JP6629540B2 - Anticorrosion coating composition, anticorrosion coating, substrate with anticorrosion coating, and method for producing the same - Google Patents
Anticorrosion coating composition, anticorrosion coating, substrate with anticorrosion coating, and method for producing the same Download PDFInfo
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- JP6629540B2 JP6629540B2 JP2015143103A JP2015143103A JP6629540B2 JP 6629540 B2 JP6629540 B2 JP 6629540B2 JP 2015143103 A JP2015143103 A JP 2015143103A JP 2015143103 A JP2015143103 A JP 2015143103A JP 6629540 B2 JP6629540 B2 JP 6629540B2
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- anticorrosion coating
- anticorrosion
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- Application Of Or Painting With Fluid Materials (AREA)
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Description
本発明は、基材鋼板表面に遊離した水分が付着している湿潤面であっても、その表面に対して直接スプレー塗装することで、防食性に優れるとともに、基材鋼板との良好な付着性を有する塗膜を形成することができる防食塗料組成物、該防食塗料組成物より形成された防食塗膜、該防食塗膜にて被覆された防食塗膜付き基材及び該防食塗膜付き基材の製造方法に関する。 The present invention provides excellent corrosion protection and good adhesion to a base steel sheet by spraying directly onto the surface of the base steel sheet, even on a wet surface to which free moisture is attached. Anticorrosion coating composition capable of forming a coating film having properties, an anticorrosion coating film formed from the anticorrosion coating composition, a substrate with an anticorrosion coating film coated with the anticorrosion coating film, and the anticorrosion coating film The present invention relates to a method for producing a substrate.
船舶、陸上構造物、橋梁等の大型の鉄鋼構造物は、腐食防止のため、例えば、タールエポキシ樹脂塗料、エポキシ樹脂塗料等の防食塗料による防食塗膜で被覆されている。しかし、その防食塗膜は、経年、屋外での曝露、没水等によって生じた塗膜欠陥部より発錆することがあるため、定期的な補修を必要とする。 Large steel structures such as ships, land structures, bridges, etc. are coated with an anticorrosion coating such as a tar epoxy resin paint or an epoxy resin paint to prevent corrosion. However, the anticorrosion coating film may rust from a coating defect caused by aging, outdoor exposure, submersion, and the like, and thus requires periodic repair.
前記大型の鉄鋼構造物を対象とするような大面積に亘る補修では、通常、発錆部に対して、ドライブラスト処理で錆の除去処理（基材鋼板の表面処理）が行われている。上記ドライブラスト処理は、粉塵を生じるため、発火や爆発の原因となる恐れがあり、集塵機等の設備を必要とする。また、上記発火等の危険を回避するため、ウェットブラスト処理やウォータージェットで基材鋼板の表面処理をすることもある。 In repairing a large area such as the large-sized steel structure, rust removal processing (surface treatment of a base steel sheet) is usually performed on a rusted part by drive-last processing. The above-mentioned drive blasting process generates dust, which may cause fire or explosion, and requires equipment such as a dust collector. Further, in order to avoid the danger such as the ignition, the surface treatment of the base steel sheet may be performed by wet blast treatment or water jet.
特に、船舶のバラストタンクでは、補修が必要な箇所に、錆以外にも泥や汚れが付着していることが多く、ドライブラスト処理による錆の除去処理工程の前に、これらの泥や汚れを水洗浄する清掃工程を必要とする。前記ウェットブラスト処理やウォータージェットによる基材鋼板の表面処理は、水洗浄による清掃工程と、錆の除去処理工程を同時に行うことができる点で有用である。 Especially, in ship ballast tanks, in addition to rust, mud and dirt often adhere to places requiring repair, and these dirt and dirt are removed before the rust removal process by drive-last processing. Requires a water-cleaning process. The surface treatment of the base steel sheet by the wet blast treatment or the water jet is useful in that a cleaning step by water washing and a rust removing step can be simultaneously performed.
しかしながら、前記ウェットブラスト処理やウォータージェットで表面処理した場合、処理した基材鋼板表面に水分が付着したり、結露を生じたりして、湿潤面を形成することが多い。この湿潤面を乾燥させることなく一般的な防食塗料で補修塗装すると、基材鋼板と十分な付着性を得られないため、割れや剥離等を生じるといった問題がある。そこで、湿潤面に補修塗装を行っても、前記問題を生じない防食性に優れた塗膜を形成できる防食塗料組成物を開発できれば、特にバラストタンクのような基材鋼板表面を完全に乾燥させることが困難な構造物の補修用途において、乾燥工程の省略による補修塗装の効率化を図ることができる。 However, when the surface treatment is performed by the wet blast treatment or the water jet, moisture is often attached to the treated base steel sheet surface or dew condensation occurs to form a wet surface in many cases. If the wet surface is repair-coated with a general anticorrosive paint without drying, sufficient adhesion to the base steel sheet cannot be obtained, and thus there is a problem that cracking or peeling occurs. Therefore, even if repair coating is performed on a wet surface, if an anticorrosion coating composition capable of forming a coating film having excellent anticorrosion properties without causing the above problems can be developed, the surface of a base steel sheet such as a ballast tank is completely dried. In a repair application of a structure in which it is difficult to perform, it is possible to improve the efficiency of repair painting by omitting a drying step.
特許文献１には、エポキシ樹脂（Ａ）と、ｍ−キシレンジアミン、ビス−（アミノメチル）シクロヘキサン、メチレンジ（シクロヘキシルアミン）、ノルボルネンジアミン からなる群から選ばれた１種または２種以上のアミン化合物を、次の（１）〜（５）からなる群：（１）フェノール類とカルボニル基を有する化合物を反応させるマンニッヒ変性方法、（２）エポキシ化合物を反応させるエポキシ化合物付加変性方法、（３）置換又は非置換のアクリル化合物を反応させるマイケル付加変性方法、（４）ポリカルボン酸を反応させるポリアミド化変性方法、（５）ケトン化合物を反応させるケチミン化変性方法、から選ばれた１種または２種以上の変性方法によって変性した変性物またはそれらの混合物からなるエポキシ樹脂硬化剤（Ｂ）と、無機充填剤（Ｃ）と、を含む湿潤面ないし水中施工用エポキシ樹脂組成物が開示されている。 Patent Document 1 discloses an epoxy resin (A) and one or more amine compounds selected from the group consisting of m-xylenediamine, bis- (aminomethyl) cyclohexane, methylenedi (cyclohexylamine), and norbornenediamine A group consisting of the following (1) to (5): (1) a Mannich modification method of reacting a phenol with a compound having a carbonyl group, (2) an epoxy compound addition modification method of reacting an epoxy compound, (3) One or two selected from a Michael addition modification method in which a substituted or unsubstituted acrylic compound is reacted, (4) a polyamide modification method in which a polycarboxylic acid is reacted, and (5) a ketimine modification method in which a ketone compound is reacted. Epoxy resin curing agent (B) comprising a modified product modified by at least one modification method or a mixture thereof; ) And an inorganic filler (C) are disclosed.
特許文献２には、（Ａ）主剤成分および（Ｂ）硬化剤成分を含有してなるエポキシ樹脂組成物において、前記主剤成分（Ａ）が、液状エポキシ樹脂（ａ１）とシランカップリング剤（ａ２）とを含有し、前記硬化剤成分（Ｂ）が、アミン系硬化剤（ｂ１）を含有し、前記主剤成分（Ａ）および／または前記硬化剤成分（Ｂ）が、液状炭化水素樹脂を含有することを特徴とする、基材との付着性、耐水性、防食性に優れる防食皮膜が形成され、特に金属基材（特にステンレス基材）の孔食、隙間腐食、異種金属接触腐食、応力腐食を防止することができるエポキシ樹脂組成物が開示されている。 Patent Document 2 discloses that in an epoxy resin composition containing (A) a main component and (B) a curing agent component, the main component (A) comprises a liquid epoxy resin (a1) and a silane coupling agent (a2). ), The curing agent component (B) contains an amine curing agent (b1), and the main component component (A) and / or the curing agent component (B) contains a liquid hydrocarbon resin. A corrosion-resistant film with excellent adhesion to substrates, water resistance, and corrosion resistance is formed. Especially, pitting, crevice corrosion, dissimilar metal contact corrosion, stress on metal substrates (especially stainless steel substrates) An epoxy resin composition capable of preventing corrosion is disclosed.
特許文献３には、少なくとも飽和水分以下の水分を含む乾燥乃至湿潤下地上に樹脂塗膜を形成するに際し、下地と樹脂塗膜間に塗布する、（Ａ）液状エポキシ樹脂、（Ｂ）液状ポリアミン、（Ｃ）低粘度脂肪族エポキシ化合物、及び（Ｄ）シランカップリング剤を含有してなるプライマーが開示されている。
しかしながら、特許文献１〜３で開示されている塗料組成物には、いずれも塗料組成物中に水を積極的に含有させるとの技術的思想が無く、さらに、特許文献１及び３で開示されている塗料組成物により形成される塗膜は、柔軟性が不十分であるため、湿潤面を有する基材鋼板に対して十分な付着性を得られない。また、特許文献２及び３で開示されている塗料組成物は、刷毛、ローラー、ヘラ、コテ等による塗装のみが記載されており、特許文献２の実施例で開示されている塗料組成物では、スプレー塗装するには粘度が高く、いずれの塗料組成物も大型の鉄鋼構造物のような大面積に亘る補修では、施工作業性に問題がある場合があった。
However, none of the coating compositions disclosed in Patent Documents 1 to 3 has a technical idea of positively including water in the coating composition, and further disclosed in
ウェットブラスト処理やウォータージェット等によって基材鋼板の錆を除去した場合、基材鋼板表面に水分が付着したり、結露を生じたりして湿潤面を形成する。本発明に係る防食塗料組成物は、上記基材鋼板の湿潤面であっても、乾燥させることなく直接スプレー塗装することで、防食性に優れるとともに、基材鋼板との良好な付着性を有する塗膜を形成することができる防食塗料組成物、防食塗膜、防食塗膜付き基材及びその塗膜付き基材の製造方法を提供することを目的としている。 When the rust of the base steel sheet is removed by wet blasting, water jet, or the like, moisture adheres to the surface of the base steel sheet or dew condensation occurs to form a wet surface. The anticorrosion coating composition according to the present invention, even on the wet surface of the base steel sheet, has excellent anticorrosion properties and has good adhesion to the base steel sheet by directly spray coating without drying. An object of the present invention is to provide an anticorrosion coating composition, an anticorrosion coating, a substrate with an anticorrosion coating, and a method for producing the substrate with a coating capable of forming a coating.
本発明者らは、前記課題を解決する方法について鋭意検討を重ねた結果、エポキシ樹脂系防食塗料に対し、水との親和性を有する硬化剤を選択し、且つ塗料中に所定量の水、水酸基を有する変性樹脂を含有させることにより、上記の目的を達成することができることを見出し、本発明を完成するに至った。 The present inventors have conducted intensive studies on a method for solving the above-mentioned problem, and as a result, for an epoxy resin-based anticorrosion paint, selected a curing agent having an affinity for water, and a predetermined amount of water in the paint, It has been found that the above object can be achieved by including a modified resin having a hydroxyl group, and the present invention has been completed.
本発明の構成は以下の通りである。
本発明は、基材鋼板の湿潤面に塗装可能な塗料組成物であって、
エポキシ樹脂（Ａ）と、
ポリオキシアルキレンポリアミン類、マンニッヒ変性アミン類及びケチミン類から選ばれる少なくとも1種のアミン硬化剤（Ｂ）と、
上記塗料組成物１００重量部（不揮発分）に対して、１〜１５重量部の水（Ｃ）と、
水酸基含有変性樹脂（Ｄ）と、
を含むことを特徴とする防食塗料組成物を提供するものである。
前記防食塗料組成物は、さらに扁平状顔料（Ｅ）を含むことが好ましい。
The configuration of the present invention is as follows.
The present invention is a coating composition that can be applied to a wet surface of a base steel sheet,
Epoxy resin (A),
At least one amine curing agent (B) selected from polyoxyalkylene polyamines, Mannich-modified amines and ketimines;
1 to 15 parts by weight of water (C) with respect to 100 parts by weight of the coating composition (non-volatile content);
A hydroxyl-containing modified resin (D),
The present invention provides an anticorrosive coating composition comprising:
It is preferable that the anticorrosion coating composition further contains a flat pigment (E).
前記アミン硬化剤（Ｂ）としては、ポリオキシアルキレンポリアミン類、マンニッヒ変性アミン類及びケチミン類の内で、少なくともポリオキシアルキレンポリアミン類を含むことが好ましい。 The amine curing agent (B) preferably contains at least a polyoxyalkylene polyamine among polyoxyalkylene polyamines, Mannich-modified amines and ketimines.
前記防食塗料組成物１００重量部（不揮発分）に対しては、前記アミン硬化剤（Ｂ）として、少なくともポリオキシアルキレンポリアミン類を０．０１〜２０重量部（不揮発分）の量で含むことが好ましい。
本発明に係る防食塗膜は、前記防食塗料組成物より形成される。
The amine curing agent (B) may contain at least a polyoxyalkylene polyamine in an amount of 0.01 to 20 parts by weight (non-volatile content) based on 100 parts by weight (non-volatile content) of the anticorrosion coating composition. preferable.
The anticorrosion coating film according to the present invention is formed from the anticorrosion coating composition.
本発明に係る防食塗膜付き基材は、前記防食塗料組成物より形成された防食塗膜にて基材鋼板が被覆されてなる。 The substrate with an anticorrosion coating according to the present invention is obtained by coating a base steel plate with an anticorrosion coating formed from the anticorrosion coating composition.
本発明に係る防食塗膜付き基材の製造方法は、前記防食塗料組成物を、基材鋼板にスプレーにて塗装する工程、及び塗装された前記防食塗料組成物を硬化させて防食塗膜を形成する工程を有する。 The method for producing a substrate with an anticorrosion coating according to the present invention comprises a step of spraying the anticorrosion coating composition on a base steel plate, and curing the coated anticorrosion coating composition to form an anticorrosion coating. Forming step.
本発明に係る防食塗料組成物は、遊離した水分が付着していない基材鋼板（以下、乾燥した基材鋼板という。）表面はもとより、基材鋼板の湿潤面であっても、種々の塗装方法を採用し得るが、特に該基材鋼板に直接スプレー塗装することで、防食性に優れるとともに、基材鋼板と良好な付着性を有する防食塗膜を形成することができる。 The anticorrosion coating composition according to the present invention can be used for various coatings, not only on the surface of a base steel sheet to which free moisture does not adhere (hereinafter referred to as a dried base steel sheet) but also on the wet surface of the base steel sheet. Although a method can be adopted, in particular, by directly spray-coating the base steel sheet, it is possible to form an anticorrosion coating film having excellent corrosion resistance and good adhesion to the base steel sheet.
以下、本発明の防食塗料組成物、防食塗膜、防食塗膜付き基材及びその製造方法について、好適な態様を含めて詳細に説明する。 Hereinafter, the anticorrosion coating composition, the anticorrosion coating film, the substrate with the anticorrosion coating film, and the method for producing the anticorrosion coating film of the present invention will be described in detail including preferred embodiments.
＜防食塗料組成物（防食塗料ともいう。）＞
本発明に係る防食塗料組成物は、エポキシ樹脂（Ａ）と、ポリオキシアルキレンポリアミン類、マンニッヒ変性アミン類、ケチミン類から選ばれる少なくとも１種のアミン硬化剤（Ｂ）と、塗料組成物１００重量部（不揮発分）に対して１〜１５重量部の水（Ｃ）と、水酸基含有変性樹脂（Ｄ）とを含むことを特徴とする。
本発明に係る防食塗料組成物は、さらに、任意で扁平状顔料（Ｅ）を含むことが好ましい。
<Anti-corrosion paint composition (also referred to as anti-corrosion paint)>
The anticorrosion coating composition according to the present invention comprises an epoxy resin (A), at least one amine curing agent (B) selected from polyoxyalkylene polyamines, Mannich-modified amines, and ketimines, and 100% by weight of the coating composition. 1 to 15 parts by weight of water (C) and a hydroxyl group-containing modified resin (D) based on parts (non-volatile content).
It is preferable that the anticorrosion paint composition according to the present invention further optionally contains a flat pigment (E).
＜基材鋼板＞
本発明における基材鋼板とは、船舶、陸上構造物、橋梁等の大型の鉄鋼構造物に一般的に使用されている、非吸水性の素材である鉄鋼材料（例：鉄、鋼、合金鉄、炭素鋼、合金鋼等）を表しており、本発明の防食塗料組成物が付着性等の性能を発揮するためには、該基材鋼板表面がＳａ２．５（ＩＳＯ−８５０１−１に準拠）以上の処理グレードで表面処理されていることが好ましい。
<Base steel sheet>
The base steel sheet in the present invention is a non-water-absorbing steel material (eg, iron, steel, alloyed iron) which is generally used for large steel structures such as ships, land structures, bridges, and the like. , Carbon steel, alloy steel, etc.). In order for the anticorrosive coating composition of the present invention to exhibit performance such as adhesion, the surface of the base steel sheet must be Sa2.5 (based on ISO-8501-1). It is preferable that the surface is treated with the above treatment grades.
＜湿潤面＞
本発明における湿潤面の水分量は、乾燥した基材鋼板の表面に対して、霧吹きで水を吹き付けて均一に付着させ、吹き付けた水分の重量（単位：ｇ）を測定することで、基材鋼板表面の水分付着量（単位：ｇ／ｍ2）を調べた。なお、鋼板の表面に既に水が付着して湿潤面となっている場合、その湿潤面の水分量（単位：ｇ／ｍ2）は、例えば、湿潤面を乾燥させることで重量減少（単位：ｇ）を求めること等により測定できる。
<Wet surface>
The water content of the wet surface in the present invention, with respect to the surface of the dried base material steel plate, uniformly attached to by spraying water spray, the weight of the sprayed water (unit: g) of by measuring the substrate The water adhesion amount (unit: g / m 2 ) on the steel sheet surface was examined. In the case where water has already adhered to the surface of the steel sheet to form a wet surface, the water content (unit: g / m 2 ) of the wet surface is reduced by, for example, drying the wet surface (unit: g) can be measured.
本発明に係る防食塗料組成物が塗装される基材鋼板の湿潤面は、その好ましい態様において、基材鋼板表面に５〜４５ｇ／ｍ２の水分が付着しており、通常、目視で遊離した水分を確認できることが多い。例えば、大型の鉄鋼構造物の基材鋼板表面に、降雨、水洗浄又は高湿度下での結露等によって水分が付着している状態が湿潤面として想定される。特に、バラストタンクのような閉鎖された空間では、基材鋼板の錆を除去するために使用したウェットブラスト処理若しくはウォータージェットの水又はバラスト水の残水の影響によって高湿度になりやすく、その基材鋼板表面に結露することで、湿潤面を生じていることが多い。 The wet surface of the base steel sheet to which the anticorrosion coating composition according to the present invention is applied has, in its preferred embodiment, water of 5 to 45 g / m 2 adhered to the base steel sheet surface and is usually released visually. Water can often be checked. For example, a state in which moisture is attached to the surface of a base steel plate of a large steel structure by rainfall, water washing, or dew condensation under high humidity is assumed as a wet surface. In particular, in closed spaces such as ballast tanks, high humidity tends to occur due to the effects of wet blasting used to remove rust on the base steel sheet or the residual water of water jet or ballast water. Condensation on the surface of a steel sheet often causes a wet surface.
＜エポキシ樹脂（Ａ）＞
本発明に係る防食塗料組成物において、前記エポキシ樹脂（Ａ）としては、分子内に２個以上のエポキシ基を含むポリマーあるいはオリゴマー、及びそのエポキシ基の開環反応によって生成するポリマーあるいはオリゴマー等が挙げられる。このようなエポキシ樹脂としては、ビスフェノール型エポキシ樹脂、グリシジルエステル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、脂肪酸変性エポキシ樹脂、水素化エポキシ樹脂等が挙げられる。
これらの中でも、基材鋼板に対する付着性に優れた防食塗膜を形成することができる等の点から、ビスフェノール型エポキシ樹脂が好ましく、さらにはビスフェノールＡ型及びビスフェノールＦ型のビスフェノール型エポキシ樹脂がより好ましい。ビスフェノールＡ型エポキシ樹脂が特に好ましい。
<Epoxy resin (A)>
In the anticorrosion coating composition according to the present invention, as the epoxy resin (A), a polymer or oligomer containing two or more epoxy groups in a molecule, and a polymer or oligomer generated by a ring-opening reaction of the epoxy group are used. No. Examples of such an epoxy resin include a bisphenol-type epoxy resin, a glycidyl ester-type epoxy resin, a glycidylamine-type epoxy resin, a phenol novolak-type epoxy resin, a cresol novolak-type epoxy resin, a fatty acid-modified epoxy resin, and a hydrogenated epoxy resin. .
Among these, bisphenol-type epoxy resins are preferred from the viewpoint that an anticorrosion coating film having excellent adhesion to the base steel sheet can be formed, and bisphenol A-type and bisphenol F-type bisphenol-type epoxy resins are more preferable. preferable. Bisphenol A type epoxy resins are particularly preferred.
また、上記エポキシ樹脂（Ａ）は、１種単独で、または２種以上を組み合わせて用いることができる。 The epoxy resin (A) can be used alone or in combination of two or more.
前記ビスフェノールＡ型エポキシ樹脂として、例えば、ビスフェノールＡ型ジグリシジルエーテル類の縮重合物が挙げられ、この縮重合物を形成するビスフェノールＡ型ジグリシジルエーテル類としては、ビスフェノールＡジグリシジルエーテル、ビスフェノールＡポリプロピレンオキシドジグリシジルエーテル、ビスフェノールＡエチレンオキシドジグリシジルエーテル等が挙げられる。 Examples of the bisphenol A type epoxy resin include condensation polymers of bisphenol A type diglycidyl ethers. Examples of the bisphenol A type diglycidyl ethers forming the condensation polymerization product include bisphenol A diglycidyl ether and bisphenol A. Examples include polypropylene oxide diglycidyl ether and bisphenol A ethylene oxide diglycidyl ether.
前記エポキシ樹脂（Ａ）は、 基材鋼板に対して優れた付着性を示す防食塗膜を形成できる等の点から、前記アミン硬化剤（Ｂ）等と反応硬化前の状態では、常温で液状または半固形状のものが好ましい。 The epoxy resin (A) is liquid at room temperature before being cured by reaction with the amine curing agent (B) and the like because it can form an anticorrosion coating film having excellent adhesion to a base steel sheet. Alternatively, a semi-solid material is preferable.
前記エポキシ樹脂（Ａ）のエポキシ当量は、防食性等の点から、好ましくは１５０〜１０００、より好ましくは１５０〜８００、特に好ましくは１８０〜７００である。なお、エポキシ当量は、ＪＩＳ Ｋ ７２３６に基づいて算出される。 The epoxy equivalent of the epoxy resin (A) is preferably from 150 to 1,000, more preferably from 150 to 800, particularly preferably from 180 to 700, from the viewpoint of anticorrosion properties and the like. The epoxy equivalent is calculated based on JIS K 7236.
前記エポキシ樹脂（Ａ）は、従来公知の方法で合成して得たものでもよく、市販品であってもよい。本発明で用いられるエポキシ樹脂（Ａ）の内、常温（１５〜２５℃の温度、以下同様。）で液状のものとして、「Ｅ０２８」（大竹明新化学（株）製、ビスフェノールＡ型エポキシ樹脂、エポキシ当量１８０〜１９０、不揮発分１００％）、「ｊＥＲ ８０７」（三菱化学（株）製、ビスフェノールＦ型エポキシ樹脂、エポキシ当量１６０〜１７５、不揮発分１００％）、「Ｅ−０２８−９０Ｘ」（大竹明新化学（株）製、ビスフェノールＡ型エポキシ樹脂のキシレン溶液（８２８タイプエポキシ樹脂溶液）、エポキシ当量２００〜２１０、不揮発分９０％）等が挙げられ、常温で半固形状のものとして、「ｊＥＲ ８３４」（三菱化学（株）製、ビスフェノールＡ型エポキシ樹脂、エポキシ当量２３０〜２７０、不揮発分１００％）、「Ｅ−８３４−８５Ｘ」（大竹明新化学（株）製、ビスフェノールＡ型エポキシ樹脂のキシレン溶液（８３４タイプエポキシ樹脂溶液）、エポキシ当量２７０〜３２０、不揮発分８５％）等が挙げられ、常温で固形状のものとして、「ｊＥＲ １００１」（三菱化学（株）製、ビスフェノールＡ型エポキシ樹脂、エポキシ当量４５０〜５００、不揮発分１００％）、「Ｅ−００１−７５」（大竹明新化学（株）製、ビスフェノールＡ型エポキシ樹脂のキシレン溶液（１００１タイプエポキシ樹脂溶液）、エポキシ当量６００〜６６０、不揮発分７５％）等が挙げられる。 The epoxy resin (A) may be obtained by synthesizing according to a conventionally known method, or may be a commercially available product. Among the epoxy resins (A) used in the present invention, "E028" (manufactured by Ohtake Meishin Chemical Co., Ltd., bisphenol A type epoxy resin) as a liquid at normal temperature (a temperature of 15 to 25 ° C., hereinafter the same). , Epoxy equivalent 180-190, nonvolatile content 100%), "jER 807" (manufactured by Mitsubishi Chemical Corporation, bisphenol F type epoxy resin, epoxy equivalent 160-175, nonvolatile content 100%), "E-028-90X" (Xylene solution of bisphenol A type epoxy resin (828 type epoxy resin solution), epoxy equivalent 200-210, nonvolatile content 90%, manufactured by Otake Meishin Chemical Co., Ltd.). , "JER 834" (manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin, epoxy equivalent 230-270, nonvolatile content 100%), "E- 834-85X "(manufactured by Ohtake Meishin Chemical Co., Ltd., xylene solution of bisphenol A type epoxy resin (834 type epoxy resin solution), epoxy equivalent 270-320, non-volatile content 85%) and the like. "JER 1001" (manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin, epoxy equivalent 450-500, nonvolatile content 100%), "E-001-75" (manufactured by Ohtake Meishin Chemical Co., Ltd.) , A xylene solution of a bisphenol A type epoxy resin (1001 type epoxy resin solution), an epoxy equivalent of 600 to 660, and a nonvolatile content of 75%).
前記エポキシ樹脂（Ａ）は、本発明の防食塗料組成物１００重量部（不揮発分）に対して、好ましくは５〜４０重量部（不揮発分）、より好ましくは１０〜３０重量部（不揮発分）の量で含まれることが望ましい。 The epoxy resin (A) is preferably 5 to 40 parts by weight (nonvolatile content), more preferably 10 to 30 parts by weight (nonvolatile content) based on 100 parts by weight (nonvolatile content) of the anticorrosion coating composition of the present invention. Is desirably included.
また、本発明の防食塗料組成物が主剤成分と硬化剤成分とからなる２成分型の組成物である場合、前記エポキシ樹脂（Ａ）は主剤成分に含まれ、該主剤成分１００重量部（不揮発分）中に、好ましくは５〜８０重量部（不揮発分）、より好ましくは５〜５０重量部（不揮発分）の量で含まれることが望ましい。 When the anticorrosion coating composition of the present invention is a two-component composition comprising a main component and a curing agent component, the epoxy resin (A) is contained in the main component and 100 parts by weight of the main component (non-volatile). ), Preferably in an amount of 5 to 80 parts by weight (non-volatile content), more preferably 5 to 50 parts by weight (non-volatile content).
なお、不揮発分とは、反応性成分（例：エポキシ樹脂（Ａ）、アミン硬化剤（Ｂ）等）を含有する本発明に係る防食塗料組成物において、該防食塗料組成物に対する十分に反応硬化した該塗料からなる塗膜の重量百分率を意味する。上記不揮発分は、ＪＩＳ Ｋ５６０１−１−２に準拠して、上記防食塗料組成物を１±０．１ｇ採取した試料を加熱温度１２５℃で１時間（常圧下）加熱し、加熱残分を得、該塗料組成物に対するその加熱残分の重量百分率として算出される。 In addition, the non-volatile component refers to a sufficiently reactive hardening of the anticorrosion coating composition in the anticorrosion coating composition according to the present invention containing a reactive component (eg, epoxy resin (A), amine curing agent (B), etc.). Means the weight percentage of the coating film composed of the paint. According to JIS K5601-1-2, a sample obtained by collecting 1 ± 0.1 g of the anticorrosive coating composition was heated at a heating temperature of 125 ° C. for 1 hour (under normal pressure) to obtain a residue after heating. , Calculated as the weight percentage of the heating residue relative to the coating composition.
同様に、本発明に係る防食塗料組成物の各成分の不揮発分は、ＪＩＳ Ｋ５６０１−１−２に準拠して、算出することができる。 Similarly, the non-volatile content of each component of the anticorrosion coating composition according to the present invention can be calculated in accordance with JIS K5601-1-2.
＜アミン硬化剤（Ｂ）＞
本発明に係る防食塗料組成物において、前記アミン硬化剤（Ｂ）として、水との親和性を有するポリオキシアルキレンポリアミン、マンニッヒ変性アミン類、ケチミン類から選ばれる少なくとも１種のアミン硬化剤を含有する。
<Amine curing agent (B)>
In the anticorrosion coating composition according to the present invention, the amine curing agent (B) contains at least one amine curing agent selected from polyoxyalkylene polyamines having affinity for water, Mannich modified amines, and ketimines. I do.
また、本発明に係る防食塗料組成物の硬化剤成分には、アミン硬化剤（Ｂ）であるポリオキシアルキレンポリアミン類、マンニッヒ変性アミン類、ケチミン類に加えて、通常のエポキシ樹脂系防食塗料に使用されるアミン硬化剤（Ｂ）以外の任意のアミン硬化剤（例：ポリアミドアミン、脂肪族アミン、脂環式アミン、芳香族アミン、脂肪族アミンアダクト等）を含むことができる。 The curing agent component of the anticorrosion coating composition according to the present invention includes, in addition to polyoxyalkylene polyamines, Mannich-modified amines, and ketimines, which are amine curing agents (B), a general epoxy resin-based anticorrosion coating. Any amine curing agent other than the amine curing agent (B) used (eg, polyamidoamine, aliphatic amine, alicyclic amine, aromatic amine, aliphatic amine adduct, etc.) can be included.
特に、前記硬化剤成分に、前記アミン硬化剤（Ｂ）としてポリオキシアルキレンポリアミン類を単独で、あるいはポリオキシアルキレンポリアミン類とその他のアミン硬化剤（Ｂ）を含有し、必要に応じて アミン硬化剤（Ｂ）以外の任意のアミン硬化剤を組み合わせて用いても良く、形成される防食塗膜は、乾燥した基材鋼板はもとより、湿潤面を有する基材鋼板、特に基材鋼板表面の水分付着量が５〜４５ｇ／ｍ２である湿潤面に対して優れた付着性を示す傾向があるため好ましい。 In particular, the curing agent component contains a polyoxyalkylene polyamine alone or the polyoxyalkylene polyamine and another amine curing agent (B) as the amine curing agent (B), and optionally comprises an amine curing agent. Any of the amine curing agents other than the agent (B) may be used in combination, and the formed anticorrosion coating film is not only a dried base steel plate but also a base steel plate having a wet surface, particularly a water content on the surface of the base steel plate. This is preferable because it tends to show excellent adhesion to a wet surface having an adhesion amount of 5 to 45 g / m 2 .
つまり、前記アミン硬化剤（Ｂ）の態様として、（ｉ）ポリオキシアルキレンポリアミン類のみ、（ｉｉ）ポリオキシアルキレンポリアミン類と、マンニッヒ変性アミン類、（ｉｉｉ）ポリオキシアルキレンポリアミン類と、ケチミン類、（ｉｖ）ポリオキシアルキレンポリアミン類と、マンニッヒ変性アミン類及びケチミン類の４態様が、乾燥した基材鋼板への付着性はもとより、 湿潤面を有する基材鋼板への付着性にも優れる点で好ましい。さらに、前記硬化剤成分としては、上記（ｉ）〜（ｉｖ）に加えて、アミン硬化剤（Ｂ）以外の任意のアミン硬化剤を含むことができる。 That is, as the embodiment of the amine curing agent (B), (i) only polyoxyalkylene polyamines, (ii) polyoxyalkylene polyamines, Mannich modified amines, (iii) polyoxyalkylene polyamines, and ketimines (Iv) Four aspects of polyoxyalkylene polyamines and Mannich-modified amines and ketimines are excellent not only in adhesion to a dried base steel sheet but also to a base steel sheet having a wet surface. Is preferred. Further, the curing agent component may include any amine curing agent other than the amine curing agent (B) in addition to the above (i) to (iv).
前記硬化剤成分にポリオキシアルキレンポリアミン類を、その他のアミン硬化剤（Ｂ）や アミン硬化剤（Ｂ）以外の任意のアミン硬化剤と組み合わせて用いる場合、防食塗料組成物１００重量部（不揮発分）に対して、前記アミン硬化剤（Ｂ）としてポリオキシアルキレンポリアミン類を、好ましくは０．０１〜２０重量部（不揮発分）、より好ましくは１〜１０重量部（不揮発分）、特に好ましくは２〜８重量部の量で含むことが望ましい。 When a polyoxyalkylene polyamine is used as the curing agent component in combination with another amine curing agent (B) or any amine curing agent other than the amine curing agent (B), 100 parts by weight of the anticorrosive coating composition (non-volatile ), As the amine curing agent (B), a polyoxyalkylene polyamine, preferably 0.01 to 20 parts by weight (non-volatile content), more preferably 1 to 10 parts by weight (non-volatile content), and particularly preferably It is desirable to include it in an amount of 2 to 8 parts by weight.
本発明に係る防食塗料組成物において、前記アミン硬化剤（Ｂ）と前記エポキシ樹脂（Ａ）とは、その当量比（活性水素当量／エポキシ当量）が、好ましくは０．３〜１．５、より好ましくは０．４〜１．０となるような量で用いることが、硬化速度、防食性等の点より望ましい。 In the anticorrosion coating composition according to the present invention, the equivalent ratio (active hydrogen equivalent / epoxy equivalent) of the amine curing agent (B) and the epoxy resin (A) is preferably 0.3 to 1.5, More preferably, it is used in an amount of 0.4 to 1.0 from the viewpoint of curing speed, corrosion resistance and the like.
本発明で用いられるポリオキシアルキレンポリアミン類としては、「Ｊｅｆｆａｍｉｎｅ Ｄ−２３０」（ハンツマン・ジャパン（株）製、ポリオキシプロピレンジアミン、活性水素当量６０、不揮発分１００％）、「Ｊｅｆｆａｍｉｎｅ Ｄ−４００」（ハンツマン・ジャパン（株）製、ポリオキシプロピレンジアミン、活性水素当量１１５）、「Ｊｅｆｆａｍｉｎｅ Ｄ−２０００」（ハンツマン・ジャパン（株）製、ポリオキシプロピレンジアミン、活性水素当量５１４）や「Ｊｅｆｆａｍｉｎｅ Ｔ−４０３」（ハンツマン・ジャパン（株）製、ポリオキシプロピレントリアミン、活性水素当量８１）などが挙げられる。 Examples of the polyoxyalkylene polyamines used in the present invention include “Jeffamine D-230” (manufactured by Huntsman Japan KK, polyoxypropylenediamine, active hydrogen equivalent 60, nonvolatile content 100%), “Jeffamine D-400”. (Huntsman Japan K.K., polyoxypropylenediamine, active hydrogen equivalent 115), "Jeffamine D-2000" (Huntsman Japan K.K., polyoxypropylenediamine, active hydrogen equivalent 514) or "Jeffamine T- 403 "(manufactured by Huntsman Japan K.K., polyoxypropylene triamine, active hydrogen equivalent: 81).
本発明で用いられるマンニッヒ変性アミン類としては、「ＭＡＤ−２０４（Ａ）」（大竹明新化学（株）製、マンニッヒ変性脂肪族ポリアミン、活性水素当量２０２、不揮発分６５％）、「アデカハードナー ＥＨ−３４２Ｗ ３」（（株）ＡＤＥＫＡ製、マンニッヒ変性ポリアミドアミン、活性水素当量１１０）、「Ｓｕｎｍｉｄｅ ＣＸ−１１５４」（三和化学（株）製、マンニッヒ変性脂肪族ポリアミン、活性水素当量２５５）、「ラッカマイド Ｖ６−２２１」（ＤＩＣ（株）製、マンニッヒ変性脂肪族ポリアミン、活性水素当量８０、不揮発分１００％）、「Ｃａｒｄｏｌｉｔｅ ＮＸ−４９１８」（カードライト社製、カルダノールとアミンのマンニッヒ変性アミン類であるフェナルカミン、活性水素当量２５５、不揮発分８０％）、「Ｃａｒｄｏｌｉｔｅ ＮＣ５５６Ｘ８０」（カードライト社製、フェナルカミンアダクト、活性水素当量１３５）、フェナルカミンとカルボン酸類との反応物であるフェナルカマイド等が挙げられる。 Examples of the Mannich-modified amines used in the present invention include "MAD-204 (A)" (mannich-modified aliphatic polyamine, manufactured by Otake Akira Shinkagaku Co., Ltd., active hydrogen equivalent 202, nonvolatile content 65%), "ADEKA HARDNER" EH-342W3 "(manufactured by ADEKA Corporation, Mannich-modified polyamidoamine, active hydrogen equivalent 110)," Sunmide CX-1154 "(manufactured by Sanwa Chemical Co., Ltd., Mannich-modified aliphatic polyamine, active hydrogen equivalent 255), "Lacamide V6-221" (manufactured by DIC Corporation, Mannich-modified aliphatic polyamine, active hydrogen equivalent 80, nonvolatile content 100%), "Cardolite NX-4918" (manufactured by Cardlight, Mannich-modified amines of cardanol and amine) Phenalkamine, active hydrogen equivalent 255, nonvolatile content 80%) , "Cardolite NC556X80" (manufactured by Cardlight Co., Ltd., phenalcamine adduct, active hydrogen equivalent: 135), phenalcamide which is a reaction product of phenalcamine and carboxylic acids, and the like.
本発明で用いられるケチミン類としては、「Ａｎｃａｍｉｎｅ ２４５９」（エアプロダクツ（株）製、活性水素当量１０１、不揮発分８０％等）、「ｊＥＲ キュア Ｈ３０」（三菱化学（株）製、活性水素当量１０５、不揮発分８０％）等が挙げられる。 Examples of the ketimines used in the present invention include “Ancamine 2459” (manufactured by Air Products, Inc., active hydrogen equivalent 101, nonvolatile content 80%, etc.), “jER Cure H30” (manufactured by Mitsubishi Chemical Corporation, active hydrogen equivalent) 105, nonvolatile content 80%).
前記アミン硬化剤（Ｂ）以外の任意のアミン硬化剤としては、「ＰＡ−２９０（Ａ）」（大竹明新化学（株）製、ポリアミドアミン、活性水素当量２７７、不揮発分５９％）、「Ｓｕｎｍｉｄｅ Ｐ−１００３」（エアプロダクツ（株）製、脂肪族アミンアダクト、活性水素当量１２５、不揮発分６０％）、「ＡＤ−２００Ｐ」（大竹明新化学（株）製、脂肪族アミンアダクト（メタキシレンジアミンのエポキシアダクト物）、活性水素当量１５５、不揮発分９０％）等が挙げられる。 Examples of the optional amine curing agent other than the amine curing agent (B) include “PA-290 (A)” (manufactured by Ohtake Meishin Chemical Co., Ltd., polyamideamine, active hydrogen equivalent 277, nonvolatile content 59%), “ Sunmide P-1003 (manufactured by Air Products Co., Ltd., aliphatic amine adduct, active hydrogen equivalent 125, nonvolatile content 60%), "AD-200P" (manufactured by Ohtake Meishin Chemical Co., Ltd.), aliphatic amine adduct (meta Epoxy adduct of xylene diamine), an active hydrogen equivalent of 155, and a nonvolatile content of 90%).
＜水（Ｃ）＞
本発明に係る防食塗料組成物において、前記水（Ｃ）は、防食塗料組成物１００重量部（不揮発分）に対して、１〜１５重量部、好ましくは１〜１０重量部、より好ましくは１〜７重量部の量で含まれることが望ましい。
<Water (C)>
In the anticorrosion coating composition according to the present invention, the water (C) is used in an amount of 1 to 15 parts by weight, preferably 1 to 10 parts by weight, more preferably 1 to 100 parts by weight (nonvolatile content) based on the anticorrosion coating composition. Preferably, it is included in an amount of up to 7 parts by weight.
前記防食塗料組成物中の前記水（Ｃ）が１重量部未満では、基材鋼板の湿潤面に塗装した際、該基材鋼板と形成される防食塗膜との付着性が不十分となる。一方、１５重量部を超えると該防食塗膜の防食性が徐々に低下する傾向にある。 If the water (C) in the anticorrosion coating composition is less than 1 part by weight, the adhesion between the base steel plate and the formed anticorrosion coating film becomes insufficient when applied to the wet surface of the base steel plate. . On the other hand, if it exceeds 15 parts by weight, the anticorrosion properties of the anticorrosion coating film tend to gradually decrease.
＜水酸基含有変性樹脂（Ｄ）＞
本発明に係る防食塗料組成物において、前記水酸基含有変性樹脂（Ｄ）として、水酸基を持つ樹脂であれば特に制限なく使用できるが、特にフェノール類を含むモノマー混合物を重合してなる樹脂が防食性の点から好ましい。
<Hydroxy group-containing modified resin (D)>
In the anticorrosion coating composition according to the present invention, as the hydroxyl-containing modified resin (D), any resin having a hydroxyl group can be used without any particular limitation. In particular, a resin obtained by polymerizing a monomer mixture containing phenols has an anticorrosive property. It is preferable from the point of view.
前記水酸基含有変性樹脂（Ｄ）としては、水酸基含有石油樹脂、水酸基含有キシレン樹脂、水酸基含有クマロン樹脂、α−メチルスチレンとフェノールの共重合物等が挙げられる。上記水酸基含有石油樹脂は、具体的には、石油ナフサ分解で副生する重質油中からスチレン誘導体、インデン、ビニルトルエン等のＣ９留分を重合させた芳香族系石油樹脂、１，３−ペンタジエン、イソプレン等のＣ５留分を重合させた脂肪族系石油樹脂、上記Ｃ９留分とＣ５留分とを共重合させた共重合系石油樹脂、シクロペンタジエン、１，３−ペンタジエン等のＣ５留分の共役ジエンが一部環化重合した脂肪族系石油樹脂、上記芳香族系石油樹脂を水素添加した樹脂、ジシクロペンタジエンを重合させた脂環族系石油樹脂等が挙げられ、これらの石油樹脂に水酸基が導入されたものである。 Examples of the hydroxyl-containing modified resin (D) include a hydroxyl-containing petroleum resin, a hydroxyl-containing xylene resin, a hydroxyl-containing cumarone resin, and a copolymer of α-methylstyrene and phenol. The hydroxyl group-containing petroleum resin is, specifically, an aromatic petroleum resin obtained by polymerizing a C9 fraction such as styrene derivative, indene, and vinyl toluene from heavy oil produced as a by-product of petroleum naphtha cracking; Aliphatic petroleum resins obtained by polymerizing C5 fractions such as pentadiene and isoprene, copolymerized petroleum resins obtained by copolymerizing the above C9 fractions and C5 fractions, and C5 fractions such as cyclopentadiene and 1,3-pentadiene Petroleum resin obtained by partially cyclopolymerizing a conjugated diene, a resin obtained by hydrogenating the above aromatic petroleum resin, an alicyclic petroleum resin obtained by polymerizing dicyclopentadiene, and the like. It is a resin in which a hydroxyl group has been introduced.
上記水酸基含有変性樹脂（Ｄ）は、１種単独で、または２種以上組み合わせて用いることができる。
前記水酸基含有変性樹脂（Ｄ）には、常温で液状のものと常温で固形のものがある。特に、常温で液状の水酸基含有変性樹脂（Ｄ）は、本発明の防食塗料組成物の低粘度化を図ることができ、さらに、塗料組成物のハイソリッド化（塗料組成物中に含まれる塗膜形成成分の含有率を高くする）に寄与することができる。したがって、常温で液状の水酸基含有変性樹脂（Ｄ）を用いた防食塗料組成物より形成される防食塗膜は、塗膜形成時に溶剤の蒸発による塗膜の収縮を抑制できるため、基材鋼板に対して良好な付着性を得られ易い。
The hydroxyl group-containing modified resin (D) can be used alone or in combination of two or more.
The hydroxyl group-containing modified resin (D) includes a liquid resin at ordinary temperature and a solid resin at ordinary temperature. In particular, the hydroxyl group-containing modified resin (D) which is liquid at normal temperature can reduce the viscosity of the anticorrosion coating composition of the present invention, and further makes the coating composition high solid (the coating composition contained in the coating composition). (Increase the content of the film-forming component). Therefore, the anticorrosion coating formed from the anticorrosion coating composition using the hydroxyl group-containing modified resin (D) which is liquid at room temperature can suppress the shrinkage of the coating due to the evaporation of the solvent during the formation of the coating. On the other hand, good adhesion is easily obtained.
本発明で用いられる水酸基含有変性樹脂（Ｄ）の内、常温で液状のものとしては、「ネシレス ＥＰＸ−Ｌ」、「ネシレス ＥＰＸ−Ｌ２」（以上、ＮＥＶＣＩＮ社製、フェノール変性炭化水素樹脂）、「ＨＩＬＥＮＯＬ ＰＬ−１０００Ｓ」（ＫＯＬＯＮケミカル社製、水酸基含有炭化水素樹脂、不揮発分９７％）、「ニカノール Ｌ」（フドー株式会社製、水酸基含有キシレン樹脂、不揮発分１００％）、常温で固形のものとしては、「ネオポリマー Ｅ−１００」、「ネオポリマー Ｋ−２」、「ネオポリマー Ｋ３」（以上、新日本石油化学（株）製、水酸基含有Ｃ９系石油樹脂）、「ＮＯＶＡＲＥＳ ＣＡ １００」（Ｒｕｔｇｅｒｓ Ｃｈｅｍｉｃａｌｓ ＡＧ社製、水酸基含有クマロン樹脂、不揮発分１００％）等が挙げられる。 Among the hydroxyl group-containing modified resins (D) used in the present invention, those which are liquid at room temperature include "Nesileth EPX-L", "Nesileth EPX-L2" (all of which are phenol-modified hydrocarbon resins manufactured by NEVCIN), "HILENOL PL-1000S" (manufactured by KOLON Chemical Co., hydroxyl group-containing hydrocarbon resin, nonvolatile content 97%), "Nicanol L" (manufactured by Fudo Co., Ltd., hydroxyl group-containing xylene resin, nonvolatile content 100%), solid at room temperature Examples thereof include "Neopolymer E-100", "Neopolymer K-2", and "Neopolymer K3" (both manufactured by Nippon Petrochemical Co., Ltd., hydroxyl group-containing C9 petroleum resin), and "NOVARES CA 100" ( Rutgers Chemicals AG, hydroxyl-containing coumarone resin, nonvolatile content 100%) and the like.
本発明に係る防食塗料組成物において、前記水酸基含有変性樹脂（Ｄ）は、前記防食塗料組成物１００重量部（不揮発分）に対して、好ましくは３〜５０重量部（不揮発分）、より好ましくは３〜２０重量部（不揮発分）の量で含まれることが望ましい。上記水酸基含有変性樹脂（Ｄ）の含有量が、３重量部（不揮発分）未満では、該防食塗料組成物より形成される防食塗膜の柔軟性が劣り、湿潤面を有する基材鋼板に対して良好な付着性を得られにくくなる傾向がある。一方、２０重量部、特に５０重量部（何れも不揮発分）を超えると、該防食塗膜の防食性が低下する傾向にある。 In the anticorrosion coating composition according to the present invention, the hydroxyl group-containing modified resin (D) is preferably 3 to 50 parts by weight (nonvolatile content), more preferably 100 parts by weight (nonvolatile content) of the anticorrosion coating composition. Is desirably contained in an amount of 3 to 20 parts by weight (nonvolatile content). If the content of the hydroxyl group-containing modified resin (D) is less than 3 parts by weight (nonvolatile content), the flexibility of the anticorrosion coating film formed from the anticorrosion coating composition is inferior, and the base steel sheet having a wet surface is inferior. And it is difficult to obtain good adhesion. On the other hand, when the amount exceeds 20 parts by weight, particularly 50 parts by weight (all of which are non-volatile components), the anticorrosion properties of the anticorrosion coating film tend to decrease.
本発明に係る防食塗料組成物 により形成された防食塗膜が、湿潤面を有する基材鋼板表面に対して優れた付着性を有する理由を、本発明者らは次のように推定している。 The present inventors presume that the reason why the anticorrosion coating formed by the anticorrosion coating composition according to the present invention has excellent adhesion to the surface of a base steel sheet having a wet surface is as follows. .
防食塗料組成物に、水との親和性を有する特定のアミン硬化剤を含有させることにより、該防食塗料組成物を基材鋼板の湿潤面に塗装した際、付着を阻害する要因となる基材鋼板表面に付着している遊離した水分の一部あるいは全部を、弾くのではなく、防食塗料中に取り込む効果を示す。ここで、水との親和性を有するアミン硬化剤とは、ポリオキシアルキレンポリミン類、マンニッヒ変性アミン類、ケチミン類から選ばれる少なくとも１種のアミン硬化剤である。上記ポリオキシアルキレンポリアミン類は分子中に極性の高いエーテル結合を有することにより、上記マンニッヒ変性アミン類は分子中に水酸基を有することにより、水との親和性を有するため、基材鋼板表面に付着している上述の遊離した水分を防食塗料中に取り込む効果を示す。また、上記ケチミン類は水分と反応し、アミン硬化剤とケトンを生成する過程で、上記遊離した水分を防食塗料中に取り込む効果を示す。さらに、上記防食塗料組成物に所定量の水を含有させることにより、塗料の親水性が高くなるため、上記遊離した水分を取り込む効果を向上させている。ただし、防食塗料組成物に、水との親和性を有する特定のアミン硬化剤、あるいは、所定量の水のいずれか一方のみを含有させているだけでは、上記遊離した水分を防食塗料中に取り込む効果は十分ではなく、湿潤面を有する基材鋼板表面への付着性は得られない。 By coating the anticorrosion coating composition with a specific amine curing agent having an affinity for water, when the anticorrosion coating composition is applied to a wet surface of a base steel sheet, a substrate that becomes a factor inhibiting adhesion. It shows the effect of taking in some or all of the free water adhering to the steel sheet surface into the anticorrosion paint, instead of flipping. Here, the amine curing agent having an affinity for water is at least one amine curing agent selected from polyoxyalkylene polymines, Mannich-modified amines, and ketimines. Since the polyoxyalkylene polyamines have a highly polar ether bond in the molecule, and the Mannich-modified amines have a hydroxyl group in the molecule, they have an affinity for water, and thus adhere to the surface of the base steel sheet. The effect of taking the above-mentioned free water into the anticorrosive paint is shown. The ketimines react with moisture to produce an amine curing agent and a ketone, and have an effect of taking the released moisture into the anticorrosion paint. Further, by adding a predetermined amount of water to the anticorrosion coating composition, the hydrophilicity of the coating is increased, so that the effect of taking in the released moisture is improved. However, the anticorrosion paint composition, a specific amine curing agent having an affinity for water, or only containing only one of a predetermined amount of water, the above-mentioned free water is taken into the anticorrosion paint The effect is not sufficient, and adhesion to the surface of the base steel sheet having a wet surface cannot be obtained.
防食塗料組成物が、湿潤面を有する基材鋼板表面に対して優れた付着性を示すには、前記遊離した水分を防食塗料中に取り込む効果だけでは不十分であり、特定のアミン硬化剤及び所定量の水に加えて、さらに水酸基含有変性樹脂を含有させることによって、上記遊離した水分を防食塗料中に取り込む効果に寄与するとともに、塗膜に柔軟性を付与することによる付着性向上効果が得られる。したがって、本発明に係る防食塗料組成物は、上記遊離した水分を防食塗料中に取り込む効果、及び、上記塗膜に柔軟性を付与することによる付着性向上効果との相乗効果によって、湿潤面を有する基材鋼板表面に対して優れた付着性を有する。 In order for the anticorrosion coating composition to exhibit excellent adhesion to the surface of the base steel sheet having a wet surface, the effect of incorporating the released moisture into the anticorrosion coating alone is not sufficient, and a specific amine curing agent and In addition to the predetermined amount of water, by further containing a hydroxyl group-containing modified resin, while contributing to the effect of taking in the free water into the anticorrosive paint, the adhesion improving effect by imparting flexibility to the coating film. can get. Therefore, the anticorrosion paint composition according to the present invention, the effect of taking the released moisture into the anticorrosion paint, and the synergistic effect of improving the adhesion by imparting flexibility to the coating film, the wet surface. Has excellent adhesion to the surface of the base steel sheet.
＜扁平状顔料（Ｅ）＞
本発明に係る防食塗料組成物において、前記扁平状顔料（Ｅ）は、メディアン径（Ｄ５０）が３０〜２００μｍであり、且つ平均アスペクト比（メディアン径／平均厚さ）が３０〜１００であることが、防食性、湿潤面を有する基材鋼板との付着性等を向上する点で望ましい。
<Flat pigment (E)>
In the anticorrosion coating composition according to the present invention, the flat pigment (E) has a median diameter (D50) of 30 to 200 μm and an average aspect ratio (median diameter / average thickness) of 30 to 100. However, it is desirable from the viewpoint of improving the anticorrosion property and the adhesion to a base steel sheet having a wet surface.
メディアン径（Ｄ５０）は、レーザー散乱回折式粒度分布測定装置、例えば「ＳＡＬＤ ２２００」（（株）島津製作所製）を用いて測定することができる。平均厚さは、走査型電子顕微鏡（ＳＥＭ）、例えば「ＸＬ−３０」（フィリップス社製）を用いて扁平状顔料（Ｅ）の主面に対して水平方向から観察し、数十〜数百個の顔料粒子の厚さを測定することで、その平均値として算出できる。 The median diameter (D50) can be measured using a laser scattering diffraction particle size distribution analyzer, for example, “SALD 2200” (manufactured by Shimadzu Corporation). The average thickness is observed from the horizontal direction with respect to the main surface of the flat pigment (E) using a scanning electron microscope (SEM), for example, “XL-30” (manufactured by Philips), and several tens to several hundreds are observed. The average value can be calculated by measuring the thickness of each pigment particle.
前記扁平状顔料（Ｅ）として、例えば、マイカ、ガラスフレーク等が挙げられ、安価で入手容易であり、前述の防食性向上効果、及び塗膜の内部応力を緩和することによる付着性向上効果をより得られ易い等の点からマイカが好ましい。上記マイカとしては、「スゾライトマイカ ２００−ＨＫ」（西日本貿易（株）製、メディアン（Ｄ５０）径：６５μｍ、平均アスペクト比：５４）等が挙げられる。
また、上記扁平状顔料（Ｅ）は、１種単独で、または２種以上を組み合わせて用いることができる。
Examples of the flat pigment (E) include mica and glass flake, which are inexpensive and easily available, and have the above-described effect of improving the anti-corrosion property and the effect of improving the adhesion by relaxing the internal stress of the coating film. Mica is preferred because it is more easily obtained. Examples of the mica include “Suzolite Mica 200-HK” (manufactured by West Japan Trading Co., Ltd., median (D50) diameter: 65 μm, average aspect ratio: 54) and the like.
The flat pigments (E) can be used alone or in combination of two or more.
前記扁平状顔料（Ｅ）は、前記効果により優れた防食塗膜を形成することができる点から、本発明の防食塗料組成物１００重量部（不揮発分）に対して、好ましくは１〜４０重量部、より好ましくは３〜２０重量部の量で含まれることが望ましい。 The flat pigment (E) is preferably 1 to 40 parts by weight with respect to 100 parts by weight (non-volatile content) of the anticorrosive coating composition of the present invention, since the flat pigment (E) can form an excellent anticorrosion coating film due to the above effects. Parts, more preferably 3 to 20 parts by weight.
＜主剤成分に添加可能なその他の塗膜形成成分＞
本発明に係る防食塗料組成物の主剤成分には、前記エポキシ樹脂（Ａ）以外に、添加剤として、エポキシ基を有する反応性希釈剤を含むことができる。
<Other coating film forming components that can be added to the main component>
The main component of the anticorrosive coating composition according to the present invention may contain, as an additive, a reactive diluent having an epoxy group in addition to the epoxy resin (A).
前記エポキシ基を有する反応性希釈剤として、例えば、フェニルグリシジルエーテル、アルキルグリシジルエーテル（アルキル基の炭素数１〜１５、好ましくは１１〜１５）、バーサティック酸（Ｖｅｒｓａｔｉｃ ａｃｉｄ）、グリシジルエステル（Ｒ１Ｒ２Ｒ３Ｃ−ＣＯＯ−Ｇｌｙ、Ｒ１＋Ｒ２＋Ｒ３＝Ｃ８〜Ｃ１０のアルキル基、Ｇｌｙ：グリシジル基）、α−オレフィンエポキサイド（ＣＨ３−（ＣＨ２）ｎ−Ｇｌｙ、ｎ＝１１〜１３、Ｇｌｙ：同上）、１，６−ヘキサンジオールジグリシジルエーテル（Ｇｌｙ-Ｏ−（ＣＨ２）６−Ｏ−Ｇｌｙ、Ｇｌｙ：同上）、ネオペンチルグリコールジグリシジルエーテル（Ｇｌｙ−Ｏ−ＣＨ２−Ｃ（ＣＨ３）２−ＣＨ２−Ｏ−Ｇｌｙ、Ｇｌｙ：同上）、トリメチロールプロパントリグリシジルエーテル（ＣＨ３−ＣＨ２−Ｃ（ＣＨ２−Ｏ−Ｇｌｙ）３ 、Ｇｌｙ：同上）、アルキルフェニルグリシジルエーテル（アルキル基の炭素数１〜２０、好ましくは１〜５、例：メチルフェニルグリシジルエーテル、エチルフェニルグリシジルエーテル、プロピルフェニルグリシジルエーテル）等が挙げられる。 Examples of the reactive diluent having an epoxy group include, for example, phenylglycidyl ether, alkyl glycidyl ether (alkyl group having 1 to 15, preferably 11 to 15), versatic acid, glycidyl ester (R 1 R 2 R 3 C-COO-Gly, R 1 + R 2 + R 3 = alkyl group of C8 to C10, Gly: glycidyl group), α-olefin epoxide (CH 3- (CH 2 ) n-Gly, n = 11 to 11) 13, Gly: the same as above), 1,6-hexanediol diglycidyl ether (Gly-O- (CH 2) 6 -O-Gly, Gly: the same as above), neopentyl glycol diglycidyl ether (Gly-O-CH 2 - C (CH 3) 2 -CH 2 -O-Gly, Gly: the same as above), trimethylolpropane Emissions triglycidyl ether (CH 3 -CH 2 -C (CH 2 -O-Gly) 3, Gly: the same as above), alkyl phenyl glycidyl ether (alkyl group having 1 to 20 carbon atoms, preferably 1 to 5, such as methyl phenyl Glycidyl ether, ethylphenyl glycidyl ether, propylphenyl glycidyl ether) and the like.
これらのエポキシ基を有する反応性希釈剤の内では、単官能のフェニルグリシジルエーテル、アルキルグリシジルエーテル、アルキルフェニルグリシジルエーテルが低粘度であるため、希釈効果（塗料の低粘度化）に優れ、塗料をハイソリッド化することができる。 Among these reactive diluents having an epoxy group, monofunctional phenyl glycidyl ether, alkyl glycidyl ether and alkyl phenyl glycidyl ether have a low viscosity, so that they have excellent dilution effect (low viscosity of the coating). It can be made high solid.
前記エポキシ基を有する反応性希釈剤は、１種単独で、または２種以上を組み合わせて用いることができる。このような反応性希釈剤としては、「Ｅｐｏｄｉｌ ７５９」（エアプロダクツ（株）製、アルキル（Ｃ１２−Ｃ１３）グリシジルエーテル、エポキシ当量２８５、不揮発分１００％）、「Ｃａｒｄｏｌｉｔｅ ２５１３ＨＰ」（カードライト社製、アルキルフェノールグリシジルエーテル、エポキシ当量４００、不揮発分１００％）等が挙げられる。 The reactive diluent having an epoxy group can be used alone or in combination of two or more. Examples of such a reactive diluent include “Epodil 759” (manufactured by Air Products, Inc., alkyl (C12-C13) glycidyl ether, epoxy equivalent 285, nonvolatile content 100%), and “Cardolite 2513HP” (manufactured by Cardlight Co., Ltd.). , Alkylphenol glycidyl ether, epoxy equivalent 400, nonvolatile content 100%) and the like.
前記エポキシ基を有する反応性希釈剤は、本発明に係る防食塗料組成物の主剤成分中に、前記エポキシ樹脂（Ａ）１００重量部（不揮発分）に対し、好ましくは０〜４０重量部（不揮発分）、より好ましくは０〜２０重量部（不揮発分）の量で含まれることが望ましい。 The reactive diluent having an epoxy group is preferably used in an amount of 0 to 40 parts by weight (nonvolatile) based on 100 parts by weight (nonvolatile content) of the epoxy resin (A) in the main component of the anticorrosion coating composition according to the present invention. Min), more preferably 0 to 20 parts by weight (non-volatile content).
＜硬化剤成分に添加可能なその他の成分＞
本発明に係る防食塗料組成物の硬化剤成分には、前記アミン硬化剤（Ｂ）以外に、硬化速度の調整、特に促進に寄与できる硬化促進剤を含むことができる。該硬化促進剤としては、例えば、３級アミン類が挙げられる。
<Other components that can be added to the curing agent component>
In addition to the amine curing agent (B), the curing agent component of the anticorrosion coating composition according to the present invention may contain a curing accelerator that can adjust the curing speed, and particularly contribute to acceleration. Examples of the curing accelerator include tertiary amines.
前記硬化促進剤としては、トリエタノールアミン（Ｎ（Ｃ２Ｈ５ＯＨ）３）、ジアルキルアミノエタノール（[ＣＨ３（ＣＨ２）ｎ]２ＮＣＨ２ＯＨ、ｎ：繰返し数）、トリエチレンジアミン（１，４−ジアザシクロ（２，２，２）オクタン）、具体的には、２，４，６−トリ（ジメチルアミノメチル）フェノール（Ｃ６Ｈ５−ＣＨ２Ｎ（ＣＨ３）２、「バーサミン ＥＨ３０」：ヘンケル白水（株）製、「Ａｎｃａｍｉｎｅ Ｋ−５４」：エアプロダクツ（株）製）等が挙げられる。これらの硬化促進剤は、本発明の防食塗料組成物１００重量部（不揮発分）に対して、必要により、０．１〜２．０重量部（不揮発分）の量で含まれる。 Examples of the curing accelerator include triethanolamine (N (C 2 H 5 OH) 3 ), dialkylaminoethanol ([CH 3 (CH 2 ) n ] 2 NCH 2 OH, n: repetition number), and triethylene diamine (1 4- Jiazashikuro (2,2,2) octane), specifically, 2,4,6-tri (dimethylaminomethyl) phenol (C 6 H 5 -CH 2 N (CH 3) 2, "Basamin EH30 ": Henkel Hakusui Co., Ltd .;" Ancamine K-54 ": Air Products Co., Ltd.). These curing accelerators are contained, if necessary, in an amount of 0.1 to 2.0 parts by weight (non-volatile content) based on 100 parts by weight (non-volatile content) of the anticorrosive coating composition of the present invention.
＜その他の成分＞
本発明に係る防食塗料組成物には、これまでに述べた諸成分の他に、必要に応じて、前記扁平状顔料（Ｅ）以外の顔料、溶剤、シランカップリング剤、湿潤分散剤、可塑剤、タレ止め・沈降防止剤、無機脱水剤（安定剤）、防汚剤等を、本発明の目的を損なわない限りで含むことができる。
<Other ingredients>
The anticorrosive coating composition according to the present invention may further contain, in addition to the above-mentioned components, a pigment other than the flat pigment (E), a solvent, a silane coupling agent, a wetting and dispersing agent, Agents, anti-sagging / sedimentation inhibitors, inorganic dehydrating agents (stabilizers), antifouling agents and the like can be included as long as the object of the present invention is not impaired.
＜扁平状顔料（Ｅ）以外の顔料＞
前記顔料としては、扁平状顔料（Ｅ）以外であれば特に限定されず、一般的に塗料組成物に用いられているものを使用することができ、例えば、硫酸バリウム、カリ長石、バライト粉、シリカ、炭酸カルシウム、タルク 等の体質顔料、チタン白、弁柄、黄色弁柄、カーボンブラック等の着色顔料が挙げられる。上記顔料は、１種単独で、または２種以上を組み合わせて用いることができる。
<Pigments other than flat pigment (E)>
The pigment is not particularly limited as long as it is other than the flat pigment (E), and those generally used in coating compositions can be used. For example, barium sulfate, potassium feldspar, barite powder, Examples include extender pigments such as silica, calcium carbonate, and talc, and coloring pigments such as titanium white, red petal, yellow petal, and carbon black. The above pigments can be used alone or in combination of two or more.
＜溶剤＞
前記溶剤は、エポキシ樹脂（Ａ）を溶解可能なものであればその沸点によっては特に限定されるものではなく、本発明に係る防食塗料組成物の塗装作業性に応じて適宜選択して用いることができる。前記溶剤として、例えば、キシレン、トルエン、ＭＩＢＫ（メチルイソブチルケトン）、１−メトキシ−２−プロパノール、ＭＥＫ（メチルエチルケトン）、酢酸ブチル、ｎ−ブタノール、ｉｓｏ−ブタノール、ＩＰＡ（イソプロピルアルコール）等が挙げられ、これらの溶剤を、１種単独で、または２種以上を組み合わせて用いる。
<Solvent>
The solvent is not particularly limited by the boiling point as long as it can dissolve the epoxy resin (A), and is appropriately selected and used according to the coating workability of the anticorrosion coating composition according to the present invention. Can be. Examples of the solvent include xylene, toluene, MIBK (methyl isobutyl ketone), 1-methoxy-2-propanol, MEK (methyl ethyl ketone), butyl acetate, n-butanol, iso-butanol, and IPA (isopropyl alcohol). These solvents are used alone or in combination of two or more.
本発明において、これら溶剤の含有量は通常、特に限定されないが、湿潤面を有する基材鋼板との付着性の点から、キシレンやトルエン等の芳香族系の溶剤を用いる場合、本発明の防食塗料組成物１００重量部（不揮発分）に対して、好ましくは０〜２０重量部、より好ましくは０〜１０重量部の量で含まれることが望ましい。 In the present invention, the content of these solvents is usually, but not particularly limited to, from the viewpoint of adhesion to a base steel sheet having a wet surface, when using an aromatic solvent such as xylene or toluene, the anticorrosion of the present invention. It is preferably contained in an amount of preferably 0 to 20 parts by weight, more preferably 0 to 10 parts by weight, based on 100 parts by weight (nonvolatile content) of the coating composition.
＜シランカップリング剤＞
前記シランカップリング剤としては、特に制限されず、従来公知のものを用いることができるが、同一分子内に少なくとも２つの加水分解性基を有し、基材に対する付着性の向上、塗料粘度の低下等に寄与できる化合物であることが好ましく、例えば、式：Ｘ−ＳｉＭｅｎＹ３−ｎ［ｎは０あるいは１、Ｘは有機質との反応が可能な反応性基（例：アミノ基、ビニル基、エポキシ基、メルカプト基、ハロゲン基、またはこれらの基を含有する炭化水素基、ならびに、上記炭化水素基の炭素原子間の結合がエーテル結合に置換してなる基等。）を示し、Ｍｅはメチル基、Ｙは加水分解性基 （例：メトキシ基、エトキシ基）を示す。］で表される化合物であることがより好ましい。このようなシランカップリング剤としては、「ＫＢＭ４０３」（信越化学工業（株）製、γ−グリシドキシプロピルトリメトキシシラン）等が挙げられる。
<Silane coupling agent>
The silane coupling agent is not particularly limited, and a conventionally known silane coupling agent can be used. The silane coupling agent has at least two hydrolyzable groups in the same molecule, improves adhesion to a substrate, and improves coating viscosity. is preferably a compound capable of contributing to the reduction or the like, for example, the formula: X-SiMe n Y 3- n [n is 0 or 1, X is capable of reaction with the organic reactive group (e.g., amino groups, vinyl A group, an epoxy group, a mercapto group, a halogen group, or a hydrocarbon group containing these groups, or a group in which a bond between carbon atoms of the hydrocarbon group is replaced with an ether bond.) Represents a methyl group, and Y represents a hydrolyzable group (eg, methoxy group, ethoxy group). Is more preferable. Examples of such a silane coupling agent include “KBM403” (manufactured by Shin-Etsu Chemical Co., Ltd., γ-glycidoxypropyltrimethoxysilane).
前記シランカップリング剤を用いる場合、本発明の防食塗料組成物１００重量部（不揮発分）に対して、好ましくは０．１〜１０重量部（不揮発分）、より好ましくは０．５〜５重量部（不揮発分）の量で含まれていることが望ましい。本発明に係る防食塗料組成物にこのような量でシランカップリング剤を用いると、得られる防食塗膜の付着性等の塗膜性能が向上し、特にハイソリッド防食塗料組成物では塗料粘度を下げることで塗装作業性が向上する。 When the silane coupling agent is used, it is preferably 0.1 to 10 parts by weight (nonvolatile), more preferably 0.5 to 5 parts by weight, based on 100 parts by weight (nonvolatile) of the anticorrosive coating composition of the present invention. It is desirable that the amount is contained in an amount of a part (non-volatile content). When the silane coupling agent is used in such an amount in the anticorrosion coating composition according to the present invention, the coating performance such as adhesion of the obtained anticorrosion coating is improved. Lowering improves the workability of coating.
＜湿潤分散剤＞
前記湿潤分散剤としては、ポリアルキルエーテル構造を有するものが好ましく、「プライサーフ Ａ２０８Ｂ」（第一工業製薬（株）製、ポリオキシエチレンラウリルエーテルリン酸エステル、不揮発分９８％）、「プライサーフ Ａ２０８Ｆ」（第一工業製薬（株）製、ポリオキシエチレンアルキル（Ｃ８）エーテルリン酸エステル）等が挙げられる。これらの湿潤分散剤は、１種単独で、または２種以上を組み合わせて用いることができる。
<Wet dispersant>
As the wetting and dispersing agent, those having a polyalkyl ether structure are preferable, and "Plysurf A208B" (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyethylene lauryl ether phosphate, nonvolatile content 98%), "Plysurf A208B" A208F "(manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyethylene alkyl (C8) ether phosphate). These wetting and dispersing agents can be used alone or in combination of two or more.
＜本発明に係る防食塗料組成物の用途＞
船舶、陸上構造物、橋梁等の大型の鉄鋼構造物には、腐食防止を目的とした防食塗膜で被覆されているが、該塗膜は経年、屋外への暴露、没水等によって生じた塗膜欠陥部より発錆するため、定期的な補修を必要とする。上記大型の鉄鋼構造物のような大面積に亘る補修では、発錆部に対して、ドライブラスト処理よりも作業効率に優れるウェットブラスト処理やウォータージェットで錆の除去処理が行われることがある。本発明に係る防食塗料組成物は、上記ウェットブラスト処理やウォータージェット等によって生じた基材鋼板の湿潤面にスプレー塗装したとしても、防食性、付着性に優れた防食塗膜を形成することができる。したがって、特にバラストタンクのような基材鋼板表面を完全に乾燥させることが困難な構造物での補修用途等の湿潤面を有する基材鋼板へ塗装する用途に適している。
<Use of anticorrosion coating composition according to the present invention>
Large steel structures such as ships, land-based structures, and bridges are coated with anticorrosion coatings for the purpose of preventing corrosion. Periodic repair is required because it rusts from defective coatings. In repairing over a large area such as the large-sized steel structure, rust removal may be performed on the rusted portion by wet blasting or water jet which is more efficient than drive blasting. The anticorrosion coating composition according to the present invention can form an anticorrosion coating having excellent anticorrosion properties and adhesion even when spray-coated on a wet surface of a base steel sheet generated by the above-mentioned wet blast treatment or water jet. it can. Therefore, it is particularly suitable for use in coating a base steel sheet having a wet surface, such as a repair application for a structure where it is difficult to completely dry the surface of the base steel sheet such as a ballast tank.
本発明に係る防食塗料組成物を、基材鋼板の湿潤面に塗装する際、基材鋼板表面の水分付着量が５〜４５ｇ／ｍ２である場合、スプレー塗装が適しており、また、該基材鋼板表面の水分付着量が４５ｇ／ｍ２より多い場合、刷毛、ローラー、ヘラ、コテによる塗装が適している。本発明に係る防食塗料組成物は、基材鋼板表面の水分付着量によって、適切な塗装方法を選択することにより、例え水中であっても塗装可能であり、該防食塗料より形成される防食塗膜は、基材鋼板の湿潤面に対して良好な付着性を有する。 When the anticorrosion coating composition according to the present invention is applied to a wet surface of a base steel sheet, spray coating is suitable when the amount of water adhered to the base steel sheet surface is 5 to 45 g / m 2. When the amount of water adhering to the surface of the base steel plate is more than 45 g / m 2 , painting with a brush, a roller, a spatula, or an iron is suitable. The anticorrosion coating composition according to the present invention can be applied even in water by selecting an appropriate coating method depending on the amount of moisture adhered to the surface of the base steel sheet, and the anticorrosion coating formed from the anticorrosion coating is used. The film has good adhesion to the wet surface of the base steel sheet.
前記スプレー塗装の条件は、形成したい防食塗膜の厚みに応じて適宜調整すればよいが、エアレススプレー時には、例えば、１次（空気）圧：０．４〜０．８ＭＰａ程度、２次（塗料）圧：１０〜２６ＭＰａ程度、ガン移動速度５０〜１２０ｃｍ／秒程度が好ましい。 The conditions for the spray coating may be appropriately adjusted according to the thickness of the anticorrosion coating film to be formed. For airless spraying, for example, a primary (air) pressure: about 0.4 to 0.8 MPa, a secondary (paint) ) Pressure: about 10 to 26 MPa, and gun moving speed about 50 to 120 cm / sec.
本発明に係る防食塗膜の膜厚は、所望の防食性を示す厚みであれば特に制限されないが、好ましくは１００〜４５０μｍ、より好ましくは２５０〜４００μｍである。 The thickness of the anticorrosion coating film according to the present invention is not particularly limited as long as it has a desired anticorrosion property, but is preferably 100 to 450 μm, more preferably 250 to 400 μm.
このような膜厚の防食塗膜を形成する際、１回の塗装で、所望の厚みの防食塗膜を形成してもよいし、求められる防食性に応じ、２回（必要によりそれ以上）の塗装で、所望の厚みの防食塗膜を形成してもよい。より均質な塗膜を形成し易いため、２回塗り（必要によりそれ以上）で前記範囲の厚みの防食塗膜を形成することが好ましい。 When forming an anticorrosion coating film having such a film thickness, a single coating may be used to form an anticorrosion coating film having a desired thickness, or twice (or more if necessary) depending on the required anticorrosion properties. May be applied to form a corrosion-resistant coating film having a desired thickness. Since it is easy to form a more uniform coating film, it is preferable to form an anticorrosion coating film having a thickness in the above-mentioned range by applying twice (or more if necessary).
本発明に係る防食塗料より形成される防食塗膜を硬化（乾燥）させる方法としては特に制限されず、硬化（乾燥）時間を短縮させるために５０〜６０℃程度に加熱することもできるが、通常は、常温、常圧下で１〜１４日程度放置することで硬化させる。 The method for curing (drying) the anticorrosion coating film formed from the anticorrosion paint according to the present invention is not particularly limited, and it may be heated to about 50 to 60 ° C. in order to shorten the curing (drying) time. Usually, it is cured by leaving it at normal temperature and normal pressure for about 1 to 14 days.
本発明に係る防食塗膜付き基材の製造方法は、基材鋼板あるいはその湿潤面に対して、適切な塗装方法で前記防食塗料組成物を塗装する工程、及び塗装された該防食塗料組成物を前述の条件で硬化させて防食塗膜を形成する工程からなる。 The method for producing a base material with an anticorrosion coating film according to the present invention includes a step of applying the anticorrosion coating composition to a base steel plate or a wet surface thereof by an appropriate coating method, and the coated anticorrosion coating composition Is cured under the conditions described above to form an anticorrosion coating.
さらに、所望の用途に応じて、前記防食塗膜付き基材の防食塗膜の上に、防汚塗料等の従来公知の上塗り塗料を塗布し、硬化させてもよい。 Further, depending on the desired use, a conventionally known overcoat paint such as an antifouling paint may be applied on the anticorrosion coating film of the base material having the anticorrosion coating film and cured.
以下、実施例により本発明をさらに具体的に説明するが、本発明はこれらによって限定されるものではない。
本発明の実施例に用いた主な材料を以下の表１に示す。
Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto.
The main materials used in the examples of the present invention are shown in Table 1 below.
［実施例１］
下記表２に示すように、容器に、エポキシ樹脂「Ｅ−０２８」（注１）２５重量部と、反応性希釈剤「Ｅｐｏｄｉｌ ７５９」（注３）３重量部と、水酸基含有炭化水素樹脂「ＨＩＬＥＮＯＬ ＰＬ−１０００Ｓ」（注４）５重量部と、キシレン６．３重量部と、ｎ−ブタノール３重量部と、ＭＩＢＫ（メチルイソブチルケトン）２重量部と、シランカップリング剤「ＫＢＭ４０３」（注７）１重量部と、タルク２５重量部、マイカ「スゾライトマイカ ２００−ＨＫ」（注８）５重量部と、カリ長石１６重量部と、チタン白５重量部と、タレ止め剤１．５重量部を入れ、そこにガラスビーズを加えて、ペイントシェーカーでこれらの配合成分を混合した。次いで、ガラスビーズを取り除き、水２重量部及び湿潤分散剤「プライサーフ Ａ２０８Ｂ」（注９）０．２重量部を入れ、ハイスピードディスパーを用い、２３℃で均一になるまで分散し、その後５６〜６０℃に加温した後、３０℃以下まで冷却し、防食塗料組成物を構成する主剤成分を調製した。
[Example 1]
As shown in Table 2 below, 25 parts by weight of an epoxy resin "E-028" (Note 1), 3 parts by weight of a reactive diluent "Epodil 759" (Note 3), and a hydroxyl group-containing hydrocarbon resin were placed in a container. 5 parts by weight of “HILENOL PL-1000S” (Note 4) and 6. 3 parts by weight, n-
また、下記表２に示すように、ポリオキシアルキレンポリアミン「Ｊｅｆｆａｍｉｎｅ Ｄ−２３０」（注１０）４重量部と、フェナルカミン「Ｃａｒｄｏｌｉｔｅ ＮＸ−４９１８」（注１１）９重量部と、三級アミン「Ａｎｃａｍｉｎｅ Ｋ−５４」（注１９）０．２重量部、および１−メトキシ−２−プロパノール０．８重量部を、ハイスピードディスパーを用いて（常温、常圧下で）混合することで、防食塗料組成物を構成する硬化剤成分を調製した。
得られた主剤成分と硬化剤成分を、塗装前に混合することで防食塗料組成物を調製した。
In addition, as shown in Table 2 below, 4 parts by weight of polyoxyalkylene polyamine “Jeffamine D-230” (Note 10), 9 parts by weight of phenalkamine “Cardolite NX-4918” (Note 11), and tertiary amine “Ancamine” K-54 "(Note 19) 0.2 parts by weight and 1-methoxy-2-propanol 0.8 parts by weight using a high-speed disperser (at ordinary temperature and pressure) to form an anticorrosive coating composition. A hardener component constituting the product was prepared.
The obtained main component and curing agent component were mixed before painting to prepare an anticorrosion coating composition.
［実施例２〜１３および比較例１〜６］
実施例１の主剤成分及び硬化剤成分にそれぞれ含まれる成分及び配合量を下記表２に示すように変更した以外は実施例１と同様にして防食塗料組成物を調製した。
[Examples 2 to 13 and Comparative Examples 1 to 6]
An anticorrosion coating composition was prepared in the same manner as in Example 1 except that the components and the amounts contained in the main component and the curing agent component of Example 1 were changed as shown in Table 2 below.
（１）乾燥した基材鋼面の防食性試験
寸法が１５０ｍｍ×７０ｍｍ×１．６ｍｍ（厚）のブラスト処理された鋼板（以下「試験板」ともいう。）の表面に防食塗料組成物を塗装する前に、温度２３℃、湿度５０％で１時間乾燥させ、基材鋼板表面に遊離した水分が付着していないことを目視で確認した。この試験板に、表２に示す防食塗料組成物を、キシレン：ＰＧＭ＝２：１の希釈用シンナーで混合物粘度を２０ポイズ（リオン粘度計で測定）に調整後、乾燥膜厚が約２５０μｍとなるようにそれぞれエアレススプレー（１次（空気）圧：０．６ＭＰａ、２次（空気）圧：１８ＭＰａ）で塗装し、ＪＩＳ Ｋ−５６００ １−６に準拠して、２３℃、５０％ＲＨの雰囲気で７日間乾燥することで、各防食塗膜付き試験板を作成し、下記耐塩水性試験、塩水噴霧試験、耐高温高湿性試験により防食性を評価した。
(1) Corrosion protection test on dried base steel surface The anticorrosion paint composition is applied to the surface of a blasted steel plate (hereinafter also referred to as “test plate”) having dimensions of 150 mm × 70 mm × 1.6 mm (thickness). Before the drying, the substrate was dried at a temperature of 23 ° C. and a humidity of 50% for 1 hour, and it was visually confirmed that no free moisture was attached to the surface of the base steel plate. After adjusting the viscosity of the mixture to 20 poise (measured with a Rion viscometer) on the test plate using a thinner for dilution of xylene: PGM = 2: 1, the anticorrosion coating composition shown in Table 2 was dried to a dry film thickness of about 250 μm. Each was coated with an airless spray (primary (air) pressure: 0.6 MPa, secondary (air) pressure: 18 MPa), and at 23 ° C. and 50% RH according to JIS K-5600 1-6. By drying in an atmosphere for 7 days, test plates with each anticorrosion coating film were prepared, and the anticorrosion properties were evaluated by the following salt water resistance test, salt water spray test, and high temperature / high humidity resistance test.
耐塩水性試験
前記（１）で作成した各防食塗膜付き試験板を、ＪＩＳ Ｋ−５６００ ６−１に準拠し、４０℃の塩水（塩分濃度３％）中に１８０日間浸漬した後の防食塗膜の外観を、下記基準に従って目視評価した。
Salt water resistance test The test plate with each anticorrosion coating film prepared in the above (1) was immersed in salt water (salt concentration: 3%) at 40 ° C. for 180 days in accordance with JIS K-5600 6-1. The appearance of the film was visually evaluated according to the following criteria.
塩水噴霧試験
前記（１）で作成した各防食塗膜付き試験板を、ＪＩＳ Ｋ−５６００ ７−１に準拠し、３５±２℃のスプレーキャビネット内に入れ、塩水（塩分濃度５％）を連続的に１８０日間噴霧した後の防食塗膜の外観を、下記基準に従って目視評価した。
Salt spray test Each test plate with an anticorrosion coating film prepared in the above (1) was placed in a spray cabinet at 35 ± 2 ° C according to JIS K-5600 7-1, and salt water (salt concentration 5%) was continuously applied. The appearance of the anticorrosion coating after spraying for 180 days was visually evaluated according to the following criteria.
耐高温高湿性試験
前記（１）で作成した各防食塗膜付き試験板を、ＪＩＳ Ｋ−５６００ ７−２に準拠し、温度５０±１℃、湿度９５％以上の高温高湿試験器内に１８０日間保持した後の防食塗膜の外観を、下記基準に従って評価した。
（評価基準）
○：フクレ、割れ、サビ、はがれ、色相のいずれも変化なし。
△：フクレ、割れ、サビ、はがれ、色相のいずれかに若干の欠陥（変化）が認められる。
×：フクレ、割れ、サビ、はがれ、色相のいずれかに明らかな欠陥（変化）が認められる。
High-temperature and high-humidity test Each test plate with an anticorrosion coating film prepared in the above (1) was placed in a high-temperature and high-humidity tester having a temperature of 50 ± 1 ° C and a humidity of 95% or more in accordance with JIS K-5600 7-2. The appearance of the anticorrosion coating film after holding for 180 days was evaluated according to the following criteria.
(Evaluation criteria)
：: No blister, crack, rust, peeling, hue change.
Δ: Some defects (changes) are observed in any of blisters, cracks, rust, peeling, and hue.
×: A clear defect (change) is recognized in any of blisters, cracks, rust, peeling, and hue.
（２）湿潤面を有する基材鋼面の防食性試験
試験板の表面に対して、防食塗料組成物を塗装する直前に、０．２ｇ（１９ｇ／ｍ２）となるように霧吹きで水を吹き付けて均一に付着させ、試験板表面に遊離した水分が付着していることを目視で確認した。続いて、表２に示す各防食塗料組成物を、前記（１）と同様にして塗装、乾燥することで各防食性試験板を作成し、（１）と同様に耐塩水性試験、塩水噴霧試験、耐高温高湿性試験により防食性を評価した。
(2) Corrosion protection test on base steel surface having wet surface Immediately before applying the anticorrosion paint composition to the surface of the test plate, water was sprayed by spraying so as to become 0.2 g (19 g / m 2 ). Spraying was performed to make the sample adhere evenly, and it was visually confirmed that free moisture had adhered to the surface of the test plate. Subsequently, each anticorrosion paint composition shown in Table 2 was applied and dried in the same manner as in the above (1) to prepare each anticorrosion test plate, and the salt water resistance test and the salt spray test were carried out in the same manner as in (1). The anti-corrosion property was evaluated by a high temperature and high humidity resistance test.
（３）乾燥した基材鋼板への付着性試験
試験板の表面に防食塗料組成物を塗装する前に、温度２３℃、湿度５０％で1時間乾燥させ、基材鋼板表面に遊離した水分が付着していないことを目視で確認した。続いて、表２に示す各防食塗料組成物を、前記（１）と同様にして塗装、乾燥することで各付着性試験板を作成した。
(3) Adhesion test on dried base steel sheet Before coating the anticorrosion coating composition on the surface of the test plate, the coating was dried at a temperature of 23 ° C. and a humidity of 50% for 1 hour, and moisture released on the base steel plate surface was reduced. It was visually confirmed that there was no adhesion. Subsequently, each anticorrosion paint composition shown in Table 2 was applied and dried in the same manner as in the above (1) to prepare each adhesion test plate.
その後、得られた各上塗り付着性試験板を４０℃の塩水（塩分濃度３％）中に３０日間浸漬した後の付着性を以下の方法で評価した。 Thereafter, each of the resulting topcoat adhesion test plates was immersed in salt water (salt concentration: 3%) at 40 ° C. for 30 days, and the adhesion was evaluated by the following method.
前記各付着性試験板（鋼板／防食塗膜の２層構成）の表面に、図１に示すように、試験板表面（防食塗膜１）に４ｃｍの切り込みが３０°で交差するＸ字状の切り込み２を、鋼板の表面に届く深さまで入れた。 On the surface of each of the adhesion test plates (two-layered structure of steel plate / anticorrosion coating), as shown in FIG. Cut 2 was made to a depth that reached the surface of the steel sheet.
次いで、Ｘ字状の切り込みを入れた部位３にセロハン粘着テープを貼り付け、テープの一端を防食塗膜面に対し９０°に近い角度で引き剥がすことで、防食塗膜の剥離状況（剥離率）を評価した。ここで、剥離率は、切り込みを入れた部位３に対する、試験板から剥離した防食塗膜の面積の割合を目視により概算し、鋼板と防食塗膜間の付着性を評価した。
Next, a cellophane adhesive tape is attached to the
なお、本発明に係る防食塗料組成物は、鋼板と防食塗膜間の付着性試験結果における剥離率が面積の全体の２０％以下であれば、実用上問題なく使用できる。
（評価基準）
○：全く剥離が認められない。
○△：全体の５％未満が剥離している。
△：全体の５〜２０％が剥離している。
×：全体の２０％を超える部分が剥離している。
In addition, the anticorrosion coating composition according to the present invention can be used without any practical problem if the peeling rate in the adhesion test result between the steel sheet and the anticorrosion coating film is 20% or less of the entire area.
(Evaluation criteria)
：: No peeling was observed at all.
△: Less than 5% of the whole is peeled.
Δ: 5 to 20% of the whole is peeled off.
X: Exceeding 20% of the whole.
（４）湿潤面を有する基材鋼板面（Ｉ）への付着性
試験板の表面に対して、防食塗料組成物を塗装する直前に、０．１ｇ（９．５ｇ／ｍ２）となるように霧吹きで水を吹き付けて均一に付着させ、試験板表面に遊離した水分が付着していることを目視で確認した。ここで、この状態の試験板表面を『湿潤面を有する基材鋼板面（Ｉ）』とする。続いて直ちに（水分量を確認後３分以内）、表２に示す各防食塗料組成物を前記（１）と同様にして塗装、乾燥することで、各付着性試験板を作成した。
その後、得られた各付着性試験板を４０℃の塩水（塩分濃度３％）中に３０日間浸漬した後、前記（３）と同様にして付着性を評価した。
(4) 0.1 g (9.5 g / m 2 ) immediately before the anticorrosion coating composition is applied to the surface of the test plate that adheres to the base steel plate surface (I) having a wet surface. Water was sprayed onto the test plate to make it adhere evenly, and it was visually confirmed that free moisture had adhered to the surface of the test plate. Here, the test plate surface in this state is referred to as “substrate steel plate surface having a wet surface (I)”. Then, immediately (within 3 minutes after confirming the water content), each of the anticorrosion coating compositions shown in Table 2 was applied and dried in the same manner as in (1) to prepare each adhesion test plate.
Thereafter, each of the obtained adhesion test plates was immersed in salt water (salt concentration: 3%) at 40 ° C. for 30 days, and the adhesion was evaluated in the same manner as in the above (3).
（５）湿潤面を有する基材鋼板（ＩＩ）への付着性
試験板の表面に対して、防食塗料組成物を塗装する直前に、０．２ｇ（１９ｇ／ｍ２）となるように霧吹きで水を吹き付けて均一に付着させ、試験板表面に遊離した水分が付着していることを目視で確認した。ここで、この状態の試験板表面を『湿潤面を有する基材鋼板面（ＩＩ）』とする。
その後、前記（４）と同様にして付着性を評価した。
(5) Adhesion to the base steel plate (II) having a wet surface Immediately before applying the anticorrosion coating composition to the surface of the test plate, spraying was performed so that the amount became 0.2 g (19 g / m 2 ). Water was sprayed to uniformly adhere, and it was visually confirmed that free moisture had adhered to the test plate surface. Here, the test plate surface in this state is referred to as “substrate steel plate surface having wet surface (II)”.
Thereafter, the adhesion was evaluated in the same manner as in the above (4).
表３の試験結果から明らかなように、本発明で規定する諸条件を満たす塗料組成物を用いることにより、乾燥した基材鋼板表面はもとより、湿潤面を有する基材鋼板に対しても、防食性に優れるとともに、良好な付着性を有する塗膜を形成することができる。 As is evident from the test results in Table 3, the use of the coating composition satisfying the conditions specified in the present invention prevents corrosion not only on the surface of the dried base steel plate but also on the base steel plate having a wet surface. It is possible to form a coating film having excellent adhesion and good adhesion.
１：防食塗膜
２：Ｘ字状の切り込み
３：切り込みを入れた部位
1: Anticorrosion coating 2: X-shaped cut 3: Site with cut
Claims (6)
エポキシ樹脂（Ａ）と、
ポリオキシアルキレンポリアミン類、マンニッヒ変性アミン類及びケチミン類から選ばれる少なくとも１種のアミン硬化剤（Ｂ）と、
上記塗料組成物１００重量部（不揮発分）に対して１〜１５重量部の水（Ｃ）と、
水酸基含有変性樹脂（Ｄ）と、
を含み、
前記アミン硬化剤（Ｂ）が、少なくともポリオキシアルキレンポリアミン類を含むことを特徴とする防食塗料組成物。 A paint composition that can be applied to the wet surface of the base steel sheet,
Epoxy resin (A),
At least one amine curing agent (B) selected from polyoxyalkylene polyamines, Mannich-modified amines and ketimines;
1 to 15 parts by weight of water (C) with respect to 100 parts by weight of the coating composition (non-volatile content);
A hydroxyl-containing modified resin (D),
Only including,
The anticorrosive coating composition, wherein the amine curing agent (B) contains at least a polyoxyalkylene polyamine .
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