JP6747907B2 - Anticorrosion coating structure - Google Patents
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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 anticorrosion 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。 2. Description of the Related Art Conventionally, in order to prevent corrosion of members constituting a structure or various devices, the surface of a substrate of the member has been coated. For example, when an undercoating film is applied to the surface of the base material of a member using a coating material containing chromium, the corrosion resistance of the coating film itself and the self-healing action of chromium elution to cover the surface of the base material when the coating film is damaged. It is possible to realize excellent anticorrosion performance.
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, from the viewpoint of compatibility with the environment, anticorrosion technology that does not use chromium has been proposed.
Patent Document 1 proposes coating a substrate with a corrosion inhibiting composition containing an oxide of molybdenum or an oxide of tungsten.
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。
Although the composition of a coating film which can prevent corrosion without using chromium has been studied, including Patent Document 1, sufficient corrosion resistance has not yet been realized.
In particular, for members that are placed in locations where maintenance such as repainting is difficult or impossible, the effect of inhibiting the corrosion of the base material by the coating film that covers the base material and the self-repairing action when the coating film is damaged Therefore, it is required to ensure anticorrosion performance for an extremely long period of 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, it is an object of the present invention to provide a coating film structure that is chromium-free and can realize sufficient anticorrosion performance.
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 is laminated on the first coating film and the first coating film that covers the surface portion of the substrate that is the food material to be protected and that contains the sacrificial anticorrosive agent that has a greater ionization tendency than the surface portion. A second coating film, wherein the second coating film contains a corrosion inhibitor that can be eluted from the second coating film and adheres to the substrate exposed by the damage of 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% of magnesium.
In the present specification, the numerical range described in the format of "AB" 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 the 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 the sacrificial anticorrosive agent 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 the 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, while avoiding the use of a substance having a large environmental load such as chromium, the sacrificial anticorrosion action of the first coating film and the self-healing action of the second coating film provide sufficient anticorrosion performance. 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 a food material to be protected.
The base material 10 constitutes members of various structures and devices and is made of an aluminum alloy.
The base material 10 can also be formed from another metal material 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 order to sufficiently prevent the corrosion by the coating film, by covering the surface portion 10A of the base material 10 as a whole, it is possible to prevent a corrosion factor such as water or oxygen from entering the surface portion 10A of the base material 10. In addition to inhibiting corrosion of the base material 10 by forming an oxide film and sacrificial anticorrosive action, it is required to maintain anticorrosion performance even when the coating film is damaged in consideration of impact or friction on the base material 10. To be 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 having a function of inhibiting corrosion of the base material 10 by a sacrificial anticorrosion action, and a second coating film 22 having a self-repairing function of recovering the corrosion protection performance when the coating film is damaged. I have it.
The first coating film 21 covers the surface portion 10A of the base material 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 respective thicknesses t1 and t2 of the first and second coating films 21 and 22 and the total 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。
A single or multiple coatings can be laminated onto the coating structure 20. For example, various paints suitable for the purpose of appearance decoration, impact resistance, etc. can be overlaid on the coating film structure 20. When another coating is laminated, the coating structure 20 corresponds to a base coating (primer).
The coating structure 20 can also be used without overcoating. For example, when the coating film structure 20 is provided on a member arranged inside the structure, it can be used without topcoating.
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, the respective configurations of the first coating film 21 and the second coating film 22 of the coating film structure 20 will be described.
The first coating film 21 is formed by solidifying the coating material supplied by an appropriate method such as spraying, dipping, coating, electrostatic powder coating, and the like and adhering to the surface portion 10A. The first coating film 21 can be composed of a single layer or a plurality of layers which are repeatedly applied and solidified to coat each other.
It should be noted that the second coating film 22 is also one in which the coating material supplied by an appropriate method solidifies and adheres to the first coating film 21, and is composed of a single layer or a plurality of layers that have been overlaid. 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 10A of a region of the base material 10 where anticorrosion is intended.
Although not shown in detail, the first coating film 21 has a sacrificial anticorrosive agent having an ionization tendency larger than that of the surface portion 10A, a resin in which the sacrificial anticorrosive agent is dispersed, and a small amount of a desiccant or a dispersant as necessary. And the additive of.
The first coating film 21 is provided on the surface portion 10A using a sacrificial food material, a resin, and a paint in which a solvent or water is added to an additive. In this paint, the solvent and some of the additives volatilize and the rest 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 particles of the sacrificial anticorrosive agent are in direct or indirect contact with the substrate 10, the sacrificial anticorrosive agent is entirely in contact with the substrate 10. That is, among the particles of the sacrificial anticorrosive agent, the particles located at the interface between the first coating film 21 and the base material 10 are in direct contact with the base material 10, and even if the particles are apart from the interface, Indirect contact with the substrate 10 via the sacrificial anticorrosive particles.
By forming a local battery using the sacrificial anticorrosive agent as the anode and the base material 10 as the cathode, the sacrificial anticorrosive agent is sacrificed and corroded.
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 this embodiment, magnesium is adopted as the sacrificial anticorrosive agent provided on the surface portion 10A of the base material 10 formed using an aluminum alloy. Employing magnesium, which has a smaller specific gravity than zinc or aluminum, contributes to the weight reduction of the coating film structure 20.
The first coating film 21 of the present embodiment is configured to include magnesium fine particles and an epoxy resin in which the magnesium fine particles are dispersed. The first coating film 21 is adhered to the surface portion 10A with an epoxy resin.
As the sacrificial anticorrosive, besides magnesium, one having a greater ionization tendency than the material of the base material 10 can be used. For example, a metal such as zinc can be used as a sacrificial anticorrosive agent.
As the resin in which the sacrificial anticorrosive is dispersed, in addition to the epoxy resin, for example, an acrylic resin, a fluorine resin, or the like can be used.
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, as shown in FIG. 1, the second coating film 22 covers the surface 21A of the first coating film 21.
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 221 for suppressing the corrosion of the base material 10, a resin 222 in which the corrosion inhibitor 221 is dispersed, and a small amount of an additive (not shown) as necessary. ) And. The corrosion inhibitor 221 is shown schematically. In each drawing, there is no intention to specifically show the particle size of the corrosion inhibitor 221 and the thickness of the first and second coating films 21 and 22.
The second coating film 22 is formed by providing the first coating film 21 on the surface portion 10A of the base material 10 and then using a coating composition in which a solvent is added to the corrosion inhibitor 221, the resin 222, and the additive. It is provided on the surface 21A of 21. In this paint, the solvent and some of the additives volatilize, 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。
In the second coating film 22, even if the first coating film 21 and the second coating film 22 are damaged and the base material of the base material 10 is exposed (see FIG. 2B), the corrosion inhibitor 221 elutes in the water. By adhering to the exposed base material 10, the anticorrosion performance of the coating film structure 20 is secured.
If the coating film structure 20 does not include the second coating film 22 but includes only the first coating film 21, corrosion of the base material 10 from the exposed portion is performed 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 an action similar to hexavalent chromium can be used. The second coating film 22 of the present embodiment is configured to include fine particles of cerium nitrate (221) and an epoxy resin (222) in which fine particles of cerium nitrate are dispersed. The second coating film 22 is adhered to the surface 21A of the first coating film 21 with an epoxy resin.
Various compounds of cerium nitrate, for example, cerium (III) nitrate ammonium tetrahydrate, one cerium (IV) nitrate ammonium, 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 the 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。
The anticorrosion action of the coating film structure 20 will be described with reference to FIG.
FIG. 2(a) shows the coating structure 20 in its undamaged state. At this time, the sacrificial anticorrosive agent included in the first coating film 21 that covers the surface portion 10A of the base material 10 exerts a sacrificial anticorrosion function of corroding instead of the base material 10, so that the corrosion of the base material 10 is prevented. Be hindered. In addition to the sacrificial anticorrosion effect, the surface portion 10A of the base material 10 is covered with the laminated coating film composed of the first coating film 21 and the second coating film 22 to prevent the penetration of the corrosion factor into the base material 10. 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 coating film structure 20 is damaged due to collision or friction and the base material 10 is exposed. A part of the coating film structure 20 covering the surface portion 10A is damaged, and the base material 10 is exposed in the range where the coating film structure 20 is damaged.
When the base material 10 is exposed due to the damage of the coating film structure 20, the corrosion inhibitor 221 that has been retained inside the second coating film 22 up to that time is changed to the second coating film 22 based on the water solubility of the corrosion inhibitor 221. It easily elutes to the outside of the second coating film 22 from the broken portion 22B of. The corrosion inhibitor 221 comes into contact with the water in the second coating film 22, is cationized, diffuses and moves between the resin molecules of the second coating film 22, and reaches the fracture portion 22B (broken line arrow in FIG. 2B). reference). 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, as shown in FIG. 2(c).
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 broken portion 22B of the second coating film 22 located around the exposed region 101 of the surface portion 10A, adheres to a wide range of the exposed region 101, and forms the oxide film 221A. By covering the base material 10 with the oxide film 221A, a function of inhibiting the corrosion of the base material 10 in the region 101 is exhibited. That is, it can be said that the coating film structure 20 is self-repaired by the action of the corrosion inhibitor 221. The coating film structure 20 has a self-repairing function of restoring the anticorrosion function to 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 result of the corrosion test on the damaged portion 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 agent is applied to the surface portion 10A of the base material 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.
The 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 10A of the base material 10 is used.
The coating film 30 contains about 35 wt% of magnesium as a sacrificial anticorrosive agent (not shown) and about 3.8 wt% of cerium nitrate as a corrosion inhibitor 301. The coating film 30 further contains an epoxy resin and an additive, and magnesium particles and cerium nitrate particles are dispersed in the epoxy resin.
As the corrosion inhibitor 301 of Comparative Example 2, the same cerium nitrate as the cerium nitrate contained in the second coating film 22 of this 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 this embodiment, a test piece having a coating film structure 20 (FIG. 1) is used. The first coating film 21 of the test piece contains about 35 wt% of magnesium as a sacrificial anticorrosive agent. The second coating film 22 of the test piece contains about 3.8 wt% of cerium nitrate as a corrosion inhibitor. Cerium (III) nitrate hexahydrate was used in the test.
（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 damage of the coating film is simulated by scraping off a part of the coating film to expose the surface portion 10A of the base material 10.
The test piece simulating the damage of the coating film is immersed in an aqueous solution containing 0.5 wt% of NaCl at 40° C. 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 results 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 in which the base material is entirely exposed by removing the coating film 31 is shown, and regions 102 where the coating film 31 is applied are respectively adjacent to the exposed regions 101 above and below. It is shown. Regions 101 and 102 are similarly shown in FIGS. 4B and 5. The width of the region 101 is about 1 mm.
From FIG. 3B, it can be seen that pitting corrosion P occurs over the entire exposed region 101 simulating the damage.
Since magnesium in the coating film 31 of Comparative Example 1 is difficult to dissolve in water, it stays inside the coating film 31 and hardly reaches the exposed region 101 of the base material 10. Therefore, the sacrificial anticorrosion function of magnesium is not exhibited in the exposed region 101.
It should be noted that no pitting corrosion P has occurred 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, corrosion is suppressed near the boundary B between the exposed region 101 and the adjacent region 102 (a range surrounded by a broken line), but a large number of pitting corrosion P is generated at a portion distant from the boundary B. Is occurring.
According to Comparative Example 2, the corrosion inhibitor 301 (cerium nitrate) contained in the single-layer coating film 30 was eluted from the coating film 30, so that the corrosion was suppressed near the boundary B.
（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, which has been subjected to the corrosion test 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 much wider range (the range surrounded by the broken line) than the test result of Comparative Example 2 (FIG. 4( b )). 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 dispersed in both the coating film 30 of Comparative Example 2 (FIG. 4A) and the second coating film 22 of the present embodiment (FIG. 2), Comparative Example In the second embodiment, cerium nitrate is present together with magnesium in the single coating film 30, whereas in the present embodiment, cerium nitrate is used as the second coating film 22 different from the first coating film 21 containing magnesium. Therefore, the two differ in the constitution 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, which is difficult to dissolve in water, becomes a resistance against migration of cerium nitrate. Since magnesium particles that are difficult to dissolve in water remain inside the coating film 30 and the content of magnesium is larger than that of cerium nitrate, magnesium is a major impediment factor to the diffusion of cerium nitrate inside the coating film 31. Becomes
On the other hand, in the present embodiment (FIG. 2), cerium nitrate (221) and magnesium are separated into separate coating films 22 and 21, so that the cerium nitrate inside the second coating film 22 is separated by magnesium. Spreads easily without hindrance. The cerium nitrate passes between the resin molecules of the second coating film 22, reaches the fractured portion 22B (FIG. 2B) of the second coating film 22, elutes to the outside of the second coating film 22, and is exposed. It also reaches the center of 101.
According to the present embodiment, cerium nitrate is more easily diffused and eluted out of the coating film earlier than in Comparative Example 2, so that the exposed region 101 of the substrate 10 is oxidized to the substrate 10 before it is corroded. Since the film 221A is formed, it is possible to suppress corrosion over a wider area 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。
As for the coating film structure 20 of the present embodiment, the content of magnesium in the first coating film 21 was changed and the same corrosion test as above was performed. As a result, the content of magnesium was 25 to 40 wt% over the entire range, It has been confirmed that the same anticorrosion effect as the above example (FIG. 5) can be obtained.
In addition, as for the coating film structure 20 of the present embodiment, the content of cerium nitrate in the second coating film 22 was changed and the same corrosion test was performed. As a result, the content of cerium nitrate was in the range of 3 to 6 wt %. It has also been confirmed that the same anticorrosion effect as that of the above example (FIG. 5) can be obtained over the whole.
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 anticorrosion action of the first coating film 21 while avoiding the use of a substance such as chromium having a large load on the environment. In addition to the above, the corrosion inhibiting performance of the second coating film 22 laminated on the first coating film 21 can be sufficiently ensured even when the coating film structure 20 is damaged by elution of the corrosion inhibitor.
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 secured for a long period of time. Therefore, the coating film structure 20 is particularly suitable for a member that is difficult to perform maintenance such as repainting a damaged portion, or that cannot be maintained 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 can be widely used for anticorrosion of the base material of members constituting railways, ships, transportation machines such as aircrafts, buildings such as buildings and bridges, and various industrial devices. it can.
The coating film structure 20 according to 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 machine body, and in the case of members for aircraft which are bent and deformed by aerodynamic load, the coating film has a small allowable thickness for weight reduction and prevention of peeling. According to the coating film structure 20 of the present embodiment, even if the allowable film thickness is thin, it is possible to realize high anticorrosion performance which is difficult to achieve with a single coating film.
In aircraft, there are some members that are hidden behind other members and are difficult or impossible to maintain. By providing the coating film structure 20 on the base material 10 of the member, it is possible to secure the 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。
Other than the above, the configurations described in the above embodiments can be selected or changed to other configurations without departing from the gist of the present invention.
In the coating film structure of the present invention, it is acceptable that another coating film or coating (coating film) is interposed between the first coating film 21 and the second coating film 22. Even in that case, since the second coating film 22 is laminated on the first coating film 21 via another coating film or coating, it is included in the present 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 likely to be damaged by impact or friction, or on the back side of another member. Therefore, the second coating film 22 may be laminated on the first coating film 21 only in an area where maintenance such as inspection or 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
10 Base Material 10A Surface Part 20 Coating Film Structure 21 First Coating Film 21A Surface 22 Second Coating Film 22B Breaking Part 30, 31 Coating Film 101 Exposed Area 102 Adjacent Area 221,301 Corrosion Inhibitor 221A Oxide Coating 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 that covers the surface portion of a substrate that is a food material to be protected and that contains a sacrificial anticorrosive agent that has a greater ionization tendency than the surface portion;
A second coating film laminated on the first coating film,
The second coating film,
A corrosion inhibitor that can be eluted from the second coating film and that adheres to the base material exposed by damage to the first coating film and the second coating film,
A coating film structure characterized in 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 agent,
The coating film structure according to claim 1, wherein:
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,
Containing 25-40 wt% magnesium,
The coating film structure according to claim 2, wherein:
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。 Cerium nitrate is used as the corrosion inhibitor,
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,
Contains 3 to 6 wt% cerium nitrate,
The coating film structure according to claim 4, wherein:
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,
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,
Contains 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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