JP6515973B2 - Surface treatment solution for zinc-based plated steel sheet, method for producing zinc-based plated steel sheet with surface treatment film, and zinc-based plated steel sheet with surface treatment film - Google Patents
Surface treatment solution for zinc-based plated steel sheet, method for producing zinc-based plated steel sheet with surface treatment film, and zinc-based plated steel sheet with surface treatment film Download PDFInfo
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- JP6515973B2 JP6515973B2 JP2017195973A JP2017195973A JP6515973B2 JP 6515973 B2 JP6515973 B2 JP 6515973B2 JP 2017195973 A JP2017195973 A JP 2017195973A JP 2017195973 A JP2017195973 A JP 2017195973A JP 6515973 B2 JP6515973 B2 JP 6515973B2
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- surface treatment
- zinc
- plated steel
- steel sheet
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- 238000004381 surface treatment Methods 0.000 title claims description 125
- 229910000831 Steel Inorganic materials 0.000 title claims description 107
- 239000010959 steel Substances 0.000 title claims description 107
- 239000011701 zinc Substances 0.000 title claims description 86
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- 229910052725 zinc Inorganic materials 0.000 title claims description 83
- 238000004519 manufacturing process Methods 0.000 title claims description 22
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- 238000000034 method Methods 0.000 claims description 28
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- 238000001035 drying Methods 0.000 claims description 27
- 238000007747 plating Methods 0.000 claims description 24
- 125000000129 anionic group Chemical group 0.000 claims description 21
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Images
Description
本発明は、亜鉛系めっき鋼板用表面処理液、表面処理皮膜付き亜鉛系めっき鋼板の製造方法、及び表面処理皮膜付き亜鉛系めっき鋼板に関する。 The present invention relates to a surface treatment solution for zinc-based plated steel sheet, a method for producing a zinc-based plated steel sheet with a surface treatment film, and a zinc-based plated steel plate with a surface treatment film.
従来、耐食性（耐白錆性、耐赤錆性）を向上させる目的で、亜鉛系めっき鋼板の表面に、クロム酸、重クロム酸またはその塩類を主要成分とした処理液によるクロメート処理を施した鋼板が広く用いられてきた。しかしながら、最近の地球環境問題から、クロメート処理によらない無公害な表面処理鋼板、所謂クロムフリー処理鋼板を採用することへの要請が高まっている。 Conventionally, in order to improve the corrosion resistance (white rust resistance, red rust resistance), the surface of a zinc-based plated steel sheet is subjected to chromate treatment with a treatment solution containing chromic acid, dichromic acid or its salts as main components Has been widely used. However, due to recent global environmental problems, there is an increasing demand for adopting a non-polished surface-treated steel plate not using chromate treatment, a so-called chromium-free treated steel plate.
このような表面処理皮膜付き亜鉛系めっき鋼板（以下、「表面処理鋼板」とも称する。）は、自動車、家電製品、ＯＡ機器、建築部材等に使用される。これらの用途で使用する場合、表面処理鋼板を溶接して使用するケースも多く、溶接の種類としては、燃焼ガスから発生する熱を利用したガス溶接、電気の放電現象を利用したアーク溶接、電気の抵抗熱を利用したスポット溶接やシーム溶接が挙げられる。上述した何れの溶接方法においても、被溶接部は鋼の融点を超える温度である約２，０００℃に晒され、溶接部近傍においてもめっき層の融点以上の温度域である約５００℃を超える箇所が存在する。溶接によって表面処理鋼板の表面温度が５００℃を超えるとめっき層が溶融し、めっき層の熱膨張によってめっき層表面の形状変化が生じる。それに伴い、めっき層上の表面処理皮膜も形状変化し、特にめっき層よりも熱膨張率の低い無機成分主体の皮膜の場合は、めっきの熱膨張とその後の冷却収縮による形状変化に追随できなくなり、溶接後に亀甲状の亀裂（以降、「クラック」と称する。）が生じる問題があった。特に、皮膜の付着量が大きい程クラックが顕著に発生する。 Such a zinc-based plated steel sheet with a surface treatment film (hereinafter also referred to as "surface-treated steel sheet") is used for automobiles, home appliances, OA equipment, building members and the like. When used in these applications, there are many cases where surface-treated steel sheets are welded and used. As welding types, gas welding using heat generated from combustion gas, arc welding using electrical discharge phenomenon, electricity Spot welding and seam welding that use the resistance heat of In any of the above-described welding methods, the weld zone is exposed to about 2,000 ° C., which is a temperature exceeding the melting point of the steel, and also exceeds about 500 ° C., which is a temperature range above the melting point of the plating layer in the vicinity of the weld. There is a place. When the surface temperature of the surface-treated steel sheet exceeds 500 ° C. by welding, the plating layer melts, and thermal expansion of the plating layer causes a change in shape of the surface of the plating layer. Along with this, the surface treatment film on the plating layer also changes its shape, and in the case of a film mainly composed of an inorganic component having a thermal expansion coefficient lower than that of the plating layer, it can not follow the shape change due to thermal expansion of plating and subsequent cooling shrinkage. There was a problem that a turtle-shaped crack (hereinafter referred to as "crack") occurs after welding. In particular, the greater the amount of adhesion of the film, the more noticeable the cracks.
また、有機樹脂を含む有機・無機複合皮膜の場合は、溶接による加熱によって有機樹脂が熱分解し、フェノール樹脂など有機樹脂の種類によっては、皮膜表面が黄変することがあった。加えて、無機成分由来のクラックも生じるため、有機・無機複合皮膜の場合は、溶接後の表面処理鋼板の外観が著しく劣るという問題があった。 In the case of an organic-inorganic composite film containing an organic resin, the organic resin is thermally decomposed by heating by welding, and the surface of the film may turn yellow depending on the type of organic resin such as a phenol resin. In addition, since a crack derived from the inorganic component is also generated, in the case of the organic / inorganic composite film, there is a problem that the appearance of the surface-treated steel sheet after welding is significantly inferior.
よって、上記のような現象を抑制した、耐熱変色性及び耐熱割れ性に優れた表面処理鋼板が求められている。さらに、表面処理鋼板が種々の用途で用いられることを考慮すると、平板部耐食性、アルカリ脱脂後耐食性、耐黒変性、耐水しみ性、耐溶剤性、耐汗性、塗装密着性に優れることも求められる。 Therefore, the surface-treated steel sheet excellent in heat discoloration resistance and heat crack resistance which suppressed the above phenomena is required. Furthermore, considering that the surface-treated steel sheet is used in various applications, it is also required to be excellent in corrosion resistance of flat plate portion, corrosion resistance after alkaline degreasing, blackening resistance, water stain resistance, solvent resistance, sweat resistance and coating adhesion. Be
特許文献１には、特定の骨格を含有するフェノール樹脂と、カチオン性ウレタン樹脂と、シランカップリング剤と、有機チタン化合物と、バナジル化合物とを特定の割合で含む表面処理液を使用して表面処理皮膜を形成し、亜鉛系めっき鋼板に、優れた耐食性、耐溶剤性、及び塗料密着性を付与する技術が開示されている。また、特許文献２には、モリブデン酸化合物をさらに含み、特許文献３には、モリブデン酸化合物とフッ素化合物をさらに含む表面処理液を用いる技術が開示されている。 Patent Document 1 discloses the surface treatment using a surface treatment solution containing a phenol resin having a specific skeleton, a cationic urethane resin, a silane coupling agent, an organic titanium compound, and a vanadyl compound in a specific ratio. There is disclosed a technology for forming a treated film to impart excellent corrosion resistance, solvent resistance and paint adhesion to a zinc-based plated steel sheet. In addition, Patent Document 2 discloses a technique using a surface treatment liquid further containing a molybdic acid compound, and Patent Document 3 further containing a molybdic acid compound and a fluorine compound.
また、特許文献４〜６には、シランカップリング剤を含まず、チタン化合物と、ニッケル化合物と、アルミニウム化合物と、フッ素化合物を含む表面処理皮膜を有する亜鉛系めっき鋼板は、５００℃以上の温度で加熱しても、黄色や茶褐色への変色が起きず、耐食性や耐黒変性も優れることを開示する。 Patent documents 4 to 6 do not contain a silane coupling agent, and a zinc-based plated steel plate having a surface treatment film containing a titanium compound, a nickel compound, an aluminum compound, and a fluorine compound has a temperature of 500 ° C. or higher. It is disclosed that even if heating is carried out, no color change to yellow or brown occurs, and corrosion resistance and blackening resistance are also excellent.
しかしながら、特許文献１〜３の技術は、シランカップリング剤が皮膜中に多く含まれるため、５００℃を超える加熱の際には、シランカップリング剤中の有機官能基が熱分解することに起因したクラックが生じやすい。さらに、フェノール樹脂、有機チタン化合物、及びフッ素化合物を含むと、加熱時間が長くなるに従い加熱後の黄変色も顕著となる。特許文献１〜３では、表面処理鋼板を３０秒で５００℃に加熱し、３０秒保持した後の耐熱変色性を評価しているが、後述する本実施例のように、保持時間を５分とした、より厳しい条件で評価する耐熱変色性及び耐熱割れ性に関しては、十分ではない。特許文献４〜６の技術は、耐水しみ性、耐汗性、塗料密着性などについては考慮されておらず十分ではなかった。 However, the techniques of Patent Documents 1 to 3 are caused by the thermal decomposition of the organic functional group in the silane coupling agent at the time of heating exceeding 500 ° C. because the coating contains a large amount of the silane coupling agent. Cracks are likely to occur. Furthermore, when a phenol resin, an organic titanium compound and a fluorine compound are contained, the yellowing after heating becomes remarkable as the heating time becomes longer. In Patent Documents 1 to 3, the heat-resistant color change property after heating the surface-treated steel sheet to 500 ° C. in 30 seconds and holding it for 30 seconds is evaluated, but the holding time is 5 minutes as in this example described later. The heat discoloration resistance and the heat cracking resistance evaluated under more severe conditions are not sufficient. The techniques of Patent Documents 4 to 6 are not sufficient because they do not consider water stain resistance, sweat resistance, paint adhesion, and the like.
このように、上記の全ての特性をバランス良く満足することが可能な表面処理鋼板は未だ得られていない。 Thus, a surface-treated steel sheet capable of satisfying all the above-mentioned properties in a well-balanced manner has not yet been obtained.
本発明は、上記課題に鑑み、表面処理皮膜にクロム化合物を含まず、耐熱変色性、耐熱割れ性、平板部耐食性、アルカリ脱脂後耐食性、耐黒変性、耐水しみ性、耐溶剤性、耐汗性、塗装密着性のいずれにも優れる表面処理皮膜付き亜鉛系めっき鋼板と、当該良好な特性を有する表面処理皮膜付き亜鉛系めっき鋼板を製造するための表面処理液及び製造方法とを提供することを目的とする。 In view of the above problems, the present invention does not contain a chromium compound in the surface treatment film, and has heat discoloration resistance, heat cracking resistance, flat plate corrosion resistance, corrosion resistance after alkaline degreasing, blackening resistance, water stain resistance, solvent resistance, sweat resistance To provide a surface-treated film-coated zinc-based plated steel sheet excellent in any of coating properties and coating adhesion, and a surface-treatment liquid and method for producing the surface-treated film-coated zinc-based plated steel sheet having the good characteristics. With the goal.
本発明者らは、鋭意検討を重ねた結果、グリシジル基を有するシランカップリング剤（Ａ）、テトラアルコキシシラン（Ｂ）、珪酸ナトリウム（Ｃ）、炭酸ジルコニウム化合物（Ｄ）、ガラス転移点（Ｔｇ）が８０℃〜１３０℃であるアニオン性ポリウレタン樹脂（Ｅ）、バナジウム化合物（Ｆ）、モリブデン酸化合物（Ｇ）、及び水が添加され、ｐＨが８．０〜１０．０で、かつ、各成分の添加量が所定の関係を満足する表面処理液を用いて、亜鉛系めっき鋼板に表面処理皮膜を形成することによって、上記課題を解決できることを見出した。特に、より厳しい条件で評価する耐熱変色性及び耐熱割れ性を向上させるには、表面処理液に珪酸ナトリウム（Ｃ）を添加することが有効であり、その添加量は、上記成分（Ａ）〜（Ｄ）の合計質量（ＸS）に対して５質量％以上とすることが重要であることを見出した。 The inventors of the present invention conducted intensive studies and found that glycidyl-containing silane coupling agent (A), tetraalkoxysilane (B), sodium silicate (C), zirconium carbonate compound (D), glass transition point (Tg) Anionic polyurethane resin (E) having a temperature of 80 ° C. to 130 ° C., a vanadium compound (F), a molybdic acid compound (G), and water are added, and the pH is 8.0 to 10.0, and each The inventors have found that the above problems can be solved by forming a surface treatment film on a zinc-based plated steel sheet using a surface treatment solution in which the addition amounts of the components satisfy a predetermined relationship. In particular, it is effective to add sodium silicate (C) to the surface treatment solution in order to improve the heat discoloration resistance and the heat cracking resistance evaluated under more severe conditions, and the addition amount thereof is the above component (A) ~ be 5 mass% or more were found to be important with respect to the total weight of (D) (X S).
本発明は、このような知見に基づきなされたものであり、その要旨構成は以下のとおりである。
［１］グリシジル基を有するシランカップリング剤（Ａ）、テトラアルコキシシラン（Ｂ）、珪酸ナトリウム（Ｃ）、炭酸ジルコニウム化合物（Ｄ）、ガラス転移点（Ｔｇ）が８０℃〜１３０℃であるアニオン性ポリウレタン樹脂（Ｅ）、バナジウム化合物（Ｆ）、モリブデン酸化合物（Ｇ）、及び水が添加され、ｐＨが８．０〜１０．０で、かつ、各成分の添加量が以下の（１）〜（６）を満足することを特徴とする亜鉛系めっき鋼板用表面処理液。
（１）グリシジル基を有するシランカップリング剤（Ａ）の固形分質量（Ａs）、テトラアルコキシシラン（Ｂ）の固形分質量（ＢS）、珪酸ナトリウム（Ｃ）の固形分質量（ＣS）、及び炭酸ジルコニウム化合物（Ｄ）中のＺｒＯ2換算質量（ＤZ）の合計質量（ＸS）の、アニオン性ポリウレタン樹脂（Ｅ）の固形分質量（ＥS）に対する質量比（ＸS／ＥS）が０．０５〜０．３８
（２）テトラアルコキシシラン（Ｂ）の固形分質量（ＢS）の、前記合計質量（ＸS）に対する質量比（ＢS／ＸS）が０．０１０〜０．３０
（３）珪酸ナトリウム（Ｃ）の固形分質量（ＣS）の、前記合計質量（ＸS）に対する質量比（ＣS／ＸS）が０．０５〜０．５０
（４）炭酸ジルコニウム化合物（Ｄ）中のＺｒＯ2換算質量（ＤZ）の、前記合計質量（ＸS）に対する質量比（ＤZ／ＸS）が０．０５〜０．６０
（５）バナジウム化合物（Ｆ）中のＶ換算質量（ＦV）の、前記合計質量（ＸS）とアニオン性ポリウレタン樹脂（Ｅ）の固形分質量（ＥS）との合計質量（ＸS＋ＥS）に対する質量比（ＦV／（ＸS＋ＥS））が０．００１０〜０．０１５
（６）モリブデン酸化合物（Ｇ）中のＭｏ換算質量（ＧM）の、前記合計質量（ＸS）とアニオン性ポリウレタン樹脂（Ｅ）の固形分質量（ＥS）との合計質量（ＸS＋ＥS）に対する質量比（ＧM／（ＸS＋ＥS））が０．００１０〜０．０１５
The present invention has been made based on such findings, and the summary of the invention is as follows.
[1] Silane coupling agent having glycidyl group (A), tetraalkoxysilane (B), sodium silicate (C), zirconium carbonate compound (D), anion having a glass transition point (Tg) of 80 ° C. to 130 ° C. Polyurethane resin (E), vanadium compound (F), molybdic acid compound (G), and water are added, pH is 8.0 to 10.0, and the addition amount of each component is the following (1) Surface treatment liquid for zinc-based plated steel plates characterized by satisfying (6).
(1) solid content of the silane coupling agent having a glycidyl group (A) (A s), the solid content mass (B S) of the tetraalkoxysilane (B), solid content of sodium silicate (C) (C S ), and the total mass (X S) of the weight ratio to the solid content mass (E S) of the anionic polyurethane resin (E) of the zirconium carbonate compound (D) ZrO 2 in terms of the mass in (D Z) (X S / E S ) is 0.05 to 0.38
(2) solid content of the tetraalkoxysilane (B) of (B S), the mass ratio relative to the total mass (X S) (B S / X S) is 0.010-.30
(3) solid mass of sodium silicate (C) of (C S), the mass ratio relative to the total mass (X S) (C S / X S) is 0.05 to 0.50
(4) ZrO 2 in terms of the mass in the zirconium carbonate compound (D) of (D Z), a mass ratio relative to the total mass (X S) (D Z / X S) is 0.05 to 0.60
(5) a vanadium compound (F) V reduced mass in the (F V), the total mass of the solid content (E S) of the total mass (X S) and the anionic polyurethane resin (E) (X S + E The mass ratio (F V / (X S + E S ))) relative to S ) is 0.0010 to 0.015
(6) molybdate compound (G) Mo reduced mass in the (G M), the total mass of the solid content (E S) of the total mass (X S) and the anionic polyurethane resin (E) (X S + E S) mass ratio (G M / (X S + E S)) is from 0.0010 to 0.015
［２］さらにワックス（Ｈ）が添加され、その添加量が以下の（７）を満足する、上記［１］に記載の亜鉛系めっき鋼板用表面処理液。
（７）ワックス（Ｈ）の固形分質量（ＨS）の、前記合計質量（ＸS）とアニオン性ポリウレタン樹脂（Ｅ）の固形分質量（ＥS）との合計質量（ＸS＋ＥS）に対する質量比（ＨS／（ＸS＋ＥS））が０．００２〜０．１０
[2] The surface treatment solution for a zinc-based plated steel sheet according to the above [1], wherein a wax (H) is further added, and the addition amount thereof satisfies the following (7).
(7) a wax solid weight of (H) (H S) of the total weight of the solid content (E S) of the total mass (X S) and the anionic polyurethane resin (E) (X S + E S) The mass ratio (H S / (X S + E S )) to the
［３］亜鉛系めっき鋼板の表面に、上記［１］又は［２］に記載の亜鉛系めっき鋼板用表面処理液を塗布する第１工程と、
その後、塗布された前記亜鉛系めっき鋼板用表面処理液を乾燥して、付着量が５０〜２，０００ｍｇ／ｍ2の表面処理皮膜を形成する第２工程と、
を有することを特徴とする表面処理皮膜付き亜鉛系めっき鋼板の製造方法。
[3] A first step of applying the surface treatment liquid for zinc-based plated steel sheet according to the above [1] or [2] onto the surface of the zinc-based plated steel sheet,
Thereafter, the coated surface treatment solution for a zinc-based plated steel sheet is dried to form a surface treatment film having an adhesion amount of 50 to 2,000 mg / m 2 ,
The manufacturing method of the zinc-based plated steel plate with a surface treatment film characterized by having.
［４］前記第１工程時の前記亜鉛系めっき鋼板の温度及び前記表面処理液の温度をそれぞれＴS及びＴLとし、ＴS−ＴLをΔＴとしたとき、ＴSが１５〜５５℃であり、ＴLが１０〜４０℃であり、ΔＴが５〜４０℃であり、
前記第２工程は、塗布された前記亜鉛系めっき鋼板用表面処理液を大気中で乾燥する、時間ｔ秒の予備乾燥工程と、その後、塗布された前記亜鉛系めっき鋼板用表面処理液を乾燥炉で加熱乾燥する加熱乾燥工程と、を含み、ΔＴ／ｔが１〜６０℃／ｓである、上記［３］に記載の表面処理皮膜付き亜鉛系めっき鋼板の製造方法。
[4] When the temperature of the zinc-based plated steel plate and the temperature of the surface treatment solution in the first step are T S and T L respectively, and T S -T L is ΔT, T S is 15 to 55 ° C. , T L is 10 to 40 ° C., ΔT is 5 to 40 ° C.,
In the second step, the applied surface treatment solution for zinc-based plated steel sheet is dried in the atmosphere, a preliminary drying step for time t seconds, and thereafter, the surface treatment solution applied to zinc-based plated steel plate is dried And a heating and drying step of heating and drying in a furnace, and the method of producing a zinc-based plated steel sheet with a surface treatment film according to the above [3], wherein ΔT / t is 1 to 60 ° C./s.
［５］亜鉛系めっき鋼板と、
該亜鉛系めっき鋼板の表面に、上記［１］又は［２］に記載の亜鉛系めっき鋼板用表面処理液を塗布し、乾燥して得た、付着量が５０〜２，０００ｍｇ／ｍ2の表面処理皮膜と、
を有することを特徴とする表面処理皮膜付き亜鉛系めっき鋼板。
[5] Zinc-based plated steel sheet,
The surface treatment solution for a zinc-based plated steel sheet according to the above [1] or [2] is applied to the surface of the zinc-based plated steel sheet and dried to obtain an adhesion amount of 50 to 2,000 mg / m 2 Surface treatment film,
A zinc-based plated steel sheet with a surface treatment film characterized by having:
［６］前記表面処理皮膜が、Ｚｒを含む相と含まない相から構成され、前記Ｚｒを含む相の体積分率が５〜４０％である、上記［５］に記載の表面処理皮膜付き亜鉛系めっき鋼板。 [6] The zinc with a surface treatment film according to the above [5], wherein the surface treatment film is composed of a phase containing Zr and a phase not containing Zr, and the volume fraction of the phase containing Zr is 5 to 40%. Base plated steel sheet.
［７］前記亜鉛系めっき鋼板が、基板である鋼板の少なくとも一方の表面に、質量％で、Ａｌ：３．０〜６．０％、Ｍｇ：０．２〜１．０％、Ｎｉ：０．０１〜０．１０％を含有し、残部がＺｎおよび不可避的不純物からなる溶融Ｚｎ−Ａｌ系合金めっき層を有する溶融Ｚｎ−Ａｌ系合金めっき鋼板である、上記［５］又は［６］に記載の表面処理皮膜付き亜鉛系めっき鋼板。 [7] The zinc-based plated steel sheet is, by mass%, Al: 3.0 to 6.0%, Mg: 0.2 to 1.0%, Ni: 0 on a surface of at least one of the steel sheets as a substrate. In the above [5] or [6], which is a hot dip Zn-Al alloy coated steel sheet having a hot dip Zn-Al alloy plating layer containing 0.10 to 0.10% and the balance being Zn and unavoidable impurities The zinc-based plated steel plate with a surface treatment film described above.
本発明の表面処理皮膜付き亜鉛系めっき鋼板は、表面処理皮膜にクロム化合物を含まず、耐熱変色性、耐熱割れ性、平板部耐食性、アルカリ脱脂後耐食性、耐黒変性、耐水しみ性、耐溶剤性、耐汗性、塗装密着性のいずれにも優れる。また、本発明の表面処理液及び製造方法は、上記のような良好な特性を有する表面処理皮膜付き亜鉛系めっき鋼板を製造することができる。 The zinc-plated steel sheet with a surface treatment film according to the present invention does not contain a chromium compound in the surface treatment film, and has heat discoloration resistance, heat cracking resistance, flat plate corrosion resistance, corrosion resistance after alkaline degreasing, blackening resistance, water stain resistance, solvent resistance Excellent in all of the properties, sweat resistance and paint adhesion. Moreover, the surface treatment liquid and manufacturing method of this invention can manufacture the zinc-based plated steel plate with a surface treatment film | membrane which has the above favorable characteristics.
＜亜鉛系めっき鋼板＞
本発明で使用する亜鉛系めっき鋼板は、電気亜鉛めっき鋼板、溶融亜鉛めっき鋼板、亜鉛−アルミニウム合金めっき鋼板、亜鉛−鉄合金めっき鋼板、亜鉛−マグネシウムめっき鋼板、亜鉛−アルミニウム−マグネシウム合金めっき鋼板等を用いることができる。
<Zinc-based plated steel sheet>
The zinc-based plated steel sheet used in the present invention includes electrogalvanized steel sheets, hot-dip galvanized steel sheets, zinc-aluminium alloy coated steel sheets, zinc-iron alloy coated steel sheets, zinc-magnesium plated steel sheets, zinc-aluminium-magnesium alloy coated steel sheets, etc. Can be used.
さらに好ましくは、基板である鋼板の少なくとも一方の表面に、質量％で、Ａｌ：３．０〜６．０％、Ｍｇ：０．２〜１．０％、Ｎｉ：０．０１〜０．１０％を含有し、残部がＺｎおよび不可避的不純物からなる溶融Ｚｎ−Ａｌ系合金めっき層を有する溶融Ｚｎ−Ａｌ系合金めっき鋼板を用いることができる。この鋼板を使用した場合、その他のめっき鋼板を用いた場合に対し耐赤錆性が優れるという利点がある。このため、屋外等、より厳しい腐食環境で使用する際に有利となる。この溶融Ｚｎ−Ａｌ系合金めっき鋼板は、溶融Ｚｎ−Ａｌ系合金めっき層にＺｎ−Ａｌ−Ｍｇ系三元共晶を含有することが、より好ましい。このＺｎ−Ａｌ−Ｍｇ系三元共晶は、めっき層表面における面積率で１〜５０％含有することが好ましい。 More preferably, Al: 3.0 to 6.0%, Mg: 0.2 to 1.0%, Ni: 0.01 to 0.10 by mass% on at least one surface of a steel plate which is a substrate. %, And the remainder is a Zn-Al-based alloy plated steel sheet having a hot-dip Zn-Al-based alloy plated layer composed of Zn and unavoidable impurities. When this steel plate is used, there is an advantage that it is excellent in anti-corrosion resistance compared with the case where other plated steel plates are used. This is advantageous for use in more severe corrosive environments, such as outdoors. It is more preferable that this hot-dip Zn-Al based alloy plated steel sheet contains Zn-Al-Mg based ternary eutectic in the hot-dip Zn-Al based alloy plated layer. The Zn-Al-Mg-based ternary eutectic is preferably contained in an area ratio of 1 to 50% on the surface of the plating layer.
本発明の表面処理皮膜付き亜鉛系めっき鋼板は、亜鉛系めっき鋼板と、該亜鉛系めっき鋼板の表面に、以下に説明する表面処理液を塗布し、乾燥して得た、片面当たりの付着量が５０〜２，０００ｍｇ／ｍ2の表面処理皮膜（以下、単に「皮膜」ともいう。）と、を有し、耐熱変色性、耐熱割れ性、平板部耐食性、アルカリ脱脂後耐食性、耐黒変性、耐水しみ性、耐溶剤性、耐汗性、塗装密着性のいずれにも優れる。 The zinc-based plated steel sheet with a surface treatment film of the present invention comprises a zinc-based plated steel sheet and a surface-treatment solution described below applied to the surface of the zinc-based plated steel sheet and dried. Has a surface treatment film of 50 to 2,000 mg / m 2 (hereinafter, also simply referred to as “film”), and has heat discoloration resistance, heat cracking resistance, flat plate corrosion resistance, corrosion resistance after alkaline degreasing, blackening resistance Excellent in all of water stain resistance, solvent resistance, sweat resistance and coating adhesion.
＜亜鉛系めっき鋼板用表面処理液＞
本発明の亜鉛系めっき鋼板用表面処理液（以下、単に「表面処理液」という。）は、グリシジル基を有するシランカップリング剤（Ａ）、テトラアルコキシシラン（Ｂ）、珪酸ナトリウム（Ｃ）、炭酸ジルコニウム化合物（Ｄ）、ガラス転移点（Ｔｇ）が８０℃〜１３０℃であるアニオン性ポリウレタン樹脂（Ｅ）、バナジウム化合物（Ｆ）、モリブデン酸化合物（Ｇ）、及び水が添加され、さらに必要に応じて、ワックス（Ｈ）が添加されてもよい。
<Surface treatment solution for galvanized steel sheets>
The surface treatment solution for zinc-based plated steel sheets of the present invention (hereinafter simply referred to as “surface treatment solution”) is a glycidyl group-containing silane coupling agent (A), tetraalkoxysilane (B), sodium silicate (C), Zirconium carbonate compound (D), anionic polyurethane resin (E) having a glass transition temperature (Tg) of 80 ° C. to 130 ° C., vanadium compound (F), molybdic acid compound (G), and water are further added and necessary Depending on, wax (H) may be added.
＜グリシジル基を有するシランカップリング剤（Ａ）＞
本発明の表面処理液には、グリシジル基を有するシランカップリング剤（Ａ）が添加される。該シランカップリング剤（Ａ）は、グリシジル基、および加水分解性基として炭素数が１〜５、好ましくは１〜３である低級アルコキシ基がＳｉ元素に直接結合したものであれば、特に限定されず、例えば、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルトリエトキシシラン、３−グリシドキシプロピルメチルジメトキシシラン、２−（３，４エポキシシクロヘキシル）エチルトリエトキシシランなどが挙げられ、なかでも、グリシジル基を有するシランカップリング剤（Ａ）同士の縮合点や、後述するテトラアルコキシシラン（Ｂ）、珪酸ナトリウム（Ｃ）、炭酸ジルコニウム化合物（Ｄ）との縮合点をより多く生成しやすく、それによって成膜後に高いバリア性が得られるという観点から、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルトリエトキシシランが好ましい。
<Silane coupling agent (A) having a glycidyl group>
A silane coupling agent (A) having a glycidyl group is added to the surface treatment liquid of the present invention. The silane coupling agent (A) is particularly limited as long as it is a glycidyl group and a hydrolyzable group in which a lower alkoxy group having 1 to 5 and preferably 1 to 3 carbon atoms as a hydrolyzable group is directly bonded to an Si element. For example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4 epoxycyclohexyl) ethyltriethoxysilane, etc. Among them, condensation points between silane coupling agents (A) having a glycidyl group and condensation points with tetraalkoxysilane (B), sodium silicate (C) and zirconium carbonate compound (D) described later are more preferable. 3-glycidoxy from the viewpoint that it is easy to form a large amount, thereby obtaining high barrier properties after film formation. B pills trimethoxysilane, 3-glycidoxypropyl triethoxysilane are preferable.
グリシジル基を有するシランカップリング剤（Ａ）は、その化合物中のＳｉ元素にアルコキシ基が直接結合しており、そのアルコキシ基は、水溶液中で水と反応することによりシラノール基を形成する。このシラノール基は、亜鉛系めっき鋼板の表面と反応したり、後述する成分（Ｂ）〜（Ｄ）との間で複合的に縮合反応したりする。 In the silane coupling agent (A) having a glycidyl group, an alkoxy group is directly bonded to an Si element in the compound, and the alkoxy group forms a silanol group by reacting with water in an aqueous solution. The silanol group reacts with the surface of the zinc-based plated steel sheet, or undergoes a complex condensation reaction with components (B) to (D) described later.
＜テトラアルコキシシラン（Ｂ）＞
成分（Ａ）を単独で使用すると耐熱割れ性に劣るため、本発明の表面処理液には、テトラアルコキシシラン（Ｂ）が添加される。成分（Ｂ）がない場合、５００℃以上の加熱雰囲気では、成分（Ａ）の有機官能基が熱酸化分解するため、大きなクラック発生の要因となる。それに対し、成分（Ｂ）を適量添加すると、成分（Ａ）の添加量を耐熱割れ性が許容される程度に抑えつつ、緻密でバリア性の高い皮膜が得られる。成分（Ａ）と成分（Ｂ）から得られる皮膜は緻密であるため、加熱時のクラックも緻密化することができ、目視で確認されるようなクラックは生じず、優れた耐熱割れ性が得られる。
<Tetraalkoxysilane (B)>
The use of the component (A) alone is inferior to the heat cracking resistance, so the tetraalkoxysilane (B) is added to the surface treatment liquid of the present invention. In the absence of the component (B), the organic functional group of the component (A) is thermally oxidized and decomposed in a heating atmosphere at 500 ° C. or higher, which causes a large crack. On the other hand, when an appropriate amount of the component (B) is added, a dense and high barrier film can be obtained while suppressing the addition amount of the component (A) to an extent that the thermal cracking resistance is acceptable. Since the film obtained from the component (A) and the component (B) is dense, cracks can be densified at the time of heating, and cracks such as those visually confirmed do not occur, and excellent thermal cracking resistance is obtained. Be
テトラアルコキシシラン（Ｂ）は、Ｓｉ元素に直接結合する加水分解性基として４個の低級アルコキシ基を有するものであり、一般式Ｓｉ（ＯＲ）4（式中、Ｒは同一の又は異なる炭素数１〜５のアルキル基を示す）で示されるものであれば、特に限定されず、例えば、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシランなどが挙げられ、これらの１種以上を用いることができる。なかでも、テトラアルコキシシラン（Ｂ）同士や、成分（Ａ）、後述する成分（Ｃ）、（Ｄ）との縮合点をより多く生成しやすく、それによって成膜後に高いバリア性が得られるという観点から、テトラエトキシシランおよびテトラメトキシシランが好ましい。 The tetraalkoxysilane (B) is one having four lower alkoxy groups as hydrolyzable groups directly bonded to the Si element, and the general formula Si (OR) 4 (wherein R is the same or different carbon number It is not particularly limited as long as it is represented by 1 to 5 alkyl groups), and examples thereof include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane and the like, and one or more of these can be used. . Among them, it is easy to generate more condensation points with tetraalkoxysilanes (B), with components (A), and components (C) and (D) described later, whereby high barrier properties can be obtained after film formation. From the viewpoint, tetraethoxysilane and tetramethoxysilane are preferable.
テトラアルコキシシラン（Ｂ）は、その化合物中のＳｉ元素にアルコキシ基が直接結合しており、そのアルコキシ基は、水溶液中で水と反応することによりシラノール基を形成する。このシラノール基は、亜鉛系めっき鋼板の表面と反応したり、成分（Ａ）や、後述する成分（Ｃ）〜（Ｄ）との間で複合的に縮合反応したりする。 In the tetraalkoxysilane (B), an alkoxy group is directly bonded to the Si element in the compound, and the alkoxy group forms a silanol group by reacting with water in an aqueous solution. The silanol group reacts with the surface of the zinc-based plated steel sheet, or undergoes a complex condensation reaction between the component (A) and components (C) to (D) described later.
テトラアルコキシシラン（Ｂ）の固形分質量（ＢS）の、合計質量（ＸS）に対する質量比（ＢS／ＸS）は０．０１０〜０．３０とする必要があり、好ましくは０．０４〜０．２４、より好ましくは０．０７〜０．１７である。質量比が０．０１０未満の場合は、耐熱割れ性が低下する。質量比が０．３０超えの場合は、平板部耐食性、アルカリ脱脂後耐食性が低下する。 The mass ratio (B S / X S ) of the solid content mass (B S ) of the tetraalkoxysilane (B) to the total mass (X S ) needs to be 0.010 to 0.30, preferably 0. 04 to 0.24, more preferably 0.07 to 0.17. When the mass ratio is less than 0.010, the thermal cracking resistance decreases. When the mass ratio exceeds 0.30, the corrosion resistance of the flat plate portion and the corrosion resistance after alkaline degreasing are lowered.
成分（Ａ）及び成分（Ｂ）は、各々単体で使用してよいもが、成分（Ａ）と成分（Ｂ）を縮合反応させて低縮合物としてから、表面処理液に添加するのが好ましく、成膜後により高いバリア性が得られる。この低縮合物は、（Ａ）および（Ｂ）のシラノール基同士の縮合反応により形成されるポリシロキサン結合を主骨格とするものであり、Ｓｉ元素に結合する末端の基の全てがアルコキシ基であるものでもよく、Ｓｉ元素に直接結合する基の一部がアルコキシ基であるものでもよい。 Component (A) and component (B) may be used alone respectively, but it is preferable to add component (A) and component (B) to the surface treatment liquid after condensation reaction to form a low condensate. Higher barrier properties can be obtained after film formation. This low condensate has as a main skeleton the polysiloxane bond formed by the condensation reaction of the silanol groups of (A) and (B), and all the terminal groups bonded to the Si element are alkoxy groups. Some of them may be used, or some of the groups directly bonded to the Si element may be alkoxy groups.
成分（Ａ）と成分（Ｂ）の縮合反応により得られる低縮合物は、縮合度が２〜３０が好適であり、２〜１０がより好適である。縮合度が３０以下であれば、水溶液中において白色沈殿を生じることなく、成分（Ａ）及び成分（Ｂ）を安定に使用することができる。この低縮合物は、成分（Ａ）と、成分（Ｂ）と、後述するキレート剤とを、反応温度１〜７０℃で１０分間〜２０時間程度反応させ、オートクレーブ処理を行うことにより得ることができる。キレート剤は、例えば、リンゴ酸、酢酸、酒石酸等のヒドロキシカルボン酸；モノカルボン酸；シュウ酸、マロン酸、コハク酸、クエン酸、アジピン酸等のジカルボン酸またはトリカルボン酸等のポリカルボン酸；およびグリシン等のアミノカルボン酸等などが挙げられ、これらの１種以上を用いることができる。 The low condensate obtained by the condensation reaction of the component (A) and the component (B) preferably has a degree of condensation of 2 to 30, and more preferably 2 to 10. If the degree of condensation is 30 or less, Component (A) and Component (B) can be used stably without producing a white precipitate in an aqueous solution. This low condensate can be obtained by reacting component (A), component (B), and a chelating agent described later at a reaction temperature of 1 to 70 ° C. for about 10 minutes to 20 hours and performing autoclave treatment. it can. Examples of the chelating agent include hydroxycarboxylic acids such as malic acid, acetic acid and tartaric acid; monocarboxylic acids; dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, citric acid and adipic acid, and polycarboxylic acids such as tricarboxylic acids; Examples thereof include aminocarboxylic acids such as glycine and the like, and one or more of these can be used.
この低縮合物の縮合状態は、ＪＩＳ−Ｋ７２５２−４に記載されているゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）、ＮＭＲ、およびＦＴ−ＩＲを用いて測定することができる。 The condensation state of this low condensate can be measured using gel permeation chromatography (GPC), NMR, and FT-IR described in JIS-K7252-4.
この低縮合物の安定化に作用するキレート剤は、成分（Ａ）のアルコキシ基と、成分（Ｂ）のアルコキシ基が、水とキレート剤によって加水分解反応する際に作用する。キレート剤による安定化作用は、その理由は定かでないが、加水分解反応によって生じる（Ａ）及び（Ｂ）に由来のシラノール基にキレート剤が適度に配位することによって得られるものと考えられる。すなわち、シラノール基へのキレート剤の適度な配位作用が、（Ａ）及び（Ｂ）の過度の縮合を抑制するため、貯蔵安定性に優れる表面処理液を得ることができる。さらには、長期に亘る表面処理液の保管後も安定した皮膜の品質が得られる。 The chelating agent which acts on the stabilization of the low condensation product acts when the alkoxy group of the component (A) and the alkoxy group of the component (B) hydrolyze by water and the chelating agent. The stabilizing effect of the chelating agent is not clear for the reason, but is considered to be obtained by appropriately coordinating the chelating agent to the silanol group derived from (A) and (B) generated by the hydrolysis reaction. That is, since the appropriate coordination action of the chelating agent to the silanol group suppresses excessive condensation of (A) and (B), it is possible to obtain a surface treatment liquid excellent in storage stability. Furthermore, stable film quality can be obtained even after storage of the surface treatment solution over a long period of time.
キレート剤は、貯蔵安定性に加え、耐食性を確保する上でも有効である。その理由は定かでないが、キレート剤は、後述するバナジウム化合物（Ｆ）とも配位すると考えられ、皮膜が腐食環境に晒されると、バナジウム化合物（Ｆ）に配位したキレート剤はバナジウム化合物（Ｆ）とともに溶出し、それによって皮膜内で配位子を失った（Ａ）及び（Ｂ）の縮合が進むことによって、より皮膜のバリア性が高まり、耐食性に寄与するものと考えられる。 In addition to storage stability, chelating agents are also effective in securing corrosion resistance. Although the reason is not clear, the chelating agent is considered to coordinate also with the vanadium compound (F) described later, and when the film is exposed to a corrosive environment, the chelating agent coordinated to the vanadium compound (F) is a vanadium compound (F It is thought that the barrier property of the film is further enhanced and the corrosion resistance is contributed by the elution of (A) and (B), which elutes together with them and thereby loses the ligand in the film.
＜珪酸ナトリウム（Ｃ）＞
本発明の表面処理液には、優れた耐熱割れ性に作用する珪酸ナトリウム（Ｃ）が添加される。珪酸ナトリウム（Ｃ）に含まれるナトリウムは、熱によってＳｉＯ4連結網から分断されたＳｉＯ4四面体の酸素原子へ結合する。そのため、ＳｉＯ4連結網の再結合が防止される。この作用によって、成分（Ｃ）は珪酸ガラスに流動性を与え、１，７００℃以上にある珪酸ガラスの軟化温度を５００℃〜７００℃に低下させる。本発明では、この作用を利用し、成分（Ａ）と、成分（Ｂ）と、後述の成分（Ｄ）とを含む硬質で熱膨張率の小さい皮膜が５００℃以上に加熱された際に、その皮膜に流動性を与えることによって、優れた耐熱割れ性を得るものと考える。
<Sodium silicate (C)>
In the surface treatment liquid of the present invention, sodium silicate (C) which exerts excellent heat crack resistance is added. The sodium contained in sodium silicate (C) is bound by heat to the oxygen atoms of the SiO 4 tetrahedra which are separated from the SiO 4 linked network. Therefore, recombination of the SiO 4 connection network is prevented. By this action, the component (C) imparts fluidity to the silica glass and lowers the softening temperature of the silica glass at 1,700 ° C. or higher to 500 ° C. to 700 ° C. In the present invention, when the hard film having a small coefficient of thermal expansion containing the component (A), the component (B), and the component (D) described later is heated to 500 ° C. or higher, utilizing this action. It is considered that excellent heat resistance cracking resistance is obtained by giving fluidity to the film.
珪酸ナトリウム（Ｃ）は、水溶性が高い成分であるものの、亜鉛に対するエッチング性がある。このため、本発明の表面処理液がめっき層と接触する際に溶出する亜鉛イオンとゲル化し、難溶性の珪酸金属塩として固定化され、皮膜の密着性を向上させる。さらに、珪酸ナトリウム（Ｃ）は、成分（Ａ）、成分（Ｂ）、後述する成分（Ｄ）を含むバリア性の高い皮膜のネットワーク中に取り込まれる。一方、腐食環境下では、上述のように皮膜中の珪酸ナトリウム（Ｃ）が適度に溶出し、亜鉛めっきの表面をアルカリ側へｐＨ操作する。この作用が亜鉛のアノード反応の遅延、抑制にも寄与する。 Although sodium silicate (C) is a component having high water solubility, it has an etching property to zinc. For this reason, the surface treatment liquid of the present invention is gelled with the zinc ion which is eluted when coming into contact with the plating layer, and is immobilized as a poorly soluble silicate metal salt to improve the adhesion of the film. In addition, sodium silicate (C) is incorporated into a highly barrier film network comprising component (A), component (B) and component (D) described later. On the other hand, in a corrosive environment, as described above, sodium silicate (C) in the film is appropriately eluted, and the pH of the surface of zinc plating is adjusted to the alkali side. This action also contributes to the delay and suppression of the anodic reaction of zinc.
本発明で用いる珪酸ナトリウム（Ｃ）は、ＳｉＯ2とＮａ2Ｏを含み、そのモル比は、ＳｉＯ2／Ｎａ2Ｏが４〜１のものであれば特に限定されない。例えば、２号珪酸ナトリウム、３号珪酸ナトリウムなどが挙げられ、これらの１種以上を用いることができる。より好ましいモル比は、ＳｉＯ2／Ｎａ2Ｏが４〜２である。ＳｉＯ2／Ｎａ2Ｏが４を超える場合、耐熱割れ性に対する効果が十分に得られない。ＳｉＯ2／Ｎａ2Ｏが１を下回る場合は、耐熱割れ性に対する効果は飽和するが、珪酸ナトリウム（Ｃ）の皮膜中への固定化が困難となるため、耐黒変性、耐水しみ性、耐汗性が劣る。 Sodium silicate (C) used in the present invention comprises SiO 2 and Na 2 O, the molar ratio is not particularly limited as long as the SiO 2 / Na 2 O is 4-1. For example, No. 2 sodium silicate, No. 3 sodium silicate and the like can be mentioned, and one or more of these can be used. A more preferred molar ratio is 4 to 2 of SiO 2 / Na 2 O. When SiO 2 / Na 2 O exceeds 4, the effect on the thermal cracking resistance can not be sufficiently obtained. When SiO 2 / Na 2 O is less than 1, although the effect on thermal cracking resistance is saturated, it is difficult to fix sodium silicate (C) in the film, so black resistance, water stain resistance, and resistance to water stain Sweaty is poor.
珪酸ナトリウム（Ｃ）の添加量は、耐熱割れ性と諸性能を両立する観点から、成分（Ａ）〜（Ｄ）の合計質量（ＸS）に対する質量比が極めて重要である。そして、珪酸ナトリウム（Ｃ）の固形分質量（ＣS）の、合計質量（ＸS）に対する質量比（ＣS／ＸS）は０．０５〜０．５０とする必要があり、好ましくは０．１〜０．４、より好ましくは０．１５〜０．３４である。質量比が０．０５未満の場合は、優れた耐熱変色性及び耐熱割れ性が得られない。さらに、平板部耐食性、アルカリ脱脂後耐食性も低下する。質量比が０．５０超えの場合には、耐黒変性、耐水しみ性、耐汗性、塗料密着性が劣る。さらに、表面処理液中にＮａイオンが多く存在することになるため、貯蔵安定性が低下する。 The addition amount of sodium silicate (C), from the viewpoint of achieving both the heat crack resistance and various properties, the weight ratio of component (A) ~ total mass of (D) (X S) is extremely important. Then, the solid mass of sodium silicate (C) (C S), the mass ratio to the total mass (X S) (C S / X S) is required to be 0.05 to 0.50, preferably 0 0.1 to 0.4, more preferably 0.15 to 0.34. When the mass ratio is less than 0.05, excellent heat discoloration resistance and heat crack resistance can not be obtained. Furthermore, the corrosion resistance of the flat plate portion and the corrosion resistance after alkaline degreasing also decrease. When the mass ratio exceeds 0.50, blackening resistance, water stain resistance, sweat resistance, and paint adhesion are poor. Furthermore, the storage stability is reduced because a large amount of Na ions will be present in the surface treatment solution.
＜炭酸ジルコニウム化合物（Ｄ）＞
本発明の表面処理液には、炭酸ジルコニウム化合物（Ｄ）が添加される。成分（Ａ）、（Ｂ）、（Ｃ）と、炭酸ジルコニウム化合物（Ｄ）を併用することにより、バリア性が高く緻密な、平板部耐食性、アルカリ脱脂後耐食性、耐水しみ性、耐汗性に優れた皮膜が得られる。バリア性が高くなるのは、炭酸ジルコニウム化合物（Ｄ）は、シラノール基との縮合点となる水酸基を有するためである。さらに、炭酸ジルコニウム化合物（Ｄ）は、乾燥させると耐水しみ性、耐汗性の高い酸化ジルコニウムと水酸化ジルコニウムを生成するため、耐水しみ性、耐汗性の高い皮膜が得られる。炭酸ジルコニウム化合物（Ｄ）としては、例えば、炭酸ジルコニウム化合物のナトリウム、カリウム、リチウム、アンモニウムなどの塩が挙げられ、これらの１種又は２種以上を用いることができる。なかでも、炭酸ジルコニウムアンモニウムが造膜性、耐水しみ性などの点から好ましい。
<Zirconium carbonate compound (D)>
A zirconium carbonate compound (D) is added to the surface treatment liquid of the present invention. By using the components (A), (B) and (C) in combination with the zirconium carbonate compound (D), the barrier property is high and dense, flat plate corrosion resistance, corrosion resistance after alkaline degreasing, water stain resistance, sweat resistance An excellent film is obtained. The barrier property is enhanced because the zirconium carbonate compound (D) has a hydroxyl group which is a condensation point with a silanol group. Furthermore, since the zirconium carbonate compound (D) produces zirconium oxide and zirconium hydroxide having high water resistance and sweat resistance when dried, a film having high water resistance and sweat resistance can be obtained. Examples of the zirconium carbonate compound (D) include salts of sodium, potassium, lithium, ammonium and the like of the zirconium carbonate compound, and one or more of these may be used. Among them, zirconium ammonium carbonate is preferable from the viewpoint of film forming property, water stain resistance and the like.
炭酸ジルコニウム化合物（Ｄ）中のＺｒＯ2換算質量（ＤZ）の、合計質量（ＸS）に対する質量比（ＤZ／ＸS）は０．０５〜０．６０とする必要があり、好ましくは０．１〜０．４７、より好ましくは０．１５〜０．３３である。質量比が０．０５未満の場合には、炭酸ジルコニウム化合物（Ｄ）由来の耐水しみ性、バリア性が不足し、平板部耐食性、アルカリ脱脂後耐食性、耐水しみ性、耐汗性が低下する。一方、質量比が０．６０超えの場合には、表面処理液の貯蔵安定性が低下する。 Zirconium carbonate compound of (D) ZrO 2 in terms of the mass in (D Z), the mass ratio to the total mass (X S) (D Z / X S) is required to be 0.05 to 0.60, preferably 0.1 to 0.47, more preferably 0.15 to 0.33. If the mass ratio is less than 0.05, the water resistance and barrier properties derived from the zirconium carbonate compound (D) will be insufficient, and the corrosion resistance of the flat plate part, the corrosion resistance after alkaline degreasing, the water resistance and the sweat resistance will be reduced. On the other hand, when the mass ratio exceeds 0.60, the storage stability of the surface treatment solution is reduced.
以上で記述した成分（Ａ）〜（Ｄ）を含む皮膜は、通常時は硬質でバリア性、平板部耐食性、アルカリ脱脂後耐食性に優れ、５００℃を超える加熱時においては、珪酸ナトリウム（Ｃ）の軟質化作用によって、耐熱変色性、耐熱割れ性に優れる。 The films containing the components (A) to (D) described above are usually hard and have excellent barrier properties, corrosion resistance at flat portions, corrosion resistance after alkaline degreasing, and sodium silicate (C) when heated over 500 ° C. It is excellent in heat discoloration resistance and heat crack resistance by the softening action of
＜アニオン性ポリウレタン樹脂（Ｅ）＞
本発明の表面処理液には、５００℃以上に加熱した際の無機成分由来のクラックを抑制するために、ガラス転移点（Ｔｇ）が８０℃〜１３０℃であるアニオン性ポリウレタン樹脂（Ｅ）が添加される。これにより、耐熱変色性、耐熱割れ性、平板部耐食性、耐黒変性、耐水しみ性、耐溶剤性、耐汗性、塗料密着性に優れた皮膜を得ることができる。ポリウレタン樹脂は高分子量であり、かつ、ウレタン結合が高い分子間凝集力を有するため、緻密でバリア性が高く、それ自体でも基材との密着性を有すが、成分（Ａ）〜（Ｄ）と併用することで、腐食成分の遮断性をさらに高めることができる。また、ウレタン結合が有する高い凝集性によって、珪酸ナトリウム（Ｃ）の適度な溶出も制御することが可能となる。そのため、上記のような優れた性能を有す皮膜を得ることができる。
<Anionic polyurethane resin (E)>
In the surface treatment liquid of the present invention, an anionic polyurethane resin (E) having a glass transition point (Tg) of 80 ° C. to 130 ° C. in order to suppress cracks derived from inorganic components when heated to 500 ° C. or higher. Is added. As a result, it is possible to obtain a film excellent in heat discoloration resistance, heat cracking resistance, corrosion resistance of flat portion, blackening resistance, water stain resistance, solvent resistance, sweat resistance, and paint adhesion. The polyurethane resin has a high molecular weight and high intermolecular cohesive force due to the high urethane bond, so it is dense and has high barrier properties, and itself has adhesion to the substrate, but the components (A) to (D In combination with the above, the barrier property of the corrosive component can be further enhanced. In addition, due to the high cohesiveness of the urethane bond, it is also possible to control the appropriate elution of sodium silicate (C). Therefore, a film having excellent performance as described above can be obtained.
ウレタン樹脂の性質を左右する基本骨格であるポリオールの種類としては、ポリエーテル系ポリオール、ポリエステル系ポリオール、ポリカーボネート系ポリオールが挙げられる。ポリエステル系ポリオール、ポリカーボネート系ポリオールは極性基を有するため、分子間の相互作用によって強靭な皮膜が得られる。ポリカーボネート系ポリオールは高価ではあるが、機械的強度に優れる。ポリエーテル系ポリオールは極性基を有していないため、機械的強度には多少劣るが、耐加水分解性など化学的には安定である。本発明で使用する成分（Ｅ）のポリオールについては特に制限はないが、本発明の目的とするアルカリ脱脂後耐食性、耐水しみ性などの観点より、ポリエーテル系ポリオールを使用することが好ましい。 As a kind of polyol which is a basic skeleton which influences the property of a urethane resin, polyether system polyol, polyester system polyol, polycarbonate system polyol is mentioned. Since polyester-based polyols and polycarbonate-based polyols have polar groups, interaction between molecules provides a tough film. Polycarbonate-based polyols are expensive but have excellent mechanical strength. Polyether-based polyols do not have polar groups and are thus somewhat inferior in mechanical strength, but are chemically stable such as hydrolysis resistance. Although there is no restriction | limiting in particular about the polyol of the component (E) used by this invention, It is preferable to use a polyether-type polyol from the viewpoints of corrosion resistance after alkali degreasing which the objective of this invention, water resistance, etc. show.
成分（Ｅ）の重量平均分子量は、ＪＩＳ−Ｋ７２５２−４に記載されているゲルパーミエーションクロマトグラフィーで測定した場合、１０，０００〜５００，０００程度であることが好ましく、５０，０００〜３００，０００程度であることがより好ましい。重量平均分子量を大きくするとウレタン樹脂のＴｇや機械物性を高めることができるため、皮膜のバリア性が向上し、平板部耐食性、アルカリ脱脂後耐食性、耐水しみ性、耐溶剤性、耐汗性などをより高めることができる。 The weight average molecular weight of the component (E) is preferably about 10,000 to 500,000, as measured by gel permeation chromatography described in JIS-K7252-4, 50,000 to 300,000. It is more preferable that it is about 000. Since the Tg and mechanical properties of the urethane resin can be enhanced by increasing the weight average molecular weight, the barrier properties of the film are improved, and the corrosion resistance of the flat portion, the corrosion resistance after alkaline degreasing, the water stain resistance, the solvent resistance, the sweat resistance, etc. It can be raised more.
アニオン性ポリウレタン樹脂（Ｅ）は、ポリエーテルポリオール（特にジオール）とポリイソシアネート（特にジイソシアネート）を原料として、一般的な合成方法により得られるものである。必要に応じて、さらに、ポリアミン（特にジアミン）、ヒドロキシル基を２個以上（特に好ましくは２個）有するカルボン酸、及び、前記カルボン酸の反応性誘導体を、原料として追加してもよい。限定的に解釈されるものではないが、より具体的な合成は、例えば、ポリエーテルジオールとジイソシアネートから両端にイソシアナト基を有するウレタンプレポリマーを製造し、これにヒドロキシル基を２個有するカルボン酸又はその反応性誘導体を溶媒中で反応させて両端にイソシアナト基を有する誘導体とし、ついでカウンターカチオンとしてトリエタノールアミンなどを加えてから、水に加えてエマルジョンとすることにより、アニオン性ポリウレタン樹脂を得ることができる。この後、必要に応じて、さらにジアミンを加えて鎖延長を行ってもよい。 Anionic polyurethane resin (E) is obtained by a general synthesis method using polyether polyol (especially diol) and polyisocyanate (especially diisocyanate) as raw materials. If necessary, a polyamine (in particular, a diamine), a carboxylic acid having two or more (particularly preferably two) hydroxyl groups, and a reactive derivative of the carboxylic acid may be added as a raw material. Although not to be construed as limiting, a more specific synthesis is, for example, the production of a urethane prepolymer having isocyanato groups at both ends from polyether diol and diisocyanate, and a carboxylic acid having two hydroxyl groups or this An anionic polyurethane resin is obtained by reacting the reactive derivative in a solvent to obtain a derivative having an isocyanato group at both ends, then adding triethanolamine or the like as a counter cation, and then adding it to water to form an emulsion. Can. After this, if necessary, further diamine may be added to carry out chain extension.
成分（Ｅ）を製造する際に用いるポリイソシアネートとしては、脂肪族、脂環式及び芳香族ポリイソシアネートがあり、いずれも使用可能である。具体的には、例えば、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、リジンジイソシアネート、水添キシリレンジイソシアネート、１，４−シクロヘキシレンジイソシアネート、４，４’−ジシクロヘキシルメタンジイソシアネート、２，４’−ジシクロヘキシルメタンジイソシアネート、イソホロンジイソシアネート、３，３’−ジメトキシ−４，４’−ビフェニレンジイソシアネート、１，５−ナフタレンジイソシアネート、１，５−テトラヒドロナフタレンジイソシアネート、２，４−トリレンジイソシアネート、２，６−トリレンジイソシアネート、４，４’−ジフェニルメタンジイソシアネート、２，４’−ジフェニルメタンジイソシアネート、フェニレンジイソシアネート、キシリレンジイソシアネート、テトラメチルキシリレンジイソシアネート等が挙げられる。これらの中で、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、リジンジイソシアネート、水添キシレンジイソシアネート、１，４−シクロヘキシレンジイソシアネート、４，４’−ジシクロヘキシルメタンジイソシアネート、２，４’−ジシクロヘキシルメタンジイソシアネート、イソホロンジイソシアネート等の脂肪族または脂環式ポリイソシアネートを用いる場合は、耐溶剤性、平板部耐食性、アルカリ脱脂後耐食性等だけではなく、耐熱変色性に優れた皮膜が得られるので好ましい。 Aliphatic, alicyclic and aromatic polyisocyanates can be used as the polyisocyanate used when producing the component (E), and any of them can be used. Specifically, for example, tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, hydrogenated xylylene diisocyanate, 1,4-cyclohexylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 2,4′-dicyclohexylmethane diisocyanate, Isophorone diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4 , 4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, phenylene diisocyanate, xylylene diisocyanate Tetramethyl xylylene diisocyanate. Among these, tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, hydrogenated xylene diisocyanate, 1,4-cyclohexylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 2,4′-dicyclohexylmethane diisocyanate, isophorone diisocyanate, etc. When an aliphatic or alicyclic polyisocyanate is used, it is preferable because not only solvent resistance, flat plate corrosion resistance, corrosion resistance after alkaline degreasing, etc., but also a film excellent in heat-resistant discoloration is obtained.
成分（Ｅ）を製造する際に用いるポリエーテルポリオール類としては、例えば、１，２−プロパンジオール、１，３−プロパンジオール、トリメチロールプロパン、グリセリン、ポリグリセリン、ペンタエリスリトール等の前記低分子ポリオールの他、ビスフェノールＡ、エチレンジアミン等のアミン化合物等へのエチレンオキサイド及び／又はプロピレンオキサイド付加物、ポリテトラメチレンエーテルグリコール等が挙げられる。 Examples of polyether polyols used in producing the component (E) include the low molecular weight polyols such as 1,2-propanediol, 1,3-propanediol, trimethylolpropane, glycerin, polyglycerin, pentaerythritol and the like. Other than these, ethylene oxide and / or propylene oxide adducts to amine compounds such as bisphenol A and ethylene diamine and the like, polytetramethylene ether glycol and the like can be mentioned.
成分（Ｅ）を製造する際に用いる、ヒドロキシル基を２個以上、好ましくは２個有するカルボン酸もしくはその反応性誘導体は、成分（Ｅ）に酸性基を導入するため、および成分（Ｅ）を水分散性にするために用いる。上記カルボン酸としては、ジメチロールプロピオン酸、ジメチロールブタン酸、ジメチロールペンタン酸、ジメチロールヘキサン酸などのジメチロールアルカン酸などが挙げられる。また、反応性誘導体としては、酸無水物などが挙げられる。このように成分（Ｅ）を自己水分散性にし、乳化剤を使用しないか極力使用しないようにすることにより、耐水しみ性に優れた皮膜が得られる。 A carboxylic acid having two or more hydroxyl groups, preferably two or more, or a reactive derivative thereof for use in producing the component (E) is for introducing an acidic group into the component (E), and the component (E) Used to make it water dispersible. Examples of the carboxylic acid include dimethylol propionic acid, dimethylol butanoic acid, dimethylol pentanoic acid, and dimethylol alkanoic acid such as dimethylol hexanoic acid. Moreover, an acid anhydride etc. are mentioned as a reactive derivative. By making the component (E) self-dispersible in water and not using an emulsifying agent or using it as much as possible, a film excellent in water stain resistance can be obtained.
成分（Ｅ）を製造する際にポリアミンや水等が用いられる。このポリアミンや水等は、調整したプレポリマーの鎖を伸長するために使用される。用いるポリアミンとしては、例えばヒドラジン、エチレンジアミン、プロピレンジアミン、１，６−ヘキサンジアミン、テトラメチレンジアミン、イソホロンジアミン、キシリレンジアミン、ピペラジン、１，１’−ビシクロヘキサン−４，４’−ジアミン、ジフェニルメタンジアミン、エチルトリレンジアミン、ジエチレントリアミン、ジプロピレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミンなどが挙げられ、これらを単独で又は数種を組み合わせて使用することができる。 A polyamine, water, etc. are used when manufacturing a component (E). The polyamine, water and the like are used to extend the chain of the prepared prepolymer. Examples of the polyamine to be used include hydrazine, ethylenediamine, propylenediamine, 1,6-hexanediamine, tetramethylenediamine, isophoronediamine, xylylenediamine, piperazine, 1,1'-bicyclohexane-4,4'-diamine, diphenylmethanediamine Ethyl tolylene diamine, diethylene triamine, dipropylene triamine, triethylene tetramine, tetraethylene pentamine and the like can be mentioned, and these can be used alone or in combination of several kinds.
成分（Ｅ）の合成時の樹脂の安定性、さらには造膜時の周囲環境が低温乾燥下にある場合の造膜性を高めるために、合成に際して造膜助剤を配合することが好ましい。造膜助剤としては、ブチルセロソルブ、Ｎ−メチル−２−ピロリドン、ブチルカルビトール、テキサノールなどが挙げられ、Ｎ−メチル−２−ピロリドンが好ましい。 In order to enhance the stability of the resin at the time of synthesis of the component (E) and further the film forming property when the surrounding environment at the time of film formation is under low temperature drying, it is preferable to blend a film forming aid at the time of synthesis. As the coalescent, butyl cellosolve, N-methyl-2-pyrrolidone, butyl carbitol, texanol and the like can be mentioned, with preference given to N-methyl-2-pyrrolidone.
成分（Ｅ）のガラス転移点（Ｔｇ）は８０℃〜１３０℃とする必要があり、好ましくは８５〜１２５℃であり、より好ましくは９０〜１２０℃である。ガラス転移点は使用するポリオールの分子量などにより調整される。ガラス転移点（Ｔｇ）が８０℃未満の場合、優れた平板部耐食性、アルカリ脱脂後耐食性、耐黒変性、耐水しみ性、耐溶剤性、耐汗性が得られない。皮膜になった際の成分（Ｅ）間や、成分（Ａ）〜（Ｄ）との凝集性が不足し、皮膜のバリア性が低下するとともに、珪酸ナトリウム（Ｃ）の溶出が過剰となるからである。一方、ガラス転移点（Ｔｇ）が１３０℃超えの場合は、皮膜が過度に硬くなり、優れた耐熱割れ性が得られない。さらに、珪酸ナトリウム（Ｃ）の適度な溶出が得られないため、平板部耐食性、アルカリ脱脂後耐食性が低下する。なお、成分（Ｅ）のガラス転移点温度（Ｔｇ）は、動的粘弾性測定装置（ＲＳＡＧ２, ＴＡ Ｉｎｓｔｒｍｅｎｔ）を用い、測定試料として、室温２４時間乾燥後、８０℃６時間乾燥、さらに１２０℃２０分乾燥し作製したフィルムを用い、動的粘弾性を測定し、ｔａnδの極大値から求めることができる。 The glass transition point (Tg) of the component (E) needs to be 80 ° C to 130 ° C, preferably 85 to 125 ° C, and more preferably 90 to 120 ° C. The glass transition point is adjusted by the molecular weight of the polyol used and the like. When the glass transition point (Tg) is less than 80 ° C., excellent flat plate corrosion resistance, corrosion resistance after alkaline degreasing, blackening resistance, water stain resistance, solvent resistance and sweat resistance can not be obtained. The cohesion between components (E) and components (A) to (D) when forming a film is insufficient, and the barrier property of the film is reduced and the elution of sodium silicate (C) is excessive. It is. On the other hand, when the glass transition point (Tg) exceeds 130 ° C., the film becomes too hard, and excellent thermal cracking resistance can not be obtained. Furthermore, since the appropriate elution of sodium silicate (C) can not be obtained, the corrosion resistance of the flat plate portion and the corrosion resistance after alkali degreasing are lowered. In addition, the glass transition temperature (Tg) of the component (E) is dried at 80 ° C. for 6 hours after drying at room temperature for 24 hours as a measurement sample using a dynamic viscoelasticity measuring device (RSAG2, TA Instrment), and further 120 ° C. Dynamic viscoelasticity can be measured using a film produced by drying for 20 minutes, and it can be determined from the maximum value of tan δ.
成分（Ａ）〜（Ｄ）の合計質量（ＸS）の、アニオン性ポリウレタン樹脂（Ｅ）の固形分質量（ＥS）に対する質量比（ＸS／ＥS）は０．０５〜０．３８とする必要があり、好ましくは０．０９〜０．３２、より好ましくは０．１４〜０．２５である。質量比が０．０５未満の場合には、優れたバリア性が得られず平板部耐食性、アルカリ脱脂後耐食性、耐溶剤性が低下する。一方、質量比が０．３８超えの場合は、皮膜が５００℃を超える加熱雰囲気に晒されると成分（Ａ）に結合している有機官能基の熱分解に由来する皮膜割れが顕著となり、優れた耐熱変色性、耐熱割れ性が得られない。さらに、珪酸ナトリウム（Ｃ）の皮膜中への固定化が困難となるため、耐黒変性、耐水しみ性、耐汗性、塗料密着性が劣る。 The total weight of components (A) ~ (D) of the (X S), the weight ratio to the solid content mass (E S) of the anionic polyurethane resin (E) (X S / E S) is 0.05 to 0.38 It is preferably from 0.09 to 0.32, more preferably from 0.14 to 0.25. When the mass ratio is less than 0.05, excellent barrier properties can not be obtained, and the corrosion resistance of the flat plate portion, the corrosion resistance after alkaline degreasing, and the solvent resistance decrease. On the other hand, when the mass ratio exceeds 0.38, when the film is exposed to a heating atmosphere exceeding 500 ° C., the film cracking derived from the thermal decomposition of the organic functional group bonded to the component (A) becomes remarkable, Heat discoloration resistance, heat cracking resistance can not be obtained. Furthermore, since it becomes difficult to fix sodium silicate (C) in the film, blackening resistance, water stain resistance, sweat resistance and paint adhesion are poor.
＜バナジウム化合物（Ｆ）＞
本発明の表面処理液には、バナジウム化合物（Ｆ）が添加される。バナジウム化合物（Ｆ）は、皮膜中では均一に分散して存在するが、腐食環境下においては適度に溶出し、同じく腐食環境下で溶出する亜鉛イオンと結合し緻密な不働態膜を形成することによって、平板部耐食性、アルカリ脱脂後耐食性を高める。バナジウム化合物（Ｆ）としては、例えば、メタバナジン酸アンモニウム、メタバナジン酸ナトリウム、バナジウムアセチルアセトネートが挙げられ、これらの１種以上を用いることができる。
<Vanadium compound (F)>
The vanadium compound (F) is added to the surface treatment liquid of the present invention. The vanadium compound (F) is uniformly dispersed in the film, but elutes appropriately in a corrosive environment, and combines with zinc ions eluting in the corrosive environment to form a dense passive film. The corrosion resistance of the flat portion after alkali degreasing is enhanced by Examples of the vanadium compound (F) include ammonium metavanadate, sodium metavanadate, and vanadium acetylacetonate, and one or more of these can be used.
バナジウム化合物（Ｆ）中のＶ換算質量（ＦV）の、成分（Ａ）〜（Ｄ）の合計質量（ＸS）と成分（Ｅ）の固形分質量（ＥS）との合計質量（ＸS＋ＥS）に対する質量比（ＦV／（ＸS＋ＥS））は０．００１０〜０．０１５とする必要があり、好ましくは０．００１６〜０．０１１であり、より好ましくは０．００２〜０．００７である。質量比が０．００１０未満の場合には、亜鉛イオンとの不働態膜形成効果が不足するため、平板部耐食性、アルカリ脱脂後耐食性が低下する。一方、質量比が０．０１５超えの場合には、良好な耐黒変性、耐水しみ性、耐汗性、塗料密着性が得られない。さらに、５００℃を超える加熱時にバナジウムの酸化変色が現れるため、耐熱変色性、耐熱割れ性も低下する。 Vanadium compound (F) V reduced mass in the (F V), the total weight of components (A) ~ total mass of (D) (X S) and solid content of the component (E) (E S) ( X S + E S) mass ratio (F V / (X S + E S)) is required to be 0.0010 to 0.015, preferably 0.0016 to 0.011, more preferably 0.002 It is -0.007. If the mass ratio is less than 0.0010, the effect of forming a passive film with zinc ions is insufficient, so the corrosion resistance of the flat plate portion and the corrosion resistance after alkaline degreasing are lowered. On the other hand, when the mass ratio exceeds 0.015, good blackening resistance, water stain resistance, perspiration resistance and paint adhesion can not be obtained. Furthermore, since the oxidation discoloration of vanadium appears at the time of heating exceeding 500 ° C., the heat discoloration resistance and the heat crack resistance also decrease.
＜モリブデン酸化合物（Ｇ）＞
本発明の表面処理液には、優れた耐黒変性を得るために、モリブデン酸化合物（Ｇ）が添加される。モリブデン酸化合物としては、モリブデン酸、モリブデン酸アンモニウム、モリブデン酸ナトリウム、モリブデン酸カリウム、モリブデン酸マグネシウム、モリブデン酸亜鉛などが挙げられ、本発明では、これらのうちから選んだ１種以上を使用することが好ましい。
<Molybdic acid compound (G)>
A molybdic acid compound (G) is added to the surface treatment liquid of the present invention in order to obtain excellent blackening resistance. Examples of molybdic acid compounds include molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, magnesium molybdate, zinc molybdate and the like, and in the present invention, one or more selected from these are used. Is preferred.
亜鉛系めっき層の黒変現象は、亜鉛系めっき層が高温高湿潤雰囲気に晒された際に、酸素欠乏型の酸化亜鉛が生成するためと考えられている。モリブデンは様々な価数を持つ第二遷移金属であり、空気中では酸素と結合してＭｏＯ2やＭｏＯ3で存在する。本発明では、ＭｏＯ4 2-等のモリブデン酸塩を使用する。このモリブデン酸塩は、皮膜に均一に添加された後、高温高湿雰囲気下においてＭｏＯ3等のモリブデン酸化物に還元されると考えられる。この作用によって、亜鉛めっき層表面の亜鉛には適度に酸素が供給されるため、酸素欠乏型の酸化亜鉛の生成が抑制されると考えられる。一方で、モリブデン酸塩を過度に添加すると、平板部耐食性、アルカリ脱脂後耐食性の低下を引き起こす。 The blackening phenomenon of the zinc-based plating layer is considered to be due to the formation of oxygen-deficient zinc oxide when the zinc-based plating layer is exposed to a high temperature and high humidity atmosphere. Molybdenum is a second transition metal with various valences, and is combined with oxygen in air and exists as MoO 2 or MoO 3 . In the present invention, molybdates such as MoO 4 2- are used. The molybdate is considered to be reduced to a molybdenum oxide such as MoO 3 under a high temperature and high humidity atmosphere after being uniformly added to the film. By this action, since oxygen is appropriately supplied to the zinc on the surface of the zinc plating layer, it is considered that the formation of oxygen-deficient zinc oxide is suppressed. On the other hand, excessive addition of molybdate causes corrosion of the flat plate portion and corrosion resistance after alkaline degreasing.
モリブデン酸化合物（Ｇ）中のＭｏ換算質量（ＧM）の、成分（Ａ）〜（Ｄ）の合計質量（ＸS）と成分（Ｅ）の固形分質量（ＥS）との合計質量（ＸS＋ＥS）に対する質量比（ＧM／（ＸS＋ＥS））は０．００１０〜０．０１５とする必要があり、好ましくは０．００２〜０．０１２であり、より好ましくは０．００４〜０．００９である。質量比が０．００１０未満の場合には、優れた耐黒変性が得られない。質量比が０．０１５超えの場合には、良好な平板部耐食性、アルカリ脱脂後耐食性が得られない。 Mo reduced mass in molybdate compound (G) of (G M), the total mass of the solid content of the components (A) ~ total mass of (D) (X S) and the component (E) (E S) ( X S + E S) mass ratio (G M / (X S + E S)) is required to be 0.0010 to 0.015, preferably from 0.002 to 0.012, more preferably 0. It is 004 to 0.009. When the mass ratio is less than 0.0010, excellent blackening resistance can not be obtained. When the mass ratio exceeds 0.015, good flat plate corrosion resistance and corrosion resistance after alkaline degreasing can not be obtained.
＜ワックス（Ｈ）＞
本発明の表面処理液には、潤滑性を向上させるためにワックス（Ｈ）が添加されてもよい。ワックス（Ｈ）としては、液に相溶するものであれば特に制限はなく、例えば、ポリエチレン等のポリオレフィンワックス、モンタンワックス、パラフィンワックス、マイクロクリスタリンワックス、カルナバワックス、ラノリン系ワックス、シリコン系ワックス、フッ素系ワックスなどが挙げられ、これらの１種以上を好適に使用することができる。また、前記ポリオレフィンワックスとしては、例えばポリエチレンワックス、酸化ポリエチレンワックス、ポリプロピレンワックスなどが挙げられ、これら１種以上を使用することができる。
<Wax (H)>
Wax (H) may be added to the surface treatment liquid of the present invention to improve lubricity. The wax (H) is not particularly limited as long as it is compatible with the liquid, and examples thereof include polyolefin waxes such as polyethylene, montan wax, paraffin wax, microcrystalline wax, carnauba wax, lanolin wax, silicone wax, A fluorine-type wax etc. are mentioned, One or more types of these can be used suitably. Examples of the polyolefin wax include polyethylene wax, oxidized polyethylene wax, and polypropylene wax. One or more of these can be used.
ワックス（Ｈ）の固形分質量（ＨS）の合計質量（ＸS＋ＥS）に対する質量比（ＨS／（ＸS＋ＥS））は０．００２〜０．１０とすることが好ましく、０．０１〜０．０８がより好ましい。質量比が０．００２以上の場合、十分な潤滑性向上効果が得られる。一方、質量比が０．１０以下の場合、潤滑性が高まりすぎてコイル製造時の巻き取り工程におけるコイル潰れを生じるという懸念がない。さらに、平板部耐食性、アルカリ脱脂後耐食性や塗料密着性が低下する懸念もない。 The mass ratio (H S / (X S + E S )) to the total mass (X S + E S ) of the solid content mass (H S ) of the wax (H) is preferably 0.002 to 0.10, 0 More preferably, .01 to 0.08. When the mass ratio is 0.002 or more, a sufficient lubricity improvement effect can be obtained. On the other hand, when the mass ratio is 0.10 or less, there is no concern that the lubricity is too high to cause coil crushing in the winding process at the time of coil production. Furthermore, there is no concern that the corrosion resistance of the flat plate portion, the corrosion resistance after alkaline degreasing, and the adhesion of the paint may be reduced.
＜ｐＨ：８．０〜１０．０＞
本発明の表面処理液は、上述した成分を脱イオン水、蒸留水等の水中で混合することにより得られる。表面処理液の固形分割合は適宜選択すればよいが１０〜２０％が好ましい。また、表面処理液のｐＨは、８．０〜１０．０に調製する必要があり、好ましくは８．５〜９．５である。ｐＨが８．０未満の場合には、表面処理液の貯蔵安定性が低下する。一方、ｐＨが１０．０超えの場合には、亜鉛系めっき層のエッチングが過多となり、平板部耐食性、アルカリ脱脂後耐食性が低下する。ｐＨを調整する場合は、アンモニアまたはその塩、及び、前述したキレート剤の何れか１種以上を適宜使用すればよい。
<PH: 8.0 to 10.0>
The surface treatment liquid of the present invention can be obtained by mixing the above-mentioned components in water such as deionized water or distilled water. Although the solid content ratio of the surface treatment liquid may be appropriately selected, it is preferably 10 to 20%. In addition, the pH of the surface treatment liquid needs to be adjusted to 8.0 to 10.0, preferably 8.5 to 9.5. When the pH is less than 8.0, the storage stability of the surface treatment solution is reduced. On the other hand, when the pH exceeds 10.0, etching of the zinc-based plating layer is excessive, and corrosion resistance in the flat plate portion and corrosion resistance after alkaline degreasing are lowered. When adjusting the pH, any one or more of ammonia or a salt thereof and the above-mentioned chelating agent may be used appropriately.
さらに、表面処理液には、必要に応じてアルコール、ケトン、セロソルブ、アミン系の水溶性溶剤、消泡剤、防菌防カビ剤、着色剤、均一塗工のための濡れ性向上剤、樹脂、界面活性剤等の添加剤を添加してもよい。ただし、これら添加剤は本発明で得られる品質を損なわない程度に添加することが重要であり、添加量は多くても表面処理液の全固形分に対して５質量％未満とすることが好ましい。 Furthermore, in the surface treatment liquid, if necessary, alcohol, ketone, cellosolve, amine-based water-soluble solvent, antifoaming agent, antifungal agent, fungicide, coloring agent, wettability improver for uniform coating, resin And additives such as surfactants may be added. However, it is important to add these additives to such an extent that the quality obtained in the present invention is not impaired, and it is preferable that the amount added is less than 5% by mass with respect to the total solid content of the surface treatment solution .
＜表面処理皮膜付き亜鉛系めっき鋼板の製造方法＞
本発明の表面処理皮膜付き亜鉛系めっき鋼板の製造方法は、亜鉛系めっき鋼板の表面に、上述の表面処理液を塗布する工程と、その後、塗布された前記表面処理液を乾燥して、付着量が５０〜２，０００ｍｇ／ｍ2の表面処理皮膜を形成する工程と、を有する。以下に、その皮膜の形成条件・方法について詳述する。
<Manufacturing method of galvanized steel sheet with surface treatment film>
The method for producing a zinc-based plated steel sheet with a surface treatment film according to the present invention comprises the steps of applying the above-mentioned surface treatment liquid to the surface of a zinc-based plated steel sheet and thereafter drying and adhering the surface treatment liquid applied. Forming a surface treatment film in an amount of 50 to 2,000 mg / m 2 . Below, the formation conditions and method of the film are explained in full detail.
加熱乾燥後の表面処理皮膜の付着量は、片面あたり５０〜２，０００ｍｇ／ｍ2であり、好ましくは５００〜１，５００ｍｇ／ｍ2である。付着量が５０ｍｇ／ｍ2未満ではバリア性が不足するため、平板部耐食性、アルカリ脱脂後耐食性、耐黒変性、耐水しみ性、耐汗性が得られない。一方、付着量が２，０００ｍｇ／ｍ2を超えると、皮膜が厚いため、耐熱変色性、耐熱割れ性が劣る。 The adhesion amount of the surface treatment film after heat drying is 50 to 2,000 mg / m 2 , preferably 500 to 1,500 mg / m 2 per one side. If the adhesion amount is less than 50 mg / m 2 , the barrier property is insufficient, and therefore corrosion resistance after flat surface part, corrosion resistance after alkaline degreasing, blackening resistance, water stain resistance, and sweat resistance can not be obtained. On the other hand, when the adhesion amount exceeds 2,000 mg / m 2 , the film is thick, so the heat discoloration resistance and the heat crack resistance are inferior.
亜鉛系めっき鋼板に表面処理液を塗布する前に、必要に応じて、亜鉛系めっき鋼板表面の油分や汚れを除去することを目的とした前処理を亜鉛系めっき鋼板に施してもよい。亜鉛系めっき鋼板は、防錆目的で防錆油が塗られている場合が多く、また、防錆油で塗油されていない場合でも、作業中に付着した油分や汚れ等がある。上記の前処理を施すことにより、亜鉛系めっき層の表面が清浄化され、均一に濡れやすくなる。亜鉛系めっき鋼板表面に油分や汚れ等がなく、表面処理液が均一に濡れる場合は、前処理工程は特に必要はない。なお、前処理の方法は特に限定されず、例えば湯洗、有機溶剤洗浄、アルカリ脱脂洗浄等の方法が挙げられる。 Before applying the surface treatment liquid to the zinc-based plated steel plate, the zinc-based plated steel plate may be subjected to pretreatment for removing oil and dirt on the surface of the zinc-based plated steel plate, if necessary. Zinc-based plated steel sheets are often coated with anti-corrosion oil for the purpose of anti-corrosion, and even if they are not coated with anti-corrosion oil, there are oil and dirt adhering during work. By applying the above pretreatment, the surface of the zinc-based plating layer is cleaned and easily wetted uniformly. In the case where the surface of the zinc-based plated steel sheet is free of oil and dirt and the surface treatment solution is uniformly wetted, the pretreatment step is not particularly required. In addition, the method of pre-processing is not specifically limited, For example, methods, such as hot water washing, organic-solvent washing | cleaning, alkali degreasing washing | cleaning, are mentioned.
表面処理液を亜鉛系めっき鋼板の表面に塗布する方法としては、処理される亜鉛系めっき鋼板の形状等によって適宜最適な方法を選択すればよく、ロールコート法、バーコート法、浸漬法、スプレー塗布法等が挙げられる。また、塗布後にエアーナイフ法やロール絞り法により塗布量の調整、外観の均一化、膜厚の均一化を行うことも可能である。 As a method of applying the surface treatment solution to the surface of the zinc-based plated steel sheet, an optimum method may be selected appropriately depending on the shape of the zinc-based plated steel sheet to be treated, roll coating, bar coating, immersion method, spray A coating method etc. are mentioned. Further, after the application, it is also possible to adjust the application amount, make the appearance uniform, and make the film thickness uniform by an air knife method or a roll drawing method.
表面処理液を塗布後、亜鉛系めっき鋼板の加熱乾燥を行う手段としては、ドライヤーの他、熱風炉、高周波誘導加熱炉、及び赤外線炉などの乾燥炉を用いることができる。 As a means to heat-dry a zinc-based plated steel plate after application of the surface treatment liquid, a drying furnace such as a hot air furnace, a high frequency induction heating furnace, and an infrared furnace can be used other than a drier.
ここで、表面処理液を塗布する際の、亜鉛系めっき鋼板の温度及び表面処理液の温度をそれぞれＴS及びＴLとし、ＴS−ＴLをΔＴとしたとき、ＴSは１５〜５５℃とし、ＴLは１０〜４０℃とし、ΔＴは５〜４０℃とすることが好ましい。また、塗布された表面処理液の乾燥に関しては、時間ｔ秒の大気中での予備乾燥工程と、その後の乾燥炉での加熱乾燥工程と、の２段階の乾燥とし、その際、ΔＴ／ｔを１〜６０℃／ｓとすることが好ましい。 Here, when the temperature of the zinc-based plated steel plate and the temperature of the surface treatment liquid at the time of applying the surface treatment liquid are T S and T L, and T S- T L is ΔT, T S is 15 to 55. It is preferable to set it as ° C, set T L to 10 to 40 ° C, and set ΔT to 5 to 40 ° C. In addition, regarding the drying of the applied surface treatment liquid, the drying is performed in two stages of a preliminary drying step in the atmosphere for a time t seconds and a subsequent heating and drying step in a drying furnace, where ΔT / t Of 1 to 60.degree. C./s.
ＴLは室温近辺、すなわち１０〜４０℃がよい。ＴLが１０℃未満の場合、表面処理液の流動性が低下し、４０℃超えの場合、表面処理液の貯蔵安定性が低下する。ＴSは、後述のＺｒを含む相が所望の体積分率となる２相分離皮膜を得るためのΔＴを確保するために、１５〜５５℃とすることが好ましい。 T L should be around room temperature, that is, 10 to 40 ° C. When T L is less than 10 ° C., the flowability of the surface treatment solution decreases, and when it exceeds 40 ° C., the storage stability of the surface treatment solution decreases. It is preferable to set T S to 15 to 55 ° C. in order to secure ΔT for obtaining a two-phase separation film in which a phase containing Zr described later has a desired volume fraction.
ここで、本実施形態では、第１に、ＴS及びＴLの温度差ΔＴを所定温度以上設けることが重要であり、第２に、その温度差ΔＴとの関係で、予備乾燥工程の時間ｔ（秒）を決定することが重要である。これにより、鋼板表面に形成された表面処理液膜中の水分を徐々に気化させることができる。すなわち、鋼板表面に形成された表面処理液膜中において、水分が気化する前にＳｉがＺｒと共に水分と縮合反応を開始し、所望の表面処理皮膜を得ることができる。ΔＴが５℃未満の場合、表面処理液膜中の水分が気化しないため、後述のＺｒを含む相が所望の体積分率となる２相分離皮膜を得ることできず、また４０℃超えの場合、上記の縮合反応を開始する前に、表面処理液膜中の水分が気化し始めるため、皮膜の骨格となる樹脂成分からなる相（後述のＺｒを含まない相）を所定量確保できない。そして、ΔＴ／ｔが１℃／ｓ未満の場合、上記の縮合反応が過剰となり、後述の体積分率となる２相分離皮膜を得ることできず、また６０℃／ｓ超えの場合、上記の縮合反応が不十分となり、皮膜の骨格となる樹脂成分からなる相（後述のＺｒを含まない相）を所定量確保できない。 Here, in the present embodiment, firstly, it is important to set the temperature difference ΔT between T S and T L to a predetermined temperature or more, and secondly, in relation to the temperature difference ΔT, the time of the preliminary drying step It is important to determine t (seconds). Thus, the water in the surface treatment liquid film formed on the surface of the steel sheet can be gradually vaporized. That is, in the surface treatment liquid film formed on the surface of the steel sheet, Si starts condensation reaction with water together with Zr before the water is vaporized, and a desired surface treatment film can be obtained. If ΔT is less than 5 ° C., the water in the surface treatment liquid film does not evaporate, so it is not possible to obtain a two-phase separation film in which the phase containing Zr described later has a desired volume fraction. Since water in the surface treatment liquid film starts to evaporate before starting the above-mentioned condensation reaction, a predetermined amount of a phase (a phase not containing Zr described later) consisting of a resin component to be a skeleton of the film can not be secured. And, when ΔT / t is less than 1 ° C./s, the above condensation reaction becomes excessive, and it is impossible to obtain a two-phase separation film which becomes the volume fraction described later, and when it exceeds 60 ° C./s, the above The condensation reaction is insufficient, and a predetermined amount of a phase (a phase not containing Zr described later) composed of a resin component to be a skeleton of the film can not be secured.
その後の加熱乾燥工程については定法のとおりとすることができ、特に限定されないが、最高到達板温（Peak Metal Temperature：ＰＭＴ）は６０〜２００℃が好ましく、８０〜１８０℃がより好ましい。ＰＭＴが２００℃以下であれば、皮膜のクラックや皮膜成分の熱分解は生じ難く、本発明が求める諸性能は低下しない。一方、ＰＭＴが６０℃以上であれば、表面処理皮膜の成分間の結合が十分に得られ、本発明が求める諸性能が低下しない。加熱時間は、使用される亜鉛系めっき鋼板の組成、製造ラインの工程および構成等によって適宜最適な条件が選択され、生産性等の観点からは、０．１〜６０秒が好ましく、１〜３０秒が特に好ましい。 The subsequent heating and drying step can be performed as usual, and is not particularly limited. However, the peak metal temperature (PMT) is preferably 60 to 200 ° C., and more preferably 80 to 180 ° C. When the PMT is 200 ° C. or less, cracks in the film and thermal decomposition of the film components do not easily occur, and the various properties required by the present invention do not decrease. On the other hand, if PMT is 60 ° C. or higher, bonding between the components of the surface treatment film is sufficiently obtained, and the various performances required by the present invention are not degraded. The heating time is appropriately selected according to the composition of the zinc-based plated steel sheet used and the process and configuration of the production line, etc. From the viewpoint of productivity etc., 0.1 to 60 seconds is preferable, and 1 to 30 Seconds are particularly preferred.
＜表面処理皮膜の形態＞
かようにして亜鉛系めっき鋼板表面に成膜された表面処理皮膜は、加熱乾燥時に、Ｚｒと共にＳｉが縮合反応を起こすことにより、Ｚｒを含む相とＺｒを含まない相に分離する。ここで、「Ｚｒを含まない相」とは、構成元素全体に対するＺｒの含有量が３質量％未満の相をいう。
<Form of surface treatment film>
The surface treatment film thus formed on the surface of the zinc-based plated steel sheet separates into a phase containing Zr and a phase not containing Zr by causing a condensation reaction with Si during heating and drying. Here, the “phase not containing Zr” refers to a phase in which the content of Zr with respect to the entire constituent elements is less than 3% by mass.
Ｚｒを含む相は、主としてＳｉ、Ｚｒ、Ｖの酸化物等の無機系物質から構成される相である。Ｚｒを含まない相は、表面処理皮膜を形成する基本骨格をなし、Ｃ、Ｏを主体とし、さらにＳｉを含む樹脂成分からなる相である。Ｚｒを含む相にはＳｉが濃縮されるため、Ｚｒを含む相のＳｉ濃度は、Ｚｒを含まない相のＳｉ濃度より高い。 The phase containing Zr is a phase mainly composed of inorganic materials such as oxides of Si, Zr and V. The phase not containing Zr forms a basic skeleton that forms a surface treatment film, and is a phase composed mainly of C, O, and a resin component containing Si. Since Si is concentrated in the Zr-containing phase, the Si concentration of the Zr-containing phase is higher than the Si concentration of the Zr-free phase.
表面処理皮膜中のＳｉは、Ｓｉ同士の結合性、Ｚｒを含む相とＺｒを含まない相との結合性、および皮膜とめっき層表面との結合性を増強し、耐食性を向上させることができる。 Si in the surface treatment film can enhance corrosion resistance by enhancing bonding between Si, bonding between a phase containing Zr and a phase not containing Zr, and bonding between the coating and the surface of the plating layer .
表面処理皮膜中のＺｒは、Ｚｒを含む無機系物質から構成される相を形成させる上で重要な元素である。Ｚｒを含む相を表面処理皮膜中に分布させることにより、Ｚｒを含む相とＺｒを含まない相との結合性を増強し、バリア性が高く緻密な皮膜とすることができる。この効果を得るためには、表面処理皮膜全体に対して、Ｚｒを含む相の体積分率が５〜４０％であることが好ましく、５〜３０％がより好ましい。Ｚｒを含む相の体積分率が５％未満では、Ｖの溶出が不十分となるため、さらなる耐食性の向上が認められない。Ｚｒを含む相の体積分率が４０％超では、有機成分による皮膜のバリア性が下がるため、さらなる耐食性の向上が認められない。 Zr in the surface treatment film is an important element in forming a phase composed of an inorganic material including Zr. By distributing the phase containing Zr in the surface treatment film, the bonding between the phase containing Zr and the phase not containing Zr can be enhanced, and a dense film can be formed with high barrier properties. In order to obtain this effect, the volume fraction of the phase containing Zr is preferably 5 to 40%, more preferably 5 to 30%, relative to the entire surface treatment film. If the volume fraction of the phase containing Zr is less than 5%, the dissolution of V is insufficient, and thus no further improvement in corrosion resistance is observed. If the volume fraction of the phase containing Zr is more than 40%, the barrier property of the film due to the organic component is reduced, and thus no further improvement in the corrosion resistance is observed.
なお、Ｚｒを含む相におけるＺｒとＳｉの濃度の割合は、Ｚｒ／（Ｓｉ＋Ｚｒ）（質量比として）としたとき、０．２０以上０．６０以下とするのが好適である。 Note that the ratio of the concentration of Zr and Si in the phase containing Zr is preferably 0.20 or more and 0.60 or less, where Zr / (Si + Zr) (as mass ratio).
表面処理皮膜中のＶは、Ｚｒを含む相に共存させることにより、腐食環境下で適度に溶出し、めっき表面から溶出する亜鉛イオンと結合して緻密な不動態膜を形成するため耐食性を向上させることができる。この効果を得るために、Ｚｒを含む相におけるＶの含有量は、Ｖ／（Ｓｉ＋Ｚｒ）（質量比として）としたとき、０．００３〜０．１が好適である。 By making V in the surface treatment film coexist with the phase containing Zr, it dissolves appropriately in a corrosive environment and combines with zinc ions eluted from the plating surface to form a dense passivation film, thus improving corrosion resistance. It can be done. In order to obtain this effect, the content of V in the phase containing Zr is preferably 0.003 to 0.1 when V / (Si + Zr) (as a mass ratio).
Ｚｒを含む相の体積分率は、皮膜の表面または断面を電子顕微鏡で観察することにより評価できる。皮膜表面の観察には、走査電子顕微鏡（ＳＥＭ）を用いることができる。近年のＳＥＭでは、メーカーや機種によりさまざまなタイプの二次電子検出器や反射電子検出器があり、観察条件により異なる情報が得られることが報告されている。従って、皮膜表面の観察には、都度使用される装置に応じて適切な観察条件を用いればよい。ただし、加速電圧については、大きく異なる場合には、情報深さが変わり評価が異なる可能性があるため、０．５ｋＶから３ｋＶの範囲で評価することが好ましい。皮膜断面の観察には、集束イオンビーム（ＦＩＢ）で加工した皮膜の断面をＳＥＭで観察するか、もしくはＦＩＢで薄片状にまで加工した試料を、透過電子顕微鏡（ＴＥＭ）または走査透過電子顕微鏡（ＳＴＥＭ）で観察する方法が適している。Ｚｒを含む相と、Ｚｒを含まない相は、電子顕微鏡像においてコントラスト差より、明瞭に判別できる。特に、皮膜表面からＳＥＭ観察により評価する場合、０．５ｋＶから３ｋＶ程度の低い加速電圧で、一般的な二次電子検出器であるＥｖｅｒｈａｒｔ−Ｔｈｏｒｎｌｅｙ型検出器を用いた二次電子像観察を行うと、無機系物質から構成される相（Ｚｒを含む相）が明るく、樹脂成分からなる相（Ｚｒを含まない相）が暗く観察される。 The volume fraction of the phase containing Zr can be evaluated by observing the surface or cross section of the film with an electron microscope. A scanning electron microscope (SEM) can be used to observe the film surface. In recent years, SEMs have various types of secondary electron detectors and backscattered electron detectors depending on manufacturers and models, and it has been reported that different information can be obtained depending on observation conditions. Therefore, for observation of the film surface, appropriate observation conditions may be used depending on the apparatus used each time. However, if the acceleration voltage is significantly different, the information depth may change and the evaluation may be different, so it is preferable to evaluate in the range of 0.5 kV to 3 kV. For observation of the film cross section, a cross section of the film processed by focused ion beam (FIB) is observed by SEM, or a sample processed into a flaky shape by FIB is a transmission electron microscope (TEM) or a scanning transmission electron microscope ( The method of observation by STEM) is suitable. The phase containing Zr and the phase not containing Zr can be clearly distinguished from the contrast difference in the electron microscope image. In particular, when evaluating by SEM observation from the film surface, secondary electron image observation is performed using a general secondary electron detector, an Everhart-Thornley detector, at a low acceleration voltage of about 0.5 kV to 3 kV. In addition, the phase composed of the inorganic material (the phase containing Zr) is bright, and the phase composed of the resin component (the phase not containing Zr) is observed dark.
従って、コントラスト差が明瞭に表れる観察条件を設定し、観察された電子顕微鏡像を二値化して、Ｚｒを含む相の面積率を算出し、体積分率とみなすことができる。二値化の手法は様々あり、閾値の選び方によって得られる数値が変わり得るため、元の画像から判別される明部と暗部の区別から大きく逸脱しない様に閾値を決定することが肝要である。例えば、加速電圧１〜２ｋＶでＥｖｅｒｈａｒｔ−Ｔｈｏｒｎｌｅｙ型検出器を用いて二次電子像を取得した場合、得られた画像に対して、最大エントロピー法により画像を２値化する方法が有効である。このとき、観察倍率としては、１〜３万倍程度が好ましい。またこのとき、観察場所によりばらつきがあることが考えられるため、ひとつの試料につき、少なくとも５視野以上の画像を取得し、その平均を評価値とすることが好ましい。また、観察像については、ノイズを除去するため平滑化処理を施すことで、より正しい評価を行うことができる。ただし、平滑化処理は強過ぎると像の解像度が劣化し、評価値にも影響を与えるため、最大でもオペレータサイズを１０ｎｍ相当程度までとすることが好ましい。また、上記顕微鏡観察において、判別される領域それぞれが、Ｚｒを含む相か含まない相のどちらかを判別するためには、上記ＴＥＭまたはＳＴＥＭによる断面観察において、エネルギー分散分光法（ＥＤＳ）による元素分析が利用できる。それぞれの相における元素分析により、それぞれの相においてＺｒを含むか含まないかを判断することができる。 Therefore, the observation conditions under which the contrast difference appears clearly are set, the observed electron microscope image is binarized, and the area ratio of the phase containing Zr can be calculated and regarded as a volume fraction. There are various kinds of binarization methods, and it is important to determine the threshold value so as not to largely deviate from the distinction between the bright part and the dark part determined from the original image because the numerical value obtained can be changed depending on how to select the threshold value. For example, when a secondary electron image is acquired using an Everhart-Thornley detector at an acceleration voltage of 1 to 2 kV, a method of binarizing the image by the maximum entropy method is effective for the obtained image. At this time, the observation magnification is preferably about 1 to 30,000 times. At this time, it is considered that there is a variation depending on the observation place, so it is preferable to acquire an image of at least 5 fields of view or more for one sample, and set the average as an evaluation value. Further, more accurate evaluation can be performed on the observation image by performing smoothing processing to remove noise. However, if the smoothing process is too strong, the resolution of the image is degraded, and the evaluation value is also affected. Therefore, it is preferable to set the operator size to about 10 nm or less at most. Further, in order to discriminate either the phase containing Zr or the phase not containing Zr in the above microscopic observation, the element by energy dispersive spectroscopy (EDS) in the cross-sectional observation by the TEM or STEM. Analysis is available. Elemental analysis in each phase makes it possible to determine whether each phase contains or does not contain Zr.
以下、実施例および比較例により本発明の効果を説明するが、本実施例はあくまで本発明を説明する一例に過ぎず、本発明を限定するものではない。 EXAMPLES The effects of the present invention will be described below with reference to examples and comparative examples, but the present examples are merely examples for explaining the present invention, and are not intended to limit the present invention.
［実施例１］
（１）供試板
以下に示す各種亜鉛系めっき鋼板を供試板として使用した。なお、亜鉛系めっき層は鋼板の両面に形成され、表１中の付着量は片面当たりの亜鉛系めっき層の付着量を意味する。また、以下の方法で求めたＺｎ−Ａｌ−Ｍｇ系三元共晶の表面面積率も表１に示す。めっき層の表面の無作為な部位を観察倍率１００倍でＳＥＭ観察する。次いで、同視野でＥＤＳによりＭｇのマッピングを行う。その分析結果を画像解析して、白黒の２階調化する。この２階調化した画像よりＺｎ−Ａｌ−Ｍｇ系三元共晶の面積割合を計算する。同様の評価を任意の８視野で実施し、最後に全視野の面積割合を算術平均し、得られた平均値をＺｎ−Ａｌ−Ｍｇ系三元共晶の表面面積率とする。
Example 1
(1) Test plate Various zinc-based plated steel plates shown below were used as test plates. The zinc-based plating layer is formed on both sides of the steel plate, and the adhesion amount in Table 1 means the adhesion amount of the zinc-based plating layer per one side. Moreover, the surface area ratio of Zn-Al-Mg-based ternary eutectic obtained by the following method is also shown in Table 1. SEM observation of the random part of the surface of a plating layer is carried out by 100 times of observation magnification. Next, mapping of Mg is performed by EDS in the same field of view. The analysis result is image-analyzed to make two gradations of black and white. The area ratio of Zn-Al-Mg-based ternary eutectic is calculated from the two-graded image. The same evaluation is carried out in any eight fields of view, and finally the area ratio of the entire field of view is arithmetically averaged, and the obtained average value is taken as the surface area ratio of the Zn-Al-Mg ternary eutectic.
（２）前処理（洗浄）
上述の供試板の表面を、日本パーカライジング（株）製パルクリーンＮ３６４Ｓを用いて処理し、表面の油分や汚れを取り除いた。次に、水道水で水洗して供試板の表面が水で１００％濡れることを確認した後、さらに純水（脱イオン水）を流しかけ、１００℃雰囲気のオーブンで水分を乾燥した。
(2) Pre-treatment (washing)
The surface of the test plate described above was treated with Palclean N364S manufactured by Nihon Parkerizing Co., Ltd. to remove oil and dirt on the surface. Next, after washing with tap water to confirm that the surface of the test plate is 100% wet with water, pure water (deionized water) was further poured to dry the moisture in an oven at 100 ° C. atmosphere.
（３）表面処理液の調製
表２−１，２−３に示す（Ａ）〜（Ｈ）の各成分を、表２−１，２−３に示す質量比にて水中で混合し、固形分が１５質量％の表面処理液を得た。
(3) Preparation of surface treatment liquid Each component of (A) to (H) shown in Tables 2-1 and 2-3 is mixed in water at a mass ratio shown in Tables 2-1 and 2-3, and solid A surface treatment liquid having a content of 15% by mass was obtained.
以下に、表２−１，２−３で使用された化合物について説明する。 The compounds used in Tables 2-1 and 2-3 will be described below.
＜グリシジル基を有すシランカップリング剤（Ａ）＞
Ａ１：３−グリシドキシプロピルトリエトキシシラン
Ａ２：３−グリシドキシプロピルトリメトキシシラン
<Silane coupling agent having a glycidyl group (A)>
A1: 3-glycidoxypropyltriethoxysilane A2: 3-glycidoxypropyltrimethoxysilane
＜テトラアルコキシシラン（Ｂ）＞
Ｂ１：テトラメトキシシラン
Ｂ２：テトラエトキシシラン
<Tetraalkoxysilane (B)>
B1: tetramethoxysilane B2: tetraethoxysilane
＜珪酸ナトリウム（Ｃ）＞
Ｃ１：３号珪酸ナトリウム（固形分：３８．５質量％）
Ｃ２：２号珪酸ナトリウム（固形分：４０．６質量％）
Ｃ３：コロイダルシリカ 日産化学（株）製 スノーテックスＸＳ（固形分：２０．０質量％）（比較例）
<Sodium silicate (C)>
C1: 3 sodium silicate (solid content: 38.5 mass%)
C2: No. 2 sodium silicate (solid content: 40.6% by mass)
C3: Colloidal silica, manufactured by Nissan Chemical Co., Ltd. Snowtex XS (solid content: 20.0% by mass) (comparative example)
＜炭酸ジルコニウム化合物（Ｄ）＞
Ｄ１：炭酸ジルコニウムカリウム（ＺｒＯ2：２０．０質量％）
Ｄ２：炭酸ジルコニウムアンモニウム（ＺｒＯ2：２０．０質量％）
<Zirconium carbonate compound (D)>
D1: Zirconium zirconium carbonate (ZrO 2 : 20.0 mass%)
D2: Zirconium ammonium carbonate (ZrO 2 : 20.0 mass%)
＜アニオン性ポリウレタン樹脂（Ｅ）＞
製造方法１（アニオン性ポリウレタン樹脂Ｅ１）
ポリエチレングリコールとポリプロピレングリコールとから得られた数平均分子量５０００のポリエーテルポリオール１００質量部、２，２−ジメチル−１，３−プロパンジオール５質量部、４，４−ジシクロヘキシルメタンジイソシアネート１００質量部、２，２−ジメチロールプロピオン酸２０質量部、および、Ｎ−メチル−２−ピロリドン１２０質量部を反応器内に加えて、不揮発分に対する遊離のイソシアナト基含有量が５％であるウレタンプレポリマーを得た。次に、テトラメチレンジアミン１６質量部及びトリエチルアミン１０質量部を脱イオン水５００質量部に加えてホモミキサーで攪拌しながら、上記ウレタンプレポリマーを加えて乳化分散した。最後に、脱イオン水を加えて固形分２５質量％の水分散性ポリウレタン樹脂を得た。なお、得られたポリウレタン樹脂（Ｅ１）のガラス転移点（Ｔｇ）を、動的粘弾性測定装置を用いて測定したところ、４０℃であった。
<Anionic polyurethane resin (E)>
Production method 1 (anionic polyurethane resin E1)
100 parts by mass of polyether polyol having a number average molecular weight of 5000 obtained from polyethylene glycol and polypropylene glycol, 5 parts by mass of 2,2-dimethyl-1,3-propanediol, 100 parts by mass of 4,4-dicyclohexylmethane diisocyanate, 2 20 parts by mass of 2-dimethylol propionic acid and 120 parts by mass of N-methyl-2-pyrrolidone are added to the reactor to obtain a urethane prepolymer having a free isocyanato group content of 5% with respect to non-volatile matter. The Next, 16 parts by mass of tetramethylene diamine and 10 parts by mass of triethylamine were added to 500 parts by mass of deionized water, and the above urethane prepolymer was added while stirring with a homomixer, followed by emulsification dispersion. Finally, deionized water was added to obtain a water-dispersible polyurethane resin having a solid content of 25% by mass. In addition, it was 40 degreeC when the glass transition point (Tg) of the obtained polyurethane resin (E1) was measured using the dynamic-viscoelasticity measuring apparatus.
製造方法２（アニオン性ポリウレタン樹脂Ｅ２）
反応器内にポリエチレングリコールとポリプロピレングリコールとから得られた数平均分子量５０００のポリエーテルポリオール１００質量部に替えて、ポリエチレングリコールとポリプロピレングリコールから得られた数平均分子量１９００のポリエーテルポリオール１００質量部を使用した以外は、製造方法１と同様にして固形分２５質量％の水分散性ウレタン樹脂を得た。なお、得られたポリウレタン樹脂（Ｅ２）のガラス転移点（Ｔｇ）を、動的粘弾性測定装置を用いて測定したところ、８５℃であった。
Production method 2 (anionic polyurethane resin E2)
Instead of 100 parts by mass of polyether polyol having a number average molecular weight of 5000 obtained from polyethylene glycol and polypropylene glycol in a reactor, 100 parts by mass of polyether polyol having a number average molecular weight of 1900 obtained from polyethylene glycol and polypropylene glycol A water-dispersible urethane resin having a solid content of 25% by mass was obtained in the same manner as in Production Method 1 except that it was used. In addition, it was 85 degreeC when the glass transition point (Tg) of the obtained polyurethane resin (E2) was measured using the dynamic-viscoelasticity measuring apparatus.
製造方法３（アニオン性ポリウレタン樹脂Ｅ３）
反応器内にポリエチレングリコールとポリプロピレングリコールとから得られた数平均分子量５０００のポリエーテルポリオール１００質量部に替えて、ポリエチレングリコールとポリプロピレングリコールから得られた数平均分子量１４００のポリエーテルポリオール１００質量部を使用した以外は、製造方法１と同様にして固形分２５質量％の水分散性ウレタン樹脂を得た。なお、得られたポリウレタン樹脂（Ｅ３）のガラス転移点（Ｔｇ）を、動的粘弾性測定装置を用いて測定したところ、１１５℃であった。
Production method 3 (anionic polyurethane resin E3)
Instead of 100 parts by mass of polyether polyol having a number average molecular weight of 5,000 obtained from polyethylene glycol and polypropylene glycol in the reactor, 100 parts by mass of polyether polyol having a number average molecular weight of 1,400 obtained from polyethylene glycol and polypropylene glycol A water-dispersible urethane resin having a solid content of 25% by mass was obtained in the same manner as in Production Method 1 except that it was used. In addition, it was 115 degreeC when the glass transition point (Tg) of the obtained polyurethane resin (E3) was measured using the dynamic-viscoelasticity measuring apparatus.
製造方法４（アニオン性ポリウレタン樹脂Ｅ４）
反応器内にポリエチレングリコールとポリプロピレングリコールとから得られた数平均分子量５０００のポリエーテルポリオール１００質量部に替えて、１，６−ヘキサンジオールとアジピン酸から得られた数平均分子量１０００のポリエステルポリオール１００質量部を使用した以外は、製造方法１と同様にして固形分２５質量％の水分散性ウレタン樹脂を得た。なお、得られたポリウレタン樹脂（Ｅ４）のガラス転移点（Ｔｇ）を、動的粘弾性測定装置を用いて測定したところ、１４０℃であった。
Production method 4 (anionic polyurethane resin E4)
Instead of 100 parts by mass of polyether polyol having a number average molecular weight of 5,000 obtained from polyethylene glycol and polypropylene glycol in a reactor, polyester polyol 100 having a number average molecular weight of 1,000 obtained from 1,6-hexanediol and adipic acid A water-dispersible urethane resin having a solid content of 25% by mass was obtained in the same manner as in Production Method 1 except that a part by mass was used. In addition, it was 140 degreeC when the glass transition point (Tg) of the obtained polyurethane resin (E4) was measured using the dynamic-viscoelasticity measuring apparatus.
＜バナジウム化合物（Ｆ）＞
Ｆ１：メタバナジン酸アンモニウム（Ｖ：４３．５質量％）
Ｆ２：メタバナジルアセチルアセトネート（Ｖ：１９．２質量％）
<Vanadium compound (F)>
F1: Ammonium metavanadate (V: 43.5% by mass)
F2: Metavanadyl acetylacetonate (V: 19.2% by mass)
＜モリブデン酸化合物（Ｇ）＞
Ｇ１：モリブデン酸アンモニウム（Ｍｏ：５４．４質量％）
Ｇ２：モリブデン酸ナトリウム（Ｍｏ：４３．８質量％）
<Molybdic acid compound (G)>
G1: ammonium molybdate (Mo: 54.4% by mass)
G2: sodium molybdate (Mo: 43.8 mass%)
＜ワックス（Ｈ）＞
Ｈ１：ポリエチレンワックス（固形分：４０．０質量％、三井化学株式会社製、ケミパール（登録商標）Ｗ９００）
Ｈ２：マイクロクリスタリンワックス（固形分：４６．０質量％、サンノプコ株式会社製 ノプコ（登録商標）１２４５−Ｍ−ＳＮ）
<Wax (H)>
H1: Polyethylene wax (solid content: 40.0% by mass, manufactured by Mitsui Chemicals, Inc., Chemipearl (registered trademark) W900)
H2: Microcrystalline wax (solid content: 46.0% by mass, Nopco (registered trademark) 1245-M-SN manufactured by San Nopco Ltd.)
（４）処理方法
表２−２，２−４の「鋼板」欄に示した前処理後の各種供試板に、表２−１，２−３の各種表面処理液をバーコーターで塗布し、その後、水洗することなく、そのままオーブンに入れて、表２−２，２−４の「ＰＭＴ」欄に示す最高到達板温（ＰＭＴ：Peak Metal Temperature）で乾燥させ、表２−２，２−４に示す付着量（片面あたり）を有する表面処理皮膜を片面に形成した。なお、付着量は、配合した炭酸ジルコニウム化合物（Ｄ）のＺｒを蛍光Ｘ線分析装置により定量し、Ｚｒ付着量から皮膜付着量へ換算して求めた。
(4) Treatment method On the various test boards after the pretreatment shown in the "steel plate" column of Tables 2-2 and 2-4, various surface treatment liquids of Tables 2-1 and 2-3 were applied by a bar coater. Then, without washing with water, it was put in the oven as it is, and dried at the highest reaching plate temperature (PMT: Peak Metal Temperature) shown in the "PMT" column of Tables 2-2 and 2-4. A surface treatment film having an adhesion amount (per one side) indicated by -4 was formed on one side. The adhesion amount was determined by quantifying Zr of the blended zirconium carbonate compound (D) with a fluorescent X-ray analyzer and converting the Zr adhesion amount to the film adhesion amount.
（５）評価試験の方法
得られた表面処理皮膜付き亜鉛系めっき鋼板（以下、単に「サンプル」という。）に対して、以下の（５−１）〜（５−１１）の評価を行った結果を、表２−２，２−４に併せて示す。
(5) Method of evaluation test The following (5-1) to (5-11) were evaluated on the obtained zinc-based plated steel sheet with surface treatment film (hereinafter simply referred to as "sample"). The results are shown together in Tables 2-2 and 2-4.
（５−１）耐熱変色性
各サンプルを赤外線イメージ炉にて３０秒で板温：５００℃に加熱し、５分間保持した後、室温まで自然放冷した時の表面外観を目視観察した。その評価基準は以下のとおりである。
（評価基準）
◎ ：変色なし
○ ：極僅かに褐色味あり
○−：僅かに褐色味あり
△ ：褐色に変色
× ：茶褐色に変色
(5-1) Thermal Discoloring Property Each sample was heated to a plate temperature of 500 ° C. for 30 seconds in an infrared image furnace and held for 5 minutes, and then the surface appearance when allowed to naturally cool to room temperature was visually observed. The evaluation criteria are as follows.
(Evaluation criteria)
:: no discoloration ○: very slightly brownish ○-: slightly brown △: brownish ×: brownish
（５−２）耐熱割れ性
各サンプルを赤外線イメージ炉にて３０秒で板温：５００℃に加熱し、５分間保持した後、室温まで自然放冷した時の表面外観を目視観察した。その評価基準は以下のとおりである。
（評価基準）
◎ ：クラックなし
○ ：極僅かにクラックあり
○−：僅かにクラックあり
△ ：全面に幅の細いクラックあり
× ：全面に幅の細いクラックに加え、広いクラックあり
(5-2) Heat Cracking Resistance Each sample was heated to a plate temperature of 500 ° C. in 30 seconds in an infrared image furnace and held for 5 minutes, and then the surface appearance when allowed to naturally cool to room temperature was visually observed. The evaluation criteria are as follows.
(Evaluation criteria)
:: no cracks ○: very slightly cracked ○-: slightly cracked :: narrow crack on the entire surface x: wide crack on the entire surface in addition to thin cracks on the entire surface
（５−３）平板部耐食性
各サンプルに対して、平板の状態で、ＪＩＳ−Ｚ−２３７１−２０００に準拠する塩水噴霧試験（ＳＳＴ）を実施した。２４０時間後の白錆発生面積率で平板部耐食性を評価した。評価基準は以下のとおりである。
（評価基準）
◎ ：白錆面積率５％未満
○ ：白錆面積率５％以上１０％未満
○−：白錆面積率１０％以上２５％未満
△ ：白錆面積率２５％以上５０％未満
× ：白錆面積率５０％以上１００％以下
(5-3) Flat-plate corrosion resistance The salt spray test (SST) based on JIS-Z-2371-2000 was implemented with respect to each sample in the state of the flat. The corrosion resistance of the flat plate portion was evaluated by the white rust occurrence area ratio after 240 hours. Evaluation criteria are as follows.
(Evaluation criteria)
:: White rust area ratio less than 5% ○: White rust area ratio 5% to less than 10% ○-: White rust area ratio 10% to less than 25% Δ: White rust area ratio 25% to less than 50% ×: White rust Area ratio 50% or more and 100% or less
（５−４）アルカリ脱脂後の耐食性
アルカリ脱脂剤ＦＣ-Ｅ６４０６（日本パーカライジング（株）製）を２０ｇ／Ｌの濃度で純水に溶解し、６０℃に加温した。このアルカリ溶液に各サンプルを２分間浸漬し、取り出して水洗して乾燥した。各サンプルについて塩水噴霧試験（ＪＩＳ−Ｚ−２３７１−２０００）を行い、１２０時間経過後の白錆発生面積率で評価した。評価基準は上記（５−３）に示したとおりである。
(5-4) Corrosion resistance after alkaline degreasing The alkaline degreasing agent FC-E 6406 (manufactured by Nippon Parkerizing Co., Ltd.) was dissolved in pure water at a concentration of 20 g / L and heated to 60 ° C. Each sample was immersed in this alkaline solution for 2 minutes, taken out, washed with water and dried. The salt spray test (JIS-Z-2371-2000) was performed about each sample, and the white rust generation | occurrence | production area rate after 120 hours progress was evaluated. The evaluation criteria are as described in (5-3) above.
（５−５）耐黒変性
各サンプルを温度：８０℃、相対湿度：９８％の雰囲気に制御された恒温恒湿機に２４時間静置した際の明度（Ｌ値）の変化（ΔＬ＝試験後のＬ値−試験前のＬ値）で算出した。評価基準は以下のとおりである。Ｌ値は、日本電色工業（株）製のＳＲ２０００を使用し、ＳＣＩモード（正反射光込み）で測定した。
（評価基準）
◎ ：−６＜△Ｌ、かつ、ムラが無い均一な外観
○ ：−１０＜△Ｌ≦−６、かつ、ムラが無い均一な外観
○−：−１４＜△Ｌ≦−１０、かつ、ムラが無い均一な外観
△ ：−１４＜△Ｌ≦−１０、かつ、微細な黒点あり
× ：△Ｌ≦−１４、または、外観ムラあり
(5-5) Blacking resistance Change of lightness (L value) when each sample is allowed to stand for 24 hours in a constant temperature and humidity controlled atmosphere at a temperature of 80 ° C. and a relative humidity of 98% (ΔL = test) It calculated by subsequent L value-L value before a test. Evaluation criteria are as follows. The L value was measured in SCI mode (including specular light) using SR2000 manufactured by Nippon Denshoku Kogyo Co., Ltd.
(Evaluation criteria)
:: -6 <ΔL and uniform appearance without unevenness ○: -10 <ΔL ≦ -6, and uniform appearance without unevenness ○-: -14 <ΔL ≦ -10, and unevenness Uniform appearance 無 い: -14 <ΔL ≦ -10 and with fine black spots x: ΔL ≦ -14, or uneven appearance
（５−６）耐水しみ性
各サンプルについて、平板の状態で、サンプル表面に脱イオン水を１００μＬ滴下し、炉内温度１００℃の熱風オーブンに１０分間投入し、オーブンから取り出した後の水滴滴下跡を目視観察して、耐水しみ性を評価した。評価基準は以下のとおりである。
（評価基準）
◎ ：水滴境界が見る角度によらず確認されない。
○ ：水滴境界が見る角度によって若干確認される。
○−：水滴境界が見る角度によらず若干確認される。
△ ：水滴境界が見る角度によらずはっきり確認される。
× ：水滴境界が滴下範囲を超えてはっきり確認される。
(5-6) Water stain resistance For each sample, 100 μL of deionized water is dropped on the surface of the sample in a flat plate state, placed in a hot air oven with an oven temperature of 100 ° C. for 10 minutes, and dropped after being removed from the oven The marks were visually observed to evaluate water stain resistance. Evaluation criteria are as follows.
(Evaluation criteria)
:: Not confirmed regardless of the angle at which the water droplet boundary is seen.
○: Slightly confirmed by the angle at which the water drop boundary looks.
−: Slightly confirmed regardless of the angle at which the water droplet boundary is seen.
Δ: Clearly confirmed regardless of the angle at which the water droplet boundary is seen.
X: The water droplet boundary is clearly confirmed beyond the dropping range.
（５−７）耐溶剤性
各サンプルの表面にエタノールを染み込ませたガーゼを４．９０Ｎ（５００ｇｆ）の荷重をかけて押し付け、その荷重のまま１０回往復するように擦った。その擦った痕を目視にて評価した。評価基準は以下のとおりである。
（評価基準）
◎ ：痕跡なし
○ ：上から見ると痕跡が見ないが、斜めから見ると明らかに見える。
○−：上から見て僅かに痕跡が見える。
△ ：上から見て痕跡が明らかに見える。
× ：皮膜が剥離している。
(5-7) Solvent Resistance A gauze impregnated with ethanol was pressed onto the surface of each sample under a load of 4.90 N (500 gf), and rubbed so as to reciprocate 10 times with the load. The scratched marks were evaluated visually. Evaluation criteria are as follows.
(Evaluation criteria)
:: no trace ○: no trace seen from above, but clearly seen from an oblique view.
○-: A trace is slightly visible when viewed from above.
Δ: The trace is clearly visible when viewed from above.
X: The film is exfoliated.
（５−８）耐汗性
各サンプルの表面に、ＪＩＳ−Ｂ７００１-１９９５に準ずる人工汗を１０μＬ滴下し、シリコン製のゴム栓を滴下部に押し付けて、一定面積の人工汗で汚染された部位を作製した。この試験片を温度：４０℃、相対湿度：８０％の雰囲気に制御された恒温恒湿機に４時間静置した後に、汚染部位の外観変化を評価した。評価基準は次のとおりである。
（評価基準）
◎ ：変色なし
○ ：極僅かに変色あり
○−：僅かに変色あり
△ ：やや黒変
× ：明らかに黒変
(5-8) Perspiration resistance 10 μL of artificial sweat according to JIS-B7001-1995 is dropped on the surface of each sample, a silicone rubber plug is pressed against the dropping part, and a site contaminated with artificial sweat of a certain area Was produced. After leaving the test piece to stand for 4 hours in a controlled temperature and humidity chamber controlled to an atmosphere of temperature: 40 ° C. and relative humidity: 80%, the appearance change of the contaminated site was evaluated. Evaluation criteria are as follows.
(Evaluation criteria)
:: no discoloration ○: very slight discoloration ○-: slight discoloration △: slightly blackened ×: apparently blackened
（５−９）塗装密着性
メラミンアルキッド系塗料であるデリコン（登録商標）＃７００（大日本塗料（株）製）を各サンプルに塗装し、１３０℃で３０分間焼付け、膜厚：３０μｍの塗膜を形成した。その後、沸騰水に２時間浸漬し、直ちに、碁盤目（１０×１０個、１ｍｍ間隔）の鋼素地まで達するカットを入れた。さらにエリクセン押し出し機にてカット部が外（表）側となる様に５ｍｍ押し出し加工を施し、接着テープによる貼着・剥離を行い、塗膜の剥離面積を測定した。評価の基準は以下のとおりである。なお、エリクセン押し出し条件は、ＪＩＳＺ−２２４７-２００６に準拠し、ポンチ径：２０ｍｍ、ダイス径：２７ｍｍ、絞り幅：２７ｍｍとした。
（評価基準）
◎ ：剥離なし
○ ：剥離面積３％未満
○−：剥離面積３％以上、１０％未満
△ ：剥離面積１０％以上、３０％未満
× ：剥離面積３０％以上
(5-9) Coating adhesion Each sample is coated with Delicon (registered trademark) # 700 (Dainippon Paint Co., Ltd.), which is a melamine alkyd paint, baked at 130 ° C. for 30 minutes, and coated with a thickness of 30 μm. A film was formed. Then, it was immersed in boiling water for 2 hours, and immediately, a cut was made to reach a steel matrix of grids (10 × 10 pieces, 1 mm intervals). Furthermore, 5 mm extrusion processing was performed so that a cut part might become an outside (front) side with an Erichsen extruder, adhesion and peeling were performed with an adhesive tape, and the peeling area of the coating film was measured. The criteria for evaluation are as follows. The Erichsen extrusion conditions were based on JIS Z-2247-2006, with a punch diameter of 20 mm, a die diameter of 27 mm, and an aperture width of 27 mm.
(Evaluation criteria)
:: no peeling ○: peeling area less than 3% ○-: peeling area 3% or more, less than 10% Δ: peeling area 10% or more, less than 30% x: peeling area 30% or more
（５−１０）潤滑性
各サンプルより直径：１００ｍｍの円板状の試験片を切り出し、ポンチ径：５０ｍｍ、ダイス径：５１．９１ｍｍ、しわ押さえ力：１トンの条件でカップ状に成型した。成型品の絞り加工を受けた面（カップの側面外側）の外観を目視によって調べ、傷つき程度および黒化程度を評価した。評価基準は次のとおりである。
（評価基準）
◎ ：全面に渡って殆ど変化なく、外観が均一
○ ：傷つきおよび黒化が少し発生し、外観が明らかに不均一
○−：局部的に傷つきおよび黒化が発生し、外観が明らかに不均一
△ ：コーナー部を中心に傷つきおよび黒化が激しく発生
× ：成型できずに割れた
(5-10) Lubricity From each sample, a disk-shaped test piece having a diameter of 100 mm was cut out and molded into a cup shape under the conditions of a punch diameter: 50 mm, a die diameter: 51.91 mm, and a wrinkle pressing force: 1 ton. The appearance of the drawn surface of the molded article (outside of the side of the cup) was visually inspected to evaluate the degree of damage and the degree of blackening. Evaluation criteria are as follows.
(Evaluation criteria)
:: Almost no change over the entire surface, uniform in appearance :: slight occurrence of scratching and blackening, apparent nonuniformity in appearance ○-: local occurrence of scratching and blackening, apparent nonuniformity in appearance :: Scratches and blackening occur violently around the corner portion x: Cracked without forming
（５−１１）貯蔵安定性
表２に示した各表面処理液を４０℃の恒温槽に３０日間保管した。取り出して、各表面処理液の外観を目視によって調べ、評価した。評価基準は次のとおりである。
（評価基準）
◎ ：変化なし
○ ：極微量の沈殿が見られる
○−：微量の沈殿がみられる
△ ：微量の沈殿が見られ、やや粘度が高くなった
× ：多量の沈殿が見られる、もしくはゲル化した
(5-11) Storage stability Each surface treatment solution shown in Table 2 was stored in a 40 ° C. thermostat for 30 days. It took out and examined the appearance of each surface treatment liquid by visual observation, and evaluated it. Evaluation criteria are as follows.
(Evaluation criteria)
:: No change ○: A very small amount of precipitation is observed −-: A slight amount of precipitation is observed :: A slight amount of precipitation is observed, the viscosity is slightly high ×: A large amount of precipitation is observed, or gelation
表２−１〜２−４に示すように、本発明例は、耐熱変色性、耐熱割れ性、平板部耐食性、アルカリ脱脂後耐食性、耐黒変性、耐水しみ性、耐溶剤性、耐汗性、塗装密着性のいずれにも優れる。これに対し、いずれかの要件が本発明の適正範囲を逸脱した比較例は、上記いずれかの特性を十分に得ることができない。また、比較例２５では、表面処理液のｐＨが低いため、表面処理液を調製できずに、供試板の評価ができなかった。 As shown in Tables 2-1 to 2-4, in the examples of the present invention, heat discoloration resistance, heat cracking resistance, corrosion resistance of flat portion, corrosion resistance after alkaline degreasing, blackening modification, water stain resistance, solvent resistance, sweat resistance , And excellent in coating adhesion. On the other hand, a comparative example in which any of the requirements deviates from the appropriate range of the present invention can not sufficiently obtain any of the above characteristics. In addition, in Comparative Example 25, since the pH of the surface treatment solution was low, the surface treatment solution could not be prepared, and the test plate could not be evaluated.
図１は、表２−１〜２−４のうち、発明例Ｎｏ．１〜４９及び比較例Ｎｏ．１６,１７,１８,２０を抜き出して、横軸を質量比（ＣS／ＸS）とし、縦軸を、耐熱変色性、耐熱割れ性、耐黒変性、及び耐水しみ性の評価としたものである。この図１からも明らかなように、本発明において特に着目した、より厳しい条件で評価した耐熱変色性及び耐熱割れ性は、質量比（ＣS／ＸS）と相関があり、質量比（ＣS／ＸS）が０．０５以上である場合に、顕著に向上することがわかった。 FIG. 1 shows Invention Example No. 1 in Tables 2-1 to 2-4. 1 to 49 and comparative example no. 16,17,18,20 were taken out, the horizontal axis was made a mass ratio (C S / X S ), and the vertical axis was made to evaluate heat discoloration resistance, heat cracking resistance, blackening resistance, and water stain resistance It is. The As is clear from FIG. 1, in particular focused in the present invention, heat discoloration resistance and heat cracking resistance was evaluated under more severe conditions, is correlated with the mass ratio (C S / X S), the mass ratio (C when S / X S) is 0.05 or more, it was found that remarkably improved.
［実施例２］
上述の実施例１と同様の（１）供試板、（２）前処理（洗浄）、（３）表面処理液の調製をした。
Example 2
The same (1) test plate as in Example 1 described above, (2) pretreatment (washing), and (3) surface treatment liquid were prepared.
（４）処理方法
表３の「鋼板」欄に示した前処理後の供試板に、表２のＮｏ．３４の表面処理液をバーコーターで塗布し、その後、水洗することなく、そのままオーブンに入れて、付着量（片面あたり）６００ｍｇ／ｍ2を有する表面処理皮膜を片面に形成した。このとき、表面処理液を塗布する際の、供試板の温度及び表面処理液の温度をそれぞれＴS及びＴLとし、ＴS−ＴLをΔＴとして、表３に示した。また、塗布された表面処理液の乾燥に関しては、供試板をオーブンに入れるまでの予備乾燥の時間ｔ（秒）と、その後のオーブンでの加熱乾燥における最高到達板温ＰＭＴを、表３に示した。なお、付着量は、配合した炭酸ジルコニウム化合物（Ｄ）のＺｒを蛍光Ｘ線分析装置により定量し、Ｚｒ付着量から皮膜付着量へ換算して求めた。
(4) Treatment method In the test plate after the pretreatment shown in the "steel plate" column of Table 3, No. 1 in Table 2 was used. The surface treatment solution of No. 34 was applied by a bar coater, and then placed in an oven as it was without washing with water, to form a surface treatment film having an adhesion amount (per side) of 600 mg / m 2 on one side. In this case, at the time of applying a surface treatment liquid, respectively the temperature of the temperature and surface treating solution of the test plates and T S and T L, the T S -T L as [Delta] T, it is shown in Table 3. In addition, for drying of the applied surface treatment liquid, Table 3 shows the pre-drying time t (seconds) until the test plate is put in the oven and the maximum reaching plate temperature PMT in the subsequent heating and drying in the oven. Indicated. The adhesion amount was determined by quantifying Zr of the blended zirconium carbonate compound (D) with a fluorescent X-ray analyzer and converting the Zr adhesion amount to the film adhesion amount.
（５）評価試験の方法
得られた表面処理皮膜付き亜鉛系めっき鋼板（以下、単に「サンプル」という。）に対して、上述の実施例１と同様の（５−１）〜（５−１１）の評価に加え、（５−１２）、（５−１３）を行った結果を、表３に示す。評価基準△及び×は性能不足のため好ましくない。
(5) Method of evaluation test (5-1) to (5-11) similar to the above-mentioned Example 1 with respect to the obtained zinc-based plated steel sheet with a surface treatment film (hereinafter, simply referred to as "sample"). Table 5 shows the results of performing (5-12) and (5-13) in addition to the evaluation of 2.). Evaluation criteria Δ and × are not preferable because of insufficient performance.
（５−１２）高度な平板部耐食性
各サンプルに対して、平板の状態で、ＪＩＳ−Ｚ−２３７１−２０００に準拠する塩水噴霧試験（ＳＳＴ）を実施した。４８０時間後の白錆発生面積率で平板部耐食性を評価した。評価基準は以下のとおりである。
（評価基準）
◎ ：白錆面積率５％未満
○ ：白錆面積率５％以上１０％未満
○−：白錆面積率１０％以上２５％未満
△ ：白錆面積率２５％以上５０％未満
× ：白錆面積率５０％以上１００％以下
(5-12) Highly Flat Plate Corrosion Resistance A salt spray test (SST) in accordance with JIS-Z-2371-2000 was performed on each sample in the flat state. The corrosion resistance of the flat plate portion was evaluated by the white rusting area ratio after 480 hours. Evaluation criteria are as follows.
(Evaluation criteria)
:: White rust area ratio less than 5% ○: White rust area ratio 5% to less than 10% ○-: White rust area ratio 10% to less than 25% Δ: White rust area ratio 25% to less than 50% ×: White rust Area ratio 50% or more and 100% or less
（５−１３）皮膜相分析
各サンプルの表面処理皮膜表面のＳＥＭ観察を実施した。加速電圧を１ｋＶとし、Ｅｖｅｒｈａｒｔ−Ｔｈｏｒｎｌｅｙ型検出器を用い、二次電子像を観察した。観察倍率は２万倍（観察領域として約６μｍ×４μｍ）とし、１０２４×７００ピクセル、グレースケール２５６階調のデジタル画像として取得した。観察像は、Ｚｒを含む無機系物質から構成される相が明るく、Ｚｒを含まない樹脂成分からなる相が暗く観察されることから、以下の手順で、Ｚｒを含む相の存在割合として、明るく観察された領域の面積率を求め、体積分率をみなした。
（Ａ）：取得されたＳＥＭ画像に対し、ノイズを除去するためオペレータサイズ1ピクセルのガウシアンフィルターで平滑化処理を施す。
（Ｂ）：（Ａ）の画像より、最大エントロピー法による画像の２値化を行う。
（Ｃ）：２値化された画像の明るい領域の割合を求める。
(5-13) Film phase analysis SEM observation of the surface treatment film surface of each sample was implemented. The acceleration voltage was set to 1 kV, and a secondary electron image was observed using an Everhart-Thornley detector. The observation magnification was set to 20,000 times (about 6 μm × 4 μm as an observation area), and acquired as a digital image of 1024 × 700 pixels and 256 gray scales. The observed image is bright because the phase composed of the inorganic material containing Zr is observed bright and the phase composed of the resin component not containing Zr is observed dark. Therefore, according to the following procedure, it is brightened as the existence ratio of the phase containing Zr The area fraction of the observed area was determined, and the volume fraction was regarded.
(A): The acquired SEM image is smoothed with an operator-sized 1-pixel Gaussian filter to remove noise.
(B): From the image of (A), the image is binarized by the maximum entropy method.
(C): The ratio of the bright area of the binarized image is determined.
表３に示すように、本発明例の中でも、塗布の際の温度条件と加熱乾燥前の予備乾燥条件を所定範囲に制御して、Ｚｒを含む相の体積分率を５〜４０％の範囲とした発明例では、高度な平板部耐食性にも優れていた。 As shown in Table 3, among the examples of the present invention, the temperature condition at the time of coating and the preliminary drying condition before heating and drying are controlled within a predetermined range, and the volume fraction of the phase containing Zr is in the range of 5 to 40%. In the invention examples described above, the high flat plate portion corrosion resistance was also excellent.
本発明の表面処理液を用いて製造された表面処理皮膜付き亜鉛系めっき鋼板は、アーク溶接に供する部材に使用する場合に好適であることはもちろん、家電製品用鋼板、建材用鋼板、自動車用鋼板など種々の用途に用いることができる。 It goes without saying that the zinc-based plated steel sheet with a surface treatment film produced using the surface treatment liquid of the present invention is suitable not only for use in members subjected to arc welding, but also for steel sheets for home appliances, steel sheets for building materials, for automobiles It can be used for various applications such as steel plates.
Claims (7)
（１）グリシジル基を有するシランカップリング剤（Ａ）の固形分質量（ＡS）、テトラアルコキシシラン（Ｂ）の固形分質量（ＢS）、珪酸ナトリウム（Ｃ）の固形分質量（ＣS）、及び炭酸ジルコニウム化合物（Ｄ）中のＺｒＯ2換算質量（ＤZ）の合計質量（ＸS）の、アニオン性ポリウレタン樹脂（Ｅ）の固形分質量（ＥS）に対する質量比（ＸS／ＥS）が０．０５〜０．３８
（２）テトラアルコキシシラン（Ｂ）の固形分質量（ＢS）の、前記合計質量（ＸS）に対する質量比（ＢS／ＸS）が０．０１０〜０．３０
（３）珪酸ナトリウム（Ｃ）の固形分質量（ＣS）の、前記合計質量（ＸS）に対する質量比（ＣS／ＸS）が０．０５〜０．５０
（４）炭酸ジルコニウム化合物（Ｄ）中のＺｒＯ2換算質量（ＤZ）の、前記合計質量（ＸS）に対する質量比（ＤZ／ＸS）が０．０５〜０．６０
（５）バナジウム化合物（Ｆ）中のＶ換算質量（ＦV）の、前記合計質量（ＸS）とアニオン性ポリウレタン樹脂（Ｅ）の固形分質量（ＥS）との合計質量（ＸS＋ＥS）に対する質量比（ＦV／（ＸS＋ＥS））が０．００１０〜０．０１５
（６）モリブデン酸化合物（Ｇ）中のＭｏ換算質量（ＧM）の、前記合計質量（ＸS）とアニオン性ポリウレタン樹脂（Ｅ）の固形分質量（ＥS）との合計質量（ＸS＋ＥS）に対する質量比（ＧM／（ＸS＋ＥS））が０．００１０〜０．０１５ A silane coupling agent (A) having a glycidyl group, a tetraalkoxysilane (B), a sodium silicate (C), a hydroxyl group to be a condensation point with a silanol group, and drying produces zirconium oxide and zirconium hydroxide zirconium carbonate compounds (D), a glass transition point (Tg) of 80 ° C. to 130 DEG ° C. and is anionic polyurethane resin (E), vanadium compound (F), molybdate compound (G), and water is added, pH The addition amount of each component satisfies the following (1) to (6) in the range of 8.0 to 10.0, and the surface treatment liquid for a zinc-based plated steel sheet containing no chromium compound .
(1) solid content of the silane coupling agent having a glycidyl group (A) (A S), the solid content mass (B S) of the tetraalkoxysilane (B), solid content of sodium silicate (C) (C S ), and the total mass (X S) of the weight ratio to the solid content mass (E S) of the anionic polyurethane resin (E) of the zirconium carbonate compound (D) ZrO 2 in terms of the mass in (D Z) (X S / E S ) is 0.05 to 0.38
(2) solid content of the tetraalkoxysilane (B) of (B S), the mass ratio relative to the total mass (X S) (B S / X S) is 0.010-.30
(3) solid mass of sodium silicate (C) of (C S), the mass ratio relative to the total mass (X S) (C S / X S) is 0.05 to 0.50
(4) ZrO 2 in terms of the mass in the zirconium carbonate compound (D) of (D Z), a mass ratio relative to the total mass (X S) (D Z / X S) is 0.05 to 0.60
(5) a vanadium compound (F) V reduced mass in the (F V), the total mass of the solid content (E S) of the total mass (X S) and the anionic polyurethane resin (E) (X S + E The mass ratio (F V / (X S + E S ))) relative to S ) is 0.0010 to 0.015
(6) molybdate compound (G) Mo reduced mass in the (G M), the total mass of the solid content (E S) of the total mass (X S) and the anionic polyurethane resin (E) (X S + E S) mass ratio (G M / (X S + E S)) is from 0.0010 to 0.015
（７）ワックス（Ｈ）の固形分質量（ＨS）の、前記合計質量（ＸS）とアニオン性ポリウレタン樹脂（Ｅ）の固形分質量（ＥS）との合計質量（ＸS＋ＥS）に対する質量比（ＨS／（ＸS＋ＥS））が０．００２〜０．１０ Furthermore, a wax (H) is added, The surface treatment liquid for zinc-based plated steel plates of Claim 1 in which the addition amount satisfies following (7).
(7) a wax solid weight of (H) (H S) of the total weight of the solid content (E S) of the total mass (X S) and the anionic polyurethane resin (E) (X S + E S) The mass ratio (H S / (X S + E S )) to the
その後、塗布された前記亜鉛系めっき鋼板用表面処理液を乾燥して、付着量が５０〜２，０００ｍｇ／ｍ2の表面処理皮膜を形成する第２工程と、
を有することを特徴とする表面処理皮膜付き亜鉛系めっき鋼板の製造方法。 The 1st process of applying the surface treatment liquid for zinc system plating steel plates of Claim 1 or 2 on the surface of a zinc system plating steel plate,
Thereafter, the coated surface treatment solution for a zinc-based plated steel sheet is dried to form a surface treatment film having an adhesion amount of 50 to 2,000 mg / m 2 ,
The manufacturing method of the zinc-based plated steel plate with a surface treatment film characterized by having.
前記第２工程は、塗布された前記亜鉛系めっき鋼板用表面処理液を大気中で乾燥する、時間ｔ秒の予備乾燥工程と、その後、塗布された前記亜鉛系めっき鋼板用表面処理液を乾燥炉で加熱乾燥する加熱乾燥工程と、を含み、ΔＴ／ｔが１〜６０℃／ｓである、請求項３に記載の表面処理皮膜付き亜鉛系めっき鋼板の製造方法。 Assuming that the temperature of the zinc-based plated steel sheet and the temperature of the surface treatment solution in the first step are T S and T L respectively, and T S -T L is ΔT, T S is 15 to 55 ° C. T L is 10 to 40 ° C., ΔT is 5 to 40 ° C.,
In the second step, the applied surface treatment solution for zinc-based plated steel sheet is dried in the atmosphere, a preliminary drying step for time t seconds, and thereafter, the surface treatment solution applied to zinc-based plated steel plate is dried The method for producing a zinc-based plated steel sheet with a surface treatment film according to claim 3, comprising: a heating and drying step of heating and drying in a furnace, and ΔT / t is 1 to 60 ° C / s.
該亜鉛系めっき鋼板の表面に、請求項１又は２に記載の亜鉛系めっき鋼板用表面処理液を塗布し、乾燥して得た、付着量が５０〜２，０００ｍｇ／ｍ2の表面処理皮膜と、
を有することを特徴とする表面処理皮膜付き亜鉛系めっき鋼板。 Zinc-based plated steel sheet,
A surface-treated film having an adhesion amount of 50 to 2,000 mg / m 2 , obtained by applying the surface treatment liquid for zinc-based plated steel sheet according to claim 1 onto the surface of the zinc-based plated steel sheet and drying it. When,
A zinc-based plated steel sheet with a surface treatment film characterized by having:
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