに加え、白色度が高いことである。そして、各種化成処理後の外観は化成処理前の亜鉛めっきの外観に大きく左右されるため、白色度が高い亜鉛めっき鋼板を得ることが求められている。
Chemically treated electrogalvanized steel sheets are used in a wide range of applications such as home appliances, automobiles, and building materials. Among them, in recent years, the demand for various chemical-treated electrogalvanized steel sheets used without coating has increased and has become an important field of application. In this application, 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. And since 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 | required to obtain a galvanized steel plate with high whiteness.
電気亜鉛めっき処理の条件の適正化を図ることで、白色度の向上を図る技術として特許文献１～４が開示されている。
特許文献１、２には、無機イオンを添加し、電解処理する亜鉛めっき鋼板の製造方法が開示されている。
特許文献３には、めっき浴にグリシン、アスパラギン酸、カルボン酸基のいずれかを二つ以上有するカルボン酸またはその塩を添加し、鋼板を電解処理する亜鉛めっき鋼板の製造方法が開示されている。
特許文献４には、めっき浴に2－ベンゾチアゾリルチオ基を持つ有機化合物を添加し、鋼板を陰極電解処理する亜鉛めっき鋼板の製造方法が開示されている。 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.
特許文献１、２には、無機イオンを添加し、電解処理する亜鉛めっき鋼板の製造方法が開示されている。
特許文献３には、めっき浴にグリシン、アスパラギン酸、カルボン酸基のいずれかを二つ以上有するカルボン酸またはその塩を添加し、鋼板を電解処理する亜鉛めっき鋼板の製造方法が開示されている。
特許文献４には、めっき浴に2－ベンゾチアゾリルチオ基を持つ有機化合物を添加し、鋼板を陰極電解処理する亜鉛めっき鋼板の製造方法が開示されている。 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.
しかしながら、特許文献１、２では、めっき皮膜中に無機物が共析し、めっき皮膜の耐食性が劣化するなど、亜鉛めっき本来の特性が変化してしまうという欠点がある。
特許文献３では、電気めっき時に電流効率が大きく低下し、製造コストアップを招く等の問題がある。
特許文献４では、耐食性にも優れ、亜鉛めっき本来の特性が変化することもなく、電気めっき時に電流効率が大きく低下することもなく、特許文献１、２、３の問題は解決される。しかしながら、特許文献４では電気亜鉛めっき浴を３日間程度攪拌することにより2－ベンゾチアゾリルチオ基を持つ有機化合物がめっき浴中で反応してしまい、安定して白色化の効果が発揮されないという問題がある。 However, 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.
In Patent Document 3, there is a problem that current efficiency is greatly reduced during electroplating, resulting in an increase in manufacturing cost.
In 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. However, in 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.
特許文献３では、電気めっき時に電流効率が大きく低下し、製造コストアップを招く等の問題がある。
特許文献４では、耐食性にも優れ、亜鉛めっき本来の特性が変化することもなく、電気めっき時に電流効率が大きく低下することもなく、特許文献１、２、３の問題は解決される。しかしながら、特許文献４では電気亜鉛めっき浴を３日間程度攪拌することにより2－ベンゾチアゾリルチオ基を持つ有機化合物がめっき浴中で反応してしまい、安定して白色化の効果が発揮されないという問題がある。 However, 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.
In Patent Document 3, there is a problem that current efficiency is greatly reduced during electroplating, resulting in an increase in manufacturing cost.
In 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. However, in 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.
本発明は、かかる事情に鑑み、安定して高い白色度を有した電気亜鉛めっき鋼板の製造方法を提供することを目的とする。
In view of such circumstances, an object of the present invention is to provide a method for producing an electrogalvanized steel sheet having high and stable whiteness.
本発明者らは、上記した特許文献４の課題を解決すべく、鋭意研究を重ねた。
ベンゾチアゾール、2－メチルベンゾチアゾール、2－アミノベンゾチアゾール、2－ベンゾチアゾロンの1種又は2種以上（これらをまとめて有機化合物と称することもある）を含有しためっき浴を用いた場合、ベンゾチアゾール、2－メチルベンゾチアゾール、2－アミノベンゾチアゾール、2－ベンゾチアゾロンの1種又は2種以上を含有しないめっき浴を用いた場合と比べて亜鉛めっき結晶の凹凸の深さが小さくなることがわかった。
このメカニズムとしては、上記有機化合物は電解処理時に亜鉛めっき表面に吸着し、亜鉛めっきの結晶成長を阻害し、また二次結晶の発生を促進する。これにより、亜鉛の結晶形態を変化させ、亜鉛めっき結晶の凹凸の深さが小さくなる。このために、凹凸の深い部分での光の吸収が少なく、拡散反射光が増加し、外観上明るく見える（白色度が向上する）、と考えられる。
また、ベンゾチアゾール、2－メチルベンゾチアゾール、2－アミノベンゾチアゾール、2－ベンゾチアゾロンの1種又は2種以上の添加量範囲を限定することにより、安定して白色度の高い電気亜鉛めっき鋼板が得られることもわかった。 The inventors of the present invention have made extensive studies in order to solve the above-described problem of Patent Document 4.
When using a plating bath containing one or more of benzothiazole, 2-methylbenzothiazole, 2-aminobenzothiazole, and 2-benzothiazolone (sometimes collectively referred to as organic compounds), benzothiazole It was found that the unevenness of the galvanized crystals was smaller than when using a plating bath that did not contain one or more of 2-methylbenzothiazole, 2-aminobenzothiazole, and 2-benzothiazolone. .
As the mechanism, 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).
In addition, by limiting the addition amount range of one or more of benzothiazole, 2-methylbenzothiazole, 2-aminobenzothiazole, and 2-benzothiazolone, a stable and highly electrogalvanized steel sheet can be obtained. I also found out.
ベンゾチアゾール、2－メチルベンゾチアゾール、2－アミノベンゾチアゾール、2－ベンゾチアゾロンの1種又は2種以上（これらをまとめて有機化合物と称することもある）を含有しためっき浴を用いた場合、ベンゾチアゾール、2－メチルベンゾチアゾール、2－アミノベンゾチアゾール、2－ベンゾチアゾロンの1種又は2種以上を含有しないめっき浴を用いた場合と比べて亜鉛めっき結晶の凹凸の深さが小さくなることがわかった。
このメカニズムとしては、上記有機化合物は電解処理時に亜鉛めっき表面に吸着し、亜鉛めっきの結晶成長を阻害し、また二次結晶の発生を促進する。これにより、亜鉛の結晶形態を変化させ、亜鉛めっき結晶の凹凸の深さが小さくなる。このために、凹凸の深い部分での光の吸収が少なく、拡散反射光が増加し、外観上明るく見える（白色度が向上する）、と考えられる。
また、ベンゾチアゾール、2－メチルベンゾチアゾール、2－アミノベンゾチアゾール、2－ベンゾチアゾロンの1種又は2種以上の添加量範囲を限定することにより、安定して白色度の高い電気亜鉛めっき鋼板が得られることもわかった。 The inventors of the present invention have made extensive studies in order to solve the above-described problem of Patent Document 4.
When using a plating bath containing one or more of benzothiazole, 2-methylbenzothiazole, 2-aminobenzothiazole, and 2-benzothiazolone (sometimes collectively referred to as organic compounds), benzothiazole It was found that the unevenness of the galvanized crystals was smaller than when using a plating bath that did not contain one or more of 2-methylbenzothiazole, 2-aminobenzothiazole, and 2-benzothiazolone. .
As the mechanism, 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).
In addition, by limiting the addition amount range of one or more of benzothiazole, 2-methylbenzothiazole, 2-aminobenzothiazole, and 2-benzothiazolone, a stable and highly electrogalvanized steel sheet can be obtained. I also found out.
本発明は、以上の知見に基づきなされたものであり、その要旨は以下の通りである。
[１]ベンゾチアゾール、2－メチルベンゾチアゾール、2－アミノベンゾチアゾール、2－ベンゾチアゾロンの1種又は2種以上を合計で0.01～3mass ppm含有する電気亜鉛めっき浴中で、鋼板を陰極電解処理することを特徴とする電気亜鉛めっき鋼板の製造方法。 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.
[１]ベンゾチアゾール、2－メチルベンゾチアゾール、2－アミノベンゾチアゾール、2－ベンゾチアゾロンの1種又は2種以上を合計で0.01～3mass ppm含有する電気亜鉛めっき浴中で、鋼板を陰極電解処理することを特徴とする電気亜鉛めっき鋼板の製造方法。 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.
本発明によれば、安定して白色度の高い電気亜鉛めっき鋼板が得られる。
そして、他の特性が大きく変化してしまう、あるいは電流効率が大きく低下してしまうなどの問題も生じない。
また、めっき処理後だけでなく、電気亜鉛めっき処理後にクロメート型またはクロメートフリー型の各種化成処理（塗布型、反応型、電解型）や更にその上に樹脂被覆処理等を実施した鋼板についても高い白色度を有しており、表面外観に優れた電気亜鉛めっき鋼板が得られることになる。 According to the present invention, 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.
そして、他の特性が大きく変化してしまう、あるいは電流効率が大きく低下してしまうなどの問題も生じない。
また、めっき処理後だけでなく、電気亜鉛めっき処理後にクロメート型またはクロメートフリー型の各種化成処理（塗布型、反応型、電解型）や更にその上に樹脂被覆処理等を実施した鋼板についても高い白色度を有しており、表面外観に優れた電気亜鉛めっき鋼板が得られることになる。 According to the present invention, 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.
本発明の対象とする電気亜鉛めっき鋼板は、酸性浴を用いて陰極電解処理することにより得られる電気亜鉛めっき鋼板である。性能面（耐食性、加工性、白色度等）と操業面のバランスから、めっき皮膜中の亜鉛含有量の好ましい範囲は98mass％以上である。
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.
そして、本発明では、前記電気亜鉛めっき鋼板を陰極電解処理により製造するにあたり、ベンゾチアゾール、2－メチルベンゾチアゾール、2－アミノベンゾチアゾール、2－ベンゾチアゾロンの1種又は2種以上を合計で0.01～3mass ppm含有する電気亜鉛めっき浴を用いることとする。
In the present invention, when the electrogalvanized steel sheet is produced by cathodic electrolytic treatment, a total of one or more of benzothiazole, 2-methylbenzothiazole, 2-aminobenzothiazole and 2-benzothiazolone is 0.01 to An electrogalvanizing bath containing 3 mass ppm is used.
以下に、本発明の詳細について説明する。
めっき浴中には、以下に示すベンゾチアゾール、2－メチルベンゾチアゾール、2－アミノベンゾチアゾール、2－ベンゾチアゾロンの1種又は2種以上を合計で0.01～3mass ppm含有する。
電気亜鉛めっき浴中に含有するベンゾチアゾール、2－メチルベンゾチアゾール、2－アミノベンゾチアゾール、2－ベンゾチアゾロンの1種又は2種以上の合計量が0.01mass ppm未満では、白色度の上昇効果が不十分である。一方、3 mass ppmを超えると、安定した白色度が得られない。また、電流効率が大きく低下してしまう。好ましくは0.01～1.0 mass ppmである。 Details of the present invention will be described below.
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.
めっき浴中には、以下に示すベンゾチアゾール、2－メチルベンゾチアゾール、2－アミノベンゾチアゾール、2－ベンゾチアゾロンの1種又は2種以上を合計で0.01～3mass ppm含有する。
電気亜鉛めっき浴中に含有するベンゾチアゾール、2－メチルベンゾチアゾール、2－アミノベンゾチアゾール、2－ベンゾチアゾロンの1種又は2種以上の合計量が0.01mass ppm未満では、白色度の上昇効果が不十分である。一方、3 mass ppmを超えると、安定した白色度が得られない。また、電流効率が大きく低下してしまう。好ましくは0.01～1.0 mass ppmである。 Details of the present invention will be described below.
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.
陰極電解処理は、電気亜鉛めっき浴中に前記有機化合物を前記濃度範囲で含有することを除き、特に限定されない。例えば、電気亜鉛めっき浴としては硫酸浴、塩酸浴あるいは両者の混合などが適用できる。
The cathodic electrolysis treatment is not particularly limited except that the organic compound is contained in the concentration range in the electrogalvanizing bath. For example, as the electrogalvanizing bath, a sulfuric acid bath, a hydrochloric acid bath, or a mixture of both can be applied.
電気亜鉛めっき浴中の亜鉛含有量は、ZnSO4 として1.0mol/L以上が望ましい。1.0mol/L以上であれば、十分に高い白色度が得られる。
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.
また、電気亜鉛めっき浴中にはZnイオンの他、添加剤あるいは不純物として硫酸ナトリウム、硫酸カリウム等の伝導度補助剤、Fe、Ni、Pb、Sn、Co等の金属イオン等を含有しても良い。
In addition to Zn ions, 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.
電気亜鉛めっき浴のその他の条件についても特に限定しない。例えば、相対流速は0～4.0m/secとすることができる。浴温は、定温保持性を考えると、30℃以上が望ましい。pHは特に規定しないが、浴電導度を考慮すると、3.0以下が望ましい。片面当たりの全めっき付着量も特に限定しないが、通常は5～40g/m2である。電流密度についても特に限定しないが、通常10～150A/dm2である。
Other conditions of the electrogalvanizing bath are not particularly limited. For example, 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 .
なお、電気亜鉛めっき鋼板の製造において通常行われる、電気亜鉛めっき処理（陰極電解処理）を行う前の処理として、鋼板表面を清浄化するための脱脂処理および水洗、さらには、鋼板表面を活性化するための酸洗処理および水洗を施すことができる。これらの前処理に引き続いて電気亜鉛めっき処理（陰極電解処理）を実施する。
脱脂処理および水洗方法は特に限定しない。通常の方法を用いることができる。
酸洗処理においては、硫酸、塩酸、硝酸、及びこれらの混合物等各種の酸が使用できる。中でも、硫酸、塩酸あるいはこれらの混合が望ましい。酸の濃度は特に規定しないが、酸化皮膜の除去能力、過酸洗による肌荒れ防止等を考慮すると、1～20 mass％程度が望ましい。また、酸洗処理液には、消泡剤、酸洗促進剤、酸洗抑制剤等を含有しても良い。 In addition, as a treatment before electrogalvanizing treatment (cathodic electrolytic treatment), which is usually performed in the production of electrogalvanized steel sheet, degreasing treatment and water washing for cleaning the steel sheet surface, and further activating the steel sheet surface Pickling treatment and water washing can be performed. Subsequent to these pretreatments, electrogalvanizing treatment (cathodic electrolysis treatment) is performed.
The degreasing treatment and the water washing method are not particularly limited. Conventional methods can be used.
In the pickling treatment, 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.
脱脂処理および水洗方法は特に限定しない。通常の方法を用いることができる。
酸洗処理においては、硫酸、塩酸、硝酸、及びこれらの混合物等各種の酸が使用できる。中でも、硫酸、塩酸あるいはこれらの混合が望ましい。酸の濃度は特に規定しないが、酸化皮膜の除去能力、過酸洗による肌荒れ防止等を考慮すると、1～20 mass％程度が望ましい。また、酸洗処理液には、消泡剤、酸洗促進剤、酸洗抑制剤等を含有しても良い。 In addition, as a treatment before electrogalvanizing treatment (cathodic electrolytic treatment), which is usually performed in the production of electrogalvanized steel sheet, degreasing treatment and water washing for cleaning the steel sheet surface, and further activating the steel sheet surface Pickling treatment and water washing can be performed. Subsequent to these pretreatments, electrogalvanizing treatment (cathodic electrolysis treatment) is performed.
The degreasing treatment and the water washing method are not particularly limited. Conventional methods can be used.
In the pickling treatment, 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.
電気亜鉛めっき処理（陰極電解処理）後、耐食性、耐疵付き性、加工性等の各種性能の更なる向上を目的として、クロメート又はクロメートフリー処理（塗布型、反応型、電解型）を行う。更にはその上に樹脂被覆処理等を実施することもできる。化成処理皮膜の種類については特に限定せず、公知の手法を用いることが出来る。例えば、クロメートフリー化成処理液を塗布し水洗することなく鋼板温度として80～300℃となる加熱乾燥処理を行うクロメートフリー化成処理により形成される。さらに具体的には、第一リン酸、シリカ、及びMn、Mg、V、Zr、Tiなどを含有する処理液をバーコーターで塗布した後、100～160℃で乾燥させる手法などが用いられる。これら化成処理皮膜は単層でも複層でもよく、複層の場合には複数の化成処理を順次行えばよい。
なお、このような化成処理を施した電気亜鉛めっき鋼板でも本発明の効果が最大限発揮される。化成処理後の鋼板を無塗装で使用する場合、外観は電気亜鉛めっき後（化成処理前）の外観に大きく左右される。このような化成処理後の鋼板を無塗装で使用する場合に、本発明の方法により製造した電気亜鉛めっき鋼板を使用することにより、高い白色度を有することになる。 After the electrogalvanizing treatment (cathodic electrolytic treatment), 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. More specifically, 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.
In addition, the effect of this invention is exhibited to the maximum even with the electrogalvanized steel sheet subjected to such chemical conversion treatment. When the steel sheet after chemical conversion treatment is used without coating, the appearance greatly depends on the appearance after electrogalvanization (before chemical conversion treatment). When using the steel plate after such a chemical conversion treatment without coating, it will have high whiteness by using the electrogalvanized steel plate manufactured by the method of the present invention.
なお、このような化成処理を施した電気亜鉛めっき鋼板でも本発明の効果が最大限発揮される。化成処理後の鋼板を無塗装で使用する場合、外観は電気亜鉛めっき後（化成処理前）の外観に大きく左右される。このような化成処理後の鋼板を無塗装で使用する場合に、本発明の方法により製造した電気亜鉛めっき鋼板を使用することにより、高い白色度を有することになる。 After the electrogalvanizing treatment (cathodic electrolytic treatment), 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. More specifically, 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.
In addition, the effect of this invention is exhibited to the maximum even with the electrogalvanized steel sheet subjected to such chemical conversion treatment. When the steel sheet after chemical conversion treatment is used without coating, the appearance greatly depends on the appearance after electrogalvanization (before chemical conversion treatment). When using the steel plate after such a chemical conversion treatment without coating, it will have high whiteness by using the electrogalvanized steel plate manufactured by the method of the present invention.
また、本発明の製造方法により製造される電気亜鉛めっき鋼板は、用途に応じて、化成処理皮膜の表面には有機樹脂を含有する単層又は複層の塗膜を形成することができる。この塗膜としては、例えば、ポリエステル系樹脂塗膜、エポキシ系樹脂塗膜、アクリル系樹脂塗膜、ウレタン系樹脂塗膜、フッ素系樹脂塗膜等が挙げられる。また、上記樹脂の一部を他の樹脂で変性した、例えばエポキシ変性ポリエステル系樹脂塗膜等も適用できる。さらに上記樹脂には必要に応じて硬化剤、硬化触媒、顔料、添加剤等を添加することができる。
Moreover, 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. Examples of 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. Further, for example, an epoxy-modified polyester resin coating film in which a part of the resin is modified with another resin can be applied. Furthermore, a curing agent, a curing catalyst, a pigment, an additive, and the like can be added to the resin as necessary.
上記塗膜を形成するための塗装方法は特に規定しないが、塗装方法としてはロールコーター塗装、カーテンフロー塗装、スプレー塗装等が挙げられる。有機樹脂を含有する塗料を塗装した後、熱風乾燥、赤外線加熱、誘導加熱等の手段により加熱乾燥して塗膜を形成することができる。
ただし、上記表面処理鋼板の製造方法は一例であり、これに限定されるものではない。 Although 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.
However, the manufacturing method of the said surface treatment steel plate is an example, and is not limited to this.
ただし、上記表面処理鋼板の製造方法は一例であり、これに限定されるものではない。 Although 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.
However, the manufacturing method of the said surface treatment steel plate is an example, and is not limited to this.
次に、本発明を実施例により更に詳細に説明する。
常法で製造した板厚0.7mmの冷延鋼板に対して、アルカリでの脱脂処理および酸洗処理を施し、次いで、以下の条件で、かつ、表１に示す条件で、鋼板を陰極として電解処理を行い、電気亜鉛めっき鋼板を製造した。電気亜鉛めっき浴に有機化合物を添加した後、１時間撹拌後又は３日間撹拌後に陰極電解処理を行った。なお、一部のものについては、電気めっき浴中に有機化合物を添加せずに上記の陰極電解処理を実施した。また、片面あたりの亜鉛めっき付着量は、亜鉛めっきを希硫酸で溶解し、溶解液中の亜鉛濃度をICP（Inductively Coupled Plasma）質量分析装置により測定し、付着量に換算して求めた。
電解条件
有機物含有量、浴温、pH、電流密度：表1に示す
電気亜鉛めっき浴：Zn2+イオンを1.5mol/L含む
相対流速：1.5m/s
電極（陽極）：酸化イリジウム電極
以上より得られた電気亜鉛めっき鋼板に対して、以下の測定方法および評価基準に基づき、白色度を測定し評価した。得られた結果を表１に併せて示す。 Next, the present invention will be described in more detail with reference to examples.
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. After adding an organic compound to the electrogalvanizing bath, cathodic electrolysis was performed after stirring for 1 hour or after stirring for 3 days. In addition, about the one part, 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.
常法で製造した板厚0.7mmの冷延鋼板に対して、アルカリでの脱脂処理および酸洗処理を施し、次いで、以下の条件で、かつ、表１に示す条件で、鋼板を陰極として電解処理を行い、電気亜鉛めっき鋼板を製造した。電気亜鉛めっき浴に有機化合物を添加した後、１時間撹拌後又は３日間撹拌後に陰極電解処理を行った。なお、一部のものについては、電気めっき浴中に有機化合物を添加せずに上記の陰極電解処理を実施した。また、片面あたりの亜鉛めっき付着量は、亜鉛めっきを希硫酸で溶解し、溶解液中の亜鉛濃度をICP（Inductively Coupled Plasma）質量分析装置により測定し、付着量に換算して求めた。
電解条件
有機物含有量、浴温、pH、電流密度：表1に示す
電気亜鉛めっき浴：Zn2+イオンを1.5mol/L含む
相対流速：1.5m/s
電極（陽極）：酸化イリジウム電極
以上より得られた電気亜鉛めっき鋼板に対して、以下の測定方法および評価基準に基づき、白色度を測定し評価した。得られた結果を表１に併せて示す。 Next, the present invention will be described in more detail with reference to examples.
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. After adding an organic compound to the electrogalvanizing bath, cathodic electrolysis was performed after stirring for 1 hour or after stirring for 3 days. In addition, about the one part, 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.
白色度：明度（L値）
分光色差計（日本電色工業(株)製 SD5000）を用いてSCE（正反射光除去）により、白色度を測定し、以下のように評価した。
◎：L値85以上
○：L値82以上、85未満
×：L値82未満 Whiteness: Lightness (L value)
Using a spectral color difference meter (SD5000 manufactured by Nippon Denshoku Industries Co., Ltd.), the whiteness was measured by SCE (removing regular reflection light) and evaluated as follows.
◎: L value 85 or more ○: L value 82 or more, less than 85 ×: L value less than 82
分光色差計（日本電色工業(株)製 SD5000）を用いてSCE（正反射光除去）により、白色度を測定し、以下のように評価した。
◎：L値85以上
○：L値82以上、85未満
×：L値82未満 Whiteness: Lightness (L value)
Using a spectral color difference meter (SD5000 manufactured by Nippon Denshoku Industries Co., Ltd.), the whiteness was measured by SCE (removing regular reflection light) and evaluated as follows.
◎: L value 85 or more ○: L value 82 or more, less than 85 ×: L value less than 82
表１より、本発明例では有機化合物を添加した後１時間撹拌後、３日間撹拌後いずれにおいてもＬ値が高い、すなわち白色度が高い電気亜鉛めっき鋼板が安定して得られているのがわかる。また、本発明例では耐食性にも優れ、亜鉛めっき本来の特性が変化することもなかった。さらに本発明例では電気めっき時に電流効率が大きく低下することもなかった。
一方、比較例では、Ｌ値が低い。また、電気亜鉛めっき浴に2－ベンゾチアゾリルチオ基を持つ有機化合物を添加し、鋼板を陰極電解処理した比較例では、3日間撹拌後の白色度が劣っている。これは、2-ベンゾチアゾリルチオ基のチオール基（O-SHの部分）が酸化され、二量体（O-S-S-O）となり、沈殿してしまったため、すなわち、電気亜鉛めっき浴中で反応してしまったためである。 From Table 1, in the present invention example, the electrogalvanized steel sheet having a high L value, that is, a high whiteness, is obtained stably after stirring for 1 hour after adding an organic compound and after stirring for 3 days. Recognize. Further, the inventive examples were excellent in corrosion resistance, and the original characteristics of galvanization were not changed. Furthermore, in the inventive examples, the current efficiency was not greatly reduced during electroplating.
On the other hand, in the comparative example, the L value is low. In the comparative example in which an organic compound having a 2-benzothiazolylthio group was added to the electrogalvanizing bath and the steel sheet was subjected to cathodic electrolysis, 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.
一方、比較例では、Ｌ値が低い。また、電気亜鉛めっき浴に2－ベンゾチアゾリルチオ基を持つ有機化合物を添加し、鋼板を陰極電解処理した比較例では、3日間撹拌後の白色度が劣っている。これは、2-ベンゾチアゾリルチオ基のチオール基（O-SHの部分）が酸化され、二量体（O-S-S-O）となり、沈殿してしまったため、すなわち、電気亜鉛めっき浴中で反応してしまったためである。 From Table 1, in the present invention example, the electrogalvanized steel sheet having a high L value, that is, a high whiteness, is obtained stably after stirring for 1 hour after adding an organic compound and after stirring for 3 days. Recognize. Further, the inventive examples were excellent in corrosion resistance, and the original characteristics of galvanization were not changed. Furthermore, in the inventive examples, the current efficiency was not greatly reduced during electroplating.
On the other hand, in the comparative example, the L value is low. In the comparative example in which an organic compound having a 2-benzothiazolylthio group was added to the electrogalvanizing bath and the steel sheet was subjected to cathodic electrolysis, 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.
本発明の電気亜鉛めっき鋼板は表面外観に優れ、無塗装で問題なく使用することができる。そのため家電製品、自動車、建材等の広範な用途での使用が可能となる。
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.
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.
Claims (1)
- ベンゾチアゾール、2－メチルベンゾチアゾール、2－アミノベンゾチアゾール、2－ベンゾチアゾロンの1種又は2種以上を合計で0.01～3mass ppm含有する電気亜鉛めっき浴中で、鋼板を陰極電解処理することを特徴とする電気亜鉛めっき鋼板の製造方法。 Characterized by cathodic electrolysis of steel sheet in an electrogalvanizing bath containing one or more of benzothiazole, 2-methylbenzothiazole, 2-aminobenzothiazole, and 2-benzothiazolone in a total of 0.01 to 3 massmasppm A method for producing an electrogalvanized steel sheet.
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| Application Number | Priority Date | Filing Date | Title |
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| KR1020147010649A KR20140063868A (en) | 2011-10-04 | 2012-10-04 | Production method for zinc-electroplated steel sheet |
| CN201280048582.XA CN103842559B (en) | 2011-10-04 | 2012-10-04 | The manufacture method of plated steel sheet |
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| JP2011219718A JP5834738B2 (en) | 2011-10-04 | 2011-10-04 | Method for producing electrogalvanized steel sheet |
| JP2011-219718 | 2011-10-04 |
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| JP (1) | JP5834738B2 (en) |
| KR (1) | KR20140063868A (en) |
| CN (1) | CN103842559B (en) |
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| KR20160078289A (en) | 2014-12-24 | 2016-07-04 | (주) 지오화인켐 | Method for multi layer plating metal surface |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0959788A (en) * | 1995-06-14 | 1997-03-04 | Kobe Steel Ltd | Production of electrogalvanized steel sheet excellent in appearance |
| JP2003073882A (en) * | 2001-08-31 | 2003-03-12 | Nippon Hyomen Kagaku Kk | Alkaline galvannealing bath and galvannealing method |
| JP2004068153A (en) * | 2002-07-23 | 2004-03-04 | Nippon Hyomen Kagaku Kk | Galvanizing method with zincate bath |
| JP2007297646A (en) * | 2006-03-22 | 2007-11-15 | Jfe Steel Kk | Method for manufacturing electrogalvanized steel sheet |
Family Cites Families (4)
| 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 (en) * | 1994-08-01 | 2001-11-26 | 日本鋼管株式会社 | Electrogalvanized steel sheet with excellent appearance |
| JP2000054186A (en) * | 1998-07-31 | 2000-02-22 | Nkk Corp | Electrogalvanized steel sheet excellent in blackening- resistance and good in whiteness degree and appearance after chemical conversion treatment of plated film and its production |
| JP4862484B2 (en) * | 2006-05-16 | 2012-01-25 | Ｊｆｅスチール株式会社 | Method for producing electrogalvanized steel sheet |
-
2011
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- 2012-10-03 TW TW101136521A patent/TWI465612B/en active
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- 2012-10-04 KR KR1020147010649A patent/KR20140063868A/en active Search and Examination
- 2012-10-04 WO PCT/JP2012/006373 patent/WO2013051269A1/en active Application Filing
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0959788A (en) * | 1995-06-14 | 1997-03-04 | Kobe Steel Ltd | Production of electrogalvanized steel sheet excellent in appearance |
| JP2003073882A (en) * | 2001-08-31 | 2003-03-12 | Nippon Hyomen Kagaku Kk | Alkaline galvannealing bath and galvannealing method |
| JP2004068153A (en) * | 2002-07-23 | 2004-03-04 | Nippon Hyomen Kagaku Kk | Galvanizing method with zincate bath |
| JP2007297646A (en) * | 2006-03-22 | 2007-11-15 | Jfe Steel Kk | Method for manufacturing electrogalvanized steel sheet |
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| Publication number | Publication date |
|---|---|
| JP5834738B2 (en) | 2015-12-24 |
| CN103842559A (en) | 2014-06-04 |
| TWI465612B (en) | 2014-12-21 |
| KR20140063868A (en) | 2014-05-27 |
| TW201315842A (en) | 2013-04-16 |
| JP2013079421A (en) | 2013-05-02 |
| CN103842559B (en) | 2016-11-09 |
| MY160990A (en) | 2017-03-31 |
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