JP2018020486A - Anti-corrosive coating structure - Google Patents
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Abstract
Description
本発明は、基材の防食を図る塗膜構造に関する。 The present invention relates to a coating film structure for preventing corrosion of a substrate.
従来、構造物や種々の装置を構成する部材の防食を図るため、部材の基材表面へのコーティングが行われてきた。例えば、クロムを含有する塗料を使用して部材の基材表面に下塗り塗膜を施すと、塗膜自体の耐食性と、塗膜の損傷時にクロムが溶出して基材表面を覆う自己修復作用により、優れた防食性能を実現することができる。 Conventionally, in order to prevent corrosion of members constituting structures and various apparatuses, the surface of the base material of the members has been coated. For example, when a primer coating is applied to the substrate surface of a member using a paint containing chromium, the corrosion resistance of the coating itself and the self-healing action to cover the substrate surface by elution of chromium when the coating is damaged Excellent anticorrosion performance can be realized.
近年は、環境への適合性の観点から、クロムを使用しない防食技術が提案されている。
特許文献１は、モリブデンの酸化物や、タングステンの酸化物を含む腐食抑制組成物によって基材にコーティングを施すことを提案している。
In recent years, anticorrosion techniques that do not use chromium have been proposed from the viewpoint of compatibility with the environment.
Patent Document 1 proposes that a substrate is coated with a corrosion-inhibiting composition containing molybdenum oxide or tungsten oxide.
特許文献１をはじめとして、クロムを使用することなく防食可能な塗膜の組成等について検討がなされてきたが、未だ、十分な防食性能を実現するには至っていない。
特に、塗り直し等のメンテナンスが困難あるいは不可能な場所に配置される部材に関しては、基材を被覆する塗膜により基材の腐食を阻害する作用と、塗膜の損傷時の自己修復作用とにより、きわめて長期間に亘り防食性能を担保することが要求される。
Starting with Patent Document 1, studies have been made on the composition of a coating film that can be prevented from corrosion without using chromium, but it has not yet achieved sufficient corrosion resistance.
In particular, for members placed in places where maintenance such as repainting is difficult or impossible, the action of inhibiting the corrosion of the base material by the coating film covering the base material and the self-healing action when the paint film is damaged Therefore, it is required to ensure the anticorrosion performance for a very long time.
以上より、本発明は、クロムフリーでありながら、十分な防食性能を実現できる塗膜構造を提供することを目的とする。 In view of the above, an object of the present invention is to provide a coating film structure capable of realizing sufficient anticorrosion performance while being chromium-free.
本発明の塗膜構造は、被防食材である基材の表面部を被覆し、表面部よりもイオン化傾向の大きい犠牲防食剤を含有する第１塗膜と、第１塗膜に積層された第２塗膜と、を備え、第２塗膜は、第２塗膜から溶出可能であって、第１塗膜および第２塗膜の損傷により露出した基材に付着する腐食抑制剤を含有することを特徴とする。 The coating film structure of the present invention was laminated on the first coating film and the first coating film which covered the surface portion of the base material which is an anticorrosive material and contained a sacrificial anticorrosive agent having a higher ionization tendency than the surface portion. A second coating film, and the second coating film can be eluted from the second coating film and contains a corrosion inhibitor that adheres to the substrate exposed by damage to the first coating film and the second coating film. It is characterized by doing.
本発明の塗膜構造では、犠牲防食剤として、マグネシウムが用いられていることが好ましい。 In the coating film structure of the present invention, magnesium is preferably used as the sacrificial anticorrosive agent.
本発明の塗膜構造では、第１塗膜は、２５〜４０ｗｔ％のマグネシウムを含有することが好ましい。
本明細書において、上記のように「Ａ〜Ｂ」の書式で記載された数値範囲は、Ａ以上、Ｂ以下を意味する。
In the coating film structure of the present invention, the first coating film preferably contains 25 to 40 wt% magnesium.
In the present specification, the numerical range described in the format of “A to B” as described above means A or more and B or less.
本発明の塗膜構造では、腐食抑制剤として、硝酸セリウムが用いられていることが好ましい。 In the coating film structure of the present invention, cerium nitrate is preferably used as a corrosion inhibitor.
本発明の塗膜構造において、第２塗膜は、３〜６ｗｔ％の硝酸セリウムを含有することが好ましい。 In the coating film structure of the present invention, the second coating film preferably contains 3 to 6 wt% of cerium nitrate.
本発明の塗膜構造において、第１塗膜は、犠牲防食剤が分散されるエポキシ系樹脂を含有することが好ましい。 In the coating film structure of the present invention, the first coating film preferably contains an epoxy resin in which a sacrificial anticorrosive is dispersed.
本発明の塗膜構造において、第２塗膜は、腐食抑制剤が分散されるエポキシ系樹脂を含有することが好ましい。 In the coating film structure of the present invention, the second coating film preferably contains an epoxy resin in which a corrosion inhibitor is dispersed.
本発明の塗膜構造によれば、クロム等、環境負荷が大きい物質の使用を回避しつつ、第１塗膜による犠牲防食作用と第２塗膜による自己修復作用とにより、十分な防食性能を確保することができる。 According to the coating film structure of the present invention, sufficient anticorrosion performance is achieved by the sacrificial anticorrosion action by the first coating film and the self-repairing action by the second coating film while avoiding the use of a substance having a large environmental load such as chromium. Can be secured.
以下、添付図面を参照しながら、本発明の実施形態について説明する。
図１は、被防食材としての基材１０の表面部１０Ａに施された塗膜構造２０を示している。
基材１０は、種々の構造物や装置の部材を構成しており、アルミニウム合金から形成されている。
基材１０は、部材の用途に適合する他の金属材料、例えば、ステンレス鋼材やチタン合金等から形成することもできる。
Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings.
FIG. 1 shows a coating film structure 20 applied to a surface portion 10A of a base material 10 as an anticorrosive material.
The base material 10 constitutes members of various structures and apparatuses, and is formed from an aluminum alloy.
The base material 10 can also be formed from other metal materials suitable for the use of the member, for example, a stainless steel material or a titanium alloy.
塗膜により防食を十分に図るにあたっては、基材１０の表面部１０Ａを全体的に被覆することで、水や酸素等の腐食因子が基材１０の表面部１０Ａに侵入するのを抑制し、かつ酸化皮膜の形成や犠牲防食作用により基材１０の腐食を阻害することに加えて、基材１０への衝撃や摩擦等を想定して塗膜の損傷時にも防食性能を維持することが要求される。 In sufficiently anticorrosion with the coating film, by covering the surface portion 10A of the base material 10 as a whole, it is possible to suppress the entry of corrosion factors such as water and oxygen into the surface portion 10A of the base material 10, In addition to inhibiting the corrosion of the base material 10 by the formation of an oxide film and sacrificial anticorrosive action, it is required to maintain the anticorrosion performance even when the coating film is damaged assuming an impact or friction on the base material 10. Is done.
塗膜構造２０は、犠牲防食作用により基材１０の腐食を阻害する機能を担う第１塗膜２１と、塗膜の損傷時に防食性能を回復する自己修復機能を担う第２塗膜２２とを備えている。
第１塗膜２１は、基材１０の表面部１０Ａを被覆しており、第２塗膜２２は、第１塗膜２１に積層されている。
The coating film structure 20 includes a first coating film 21 that has a function of inhibiting the corrosion of the base material 10 by sacrificial anticorrosive action, and a second coating film 22 that has a self-repairing function that restores the anticorrosion performance when the coating film is damaged. I have.
The first coating film 21 covers the surface portion 10 </ b> A of the substrate 10, and the second coating film 22 is laminated on the first coating film 21.
第１塗膜２１および第２塗膜２２は、それぞれ、所定の膜厚で形成されている。第１塗膜２１および第２塗膜２２の合計の厚みｔは、例えば、２０〜１００μｍである。第１塗膜２１の厚みｔ１は、例えば、１０〜５０μｍである。第２塗膜２２の厚みｔ２は、例えば、１０〜５０μｍである。
第１、第２塗膜２１，２２のそれぞれの厚みｔ１，ｔ２および全体の厚みｔは、部材に要求される防食性能に応じて適宜に定めることができる。
The first coating film 21 and the second coating film 22 are each formed with a predetermined film thickness. The total thickness t of the first coating film 21 and the second coating film 22 is, for example, 20 to 100 μm. The thickness t1 of the first coating film 21 is, for example, 10 to 50 μm. The thickness t2 of the second coating film 22 is, for example, 10 to 50 μm.
The thicknesses t1 and t2 of the first and second coating films 21 and 22 and the overall thickness t can be appropriately determined according to the anticorrosion performance required for the member.
塗膜構造２０の上に、単一または複数の塗膜を積層することができる。例えば、外観装飾や耐衝撃等の目的に適した種々の塗料を塗膜構造２０に塗り重ねることができる。他の塗膜が積層される場合、塗膜構造２０は、下塗り塗膜（プライマ）に相当する。
塗膜構造２０は、上塗り塗装なしで使用することもできる。例えば、構造物の内部に配置される部材に塗膜構造２０が設けられる場合は、上塗り塗装なしで使用することができる。
本実施形態の塗膜構造２０に他の塗膜が積層されていたとしても、塗膜構造２０のみを図示して説明する。
Single or multiple coatings can be laminated on the coating structure 20. For example, various coating materials suitable for purposes such as appearance decoration and impact resistance can be applied to the coating film structure 20. When another coating film is laminated, the coating film structure 20 corresponds to an undercoat coating film (primer).
The coating structure 20 can also be used without a top coat. For example, when the coating film structure 20 is provided on a member disposed inside the structure, it can be used without top coating.
Even if another coating film is laminated on the coating film structure 20 of the present embodiment, only the coating film structure 20 will be illustrated and described.
以下、塗膜構造２０の第１塗膜２１および第２塗膜２２の各々の構成を説明する。
第１塗膜２１は、噴霧、浸漬、塗布、静電粉体塗装等の適宜な方法で供給された塗料が固化して表面部１０Ａに付着したものである。第１塗膜２１は、単一の層、あるいは、塗料の供給および固化を繰り返して塗り重ねられた複数の層から構成することができる。
なお、第２塗膜２２も、適宜な方法で供給された塗料が固化して第１塗膜２１に付着したものであり、単一の層、あるいは、塗り重ねられた複数の層から構成することができる。
Hereinafter, each structure of the 1st coating film 21 of the coating-film structure 20 and the 2nd coating film 22 is demonstrated.
The first coating film 21 is obtained by solidifying a paint supplied by an appropriate method such as spraying, dipping, coating, electrostatic powder coating, etc., and adhering to the surface portion 10A. The first coating film 21 can be composed of a single layer or a plurality of layers that are repeatedly applied by repeatedly supplying and solidifying the paint.
In addition, the 2nd coating film 22 is also a thing which the coating material supplied with the appropriate method solidified, and adhered to the 1st coating film 21, and is comprised from a single layer or the several layer by which it was repeated. be able to.
図１に示す第１塗膜２１は、基材１０において防食が図られる領域の表面部１０Ａ全体に亘り設けられている。
第１塗膜２１は、詳しい図示を省略するが、表面部１０Ａよりもイオン化傾向が大きい犠牲防食剤と、犠牲防食剤が分散される樹脂と、必要に応じて乾燥剤や分散剤等の少量の添加剤と、を備えている。
第１塗膜２１は、犠牲防食材、樹脂、および添加剤に溶剤や水が加えられた塗料を用いて表面部１０Ａに設けられている。かかる塗料は、溶剤や、添加剤の一部が揮発し、その他が第１塗膜２１として残存する。
The first coating film 21 shown in FIG. 1 is provided over the entire surface portion 10 </ b> A in the region where the anticorrosion is achieved in the base material 10.
Although detailed illustration is omitted, the first coating film 21 is a sacrificial anticorrosive having a higher ionization tendency than the surface portion 10A, a resin in which the sacrificial anticorrosive is dispersed, and a small amount of a desiccant or a dispersant as necessary. And additives.
The 1st coating film 21 is provided in 10 A of surface parts using the sacrificial anticorrosive material, resin, and the coating material with which the solvent and water were added to the additive. In such a paint, a part of the solvent and the additive is volatilized, and the other remains as the first coating film 21.
犠牲防食剤の粒子は直接にあるいは間接に基材１０と接触しているため、犠牲防食剤は全体的に基材１０と接触している。つまり、犠牲防食剤の粒子のうち第１塗膜２１と基材１０との界面に位置する粒子は基材１０と直接的に接触し、界面とは離れている粒子であっても、他の犠牲防食剤粒子を介して間接的に基材１０と接触している。
犠牲防食剤をアノード、基材１０をカソードとして局部電池が形成されることにより、犠牲防食剤は犠牲的に腐食する。
Since the sacrificial anticorrosive particles are in contact with the substrate 10 directly or indirectly, the sacrificial anticorrosive is in contact with the substrate 10 as a whole. That is, among the sacrificial anticorrosive particles, the particles located at the interface between the first coating film 21 and the substrate 10 are in direct contact with the substrate 10 and are separated from the interface. Indirect contact with the substrate 10 via the sacrificial anticorrosive particles.
The sacrificial anticorrosive is sacrificially corroded by forming the local cell with the sacrificial anticorrosive as the anode and the substrate 10 as the cathode.
本実施形態では、アルミニウム合金を用いて形成された基材１０の表面部１０Ａに設けられる犠牲防食剤として、マグネシウムを採用している。亜鉛やアルミニウム等と比べて比重の小さいマグネシウムを採用することで、塗膜構造２０の軽量化に寄与する。
本実施形態の第１塗膜２１は、マグネシウムの微粒子と、マグネシウムの微粒子が分散されるエポキシ系樹脂と、を備えて構成されている。エポキシ系樹脂により、第１塗膜２１は表面部１０Ａに接着されている。
犠牲防食剤としては、マグネシウムの他にも、基材１０の材料に比べてイオン化傾向が大きいものを用いることができる。例えば、亜鉛等の金属を犠牲防食剤として用いることができる。
犠牲防食剤が分散される樹脂としては、エポキシ系樹脂の他に、例えば、アクリル系樹脂、フッ素系樹脂等を用いることもできる。
In the present embodiment, magnesium is employed as the sacrificial anticorrosive provided on the surface portion 10A of the base material 10 formed using an aluminum alloy. By adopting magnesium having a specific gravity lower than that of zinc, aluminum or the like, it contributes to weight reduction of the coating film structure 20.
The first coating film 21 of the present embodiment includes magnesium fine particles and an epoxy resin in which the magnesium fine particles are dispersed. The 1st coating film 21 is adhere | attached on the surface part 10A with the epoxy resin.
As the sacrificial anticorrosive agent, in addition to magnesium, those having a greater ionization tendency than the material of the substrate 10 can be used. For example, a metal such as zinc can be used as a sacrificial anticorrosive.
As the resin in which the sacrificial anticorrosive is dispersed, for example, an acrylic resin, a fluorine resin, or the like can be used in addition to the epoxy resin.
次に、第２塗膜２２は、図１に示すように、第１塗膜２１の表面２１Ａを被覆している。 Next, the second coating film 22 covers the surface 21A of the first coating film 21 as shown in FIG.
第２塗膜２２は、基材１０の腐食を抑制するための腐食抑制剤（インヒビター）２２１と、腐食抑制剤２２１が分散された樹脂２２２と、必要に応じて少量の添加剤（図示せず）とを備えている。腐食抑制剤２２１は、模式的に図示されている。各図において、腐食抑制剤２２１の粒径や第１、第２塗膜２１，２２の厚みを具体的に示す意図はない。
第２塗膜２２は、第１塗膜２１を基材１０の表面部１０Ａに設けた後、腐食抑制剤２２１、樹脂２２２、および添加剤に溶剤が加えられた塗料を用いて第１塗膜２１の表面２１Ａに設けられている。かかる塗料は、溶剤や、添加剤の一部が揮発し、その他が第２塗膜２２として残存する。
The second coating film 22 includes a corrosion inhibitor (inhibitor) 221 for suppressing corrosion of the substrate 10, a resin 222 in which the corrosion inhibitor 221 is dispersed, and a small amount of additives (not shown) as necessary. ). The corrosion inhibitor 221 is schematically illustrated. In each figure, there is no intention to specifically show the particle size of the corrosion inhibitor 221 and the thicknesses of the first and second coating films 21 and 22.
After the first coating film 21 is provided on the surface portion 10A of the base material 10, the second coating film 22 is formed by using a corrosion inhibitor 221, a resin 222, and a paint in which a solvent is added to the additive. 21 is provided on the surface 21A. In such a paint, a part of the solvent and the additive is volatilized, and the other remains as the second coating film 22.
第２塗膜２２は、第１塗膜２１および第２塗膜２２が損傷して基材１０の素地が露出したとしても（図２（ｂ）参照）、水分に腐食抑制剤２２１が溶出し、露出した基材１０に付着することで、塗膜構造２０による防食性能を担保する。
仮に、塗膜構造２０が第２塗膜２２を備えておらず、第１塗膜２１のみを備えているとすれば、後述する比較例１と同様に、露出した部位から基材１０の腐食が進行してしまう。
Even if the 1st coating film 21 and the 2nd coating film 22 are damaged and the base material of the base material 10 is exposed as for the 2nd coating film 22, the corrosion inhibitor 221 elutes to a water | moisture content. By adhering to the exposed base material 10, the anticorrosion performance by the coating film structure 20 is ensured.
If the coating film structure 20 does not include the second coating film 22 but includes only the first coating film 21, the corrosion of the base material 10 from the exposed portion as in Comparative Example 1 described later. Will progress.
腐食抑制剤２２１としては、例えば、六価クロムと類似の作用が見込める硝酸セリウム（Ｃｅ（ＮＯ３）３）を採用することができる。本実施形態の第２塗膜２２は、硝酸セリウムの微粒子（２２１）と、硝酸セリウムの微粒子が分散されたエポキシ系樹脂（２２２）とを備えて構成されている。エポキシ系樹脂により、第２塗膜２２は第１塗膜２１の表面２１Ａに接着されている。
硝酸セリウムの種々の化合物、例えば、硝酸セリウム(III)アンモニウム四水和物、硝酸セリウム(IV)アンモニウム、硝酸セリウム(III)六水和物 (Ce(NO3)3・6H2O)のいずれをも腐食抑制剤２２１として使用できる。
腐食抑制剤が分散される樹脂２２２としては、エポキシ系樹脂には限らず、例えば、アクリル系樹脂、フッ素系樹脂等を用いることもできる。
As the corrosion inhibitor 221, for example, cerium nitrate (Ce (NO 3 ) 3 ) that can be expected to have a similar effect to hexavalent chromium can be employed. The second coating film 22 of the present embodiment includes cerium nitrate fine particles (221) and an epoxy resin (222) in which cerium nitrate fine particles are dispersed. The second coating film 22 is bonded to the surface 21 </ b> A of the first coating film 21 with an epoxy resin.
Various compounds of cerium nitrate, such as cerium (III) ammonium tetrahydrate, cerium (IV) ammonium nitrate, cerium (III) nitrate hexahydrate (Ce (NO 3 ) 3 6H 2 O) Can also be used as the corrosion inhibitor 221.
The resin 222 in which the corrosion inhibitor is dispersed is not limited to an epoxy resin, and for example, an acrylic resin, a fluorine resin, or the like can be used.
図２を参照し、塗膜構造２０による防食の作用について説明する。
図２（ａ）は、損傷していない状態の塗膜構造２０を示している。このとき、基材１０の表面部１０Ａを覆う第１塗膜２１に含まれている犠牲防食剤が基材１０の代わりに腐食する犠牲防食の機能を発現することで、基材１０の腐食が阻害される。その犠牲防食作用に加え、第１塗膜２１および第２塗膜２２からなる積層塗膜により基材１０の表面部１０Ａが覆われていて基材１０への腐食因子の侵入が抑えられていることも防食に寄与する。
本実施形態の塗膜構造２０は、単一の塗膜によっては実現困難な高い防食性能を実現する。
With reference to FIG. 2, the anticorrosive action by the coating film structure 20 will be described.
FIG. 2A shows the coating structure 20 in an undamaged state. At this time, the sacrificial anticorrosive contained in the first coating film 21 covering the surface portion 10 </ b> A of the base 10 exhibits a sacrificial anticorrosive function that corrodes instead of the base 10, so that the base 10 is not corroded. Be inhibited. In addition to the sacrificial anticorrosive action, the surface portion 10A of the substrate 10 is covered with the laminated coating film composed of the first coating film 21 and the second coating film 22, and the invasion of the corrosion factor into the substrate 10 is suppressed. That also contributes to corrosion protection.
The coating film structure 20 of the present embodiment realizes high anticorrosion performance that is difficult to achieve with a single coating film.
図２（ｂ）は、衝突や摩擦等によって塗膜構造２０が損傷して基材１０が露出した状態を示している。表面部１０Ａを覆っていた塗膜構造２０の一部が欠損し、塗膜構造２０が欠損した範囲において基材１０が露出している。
塗膜構造２０の損傷により基材１０が露出すると、それまで第２塗膜２２の内部に保持されていた腐食抑制剤２２１が、腐食抑制剤２２１の水溶性に基づいて、第２塗膜２２の破断した部分２２Ｂから第２塗膜２２の外部へと容易に溶出する。腐食抑制剤２２１は、第２塗膜２２中の水分に接触し陽イオン化して第２塗膜２２の樹脂分子の間を拡散移動し、破断部分２２Ｂに至る（図２（ｂ）の破線矢印参照）。破断部分２２Ｂから第２塗膜２２の外部へと溶出した腐食抑制剤２２１は、図２（ｃ）に示すように、基材１０の露出した領域１０１に付着し、酸化皮膜２２１Ａを形成する。
FIG. 2B shows a state in which the base material 10 is exposed due to damage to the coating film structure 20 due to collision or friction. A part of the coating film structure 20 covering the surface portion 10A is lost, and the substrate 10 is exposed in a range where the coating film structure 20 is lost.
When the base material 10 is exposed due to damage to the coating film structure 20, the corrosion inhibitor 221 that has been held inside the second coating film 22 until then is based on the water solubility of the corrosion inhibitor 221. It elutes easily from the broken portion 22B to the outside of the second coating film 22. The corrosion inhibitor 221 comes into contact with moisture in the second coating film 22 to be cationized, diffusely move between the resin molecules of the second coating film 22, and reach the fracture portion 22B (broken line arrow in FIG. 2B). reference). As shown in FIG. 2C, the corrosion inhibitor 221 eluted from the broken portion 22B to the outside of the second coating film 22 adheres to the exposed region 101 of the base material 10 to form an oxide film 221A.
腐食抑制剤２２１は、表面部１０Ａの露出した領域１０１の周囲に位置する第２塗膜２２の破断部分２２Ｂから溶出し、露出領域１０１の広い範囲に付着して酸化皮膜２２１Ａを形成する。その酸化皮膜２２１Ａにより基材１０が覆われていることで、領域１０１の基材１０の腐食を阻害する機能が発現する。つまり、塗膜構造２０は、腐食抑制剤２２１の作用によって自己修復されたと言える。塗膜構造２０は、損傷した箇所に防食機能を回復する自己修復機能を有している。 The corrosion inhibitor 221 elutes from the fractured portion 22B of the second coating film 22 located around the exposed area 101 of the surface portion 10A and adheres to a wide area of the exposed area 101 to form the oxide film 221A. Since the base material 10 is covered with the oxide film 221 </ b> A, a function of inhibiting the corrosion of the base material 10 in the region 101 appears. That is, it can be said that the coating film structure 20 was self-repaired by the action of the corrosion inhibitor 221. The coating film structure 20 has a self-repairing function for recovering the anticorrosion function at the damaged portion.
以下、損傷箇所に対する腐食試験の結果について、比較例１および比較例２と比較しながら説明する。
（比較例１）
比較例１では、図３（ａ）に示すように、基材１０の表面部１０Ａに、犠牲防食剤としてのマグネシウムを約３５ｗｔ％含有する単一の塗膜３１が施された試験片を用いる。塗膜３１は、マグネシウムの他に、エポキシ系樹脂と、添加剤を含んでおり、マグネシウムの粒子がエポキシ系樹脂に分散されている。
塗膜３１には、腐食抑制剤２２１を含有する塗膜は積層されていない。
Hereinafter, the results of the corrosion test on the damaged part will be described in comparison with Comparative Example 1 and Comparative Example 2.
(Comparative Example 1)
In Comparative Example 1, as shown in FIG. 3A, a test piece in which a single coating film 31 containing about 35 wt% of magnesium as a sacrificial anticorrosive is applied to the surface portion 10A of the substrate 10 is used. . The coating film 31 contains an epoxy resin and an additive in addition to magnesium, and magnesium particles are dispersed in the epoxy resin.
A coating film containing the corrosion inhibitor 221 is not laminated on the coating film 31.
（比較例２）
比較例２では、図４（ａ）に示すように、基材１０の表面部１０Ａに、単一の塗膜３０が施された試験片を用いる。
塗膜３０は、犠牲防食剤（図示しない）としてのマグネシウムを約３５ｗｔ％含有するとともに、腐食抑制剤３０１としての硝酸セリウムを約３．８ｗｔ％含有する。この塗膜３０は、その他に、エポキシ系樹脂と、添加剤を含んでおり、マグネシウムの粒子および硝酸セリウムの粒子がエポキシ系樹脂に分散されている。
比較例２の腐食抑制剤３０１には、本実施形態の第２塗膜２２が含有する硝酸セリウムと同一の硝酸セリウムを使用する。
(Comparative Example 2)
In Comparative Example 2, as shown in FIG. 4A, a test piece in which a single coating film 30 is applied to the surface portion 10 </ b> A of the base material 10 is used.
The coating film 30 contains about 35 wt% magnesium as a sacrificial anticorrosive (not shown) and contains about 3.8 wt% cerium nitrate as the corrosion inhibitor 301. In addition, the coating film 30 contains an epoxy resin and an additive, and magnesium particles and cerium nitrate particles are dispersed in the epoxy resin.
For the corrosion inhibitor 301 of Comparative Example 2, the same cerium nitrate as the cerium nitrate contained in the second coating film 22 of the present embodiment is used.
（本実施形態）
本実施形態では、塗膜構造２０（図１）を備えた試験片を用いる。試験片の第１塗膜２１は、犠牲防食剤としてのマグネシウムを約３５ｗｔ％含有する。試験片の第２塗膜２２は、腐食抑制剤としての硝酸セリウムを約３．８ｗｔ％含有する。試験では、硝酸セリウム(III)六水和物を用いている。
(This embodiment)
In the present embodiment, a test piece having a coating film structure 20 (FIG. 1) is used. The 1st coating film 21 of a test piece contains about 35 wt% of magnesium as a sacrificial anticorrosive agent. The 2nd coating film 22 of a test piece contains about 3.8 wt% of cerium nitrate as a corrosion inhibitor. In the test, cerium (III) nitrate hexahydrate is used.
（腐食試験）
損傷箇所に対する腐食試験を行うにあたり、塗膜の一部を削り取って基材１０の表面部１０Ａを露出させることで、塗膜の損傷を模擬する。
塗膜の損傷を模擬した試験片を、０．５ｗｔ％のＮａＣｌを含有する４０℃の水溶液に、２４時間浸漬する。
(Corrosion test)
In performing the corrosion test on the damaged portion, the coating film is simulated to be damaged by scraping off a part of the coating film to expose the surface portion 10A of the substrate 10.
A test piece simulating damage to the coating film is immersed in a 40 ° C. aqueous solution containing 0.5 wt% NaCl for 24 hours.
（比較例１の試験結果）
図３（ｂ）は、比較例１の試験片の腐食試験後の外観を示す。図３の中央に、塗膜３１が除去されることで基材が全面的に露出した領域１０１が示され、その露出領域１０１の上下にそれぞれ隣接して、塗膜３１の施された領域１０２が示されている。図４（ｂ）および図５でも、領域１０１，１０２を同様に示している。領域１０１の幅は約１ｍｍである。
図３（ｂ）から、損傷を模擬した露出領域１０１の全体に亘り、孔食Ｐが発生していることがわかる。
比較例１の塗膜３１中のマグネシウムは水分に溶け難いため、塗膜３１の内部に留まり、基材１０の露出領域１０１には殆ど到達しない。そのため、マグネシウムによる犠牲防食の機能は、露出領域１０１においては発現されない。
なお、塗膜３１が残存している領域１０２では孔食Ｐが発生していない。
(Test result of Comparative Example 1)
FIG. 3B shows the appearance of the test piece of Comparative Example 1 after the corrosion test. In the center of FIG. 3, a region 101 where the base material is completely exposed by removing the coating film 31 is shown, and a region 102 to which the coating film 31 is applied is adjacent to the top and bottom of the exposed region 101. It is shown. 4B and 5 also show the regions 101 and 102 in the same manner. The width of the region 101 is about 1 mm.
It can be seen from FIG. 3B that pitting corrosion P has occurred over the entire exposed region 101 simulating damage.
Magnesium in the coating film 31 of Comparative Example 1 hardly dissolves in moisture, so that it stays inside the coating film 31 and hardly reaches the exposed region 101 of the substrate 10. Therefore, the sacrificial anticorrosion function by magnesium is not expressed in the exposed region 101.
Note that no pitting corrosion P occurs in the region 102 where the coating film 31 remains.
（比較例２の試験結果）
図４（ｂ）は、比較例２の試験片の腐食試験後の外観を示す。
図４（ｂ）より、露出領域１０１と隣接領域１０２との境界Ｂ付近では、腐食が抑制されているが（破線で囲んだ範囲）、境界Ｂから離れている部位では、多数の孔食Ｐが発生している。
この比較例２によると、単層の塗膜３０に含まれる腐食抑制剤３０１（硝酸セリウム）が塗膜３０から溶出したことで、境界Ｂ付近では腐食が抑制されている。
(Test result of Comparative Example 2)
FIG. 4B shows the appearance of the test piece of Comparative Example 2 after the corrosion test.
As shown in FIG. 4B, the corrosion is suppressed in the vicinity of the boundary B between the exposed region 101 and the adjacent region 102 (the range surrounded by the broken line). Has occurred.
According to the comparative example 2, the corrosion is suppressed in the vicinity of the boundary B because the corrosion inhibitor 301 (cerium nitrate) contained in the single-layer coating film 30 is eluted from the coating film 30.
（本実施形態の試験結果）
図５は、上記の比較例１，２と同じ条件で腐食試験が行われた本実施形態の試験片の外観を示す。
図５より、比較例２の試験結果（図４（ｂ））と比べて大幅に広い範囲に亘り（破線で囲んだ範囲）、基材１０の腐食が抑制されている。境界Ｂ付近に限らず、境界Ｂから離れた領域１０１の中央部でも腐食が抑制されている。
(Test results of this embodiment)
FIG. 5 shows the appearance of the test piece of the present embodiment in which the corrosion test was performed under the same conditions as in Comparative Examples 1 and 2 above.
From FIG. 5, the corrosion of the base material 10 is suppressed over a significantly wider range (the range surrounded by the broken line) than the test result of Comparative Example 2 (FIG. 4B). Corrosion is suppressed not only in the vicinity of the boundary B but also in the central portion of the region 101 away from the boundary B.
比較例２（図４（ａ））の塗膜３０と本実施形態（図２）の第２塗膜２２とのいずれにも硝酸セリウムが同じ量だけ均一に分散しているとしても、比較例２では硝酸セリウムがマグネシウムと共に単一の塗膜３０に存在しているのに対して、本実施形態では、硝酸セリウムが、マグネシウムを含有する第１塗膜２１とは別の第２塗膜２２に存在しているから、両者は塗膜構造の構成が相違している。 Even if the same amount of cerium nitrate is uniformly dispersed in both the coating film 30 of Comparative Example 2 (FIG. 4A) and the second coating film 22 of this embodiment (FIG. 2), the Comparative Example In FIG. 2, cerium nitrate is present together with magnesium in a single coating film 30, whereas in this embodiment, cerium nitrate is a second coating film 22 that is different from the first coating film 21 containing magnesium. Therefore, they are different in the structure of the coating film structure.
比較例２（図４（ａ））のように、硝酸セリウム（３０１）とマグネシウムとが同じ塗膜３０に含まれていると、水分に溶け難いマグネシウムが硝酸セリウムの移動の抵抗となる。水分に溶け難いマグネシウムの粒子が塗膜３０の内部に留まっており、しかも、マグネシウムの含有量が硝酸セリウムよりも多いため、マグネシウムは、塗膜３１内部における硝酸セリウムの拡散に対して大きな阻害要因となる。
それに対して、本実施形態（図２）では、硝酸セリウム（２２１）とマグネシウムとが別々の塗膜２２，２１に分離しているため、第２塗膜２２の内部の硝酸セリウムは、マグネシウムにより妨げられることなく容易に拡散する。硝酸セリウムは、第２塗膜２２の樹脂分子の間を通過し、第２塗膜２２の破断部分２２Ｂ（図２（ｂ））に至り、第２塗膜２２の外側に溶出して露出領域１０１の中央部にも到達する。
本実施形態によれば、比較例２と比べて硝酸セリウムが容易に拡散して塗膜外部に早期に溶出することで、基材１０の露出領域１０１が未だ腐食しないうちに基材１０に酸化皮膜２２１Ａを形成するため、露出領域１０１のより広い範囲に亘って腐食を抑制することができる。
As in Comparative Example 2 (FIG. 4A), when cerium nitrate (301) and magnesium are contained in the same coating film 30, magnesium that is difficult to dissolve in moisture becomes resistance to movement of cerium nitrate. Magnesium particles are a major obstacle to the diffusion of cerium nitrate in the coating film 31 because magnesium particles that are hardly soluble in water remain inside the coating film 30 and the magnesium content is higher than that of cerium nitrate. It becomes.
On the other hand, in this embodiment (FIG. 2), since cerium nitrate (221) and magnesium are separated into separate coatings 22 and 21, the cerium nitrate inside the second coating 22 is made of magnesium. It spreads easily without being disturbed. The cerium nitrate passes between the resin molecules of the second coating film 22, reaches the fractured portion 22B of the second coating film 22 (FIG. 2B), and elutes outside the second coating film 22 to expose the exposed area. The center part of 101 is also reached.
According to the present embodiment, cerium nitrate is easily diffused and eluted earlier than the coating film as compared with Comparative Example 2, so that the exposed region 101 of the base material 10 is oxidized to the base material 10 before it is still corroded. Since the coating 221 </ b> A is formed, corrosion can be suppressed over a wider range of the exposed region 101.
本実施形態の塗膜構造２０について、第１塗膜２１のマグネシウムの含有量を変更して上記と同様の腐食試験を行った結果、マグネシウムの含有量が２５〜４０ｗｔ％の範囲全体に亘り、上記の例（図５）と同様の防食効果を得られることが確認されている。
また、本実施形態の塗膜構造２０について、第２塗膜２２の硝酸セリウムの含有量を変更して上記と同様の腐食試験を行った結果、硝酸セリウムの含有量が３〜６ｗｔ％の範囲全体に亘り、上記の例（図５）と同様の防食効果を得られることも確認されている。
About the coating film structure 20 of this embodiment, as a result of changing the magnesium content of the first coating film 21 and performing a corrosion test similar to the above, the magnesium content spans the entire range of 25 to 40 wt%. It has been confirmed that the same anticorrosion effect as in the above example (FIG. 5) can be obtained.
Moreover, about the coating-film structure 20 of this embodiment, as a result of changing the content of cerium nitrate of the 2nd coating film 22 and performing a corrosion test similar to the above, the content of cerium nitrate is in the range of 3 to 6 wt% It has also been confirmed that the same anticorrosion effect as in the above example (FIG. 5) can be obtained throughout.
以上で説明したように、本実施形態の塗膜構造２０は、環境への負荷が大きいクロム等の物質の使用を回避しつつ、主として第１塗膜２１による犠牲防食の作用により優れた防食性能を得るとともに、第１塗膜２１に積層されている第２塗膜２２の腐食抑制剤の溶出によって、塗膜構造２０の損傷時にも防食性能を十分に担保することができる。 As described above, the coating film structure 20 of the present embodiment has excellent anticorrosion performance mainly due to the sacrificial anticorrosive action by the first coating film 21 while avoiding the use of a substance such as chromium having a large environmental load. In addition, by the elution of the corrosion inhibitor of the second coating film 22 laminated on the first coating film 21, the anticorrosion performance can be sufficiently ensured even when the coating film structure 20 is damaged.
塗膜構造２０は、塗膜の損傷時に自己修復されるため、長期間に亘り防食性能を確保することができる。そのため、塗膜構造２０は、損傷した箇所を塗り直す等のメンテナンスが困難、あるいは周囲の構造を破壊しない限りメンテナンスが不可能な場所に配置される部材に特に適合する。 Since the coating film structure 20 is self-repaired when the coating film is damaged, the anticorrosion performance can be ensured over a long period of time. Therefore, the coating film structure 20 is particularly suitable for a member that is difficult to maintain such as repainting a damaged portion, or that is placed in a place where maintenance is impossible unless the surrounding structure is destroyed.
本実施形態の塗膜構造は、鉄道、船舶、航空機等の輸送機械、建物や橋梁等の建造物、種々の産業用装置等を構成する部材の基材の防食を図るために広く用いることができる。
本実施形態の塗膜構造２０は、非常に高い防食性能が要求される航空機の構造部材にも適合する。燃費向上のため機体重量の低減が重要であり、空力荷重により曲げ変形する航空機用途の部材にあっては、軽量化および剥離防止のため、塗膜に許容される厚みが小さい。本実施形態の塗膜構造２０によれば、許容される膜厚が薄いとしても、単一の塗膜によっては実現困難な高い防食性能を実現することができる。
航空機にも、他の部材の裏側に隠れていてメンテナンスが困難あるいは不可能な部材が存在する。その部材の基材１０に塗膜構造２０を設けることにより、航空機のライフサイクルに相当する数十年もの長期間に亘る防食性能を確保することができる。
The coating film structure of the present embodiment is widely used to prevent corrosion of the base material of members constituting a transport machine such as a railway, a ship, an aircraft, a building such as a building or a bridge, and various industrial devices. it can.
The coating film structure 20 of the present embodiment is also suitable for aircraft structural members that require extremely high anticorrosion performance. In order to improve fuel efficiency, it is important to reduce the weight of the fuselage. In an aircraft-use member that is bent and deformed by an aerodynamic load, the thickness allowed for the coating film is small in order to reduce weight and prevent peeling. According to the coating film structure 20 of this embodiment, even if the allowable film thickness is thin, it is possible to achieve high anticorrosion performance that is difficult to achieve with a single coating film.
In aircraft, there are members that are hidden behind other members and difficult or impossible to maintain. By providing the base material 10 of the member with the coating film structure 20, it is possible to ensure anticorrosion performance for a long period of several decades corresponding to the life cycle of the aircraft.
上記以外にも、本発明の主旨を逸脱しない限り、上記実施形態で挙げた構成を取捨選択したり、他の構成に適宜変更することが可能である。
本発明の塗膜構造において、第１塗膜２１と第２塗膜２２との間に他の塗膜やコーティング（被膜）が介在していることも許容される。その場合も、第２塗膜２２が、他の塗膜やコーティングを介して第１塗膜２１に積層されているため、本願発明に包含される。
In addition to the above, as long as the gist of the present invention is not deviated, the configuration described in the above embodiment can be selected or changed to another configuration as appropriate.
In the coating film structure of the present invention, it is allowed that another coating film or coating (coating film) is interposed between the first coating film 21 and the second coating film 22. Also in that case, since the 2nd coating film 22 is laminated | stacked on the 1st coating film 21 through another coating film or coating, it is included by this invention.
第１塗膜２１の全面に亘って第２塗膜が積層されることが好ましいが、衝撃や摩擦等により塗膜の損傷が生じ易い領域や、他の部材の裏側に設置されていること等を理由として点検や塗り直し等の整備が困難あるいは不可能な領域に限り、第２塗膜２２が第１塗膜２１に積層されることも許容される。
つまり、本発明の塗膜構造は、第１塗膜の一部にのみ、第２塗膜２２が積層されている構成も包含する。
It is preferable that the second coating film is laminated over the entire surface of the first coating film 21, but it is installed in a region where the coating film is easily damaged due to impact, friction, or the like, or on the back side of other members, etc. For this reason, the second coating 22 is allowed to be laminated on the first coating 21 only in a region where maintenance such as inspection and repainting is difficult or impossible.
That is, the coating film structure of the present invention includes a configuration in which the second coating film 22 is laminated only on a part of the first coating film.
１０ 基材
１０Ａ 表面部
２０ 塗膜構造
２１ 第１塗膜
２１Ａ 表面
２２ 第２塗膜
２２Ｂ 破断部分
３０，３１ 塗膜
１０１ 露出領域
１０２ 隣接領域
２２１，３０１ 腐食抑制剤
２２１Ａ 酸化皮膜
２２２ 樹脂
Ｐ 孔食
DESCRIPTION OF SYMBOLS 10 Base material 10A Surface part 20 Coating film structure 21 1st coating film 21A Surface 22 2nd coating film 22B Fracture part 30,31 Coating film 101 Exposed area 102 Adjacent area 221,301 Corrosion inhibitor 221A Oxide film 222 Resin P Pitting corrosion
Claims (7)
前記第１塗膜に積層された第２塗膜と、を備え、
前記第２塗膜は、
前記第２塗膜から溶出可能であって、前記第１塗膜および前記第２塗膜の損傷により露出した前記基材に付着する腐食抑制剤を含有する、
ことを特徴とする塗膜構造。 A first coating film containing a sacrificial anticorrosive agent that covers a surface portion of a base material that is an anticorrosive material and has a greater ionization tendency than the surface portion;
A second coating film laminated on the first coating film,
The second coating film is
A corrosion inhibitor that can be eluted from the second coating film and adheres to the substrate exposed by damage to the first coating film and the second coating film;
A coating structure characterized by that.
ことを特徴とする請求項１に記載の塗膜構造。 Magnesium is used as the sacrificial anticorrosive,
The coating film structure according to claim 1.
２５〜４０ｗｔ％のマグネシウムを含有する、
ことを特徴とする請求項２に記載の塗膜構造。 The first coating film is
Containing 25-40 wt% magnesium,
The coating film structure according to claim 2.
ことを特徴とする請求項１から３のいずれか一項に記載の塗膜構造。 As the corrosion inhibitor, cerium nitrate is used,
The coating film structure according to any one of claims 1 to 3, wherein:
３〜６ｗｔ％の硝酸セリウムを含有する、
ことを特徴とする請求項４に記載の塗膜構造。 The second coating film is
Containing 3-6 wt% cerium nitrate,
The coating film structure according to claim 4.
前記犠牲防食剤が分散されるエポキシ系樹脂を含有する、
ことを特徴とする請求項１から５のいずれか一項に記載の塗膜構造。 The first coating film is
Containing an epoxy resin in which the sacrificial anticorrosive is dispersed;
The coating film structure according to any one of claims 1 to 5, wherein:
前記腐食抑制剤が分散されるエポキシ系樹脂を含有する、
ことを特徴とする請求項１から６のいずれか一項に記載の塗膜構造。 The second coating film is
Containing an epoxy resin in which the corrosion inhibitor is dispersed,
The coating film structure according to any one of claims 1 to 6, wherein:
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