JP6333324B2 - Rust conversion agent composition and method for producing the same - Google Patents
Rust conversion agent composition and method for producing the same Download PDFInfo
- Publication number
- JP6333324B2 JP6333324B2 JP2016168519A JP2016168519A JP6333324B2 JP 6333324 B2 JP6333324 B2 JP 6333324B2 JP 2016168519 A JP2016168519 A JP 2016168519A JP 2016168519 A JP2016168519 A JP 2016168519A JP 6333324 B2 JP6333324 B2 JP 6333324B2
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- Prior art keywords
- rust
- component
- isocyanate compound
- acid
- weight
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- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
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Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Description
本発明は、錆転換剤組成物及びその製造方法に関し、より詳しくは、錆が発生した鉄鋼基材を塗装する際錆除去を行う必要がないため、労力を著しく低減でき、耐久性に優れた上塗り塗装を可能にする技術である錆転換剤組成物及びその製造方法に関する。 The present invention relates to a rust conversion agent composition and a method for producing the same, and more specifically, since it is not necessary to remove rust when coating a steel substrate on which rust has occurred, the labor can be significantly reduced and the durability is excellent. The present invention relates to a rust conversion agent composition, which is a technique that enables top coating, and a method for producing the same.
従来、鉄鋼基材の錆面を塗装する際、サンドブラスト等の機械的除去によって鉄錆を除去しなければ塗装塗膜の密着性の低下が起こり、鉄面の酸化の進行を抑制できず、塗膜の剥離と鉄鋼基材の劣化を防止することができなかった。
しかし、鉄錆を機械的に全て除去するには多大な労力を要した。
Conventionally, when the rust surface of a steel substrate is painted, if the iron rust is not removed by mechanical removal such as sandblasting, the adhesion of the coating film is lowered, and the progress of oxidation of the iron surface cannot be suppressed. The film peeling and the deterioration of the steel substrate could not be prevented.
However, it took a lot of labor to mechanically remove all iron rust.
そこで、鉄鋼基材表面の赤錆を黒錆に転換することで、赤錆を全て機械的に除去しなくても鉄面の酸化の進行が抑制でき、塗膜の剥離と鉄鋼基材の劣化を防止できる防錆塗料が開発されている。
例えば、特許文献１には、熔融亜鉛メッキ鋼板の保護皮膜形成方法が開示されている。具体的には、該保護皮膜は水溶性又は水分散性有機高分子化合物の３−１０％水溶液、０．１−２０％のタンニン又はタンニン酸、及び０．１−１％のチオ尿素、水溶性チタン化合物、水溶性ジルコニウム化合物の１種以上（ｐＨ２−６．５）を含むと記載されている。この保護皮膜を使用することで熔融亜鉛メッキ鋼板の耐食性及び塗膜付着性を向上させることができると記載されている。
Therefore, by converting red rust on the steel base surface to black rust, the progress of oxidation on the iron surface can be suppressed without mechanically removing all red rust, and peeling of the coating and deterioration of the steel base can be prevented. Anti-corrosion paints that can be developed have been developed.
For example, Patent Document 1 discloses a method for forming a protective coating on a hot dip galvanized steel sheet. Specifically, the protective film is a 3-10% aqueous solution of a water-soluble or water-dispersible organic polymer compound, 0.1-20% tannin or tannic acid, and 0.1-1% thiourea, water-soluble In addition, it contains at least one kind of water-soluble titanium compound and water-soluble zirconium compound (pH 2-6.5). It is described that the corrosion resistance and coating film adhesion of the hot-dip galvanized steel sheet can be improved by using this protective film.
また、特許文献２には、ウレタン系水性接着剤組成物が開示されている。具体的には、ウレタン系水性接着剤組成物は水分散ウレタンポリマー（１００重量部）及びポリタンニン酸化合物（０．５−２０重量部）を含み、水分散ウレタンポリマーはポリイソシアネート化合物、水酸基を２個以上有するポリオール化合物、イソシアネート基と反応可能な活性水素を２個以上有し、且つカルボキシル基とスルホニル基から選ばれる１種以上の親水基を有する官能性化合物を重合することを特徴とすることが記載されている。これにより、鋼板等の金属製被着体に対する耐水接着性および水性接着剤としての貯蔵安定性に優れ、更に毒性の面でも問題のないウレタン系水性接着剤組成物を提供することができると記載されている。 Patent Document 2 discloses a urethane-based aqueous adhesive composition. Specifically, the urethane-based aqueous adhesive composition contains a water-dispersed urethane polymer (100 parts by weight) and a polytannic acid compound (0.5-20 parts by weight), and the water-dispersed urethane polymer contains a polyisocyanate compound and a hydroxyl group. It is characterized by polymerizing a polyol compound having two or more, a functional compound having two or more active hydrogens capable of reacting with an isocyanate group, and one or more hydrophilic groups selected from a carboxyl group and a sulfonyl group. It is described. According to this, it is described that it is possible to provide a urethane-based aqueous adhesive composition that is excellent in water-resistant adhesion to a metal adherend such as a steel plate and storage stability as a water-based adhesive and has no problem in terms of toxicity. Has been.
特許文献３には、錆転換用水系塗料が開示されている。具体的には、該錆転換用水系塗料はアクリル変性複合エマルジョンを１００重量部、タンニン酸等のポリフェノール誘導体を２−２０重量部、亜リン酸塩を２−２０重量部、ステンレス粉末を５−２０重量部含むことが記載されている。これにより、浮き錆を簡易に除去する程度の素地調整で鉄被塗物の錆面に塗装可能で、しかも優れた防錆性と耐候性を有する錆転換用水系塗料を提供することができると記載されている。 Patent Document 3 discloses a water-based paint for rust conversion. Specifically, the water-based paint for converting rust is 100 parts by weight of an acrylic-modified composite emulsion, 2-20 parts by weight of a polyphenol derivative such as tannic acid, 2-20 parts by weight of phosphite, 5- It contains 20 parts by weight. As a result, it is possible to provide a rust conversion water-based paint that can be applied to the rust surface of an iron coated object by adjusting the substrate so as to easily remove floating rust, and has excellent rust prevention and weather resistance. Have been described.
特許文献４には、鉄錆還元水系防錆塗料の製造方法が開示されている。具体的には、アクリル系樹脂に還元性リン酸系鉱酸とタンニン酸を配合することにより、鋼鉄の赤錆を還元して黒錆に転換し、また鋼鉄基剤とも反応して、防錆性、密着性が優れた塗膜を形成する鉄錆還元水系防錆塗料を提供することが出来ると記載されている。 Patent Document 4 discloses a method for producing an iron rust reduced water-based anticorrosive paint. Specifically, by combining reductive phosphoric acid mineral acid and tannic acid with acrylic resin, the red rust of steel is reduced to black rust, and also reacts with the steel base to prevent rust. It is described that an iron rust-reduced water-based anticorrosive paint that forms a coating film with excellent adhesion can be provided.
しかし、上記の特許文献１−４は全て赤錆から黒錆へ転換する速度が遅く、乾燥後の塗膜の基材への密着力が弱いものである。耐水性も不十分で、塗料を塗布して暴露するとすぐに錆が発生し、雨水による塗膜の膨れやはがれが発生するという問題点を有する。
よって、性能が改善された錆転換被膜が強く求められている。
However, all of Patent Documents 1 to 4 described above are slow in conversion from red rust to black rust, and the adhesion of the coating film after drying to the substrate is weak. Water resistance is also insufficient, and rust is generated as soon as the paint is applied and exposed, and there is a problem that the paint film swells or peels off due to rainwater.
Therefore, there is a strong demand for a rust conversion coating with improved performance.
本発明は、上記した従来技術の問題点を解決すべくなされたものであって、水性エマルジョン樹脂（Ａ）、ポリフェノール誘導体（Ｂ）及び有機酸（Ｃ）からなる主剤成分、及び親水性イソシアネート化合物（Ｄ）又は親水性イソシアネート化合物（Ｄ）及び疎水性イソシアネート化合物（Ｅ）の混合物、又は疎水性イソシアネート化合物（Ｅ）及び有機溶剤（Ｆ）の混合物からなる硬化剤成分を含む錆転換剤組成物とすることで、サンドブラスト等機械的な除去を行わなくても、錆びた鉄面の赤錆を黒錆に転換し、密着性、耐水性、耐溶剤性、防錆性、耐候性に格段に優れた被膜を形成する、水系２液型錆転換剤組成物を提供するものである。 The present invention has been made to solve the above-mentioned problems of the prior art, and comprises a main component composed of an aqueous emulsion resin (A), a polyphenol derivative (B) and an organic acid (C), and a hydrophilic isocyanate compound. A rust conversion agent composition comprising a curing agent component comprising (D) or a mixture of a hydrophilic isocyanate compound (D) and a hydrophobic isocyanate compound (E), or a mixture of a hydrophobic isocyanate compound (E) and an organic solvent (F). By converting the red rust on the rusted iron surface to black rust without mechanical removal such as sandblasting, it has outstanding adhesion, water resistance, solvent resistance, rust resistance, and weather resistance. An aqueous two-component rust conversion agent composition that forms a coated film is provided.
請求項１に係る発明は、主剤成分と硬化剤成分を含む水系２液型錆転換剤組成物であって、
主剤成分は、（Ａ）水性エマルジョン樹脂、（Ｂ）ポリフェノール誘導体、及び（Ｃ）有機酸、からなり、硬化剤成分は、（Ｄ）親水性イソシアネート化合物、（Ｄ）親水性イソシアネート化合物及び（Ｅ）疎水性イソシアネート化合物の混合物、又は（Ｅ）疎水性イソシアネート化合物及び（Ｆ）有機溶剤の混合物からなることを特徴とする、水系２液型錆転換剤組成物に関する。
The invention according to claim 1 is an aqueous two-component rust conversion agent composition comprising a main component and a curing agent component,
The main component is composed of (A) an aqueous emulsion resin, (B) a polyphenol derivative, and (C) an organic acid, and the curing agent component is (D) a hydrophilic isocyanate compound, (D) a hydrophilic isocyanate compound, and (E And (E) a mixture of a hydrophobic isocyanate compound, or (E) a mixture of a hydrophobic isocyanate compound and (F) an organic solvent.
請求項１に係る発明は、硬化剤成分が（Ｄ）親水性イソシアネート化合物及び（Ｅ）疎水性イソシアネート化合物の混合物である場合、（Ｄ）親水性イソシアネート化合物を５０−９９．９質量％、（Ｅ）疎水性イソシアネート化合物を０．１−５０質量％の範囲内で含むことを特徴とする水系２液型錆転換剤組成物に関する。
In the invention according to claim 1 , when the curing agent component is a mixture of (D) a hydrophilic isocyanate compound and (E) a hydrophobic isocyanate compound, (D) 50-99.9% by mass of the hydrophilic isocyanate compound, ( E) hydrophobic isocyanate compound and water-based two-characterized rust converted composition that includes in the range of 0.1-50% by weight related.
請求項１に係る発明は、硬化剤成分が（Ｅ）疎水性イソシアネート化合物及び（Ｆ）有機溶剤の混合物である場合、（Ｅ）疎水性イソシアネート化合物を１０−９０質量％及び（Ｆ）有機溶剤を１０−９０質量％の範囲内で含むことを特徴とする、水系２液型錆転換剤組成物に関する。
In the invention according to claim 1 , when the curing agent component is a mixture of (E) hydrophobic isocyanate compound and (F) organic solvent, (E) 10-90% by mass of hydrophobic isocyanate compound and (F) organic solvent the characterized in that it comprises in the range of 10-90 wt%, on water-based two-rust conversion agent composition.
請求項１に係る発明は、前記水性エマルジョン樹脂（Ａ）は水酸基価が１０ｍｇＫＯＨ／ｇ以下であって、イソシアネート化合物とはウレタン結合しない水性エマルジョン樹脂である水系２液型錆転換剤組成物に関する。
The invention according to claim 1, wherein the aqueous emulsion resin (A) is a hydroxyl value is not more than 10 mgKOH / g, about an isocyanate compound and water-based two-rust conversion agent composition is an aqueous emulsion resin which is not a urethane bond .
請求項２に係る発明は、錆転換黒色被膜の形成方法であって、（１）鉄鋼面上の錆を予め研磨し、あるいは研磨を行わず、（２）請求項１記載の主剤成分と硬化剤成分を混合した混合物を調製し、（３）前記混合物を、錆面を持つ鉄鋼面上に広く又は全面にわたり塗布し、（４）鉄鋼面上に錆転換黒色被膜を形成する、ことからなる、錆転換黒色被膜の形成方法に関する。
The invention according to claim 2 is a method for forming a rust-converting black coating, wherein (1) rust on the steel surface is previously polished or not polished, and (2) the main ingredient component and curing according to claim 1 (3) The mixture is applied widely or over the steel surface having a rust surface, and (4) a rust-converting black coating is formed on the steel surface. The invention relates to a method for forming a rust-converting black coating.
請求項１に係る発明によれば、主剤成分が水性エマルジョン樹脂（Ａ）とポリフェノール誘導体（Ｂ）と有機酸（Ｃ）を含むことにより、有機酸の水溶液中の水性エマルジョン樹脂（Ａ）粒子表面に親和したポリフェノール誘導体（Ｂ）が、親水性イソシアネート化合物（Ｄ）、又は親水性イソシアネート化合物（Ｄ）及び疎水性イソシアネート化合物（Ｅ）の混合物、又は疎水性イソシアネート化合物（Ｅ）及び有機溶剤（Ｆ）の混合物からなる硬化剤成分と反応硬化して、水性エマルジョン樹脂（Ａ）粒子間に絡み合い強固な高性能被膜を形成することができる。これは、本発明者らの実験的知得によれば、ポリフェノール誘導体（Ｂ）とイソシアネート化合物が架橋反応により相互貫入高分子網目構造（ＩＰＮ：Interpenetrating Polymer Network）を形成する。これにより、水性エマルジョン樹脂（Ａ）粒子間の隙間に緻密な網目構造高分子体ができるので、乾燥後に強固な被膜を形成すると考えられている（図１参照）。その結果、密着性、耐水性、耐溶剤性、防錆性、耐候性に優れた水系２液型錆転換剤組成物とすることができる。
主剤成分のポリフェノール誘導体（Ｂ）は、さらに鉄の酸化物（赤錆）と反応して黒色に転換することができる。
また、主剤成分に有機酸（Ｃ）が存在することで錆面を赤錆色から黒色に転換する速度を速めることができる。
硬化剤成分に疎水性イソシアネート化合物（Ｅ）を使用する場合、耐溶剤性が著しく向上するという効果を奏する。
According to the first aspect of the invention, the main component contains the aqueous emulsion resin (A), the polyphenol derivative (B), and the organic acid (C), whereby the surface of the aqueous emulsion resin (A) particles in the aqueous solution of the organic acid. The polyphenol derivative (B) having an affinity for is a hydrophilic isocyanate compound (D), a mixture of a hydrophilic isocyanate compound (D) and a hydrophobic isocyanate compound (E), or a hydrophobic isocyanate compound (E) and an organic solvent (F ) And a curing agent component made of a mixture of the aqueous emulsion resin (A) and entangled between the particles to form a strong high-performance film. According to the experimental knowledge of the present inventors, the polyphenol derivative (B) and the isocyanate compound form an interpenetrating polymer network (IPN) by a crosslinking reaction. As a result, a dense network polymer is formed in the gaps between the aqueous emulsion resin (A) particles, and it is considered that a strong film is formed after drying (see FIG. 1). As a result, an aqueous two-component rust converter composition excellent in adhesion, water resistance, solvent resistance, rust resistance, and weather resistance can be obtained.
The main component polyphenol derivative (B) can be further converted to black by reacting with an iron oxide (red rust).
Moreover, the speed | rate which converts a rust surface from red rust color to black can be accelerated because organic acid (C) exists in a main ingredient component.
When the hydrophobic isocyanate compound (E) is used for the curing agent component, there is an effect that the solvent resistance is remarkably improved.
請求項１に係る発明によれば、硬化剤成分が（Ｄ）親水性イソシアネート化合物及び（Ｅ）疎水性イソシアネート化合物の混合物である場合、（Ｄ）親水性イソシアネート化合物を５０−９９．９質量％、（Ｅ）疎水性イソシアネート化合物を０．１−５０質量％の範囲内で含むことで、密着性、耐水性、防錆性、耐候性に加えて耐溶剤性が著しく優れた水系２液型錆転換剤組成物とすることができる。
疎水性イソシアネート化合物（Ｅ）が５０質量％を超えて使用すると、主剤成分との相溶性が悪くなり手攪拌だけでは均一に混合できず、塗膜にブツが発生したり光沢が低下する。攪拌機を使用せざるをえないため作業効率が悪くなる。
According to the invention which concerns on Claim 1 , when a hardening | curing agent component is a mixture of (D) hydrophilic isocyanate compound and (E) hydrophobic isocyanate compound, (D) hydrophilic isocyanate compound is 50-99.9 mass%. , (E) A water-based two-component type that includes a hydrophobic isocyanate compound within a range of 0.1 to 50% by mass, and has excellent solvent resistance in addition to adhesion, water resistance, rust prevention, and weather resistance. It can be set as a rust conversion agent composition.
When the hydrophobic isocyanate compound (E) is used in an amount exceeding 50% by mass, the compatibility with the main ingredient component is deteriorated, and it cannot be uniformly mixed only by hand stirring. The work efficiency becomes worse because a stirrer must be used.
請求項１に係る発明によれば、硬化剤成分が（Ｅ）疎水性イソシアネート化合物及び
（Ｆ）有機溶剤の混合物である場合、（Ｅ）疎水性イソシアネート化合物を１０−９０質量％及び（Ｆ）有機溶剤を１０−９０質量％の範囲内で含むことで、密着性、耐水性、防錆性、耐候性に加えて耐溶剤性が著しく優れた水系２液型錆転換剤組成物とすることができる。有機溶剤（Ｆ）が１０質量％を下回ると主剤成分との相溶性が悪くなり手攪拌だけでは均一に混合できず、塗膜にブツが発生するかあるいは光沢が低下する。有機溶剤（Ｆ）が９０質量％を上回ると主剤成分との相溶性は良くなるが、主剤成分との混和安定性が悪くなりゲル化したり、ブツが発生して正常な塗膜が得られない。
According to the invention of claim 1 , when the curing agent component is a mixture of (E) a hydrophobic isocyanate compound and (F) an organic solvent, (E) the hydrophobic isocyanate compound is 10-90% by mass and (F) By including an organic solvent in the range of 10 to 90% by mass, an aqueous two-component rust conversion agent composition having remarkably excellent solvent resistance in addition to adhesion, water resistance, rust prevention, and weather resistance Can do. When the organic solvent (F) is less than 10% by mass, the compatibility with the main ingredient component is deteriorated, and the mixture cannot be uniformly mixed only by hand stirring, and the coating film is blurred or the gloss is lowered. When the organic solvent (F) exceeds 90% by mass, the compatibility with the main ingredient component is improved, but the mixing stability with the main ingredient component is deteriorated and gelation occurs, and a normal coating film cannot be obtained. .
請求項１に係る発明によれば、水性エマルジョン樹脂は、水酸基価１０ｍｇＫＯＨ／ｇ以下であってイソシアネートと反応する必要はなく（水酸基をほとんど含有しない、即ちウレタン結合しない）、有機酸（Ｃ）の水溶液中の水性エマルジョン樹脂（Ａ）粒子表面に親和したポリフェノール誘導体（Ｂ）が、親水性イソシアネート化合物（Ｄ）、又は親水性イソシアネート化合物（Ｄ）及び疎水性イソシアネート化合物（Ｅ）の混合物、又は疎水性イソシアネート化合物（Ｅ）及び有機溶剤（Ｆ）の混合物からなる硬化剤成分と反応硬化して、水性エマルジョン樹脂（Ａ）粒子間に絡み合い強固な高性能被膜を形成するので、その結果優れた密着性、耐水性、防錆性、耐候性に加えて耐溶剤性を有する水系２液型錆転換剤組成物とすることができる。
According to the invention according to claim 1 , the aqueous emulsion resin has a hydroxyl value of 10 mgKOH / g or less and does not need to react with isocyanate (contains almost no hydroxyl group, that is, does not have a urethane bond), and is an organic acid (C). Aqueous emulsion resin (A) in aqueous solution (A) The polyphenol derivative (B) having affinity for the particle surface is a hydrophilic isocyanate compound (D), or a mixture of a hydrophilic isocyanate compound (D) and a hydrophobic isocyanate compound (E), or hydrophobic Reactive curing with a curing agent component consisting of a mixture of a functional isocyanate compound (E) and an organic solvent (F), and entangled between the aqueous emulsion resin (A) particles to form a strong high performance film, resulting in excellent adhesion Water-based two-component rust converter composition that has solvent resistance in addition to water resistance, water resistance, rust resistance, and weather resistance It can be.
請求項２に係る発明によれば、主剤成分と硬化剤成分を混合して水系２液型錆転換剤組成物とし、その水系２液型錆転換剤組成物を錆の上に塗布して鉄鋼面上に錆転換黒色被膜を形成することで、錆びた鉄面の赤錆を黒錆に転換し、密着性、耐水性、耐溶剤性、防錆性、耐候性に格段に優れた被膜（錆転換黒色被膜）を形成することができる。 According to the second aspect of the present invention, the main component component and the curing agent component are mixed to form an aqueous two-component rust conversion agent composition, and the aqueous two-component rust conversion agent composition is applied onto rust to produce steel. By forming a rust conversion black coating on the surface, the red rust on the rusted iron surface is converted to black rust, and the coating (rust rust) with outstanding adhesion, water resistance, solvent resistance, rust resistance, and weather resistance Conversion black film) can be formed.
１．水系２液型錆転換剤組成物に含まれる成分
以下、本発明に係る水系２液型錆転換剤組成物について詳細に説明する。
1. Components contained in the aqueous two-component rust converting agent composition Hereinafter, the aqueous two-component rust converting agent composition according to the present invention will be described in detail.
本発明の目的は、水性エマルジョン樹脂（Ａ）、ポリフェノール誘導体（Ｂ）及び有機酸（Ｃ）からなる主剤成分、及び親水性イソシアネート化合物（Ｄ）又は親水性イソシアネート化合物（Ｄ）及び疎水性イソシアネート化合物（Ｅ）の混合物、又は疎水性イソシアネート化合物（Ｅ）及び有機溶剤（Ｆ）の混合物からなる硬化剤成分を含む錆転換剤組成物とすることで、サンドブラスト等機械的な除去を行わなくても、錆びた鉄面の赤錆を黒錆に転換し、密着性、耐水性、耐溶剤性、防錆性、耐候性に格段に優れた被膜を形成する、水系２液型錆転換剤組成物を提供することにある。 An object of the present invention is to provide an aqueous emulsion resin (A), a main component composed of a polyphenol derivative (B) and an organic acid (C), and a hydrophilic isocyanate compound (D) or a hydrophilic isocyanate compound (D) and a hydrophobic isocyanate compound. By using a mixture of (E) or a rust conversion agent composition containing a curing agent component comprising a mixture of a hydrophobic isocyanate compound (E) and an organic solvent (F), mechanical removal such as sandblasting is not required. An aqueous two-component rust converter composition that converts red rust on a rusted iron surface to black rust and forms a coating with outstanding adhesion, water resistance, solvent resistance, rust resistance, and weather resistance. It is to provide.
＜主剤成分＞
主剤成分は、水性エマルジョン樹脂（Ａ）、ポリフェノール誘導体（Ｂ）及び有機酸（Ｃ）からなる。
<Main ingredient>
The main component is composed of an aqueous emulsion resin (A), a polyphenol derivative (B), and an organic acid (C).
（水性エマルジョン樹脂）
水性エマルジョン樹脂（Ａ）として、水酸基価１０ｍｇＫＯＨ／ｇのイソシアネートとは反応性のない、即ち水酸基をほとんど含有せず、ウレタン結合しない通常のアクリル樹脂エマルジョン、スチレン−アクリル樹脂エマルジョン、酢酸ビニル−アクリル樹脂エマルジョン、エチレン酢酸ビニル−アクリル樹脂エマルジョン、シリコン−アクリル樹脂エマルジョン、アクリルニトリル−塩化ビニル−塩化ビニリデン共重合樹脂エマルジョン、エポキシ−アクリル樹脂エマルジョンを使用することが好ましい。アクリル樹脂エマルジョンが好適に使用できる。
水性エマルジョン樹脂（Ａ）の濃度は、主剤成分全体に対して１０−８０重量％、好ましくは３０−７０重量％である。
上記のような水性エマルジョン樹脂（Ａ）を含むことにより、本発明は強固な被膜を形成できる。
(Aqueous emulsion resin)
As an aqueous emulsion resin (A), a normal acrylic resin emulsion, a styrene-acrylic resin emulsion, a vinyl acetate-acrylic resin which is not reactive with an isocyanate having a hydroxyl value of 10 mgKOH / g, that is, contains almost no hydroxyl group and does not have a urethane bond. It is preferable to use an emulsion, an ethylene vinyl acetate-acrylic resin emulsion, a silicon-acrylic resin emulsion, an acrylonitrile-vinyl chloride-vinylidene chloride copolymer resin emulsion, or an epoxy-acrylic resin emulsion. An acrylic resin emulsion can be suitably used.
The concentration of the aqueous emulsion resin (A) is 10 to 80% by weight, preferably 30 to 70% by weight, based on the entire main ingredient component.
By including the aqueous emulsion resin (A) as described above, the present invention can form a strong film.
（ポリフェノール誘導体）
ポリフェノール誘導体（Ｂ）としては、タンニン酸や、加水分解性タンニンでも縮合性タンニンでも良く、タンニンを加水分解して得られる没食子酸又は没食子酸を加熱し、脱炭酸して得られるピロガロールを使用することもできる。
ポリフェノール誘導体（Ｂ）の濃度は、主剤成分全体に対して１−８重量％、好ましくは２−７重量％である。
主剤成分がさらにポリフェノール誘導体（Ｂ）を含むことで、鉄の酸化物（赤錆）と反応して黒色に転換することができる。また、有機酸（Ｃ）の水溶液中の水性エマルジョン樹脂（Ａ）粒子表面に親和したポリフェノール誘導体（Ｂ）が、親水性イソシアネート化合物（Ｄ）、又は親水性イソシアネート化合物（Ｄ）及び疎水性イソシアネート化合物（Ｅ）の混合物、又は疎水性イソシアネート化合物（Ｅ）及び有機溶剤（Ｆ）の混合物からなる硬化剤成分と反応硬化して、水性エマルジョン樹脂（Ａ）粒子間に絡み合い強固な高性能被膜を形成することができる。
本発明者らの実験的知得によれば、ポリフェノール誘導体（Ｂ）が水性エマルジョン樹脂（Ａ）の粒子表面に親和し、このポリフェノール誘導体（Ｂ）と、硬化剤成分に含まれるイソシアネート化合物（親水性イソシアネート化合物（Ｄ）であっても、疎水性イソシアネート化合物（Ｅ）であっても、その両方であっても良い）が架橋反応により相互貫入高分子網目構造（ＩＰＮ：Interpenetrating Polymer Network）を形成することで、水性エマルジョン樹脂（Ａ））粒子間の隙間に緻密な網目構造高分子体ができるので互いに密着し合い、強固な被膜となると考えられている（図１参照）。
(Polyphenol derivative)
The polyphenol derivative (B) may be tannic acid, hydrolyzable tannin or condensable tannin, and pyrogallol obtained by heating gallic acid or gallic acid obtained by hydrolyzing tannin and decarboxylation is used. You can also.
The density | concentration of a polyphenol derivative (B) is 1-8 weight% with respect to the whole main ingredient component, Preferably it is 2-7 weight%.
When the main component further contains the polyphenol derivative (B), it can be converted to black by reacting with the iron oxide (red rust). The polyphenol derivative (B) having affinity for the surface of the aqueous emulsion resin (A) particles in the aqueous solution of the organic acid (C) is a hydrophilic isocyanate compound (D), or a hydrophilic isocyanate compound (D) and a hydrophobic isocyanate compound. Reaction hardens with a hardener component consisting of a mixture of (E) or a mixture of hydrophobic isocyanate compound (E) and organic solvent (F) to form a strong high performance film entangled between aqueous emulsion resin (A) particles. can do.
According to the experimental knowledge of the present inventors, the polyphenol derivative (B) has an affinity for the particle surface of the aqueous emulsion resin (A), and the polyphenol derivative (B) and an isocyanate compound (hydrophilic) contained in the curing agent component. An isocyanate compound (D), a hydrophobic isocyanate compound (E), or both) can form an interpenetrating polymer network (IPN) by a crosslinking reaction. By doing so, it is considered that a dense network polymer is formed in the gaps between the aqueous emulsion resin (A)) particles, so that they are in close contact with each other and become a strong coating (see FIG. 1).
（有機酸）
有機酸（Ｃ）としては、シュウ酸、クエン酸、リンゴ酸、酒石酸、乳酸、ギ酸、グルタル酸、グリコール酸、コハク酸、マロン酸などが好適に使用できる。
有機酸（Ｃ）の濃度は、主剤成分全体に対して１−８重量％、好ましくは２−７重量％である。
ｐＨを１．５−６．０の範囲に調整することにより、錆面を赤錆色から黒色に転換する速度を速め、鉄鋼面への密着性を向上させる。
(Organic acid)
As the organic acid (C), oxalic acid, citric acid, malic acid, tartaric acid, lactic acid, formic acid, glutaric acid, glycolic acid, succinic acid, malonic acid and the like can be suitably used.
The concentration of the organic acid (C) is 1 to 8% by weight, preferably 2 to 7% by weight, based on the entire main ingredient component.
By adjusting pH to the range of 1.5-6.0, the speed which converts a rust surface from a red rust color to black is accelerated, and the adhesiveness to a steel surface is improved.
＜硬化剤成分＞
硬化剤成分として、親水性イソシアネート化合物（Ｄ）のみから構成されていても良く、親水性イソシアネート化合物（Ｄ）と疎水性イソシアネート化合物（Ｅ）の混合物であっても良く、疎水性イソシアネート化合物（Ｅ）及び有機溶剤（Ｆ）の混合物であっても良い。
疎水性イソシアネート化合物（Ｅ）を含むことで耐溶剤性が向上するという効果を奏する。
硬化剤成分として親水性イソシアネート化合物（Ｄ）及び疎水性イソシアネート化合物（Ｅ）の混合物である場合、親水性イソシアネート化合物（Ｄ）は疎水性イソシアネート化合物（Ｅ）よりも多く含んでいることが望ましく、よって親水性イソシアネート化合物（Ｄ）を５０−９９．９質量％、疎水性イソシアネート化合物（Ｅ）を０．１−５０質量％の範囲内で含むことが好ましい。また、硬化剤成分として疎水性イソシアネート化合物（Ｅ）及び有機溶剤（Ｆ）の混合物である場合、（Ｅ）疎水性イソシアネート化合物を１０−９０質量％及び（Ｆ）有機溶剤を１０−９０質量％の範囲内で含むことが好ましい。
硬化剤成分の濃度は、主剤１００部に対して０．５−３０部、好ましくは１−２０部である。
<Curing agent component>
As a hardening | curing agent component, it may be comprised only from hydrophilic isocyanate compound (D), may be a mixture of hydrophilic isocyanate compound (D) and hydrophobic isocyanate compound (E), and hydrophobic isocyanate compound (E ) And an organic solvent (F).
By including the hydrophobic isocyanate compound (E), there is an effect that the solvent resistance is improved.
When it is a mixture of a hydrophilic isocyanate compound (D) and a hydrophobic isocyanate compound (E) as a curing agent component, it is desirable that the hydrophilic isocyanate compound (D) contains more than the hydrophobic isocyanate compound (E), Therefore, it is preferable that the hydrophilic isocyanate compound (D) is contained in the range of 50-99.9% by mass and the hydrophobic isocyanate compound (E) in the range of 0.1-50% by mass. Moreover, when it is a mixture of hydrophobic isocyanate compound (E) and organic solvent (F) as a hardening | curing agent component, 10-90 mass% of (E) hydrophobic isocyanate compound and 10-90 mass% of (F) organic solvent are used. It is preferable to contain within the range.
The density | concentration of a hardening | curing agent component is 0.5-30 parts with respect to 100 parts of main agents, Preferably it is 1-20 parts.
（親水性イソシアネート化合物）
親水性イソシアネート化合物（Ｄ）として、例えばアクアネート１００、アクアネート１１０、アクアネート２００及びアクアネート２１０（日本ポリウレタン工業社製）、バイヒジュールＴＰＬＳ−２０３２、ＳＵＶ−イソシアネートＬ８０１、バイヒジュールＶＰＬＳ−２３１９、バイヒジュール３１００、ＶＰＬＳ−２３３６及びＶＰＬＳ−２１５０／１（住化バイエルウレタン社製）、タケネートＷＤ−７２０、タケネートＷＤ−７２５及びタケネートＷＤ−２２０（三井武田ケミカル社製）、レザミンＤ−５６（大日精化工業社製）等の１種又は２種以上の組み合わせを用いることができる。
(Hydrophilic isocyanate compound)
Examples of the hydrophilic isocyanate compound (D) include AQUANATE 100, AQUANATE 110, AQUANATE 200, and AQUANATE 210 (manufactured by Nippon Polyurethane Industry Co., Ltd.), Bihydur TPLS-2032, SUV-isocyanate L801, Bihydur VPLS-2319, Bihidur 3100. , VPLS-2336 and VPLS-2150 / 1 (manufactured by Sumika Bayer Urethane Co., Ltd.), Takenate WD-720, Takenate WD-725 and Takenate WD-220 (manufactured by Mitsui Takeda Chemical Co., Ltd.), Resamine D-56 (Daiichi Seika Kogyo) 1 type) or a combination of two or more types can be used.
（疎水性イソシアネート化合物）
疎水性イソシアネート化合物（Ｅ）は通常溶媒系においてハイブリッドタイプとして使用されるものが好ましく、例えばデスモジュールＮ３４００、デスモジュールＮ３６００、デスモジュールＶＰＬＳ２２９４（住化バイエルウレタン社製）、タケネートＤ−１７０ＨＮ（三井武田ケミカル社製）等の１種又は２種以上の組み合わせを用いることができる。
(Hydrophobic isocyanate compound)
The hydrophobic isocyanate compound (E) is preferably one that is usually used as a hybrid type in a solvent system. For example, Desmodur N3400, Desmodur N3600, Desmodur VPLS2294 (manufactured by Sumika Bayer Urethane Co., Ltd.), Takenate D-170HN (Mitsui Takeda) 1 type or 2 or more types of combinations, such as a chemical company), can be used.
（有機溶剤）
有機溶剤（Ｆ）は疎水性イソシアネートと反応性がなく、混合して良好に相溶するものであれば、水溶性であっても非水溶性であっても使用できる。これらの有機溶剤の中で２５℃の水１００ｇに対する溶解量が５０ｇ以下、好ましくは０．１−３０ｇの範囲内にある有機溶剤を使用することにより、主剤成分と硬化剤成分の混和性が良好になり強固な高性能被膜を形成することができる。有機溶剤は１種類でも２種類以上でも、水１００ｇに対する溶解量を調整すればよい。
かかる有機溶剤としては、沸点が１００℃以上、好ましくは１１０−２５０℃の範囲のものが使用できる。例えばキシレン、酢酸イソブチル、酢酸ブチル、酢酸イソアミル、エチレングリコールモノブチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、メチルメトキシブチルアセテート、メトキシプロピルアセテート、エチルエトキシプロピオネート、ニトロプロパン、メチルイソブチルケトン、メチルアミルケトン、オキソヘキシルアセテート、グルタル酸ジメチル、コハク酸ジメチル、アジピン酸ジメチル等があげられる。
(Organic solvent)
The organic solvent (F) can be used either water-soluble or water-insoluble as long as it is not reactive with hydrophobic isocyanate and can be mixed well. Among these organic solvents, by using an organic solvent having a solubility in 100 g of water at 25 ° C. of 50 g or less, preferably in the range of 0.1-30 g, the miscibility of the main component and the curing agent component is good. Thus, a strong high-performance film can be formed. The organic solvent may be one type or two or more types, and the amount dissolved in 100 g of water may be adjusted.
As such an organic solvent, one having a boiling point of 100 ° C. or higher, preferably 110 to 250 ° C. can be used. For example, xylene, isobutyl acetate, butyl acetate, isoamyl acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate, methyl methoxybutyl acetate, methoxypropyl acetate, ethyl ethoxypropionate, nitropropane, methyl isobutyl ketone Methyl amyl ketone, oxohexyl acetate, dimethyl glutarate, dimethyl succinate, dimethyl adipate and the like.
＜その他に含み得る任意の成分＞
本発明は、主剤成分及び硬化剤成分の他に、以下の成分を含み得る。
（増粘剤）
主剤成分と硬化剤成分を塗装前に混合して塗装する際、粘度が低すぎると液だれを起こし塗布量が少なくなってしまうため、水性塗料に一般的に使用される増粘剤を使用して高粘度に調製することができる。
増粘剤の濃度は、主剤成分と硬化剤成分の混合物に対して０．５〜５．０重量％含み得る。
増粘剤として、ヒドロキシエチルセルロース等のセルロース系増粘剤、ポリアクリル酸ナトリウム等のアクリル系増粘剤、ケイ酸アンモニウムマグネシウム、有機ヘクトライト等の天然鉱物系増粘剤、キサンタンガム等の天然植物系増粘剤及びウレタン会合型増粘剤等を使用することができる。
<Other optional components>
In addition to the main component and the curing agent component, the present invention may include the following components.
(Thickener)
When mixing the base agent component and curing agent component before painting, if the viscosity is too low, dripping will occur and the coating amount will decrease, so use a thickener commonly used in water-based paints. And can be prepared to have a high viscosity.
The concentration of the thickener may be 0.5 to 5.0% by weight with respect to the mixture of the main component and the hardener component.
As thickeners, cellulose thickeners such as hydroxyethylcellulose, acrylic thickeners such as sodium polyacrylate, natural mineral thickeners such as ammonium magnesium silicate and organic hectorite, natural plant systems such as xanthan gum Thickeners and urethane associative thickeners can be used.
（消泡剤）
主剤成分と硬化剤成分を塗装前に混合する際、泡立ちを起こすと被膜にピンホールが生じ、耐水性、防錆性が低下するため、水性塗料に一般的に使用されるシリコン系消泡剤、鉱物油系消泡剤を配合することができる。
消泡剤の濃度は、主剤成分と硬化剤成分の混合物に対して０．０５〜１．５重量％含み得る。
(Defoamer)
Silicone antifoaming agent commonly used in water-based paints, when foaming occurs when mixing the main ingredient component and curing agent component before coating, pinholes are formed in the coating and the water resistance and rust resistance are reduced. A mineral oil-based antifoaming agent can be blended.
The concentration of the antifoaming agent may be 0.05 to 1.5% by weight based on the mixture of the main component and the curing agent component.
（体質顔料）
本発明では、必要に応じて体質顔料を配合することができる。体質顔料の配合は、より塗膜厚を厚くしたい場合や上塗り塗料との密着性を向上させたい場合に有効である。体質顔料としては、酸性下で安定なものであれば良く、カオリン、硫酸バリウム、シリカ、タルク、マイカ、ウオラストナイト等が例示できる。
配合量は特に限定されないが、組成物中３０％以下が好ましい。３０％を超えると塗膜強度が悪化する。
(External pigment)
In the present invention, extender pigments can be blended as necessary. The composition of the extender pigment is effective when it is desired to increase the thickness of the coating film or to improve the adhesion with the top coat. The extender pigment is not particularly limited as long as it is stable under acidic conditions, and examples thereof include kaolin, barium sulfate, silica, talc, mica, and wollastonite.
The blending amount is not particularly limited, but is preferably 30% or less in the composition. If it exceeds 30%, the coating strength deteriorates.
（造膜助剤）
本発明では、使用する水性エマルジョン樹脂（Ａ）の造膜温度（ＭＦＴ）に応じて通常の水性塗料組成物に使用される造膜助剤を配合することができる。造膜助剤としては、ブチルセロソルブ、酢酸ブチルセロソルブ、ブチルカルビトール、酢酸カルビトール、酢酸ブチルカルビトール、ベンジルアルコール、２，２，４−トリメチル−１，３−ペンタンジオールモノイソブチレート（商品名：テキサノール）等が例示できる。
(Film forming aid)
In the present invention, a film-forming auxiliary used in a normal aqueous coating composition can be blended according to the film-forming temperature (MFT) of the aqueous emulsion resin (A) to be used. As a film-forming aid, butyl cellosolve, butyl cellosolve, butyl carbitol, carbitol acetate, butyl carbitol acetate, benzyl alcohol, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (trade name: Texanol) and the like.
本発明では、上記成分の他、必要に応じて通常の水性塗料組成物に使用される凍結防止剤、可塑剤、防腐・防カビ剤、レベリング剤、沈降防止剤、タレ防止剤、艶消し剤等を配合することができる。 In the present invention, in addition to the above components, antifreezing agents, plasticizers, antiseptic / antifungal agents, leveling agents, anti-settling agents, anti-sagging agents, matting agents used in ordinary aqueous coating compositions as necessary Etc. can be blended.
２．錆転換黒色被膜の形成方法
次に、本発明の水系２液型錆転換剤組成物を使用した、錆転換黒色被膜の形成方法について説明する。
まず、水系２液型錆転換剤組成物を塗布する鉄鋼面上の錆の量が多い場合、予め錆面を研磨して浮いた錆を除去する。（４種ケレン処理）
研磨する方法は特に限定されず、サンドブラスト等によらず物理的に浮いた錆を取り除く方法であればいずれであっても良い。
予め浮き錆を除去し研磨することで、水系２液型錆転換剤組成物が良く浸透し、錆面をくまなく赤錆色から黒色に転換することができる。錆面の奥まで水系２液型錆転換剤組成物が浸透するため、密着性が向上し錆が再びできにくくなる。
錆の量が少なければ、研磨を行わずに直接水系２液型錆転換剤組成物を錆面に塗布しても良い。
2. Next, a method for forming a rust-converting black film using the aqueous two-component rust converting agent composition of the present invention will be described.
First, when the amount of rust on the steel surface to which the aqueous two-component rust converter composition is applied is large, the rust surface is previously polished to remove floating rust. (4 types of keren treatment)
The method of polishing is not particularly limited, and any method may be used as long as it is a method of removing rust that has physically floated regardless of sandblasting or the like.
By removing floating rust in advance and polishing, the aqueous two-component rust conversion agent composition penetrates well, and the rust surface can be converted from red rust color to black throughout. Since the aqueous two-component rust conversion agent composition penetrates to the back of the rust surface, the adhesion is improved and rust is difficult to be formed again.
If the amount of rust is small, the aqueous two-component rust conversion agent composition may be directly applied to the rust surface without polishing.
次に、主剤成分と硬化剤成分を均一に混合した混合物（水系２液型錆転換剤組成物）を調製する。
主剤成分は、上記のような水性エマルジョン樹脂（Ａ）、ポリフェノール誘導体（Ｂ）及び有機酸（Ｃ）からなり、硬化剤成分は、上記のような親水性イソシアネート化合物（Ｄ）のみから構成されていても良く、親水性イソシアネート化合物（Ｄ）と疎水性イソシアネート化合物（Ｅ）の混合物であっても良く、疎水性イソシアネート化合物（Ｅ）及び有機溶剤（Ｆ）の混合物であっても良い。
混合する方法は特に限定されず、手撹拌であっても、攪拌機による撹拌であっても良い。
主剤成分と硬化剤成分を混合する割合は、主剤成分１００部に対して、硬化剤成分を０．５−３０部、好ましくは１−２０部である。
Next, a mixture (aqueous two-component rust conversion agent composition) in which the main component and the curing agent component are uniformly mixed is prepared.
The main component is composed of the above aqueous emulsion resin (A), polyphenol derivative (B) and organic acid (C), and the curing agent component is composed of only the above hydrophilic isocyanate compound (D). It may be a mixture of a hydrophilic isocyanate compound (D) and a hydrophobic isocyanate compound (E), or a mixture of a hydrophobic isocyanate compound (E) and an organic solvent (F).
The method of mixing is not particularly limited, and may be hand stirring or stirring with a stirrer.
The mixing ratio of the main agent component and the hardener component is 0.5-30 parts, preferably 1-20 parts, of the hardener component with respect to 100 parts of the main agent component.
その後前記混合物（水系２液型錆転換剤組成物）を、錆面を持つ鉄鋼面上に広く又は全面にわたり塗布する。
塗布方法は特に限定されず、スプレーによって塗布しても、刷毛等で直接錆面に塗布しても良い。
Thereafter, the mixture (aqueous two-component rust conversion agent composition) is applied widely or over the entire steel surface having a rust surface.
The application method is not particularly limited, and it may be applied by spraying or directly on the rust surface with a brush or the like.
前記混合物を錆面に塗布することにより、鉄鋼面上に錆転換黒色被膜が形成される。
上記方法で本発明の水系２液型錆転換剤組成物を調製・使用することにより、赤錆から黒錆への転換速度が速く、密着性、耐水性、耐溶剤性、防錆性、耐候性に格段に優れた被膜を得ることができる。
By applying the mixture to the rust surface, a rust-converting black coating is formed on the steel surface.
By preparing and using the aqueous two-component rust conversion agent composition of the present invention by the above method, the conversion rate from red rust to black rust is fast, adhesion, water resistance, solvent resistance, rust resistance, weather resistance It is possible to obtain a coating that is extremely excellent.
以下、本発明に係る水系２液型錆転換剤組成物に関する実施例を示すことにより、本発明の効果をより明確なものとする。但し、本発明は以下の実施例に限定されるものではない。 Hereinafter, the effect of the present invention will be made clearer by showing examples relating to the aqueous two-component rust converting agent composition according to the present invention. However, the present invention is not limited to the following examples.
水系２液型錆転換剤組成物の製造
（実施例１）
６０重量％のポリゾールＡＰ−１３５０（アクリル樹脂エマルジョン、昭和電工株式会社製）、６重量％のタンニン酸、３重量％の酒石酸、３１重量％の水からなる主剤成分と、主剤成分１００部に対してアクアネート１３０（親水性イソシアネート化合物、日本ポリウレタン工業株式会社製）１５部からなる硬化剤成分を均一に混合した。これを実施例１とした。
Production of aqueous two-component rust conversion agent composition (Example 1)
For main ingredient component consisting of 60 wt% Polysol AP-1350 (acrylic resin emulsion, Showa Denko KK), 6 wt% tannic acid, 3 wt% tartaric acid, 31 wt% water, and 100 parts main ingredient component Then, a hardener component consisting of 15 parts of Aquanate 130 (hydrophilic isocyanate compound, manufactured by Nippon Polyurethane Industry Co., Ltd.) was uniformly mixed. This was designated Example 1.
（実施例２）
６０重量％のポリゾールＡＰ−１３５０（アクリル樹脂エマルジョン、昭和電工株式会社製）、６重量％のタンニン酸、３重量％の酒石酸、３１重量％の水からなる主剤成分と、主剤成分１００部に対してアクアネート１３０（親水性イソシアネート化合物、日本ポリウレタン工業株式会社製）１３部及びデスモジュールＮ３４００（疎水性イソシアネート化合物、住化バイエルウレタン株式会社製）２部からなる硬化剤成分を均一に混合した。これを実施例２とした。
(Example 2)
For main ingredient component consisting of 60 wt% Polysol AP-1350 (acrylic resin emulsion, Showa Denko KK), 6 wt% tannic acid, 3 wt% tartaric acid, 31 wt% water, and 100 parts main ingredient component A hardener component consisting of 13 parts Aquanate 130 (hydrophilic isocyanate compound, manufactured by Nippon Polyurethane Industry Co., Ltd.) and 2 parts Desmodur N3400 (hydrophobic isocyanate compound, manufactured by Sumika Bayer Urethane Co., Ltd.) was uniformly mixed. This was designated Example 2.
（実施例３）
６０重量％のポリゾールＡＰ−１３５０（アクリル樹脂エマルジョン、昭和電工株式会社製）、６重量％のタンニン酸、３重量％の酒石酸、３１重量％の水からなる主剤成分と、主剤成分１００部に対してアクアネート１３０（親水性イソシアネート化合物、日本ポリウレタン工業株式会社製）１０部及びデスモジュールＮ３４００（疎水性イソシアネート化合物、住化バイエルウレタン株式会社製）５部からなる硬化剤成分を均一に混合した。これを実施例３とした。
(Example 3)
For main ingredient component consisting of 60 wt% Polysol AP-1350 (acrylic resin emulsion, Showa Denko KK), 6 wt% tannic acid, 3 wt% tartaric acid, 31 wt% water, and 100 parts main ingredient component Then, a hardener component consisting of 10 parts Aquanate 130 (hydrophilic isocyanate compound, manufactured by Nippon Polyurethane Industry Co., Ltd.) and 5 parts Desmodur N3400 (hydrophobic isocyanate compound, manufactured by Sumika Bayer Urethane Co., Ltd.) was uniformly mixed. This was designated as Example 3.
（実施例４）
６０重量％のアクロナールＹＪ１２１０ＤＡ（アクリル樹脂エマルジョン、ＢＡＳＦジャパン株式会社製）、６重量％のタンニン酸、３重量％のシュウ酸、３１重量％の水からなる主剤成分と、主剤成分１００部に対してバイヒジュール３１００（親水性イソシアネート化合物、住化バイエルウレタン株式会社製）１０部からなる硬化剤成分を均一に混合した。これを実施例４とした。
Example 4
60 parts by weight of Acronal YJ1210DA (acrylic resin emulsion, manufactured by BASF Japan Ltd.), 6% by weight of tannic acid, 3% by weight of oxalic acid, 31% by weight of water, and 100 parts of the main ingredient A curing agent component consisting of 10 parts of Bihijoule 3100 (hydrophilic isocyanate compound, manufactured by Sumika Bayer Urethane Co., Ltd.) was uniformly mixed. This was designated Example 4.
（実施例５）
６０重量％のアクロナールＹＪ１２１０ＤＡ（アクリル樹脂エマルジョン、ＢＡＳＦジャパン株式会社製）、６重量％のタンニン酸、３重量％のシュウ酸、３１重量％の水からなる主剤成分と、主剤成分１００部に対してバイヒジュール３１００（親水性イソシアネート化合物、住化バイエルウレタン株式会社製）８．５部及びタケネートＤ１７０ ＨＮ（疎水性イソシアネート化合物、三井武田ケミカル株式会社製）１．５部からなる硬化剤成分を均一に混合した。これを実施例５とした。
(Example 5)
60 parts by weight of Acronal YJ1210DA (acrylic resin emulsion, manufactured by BASF Japan Ltd.), 6% by weight of tannic acid, 3% by weight of oxalic acid, 31% by weight of water, and 100 parts of the main ingredient Uniform mixing of hardener components consisting of 8.5 parts of Bihijoule 3100 (hydrophilic isocyanate compound, manufactured by Sumika Bayer Urethane Co., Ltd.) and 1.5 parts of Takenate D170 HN (hydrophobic isocyanate compound, manufactured by Mitsui Takeda Chemical Co., Ltd.) did. This was designated as Example 5.
（実施例６）
６０重量％のアクロナールＹＪ１２１０ＤＡ（アクリル樹脂エマルジョン、ＢＡＳＦジャパン株式会社製）、６重量％のタンニン酸、３重量％のシュウ酸、３１重量％の水からなる主剤成分と、主剤成分１００部に対してバイヒジュール３１００（親水性イソシアネート化合物、住化バイエルウレタン株式会社製）７部及びタケネートＤ１７０ ＨＮ（疎水性イソシアネート化合物、三井武田ケミカル株式会社製）３部からなる硬化剤成分を均一に混合した。これを実施例６とした。
(Example 6)
60 parts by weight of Acronal YJ1210DA (acrylic resin emulsion, manufactured by BASF Japan Ltd.), 6% by weight of tannic acid, 3% by weight of oxalic acid, 31% by weight of water, and 100 parts of the main ingredient A curing agent component consisting of 7 parts of Bihijoule 3100 (hydrophilic isocyanate compound, manufactured by Sumika Bayer Urethane Co., Ltd.) and 3 parts of Takenate D170 HN (hydrophobic isocyanate compound, manufactured by Mitsui Takeda Chemical Co., Ltd.) was uniformly mixed. This was designated Example 6.
（実施例７）
６０重量％のボンコートＣＧ−８４９０（スチレン−アクリル樹脂エマルジョン、ＤＩＣ株式会社製）、６重量％の没食子酸、３重量％の酒石酸、３１重量％の水からなる主剤成分と、主剤成分１００部に対してアクアネート１３０（親水性イソシアネート化合物、日本ポリウレタン工業株式会社製）５部からなる硬化剤成分を均一に混合した。これを実施例７とした。
(Example 7)
A main agent component consisting of 60% by weight Boncoat CG-8490 (styrene-acrylic resin emulsion, manufactured by DIC Corporation), 6% by weight gallic acid, 3% by weight tartaric acid, 31% by weight water, and 100 parts by weight of the main component On the other hand, a curing agent component consisting of 5 parts of Aquanate 130 (hydrophilic isocyanate compound, manufactured by Nippon Polyurethane Industry Co., Ltd.) was uniformly mixed. This was designated as Example 7.
（実施例８）
６０重量％のボンコートＣＧ−８４９０（スチレン−アクリル樹脂エマルジョン、ＤＩＣ株式会社製）、６重量％の没食子酸、３重量％の酒石酸、３１重量％の水からなる主剤成分と、主剤成分１００部に対してアクアネート１３０（親水性イソシアネート化合物、日本ポリウレタン工業株式会社製）４部及びタケネートＤ−１７０ ＨＮ（疎水性イソシアネート化合物、三井武田ケミカル株式会社製）１部からなる硬化剤成分を均一に混合した。これを実施例８とした。
(Example 8)
A main agent component consisting of 60% by weight Boncoat CG-8490 (styrene-acrylic resin emulsion, manufactured by DIC Corporation), 6% by weight gallic acid, 3% by weight tartaric acid, 31% by weight water, and 100 parts by weight of the main component On the other hand, a hardener component consisting of 4 parts Aquanate 130 (hydrophilic isocyanate compound, manufactured by Nippon Polyurethane Industry Co., Ltd.) and 1 part Takenate D-170 HN (hydrophobic isocyanate compound, manufactured by Mitsui Takeda Chemical Co., Ltd.) is uniformly mixed. did. This was designated Example 8.
（実施例９）
６０重量％のボンコートＣＧ−８４９０（スチレン−アクリル樹脂エマルジョン、ＤＩＣ株式会社製）、６重量％の没食子酸、３重量％の酒石酸、３１重量％の水からなる主剤成分と、主剤成分１００部に対してアクアネート１３０（親水性イソシアネート化合物、日本ポリウレタン工業株式会社製）３部及びタケネートＤ−１７０ ＨＮ（疎水性イソシアネート化合物、三井武田ケミカル株式会社製）２部からなる硬化剤成分を均一に混合した。これを実施例９とした。
Example 9
A main agent component consisting of 60% by weight Boncoat CG-8490 (styrene-acrylic resin emulsion, manufactured by DIC Corporation), 6% by weight gallic acid, 3% by weight tartaric acid, 31% by weight water, and 100 parts by weight of the main component On the other hand, a hardener component consisting of 3 parts Aquanate 130 (hydrophilic isocyanate compound, manufactured by Nippon Polyurethane Industry Co., Ltd.) and 2 parts Takenate D-170 HN (hydrophobic isocyanate compound, manufactured by Mitsui Takeda Chemical Co., Ltd.) is uniformly mixed. did. This was designated as Example 9.
（実施例１０）
６０重量％のポリゾールＡＰ−１３５０（アクリル樹脂エマルジョン、昭和電工株式会社製）、６重量％のタンニン酸、３重量％の酒石酸、３１重量％の水からなる主剤成分と、主剤成分１００部に対してタケネートＤ−１７０ＨＮ（疎水性イソシアネート化合物、三井武田ケミカル株式会社製）１０部、キシレン（有機溶剤）９部及びプロピレングリコールメチルエーテルアセテート（有機溶剤）１部からなる硬化剤成分を均一に混合した。これを実施例１０とした。
(Example 10)
For main ingredient component consisting of 60 wt% Polysol AP-1350 (acrylic resin emulsion, Showa Denko KK), 6 wt% tannic acid, 3 wt% tartaric acid, 31 wt% water, and 100 parts main ingredient component Takenate D-170HN (hydrophobic isocyanate compound, manufactured by Mitsui Takeda Chemical Co., Ltd.) 10 parts, xylene (organic solvent) 9 parts and propylene glycol methyl ether acetate (organic solvent) 1 part were mixed uniformly. . This was designated Example 10.
（実施例１１）
６０重量％のポリゾールＡＰ−１３５０（アクリル樹脂エマルジョン、昭和電工株式会社製）、６重量％のタンニン酸、３重量％の酒石酸、３１重量％の水からなる主剤成分と、主剤成分１００部に対してタケネートＤ−１７０ＨＮ（疎水性イソシアネート化合物、三井武田ケミカル株式会社製）５部、キシレン（有機溶剤）４．５部及びプロピレングリコールメチルエーテルアセテート（有機溶剤）０．５部からなる硬化剤成分を均一に混合した。これを実施例１１とした。
(Example 11)
For main ingredient component consisting of 60 wt% Polysol AP-1350 (acrylic resin emulsion, Showa Denko KK), 6 wt% tannic acid, 3 wt% tartaric acid, 31 wt% water, and 100 parts main ingredient component Takenate D-170HN (hydrophobic isocyanate compound, manufactured by Mitsui Takeda Chemical Co., Ltd.) 5 parts, xylene (organic solvent) 4.5 parts and propylene glycol methyl ether acetate (organic solvent) 0.5 parts Mix evenly. This was designated as Example 11.
（比較例１）
８２重量％のポリゾールＡＰ−１３５０（アクリル樹脂エマルジョン、昭和電工株式会社製）、９重量％のタンニン酸、９重量％のシュウ酸からなる主剤成分と、主剤成分１００部に対してアクアネート１３０（親水性イソシアネート化合物、日本ポリウレタン工業株式会社製）０．４部からなる硬化剤成分を均一に混合した。これを比較例１とした。
(Comparative Example 1)
A main component composed of 82% by weight Polysol AP-1350 (acrylic resin emulsion, Showa Denko KK), 9% by weight tannic acid, 9% by weight oxalic acid, and 100 parts of the main component 100 A hardener component consisting of 0.4 part of a hydrophilic isocyanate compound (manufactured by Nippon Polyurethane Industry Co., Ltd.) was uniformly mixed. This was designated as Comparative Example 1.
（比較例２）
８１重量％のポリゾールＡＰ−１３５０（アクリル樹脂エマルジョン、昭和電工株式会社製）、９重量％の没食子酸、０．５重量％の酒石酸、９．５重量％の水からなる主剤成分と、主剤成分１００部に対してバイヒジュール３１００（親水性イソシアネート化合物、住化バイエルウレタン株式会社製）２．５部及びデスモジュールＮ３４００（疎水性イソシアネート化合物、住化バイエルウレタン株式会社製）１０部からなる硬化剤成分を均一に混合した。これを比較例２とした。
(Comparative Example 2)
Main ingredient component consisting of 81% by weight Polysol AP-1350 (acrylic resin emulsion, Showa Denko KK), 9% by weight gallic acid, 0.5% by weight tartaric acid, 9.5% by weight water, and the main ingredient component Hardener component consisting of 2.5 parts of Bayhijoule 3100 (hydrophilic isocyanate compound, manufactured by Sumika Bayer Urethane Co., Ltd.) and 10 parts of Death Module N3400 (hydrophobic isocyanate compound, manufactured by Sumika Bayer Urethane Co., Ltd.) per 100 parts Were mixed uniformly. This was designated as Comparative Example 2.
（比較例３）
８２重量％のアクロナールＹＪ１２１０ＤＡ（アクリル樹脂エマルジョン、ＢＡＳＦジャパン株式会社製）、９重量％のタンニン酸、９重量％のシュウ酸からなる主剤成分を使用し、硬化剤成分は使用しなかった。これを比較例３とした。
(Comparative Example 3)
A main ingredient component consisting of 82% by weight of acronal YJ1210DA (acrylic resin emulsion, manufactured by BASF Japan Ltd.), 9% by weight of tannic acid and 9% by weight of oxalic acid was used, and no curing agent component was used. This was designated as Comparative Example 3.
（比較例４）
８１重量％のボンコートＣＧ−８４９０（スチレン−アクリル樹脂エマルジョン、ＤＩＣ株式会社製）、９重量％の没食子酸、０．５重量％の酒石酸、９．５重量％の水からなる主剤成分を使用し、硬化剤成分は使用しなかった。これを比較例４とした。
(Comparative Example 4)
A main ingredient component comprising 81% by weight of Boncoat CG-8490 (styrene-acrylic resin emulsion, manufactured by DIC Corporation), 9% by weight of gallic acid, 0.5% by weight of tartaric acid, and 9.5% by weight of water is used. The curing agent component was not used. This was designated as Comparative Example 4.
（比較例５）
８２重量％のボンコートＣＧ−８４９０（スチレン−アクリル樹脂エマルジョン、ＤＩＣ株式会社製）、９重量％のタンニン酸、９重量％のシュウ酸からなる主剤成分を使用し、硬化剤成分は使用しなかった。これを比較例５とした。
(Comparative Example 5)
82% by weight of Boncoat CG-8490 (styrene-acrylic resin emulsion, manufactured by DIC Corporation), 9% by weight of tannic acid, and 9% by weight of oxalic acid were used as the main component, and no curing agent component was used. . This was designated as Comparative Example 5.
実施例１−１１及び比較例１−５の組成を、以下の表１−３にまとめた。 The compositions of Example 1-11 and Comparative Example 1-5 are summarized in Table 1-3 below.
２．水系２液型錆転換剤組成物の性能試験
次に、水系２液型錆転換剤組成物の性能試験を説明する。
2. Performance test of aqueous two-component rust converter composition Next, a performance test of the aqueous two-component rust converter composition will be described.
（試験片の作成）
浮き錆を除いた鋼板（４種ケレン処理）に、実施例１−１１及び比較例１−５の組成物を塗布量２００ｇ／ｍ２で塗布し、１０日間２５℃で乾燥させ、試験片とした。
(Creation of specimen)
On the steel plate (type 4 keren treatment) excluding floating rust, the compositions of Example 1-11 and Comparative Example 1-5 were applied at a coating amount of 200 g / m 2 and dried at 25 ° C. for 10 days. did.
（耐水密着試験）
実施例１−１１及び比較例１−５の試験片を、２０℃の温水中に３０日間浸漬し、取り出して塗膜の外観の異常の有無を観察するとともに、碁盤目付着性試験を行った。
碁盤目付着性試験においては、試験片に塗膜を貫通して素地面に達する切り傷を１００マスの碁盤目状に付け、その上にセロテープ（登録商標）を貼り付けたのちセロテープ（登録商標）を勢いよく引き剥がした時の状態を観察し、付着性を評価した。例えば、１００マス全てが剥離せずに付着性が高ければ１００／１００となり、１００マス全てが剥離した場合０／１００と評価した。
(Water resistance adhesion test)
The test pieces of Example 1-11 and Comparative Example 1-5 were immersed in warm water at 20 ° C. for 30 days, removed, and observed for the presence or absence of abnormal appearance of the coating film, and a cross-cut adhesion test was performed. .
In the cross-cut adhesion test, cuts reaching the ground surface through the coating film are applied to the test piece in a checkered pattern of 100 squares, and then cellotape (registered trademark) is pasted on it, and then cellotape (registered trademark). The state when the film was peeled off vigorously was observed to evaluate the adhesion. For example, 100/100 was evaluated when all 100 squares were not peeled and adhesion was high, and 0/100 was evaluated when all 100 squares were peeled off.
（温水浸漬試験）
実施例１−１１及び比較例１−５の試験片を、８０℃の温水中に２時間浸漬し、取り出して塗膜の外観の異常の有無を観察するとともに、碁盤目付着性試験を行った。
碁盤目付着性試験においては、試験片に塗膜を貫通して素地面に達する切り傷を１００マスの碁盤目状に付け、その上にセロテープ（登録商標）を貼り付けたのちセロテープ（登録商標）を勢いよく引き剥がした時の状態を観察し、付着性を評価した。例えば、１００マス全てが剥離せずに付着性が高ければ１００／１００となり、１００マス全てが剥離した場合０／１００と評価した。
(Hot water immersion test)
The test pieces of Example 1-11 and Comparative Example 1-5 were immersed in warm water at 80 ° C. for 2 hours, taken out and observed for the presence or absence of abnormal appearance of the coating film, and a cross-cut adhesion test was performed. .
In the cross-cut adhesion test, cuts reaching the ground surface through the coating film are applied to the test piece in a checkered pattern of 100 squares, and then cellotape (registered trademark) is pasted on it, and then cellotape (registered trademark). The state when the film was peeled off vigorously was observed to evaluate the adhesion. For example, 100/100 was evaluated when all 100 squares were not peeled and adhesion was high, and 0/100 was evaluated when all 100 squares were peeled off.
（塩水噴霧試験）
実施例１−１１及び比較例１−５の試験片を、３５℃中で５％の食塩水を２００時間及び５００時間噴霧し、錆の発生の有無を観察した。
(Salt spray test)
The test pieces of Example 1-11 and Comparative Example 1-5 were sprayed with 5% saline at 35 ° C. for 200 hours and 500 hours, and the presence or absence of rust was observed.
（耐溶剤試験）
実施例１−１１及び比較例１−５の試験片について、キシレンスポット試験を行った。具体的には、キシレン０．１ｃｃをスポイトで上記試験片に滴下し、５分間放置した後、布で軽くふき取り、直ちに表面を指触時のタックの有無を調べた。調べた結果を×（タックあり）、△（タックが少しあり）、及び○（タックが全くない）の三段階で評価した。
(Solvent resistance test)
The test pieces of Example 1-11 and Comparative Example 1-5 were subjected to a xylene spot test. Specifically, 0.1 cc of xylene was dropped onto the above test piece with a dropper, allowed to stand for 5 minutes, and then lightly wiped with a cloth, and immediately the surface was examined for tackiness when touched with a finger. The examination results were evaluated in three stages: x (with tack), Δ (with a little tack), and ○ (no tack at all).
（耐候性試験）
実施例１−１１及び比較例１−５の試験片について、太陽光による劣化を評価するサンシャインウエザーメーター試験を１０００時間行い、その後の塗膜の外観の異常の有無を観察した。
本試験においては、促進倍率は屋外曝露と比較して約８．３倍の条件で試験した。
(Weather resistance test)
About the test piece of Example 1-11 and Comparative Example 1-5, the sunshine weather meter test which evaluates deterioration by sunlight was performed for 1000 hours, and the presence or absence of the abnormality of the external appearance of the coating film after that was observed.
In this test, the accelerated magnification was tested under the condition of about 8.3 times that of outdoor exposure.
以上の実施例及び比較例における性能試験の結果を表４−６に示す。 The results of the performance test in the above examples and comparative examples are shown in Table 4-6.
＜評価＞
上記表４−６の結果は、実施例１−１１は浮き錆を簡易に除去する程度の素地調整で鉄錆面に塗装可能で、塗装後は錆転換黒色被膜を形成することを示す。
これに対し、水性エマルジョン樹脂（Ａ）が主剤成分に対して８０重量％よりも多く、タンニン酸及び有機酸がそれぞれ主剤成分に対して８重量％よりも多い比較例１は、塩水噴霧試験（２００時間）以外の性能試験で異常が見られ、錆転換速度も実施例と比較して遅かった。
硬化剤成分の割合が主剤１００部に対して３０部以上である比較例２は、全ての性能試験において異常が見られ、錆転換速度も実施例よりも遅かった。
さらに、硬化剤成分を全く含まない比較例３−５も、全ての性能試験において異常が見られ、錆転換速度も実施例よりも遅かった。
<Evaluation>
The result of the said Table 4-6 shows that Example 1-11 can be painted on an iron rust surface by the foundation adjustment of the grade which removes floating rust easily, and forms a rust conversion black film after painting.
On the other hand, Comparative Example 1 in which the aqueous emulsion resin (A) is more than 80% by weight based on the main ingredient component and each of the tannic acid and the organic acid is more than 8% by weight based on the main ingredient component is the salt spray test ( Abnormalities were observed in performance tests other than (200 hours), and the rust conversion rate was also slower than in the examples.
In Comparative Example 2 in which the ratio of the curing agent component was 30 parts or more with respect to 100 parts of the main agent, abnormalities were observed in all performance tests, and the rust conversion rate was also slower than in the Examples.
Further, Comparative Example 3-5 containing no curing agent component also showed abnormalities in all performance tests, and the rust conversion rate was also slower than in the examples.
上記の実施例及び比較例の性能試験結果の比較は、本発明が以下の条件を満たすことが望ましいことを示す。
・水性エマルジョン樹脂（Ａ）の割合が主剤全体に対して８０重量％を超えない。
・ポリフェノール誘導体（Ｂ）及び有機酸（Ｃ）の割合が主剤全体に対して８重量％を超えない。
・硬化剤の割合を主剤１００部に対して０．５−３０部とする。
Comparison of the performance test results of the above examples and comparative examples shows that it is desirable for the present invention to satisfy the following conditions.
-The ratio of water-based emulsion resin (A) does not exceed 80 weight% with respect to the whole main ingredient.
-The ratio of polyphenol derivative (B) and organic acid (C) does not exceed 8 weight% with respect to the whole main ingredient.
-The ratio of a hardening | curing agent shall be 0.5-30 parts with respect to 100 parts of main agents.
上記の結果から、本発明である実施例１−８の水系２液型錆転換剤組成物は比較例１−５に比べて、いずれも密着性、耐水性、耐溶剤性、防錆性、耐候性に優れていることがわかる。 From the above results, the aqueous two-component rust conversion agent composition of Example 1-8, which is the present invention, has adhesion, water resistance, solvent resistance, rust resistance, as compared with Comparative Example 1-5. It turns out that it is excellent in weather resistance.
本発明である水系２液型錆転換剤組成物及び錆転換黒色被膜の形成方法は、建材等様々な用途で使用される鉄鋼面上に塗布される防錆被膜及び／又は錆転換被膜として好適に利用される。 The water-based two-component rust conversion agent composition and the method of forming a rust conversion black coating according to the present invention are suitable as a rust prevention coating and / or a rust conversion coating applied on a steel surface used in various applications such as building materials. Used for
１ 水性エマルジョン樹脂
２ ポリフェノール誘導体
３ イソシアネート化合物
1 Aqueous emulsion resin 2 Polyphenol derivative 3 Isocyanate compound
Claims (2)
主剤成分は、
（Ａ）主剤成分全体に対して１０−８０重量％の水性エマルジョン樹脂、
（Ｂ）主剤成分全体に対して１−８重量％のポリフェノール誘導体、及び
（Ｃ）シュウ酸、クエン酸、リンゴ酸、酒石酸、乳酸、ギ酸、グルタル酸、グリコール酸、コハク酸、およびマロン酸からなる群から選択される１種以上を含み、且つ主剤成分全体に対して１−８重量％の酸からなり、
前記硬化剤成分は、前記主剤成分１００部に対して０．５−３０部配合されるとともにその成分は、
親水性イソシアネート化合物又は、
親水性イソシアネート化合物を５０−９９．９質量％及び疎水性イソシアネート化合物を０．１−５０質量％の範囲内で含む混合物あるいは、
疎水性イソシアネート化合物を１０−９０質量％及び有機溶剤の混合物を１０−９０質量％の範囲内で含む混合物、のいずれかであって、
前記水性エマルジョン樹脂（Ａ）は水酸基価が１０ｍｇＫＯＨ／ｇ以下であって、イソシアネート化合物とはウレタン結合しない水性エマルジョン樹脂である
ことを特徴とする、水系２液型錆転換剤組成物。 An aqueous two-component rust converter composition comprising a main component and a curing agent component,
The main ingredient is
(A) 10 -80 wt% of the aqueous emulsion resin to the entire base resin component,
(B) 1-8% by weight of polyphenol derivative with respect to the whole main ingredient, and (C) oxalic acid, citric acid, malic acid, tartaric acid, lactic acid, formic acid, glutaric acid, glycolic acid, succinic acid, and malonic acid Comprising at least one selected from the group consisting of 1 to 8% by weight of acid based on the total amount of the main component,
The curing agent component is blended in an amount of 0.5-30 parts with respect to 100 parts of the main ingredient component,
A hydrophilic isocyanate compound or
A mixture comprising 50-99.9% by weight of a hydrophilic isocyanate compound and 0.1-50% by weight of a hydrophobic isocyanate compound, or
A mixture comprising 10 to 90% by weight of a hydrophobic isocyanate compound and 10 to 90% by weight of a mixture of organic solvents,
The aqueous emulsion resin (A) has a hydroxyl value of 10 mgKOH / g or less, and is an aqueous emulsion resin that does not undergo urethane bonding with an isocyanate compound.
鉄鋼面上の錆を予め研磨し、あるいは研磨を行わず、
請求項１記載の主剤成分と硬化剤成分を混合した混合物を調製し、
前記混合物を、錆面を持つ鉄鋼面上に広く又は全面にわたり塗布し、
鉄鋼面上に錆転換黒色被膜を形成する、
ことからなる、錆転換黒色被膜の形成方法。 A method for forming a rust conversion black coating,
Polish the rust on the steel surface in advance, or do not polish,
A mixture is prepared by mixing the main ingredient component and the curing agent component according to claim 1,
Applying the mixture widely or over the steel surface with a rust surface;
Forming a rust-converting black coating on the steel surface;
The formation method of the rust conversion black film which consists of this.
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