JP2007291440A - Corrosion protection coating and method for forming the same - Google Patents
Corrosion protection coating and method for forming the same Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 114
- 239000011248 coating agent Substances 0.000 title claims abstract description 113
- 230000007797 corrosion Effects 0.000 title claims abstract description 41
- 238000005260 corrosion Methods 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000007789 sealing Methods 0.000 claims abstract description 110
- 229910052751 metal Inorganic materials 0.000 claims abstract description 83
- 239000002184 metal Substances 0.000 claims abstract description 83
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000000758 substrate Substances 0.000 claims abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000839 emulsion Substances 0.000 claims abstract description 20
- 230000035699 permeability Effects 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- 239000008119 colloidal silica Substances 0.000 claims abstract description 15
- 239000005871 repellent Substances 0.000 claims abstract description 14
- 230000002940 repellent Effects 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 3
- 238000005507 spraying Methods 0.000 claims description 40
- XJKVPKYVPCWHFO-UHFFFAOYSA-N silicon;hydrate Chemical compound O.[Si] XJKVPKYVPCWHFO-UHFFFAOYSA-N 0.000 claims description 12
- 239000010953 base metal Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 description 35
- 239000011148 porous material Substances 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 16
- 229910000831 Steel Inorganic materials 0.000 description 13
- 239000010959 steel Substances 0.000 description 13
- 239000011347 resin Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 239000007921 spray Substances 0.000 description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 229910052725 zinc Inorganic materials 0.000 description 10
- 239000011701 zinc Substances 0.000 description 10
- 230000008961 swelling Effects 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- 238000011049 filling Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 238000005536 corrosion prevention Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000007751 thermal spraying Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 125000005103 alkyl silyl group Chemical group 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000005246 galvanizing Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 229910000861 Mg alloy Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- UTPYQWVXECMZMA-UHFFFAOYSA-N [dimethyl(sulfo)silyl]methane Chemical compound C[Si](C)(C)S(O)(=O)=O UTPYQWVXECMZMA-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005422 blasting Methods 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 239000000567 combustion gas Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- -1 polyalkylsiloxane Chemical compound 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
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- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- KOOADCGQJDGAGA-UHFFFAOYSA-N [amino(dimethyl)silyl]methane Chemical compound C[Si](C)(C)N KOOADCGQJDGAGA-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000005002 finish coating Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 238000013008 moisture curing Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- MBHJFHKNCUQKCQ-UHFFFAOYSA-N trimethylsilylformic acid Chemical compound C[Si](C)(C)C(O)=O MBHJFHKNCUQKCQ-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Coating By Spraying Or Casting (AREA)
Abstract
Description
本発明は金属基材の防蝕性能に優れた被膜とその形成方法関する。より詳しくは、本発明は、金属基材表面に設けた溶射金属被膜（単に「溶射被膜」ということがある）の表面にさらに封孔被膜を設けた防蝕性能に優れた防蝕被膜とその形成方法に関する。 The present invention relates to a film excellent in corrosion resistance of a metal substrate and a method for forming the same. More specifically, the present invention relates to a corrosion-resistant coating excellent in corrosion resistance performance, in which a sealing coating is further provided on the surface of a sprayed metal coating (sometimes referred to simply as “thermal spray coating”) provided on the surface of a metal substrate, and a method for forming the same. About.
鋼構造物等の腐蝕を防止するために、金属基材よりも卑な電位の金属被膜を基材表面に設け、この卑金属の犠牲防蝕作用によって金属基材を保護する防蝕方法が従来から知られている。この具体例として溶融亜鉛めっき方法が広く普及しているが、溶融亜鉛めっき方法は溶融亜鉛めっき槽の大きさによって基材の形状および寸法の制約を受け、また溶融亜鉛めっき時に基材が熱的影響を受ける等の問題がある。一方、金属溶射によって防蝕被膜を形成する方法は基材の形状や寸法の制約がなく、また基材に対する熱的影響が少なく、かつ現場施工ができるなどの利点がある。 In order to prevent corrosion of steel structures and the like, there has been conventionally known a corrosion prevention method in which a metal film having a base potential lower than that of a metal base material is provided on the surface of the base material and the metal base material is protected by the sacrificial anticorrosive action of the base metal. ing. As a specific example of this, the hot dip galvanizing method is widely used. However, the hot dip galvanizing method is limited by the shape and dimensions of the base material depending on the size of the hot dip galvanizing tank. There are problems such as being affected. On the other hand, the method of forming the anticorrosion coating by metal spraying has advantages that there are no restrictions on the shape and dimensions of the base material, there is little thermal influence on the base material, and construction on site is possible.
鋼構造物の防蝕に用いられる溶射金属としては、亜鉛、アルミニウム、亜鉛・アルミニウム合金、アルミニウム・マグネシウム合金等が用いられており、溶射金属被膜として上記金属の積層物や亜鉛・アルミニウムの積層物(亜鉛・アルミニウム擬合金)などが実施されている。溶射金属被膜は、溶射材料を溶融またはそれに近い状態にした粒子を基材表面に吹き付けて形成するので、被膜を形成している粒子間に気孔が残り、多孔質な被膜が形成される。この気孔は溶射被膜の表面から基材表面まで連通している。 Zinc, aluminum, zinc-aluminum alloy, aluminum-magnesium alloy, etc. are used as the sprayed metal used for corrosion prevention of steel structures, and the above metal laminate or zinc-aluminum laminate ( Zinc / aluminum pseudo-alloys) have been implemented. Since the sprayed metal coating is formed by spraying particles having a sprayed material melted or close to the surface of the substrate, pores remain between the particles forming the coating, and a porous coating is formed. The pores communicate from the surface of the sprayed coating to the substrate surface.
溶射被膜は多孔質であるが、時間の経過と共に徐々に溶射被膜の金属が水と反応して金属化合物を形成し、この金属化合物によってしだいに気孔が充填されて無気孔状態になり、優れた環境遮断性を発揮するようになり、溶射金属の犠牲防蝕作用と合わせて防蝕効果が向上する。例えば、溶射金属が亜鉛の場合は水酸化亜鉛や炭酸亜鉛または含水酸化物が生成し、アルミニウムの場合は水酸化アルミニウムや水酸化アルミニウムのコロイド状水和物が生成すると考えられている。 Although the thermal spray coating is porous, the metal of the thermal spray coating gradually reacts with water to form a metal compound with the passage of time, and the metal compound gradually fills the pores, resulting in a non-porous state. The environmental barrier properties are exhibited, and the corrosion protection effect is improved in combination with the sacrificial corrosion protection action of the sprayed metal. For example, it is considered that when the sprayed metal is zinc, zinc hydroxide, zinc carbonate or a hydrated oxide is formed, and when aluminum is used, colloidal hydrates of aluminum hydroxide or aluminum hydroxide are formed.
溶射被膜は時間の経過と共に無気孔になるが、無気孔になるまでの間に、気孔内に水や酸素、腐蝕を促進する酸性ガス、海岸近辺では塩化物等が浸入して溶射金属を急速に腐蝕させると、被膜内に発生した水素ガス等が、被膜表面が無気孔化されたときに外部に拡散することができず、被膜の膨れや剥離を生じる場合がある。 Thermal sprayed coatings become non-porous over time, but before they become non-porous, water, oxygen, acidic gas that promotes corrosion, and chlorides infiltrate the coast to rapidly spray the sprayed metal. When the film is corroded, hydrogen gas or the like generated in the film cannot be diffused to the outside when the film surface is made non-porous, and the film may swell or peel off.
そこで、溶射被膜の気孔を予め充填して気孔内の腐蝕を防止ないし抑制することが行なわれている。例えば、日本工業規格（JIS H 8200）では、溶射被膜の開口気孔に封孔剤を浸透させて気孔を密閉し、被膜の化学的性質および物理的性質を改善する処置が規定されており、封孔処理剤としてエポキシ系樹脂、フェノール系樹脂、シリコン系樹脂、ワックス塗料が例示されている。その一例として、特開２００４−２２５１１６号公報（特許文献１）には、溶射被膜の気孔内部まで浸透するアクリルシリコーン樹脂からなる封孔剤が開示されている。 Therefore, it has been practiced to prevent or suppress corrosion in the pores by previously filling the pores of the sprayed coating. For example, the Japanese Industrial Standard (JIS H 8200) stipulates measures to improve the chemical and physical properties of the coating by impregnating the sealing agent by infiltrating the pores of the thermal spray coating and sealing the pores. Examples of pore treating agents include epoxy resins, phenol resins, silicon resins, and wax paints. As an example, Japanese Patent Laid-Open No. 2004-225116 (Patent Document 1) discloses a sealing agent made of an acrylic silicone resin that penetrates into the pores of a sprayed coating.
このように溶射直後に溶射金属被膜の封孔処理が行なわれているが、従来は封孔処理が充分ではないため溶射被膜の剥離事故が頻発している。溶射被膜の剥離を防止する方法として、例えば、特開平９−１２５２２１号公報（特許文献２）には、燐酸を含む樹脂類からなる封孔処理剤を用い、樹脂類によって気孔を充填する一方、燐酸によって溶射被膜を腐蝕させ、この腐蝕生成物によって自己封孔を行わせる方法が示されている。
従来の上記封孔処理は必ずしも充分な効果を得られない場合がある。また、溶射被膜の剥離の他に、施工条件によっては封孔処理剤の膨れが発生する問題がある。即ち、基材表面部に結露が発生している状況で封孔処理剤を施工すると、内部で発生した水素ガスによって、また温度上昇による結露水の膨張によって封孔処理剤の膨れが起こる。同様に、溶射被膜内に空隙を残したままで封孔処理を行うと、溶射被膜の空隙に残留している空気が温度上昇によって膨張し、封孔処理剤の膨れが起こる。これらの封孔処理剤の膨れは外観を劣化させるだけでなく溶射被膜の欠陥部となり、基材金属の腐蝕につながる溶射被膜の局部的な消耗や、溶射被膜の付着が弱い場合は溶射被膜の剥離を招く場合もある。 The conventional sealing treatment may not always provide a sufficient effect. In addition to peeling off the sprayed coating, there is a problem that the sealing agent swells depending on the construction conditions. That is, when the sealing agent is applied in a state where dew condensation occurs on the surface of the base material, the sealing agent swells due to the hydrogen gas generated inside and the expansion of the dew condensation water due to the temperature rise. Similarly, when the sealing treatment is performed with the voids remaining in the thermal spray coating, the air remaining in the voids of the thermal spray coating expands due to the temperature rise, and the sealing agent is swollen. The swelling of these sealing agents not only deteriorates the appearance, but also becomes a defective part of the sprayed coating.If the local spraying of the sprayed coating leads to corrosion of the base metal or the adhesion of the sprayed coating is weak, the sprayed coating It may cause peeling.
本発明は、従来の溶射被膜の封孔処理方法で発生する溶射被膜の膨れや剥離、溶射被膜の欠陥となる封孔処理剤の膨れを解決し、且つ防蝕効果が持続する耐久性に優れた環境汚染の少ない封孔処理方法とその防蝕被膜を提案するものである。 The present invention solves the blistering and peeling of the thermal spray coating generated by the conventional thermal spray coating sealing treatment method, solves the swelling of the sealing agent that becomes a defect of the thermal spray coating, and has excellent durability for maintaining the anticorrosion effect. This paper proposes a sealing treatment method with little environmental pollution and its anticorrosive coating.
本発明は、上記課題を解決する手段として以下の構成を有する封孔処理方法およびその防蝕被膜に関する。
（１）金属基材表面に設けた該基材の金属より卑な金属の溶射被膜と、該溶射金属被膜の表面に設けた通気性と撥水性を有する封孔被膜とを有することを特徴とする防蝕被膜。
（２）封孔被膜が、水性ポリマーエマルジョンにコロイダルシリカと反応型シリコン撥水剤を混合してなる水系封孔処理剤によって形成したものである上記(１)に記載する防蝕被膜。
（３）水系封孔処理剤が、固形物換算で、水性ポリマーエマルジョンにコロイダルシリカを混合してなる被膜形成剤１００重量部当たり、反応型シリコン撥水剤を１０〜１００重量部添加したものである上記(２)の防蝕被膜。
（４）金属基材の表面に該基材の金属よりも卑な金属を溶射し、さらに該溶射金属被膜の表面に水系封孔処理剤を塗布して通気性と撥水性を有する封孔被膜を形成することを特徴とする防蝕被膜の形成方法。
（５）上記(４)の方法において、固形物換算で、水性ポリマーエマルジョンにコロイダルシリカを混合してなる被膜形成剤１００重量部当たり、反応型シリコン撥水剤を１０〜１００重量部添加した水系封孔処理剤を用いて溶射金属被膜の表面に通気性と撥水性を有する封孔被膜を形成する防蝕被膜の形成方法。
The present invention relates to a sealing treatment method having the following configuration and a corrosion-resistant coating film as means for solving the above-described problems.
(1) It has a thermal spray coating of a base metal provided on the surface of the metal base material and a sealing coating having air permeability and water repellency provided on the surface of the thermal spray metal coating. Corrosion protection coating.
(2) The anticorrosive film as described in (1) above, wherein the sealing film is formed by an aqueous sealing agent obtained by mixing colloidal silica and a reactive silicon water repellent in an aqueous polymer emulsion.
(3) The water-based sealing agent is added in the form of solid matter and added with 10 to 100 parts by weight of a reactive silicon water repellent per 100 parts by weight of a film forming agent obtained by mixing colloidal silica with an aqueous polymer emulsion. A certain anticorrosion film of the above (2).
(4) Sealing film having air permeability and water repellency by spraying a base metal rather than the metal of the base material on the surface of the metal base material, and further applying an aqueous sealing agent on the surface of the sprayed metal film A method for forming a corrosion-resistant coating, characterized by comprising:
(5) In the above method (4), an aqueous system in which 10 to 100 parts by weight of a reactive silicon water repellent is added per 100 parts by weight of a film forming agent obtained by mixing colloidal silica with an aqueous polymer emulsion in terms of solid matter. A method for forming a corrosion-resistant coating, wherein a sealing coating having air permeability and water repellency is formed on the surface of a sprayed metal coating using a sealing agent.
本発明の防蝕被膜は、金属基材表面の溶射金属被膜の表面に更に通気性と撥水性を有する封孔被膜を有するので、溶射金属被膜の気孔内に残留している空気や犠牲防蝕反応などによって発生した水素ガスなどが、封孔被膜の通気性によって外部に放出されるので、残留空気や発生ガスが溶射被膜内部で膨張することがなく、被膜の膨れや剥離を生じない。また、上記封孔被膜は撥水性を有するので外部から水が浸入せず、溶射被膜の防蝕による無気孔化が安定に進行するので、優れた防蝕効果を得ることができる。 Since the corrosion-resistant coating of the present invention has a sealing film having air permeability and water repellency on the surface of the sprayed metal coating on the surface of the metal substrate, air remaining in the pores of the sprayed metal coating, sacrificial corrosion-resistant reaction, etc. Since the hydrogen gas generated by the gas is released to the outside due to the air permeability of the sealing coating, the residual air and the generated gas do not expand inside the sprayed coating, and the coating does not swell or peel off. Moreover, since the sealing film has water repellency, water does not enter from the outside, and the formation of pores by the corrosion prevention of the sprayed coating proceeds stably, so that an excellent anticorrosive effect can be obtained.
本発明の封孔被膜は、水性ポリマーエマルジョンにコロイダルシリカと反応型シリコン撥水剤を混合してなる水系封孔処理剤によって形成することができる。例えば、固形物換算で、水性ポリマーエマルジョンにコロイダルシリカを混合してなる被膜形成剤１００重量部当たり、反応型シリコン撥水剤を１０〜１００重量部添加した水系封孔処理剤を用いると良い。この水系封孔処理剤によれば適度な通気性と撥水性を有する封孔被膜を形成することができる。 The sealing film of the present invention can be formed by an aqueous sealing agent obtained by mixing a colloidal silica and a reactive silicon water repellent in an aqueous polymer emulsion. For example, an aqueous sealing agent in which 10 to 100 parts by weight of a reactive silicon water repellent is added per 100 parts by weight of a film forming agent obtained by mixing colloidal silica with an aqueous polymer emulsion in terms of solid matter. According to this water-based sealing agent, a sealing film having appropriate air permeability and water repellency can be formed.
本発明の防蝕被膜の形成方法は、溶射金属被膜表面に上記封孔被膜を形成すれば良く、封孔被膜の膨れや剥離が発生しない優れた防蝕被膜を容易に形成することができる。 The formation method of the anticorrosion film of the present invention may be such that the sealing film is formed on the surface of the sprayed metal film, and an excellent anticorrosion film that does not cause swelling or peeling of the sealing film can be easily formed.
以下、本発明を実施例と共に具体的に説明する。
従来から使用されているエポキシ系樹脂、フェノール系樹脂、シリコン系樹脂、ワックス塗料等の含浸性樹脂を用いた封孔処理剤は溶射被膜の気孔に樹脂を含浸させて封孔する方法であり、また、燐酸を含む含浸性樹脂を用いるものは溶射被膜の気孔に樹脂を充填すると共に溶射被膜の腐蝕による自己充填で気孔を充填する方法（特許文献２）である。
Hereinafter, the present invention will be specifically described together with examples.
A sealing agent using an impregnating resin such as an epoxy resin, a phenolic resin, a silicon resin, and a wax paint, which has been used conventionally, is a method of impregnating a resin by impregnating the pores of the sprayed coating with a resin, A method using an impregnating resin containing phosphoric acid is a method of filling the pores of the sprayed coating with the resin and filling the pores by self-filling by corrosion of the sprayed coating (Patent Document 2).
〔防蝕被膜の構成〕
本発明の封孔被膜は、溶射被膜の気孔に樹脂を含浸させて封孔する従来の上記封孔処理とは異なり、通気性と撥水性に優れる被膜を溶射金属被膜表面に設け、溶射被膜の犠牲防蝕などによって発生する水素ガスなどは被膜の通気性によって外部に放出し、また水蒸気は浸透するが腐蝕因子を含む外部の水は被膜の撥水性によって浸透を遮断し、急激な腐蝕を防止して溶射被膜の防蝕を安定に進行させて溶射被膜の無気孔化を行なう。
[Composition of corrosion protection coating]
Unlike the conventional sealing treatment in which the pores of the thermal spray coating are impregnated with a resin, the sealing coating of the present invention is provided with a coating having excellent air permeability and water repellency on the surface of the thermal spray coating. Hydrogen gas generated by sacrificial corrosion prevention is released to the outside by the breathability of the film, and water penetrates but external water containing corrosion factors blocks the penetration by the water repellency of the film, preventing sudden corrosion. In this way, the sprayed coating is made non-porous by stably advancing the corrosion protection of the sprayed coating.
本発明の通気性と撥水性を有する封孔被膜は、水性ポリマーエマルジョンにコロイダルシリカと反応型シリコン撥水剤を混合してなる水系封孔処理剤によって形成することができる。具体的には、例えば、本発明の封孔被膜は、固形物換算で、水性ポリマーエマルジョンにコロイダルシリカを混合してなる水性樹脂組成物からなる塗膜形成剤に、該組成物１００重量部当たり、反応型シリコン撥水剤を１０〜１００重量部添加してなる水系封孔処理剤によって形成したものである。 The sealing film having air permeability and water repellency of the present invention can be formed by an aqueous sealing agent obtained by mixing a colloidal silica and a reactive silicon water repellent in an aqueous polymer emulsion. Specifically, for example, the sealing film of the present invention is, in terms of solid matter, added to a film-forming agent comprising an aqueous resin composition obtained by mixing colloidal silica with an aqueous polymer emulsion per 100 parts by weight of the composition. The water-based sealing agent is formed by adding 10 to 100 parts by weight of a reactive silicon water repellent.
本発明の封孔処理剤に含まれるポリマーエマルジョンとしては、（メタ）アクリル酸エステル系ポリマーエマルジョン、酢酸ビニル系ポリマーエマルジョン、スチレンブタジエン系ラバーエマルジョン、ポリアミド系ポリマーエマルジョン、クロロプレンエマルジョン等を用いることができる。 As the polymer emulsion contained in the sealing agent of the present invention, (meth) acrylate polymer emulsion, vinyl acetate polymer emulsion, styrene butadiene rubber emulsion, polyamide polymer emulsion, chloroprene emulsion and the like can be used. .
本発明の封孔処理剤に含まれるコロイダルシリカとしては、サイトン（モンサントケミカル社）、ルドックス（Ｅ．Ｉ．デュポン社）、ナルコーグ（ナショナルアルミネート社）、キャタロイド（触媒化学社）等の商品名で市販されている、約１〜１００ミリミクロンのシリカ粒子の水性分散体などを用いることができる。このようなコロイダルシリカは媒体である水の除去または蒸発によって被膜を形成し、被膜形成後は水分に接触しても被膜が損なわれない。 As colloidal silica contained in the sealing agent of the present invention, trade names such as Cyton (Monsanto Chemical Co.), Ludox (EI DuPont), Nalcogue (National Aluminate), Cataroid (Catalytic Chemical) For example, an aqueous dispersion of silica particles having a particle size of about 1 to 100 millimicrons can be used. Such colloidal silica forms a film by removing or evaporating water as a medium. After the film is formed, the film is not damaged even when it comes into contact with moisture.
本発明の封孔処理剤に含まれる反応型シリコン撥水剤は、反応性アルキルシリル誘導体、例えば、トリメチルシリルスルフォン酸、トリメチルシリルアミン、ポリアルキルシロキサン、トリメチルシリルカルボン酸等の反応基を有する化合物である。これらの化合物はコロイダルシリカ、または（メタ）アクリル酸エステル系ポリマーエマルジョンと反応して極めて耐候性の強い被膜を形成し、かつ撥水性にも優れている。 The reactive silicon water repellent contained in the sealing agent of the present invention is a compound having a reactive group such as a reactive alkylsilyl derivative, for example, trimethylsilylsulfonic acid, trimethylsilylamine, polyalkylsiloxane, trimethylsilylcarboxylic acid. These compounds react with colloidal silica or a (meth) acrylic acid ester polymer emulsion to form a highly weather-resistant film, and are excellent in water repellency.
本発明の封孔処理剤には、上記成分と共に、各種の顔料、分散剤、粘度調整剤、消泡剤等の一般の塗料に使用される各種成分を含むことができる。 The sealing agent of the present invention can contain various components used for general paints such as various pigments, dispersants, viscosity modifiers and antifoaming agents, in addition to the above components.
上記封孔処理剤によって形成した本発明の封孔被膜は、通気性を有するので水蒸気は被膜を通過して溶射被膜に浸透し、時間の経過と共に溶射金属と水分が反応して犠牲腐蝕を生じ、この犠牲腐蝕生成物によって溶射被膜の気孔が充填され無気孔化される。 The sealing film of the present invention formed by the above-mentioned sealing agent has air permeability, so that water vapor passes through the coating and penetrates into the sprayed coating, and as time passes, the sprayed metal and moisture react to cause sacrificial corrosion. The pores of the sprayed coating are filled with the sacrificial corrosion product to make it non-porous.
また、本発明の封孔被膜は、通気性と共に撥水性を有するので、水蒸気は被膜を透過するが水蒸気に比べ粒子径の大きい水分は被膜を透過することができず、溶射金属被膜の腐蝕因子を含む水は溶射被膜内に浸透せず、溶射金属被膜の急速な腐蝕が抑制される。このような封孔被膜の撥水性は、降雨時などに水を弾き溶射金属被膜表面に水を滞留させないため、溶射金属被膜内への水の浸入を防ぐと共に水に含まれる腐蝕性因子、例えば塩化ナトリウム等の溶射金属被膜表面への蓄積を防ぎ、溶射金属被膜の急速な腐蝕消耗が抑制される。 In addition, since the sealing coating of the present invention has air permeability and water repellency, water vapor permeates the coating, but moisture having a particle size larger than that of water vapor cannot permeate the coating. Water containing water does not penetrate into the sprayed coating, and rapid corrosion of the sprayed metal coating is suppressed. The water repellency of such a sealing coating prevents the infiltration of water into the sprayed metal coating and prevents corrosion from being contained in the water, for example, because it repels water during raining and does not retain water on the surface of the sprayed metal coating. Accumulation on the surface of the sprayed metal film such as sodium chloride is prevented, and rapid corrosion consumption of the sprayed metal film is suppressed.
一方、溶射金属被膜の犠牲腐蝕によって発生する水素ガスは、封孔被膜の通気性によって速やかに外部に拡散するために、溶射金属被膜の膨れや剥離は生じない。また、冬場等の封孔処理剤施工時に基材表面の結露に気づかず封孔処理を行った場合でも、結露水が封孔処理剤の気孔から水蒸気として飛散するために、封孔被膜の膨れが起こらず、溶射金属被膜の膨れや剥離も生じない。同様に、何らかの原因で封孔被膜内に空気泡が残った場合でも、この空気泡が封孔被膜の通気性によって外部に逃げるために、封孔被膜の膨れが起こらず溶射金属被膜の膨れおよび剥離も生じない。 On the other hand, the hydrogen gas generated by the sacrificial corrosion of the sprayed metal coating diffuses rapidly to the outside due to the air permeability of the sealing coating, so that the sprayed metal coating does not swell or peel off. In addition, even when a sealing treatment is performed without noticing condensation on the surface of the base material during construction of the sealing agent in winter, etc., the condensed water scatters as water vapor from the pores of the sealing agent, so that the sealing film swells. Does not occur, and the sprayed metal coating does not swell or peel off. Similarly, even if air bubbles remain in the sealing film for some reason, the air bubbles escape to the outside due to the air permeability of the sealing film, so that the sealing film does not swell and the sprayed metal film swells. No peeling occurs.
さらに、本発明の封孔被膜を形成する封孔処理剤は水系の塗材であり、揮発性有機物や有害物を含有しておらず、環境を汚染しない。しかも耐久性に優れているために溶射金属被膜の消耗速度が小さくなる。 Furthermore, the sealing agent for forming the sealing film of the present invention is an aqueous coating material, does not contain volatile organic substances or harmful substances, and does not pollute the environment. In addition, since the durability is excellent, the consumption rate of the sprayed metal coating is reduced.
〔防蝕被膜の形成方法〕
本発明の防蝕被膜は、金属基材の表面に該基材の金属よりも卑な金属を溶射し、さらに該溶射金属被膜の表面に通気性と撥水性を有する水系封孔処理剤を塗布して封孔被膜を積層して形成される。この防蝕被膜は、一部が溶射被膜の気孔に含浸していても良い。
[Method of forming anticorrosion coating]
The anticorrosive coating of the present invention is obtained by spraying a base metal rather than the metal of the base material on the surface of the metal base material, and further applying a water-based sealing agent having air permeability and water repellency to the surface of the sprayed metal film. And a sealing film is laminated. Part of this anticorrosion coating may be impregnated into the pores of the thermal spray coating.
金属基材表面の溶射金属被膜は、金属基材より卑な電位の金属を基材表面に溶射して形成され、犠牲防蝕作用によって金属基材を防蝕する。本発明の封孔被膜はこの溶射金属被膜の封孔処理に適用される。金属溶射は、金属基材に溶射材料が物理的に付着するように基材表面を粗らした上に、溶射ガンによって電気エネルギーまたは燃焼ガスを用いて溶射金属を溶融またはそれに近い粒子状態にして吹き付け溶射金属被膜を形成する。 The sprayed metal coating on the surface of the metal substrate is formed by spraying a metal having a lower potential than that of the metal substrate onto the surface of the substrate, and corrodes the metal substrate by sacrificial corrosion protection. The sealing coating of the present invention is applied to the sealing treatment of this sprayed metal coating. In metal spraying, the surface of the substrate is roughened so that the sprayed material physically adheres to the metal substrate, and then the sprayed metal is melted or brought into a particle state close to that using electric energy or combustion gas by a spray gun. Spray sprayed metal coating is formed.
金属基材の表面を荒らす方法は、ブラストによる方法、または特公平０２−０５４４２２号公報に一例が示されているように粗面形成材を基材表面に塗布して粗面を形成する方法等がある。いずれも溶射された金属が物理的に付着するためのアンカー効果を得るためのものである。溶射方法は、特公平０２−０５６４２４号公報に一例が示されているように、溶射ガンによって電気エネルギーまたは燃焼ガスを用いて溶射材料を溶融またはそれに近い状態にした粒子を吹き付けて被膜を形成する方法などが知られている。溶射金属は亜鉛、アルミニウム、亜鉛・アルミニウム擬合金、亜鉛・アルミニウム合金、アルミニウム・マグネシウム合金等が用いられている。亜鉛・アルミニウム擬合金は亜鉛とアルミニウムの二本の線材を同時に溶射し、亜鉛とアルミニウムがランダムに積層した状態のものである。溶射被膜の厚さは通常５０〜３００μm程度である。 The method of roughening the surface of the metal substrate is a blasting method, or a method of forming a rough surface by applying a rough surface forming material to the surface of the substrate as shown in Japanese Patent Publication No. 02-054422. There is. Both are for obtaining an anchor effect for the thermally sprayed metal to physically adhere. As an example of the thermal spraying method, as shown in Japanese Examined Patent Publication No. 02-056424, a coating is formed by spraying particles in which a thermal spray material is melted or brought into a state close to that by using a thermal spray gun using electric energy or combustion gas. Methods are known. As the spray metal, zinc, aluminum, zinc-aluminum pseudo-alloy, zinc-aluminum alloy, aluminum-magnesium alloy, or the like is used. A zinc-aluminum pseudo-alloy is a state in which two wires of zinc and aluminum are sprayed simultaneously, and zinc and aluminum are randomly laminated. The thickness of the sprayed coating is usually about 50 to 300 μm.
溶射金属被膜は、溶射金属を溶融またはそれに近い状態の粒子として基材表面に吹き付けて被膜を形成するため、吹付けられた粒子と粒子の間隙に気孔が残り多孔質な被膜が形成される。この気孔に腐蝕因子が浸入して溶射金属被膜が腐蝕した場合、溶射金属被膜表面部で腐蝕生成物が気孔を塞ぐため、被膜内部で発生する水素ガスが外部に拡散できなくなる等の理由によって溶射金属被膜の膨れや剥離が発生する。 Since the sprayed metal coating is formed by spraying the sprayed metal on the surface of the substrate as particles in a melted state or close to it, pores remain in the gap between the sprayed particles and a porous coating is formed. When corrosion factors enter the pores and the sprayed metal coating corrodes, the corrosion product closes the pores on the surface of the sprayed metal coating, so that the hydrogen gas generated inside the coating cannot be diffused to the outside. Swelling or peeling of the metal coating occurs.
先に述べたように、従来は、このような溶射金属被膜の膨れや剥離を防ぐため、溶射被膜の表面に含浸性の強い封孔処理剤を塗布することによって、溶射金属被膜の気孔を充填する方法が一般的に行われており、また、燐酸を含む封孔処理材を用い、樹脂類で気孔を充填すると共に燐酸によって溶射金属被膜を腐蝕させ、この腐蝕生成物によって自己封孔を行わせる方法が行われている。本発明の防蝕被膜の形成方法は、このような気孔を単に充填する従来の方法とは異なり、溶射金属被膜の表面に上述の通気性と撥水性を有する封孔被膜を形成する方法である。 As mentioned earlier, in order to prevent such blistering and peeling of the sprayed metal film, the pores of the sprayed metal film are filled by applying a highly impregnating sealing agent on the surface of the sprayed film. In addition, a sealing treatment material containing phosphoric acid is used, the pores are filled with resins, the sprayed metal film is corroded with phosphoric acid, and self-sealing is performed with this corrosion product. A way to make it happen. Unlike the conventional method of simply filling such pores, the method of forming the anticorrosive coating of the present invention is a method of forming the above-described sealed coating having air permeability and water repellency on the surface of the sprayed metal coating.
本発明の封孔被膜は上記封孔処理剤を溶射金属被膜表面に塗布して形成すればよい。塗布量は０.２kg／ｍ2程度でよい。この塗布量は従来の含浸性樹脂を用いた場合と変わらない。また、塗布方法は上記被膜形成材を刷毛またはスプレーで塗布すればよい。 What is necessary is just to form the sealing film of this invention by apply | coating the said sealing agent to the thermal spray metal coating surface. The application amount may be about 0.2 kg / m 2 . The amount of coating is the same as when a conventional impregnating resin is used. Moreover, what is necessary is just to apply | coat the said film forming material with a brush or spray.
本発明の封孔被膜は、従来の封孔処理による溶射金属被膜の気孔を単に充填する考え方に代えて、造膜性に優れ、通気性および撥水性を有する封孔被膜を溶射金属被膜の表面に設けることによって、溶射金属被膜の膨れや剥離、封孔被膜の膨張を防止する。溶射金属被膜は、犠牲防蝕作用による防蝕に加え金属基材の防蝕因子である水や酸素の遮断効果による防蝕効果を発揮する。 The sealing film of the present invention replaces the conventional idea of simply filling the pores of the sprayed metal film by the sealing treatment with a sealing film having excellent film-forming properties, air permeability and water repellency. By providing in, it prevents the thermal spraying metal film from swelling and peeling, and the sealing film from expanding. The thermally sprayed metal coating exhibits a corrosion prevention effect due to the blocking effect of water and oxygen, which are corrosion prevention factors of the metal substrate, in addition to the corrosion prevention due to the sacrificial corrosion protection action.
以下、本発明の実施例および比較例を示す。なお、実施例および比較例で使用した封孔処理剤は、使用に先立ちガラス板に亜鉛・アルミニウムを溶射した溶射金属被膜の表面に塗布して被膜を形成し、溶射ガラス板裏面を観察して封孔処理剤が全面に含浸することを確認し、含浸性に優れていることを確認した。 Examples of the present invention and comparative examples are shown below. In addition, the sealing agent used in the examples and comparative examples was applied to the surface of a sprayed metal coating obtained by spraying zinc / aluminum onto a glass plate before use to form a coating, and the back surface of the sprayed glass plate was observed. It was confirmed that the sealing agent was impregnated over the entire surface, and it was confirmed that the impregnation property was excellent.
〔基材となる金属溶射鋼材の作製〕
ショットブラスト処理で表面を清浄にした鋼板（3.2×70×150mm）に、溶射金属を付着させるための粗面形成材（大日本塗料社製品：ブラスノン21♯（商品名））１００g/ｍ2をエアスプレーガンで塗布、乾燥後、その上にアーク溶射機（エムエスエンジニアリング社製ＭＳ-２９９Ａz）を用い、亜鉛・アルミニウム擬合金溶射（亜鉛：アルミニウム容積比５：５）を行った。溶射には直径１.３ｍｍの純亜鉛および純アルミニウムの線材を用いた。これらを搬線速度１０ｍ／分、電圧１８Ｖ、電流２５０Ａ、空気圧７.０kg/ｍ２、溶射距離２
０cm、溶射角度９０度の条件で溶射し、１００μｍの溶射被膜を形成した。
[Production of metal-sprayed steel material as base material]
Rough surface forming material (Dainippon Paint Co., Ltd. product: Brassnon 21 # (trade name)) 100 g / m 2 for attaching sprayed metal to steel plate (3.2 × 70 × 150 mm) whose surface has been cleaned by shot blasting After coating and drying with an air spray gun, zinc / aluminum pseudoalloy spraying (zinc: aluminum volume ratio 5: 5) was performed thereon using an arc sprayer (MS-299Az manufactured by MS Engineering). Pure zinc and pure aluminum wires with a diameter of 1.3 mm were used for thermal spraying. These are 10 m / min in line speed, voltage 18 V, current 250 A, air pressure 7.0 kg / m 2 , spraying distance 2
Thermal spraying was performed under the conditions of 0 cm and a thermal spraying angle of 90 degrees to form a thermal spray coating of 100 μm.
〔実施例１、比較例１〜３〕
上記金属溶射鋼材の溶射金属被膜表面に、以下に示す封孔処理剤２００g／ｍ2をエアースプレーで供試体表面に塗布し、封孔被膜を形成した。これらの供試体について、規格（ＪＩＳ Ｈ ８５０２「めっきの耐食性試験方法」）に定めるキャス試験を行った。このキャス試験は酢酸酸性の塩化ナトリウム溶液に塩化第二銅二水和物を添加した溶液（以下「酢酸酸性塩水」という）を供試体表面に連続噴霧した。試験結果を表１に示した。
[Example 1, Comparative Examples 1-3]
The sealing agent 200 g / m 2 shown below was applied to the surface of the specimen by air spraying on the surface of the metal sprayed metal coating of the metal sprayed steel material to form a sealing coating. These specimens were subjected to a cast test defined in the standard (JIS H 8502 “Plating corrosion resistance test method”). In this casting test, a solution obtained by adding cupric chloride dihydrate to an acetic acid acidic sodium chloride solution (hereinafter referred to as “acetic acid acidic brine”) was continuously sprayed on the surface of the specimen. The test results are shown in Table 1.
実施例１は以下に示す方法で調製した本発明の封孔処理剤２００g／ｍ2を塗布した供試体を用いた。
（１）（メタ）アクリル酸エステル系ポリマーエマルジョンに３０％コロイダルシリカと反応型アルキルシリル誘導体を添加し、ディゾルバーで１時間攪拌して被膜形成剤を調製した。
（２）５５％トリメチルシリルスルフォン酸１００部をディゾルバーで攪拌しながら、ゆっくりと３０％コロイダルシリカ１００部を加えた後、メチルセルロース３部を５０℃で２時間ホモミキサーでよく混合分散させた。得られた分散体はシリカでコーティングされたアルキルシリル誘導体からなる反応型シリコン撥水剤である。
（３）上記(１)の４８％濃度の被膜形成剤１００重量部と、上記(２)の反応型シリコン撥水剤６０部を常温でディゾルバーにより２時間混合して封孔処理剤Ａを得た。
In Example 1, a specimen coated with 200 g / m 2 of the sealing agent of the present invention prepared by the method described below was used.
(1) A 30% colloidal silica and a reactive alkylsilyl derivative were added to a (meth) acrylic acid ester polymer emulsion and stirred for 1 hour with a dissolver to prepare a film forming agent.
(2) While 100 parts of 55% trimethylsilylsulfonic acid was stirred with a dissolver, 100 parts of 30% colloidal silica was slowly added, and then 3 parts of methylcellulose was well mixed and dispersed at 50 ° C. for 2 hours with a homomixer. The obtained dispersion is a reactive silicon water repellent composed of an alkylsilyl derivative coated with silica.
(3) The sealing agent A is obtained by mixing 100 parts by weight of the 48% concentration film-forming agent of (1) above and 60 parts of the reactive silicon water repellent of (2) above with a dissolver at room temperature for 2 hours. It was.
比較例１は、一般に使用されている市販のブチラール樹脂系溶射金属被膜用封孔処理剤（特開平９−１２５２２１号の封孔処理剤）２００g／ｍ2を塗布した供試体を用いた。
比較例２は、シリコーン乳化物（アルキルアルコキシシランおよびアルキルアルコキシシロキサン含有）の浸透性吸水防止剤（非造膜型、市販品）２００g／ｍ2を塗布した供試体を用いた。
比較例３は、封孔処理を行わない供試体を用いた。
In Comparative Example 1, a test specimen coated with 200 g / m 2 of a commonly used butyral resin-based thermal spray metal coating sealing agent (sealing agent of JP-A-9-125221) was used.
In Comparative Example 2, a test specimen coated with 200 g / m 2 of a permeable water absorption inhibitor (non-film-forming type, commercially available) of a silicone emulsion (containing alkylalkoxysilane and alkylalkoxysiloxane) was used.
In Comparative Example 3, a specimen not subjected to sealing treatment was used.
実施例１を除き、いずれの供試体も酢酸酸性塩水の噴霧初期に溶射被膜金属の酸化物である白錆が発生し、徐々に被膜が消耗し、やがて基材の鋼材が発錆した。比較例１は噴霧１７日で鋼材が発錆した。浸透性の吸水防水剤を用いた比較例２と無封孔処理の比較例３は何れも噴霧１４日で基材の鋼材が発錆した。一方、実施例１は噴霧４０日でも鋼材が発錆せず、優れた防蝕効果が得られた。 Except for Example 1, in all specimens, white rust which is an oxide of a sprayed coating metal was generated at the initial stage of spraying of acetic acid acidic salt water, the coating was gradually consumed, and the steel material of the base material eventually rusted. In Comparative Example 1, the steel material rusted after 17 days of spraying. In both Comparative Example 2 using a permeable water-absorbing waterproofing agent and Comparative Example 3 of non-sealing treatment, the steel material of the base material rusted after 14 days of spraying. On the other hand, in Example 1, the steel material did not rust even after 40 days of spraying, and an excellent anticorrosive effect was obtained.
〔実施例２、３、比較例４〜６〕
景観等の目的から着色仕上げを行うケースを想定して、着色仕上げを行った場合の封孔効果の試験を行った。供験体は実施例１および比較例１〜３と同様に前述の基材となる金属溶射鋼材の溶射金属被膜表面に、以下に示す封孔処理またはその上に仕上げ塗装を行ったものである。
[Examples 2 and 3, Comparative Examples 4 to 6]
Assuming the case of coloring finish for the purpose of landscape, etc., the sealing effect test when coloring finish was performed was performed. The test body is the same as in Example 1 and Comparative Examples 1 to 3, on the surface of the thermally sprayed metal coating of the metal sprayed steel material used as the base material described above, or the following sealing treatment or finish coating is performed thereon. .
実施例２は、プライマー（水性アクリル系樹脂）１００g／ｍ2の下地に実施例１の封孔処理剤Ａ（無着色）２００g／ｍ2を塗布したものである。実施例３は、プライマー（水性アクリル系樹脂）１００g／ｍ2の下地に封孔処理剤Ｂを２００g／ｍ2塗布したものである。孔処理剤Ｂは封孔処理剤Ａに超微粒子炭酸カルシウム７部と水分散グレーペースト２部を添加してグレーに着色した封孔処理と仕上げを兼ねた封孔処理剤である。 In Example 2, 200 g / m 2 of the sealing agent A (uncolored) of Example 1 was applied to a primer (aqueous acrylic resin) 100 g / m 2 . In Example 3, 200 g / m 2 of the sealing agent B was applied to the base of 100 g / m 2 of the primer (aqueous acrylic resin). The pore-treating agent B is a pore-treating agent that combines the sealing treatment A with 7 parts of ultrafine calcium carbonate and 2 parts of a water-dispersed gray paste and is colored gray.
比較例４は封孔処理をしない供試体である。比較例５は、気孔充填型の封孔処理の上に着色封孔処理剤をエアースプレーで塗布したものであり、気孔充填型の封孔処理剤として浸透性湿気硬化型ウレタン樹脂封孔処理剤を用い、このウレタン樹脂封孔処理剤１００g／ｍ2の下地に封孔処理剤Ｂを２００g／ｍ2塗布したものである。 Comparative Example 4 is a specimen that is not sealed. In Comparative Example 5, a colored sealing agent is applied by air spray on a pore-filling type sealing treatment, and a permeable moisture curable urethane resin sealing agent is used as the pore-filling type sealing agent. And 200 g / m 2 of sealing agent B is applied to the base of 100 g / m 2 of this urethane resin sealing agent.
実施例２は、噴霧日数４０日経過しても塗膜の膨れおよび発錆が無く、最も優れた防蝕性能を示した。実施例３は噴霧４０日で塗膜の膨れは無かったが噴霧４０日に鋼材の発錆が見られたものの、比較例４、５よりも優れた防蝕効果が得られた。一方、比較例４は噴霧２０日で被膜の膨れと鋼材の発錆が見られた。比較例５は封孔処理剤Ｂを用いているが、浸透性湿気硬化型ウレタン樹脂封孔処理剤を下地に用いているため、溶射被膜の膨れが発生し、封孔処理剤Ｂの防蝕効果が発揮されず、噴霧１０日で早々に被膜の膨れと鋼材の発錆が見られた。 Example 2 showed the most excellent anticorrosion performance without the swelling and rusting of the coating film even after 40 days of spraying. In Example 3, there was no swelling of the coating film on the 40th day of spraying, but although corrosion of the steel material was observed on the 40th day of spraying, an anticorrosive effect superior to Comparative Examples 4 and 5 was obtained. On the other hand, in Comparative Example 4, swelling of the coating and rusting of the steel material were observed after 20 days of spraying. In Comparative Example 5, the sealing agent B is used. However, since the permeable moisture-curing urethane resin sealing agent is used as a base, the sprayed coating swells, and the anticorrosive effect of the sealing agent B. However, the swelling of the coating and the rusting of the steel material were observed quickly after 10 days of spraying.
Claims (5)
A corrosion-resistant coating comprising a spray coating of a base metal provided on the surface of the metal substrate and a sealing coating having air permeability and water repellency provided on the surface of the spray coating. .
The anticorrosion coating according to claim 1, wherein the sealing coating is formed by an aqueous sealing agent obtained by mixing colloidal silica and a reactive silicon water repellent in an aqueous polymer emulsion.
The water-based sealing agent is obtained by adding 10 to 100 parts by weight of a reactive silicon water repellent per 100 parts by weight of a film-forming agent obtained by mixing colloidal silica with an aqueous polymer emulsion in terms of solid matter. 2. Corrosion resistant coating.
A base metal is sprayed on the surface of the metal substrate, and a water-based sealing agent is applied to the surface of the sprayed metal coating to form a sealing coating having air permeability and water repellency. A method of forming an anticorrosion film.
5. The water-based sealing agent according to claim 4, wherein 10-100 parts by weight of a reactive silicone water repellent is added per 100 parts by weight of a film-forming agent obtained by mixing colloidal silica with an aqueous polymer emulsion in terms of solid matter. A method for forming a corrosion-resistant coating film, wherein a sealing coating film having air permeability and water repellency is formed on the surface of the sprayed metal coating.
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| JP2009263739A (en) * | 2008-04-28 | 2009-11-12 | Sho Bond Constr Co Ltd | Electric corrosion protection method of reinforced concrete structure |
| JP2012007209A (en) * | 2010-06-25 | 2012-01-12 | Kubota Corp | Surface treated ferrous member and method for treating surface of ferrous member |
| WO2013105332A1 (en) * | 2012-01-10 | 2013-07-18 | 日立オートモティブシステムズ株式会社 | Power semiconductor module, power module, and power module manufacturing method |
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