JP5372305B2 - Painted steel with excellent anti-corrosion paint and corrosion resistance - Google Patents
Painted steel with excellent anti-corrosion paint and corrosion resistance Download PDFInfo
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- JP5372305B2 JP5372305B2 JP2000236580A JP2000236580A JP5372305B2 JP 5372305 B2 JP5372305 B2 JP 5372305B2 JP 2000236580 A JP2000236580 A JP 2000236580A JP 2000236580 A JP2000236580 A JP 2000236580A JP 5372305 B2 JP5372305 B2 JP 5372305B2
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Description
本発明は、防錆塗料および塗装鋼材に関するものであり、家電用、建材用、土木用、機械用、自動車用、家具用、容器用などにおいて、特に有毒とされている６価クロムを用いずに鋼材の防錆効果を発揮することを特徴とする防錆塗料およびそれを用いた塗装鋼材に関する。 The present invention relates to a rust preventive paint and a coated steel material, and does not use hexavalent chromium which is particularly toxic in home appliances, building materials, civil engineering, machinery, automobiles, furniture, containers and the like. In particular, the present invention relates to a rust preventive paint characterized by exhibiting a rust preventive effect of a steel material and a coated steel material using the same.
鋼材に被覆される塗料には、鋼材の腐食を防止するすることを目的とした防錆塗料がある。防錆塗料中には防錆顔料と呼ばれる防錆剤を含むことが一般的である。防錆顔料には多くの種類のものがあるが、代表的なものとして、クロム系防錆顔料が広く知られている。 Examples of the coating material coated on the steel material include a rust preventive coating material for the purpose of preventing the corrosion of the steel material. In general, the rust preventive paint contains a rust preventive agent called a rust preventive pigment. There are many types of rust preventive pigments, and as a typical one, chromium-based rust preventive pigments are widely known.
クロム系顔料に含まれる６価のクロムは水溶性であり、これが溶出することによって、被膜に発生した塗膜の傷を補修する性質がある。従って、耐食性付与として今日まで使用されてきている。しかしながら、クロム系防錆顔料を含む有機皮膜から溶出する可能性のある６価のクロムの毒性問題から、最近ではノンクロム防錆顔料及び塗料に対する要望が高まっている。
そこで、本発明においては、このような要望に答え、耐食性に優れるノンクロム系防錆塗料およびこれらを被覆した塗装鋼材を提供することを目的とする。Hexavalent chromium contained in the chromium-based pigment is water-soluble, and when it dissolves, it has a property of repairing scratches on the coating film generated on the coating film. Therefore, it has been used to date to impart corrosion resistance. However, recently, there is an increasing demand for non-chromium rust preventive pigments and paints due to the toxicity problem of hexavalent chromium that may be eluted from an organic film containing a chromium-based rust preventive pigment.
Therefore, in the present invention, an object of the present invention is to provide a non-chromium-based anticorrosive paint excellent in corrosion resistance and a coated steel material coated therewith in response to such a demand.
発明者らは、鋼材の主成分であるＦｅよりも還元性の高い金属を含む塗料を鋼材に被覆し、成膜させることで鋼材の耐食性が向上することを知見した。
金属の酸化還元平衡を表す状態図にエリンガム状態図がある。これは縦軸に標準生成自由エネルギー△Ｇをとり、横軸に温度をとった時の各種金属の酸化還元平衡を表す図であり、この図より各温度条件における各種金属の酸素ポテンシャルの順位がわかる。酸化還元平衡線図がＦｅのそれより小さい金属は、Ｆｅよりも還元性が高いことを示している。The inventors have found that the corrosion resistance of a steel material is improved by coating the steel material with a paint containing a metal having a higher reducing property than Fe, which is the main component of the steel material, and forming the film.
There is an Ellingham phase diagram as a phase diagram representing a redox equilibrium of a metal. This is a graph showing the oxidation-reduction equilibrium of various metals when the standard free energy ΔG is taken on the vertical axis and the temperature is taken on the horizontal axis. From this figure, the order of the oxygen potential of each metal under each temperature condition is shown. Recognize. A metal whose oxidation-reduction equilibrium diagram is smaller than that of Fe indicates that it is more reducible than Fe.
そこで、エリンガム状態図で標準生成自由エネルギー△Ｇが０〜１００℃の温度範囲においてＦｅより低い金属を含むことを特徴とする防錆塗料および塗装鋼材を考案した。ここで、本発明で定義しているＦｅの酸化還元平衡線図とは、本発明の温度領域で見られるＦｅとＦｅ2 Ｏ3 の酸化還元平衡を示す状態線図のことである。ちなみに約６５０℃以上の高温雰囲気ではＦｅとＦｅＯの酸化還元を表す平衡線図とＦｅＯとＦｅ2 Ｏ3 の酸化還元を表す平衡線図が見られるが、この温度領域でみられる酸化還元反応は、本発明の目的とする腐食もしくは防食の酸化還元反応とは若干意味合いが異なるため、本発明の規定するところではない。本発明の要旨とするところは以下の通りである。In view of this, the present inventors have devised a rust-preventing paint and a coated steel material characterized by containing a metal whose standard generation free energy ΔG is lower than Fe in the temperature range of 0-100 ° C. in the Ellingham phase diagram. Here, the Fe redox equilibrium diagram defined in the present invention is a state diagram showing the redox equilibrium of Fe and Fe 2 O 3 observed in the temperature range of the present invention. Incidentally, in a high-temperature atmosphere of about 650 ° C. or higher, there are an equilibrium diagram showing the oxidation and reduction of Fe and FeO and an equilibrium diagram showing the oxidation and reduction of FeO and Fe 2 O 3 , but the oxidation-reduction reaction seen in this temperature range is The meaning is slightly different from the target oxidation or reduction reaction of corrosion or anticorrosion of the present invention, and is not specified by the present invention. The gist of the present invention is as follows.
（１）エリンガム状態図で、標準生成自由エネルギー△Ｇが、０〜１００℃の温度範囲に
おいてＦｅより低い金属もしくは合金である、金属ケイ素、フェロシリコン、フェロマン
ガン、及び、リン酸／バナジン酸混合系の防錆顔料、微粒シリカ、イオン交換シリカのい
ずれか一種以上のみを防錆顔料として含み、かつ、前記防錆顔料のうち、金属ケイ素、フ
ェロシリコン、フェロマンガンのいずれか一種以上を含むことが必須であることを特徴と
するノンクロム系防錆塗料。
（２）前記（１）記載の防錆塗料を塗布し、成膜させた被膜を表面に有することを特徴と
する塗装鋼材。
（３）前記（１）記載の防錆塗料塗布し、成膜させた被膜を少なくとも片面に有すること
を特徴とする塗装鋼帯。
（４）前記（１）記載の防錆塗料を塗布し、成膜させた皮膜を少なくとも片面に有するこ
とを特徴とするプレコート鋼帯ある。(1) Metallic silicon, ferrosilicon, ferromanganese , and phosphoric / vanadic acid mixture , which is a metal or alloy whose standard formation free energy ΔG is lower than Fe in the temperature range of 0 to 100 ° C. in the Ellingham phase diagram Only one or more of anti-corrosive pigments, fine-grained silica and ion-exchange silica are used as anti-rust pigments, and among the anti-corrosion pigments, metallic silicon,
A non-chromium rust preventive paint characterized by containing at least one of erosilicon and ferromanganese .
(2) A coated steel material having a coating film formed by applying the rust preventive paint according to (1) and forming a film thereon.
(3) A coated steel strip characterized by having a film formed by applying a rust preventive paint as described in (1) and forming a film on at least one side.
(4) A precoated steel strip characterized by having a film formed by applying the rust preventive paint according to (1) and having a film formed on at least one side.
本発明の防錆塗料中に含まれる金属もしくは合金もしくは金属化合物はエリンガム状態図で、標準生成自由エネルギー△Ｇが０〜１００℃の温度範囲においてＦｅより低いことを特徴としている。
ここで、定義した温度範囲について説明する。エリンガム線図を見れば明らかなように全ての金属種は温度により酸化還元性を示す標準生成自由エネルギー△Ｇが異なる。本発明にて、０〜１００℃の温度範囲でＦｅとの標準生成自由エネルギー△Ｇを比較した理由は、実際に鋼材がさらされる腐食環境温度がこの範囲内だからである。０℃未満の低温もしくは１００℃を超える高温の特種な環境での腐食については、本発明の規定するところではない。しかし、これらの特殊環境においても本発明の概念は適用できると考える。The metal, alloy or metal compound contained in the anticorrosive paint of the present invention is an Ellingham phase diagram and is characterized in that the standard formation free energy ΔG is lower than Fe in the temperature range of 0 to 100 ° C.
Here, the defined temperature range will be described. As is apparent from the Ellingham diagram, the standard formation free energy ΔG indicating redox properties varies depending on the temperature, as is apparent from all metal species. In the present invention, the reason why the standard free energy of formation ΔG with Fe is compared in the temperature range of 0 to 100 ° C. is that the corrosion environment temperature to which the steel material is actually exposed is within this range. Corrosion in a special environment at a low temperature lower than 0 ° C. or higher than 100 ° C. is not specified by the present invention. However, the concept of the present invention can be applied in these special environments.
これらは金属単体として添加しても良いし、他の金属との合金として添加しても効果を発揮する。合金についてはエリンガム線図上には明記されていないが、含まれる金属成分の比率によって計算し求めることができる。製鋼の過程において脱酸剤として用いられるフェロシリコン、フェロマンガン、金属ケイ素は効果的である。 These may be added as a simple metal or exert an effect even when added as an alloy with another metal. The alloy is not specified on the Ellingham diagram, but can be calculated and determined by the ratio of the metal components contained. That are used in the process of steelmaking as a deoxidizer off Eroshirikon, ferro manganese, metal silicon is effective.
これら金属は、微細な粒状に粉砕して用いることが好ましい。粒径については特に規定するものではない。成膜したときに塗膜厚より粒径が大きいと、ブツ状の塗膜外観となり塗装外観が損ねられる等の問題が発生する一方、塗膜に導電性も付与したい場合などは、成摸した塗膜厚よりも粒径が大きい方が効果的である。また、耐食性に対する効果も粒径によって異なる。必要に応じて最適粒径を選ぶ必要がある。 These metals are preferably used after being pulverized into fine particles. The particle size is not particularly specified. If the particle size is larger than the coating thickness when the film is formed, problems such as the appearance of a rugged coating appearing and the appearance of the coating being damaged occur. A larger particle diameter than the coating thickness is more effective. In addition, the effect on corrosion resistance varies depending on the particle size. It is necessary to select the optimum particle size as necessary.
本発明の防錆塗料に用いられる樹脂としては、用途に応じて一般に公知の樹脂、例えば、ポリエステル樹脂、ウレタン樹脂、アクリル樹脂、エポキシ樹脂、メラミン樹脂などを使用することができる。また架橋剤を用いた熱硬化型の樹脂でも架橋剤を必要としない熱可塑型の樹脂でも効果を発揮する。これらの樹脂は、必要に応じて数種のものをブレンドして用いてもよい。
塗料としての形態も特に限定する物ではなく、用途に応じて適宜使い分けることができる。例えば、有機溶剤系塗料、水系塗料、コロイド分散系塗料、粉体塗料、電着塗料、熱硬化型塗料、常温乾燥型塗料などが挙げられる。As the resin used in the anticorrosive paint of the present invention, generally known resins such as polyester resin, urethane resin, acrylic resin, epoxy resin, melamine resin and the like can be used depending on the application. In addition, even a thermosetting resin using a crosslinking agent or a thermoplastic resin that does not require a crosslinking agent is effective. These resins may be used by blending several kinds as required.
The form as a paint is not particularly limited, and can be properly used depending on the application. Examples thereof include organic solvent-based paints, water-based paints, colloidal dispersion paints, powder paints, electrodeposition paints, thermosetting paints, and room temperature drying paints.
また、本発明の防錆塗料はそれぞれの形態に応じて、溶剤を含むと塗装時の粘度を変えることができ、塗装作業性の面で好適である。溶剤は塗料の形態に応じて異なるが、一般に公知の溶剤を用いることができる。本発明の防錆塗料に含まれる金属の添加量は、特に限定する物ではなく、用途、形態に応じて適した量を添加することができるが、塗料の種類や膜厚、被塗装物の種類によっても効果の度合いが異なると考えられるため、必要に応じて適宜調整する必要がある。 Moreover, when the rust preventive paint of the present invention contains a solvent according to each form, the viscosity at the time of painting can be changed, which is preferable in terms of coating workability. Although a solvent changes according to the form of a coating material, generally a well-known solvent can be used. The addition amount of the metal contained in the rust preventive paint of the present invention is not particularly limited, and an appropriate amount can be added according to the application and form, but the type and film thickness of the paint, Since the degree of effect varies depending on the type, it is necessary to adjust as necessary.
本発明の防錆塗料は必要に応じ、下記の防錆顔料や一般に公知の着色顔料を含んでもよ
い。防錆顔料はリン酸／バナジン酸混合系の防錆顔料（以降ＶＰ顔料と称す）または／も
しくは微粒シリカまたは／もしくはイオン交換シリカとの併用は耐食性が更に向上し、好
適である。イオン交換シリカとしてはＣａイオン交換性の非晶質シリカ（シールデックス
／グレイス社製）が良く知られている。The rust preventive paint of the present invention may contain the following rust preventive pigments and generally known color pigments as required. Antirust pigment (referred to hereinafter VP pigment) anticorrosive pigment of phosphate / vanadate mixed system or / or in combination with fine silica or / or ion exchange silica is further improved corrosion resistance, which is preferable. As ion exchange silica, Ca ion exchangeable amorphous silica (manufactured by Shielddex / Grace) is well known.
防錆塗料の塗布方法は一般に公知の塗装方法、例えば、刷毛塗り、浸漬塗装、バーコート塗装、スプレー塗装、電着塗装、静電塗装、ロールコーター塗装、ダイコーター塗装、カーテンフロー塗装、ローラーカーテン塗装などが挙げられる。防錆塗料の塗料の膜厚は、塗料の樹脂の種類、塗料の形態、目的とする用途によっても異なるため、必要に応じて適宜決める必要がある。防錆塗料の乾燥、硬化方法は、常温乾燥でも熱を加えた乾燥硬化でもいずれでも良い。熱を加える場合、一般に公知の方法、例えば熱風加熱炉、遠赤外線炉、誘導加熱炉、直下炉などを用いることができる。加熱時の温度条件は、塗料に用いる樹脂の種類によっても異なるため、必要に応じて適宜決める必要がある。 The coating method of the rust preventive paint is generally known coating methods such as brush coating, dip coating, bar coating, spray coating, electrodeposition coating, electrostatic coating, roll coater coating, die coater coating, curtain flow coating, roller curtain. Examples include painting. The film thickness of the anticorrosive paint varies depending on the type of the resin of the paint, the form of the paint, and the intended use, and therefore needs to be determined as needed. The drying and curing method of the anticorrosive paint may be either room temperature drying or dry curing with heat. When heat is applied, generally known methods such as a hot air heating furnace, a far-infrared furnace, an induction heating furnace, and a direct furnace can be used. Since the temperature condition at the time of heating varies depending on the type of resin used in the coating material, it is necessary to appropriately determine it as necessary.
本発明の耐食性に優れた塗装鋼材は、前述の防錆塗料を鋼材上に塗布、硬化乾燥したものである。塗装鋼材の母材に用いる鋼材は、特に限定する物ではなく一般に公知の鋼材を用いることができ、例えば、Ｔｉ，Ｎｂ，Ｂ等を添加したＩＦ鋼、Ａｌ−Ｋ鋼、Ｃｒ含有鋼、ステンレス鋼、ハイテン等などが挙げられる。また、鋼に他の金属をめっきしたものを用いても良く、溶融亜鉛めっき、合金化溶融亜鉛めっき、電気亜鉛めっき、アルミ亜鉛合金化めっき、アルミめっき、錫めっき、ティンフリースチールなど、Ａｌ，Ｚｎ，Ｓｎ，Ｃｕ，Ｐｂの１以上から構成されるめっき層を有する鋼材がより効果的である。 The coated steel material having excellent corrosion resistance according to the present invention is obtained by applying the above-mentioned rust preventive paint onto a steel material, followed by curing and drying. The steel material used for the base material of the painted steel material is not particularly limited, and generally known steel materials can be used. For example, IF steel, Al-K steel, Cr-containing steel, stainless steel to which Ti, Nb, B, etc. are added. Steel, high tension, etc. are mentioned. Also, steel with other metals plated may be used, such as hot dip galvanizing, alloying hot dip galvanizing, electrogalvanizing, aluminum zinc alloying plating, aluminum plating, tin plating, tin-free steel, Al, A steel material having a plating layer composed of one or more of Zn, Sn, Cu, and Pb is more effective.
鋼材最表面もしくはめっき層の最表面には，塗装前処理としてクロメート処理、リン酸亜鉛処理などの化成処理皮膜を必要に応じて被覆することもできる。近年、開発が進んでいるノンクロメート処理を塗装前処理として用いると人体に対する有毒性も少なく好適である。
鋼材の形状は特に限定するものではなく、条鋼、線材、鋼管、鋼帯など一般に公知のものを用いることができる。鋼帯においては本発明の防錆塗料が少なくとも片面に被覆されていれば効果を発揮する。また、本発明の塗装鋼帯は、塗装端面で鉄地が露出するプレコート鋼板として用いると大いに効果的である。The outermost surface of the steel material or the outermost surface of the plating layer can be coated with a chemical conversion treatment film such as chromate treatment or zinc phosphate treatment as a pretreatment for coating as necessary. The use of non-chromate treatment, which has been developed in recent years, as a pre-coating treatment is preferred because it is less toxic to the human body.
The shape of the steel material is not particularly limited, and generally known materials such as a strip steel, a wire rod, a steel pipe, and a steel strip can be used. In the steel strip, the effect is exhibited if the anticorrosive paint of the present invention is coated on at least one side. Moreover, the coated steel strip of the present invention is very effective when used as a precoated steel sheet in which the iron ground is exposed at the painted end face.
エリンガム状態図で標準生成自由エネルギー△Ｇが０〜１００℃の温度範囲においてＦｅより低い金属として、金属ケイ素（Ｓｉを主成分として９８％以上含むＪＩＳ−Ｇ２３１２−１号を使用／表中にはＭＳｉと記載）、フェロシリコン（Ｓｉを主成分として７５〜８０％含むＪＩＳ−Ｇ２３０２−１号を使用／表中にはＦｅＳｉと記載）、フェロマンガン（Ｍｎを主成分として７５〜８０％含むＪＩＳ−Ｇ２３０１−中炭素フェロマンガン２号を使用／表中にはＦｅＭｎと記載）、エリンガム状態図で酸素ポテンシャルが０〜１００℃の温度範囲においてＦｅより高い金属として、Ｎｉを主成分として９８％以上含む金属ニッケル（表中にはＮｉと記載）、Ｓｎを主成分として９８％以上含有する金属スズ（表中にはＮｉと記載）を準備した。 In the Ellingham phase diagram, as a metal whose standard free energy of formation ΔG is lower than Fe in the temperature range of 0 to 100 ° C., metal silicon (JIS-G2312-1 containing Si at 98% or more is used / in the table) MSI), ferrosilicon (uses JIS-G2302-1 containing 75-80% of Si as the main component / indicated in the table as FeSi), ferromanganese (JIS containing 75-80% of Mn as the main component) -G2301-medium carbon ferromanganese No. 2 used / denoted as FeMn in the table), a metal higher than Fe in the temperature range of 0 to 100 ° C. in the oxygen potential in the Ellingham phase diagram, 98% or more mainly composed of Ni Contains metallic nickel (indicated in the table as Ni) and metallic tin containing 98% or more of Sn as a main component (indicated in the table as Ni) It was.
これらの金属を粉砕機で粉砕し、粉砕したものを３２５ｍｅｓｈフィルターにてふるいをかけ、最大粒径４０μｍの微粒化した金属を防錆顔料として用いた。０〜１００℃の温度範囲におけるこれら金属の主成分とＦｅとの酸素ポテンシャルの比較を表中に記載する。表中にはＦｅより標準生成自由エネルギー△Ｇが高いものを×、低いものを○と記述する。また、必要に応じて一般に公知の非クロム系防錆顔料であるＶＰ顔料（表中にはＶＰと記載）とＣａイオン交換シリカ（（シールデツクスＣ３０３／グレイス社製／表中にはＣａＳｉと記載）も用いた。比較には一般に公知で市販されているストロンチウムクロメート（表中にはＳｒＣｒと記載）を用いた。 These metals were pulverized with a pulverizer, and the pulverized product was sieved with a 325 mesh filter, and the atomized metal having a maximum particle size of 40 μm was used as a rust preventive pigment. A comparison of the oxygen potential between the main components of these metals and Fe in the temperature range of 0 to 100 ° C. is described in the table. In the table, x indicates that the standard free energy of formation ΔG is higher than Fe, and o indicates that it is lower. Further, if necessary, VP pigment (indicated in the table as VP) and Ca ion-exchanged silica ((Sealdex C303 / Grace, Inc./indicated as CaSi in the table) which are generally known non-chromium anticorrosive pigments. For comparison, generally known and commercially available strontium chromate (denoted as SrCr in the table) was used.
次に、市販の有機溶剤系のクリヤー塗料に、前述の防錆顔料を添加し、分散機にて防錆顔料を塗料中に分散させることで、防錆塗料を作製した。なお、比較として防錆顔料を全く含まない塗料も用いた。防錆顔料の添加量は表中に記載する。なお、防錆塗料に用いたクリヤー塗料はエポキシ系塗料、ポリエステル系塗料、ウレタン系塗料の３種を用いた。
次に、０．５ｍｍの冷延鋼板、電気亜鉛めっき鋼板、溶融亜鉛めっき鋼板の両面に、前処理としクロムを含まない樹脂ベースのノンクロメート処理もしくはクロメート処理を施した。前処理を施した鋼板の片面（Ｂ面）上に作製した防錆塗料をバーコーターにて塗装し、熱風炉にて到達板温が２１０℃となる条件で焼き付けることで硬化乾燥した。また、焼き付け乾燥後には塗装金属板を空冷した。防錆塗料の膜厚は焼き付け乾燥後の膜厚にして５μｍとなるように塗装した。Next, the above-mentioned rust preventive pigment was added to a commercially available organic solvent-based clear paint, and the rust preventive pigment was dispersed in the paint with a disperser to prepare a rust preventive paint. For comparison, a paint containing no rust preventive pigment was also used. The amount of rust preventive pigment added is described in the table. The clear paint used for the rust preventive paint was an epoxy paint, a polyester paint, and a urethane paint.
Next, a resin-based non-chromate treatment or chromate treatment containing no chromium as a pretreatment was performed on both surfaces of a 0.5 mm cold-rolled steel plate, an electrogalvanized steel plate, and a hot-dip galvanized steel plate. The rust preventive paint produced on one side (B side) of the pretreated steel plate was coated with a bar coater, and baked in a hot air oven under the condition that the ultimate plate temperature was 210 ° C. to be cured and dried. In addition, the painted metal plate was air-cooled after baking and drying. The film thickness of the anticorrosive paint was 5 μm after baking and drying.
さらに、前処理を施した鋼板のもう片方の面（Ａ面）上に作製した防錆塗料をバーコーターにて塗装し、熱風炉にて到達板温が２１０℃となる条件で焼き付けることで硬化乾燥した。また、焼き付け乾燥後には塗装金属板を水冷した。防錆塗料の膜厚は焼き付け乾燥後の膜厚にして５μｍとなるように塗装した。この防錆塗料の塗膜層上には、上塗り塗料として市販の着色顔料入りポリエステル系塗料をバーコーターにて、乾燥後膜厚にして１５μｍ塗装し、熱風炉にて到達板温が２３０℃となる条件にて焼き付けることで硬化乾燥し、水冷することで塗装金属板を得た。 Furthermore, the anticorrosion paint produced on the other side (A side) of the pretreated steel plate is coated with a bar coater and hardened by baking in a hot air oven under conditions where the ultimate plate temperature is 210 ° C. Dried. Further, after baking and drying, the coated metal plate was cooled with water. The film thickness of the anticorrosive paint was 5 μm after baking and drying. On the coating layer of this anti-corrosion paint, a commercially available polyester paint containing a colored pigment is applied as a top coat paint with a bar coater and dried to a film thickness of 15 μm, and the final plate temperature is 230 ° C. in a hot air oven. It hardened and dried by baking on the conditions which become, and the coating metal plate was obtained by water cooling.
なお、上塗り塗料中に含まれる着色顔料には、白色顔料である酸化チタン（ＴｉＯ2 ）を用いており、添加量は塗料の乾燥塗膜質量にして５０質量％である。
このようにして作製した塗装鋼材（Ａ面は２コート、Ｂ面は１コートの塗装鋼材）についてＪＩＳ−Ｋ５４００．９．１記載の方法で塩水噴霧試験を実施した。本試験ではＡ面を評価面とし、この面に塩水を吹き付けた。試験時間は冷延鋼板の場合には７２ｈ、電気亜鉛めっき鋼板の場合には１２０ｈ、溶融亜鉛めっき鋼板の場合には２４０ｈとした。In addition, the colored pigment contained in the top coating material uses titanium oxide (TiO 2 ), which is a white pigment, and the addition amount is 50% by mass in terms of the dry coating mass of the coating material.
A salt spray test was carried out on the coated steel material thus prepared (coated steel material with 2 coats on the A side and 1 coat on the B surface) by the method described in JIS-K5400.99.1. In this test, surface A was used as the evaluation surface, and salt water was sprayed onto this surface. The test time was 72 h for cold-rolled steel sheets, 120 h for electrogalvanized steel sheets, and 240 h for hot-dip galvanized steel sheets.
塩水噴霧試験を行う際、塗装鋼材のＡ面には、カッターナイフにて塗膜を貫通して素地である金属に達するクロス状の切傷（以降クロスカットと称する）を設けてクロスカットからの塗膜の膨れ幅を観察し評価した。クロスカット部の評価方法は、評価面であるＡ面の塗膜のクロスカット片側の最大膨れ幅が１ｍｍ未満の場合に◎、１ｍｍ以上３ｍｍ未満の場合に○、３ｍｍ以上５ｍｍ未満の場合に△、５ｍｍ以上の場合に×と評価した。 When the salt spray test is performed, a cross-shaped cut (hereinafter referred to as a cross cut) that penetrates the coating film with a cutter knife and reaches the base metal is provided on the surface A of the coated steel material. The swelling width of the film was observed and evaluated. The evaluation method of the crosscut portion is as follows: when the maximum swollen width on the crosscut piece side of the A-side coating film of the evaluation surface is less than 1 mm, ◯ when 1 mm or more and less than 3 mm, △ when 3 mm or more and less than 5 mm In the case of 5 mm or more, it evaluated as x.
また、本発明の塗装金属板を端面部で金属部が露出するプレコート鋼板に適用した時を考慮し、切断機にて塗装金属板を切断し、金属が露出した切断端面部を設け、切断端面部からの塗膜の膨れ幅を観察し評価した。端面部の評価方法は評価面であるＡ面の端面からの塗膜最大膨れ幅が１ｍｍ未満の場合に◎、１ｍｍ以上３ｍｍ未満の場合に○、３ｍｍ以上５ｍｍ未満の場合に△、５ｍｍ以上の場合に×と評価した。 In addition, in consideration of when the coated metal plate of the present invention is applied to a precoated steel sheet in which the metal portion is exposed at the end surface portion, the coated metal plate is cut with a cutting machine, a cut end surface portion in which the metal is exposed is provided, and the cut end surface The swollen width of the coating film from the part was observed and evaluated. The evaluation method of the end face part is ◎ when the maximum swollen width of the coating film from the end face of the A surface, which is the evaluation face, is less than 1 mm, ◯ if it is 1 mm or more and less than 3 mm, △ if it is 3 mm or more and less than 5 mm, △ 5 mm or more The case was rated as x.
以下、評価結果の詳細を表１に示した。
エリンガム状態図で標準生成自由エネルギー△Ｇが０〜１００℃の温度範囲においてＦｅより低い金属を含む防錆塗料を被覆した本発明の塗装鋼材（本発明例Ｎｏ．１〜１２）は、優れた耐食性を示し、従来のＣｒ系防錆顔料を含む防錆塗料を被覆した鋼材（比較例Ｎｏ．１８〜２１）と比較してもほぼ同等の性能を有することがわかる。また、本発明の塗装鋼材は、塗料の樹脂種、鋼材種に限定することなく効果的である（本発明例Ｎｏ．３〜７）。The details of the evaluation results are shown in Table 1.
The coated steel materials of the present invention (invention examples Nos. 1 to 12) coated with a rust preventive coating containing a metal lower than Fe in the temperature range of 0 to 100 ° C. in the standard free energy of formation ΔG in the Ellingham phase diagram are excellent. It can be seen that even when compared with steel materials (Comparative Examples No. 18 to 21) which show corrosion resistance and are coated with a conventional anti-corrosion paint containing a Cr-based anti-corrosion pigment, they are comparable. Moreover, the coated steel material of this invention is effective, without being limited to the resin seed | species and steel material kind of a coating material (invention example No. 3-7).
また、本発明の塗装鋼材が鋼帯であり、且つ本発明の防錆塗料を片面にのみ塗布乾燥（本発明例１０〜１２）しても優れた耐食性を有する。本発明の防錆塗料は、ＶＰ顔料やカルシウムイオン交換シリカと組み合わせる（本発明例Ｎｏ．８，９）と耐食性が更に向上し、好適である。
一方、エリンガム状態図で標準生成自由エネルギー△Ｇが０〜１００℃の温度範囲においてＦｅより高い金属を含む防錆塗料を被覆した塗装鋼材（比較例Ｎｏ．１３〜１６）は耐食性に劣り、防錆顔料を含まない塗料で被覆した塗装鋼材（比較例Ｎｏ．１７）とほぼ同等の耐食性で有る。In addition, the coated steel material of the present invention is a steel strip, and has excellent corrosion resistance even when the anticorrosive paint of the present invention is applied and dried only on one side (Invention Examples 10 to 12). The anticorrosive paint of the present invention is suitable because it further improves the corrosion resistance when combined with a VP pigment or calcium ion exchanged silica (Examples Nos. 8 and 9).
On the other hand, the coated steel materials (Comparative Examples No. 13 to 16) coated with a rust preventive paint containing a metal higher than Fe in the temperature range of 0 to 100 ° C. in the standard generation free energy ΔG in the Ellingham phase diagram are inferior in corrosion resistance and It has almost the same corrosion resistance as a coated steel material (Comparative Example No. 17) coated with a paint that does not contain a rust pigment.
本発明により、環境上有毒である６価クロムを使用せずに、耐食性に優れた防錆塗料及び塗装金属板を提供することが可能となった。従って、本発明は工業的価値の極めて高い発明であるといえる。According to the present invention, it is possible to provide a rust preventive paint and a coated metal plate excellent in corrosion resistance without using environmentally toxic hexavalent chromium. Therefore, the present invention can be said to be an invention with extremely high industrial value.
Claims (4)
Ｆｅより低い金属もしくは合金である、金属ケイ素、フェロシリコン、フェロマンガン、
及び、リン酸／バナジン酸混合系の防錆顔料、微粒シリカ、イオン交換シリカのいずれか
一種以上のみを防錆顔料として含み、かつ、前記防錆顔料のうち、金属ケイ素、フェロシ
リコン、フェロマンガンのいずれか一種以上を含むことが必須であることを特徴とするノ
ンクロム系防錆塗料。
In Ellingham state diagram, standard free energy △ G is a lower metal or alloy than Fe in the temperature range of 0 to 100 ° C., metal silicon, ferrosilicon, ferromanganese,
And a phosphoric acid / vanadic acid mixed rust preventive pigment, fine silica, or ion-exchanged silica as a rust preventive pigment, and among the rust preventive pigments, metallic silicon, ferro
A non-chromium rust preventive paint characterized by containing at least one of recon and ferromanganese .
鋼材。
A coated steel material having a film formed by applying the rust preventive paint according to claim 1 and forming a film thereon.
とする塗装鋼帯。
A coated steel strip having a film formed by applying the rust preventive paint according to claim 1 and forming a film on at least one side.
とするプレコート鋼帯。A precoated steel strip having a film formed by applying the rust preventive paint according to claim 1 and forming a film on at least one side.
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| JPS58219274A (en) * | 1982-06-10 | 1983-12-20 | バツテル・デイベロプメント・コ−ポレ−シヨン | Anticorrosive paint for anticorrosive cathode |
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