JP2009174010A - Chemical conversion treated steel sheet - Google Patents
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- JP2009174010A JP2009174010A JP2008014272A JP2008014272A JP2009174010A JP 2009174010 A JP2009174010 A JP 2009174010A JP 2008014272 A JP2008014272 A JP 2008014272A JP 2008014272 A JP2008014272 A JP 2008014272A JP 2009174010 A JP2009174010 A JP 2009174010A
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本発明は、化成処理鋼板に関する。 The present invention relates to a chemical conversion treated steel sheet.
めっき層にＺｎを含む亜鉛系めっき鋼板は、建材、自動車、家電などの各分野で幅広く使用されている。特に、クロメート処理がなされた亜鉛系めっき鋼板は、耐食性、塗膜との密着性、フィルムとの密着性に優れることから、当該鋼板の上に樹脂フィルムをラミネートしたラミネート鋼板として、家電製品の筐体等の外観が重視される用途に使用されている。 Zinc-based plated steel sheets containing Zn in the plating layer are widely used in various fields such as building materials, automobiles, and home appliances. In particular, zinc-plated steel sheets that have been chromate-treated have excellent corrosion resistance, adhesion to coating films, and adhesion to films. Therefore, laminated steel sheets in which resin films are laminated on the steel sheets are used as housings for home appliances. Used in applications where the appearance of the body is important.
ところで、近年、環境適合性の観点からクロメート処理に代わり、非クロム系処理が行われるようなってきた。例えば特許文献１には、めっき鋼板にリン酸塩皮膜が形成された化成処理鋼板が開示されている。
しかしながら、非クロム系処理を施した亜鉛めっき鋼板に塩化ビニル樹脂フィルムをラミネートしたラミネート鋼板は、クロメート処理が施された亜鉛めっき鋼板に塩化ビニル樹脂フィルムをラミネートした鋼板に比べて、フィルム密着性が劣るという問題があった。この点を改善するために、特許文献２には、リン酸塩皮膜の厚みおよびリン酸塩結晶サイズを特定の範囲に調整してなる化成処理鋼板が開示されている。この構成により、化成処理鋼板とフィルムとの密着性が向上するとされているが、その機構については一切開示がない。
However, a laminated steel sheet in which a vinyl chloride resin film is laminated on a zinc-plated steel sheet that has been subjected to non-chromium treatment has film adhesion compared to a steel sheet in which a vinyl chloride resin film is laminated on a zinc-plated steel sheet that has been subjected to chromate treatment. There was a problem of being inferior. In order to improve this point, Patent Document 2 discloses a chemical conversion treated steel sheet in which the thickness of the phosphate film and the phosphate crystal size are adjusted to a specific range. Although this structure is supposed to improve the adhesion between the chemical conversion treated steel sheet and the film, there is no disclosure about the mechanism.
発明者らは、非クロム系処理を施した亜鉛系めっき鋼板と、樹脂との密着性について予備的に検討した。その結果、特許文献２に開示のラミネート鋼板や、公知の方法で非クロム処理された亜鉛系めっき鋼板を用いたラミネート鋼板は、高温多湿の環境で使用した際に、塗膜との密着性、フィルムとの密着性が不十分となることを見出した。さらに、発明者らは、高温多湿下におけるフィルムや接着剤や塗膜との密着性（以下単に「樹脂層との密着性」ともいう）の低下の原因が、化成処理皮膜とめっき層表面との密着性不足に起因していることを見出した。 The inventors preliminarily examined the adhesion between the zinc-based plated steel sheet subjected to the non-chromium treatment and the resin. As a result, the laminated steel sheet disclosed in Patent Document 2 and the laminated steel sheet using a zinc-based plated steel sheet that has been non-chromed by a known method, when used in a high-temperature and high-humidity environment, It has been found that the adhesion with the film is insufficient. Furthermore, the inventors have found that the cause of the decrease in adhesion with a film, an adhesive or a coating film under high temperature and humidity (hereinafter also simply referred to as “adhesion with a resin layer”) is the chemical conversion treatment film and the plating layer surface. It was found that this was caused by insufficient adhesion.
従って、樹脂層との密着性に優れた化成処理鋼板からなるラミネート鋼板または塗装鋼板（以下ラミネート鋼板または塗装鋼板を合わせて「ラミネート鋼板等」ともいう）が望まれていたものの、このような化成処理鋼板またはラミネート鋼板等は提案されてこなかった。
かかる事情に鑑み、本発明は、樹脂層との密着性に優れた化成処理鋼板、およびこれを用いてなるラミネート鋼板または塗装鋼板を提供することを目的とする。
Therefore, although a laminated steel plate or a coated steel plate (hereinafter also referred to as a “laminated steel plate or the like” together with a laminated steel plate or a coated steel plate) made of a chemically treated steel plate having excellent adhesion to the resin layer is desired, such a chemical conversion steel plate is desired. No treated steel sheets or laminated steel sheets have been proposed.
In view of such circumstances, an object of the present invention is to provide a chemical conversion treated steel sheet having excellent adhesion to a resin layer, and a laminated steel sheet or a coated steel sheet using the chemical conversion treated steel sheet.
発明者らは、鋭意研究の結果、亜鉛系めっき鋼板に特定の化成処理を施した化成処理鋼板が上記課題を解決できることを見出し、本発明を完成させた。
すなわち、上記課題は、以下の本発明により解決される。
As a result of intensive studies, the inventors have found that a chemical conversion treated steel sheet obtained by subjecting a zinc-based plated steel sheet to a specific chemical conversion treatment can solve the above problems, and have completed the present invention.
That is, the said subject is solved by the following this invention.
［１］Ｚｎを含むめっき層を有する亜鉛系めっき鋼板と、前記めっき層の上に設けられた化成処理皮膜を含む化成処理鋼板であって、
前記めっき層は、表面に、Ｆｅ、ＣｏおよびＮｉから選ばれる１種以上の金属および前記金属の酸化物を有し、
前記化成処理皮膜は、バルブメタル酸化物または水酸化物と、多価フェノール化合物を含む、化成処理鋼板。
［２］前記化成処理皮膜は、単位面積当たりのバルブメタル元素の含有量が１〜１５０ｍｇ／ｍ２であり、かつ、前記多価フェノール化合物と前記バルブメタル元素の質量比が１〜１５である、［１］に記載の化成処理鋼板。
［３］前記多価フェノール化合物は、タンニンまたはタンニン酸類である［１］または［２］に記載の化成処理鋼板。
［４］前記バルブメタル酸化物または水酸化物は、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、Ｎｂ、Ｔａ、ＭｏおよびＷから選ばれた１種以上のバルブメタルの酸化物または水酸化物である、［１］〜［３］いずれかに記載の化成処理鋼板。
［５］前記めっき層は、ＡｌおよびＭｇをさらに含む、［１］〜［４］いずれかに記載の化成処理鋼板。
［６］前記［１］に記載の化成処理鋼板を含むラミネート鋼板または塗装鋼板。
［７］前記［１］に記載の化成処理鋼板を製造する方法であって、
（Ａ）亜鉛系めっき鋼板を準備する工程と、
（Ｂ）前記鋼板のめっき層表面にＦｅ、ＣｏおよびＮｉから選ばれる１種以上の金属、または前記金属の酸化物を形成する表面調整工程と、
（Ｃ）前記表面調整工程で得た鋼板に、バルブメタル化合物と多価フェノール化合物を含む化成処理液を塗布して乾燥させる工程を含む、化成処理皮膜の製造方法。
[1] A zinc-based plated steel sheet having a plated layer containing Zn, and a chemical conversion-treated steel sheet including a chemical conversion film provided on the plated layer,
The plating layer has at least one metal selected from Fe, Co, and Ni and an oxide of the metal on the surface,
The said chemical conversion treatment film is a chemical conversion treatment steel plate containing a valve metal oxide or a hydroxide, and a polyhydric phenol compound.
[2] The chemical conversion treatment film has a valve metal element content of 1 to 150 mg / m 2 per unit area, and a mass ratio of the polyhydric phenol compound and the valve metal element of 1 to 15. The chemical conversion treated steel sheet according to [1].
[3] The chemical conversion treated steel sheet according to [1] or [2], wherein the polyhydric phenol compound is tannin or tannic acid.
[4] The valve metal oxide or hydroxide is one or more valve metal oxides or hydroxides selected from Ti, Zr, Hf, V, Nb, Ta, Mo and W. [ The chemical conversion treated steel sheet according to any one of [1] to [3].
[5] The chemical conversion treated steel sheet according to any one of [1] to [4], wherein the plating layer further includes Al and Mg.
[6] A laminated steel sheet or a coated steel sheet including the chemical conversion treated steel sheet according to [1].
[7] A method for producing the chemical conversion treated steel sheet according to [1],
(A) preparing a galvanized steel sheet;
(B) a surface conditioning step of forming one or more metals selected from Fe, Co and Ni on the surface of the plated layer of the steel sheet, or an oxide of the metal;
(C) The manufacturing method of a chemical conversion treatment film including the process of apply | coating and drying the chemical conversion liquid containing a valve metal compound and a polyhydric phenol compound to the steel plate obtained at the said surface adjustment process.
本発明により、樹脂層との密着性に優れた化成処理鋼板、およびこれを用いてなるラミネート鋼板または塗装鋼板を提供できる。 ADVANTAGE OF THE INVENTION By this invention, the chemical conversion treatment steel plate excellent in adhesiveness with a resin layer, and the laminated steel plate or coated steel plate using this can be provided.
１．化成処理鋼板
化成処理鋼板とは鋼板表面に化成処理が施された鋼板である。本発明の化成処理鋼板はＺｎを含むめっき層を有する亜鉛系めっき鋼板と、前記めっき層の上に設けられた化成処理皮膜を含む。前記めっき層は、表面に、Ｆｅ、ＣｏおよびＮｉから選ばれる１種以上の金属および前記金属の酸化物を有し、前記化成処理皮膜は、バルブメタル酸化物または水酸化物と、多価フェノール化合物を含むことを特徴とする。めっき層とは、鋼板の上にめっきにより形成される金属層である。
1. Chemical conversion treated steel sheet A chemical conversion treated steel sheet is a steel sheet whose surface is subjected to chemical conversion treatment. The chemical conversion treated steel sheet of the present invention includes a zinc-based plated steel sheet having a plated layer containing Zn and a chemical conversion film provided on the plated layer. The plating layer has at least one metal selected from Fe, Co, and Ni and an oxide of the metal on the surface, and the chemical conversion film includes a valve metal oxide or a hydroxide and a polyhydric phenol. It is characterized by including a compound. A plating layer is a metal layer formed by plating on a steel plate.
（１）亜鉛系めっき鋼板
本発明の亜鉛系めっき鋼板（以下単に「めっき鋼板」ともいう）は、Ｚｎ含むめっき層、またはＺｎとＺｎ以外の金属を含むめっき層を有する。ＺｎとＺｎ以外の金属を含むめっき層の例には、Ｚｎ−Ｍｇめっき層、Ｚｎ−Ａｌめっき層、Ｚｎ−Ｎｉめっき層およびＺｎ−Ａｌ−Ｍｇめっき層が含まれる。本発明の亜鉛系めっき鋼板は、電気めっき、溶融めっき、または蒸着めっき等を施して得られる。また、本発明の亜鉛系めっき鋼板には、溶融めっきした後に、加熱して合金化処理を施した合金化亜鉛めっき鋼板も含まれる。
(1) Zinc-based plated steel sheet The zinc-based plated steel sheet of the present invention (hereinafter also simply referred to as “plated steel sheet”) has a plated layer containing Zn or a plated layer containing a metal other than Zn and Zn. Examples of the plating layer containing Zn and a metal other than Zn include a Zn—Mg plating layer, a Zn—Al plating layer, a Zn—Ni plating layer, and a Zn—Al—Mg plating layer. The zinc-based plated steel sheet of the present invention is obtained by performing electroplating, hot dipping, vapor deposition plating or the like. Moreover, the galvanized steel sheet of the present invention includes an alloyed galvanized steel sheet that has been hot-plated and then subjected to an alloying treatment.
本発明のめっき鋼板としては、溶融Ｚｎ−Ａｌ−Ｍｇめっき浴を用いて製造された溶融Ｚｎ−Ａｌ−Ｍｇめっき鋼板が好ましい。後述するように、本発明の化成処理液がフッ素化合物を含有する場合に、めっき層表面にＡｌおよびＭｇのフッ化物を含む反応層が形成され、化成処理皮膜とめっき層表面との密着力をより高められるからである。 As the plated steel sheet of the present invention, a molten Zn—Al—Mg plated steel sheet produced using a molten Zn—Al—Mg plating bath is preferable. As will be described later, when the chemical conversion treatment liquid of the present invention contains a fluorine compound, a reaction layer containing Al and Mg fluoride is formed on the plating layer surface, and the adhesion between the chemical conversion treatment film and the plating layer surface is improved. This is because it can be further enhanced.
溶融Ｚｎ−Ａｌ−Ｍｇめっき鋼板は公知の方法で得てよいが、Ａｌを２．５〜１５質量％、Ｍｇを２．０〜４．０質量％含み、残部が実質的にＺｎである合金めっき浴を用いた溶融めっき法で製造されることが好ましい。また、外観および耐食性に悪影響を与えるＺｎ１１Ｍｇ２相の生成・成長を抑制するためにＴｉ、Ｂ、Ｔｉ−Ｂ合金またはＴｉ、Ｂ含有化合物をめっき浴に添加することがより好ましい。これらの金属または化合物の添加量は、めっき浴に対し、金属換算にして、Ｔｉが０．００１〜０．１質量％、Ｂが０．００１〜０．０４５質量％とすることが好ましい。Ｔｉ、Ｂが過剰であると、めっき層に析出物が生成することがある。さらに、加工時の素地鋼とめっき層との密着性を向上させるため、めっき層と素地鋼との界面におけるＡｌ−Ｆｅ合金層の成長を抑制する作用のあるＳｉを０．００５〜０．５質量％の範囲で添加してもよい。 A hot-dip Zn—Al—Mg plated steel sheet may be obtained by a known method, but an alloy containing 2.5 to 15% by mass of Al and 2.0 to 4.0% by mass of Mg, with the balance being substantially Zn. It is preferable to manufacture by a hot dipping method using a plating bath. Further, it is more preferable to add Ti, B, Ti—B alloy or Ti, B-containing compound to the plating bath in order to suppress the formation and growth of the Zn 11 Mg 2 phase which adversely affects the appearance and corrosion resistance. The addition amount of these metals or compounds is preferably 0.001 to 0.1% by mass of Ti and 0.001 to 0.045% by mass of B in terms of metal with respect to the plating bath. When Ti and B are excessive, precipitates may be generated in the plating layer. Furthermore, in order to improve the adhesion between the base steel and the plating layer during processing, Si having an action of suppressing the growth of the Al—Fe alloy layer at the interface between the plating layer and the base steel is 0.005 to 0.5. You may add in the range of the mass%.
本発明の亜鉛系めっき鋼板は、表面にＦｅ、ＣｏおよびＮｉから選ばれる１種以上の金属、または前記金属の酸化物が形成されている。以下、Ｆｅ、ＣｏおよびＮｉから選ばれる１種以上の金属を「Ｎｉ等」と、Ｆｅ、ＣｏおよびＮｉから選ばれる１種以上の金属の酸化物を「Ｎｉ酸化物等」と呼ぶことがある。また、表面にＮｉ等およびＮｉ酸化物等が形成されていることを「表面調整がなされている」ということがある。
表面に「Ｎｉ等」または「Ｎｉ酸化物等」を形成する方法は特に限定されないが、公知の方法に準じて行うことが好ましい（例えば特開２００４−２３８６９９号公報）。本発明においては、Ｆｅ、ＣｏまたはＮｉを含む硫酸塩水溶液、あるいはＦｅ、ＣｏまたはＮｉを含む硝酸水溶液をめっき鋼板に塗布した後に、水洗して乾燥することが好ましい。前記水溶液を塗布する方法も特に限定されないが、水溶液をめっき鋼板表面にスプレーする方法や、水溶液にめっき鋼板を浸漬して行えばよい。
In the galvanized steel sheet of the present invention, one or more metals selected from Fe, Co and Ni, or oxides of the metals are formed on the surface. Hereinafter, one or more metals selected from Fe, Co, and Ni may be referred to as “Ni”, and an oxide of one or more metals selected from Fe, Co, and Ni may be referred to as “Ni oxides”. . Further, the formation of Ni or the like and Ni oxide or the like on the surface may be referred to as “surface adjustment being made”.
The method of forming “Ni etc.” or “Ni oxide etc.” on the surface is not particularly limited, but it is preferably carried out according to a known method (for example, JP-A-2004-238699). In the present invention, it is preferable to apply a sulfate aqueous solution containing Fe, Co or Ni, or a nitric acid aqueous solution containing Fe, Co or Ni to the plated steel sheet, and then wash and dry it. The method of applying the aqueous solution is not particularly limited, but may be performed by spraying the aqueous solution on the surface of the plated steel plate or by immersing the plated steel plate in the aqueous solution.
めっき層表面に存在するＮｉ等は、めっき層の主成分であるＺｎよりも貴であるため、Ｚｎが溶出しやすくなり、めっき層表面がエッチングされる。その結果、めっき層表面積が大きくなり、めっき層表面の上に形成される化成処理皮膜との密着性が向上する。またＮｉ等はＺｎより表面電位が高いため、極性基を有する多価フェノール化合物との親和性が高い。よって、本発明のめっき層は化成処理皮膜との密着性により優れる。 Since Ni or the like present on the surface of the plating layer is noble than Zn which is the main component of the plating layer, Zn is easily eluted and the surface of the plating layer is etched. As a result, the plating layer surface area is increased, and the adhesion with the chemical conversion film formed on the plating layer surface is improved. Further, since Ni and the like have a higher surface potential than Zn, the affinity for polyhydric phenol compounds having a polar group is high. Therefore, the plating layer of this invention is excellent by adhesiveness with a chemical conversion treatment film.
Ｎｉ、ＦｅまたはＣｏの酸化物における２価のＮｉ、ＦｅまたはＣｏは、Ｚｎより配位結合の安定性が高い。従って、これらの金属は、化成処理膜中のフェノール化合物と強固なキレートを形成するものと推察される。本発明では後述するとおり、分子内に２以上の多価フェノール化合物を用いるため、より強固なキレートが生成する。以上から、本発明の化成処理鋼板はめっき層と化成処理膜の密着性に優れる。めっき層表面のＦｅ、ＣｏまたはＮｉの状態はＥＳＣＡ分析により確認できる。 Divalent Ni, Fe or Co in the oxide of Ni, Fe or Co has higher coordination bond stability than Zn. Therefore, it is inferred that these metals form a strong chelate with the phenol compound in the chemical conversion film. In the present invention, as described later, since two or more polyhydric phenol compounds are used in the molecule, a stronger chelate is generated. As mentioned above, the chemical conversion treatment steel plate of this invention is excellent in the adhesiveness of a plating layer and a chemical conversion treatment film. The state of Fe, Co or Ni on the plating layer surface can be confirmed by ESCA analysis.
また、Ｎｉ等とＮｉ酸化物等の合計の付着量は、金属元素換算にして０．１〜５０ｍｇ／ｍ２であることが好ましい。前記付着量が０．１ｍｇ／ｍ２未満であると、化成処理皮膜とめっき層表面との密着性が十分でないことがある。前記付着量が、５０ｍｇ／ｍ２を超えると、めっき層表面のＮｉ等の量が多くなりすぎ、めっき層成分の溶出が顕著になるため裸耐食性が低下することがある。裸耐食性とはめっき鋼板や化成処理鋼板の耐食性である。本発明においては、ラミネート鋼板等の耐食性と区別するために、めっき鋼板や化成処理鋼板の耐食性を裸耐食性と呼ぶことがある。Ｎｉ等とＮｉ酸化物等の合計の付着量は、前記水溶液中のＮｉ等の濃度や、処理温度および処理時間により制御できる。Ｎｉ等とＮｉ酸化物等の合計の付着量は、ＩＣＰ分析等により確認できる。 Moreover, it is preferable that the total adhesion amount of Ni etc. and Ni oxide etc. is 0.1-50 mg / m < 2 > in conversion of a metal element. When the adhesion amount is less than 0.1 mg / m 2, the adhesion between the chemical conversion film and the plating layer surface may not be sufficient. When the adhesion amount exceeds 50 mg / m 2 , the amount of Ni or the like on the surface of the plating layer becomes excessive, and the elution of the plating layer components becomes remarkable, so that the bare corrosion resistance may be lowered. Bare corrosion resistance is the corrosion resistance of a plated steel sheet or a chemically treated steel sheet. In the present invention, in order to distinguish from the corrosion resistance of laminated steel sheets and the like, the corrosion resistance of plated steel sheets and chemical conversion treated steel sheets may be referred to as bare corrosion resistance. The total adhesion amount of Ni or the like and Ni oxide or the like can be controlled by the concentration of Ni or the like in the aqueous solution, the processing temperature and the processing time. The total adhesion amount of Ni or the like and Ni oxide or the like can be confirmed by ICP analysis or the like.
（２）化成処理皮膜
本発明の化成処理皮膜は多価フェノール化合物を含む。多価フェノール化合物とは、分子内にフェノール性水酸基を２以上含む化合物をいう。本発明の多価フェノール化合物は、その水酸基が、後述するとおり、バルブメタル水酸化物等の他の化合物と縮合して化成処理皮膜に存在することがある。よって、本発明において「化成処理皮膜は多価フェノール化合物を含む」とは、化成処理皮膜中に多価フェノール化合物が他の化合物と縮合して存在していることも意味する。
(2) Chemical conversion coating The chemical conversion coating of the present invention contains a polyhydric phenol compound. A polyhydric phenol compound refers to a compound containing two or more phenolic hydroxyl groups in the molecule. In the polyhydric phenol compound of the present invention, the hydroxyl group thereof may be present in the chemical conversion film by condensation with other compounds such as valve metal hydroxide, as will be described later. Therefore, in the present invention, “the chemical conversion film contains a polyphenol compound” also means that the polyphenol compound is present in the chemical conversion film in a condensed state with other compounds.
多価フェノール化合物の例には、タンニン、タンニン酸類、ハイドロキノン、カテコール、フロログルシノール、カテキン類、ロイコアントシアニン類、およびクロロゲン類が含まれる。中でも、本発明の多価フェノール化合物としては、タンニンまたはタンニン酸類が好適である。多価フェノール化合物は前述の通り、めっき層との密着性に優れるが、特にタンニンまたはタンニン酸類は、化成処理皮膜の上に形成される樹脂層との密着性により優れるからである。 Examples of the polyhydric phenol compound include tannin, tannic acids, hydroquinone, catechol, phloroglucinol, catechins, leucoanthocyanins, and chlorogens. Of these, tannin or tannic acids are preferred as the polyhydric phenol compound of the present invention. This is because, as described above, the polyhydric phenol compound is excellent in adhesion to the plating layer, and in particular, tannin or tannic acid is excellent in adhesion to the resin layer formed on the chemical conversion film.
タンニンとは、植物界に分布する多数のフェノール性水酸基を有する芳香族化合物をいう。タンニンは、フラバノール骨格が重合した縮合型タンニンと、加水分解して生成した芳香族有機酸が糖とデプシド結合してなる加水分解型タンニンがあるが、本発明においてはいずれを用いてもよく、これらの一部が加水分解されたものを用いてもよい。
タンニン酸とは、ｍ−ガロイル没食子酸であり、タンニンを加水分解して得られる。タンニン酸類とは、ｍ−ガロイル没食子酸またはこの誘導体をいう。タンニンとタンニン酸類を合わせて、以下「タンニン等」ということがある。タンニン等は、化成処理皮膜の上に塗布される接着剤等の樹脂層が極性基を有する場合に、樹脂層と極めて良好な密着性を示す。タンニン等には、結晶状のものや樹脂状のものが存在するが、いずれも分子量が高いため、化成処理皮膜において膜のマトリックスを形成する。
カテキンとは、３，３’，４’，５，７−ペンタヒドロキシフラバンであり、カテキン類とはその誘導体をいう。
Tannin refers to an aromatic compound having a large number of phenolic hydroxyl groups distributed in the plant kingdom. Tannins include condensed tannins obtained by polymerizing flavanol skeletons and hydrolyzed tannins in which aromatic organic acids produced by hydrolysis are depside-bonded to sugars, and any of them may be used in the present invention. You may use what some of these hydrolyzed.
Tannic acid is m-galloyl gallic acid and is obtained by hydrolyzing tannin. Tannic acid refers to m-galloyl gallic acid or a derivative thereof. Tannins and tannic acids may be collectively referred to as “tannins” hereinafter. Tannin and the like exhibit extremely good adhesion to the resin layer when the resin layer such as an adhesive applied on the chemical conversion film has a polar group. There are crystalline and resinous tannins, but all of them have a high molecular weight, so that a film matrix is formed in the chemical conversion coating.
Catechin is 3,3 ′, 4 ′, 5,7-pentahydroxyflavan, and catechins are derivatives thereof.
本発明の化成処理皮膜は、バルブメタルの酸化物または水酸化物を含む。バルブメタルとは、一般に、その酸化物が高絶縁性で整流作用を示す金属をいう。バルブメタルの酸化物または水酸化物（以下「バルブメタル酸化物等」ともいう）は、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、Ｎｂ、Ｔａ、ＭｏおよびＷから選ばれた１種以上のバルブメタルの酸化物または水酸化物であることが好ましい。バルブメタル酸化物等は、高い絶縁性を有するため電子の移動を妨げる。よって、バルブメタル酸化物等を含む本発明の化成処理皮膜は、化成処理鋼板が置かれている雰囲気中の水分に含まれている溶存酸素と、めっき層や下地鋼との酸化反応を抑制し、めっき鋼板の裸耐食性を向上させる。前記表面調整が施されためっき鋼板は、めっき層表面が活性であるため、裸耐食性が十分でないことが懸念されるが、本発明の化成処理鋼板は、前記の通りバルブメタル酸化物等を含む化成処理皮膜を有し、かつ化成処理皮膜とめっき層表面が強固に密着しているため裸耐食性に優れる。裸耐食性に優れた化成処理鋼板は、化成処理皮膜の上に形成される樹脂層との密着性、特に高温高湿下にさらされた際の密着性に優れる。 The chemical conversion film of the present invention contains a valve metal oxide or hydroxide. The valve metal generally refers to a metal whose oxide is highly insulating and exhibits a rectifying action. The valve metal oxide or hydroxide (hereinafter also referred to as “valve metal oxide”) is an oxidation of one or more valve metals selected from Ti, Zr, Hf, V, Nb, Ta, Mo, and W. It is preferable that it is a thing or a hydroxide. Valve metal oxides and the like have high insulating properties and thus hinder movement of electrons. Therefore, the chemical conversion coating of the present invention containing valve metal oxide or the like suppresses the oxidation reaction between dissolved oxygen contained in the moisture in the atmosphere where the chemical conversion processed steel plate is placed and the plating layer or the base steel. , Improve the bare corrosion resistance of the plated steel sheet. Although the plated steel sheet subjected to the surface adjustment has an active plating layer surface, there is a concern that the bare corrosion resistance is not sufficient, but the chemical conversion treated steel sheet of the present invention includes a valve metal oxide or the like as described above. Since it has a chemical conversion treatment film and the chemical conversion treatment film and the plating layer surface are in close contact with each other, it has excellent bare corrosion resistance. A chemically treated steel sheet having excellent bare corrosion resistance is excellent in adhesion to a resin layer formed on a chemically treated film, particularly when exposed to high temperature and high humidity.
また、バルブメタル水酸化物は、加熱等により化成処理皮膜に含まれる多価フェノール化合物と脱水縮合反応できるため、緻密でバリアー性の高い化成処理皮膜を形成できる。
さらに、化成処理皮膜の多価フェノール化合物は有機化合物であるため、化成処理鋼板の上に形成される樹脂層との密着性にも優れる。
Further, since the valve metal hydroxide can be dehydrated and condensed with a polyhydric phenol compound contained in the chemical conversion treatment film by heating or the like, a dense chemical conversion treatment film having a high barrier property can be formed.
Furthermore, since the polyhydric phenol compound of the chemical conversion treatment film is an organic compound, the adhesiveness with the resin layer formed on the chemical conversion treatment steel plate is also excellent.
すなわち、本発明の化成処理鋼板は、バリアー性の高い化成処理皮膜を有し、当該化成処理皮膜とめっき層表面、および樹脂層の親和性に優れるため、化成処理鋼板の上に形成される樹脂層との密着性、特に高温高湿下における前記樹脂層との密着性に優れる。 That is, the chemical conversion treatment steel sheet of the present invention has a chemical conversion treatment film having a high barrier property, and is excellent in the affinity between the chemical conversion treatment film, the plating layer surface, and the resin layer. It is excellent in adhesiveness with the layer, particularly adhesiveness with the resin layer under high temperature and high humidity.
後述するとおり、バルブメタル水酸化物は、他の化合物と縮合して化成処理皮膜に存在しうる。よって、本発明において「化成処理皮膜がバルブメタル水酸化物を含む」とは、化成処理皮膜中にバルブメタル水酸化物が他の化合物と縮合して存在していることも意味する。 As will be described later, the valve metal hydroxide may be present in the chemical conversion film by condensing with other compounds. Therefore, in the present invention, “the chemical conversion treatment film contains a valve metal hydroxide” also means that the valve metal hydroxide is condensed with other compounds in the chemical conversion treatment film.
本発明の化成処理皮膜にバルブメタル酸化物等を含ませる方法は特に限定されない。例えば、所望の量のバルブメタル酸化物またはバルブメタル水酸化物を含む化成処理液を調製して、これをめっき鋼板に塗布して乾燥させればよい。しかしながら、本発明においては、バルブメタル元素を含むバルブメタル化合物を含む化成処理液を調製し、これを表面調整されためっき鋼板に塗布して乾燥させ、この間にバルブメタル化合物をバルブメタル酸化物またはバルブメタル水酸化物に化学変化させることが好ましい。この方法で製造された化成処理鋼板は、その上に接着される樹脂層とめっき鋼板の密着性に極めて優れるからである。 The method for including valve metal oxide or the like in the chemical conversion film of the present invention is not particularly limited. For example, a chemical conversion treatment solution containing a desired amount of valve metal oxide or valve metal hydroxide may be prepared, applied to a plated steel sheet, and dried. However, in the present invention, a chemical conversion treatment solution containing a valve metal compound containing a valve metal element is prepared, and this is applied to a surface-conditioned plated steel sheet and dried, during which the valve metal compound is added to the valve metal oxide or It is preferable to chemically change to valve metal hydroxide. It is because the chemical conversion treatment steel plate manufactured by this method is very excellent in the adhesiveness of the resin layer adhere | attached on it and a plating steel plate.
この理由は次のように推察される。
化成処理時には、めっき層からのめっき成分の溶出にともない電子が放出される。当該電子は、バルブメタル化合物よりも、化成処理液中の水素イオンを主として還元する。その結果、めっき層と化成処理液の界面におけるｐＨは上昇する。よって、バルブメタル化合物の一部は水酸化物となる。バルブメタル水酸化物は、化成処理における乾燥過程で加熱され、多価フェノール化合物と脱水縮合反応する。よって密でバリアー性の高い化成処理皮膜が形成される。さらに、化成処理液中のバルブメタル化合物の一部は、前記処理において酸化物となるため、前述の通り、高い絶縁性を化成処理皮膜に付与する。
The reason is presumed as follows.
During the chemical conversion treatment, electrons are emitted as the plating components are eluted from the plating layer. The electrons mainly reduce hydrogen ions in the chemical conversion solution rather than the valve metal compound. As a result, the pH at the interface between the plating layer and the chemical conversion solution increases. Therefore, a part of the valve metal compound becomes a hydroxide. The valve metal hydroxide is heated during the drying process in the chemical conversion treatment, and undergoes a dehydration condensation reaction with the polyhydric phenol compound. Therefore, a dense chemical conversion film having a high barrier property is formed. Furthermore, since a part of the valve metal compound in the chemical conversion treatment liquid becomes an oxide in the treatment, as described above, high insulation is imparted to the chemical conversion treatment film.
従来、表面調整がなされためっき層表面に、本発明以外の非クロム系化成処理が施された化成処理鋼板（以下単に「従来の非クロム系化成処理鋼板」ともいう）は、表面調整がなされためっき層表面にクロメート処理が施された化成処理鋼板（以下単に「クロメート化成処理鋼板」ともいう）に比べて、裸耐食性が劣るとされてきた。これは、クロメート化成処理鋼板は、化成処理おいて放出された電子が６価クロムを３価クロムに還元し、化成処理皮膜中に難溶性の三価Ｃｒ化合物を形成するのに対し、従来の非クロム系化成処理鋼板は、前記電子により裸耐食性の向上に寄与する化合物を生成しないからであると考えられる。
しかし、本発明の化成処理鋼板は、上記の通り、放出された電子に起因して、裸耐食性の向上に寄与するバルブメタル水酸化物が生成されるため、従来の非クロム系化成処理鋼板とは異なり、優れた裸耐食性を有する。ただし、メカニズムはこれに限定されない。
Conventionally, a surface-adjusted steel sheet (hereinafter simply referred to as “conventional non-chromium chemical conversion treated steel sheet”) in which the surface of the plated layer is subjected to non-chromium chemical conversion treatment other than the present invention is subjected to surface adjustment. It has been considered that the bare corrosion resistance is inferior to that of a chemically treated steel sheet (hereinafter also referred to simply as a “chromated chemically treated steel sheet”) whose surface is plated with a chromate layer. This is because, in the chromate chemical conversion treated steel plate, the electrons emitted in the chemical conversion treatment reduce hexavalent chromium to trivalent chromium, and form a hardly soluble trivalent Cr compound in the chemical conversion treatment film. It is considered that the non-chromium chemical conversion treated steel sheet does not generate a compound that contributes to improvement of bare corrosion resistance by the electrons.
However, the chemical conversion treated steel sheet according to the present invention, as described above, is caused by the emitted electrons to generate valve metal hydroxide that contributes to the improvement of bare corrosion resistance. Is different and has excellent bare corrosion resistance. However, the mechanism is not limited to this.
本発明で用いられるバルブメタル化合物の好ましい例には、以下の化合物が含まれる。
Ｈ２ＴｉＦ6、ＫnＴｉＦ6（Ｋはアルカリ金属またはアルカリ土類金属であり、ｎは１または２である）、Ｋ2[ＴｉＯ(ＣＯＯ)2]、(ＮＨ4)2ＴｉＦ6、ＴｉＣｌ4、ＴｉＯＳＯ4、Ｔｉ(ＳＯ4)2、Ｔｉ(ＯＨ)4等のＴｉ化合物。
Preferred examples of the valve metal compound used in the present invention include the following compounds.
H 2 TiF 6 , K n TiF 6 (K is an alkali metal or alkaline earth metal, n is 1 or 2), K 2 [TiO (COO) 2 ], (NH 4 ) 2 TiF 6 , TiCl 4 , Ti compounds such as TiOSO 4 , Ti (SO 4 ) 2 , and Ti (OH) 4 .
Ｈ２ＺｒＦ6、(ＮＨ4)2ＺｒＦ6、Ｚｒ(ＳＯ4)2、（ＮＨ４）２ＺｒＯ（ＣＯ３）２等のＺｒ化合物。 Zr compounds such as H 2 ZrF 6 , (NH 4 ) 2 ZrF 6 , Zr (SO 4 ) 2 , (NH 4 ) 2 ZrO (CO 3 ) 2 .
（ＮＨ４）６Ｍｏ７Ｏ２４、Ｋ２（ＭｏＯ２Ｆ４）等のＭｏ化合物。 Mo compounds such as (NH 4 ) 6 Mo 7 O 24 and K 2 (MoO 2 F 4 ).
その他、（ＮＨ４）２ＶＯ３、Ｎａ２ＷＯ４（ＮＨ４）２ＴｉＦ６、ＴｉＯＳＯ４ＶＦ４、Ｋ５ＮｂＦ７等の化合物。 Other compounds such as (NH 4 ) 2 VO 3 , Na 2 WO 4 (NH 4 ) 2 TiF 6 , TiOSO 4 VF 4 , K 5 NbF 7 and the like.
この中でも入手の容易さ等から、バルブメタル化合物としては、Ｈ２ＴｉＦ6、(ＮＨ4)2ＴｉＦ6、Ｔｉ(ＳＯ4)2、Ｈ２ＺｒＦ6、Ｚｒ(ＳＯ4)2、Ｋ２（ＭｏＯ２Ｆ４）、または（ＮＨ４）２ＶＯ３がより好ましい。バルブメタル化合物として、前記の化合物を２種以上併用してもよい。 Among these, as a valve metal compound, H 2 TiF 6 , (NH 4 ) 2 TiF 6 , Ti (SO 4 ) 2 , H 2 ZrF 6 , Zr (SO 4 ) 2 , K 2 ( MoO 2 F 4 ) or (NH 4 ) 2 VO 3 is more preferable. Two or more of the above compounds may be used in combination as the valve metal compound.
本発明の化成処理皮膜における、単位面積当たりのバルブメタル元素の含有量は、１〜１５０ｍｇ／ｍ２であることが好ましい。単位面積当たりのバルブメタル元素の含有量は、単位面積当たりのバルブメタル酸化物等の含有量の金属換算量と同義である。前記含有量が１ｍｇ／ｍ２未満ではめっき層表面を十分に被覆できないため、化成処理鋼板の裸耐食性が低下し、ラミネート鋼板や塗装鋼板としたときのフィルム密着性や塗膜密着性が低下することがある。前記付着量が、１５０ｍｇ／ｍ２を超えると、化成処理皮膜中の可溶性成分が多くなりすぎるため、高温多湿下での塗膜密着性およびフィルム密着性が低下することがある。化成処理皮膜における単位面積当たりのバルブメタル元素の含有量は、ＩＣＰ等の分析により求められる。 The content of the valve metal element per unit area in the chemical conversion film of the present invention is preferably 1 to 150 mg / m 2 . The content of the valve metal element per unit area is synonymous with the metal equivalent of the content of valve metal oxide or the like per unit area. When the content is less than 1 mg / m 2 , the surface of the plating layer cannot be sufficiently covered, so that the bare corrosion resistance of the chemical conversion treated steel sheet is lowered, and the film adhesion and the coating film adhesion when the laminated steel sheet and the coated steel sheet are reduced. Sometimes. When the adhesion amount exceeds 150 mg / m 2 , the soluble component in the chemical conversion film is excessively increased, so that the coating film adhesion and the film adhesion under high temperature and high humidity may be deteriorated. The content of the valve metal element per unit area in the chemical conversion film is determined by analysis such as ICP.
本発明の化成処理皮膜における、多価フェノール化合物とバルブメタル元素の質量比は、１〜１５であることが好ましい。前記質量比が１未満であると、ラミネート鋼板等としたときのめっき鋼板と樹脂層との十分な密着性が得られないことがある。また、前記質量比が１５を超えると、化成処理皮膜中にＮｉ等とキレートを形成しないフェノール化合物が多くなり、化成処理鋼板の耐水性が低下することがある。このため、ラミネート鋼板等としたときのめっき鋼板と樹脂層との密着性が不十分となることがある。 The mass ratio of the polyhydric phenol compound and the valve metal element in the chemical conversion film of the present invention is preferably 1-15. When the mass ratio is less than 1, sufficient adhesion between the plated steel sheet and the resin layer may not be obtained when a laminated steel sheet is used. Moreover, when the said mass ratio exceeds 15, the phenolic compound which does not form chelate with Ni etc. in a chemical conversion treatment film will increase, and the water resistance of a chemical conversion treatment steel plate may fall. For this reason, when it is set as a laminated steel plate etc., the adhesiveness of a plated steel plate and a resin layer may become inadequate.
化成処理皮膜における多価フェノール化合物の含有量は、例えば化成処理皮膜から多価フェノール化合物を抽出して、その量をクロマトグラフィー等で定量することにより求めてよい。一方、化成処理皮膜におけるバルブメタル元素の含有量は前述の通り求められるので、双方の値から化成処理皮膜における多価フェノール化合物とバルブメタル元素の質量比の含有量が求められる。 The content of the polyhydric phenol compound in the chemical conversion coating may be determined by, for example, extracting the polyhydric phenol compound from the chemical conversion coating and quantifying the amount by chromatography or the like. On the other hand, since the content of the valve metal element in the chemical conversion coating is obtained as described above, the content of the mass ratio of the polyhydric phenol compound and the valve metal element in the chemical conversion coating is obtained from both values.
ところで、化成処理皮膜には、化成処理や加工において皮膜欠陥部が形成され、その部分を基点にして腐食が生じることがある。そのため本発明においては、化成処理皮膜にバルブメタル化合物の水溶性フッ化物（「バルブメタルフッ化物」ともいう）を含有させることが好ましい。バルブメタルフッ化物は化成処理皮膜に自己修復作用機能を付与する。すなわち、バルブメタルフッ化物は、雰囲気中の水分に溶解し、皮膜欠陥部から露出している下地鋼の表面に難溶性の酸化物または水酸化物となって再析出し、皮膜欠陥部を被覆する。 By the way, in a chemical conversion treatment film, a film defect part is formed in chemical conversion treatment or processing, and corrosion may occur on the basis of the part. Therefore, in the present invention, it is preferable to contain a water-soluble fluoride (also referred to as “valve metal fluoride”) of the valve metal compound in the chemical conversion coating. Valve metal fluoride imparts a self-repairing function to the chemical conversion coating. That is, the valve metal fluoride dissolves in the moisture in the atmosphere and re-deposits as a poorly soluble oxide or hydroxide on the surface of the underlying steel exposed from the film defects, covering the film defects. To do.
化成処理皮膜にバルブメタルフッ化物を含ませるには、化成処理液にバルブメタルフッ化物を含ませればよい。すなわち、バルブメタル化合物として、Ｈ２ＴｉＦ６やＨ２ＺｒＦ６や（ＮＨ４）２ＴｉＦ６等の、バルブメタル元素とフッ素元素を含む化合物を用いることが好ましい。
また、フッ素化合物と前記バルブメタル化合物を含む化成処理液を調製し、化成処理中にフッ素とバルブメタルを反応させて、バルブメタルフッ化物を皮膜中に生成させてもよい。この場合のフッ素化合物の例には、ＮＨ４ＦやＭＦ６が含まれる（Ｍは金属元素）。
In order to include the valve metal fluoride in the chemical conversion coating, the valve metal fluoride may be included in the chemical conversion solution. That is, it is preferable to use a compound containing a valve metal element and a fluorine element, such as H 2 TiF 6 , H 2 ZrF 6, or (NH 4 ) 2 TiF 6 , as the valve metal compound.
Alternatively, a chemical conversion treatment liquid containing a fluorine compound and the valve metal compound may be prepared, and fluorine and valve metal may be reacted during the chemical conversion treatment to produce valve metal fluoride in the coating. Examples of the fluorine compound in this case include NH 4 F and MF 6 (M is a metal element).
さらに、本発明の化成処理液がフッ素化合物を含む場合に、めっき層にＡｌおよびＭｇのフッ化物を含むめっき鋼板を用いると、前述の通り、めっき層表面にＦとＡｌとＭｇを含む反応層が形成され、化成処理皮膜とめっき層表面との密着力をより高められる。 Furthermore, when the chemical conversion treatment liquid of the present invention contains a fluorine compound, when a plated steel sheet containing Al and Mg fluoride is used for the plating layer, as described above, the reaction layer containing F, Al, and Mg on the plating layer surface Thus, the adhesion between the chemical conversion film and the plating layer surface can be further enhanced.
化成処理皮膜の厚みは特に限定されないが、化成処理皮膜が薄すぎると化成処理鋼板の裸耐食性が十分でないことがある。一方、化成処理皮膜が厚すぎても化成処理皮膜性能は飽和してしまう。以上から化成処理皮膜は０．０１〜２μｍとすることが好ましい。 Although the thickness of a chemical conversion treatment film is not specifically limited, When a chemical conversion treatment film is too thin, the bare corrosion resistance of a chemical conversion treatment steel plate may not be enough. On the other hand, even if the chemical conversion coating is too thick, the chemical conversion coating performance is saturated. From the above, the chemical conversion film is preferably 0.01 to 2 μm.
２．化成処理鋼板の製造方法
本発明の化成処理鋼板は発明の効果を損なわない範囲で任意に製造されうるが、以下好ましい製造方法を説明する。
2. The manufacturing method of a chemical conversion treatment steel plate Although the chemical conversion treatment steel plate of this invention can be arbitrarily manufactured in the range which does not impair the effect of invention, the preferable manufacturing method is demonstrated below.
本発明の化成処理鋼板は、（Ａ）亜鉛系めっき鋼板を準備する工程と、（Ｂ）前記鋼板のめっき層表面にＦｅ、ＣｏおよびＮｉから選ばれる１種以上の金属、または前記金属の酸化物を形成する表面調整工程と、（Ｃ）前記表面調整工程で得た鋼板に、バルブメタル化合物と多価フェノール化合物を含む化成処理液を塗布して乾燥させる工程を含む方法で製造されることが好ましい。 The chemical conversion treated steel sheet of the present invention includes (A) a step of preparing a zinc-based plated steel sheet, and (B) one or more metals selected from Fe, Co and Ni on the surface of the plated layer of the steel sheet, or oxidation of the metal Manufactured by a method including a step of forming a surface and a step of applying and drying a chemical conversion solution containing a valve metal compound and a polyhydric phenol compound on the steel plate obtained in the surface adjustment step (C). Is preferred.
（Ａ）工程
本工程では、亜鉛系めっき鋼板を準備する。準備する手段は特に限定されないが、既に述べたとおりの方法で準備することが好ましい。
(A) Process In this process, a galvanized steel sheet is prepared. The means for preparing is not particularly limited, but it is preferable to prepare by the method as already described.
（Ｂ）工程
本工程では、前記めっき鋼板の表面調整を行う。表面調整は、既に述べたとおり、Ｆｅ、ＣｏまたはＮｉを含む処理液を調製して、これを鋼板表面にスプレー等により塗布し、乾燥させて行えばよい。
(B) Process In this process, the surface adjustment of the said plated steel plate is performed. As described above, the surface adjustment may be performed by preparing a treatment liquid containing Fe, Co, or Ni, applying it to the steel sheet surface by spraying, and drying.
（Ｃ）工程
本工程では、前記表面調整がなされた鋼板に、バルブメタル化合物と多価フェノール化合物を含む化成処理液を塗布して乾燥させる。化成処理液は、ロールコート法、スピンコート法、スプレー法などでめっき鋼板のめっき層の上に塗布される。塗布後、水洗することなく塗布膜を乾燥して、めっき層の上に化成処理皮膜を形成する。本発明においては、処理液を塗布して得た未乾燥の膜を「塗布膜」、塗布膜を乾燥させたものを「化成処理皮膜」という。塗布膜の乾燥温度は特に限定されないが、バルブメタル化合物の反応を促進させるため、１００℃以上が好ましく、１５０℃以上がより好ましい。過度に高温で乾燥すると、多価フェノール化合物が分解して化成処理皮膜の性能が低下するため、乾燥温度の上限は２００℃が好ましい。
化成処理液の各成分の含有量は、化成処理皮膜としたときに既に述べたとおりの含有量になるように適宜調整される。
(C) Process In this process, the chemical conversion liquid containing a valve metal compound and a polyhydric phenol compound is apply | coated and dried to the steel plate by which the said surface adjustment was made. The chemical conversion treatment liquid is applied on the plated layer of the plated steel sheet by a roll coating method, a spin coating method, a spray method or the like. After coating, the coating film is dried without washing with water, and a chemical conversion film is formed on the plating layer. In the present invention, the undried film obtained by applying the treatment liquid is referred to as “coating film”, and the dried film is referred to as “chemical conversion coating”. Although the drying temperature of a coating film is not specifically limited, In order to accelerate | stimulate reaction of a valve metal compound, 100 degreeC or more is preferable and 150 degreeC or more is more preferable. When dried at an excessively high temperature, the polyhydric phenol compound is decomposed and the performance of the chemical conversion film is lowered.
Content of each component of a chemical conversion liquid is suitably adjusted so that it may become content as already stated, when it is set as a chemical conversion treatment film.
３．ラミネート鋼板、塗装鋼板
本発明の化成処理鋼板は、ラミネート鋼板または塗装鋼板として用いられる。既に述べたとおり、化成処理鋼板の上に形成される、塗膜、フィルムまたは接着剤との密着性に優れるからである。
3. Laminated steel plate, coated steel plate The chemical conversion treated steel plate of the present invention is used as a laminated steel plate or a coated steel plate. It is because it is excellent in adhesiveness with the coating film, film, or adhesive agent formed on a chemical conversion treatment steel plate as already stated.
ラミネート鋼板とは、鋼板の上に樹脂フィルム層を形成してなる鋼板である。図１は、本発明のラミネート鋼板の一例を示す断面図である。図１中、１は鋼板、２は表面調整がなされためっき層、３は化成処理皮膜、４は接着剤層、５は樹脂フィルム層である。めっき鋼板の上に樹脂フィルム層を形成する方法は特に限定されないが、接着剤を用いて、鋼板の上に樹脂フィルムを接着する方法が好ましい。樹脂フィルムの例には、塩化ビニルフィルムやポリエステルフィルムが含まれる。接着剤の例には、エポキシ系接着剤やウレタン系接着剤が含まれる。 A laminated steel plate is a steel plate formed by forming a resin film layer on a steel plate. FIG. 1 is a cross-sectional view showing an example of a laminated steel sheet according to the present invention. In FIG. 1, 1 is a steel plate, 2 is a plated layer whose surface is adjusted, 3 is a chemical conversion coating, 4 is an adhesive layer, and 5 is a resin film layer. The method of forming the resin film layer on the plated steel plate is not particularly limited, but a method of bonding the resin film on the steel plate using an adhesive is preferable. Examples of the resin film include a vinyl chloride film and a polyester film. Examples of the adhesive include an epoxy adhesive and a urethane adhesive.
塗装鋼板とは、鋼板の上に塗膜を形成してなる鋼板である。塗膜は公知の方法で形成してよいが、その例には、メラミン系塗料、エポキシ系塗料、アクリル系塗料、ウレタン系塗料を塗装する方法が含まれる。 A coated steel plate is a steel plate formed by forming a coating film on a steel plate. The coating film may be formed by a known method, and examples thereof include a method of applying a melamine paint, an epoxy paint, an acrylic paint, or a urethane paint.
［実施例１Ａ、１Ｂ］
電気亜鉛めっき鋼板（板厚：０．５ｍｍ、片面めっき付着量：１０ｇ／ｍ2）と、溶融Ｚｎ−６質量％Ａｌ−３質量％Ｍｇめっき鋼板（板厚：０．５ｍｍ、片面めっき付着量：６０ｇ／ｍ2）を準備した。前者をめっき鋼板Ａと、後者をめっき鋼板Ｂとした。
各めっき鋼板に脱脂処理、水洗処理を施した。
[Examples 1A and 1B]
Electrogalvanized steel sheet (plate thickness: 0.5 mm, single-sided plating adhesion amount: 10 g / m 2 ) and molten Zn-6 mass% Al-3 mass% Mg-plated steel sheet (plate thickness: 0.5 mm, single-sided plating adhesion amount) : 60 g / m 2 ) was prepared. The former was a plated steel plate A and the latter was a plated steel plate B.
Each plated steel sheet was degreased and washed with water.
次に、表１に示す水溶液を調製した。例えば、水溶液１は、４０℃の純水に、硫酸第一鉄を、Ｆｅ元素濃度が２ｇ／Ｌとなるように混合して得た。具体的には、硫酸第一鉄（ＦｅＳＯ４）は分子量が１５１．９であるため、純水１Ｌに対して、硫酸第一鉄を５．４４ｇ混合することにより、表１に示す水溶液１を得た。
Next, aqueous solutions shown in Table 1 were prepared. For example, the
このようにして得た水溶液１に、前記めっき鋼板ＡとＢをそれぞれ浸漬した。浸漬時間を２〜９０ｓの間で変化させて、付着量を調整した。浸漬後のめっき鋼板は、水洗処理、乾燥処理が施された。
The plated steel sheets A and B were immersed in the
１Ｌの純水に、Ｈ２ＴｉＦ６を、Ｔｉ元素換算で３ｇ／Ｌになるように混合した。さらに当該混合液に、多価フェノール化合物としてタンニン酸（大日本住友製薬製）を４５ｇ混合して、タンニン酸の質量と前記Ｔｉ元素量の比が１５である表２に示す化成処理液４を得た。このようにして得た化成処理液を、バーコーターを用いて、前記表面調整がなされためっき鋼板に塗布した。この際、塗膜の単位面積当たりのバルブメタル化合物の含有量が、Ｔｉ元素換算で８０ｍｇ／ｍ２となるように、膜厚を調整した。続いて当該めっき鋼板を、到達板温が１００℃となるようにオーブンにて乾燥し、化成処理鋼板を得た。
このようにして得た化成処理鋼板から試験片を切り出し、以下に示すようにして、裸耐食性、塗膜密着性およびフィルム密着性を評価した。結果を表３に示す。
H 2 TiF 6 was mixed with 1 L of pure water so as to be 3 g / L in terms of Ti element. Furthermore, 45 g of tannic acid (manufactured by Dainippon Sumitomo Pharma Co., Ltd.) as a polyhydric phenol compound is mixed into the mixed solution, and the chemical conversion treatment solution 4 shown in Table 2 in which the ratio of the mass of tannic acid to the amount of Ti element is 15 is shown in Table 2. Obtained. The chemical conversion treatment liquid thus obtained was applied to the plated steel sheet with the surface adjusted using a bar coater. At this time, the film thickness was adjusted so that the content of the valve metal compound per unit area of the coating film was 80 mg / m 2 in terms of Ti element. Subsequently, the plated steel plate was dried in an oven so that the ultimate plate temperature was 100 ° C., to obtain a chemical conversion treated steel plate.
A test piece was cut out from the chemical conversion treated steel plate thus obtained, and naked corrosion resistance, coating film adhesion and film adhesion were evaluated as described below. The results are shown in Table 3.
（１）裸耐食性試験
試験片の端面にシールを施し、ＪＩＳＺ２３７１に準拠して３５℃のＮａＣｌ水溶液を試験片に噴霧した。８ｈおよび２４ｈ噴霧した後の試験片表面を観察し、白錆の発生面積率により、裸耐食性を評価した。この際、前記面積率が、１０面積％未満である場合を◎、１０以上〜２０面積％未満である場合を○、２０以上〜５０面積％未満である場合を△、５０面積％以上である場合を×と評価した。
裸耐食性は、めっき層表面と化成処理皮膜の密着性の指標となる。
(1) Bare corrosion resistance test An end surface of the test piece was sealed, and an aqueous NaCl solution at 35 ° C. was sprayed on the test piece in accordance with JISZ2371. The surface of the test piece after spraying for 8 hours and 24 hours was observed, and the bare corrosion resistance was evaluated by the area ratio of white rust. At this time, the case where the area ratio is less than 10 area% is ◎, the case where it is 10 or more and less than 20 area% is ◯, the case where it is 20 or more and less than 50 area% is Δ, and the area ratio is 50 area% or more. The case was rated as x.
Bare corrosion resistance is an index of adhesion between the plating layer surface and the chemical conversion coating.
（２）塗膜密着性試験
試験片表面に、メラミンアルキド塗料を塗装して、膜厚３０μｍの塗膜を形成し、塗装鋼板を得た。この塗装鋼板を沸騰水に４ｈ浸せきした後、ＪＩＳ Ｋ ５４００に準じ、碁盤目試験を行い、塗膜残存率を観察した。この際、塗膜残存率が９０％以上である場合を◎、８０以上〜９０％未満である場合を○、６０以上〜８０％未満である場合を△、６０％未満である場合を×として塗膜密着性を評価した。
(2) Coating Film Adhesion Test A melamine alkyd paint was applied to the surface of the test piece to form a coating film having a thickness of 30 μm, and a coated steel sheet was obtained. After this coated steel plate was immersed in boiling water for 4 hours, a cross-cut test was performed in accordance with JIS K 5400 to observe the coating film residual rate. At this time, when the coating film residual ratio is 90% or more, ◎, when it is 80 or more and less than 90%, ◯, when it is 60 or more and less than 80%, Δ, and when it is less than 60%, ×. The coating film adhesion was evaluated.
（３）フィルム密着性試験
試験片表面にエポキシ系接着剤を塗布し、塩化ビニルフィルムを貼り合わせ、ラミネート鋼板を得た。このラミネート鋼板を、沸騰水に４ｈ浸せきした後、フィルムの先端を強制的に引き剥がす試験を行い、剥離強度を測定した。剥離強度が１００（Ｎ／４０ｍｍ）以上である場合を◎、１００未満〜８０（Ｎ／４０ｍｍ）以上である場合を○、８０未満〜６０（Ｎ／４０ｍｍ）以上である場合を△、６０（Ｎ／４０ｍｍ）未満である場合を×として評価した。
(3) Film adhesion test An epoxy adhesive was applied to the surface of the test piece, and a vinyl chloride film was bonded together to obtain a laminated steel sheet. The laminate steel sheet was immersed in boiling water for 4 hours, and then a test for forcibly peeling the tip of the film was performed to measure the peel strength. When the peel strength is 100 (N / 40 mm) or more, ◎, when less than 100 to 80 (N / 40 mm) or more, ○, when less than 80 to 60 (N / 40 mm) or more, Δ, 60 ( N / 40 mm) was evaluated as x.
［実施例２〜１６］
表１に示す水溶液１〜３および表２に示す化成処理液１〜１１を用い、実施例１と同様にして、化成処理皮膜を製造した。次に、実施例１と同様にして、裸耐食性、塗膜密着性およびフィルム密着性を評価した。結果を表３に示す。
[Examples 2 to 16]
Using the
カテコール 山陽資材（株）製
カテキン 長良サイエンス（株）製
表３から明らかな通り、本発明の化成処理鋼板は、高温高湿下での裸耐食性、および樹脂層との密着性に優れる。特に、化成処理皮膜中のバルブメタル含有量、および多価フェノール化合物とバルブメタル含有量の比が特定の範囲にある実施例１〜１２の化成処理鋼板は、高温高湿下での裸耐食性、樹脂層との密着性に極めて優れることが明らかである。 As is apparent from Table 3, the chemical conversion treated steel sheet of the present invention is excellent in bare corrosion resistance under high temperature and high humidity and in adhesion to the resin layer. In particular, the valve metal content in the chemical conversion coating, and the chemical conversion steel sheets of Examples 1 to 12 in which the ratio of the polyhydric phenol compound and the valve metal content is in a specific range are bare corrosion resistance under high temperature and high humidity, It is clear that the adhesiveness with the resin layer is extremely excellent.
本発明の化成処理鋼板は高温高湿下での裸耐食性、および樹脂層との密着性に優れるため、塗装鋼板やラミネート鋼板として有用である。 The chemical conversion treated steel sheet of the present invention is useful as a coated steel sheet or a laminated steel sheet because it is excellent in naked corrosion resistance under high temperature and high humidity and in adhesion with a resin layer.
１ 鋼板
２ 表面調整がなされためっき層
３ 化成処理皮膜
４ 接着剤層
５ 樹脂フィルム層
DESCRIPTION OF
Claims (7)
前記めっき層は、表面に、Ｆｅ、ＣｏおよびＮｉから選ばれる１種以上の金属および前記金属の酸化物を有し、
前記化成処理皮膜は、バルブメタル酸化物または水酸化物と、多価フェノール化合物を含む、化成処理鋼板。 A zinc-based plated steel sheet having a plating layer containing Zn, and a chemical conversion-treated steel sheet including a chemical conversion film provided on the plating layer,
The plating layer has at least one metal selected from Fe, Co, and Ni and an oxide of the metal on the surface,
The said chemical conversion treatment film is a chemical conversion treatment steel plate containing a valve metal oxide or a hydroxide, and a polyhydric phenol compound.
（Ａ）亜鉛系めっき鋼板を準備する工程と、
（Ｂ）前記鋼板のめっき層表面にＦｅ、ＣｏおよびＮｉから選ばれる１種以上の金属、または前記金属の酸化物を形成する表面調整工程と、
（Ｃ）前記表面調整工程で得た鋼板に、バルブメタル化合物と多価フェノール化合物を含む化成処理液を塗布して乾燥させる工程を含む、化成処理皮膜の製造方法。 It is a method of manufacturing the chemical conversion treatment steel plate according to claim 1,
(A) preparing a galvanized steel sheet;
(B) a surface conditioning step of forming one or more metals selected from Fe, Co and Ni on the surface of the plated layer of the steel sheet, or an oxide of the metal;
(C) The manufacturing method of a chemical conversion treatment film including the process of apply | coating and drying the chemical conversion liquid containing a valve metal compound and a polyhydric phenol compound to the steel plate obtained at the said surface adjustment process.
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| US10400337B2 (en) | 2012-08-29 | 2019-09-03 | Ppg Industries Ohio, Inc. | Zirconium pretreatment compositions containing lithium, associated methods for treating metal substrates, and related coated metal substrates |
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