JP5655649B2 - Method for producing chemical conversion treated steel sheet - Google Patents
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Description
本発明は、白色度の高い化成処理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 a chemically treated steel sheet having high whiteness.
化成処理鋼板は家電製品、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家電用途向け各種化成処理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 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 types of chemical conversion treated steel sheets for home appliances that are used without coating is increasing, which is an important application field. 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が開発されている。特許文献１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 Document 1 has been developed 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.
しかしながら、特許文献１では、クロメートフリー化成処理を行い表層に化成処理皮膜を形成した場合に白色度が下がってしまい、所定の白色度が得られない。 However, in Patent Document 1, when a chromate-free chemical conversion treatment is performed and a chemical conversion treatment film is formed on the surface layer, the whiteness decreases, and a predetermined whiteness cannot be obtained.
以上のように、従来技術では、めっき処理後および化成処理後のいずれにおいても白色度の高い化成処理鋼板を得るのは難しい状況であった。 As described above, in the prior art, it has been difficult to obtain a chemically treated steel sheet having high whiteness both after plating and after chemical conversion.
本発明は、かかる事情に鑑み、めっき処理後、かつ、化成処理後に高い白色度を有した化成処理鋼板の製造方法を提供することを目的とする。 An object of this invention is to provide the manufacturing method of the chemical conversion treatment steel plate which has high whiteness after a plating process and after a chemical conversion treatment in view of this situation.
本発明者らは、上記課題を解決すべく、鋭意研究を重ねた。
本発明者らは、2-ベンゾチアゾリルチオ基を持つ有機化合物の１種又は２種以上を合計で0.01〜3ppm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により、耐食性を低下させることなく光沢化を生じさせずに、高い白色度を有する電気亜鉛めっき鋼板が得られることを見出し、特許文献１として出願を行った。しかし、上述したように、化成処理後の白色度は十分でない。
The inventors of the present invention have made extensive studies to solve the above problems.
The present inventors reduced the corrosion resistance by cathodic electrolytic treatment of a steel sheet in an electrogalvanizing bath containing a total of 0.01 to 3 ppm of one or more organic compounds having a 2-benzothiazolylthio group. The inventors have found that an electrogalvanized steel sheet having high whiteness can be obtained without causing glossing, and filed an application as Patent Document 1. However, as described above, the whiteness after the chemical conversion treatment is not sufficient.
そこで、さらに、研究を行った結果、2-ベンゾチアゾリルチオ基を持つ有機化合物を含有するめっき浴を使用した場合には、電流密度10A/dm2未満で陰極電解処理を行うと急激に高い白色度が得られることを見出した。電流密度低下により亜鉛析出の過電圧が低下し、表面凹凸の小さな結晶面が優先的に生成するためと考えられる。 Therefore, as a result of further research, when a plating bath containing an organic compound having a 2-benzothiazolylthio group was used, it was rapidly increased when cathodic electrolysis was performed at a current density of less than 10 A / dm 2. It was found that whiteness can be obtained. This is thought to be because the overvoltage of zinc precipitation decreases due to the decrease in current density, and crystal planes with small surface irregularities are preferentially generated.
しかしながら、電流密度10A/dm2未満では所定のめっき付着量を鋼板表面に形成するのに極めて長時間を要するため、実操業においては不利となる。そこで、通電パターンを研究した結果、2-ベンゾチアゾリルチオ基を持つ有機化合物の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電気亜鉛めっき処理を行うにあたり、前段と後段からなる二段処理とし、前段では、電流密度を10A/dm2以上で陰極電解し、後段では、電流密度を10A/dm2未満で陰極電解処理し、かつ、鋼板表面に片面当たり0.1g/m2以上のめっき層を形成することにより、長時間を要することなく、めっき処理後、かつ、化成処理後に良好な白色度が得られることを知見した。 However, if the current density is less than 10 A / dm 2 , it takes a very long time to form a predetermined coating amount on the steel sheet surface, which is disadvantageous in actual operation. Therefore, as a result of studying the energization pattern, in performing electrogalvanizing treatment in an electrogalvanizing bath containing 0.01 to 3 mass ppm of one or more organic compounds having a 2-benzothiazolylthio group in total, It is a two-stage process consisting of a front stage and a rear stage. In the front stage, cathodic electrolysis is performed at a current density of 10 A / dm 2 or more, and in the rear stage, cathodic electrolysis is performed at a current density of less than 10 A / dm 2 It was found that by forming a plating layer of 0.1 g / m 2 or more, good whiteness can be obtained after the plating treatment and after the chemical conversion treatment without requiring a long time.
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] 2-ベンゾチアゾリルチオ基を持つ有機化合物の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、下記に示す前段と後段の二段処理からなる電気亜鉛めっき処理を行い、次いで、クロメートフリー化成処理を施すことを特徴とする化成処理鋼板の製造方法。
前記前段では、電流密度を10A/dm2以上で陰極電解処理する。
前記後段では、電流密度を10A/dm2未満で陰極電解処理し、鋼板表面に片面当たり0.1g/m2以上のめっき層を形成する。
[２]前記後段の処理により形成されるめっき付着量は、めっき層全体の10％以下であることを特徴とする[１]の化成処理鋼板の製造方法。
[３]前記2-ベンゾチアゾリルチオ基を持つ有機化合物が2-メルカプトベンゾチアゾール又は2-メルカプトベンゾチアゾールの塩であることを特徴とする[１]または[２]の化成処理鋼板の製造方法。
The present invention has been made based on the above findings, and the gist thereof is as follows.
[1] An electric galvanizing bath containing one or more organic compounds having a 2-benzothiazolylthio group in a total of 0.01 to 3 mass ppm. A method for producing a chemical conversion treated steel sheet, characterized by performing a galvanizing treatment and then performing a chromate-free chemical conversion treatment.
In the previous stage, cathodic electrolysis is performed at a current density of 10 A / dm 2 or more.
In the latter stage, cathodic electrolysis is performed at a current density of less than 10 A / dm 2 to form a plating layer of 0.1 g / m 2 or more per side on the steel sheet surface.
[2] The method for producing a chemical conversion treated steel sheet according to [1], wherein an amount of plating formed by the subsequent treatment is 10% or less of the entire plating layer.
[3] The method for producing a chemically treated steel sheet according to [1] or [2], wherein the organic compound having a 2-benzothiazolylthio group is 2-mercaptobenzothiazole or a salt of 2-mercaptobenzothiazole. .
本発明によれば、白色度の高い化成処理鋼板が得られる。特に、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、表面外観に優れた化成処理鋼板が得られることになる。 ADVANTAGE OF THE INVENTION According to this invention, a chemical conversion treatment steel plate with high whiteness is obtained. In particular, not only after plating, but also for chromate-free chemical conversion treatment (coating type, reaction type, electrolytic type) after electrogalvanization, and steel sheets that have been further coated with resin coating, etc. have high whiteness. Therefore, a chemical conversion treated steel sheet having an excellent surface appearance can be obtained.
本発明の対象とする化成処理鋼板は、酸性浴を用いて電気亜鉛めっき処理することにより得られる電気亜鉛めっき鋼板にクロメートフリー化成処理を施したものである。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 chemical conversion treatment steel plate which is the object of the present invention is obtained by subjecting an electrogalvanized steel plate obtained by electrogalvanization treatment using an acidic bath to chromate-free chemical conversion treatment. 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、前記化成処理鋼板を電気亜鉛めっき処理により製造するにあたり、2-ベンゾチアゾリルチオ基を持つ有機化合物の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、前段と後段からなる二段処理とする。さらに、前段では電流密度を10A/dm2以上で処理を行い、後段では電流密度を10A/dm2未満で処理を行い、かつ、後段の処理では、鋼板表面に片面当たり0.1g/m2以上めっき層を形成させる。 And, in the present invention, in producing the chemical conversion treated steel sheet by electrogalvanizing treatment, electrogalvanizing containing a total of 0.01 to 3 mass ppm of one or more organic compounds having a 2-benzothiazolylthio group Using a bath, a two-stage process consisting of a first stage and a second stage is performed. Furthermore, in the former stage, the current density is processed at 10 A / dm 2 or more, in the latter stage, the current density is processed at less than 10 A / dm 2 , and in the latter stage, 0.1 g / m 2 or more per side on the steel sheet surface A plating layer is formed.
電気亜鉛めっき処理後、クロメートフリー化成処理を施す。以上により、クロメートフリー化成処理後に高い白色度を有する化成処理鋼板が得られることになる。 Chromate-free chemical conversion treatment is applied after electrogalvanization. By the above, the chemical conversion treatment steel plate which has high whiteness after chromate-free chemical conversion treatment will be obtained.
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2-ベンゾチアゾリルチオ基を持つ有機化合物の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添加する2-ベンゾチアゾリルチオ基を持つ有機化合物の合計濃度が0.01 mass ppm未満では、白色度の上昇効果が不十分となる。一方、3 mass ppmを超えると、めっき処理後（めっきまま）の鋼板では、表面が極端に平滑化して金属光沢のある外観となってしまい、白色度が逆に低下してしまう。また、0.5 mass ppmを超えると、電流効率が低下する場合があるため、上限は0.5 mass ppm以下が望ましい。以上より、2-ベンゾチアゾリルチオ基を持つ有機化合物は、１種又は２種以上の合計で0.01mass ppm以上3mass ppm以下、望ましくは0.01mass ppm以上0.5mass ppm以下を、電気亜鉛めっき浴中に含有することとする。
Details of the present invention will be described below.
The plating bath contains 0.01 to 3 mass ppm of one or more organic compounds having a 2-benzothiazolylthio group shown below.
When the total concentration of the organic compounds having 2-benzothiazolylthio group added to the electrogalvanizing bath is less than 0.01 mass ppm, the effect of increasing whiteness becomes insufficient. On the other hand, if it exceeds 3 mass ppm, the surface of the steel plate after plating treatment (as plated) becomes extremely smooth and has a metallic luster appearance, and the whiteness is decreased. Moreover, since current efficiency may fall when it exceeds 0.5 mass ppm, the upper limit is desirably 0.5 mass ppm or less. From the above, the organic compound having 2-benzothiazolylthio group should be 0.01mass ppm or more and 3massppm or less, preferably 0.01massppm or more and 0.5massppm or less in total in one or more kinds in the electrogalvanizing bath. It is supposed to be contained in
2-ベンゾチアゾリルチオ基を持つ有機化合物として、以下に示す２-メルカプトベンゾチアゾール又は２-メルカプトベンゾチアゾールの塩を使用することが好ましい。白色度を更に効果的に上昇させることができる。２-メルカプトベンゾチアゾールの塩としては、Na塩、K塩、Zn塩及びCu塩などが例示できる。 As 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. Examples of the salt of 2-mercaptobenzothiazole include Na salt, K salt, Zn salt and Cu salt.
陰極電解処理は、前段と後段からなる二段処理とし、前段の電流密度を10A/dm2以上、後段の電流密度を10A/dm2未満とし、陰極電解処理する。さらに、後段の処理では鋼板表面に片面当たり0.1g/m2以上のめっき層を形成させる。 Cathodic electrolysis is a two-stage process consisting of a front stage and a rear stage. The current density of the front stage is 10 A / dm 2 or more and the current density of the rear stage is less than 10 A / dm 2 . Further, in the subsequent treatment, a plating layer of 0.1 g / m 2 or more per side is formed on the steel sheet surface.
前段の電流密度が10A/dm2未満では、長時間のめっき電解時間を要することになる。一方、後段の電流密度が10A/dm2以上では、十分な白色度が得られない。後段の処理を電流密度10A/dm2未満で行い、鋼板表面に片面当たり0.1g/m2以上のめっき層を形成させることにより、めっき処理後、かつ、化成処理後も高い白色度を有することになる。さらに、後段の処理は、全体での電流効率の観点から、めっき層全体の10％以下にあたる領域で行うことが好ましい。 If the current density in the previous stage is less than 10 A / dm 2 , a long plating electrolysis time is required. On the other hand, when the current density at the latter stage is 10 A / dm 2 or more, sufficient whiteness cannot be obtained. By performing the subsequent treatment at a current density of less than 10 A / dm 2 and forming a plating layer of 0.1 g / m 2 or more per side on the steel sheet surface, it should have high whiteness after the plating treatment and after the chemical conversion treatment. become. Furthermore, it is preferable to perform the subsequent processing in a region corresponding to 10% or less of the entire plating layer from the viewpoint of the overall current efficiency.
電気亜鉛めっき処理は、電気めっき浴中に前記有機化合物を前記濃度範囲で含有し、前述の二段処理することを除き、特に限定されない。例えば、電気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 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. For example, as the electroplating 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。
また、電気めっき浴中には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。
電気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、2.5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。
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.
In addition to Zn ions, 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. .
Other conditions for the electroplating 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 2.5 or less in consideration of bath conductivity. The total plating adhesion amount per side is not particularly limited, but is usually 5 to 40 g / m 2 .
なお、化成処理鋼板の製造において通常行われる、電気亜鉛めっき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 the process before performing electrogalvanization process normally performed in manufacture of a chemical conversion treatment steel plate, the degreasing process and water washing for cleaning the steel plate surface, and also the pickling process for activating the steel plate surface And can be washed with water. Following these pretreatments, electrogalvanization 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 acid concentration is not particularly specified, but it is preferably about 1 to 20 mass% in consideration of the ability to remove the oxide film, prevention of rough skin by peracid washing, and the like. 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。そして、化成処理皮膜は、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。例えば、P2O5換算で0.32mol/Lの第一リン酸、SiO2換算で0.50mol/Lのコロイダルシリカ、及び0.16mol/LのMnを含有する処理液をバーコーターで塗布した後、140℃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、本発明は、これらの処理を施した鋼板において高い白色度を有することを主たる目的とするため、このような化成処理を施した化成処理鋼板で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化成処理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 electrogalvanization treatment, chromate-free treatment (coating type, reaction type, electrolytic type) 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. And a chemical conversion treatment film is formed by the chromate-free chemical conversion treatment which performs the heat drying process which becomes 80-300 degreeC as steel plate temperature, for example, without apply | coating a chromate-free chemical conversion treatment liquid and washing with water. For example, after applying a treatment liquid containing 0.32 mol / L of primary phosphoric acid in terms of P 2 O 5 , 0.50 mol / L of colloidal silica in terms of SiO 2 , and 0.16 mol / L of Mn with a bar coater, A technique of drying at 140 ° 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, since this invention makes it the main objective to have high whiteness in the steel plate which performed these processes, the effect of this invention is exhibited to the maximum with the chemical conversion treatment steel plate which performed such a chemical conversion process. 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 has a high whiteness by using the chemical conversion treatment steel plate manufactured by the method of the present invention.
また、本発明の化成処理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 chemical conversion treatment steel plate of this invention can form the single layer or multiple layer coating film containing an organic resin on the surface of a chemical conversion treatment film according to a use. 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. Further, 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.
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および化３に示す有機化合物の種類および濃度で、鋼板を陰極として電気亜鉛めっき処理を行った。次いで、クロメートフリー処理を施し、化成処理鋼板を製造した。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めっき処理を実施した。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。また、上記クロメートフリー処理は、P2O5換算で0.32mol/Lの第一リン酸、SiO2換算で0.50mol/Lのコロイダルシリカ、及び0.16mol/LのMnを含有する処理液をバーコーターで塗布した後、140℃で乾燥させ、クロメートフリー処理皮膜（第一層）を形成した。Mnは第一リン酸塩で供給した。次に、第一層の上に、エポキシ系樹脂を含有する有機樹脂溶液を塗布し、140℃で焼付け、シリカ含有有機樹脂皮膜（第二層）を形成した。第一層、第二層の合計平均膜厚は0.5μmとした。
電解条件
有機物含有量、電流密度、浴温、pH：表1に示す
相対流速：1.5m/s
電極（陽極）：酸化イリジウム電極
以上より得られた化成処理鋼板に対して、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。また、電流効率を求め、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, under the following conditions, the types of organic compounds shown in Table 1 and Chemical Formula 3 and The electrogalvanizing treatment was performed using the steel sheet as the cathode at the concentration. Next, a chromate-free treatment was performed to produce a chemical conversion treated steel sheet. 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 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. In addition, the chromate-free treatment is performed using a treatment solution containing 0.32 mol / L primary phosphoric acid in terms of P 2 O 5 , 0.50 mol / L colloidal silica in terms of SiO 2 , and 0.16 mol / L Mn. After coating with a coater, it was dried at 140 ° C. to form a chromate-free treated film (first layer). Mn was supplied as the primary phosphate. Next, an organic resin solution containing an epoxy resin was applied on the first layer and baked at 140 ° C. to form a silica-containing organic resin film (second layer). The total average film thickness of the first layer and the second layer was 0.5 μm.
Electrolysis conditions Organic matter content, current density, bath temperature, pH: Relative flow rate shown in Table 1: 1.5 m / s
Electrode (Anode): Iridium Oxide Electrode The degree of whiteness was measured and evaluated based on the following measurement method and evaluation criteria for the chemical conversion treated steel sheet obtained as described above. In addition, the current efficiency was obtained and evaluated. 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。
＜めっきまま＞
◎：L値85以上
○：L値82以上、85未満
×：L値82未満
＜化成処理皮膜塗布後＞
◎：Ｌ値66以上
○：Ｌ値64以上、66未満
×：Ｌ値64未満
電流効率
亜鉛めっき付着量の値と、めっき時に通電した電気量から得られる理論値から、以下の式に従って、電流効率を求めた。
電流効率（％）＝（測定により得られた亜鉛めっき付着量）／（理論付着量）×100
◎：電流効率90%以上
○：電流効率85％以上、90%未満
×：電流効率85%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.
<As plated>
◎: L value 85 or more ○: L value 82 or more, less than 85 ×: L value less than 82 <After chemical conversion coating>
◎: L value of 66 or more ○: L value of 64 or more, less than 66 ×: L value of less than 64 Current efficiency From the theoretical value obtained from the value of galvanized adhesion amount and the amount of electricity energized during plating, We asked for efficiency.
Current efficiency (%) = (Amount of zinc plating obtained by measurement) / (Theoretical adhesion amount) x 100
◎: Current efficiency 90% or more ○: Current efficiency 85% or more, less than 90% ×: Current efficiency less than 85%
表１より、本発明例ではめっき処理後（めっきまま）および化成処理後のいずれにおいても、Ｌ値が高い、すなわち白色度が高い化成処理鋼板が効率良く得られているのがわかる。
一方、比較例では、Ｌ値が低い。
From Table 1, it can be seen that in the present invention example, a chemically treated steel sheet having a high L value, that is, high whiteness, is obtained efficiently both after plating (as plated) and after chemical conversion.
On the other hand, in the comparative example, the L value is low.
Claims (3)
前記前段では、電流密度を10A/dm2以上で陰極電解処理する。
前記後段では、電流密度を10A/dm2未満で陰極電解処理し、鋼板表面に片面当たり0.1g/m2以上のめっき層を形成する。 Electrogalvanizing treatment consisting of the following two-stage treatment in the electrogalvanizing bath containing 0.01 to 3 mass ppm of one or more organic compounds having 2-benzothiazolylthio group in total And then subjecting it to a chromate-free chemical conversion treatment.
In the previous stage, cathodic electrolysis is performed at a current density of 10 A / dm 2 or more.
In the latter stage, cathodic electrolysis is performed at a current density of less than 10 A / dm 2 to form a plating layer of 0.1 g / m 2 or more per side on the steel sheet surface.
に記載の化成処理鋼板の製造方法。 3. The organic compound having the 2-benzothiazolylthio group is 2-mercaptobenzothiazole or a salt of 2-mercaptobenzothiazole.
The manufacturing method of the chemical conversion treatment steel plate of description.
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