JP2017101146A - ONE LIQUID TYPE HIGH CORROSION RESISTANT COATING COMPOSITION USING Sn ION - Google Patents
ONE LIQUID TYPE HIGH CORROSION RESISTANT COATING COMPOSITION USING Sn ION Download PDFInfo
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- 239000008199 coating composition Substances 0.000 title claims abstract description 33
- 238000005260 corrosion Methods 0.000 title claims abstract description 24
- 230000007797 corrosion Effects 0.000 title claims abstract description 22
- 239000007788 liquid Substances 0.000 title abstract 3
- 239000000049 pigment Substances 0.000 claims abstract description 73
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 66
- 239000010959 steel Substances 0.000 claims abstract description 66
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000000576 coating method Methods 0.000 claims abstract description 29
- 239000011248 coating agent Substances 0.000 claims abstract description 26
- 239000011347 resin Substances 0.000 claims abstract description 24
- 229920005989 resin Polymers 0.000 claims abstract description 24
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims abstract description 17
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims abstract description 17
- 239000004606 Fillers/Extenders Substances 0.000 claims abstract description 14
- 230000003449 preventive effect Effects 0.000 claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000000391 magnesium silicate Substances 0.000 claims abstract description 5
- 229910052919 magnesium silicate Inorganic materials 0.000 claims abstract description 5
- 235000019792 magnesium silicate Nutrition 0.000 claims abstract description 5
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 4
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000003973 paint Substances 0.000 claims description 26
- 229910000870 Weathering steel Inorganic materials 0.000 claims description 10
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003921 oil Substances 0.000 claims description 6
- 238000010422 painting Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 24
- 230000003647 oxidation Effects 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 239000007787 solid Substances 0.000 abstract description 3
- 238000004040 coloring Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 8
- 230000008439 repair process Effects 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 229920000180 alkyd Polymers 0.000 description 4
- ZADYMNAVLSWLEQ-UHFFFAOYSA-N magnesium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[Mg+2].[Si+4] ZADYMNAVLSWLEQ-UHFFFAOYSA-N 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 229910001432 tin ion Inorganic materials 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000012756 surface treatment agent Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical group CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 244000181025 Rosa gallica Species 0.000 description 1
- 235000000533 Rosa gallica Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- QBLDFAIABQKINO-UHFFFAOYSA-N barium borate Chemical compound [Ba+2].[O-]B=O.[O-]B=O QBLDFAIABQKINO-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 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
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- -1 sericite Chemical compound 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
本発明は、製鉄所、化学プラント、海洋構造物等の過酷な環境下にある普通鋼材または耐候性鋼材からなる鋼構造物や鋼製配管等の維持補修に用いられる１液型高耐食性塗料組成物に関する。 The present invention relates to a one-pack type high corrosion resistance paint composition used for maintenance and repair of steel structures and steel pipes made of ordinary steel or weathering steel under harsh environments such as steelworks, chemical plants, and marine structures. Related to things.
従来から、製鉄所、化学プラント、海洋構造物等の過酷な環境下にある普通鋼からなる鋼構造物や鋼製配管等の防食には、アルキド樹脂系塗料を下塗りとした塗装システムが用いられてきており、さらに必要に応じて各種の上塗り塗料が塗り重ねられている。 Conventionally, a coating system with an undercoat of alkyd resin-based paint has been used for corrosion protection of steel structures and steel pipes made of ordinary steel in harsh environments such as steelworks, chemical plants, and marine structures. In addition, various top coats are applied as necessary.
一方、鋼製の橋梁等には安定錆の保護機能により塗装が不要である耐候性鋼材が多く用いられている。しかし、耐候性鋼材においても融雪剤等によって安定錆の形成が阻害される場合には、特許文献１に示されるように表面処理剤が塗装される。この場合、表面処理剤は、安定錆が形成されるまでの期間、耐候性鋼材の上に存在すればよいので、その膜厚は１０〜１００μｍ程度と薄く、バインダーとして用いられる樹脂としては、ブチラール樹脂、フェノール樹脂、ビニルエステル樹脂等の非架橋タイプが主である。 On the other hand, many weather-resistant steel materials are used for steel bridges and the like, which do not require painting due to the protection function of stable rust. However, even in the weather resistant steel material, when the formation of stable rust is hindered by a snow melting agent or the like, a surface treatment agent is applied as shown in Patent Document 1. In this case, since the surface treatment agent only needs to be present on the weathering steel material until stable rust is formed, the film thickness is as thin as about 10 to 100 μm, and the resin used as the binder is butyral. Mainly non-crosslinked types such as resin, phenol resin, vinyl ester resin.
製鉄所、化学プラント、海洋構造物等における普通鋼からなる鋼構造物や鋼製配管等では、厚膜塗装システムを採用していても、供用中の塗膜の劣化、すなわち塗膜に鋼材にまで達する傷が付くことは不可避であり、その傷から錆が発生することを如何に抑制するかが施設管理者の課題である。鋼材の水平方向に拡がる錆は、初期段階では外観の悪化にとどまるが、深さ方向に進行する錆は、構造物の内部に保管されている物質の漏出や強度低下ひいては構造物の寿命にも関わる問題であり、その対策が求められている。 Steel structures and steel pipes made of ordinary steel in steelworks, chemical plants, offshore structures, etc., even if a thick film coating system is adopted, the coating film in service is deteriorated, that is, the coating film is made of steel. It is inevitable that the damage reaches the maximum, and how to suppress the generation of rust from the damage is a problem for the facility manager. Rust that spreads in the horizontal direction of the steel material only deteriorates the appearance at the initial stage, but rust that progresses in the depth direction can cause leakage of materials stored inside the structure, decrease in strength, and even the life of the structure. It is a related issue and countermeasures are required.
また、補修塗装においては、構造上の制約や危険物が存在する等の周辺環境の制約のため、粉塵が多量に発生するブラスト処理や火花が生じるディスクサンダー処理といった有効性の高いケレン処理作業が行えない場合が殆どであり、そのため被塗面に錆や塩化物等が残留し、早期に補修塗膜に膨れや剥がれ等が生じることがある。さらに、残留した錆や塩化物等の作用により塗膜下での局所的な深い腐食も生じている。 In addition, in repair coating, due to structural restrictions and restrictions on the surrounding environment such as the presence of dangerous materials, highly effective kelen processing operations such as blast processing that generates a large amount of dust and disc sander processing that generates sparks are performed. In most cases, this is not possible, and as a result, rust, chloride, etc. remain on the surface to be coated, and the repair coating film may swell or peel off at an early stage. Furthermore, local deep corrosion under the coating film is also caused by the action of residual rust and chloride.
出願人は、かかる問題を克服するために、鋼材の深さ方向に進行する錆を抑制する手段としてＳｎイオンを利用した高耐食性塗料組成物を提案したが（特許文献２参照）、鋼材の深さ方向の進行錆を効果的に抑制する１液型塗料組成物がさらに求められている。 In order to overcome this problem, the applicant has proposed a highly corrosion-resistant coating composition using Sn ions as means for suppressing rust that progresses in the depth direction of the steel material (see Patent Document 2). There is a further need for a one-component coating composition that effectively suppresses the forward rust.
本発明は、かかる従来技術の現状に鑑みなされたものであり、その目的は、普通鋼材または耐候性鋼材からなる鋼構造物または鋼製配管等の表面の深さ方向に進行する錆を抑制するための１液型高耐食性塗料組成物、及びそれを使用した塗装方法を提供することにある。 This invention is made | formed in view of the present condition of this prior art, The objective suppresses the rust which advances to the depth direction of the surface of steel structures, steel pipes, etc. which consist of a normal steel material or a weathering steel material. An object of the present invention is to provide a one-component high-corrosion-resistant coating composition and a coating method using the same.
上記目的を達成するためには、鋼材の深さ方向に進行する錆を抑制する手段として、塗料組成物中に特定量の二価のスズイオン（硫酸第一スズ）の存在が重要である。 In order to achieve the above object, the presence of a specific amount of divalent tin ions (stannous sulfate) in the coating composition is important as a means for suppressing rust that progresses in the depth direction of the steel material.
具体的には、二価のスズイオンによる錆抑制メカニズムは以下の通りである。
飛来塩分量の多い環境下濡れ状態では、ＦｅＣｌ３溶液による腐食が本質的な条件となり、Ｆｅ３＋の加水分解によりｐＨが低下した状態でＦｅ３＋が酸化剤として作用する。
カソード反応：Ｆｅ３＋＋ｅ−→Ｆｅ２＋
アノード反応：Ｆｅ→Ｆｅ２＋＋２ｅ−
従って、腐食の総括反応は２Ｆｅ３＋＋Ｆｅ→３Ｆｅ２＋となる。
Ｓｎは、Ｓｎ２＋として溶解すると、空気酸化あるいは２Ｆｅ３＋＋Ｓｎ２＋→２Ｆｅ２＋＋Ｓｎ４＋という反応によってＳｎ４＋を生成する。Ｓｎ２＋およびＳｎ４＋はいずれも鋼のアノード溶解を抑制するという作用がある。結果として、スズイオンの存在は、防錆顔料として有効に作用する。なお、乾燥過程でのカソード反応は酸素還元反応であることはいうまでもない。
Specifically, the mechanism of rust suppression by divalent tin ions is as follows.
In a wet state under an environment with a large amount of flying salt, corrosion by the FeCl 3 solution becomes an essential condition, and Fe 3+ acts as an oxidizing agent in a state where the pH is lowered by the hydrolysis of Fe 3+ .
Cathode reaction: Fe 3+ + e − → Fe 2+
Anode reaction: Fe → Fe 2+ + 2e −
Therefore, the overall reaction of corrosion is 2Fe 3+ + Fe → 3Fe 2+ .
When Sn is dissolved as Sn 2+ , Sn 4+ is generated by air oxidation or a reaction of 2Fe 3+ + Sn 2+ → 2Fe 2+ + Sn 4+ . Both Sn 2+ and Sn 4+ have the effect of suppressing anodic dissolution of steel. As a result, the presence of tin ions effectively acts as a rust preventive pigment. Needless to say, the cathode reaction in the drying process is an oxygen reduction reaction.
本発明は、上記の知見を前提として鋼材の深さ方向の進行錆を効果的に抑制する１液型高耐食性塗料組成物をさらに検討した結果、完成されたものであり、以下の（１）〜（３）の構成を有するものである。
（１）普通鋼材または耐候性鋼材からなる鋼構造物または鋼製配管の表面に使用される１液型高耐食性塗料組成物であって、塗料組成物が、（Ａ）不飽和結合を有する酸化重合性樹脂、（Ｂ）硫酸第一スズ、（Ｃ）防錆顔料、（Ｄ）体質顔料、及び（Ｅ）着色顔料を含有し、（Ｂ）硫酸第一スズの含有量が、塗料組成物の１００重量部に対して２．０〜８．０重量部であり、（Ｃ）防錆顔料の含有量が、（Ａ）不飽和結合を有する酸化重合性樹脂固形分１００重量部に対して１０〜２０重量部であり、（Ｄ）体質顔料が、セリサイト系顔料、二酸化ケイ素系顔料、含水ケイ酸マグネシウム系顔料、及び炭酸カルシウム系顔料からなる群から選ばれる少なくとも１種の顔料を含有し、形成される塗膜における顔料体積濃度が、３０〜４０％の範囲であることを特徴とする１液型高耐食性塗料組成物。
（２）（１）に記載の１液型高耐食性塗料組成物を下塗り塗料（Ｉ）として、１回あたりの硬化膜厚が３５〜７０μｍとなるようにして鋼構造物または鋼製配管の表面に複数回塗装し、次いで長油性フタル酸樹脂系塗料及び中油性フタル酸樹脂系塗料からなる群から選ばれる上塗り塗料（ＩＩ）を硬化膜厚で２０〜５０μｍとなるようにその表面に塗装することを特徴とする塗装方法。
（３）（２）に記載の塗装方法によって塗装されていることを特徴とする普通鋼材または耐候性鋼材の鋼構造物または鋼製配管。
The present invention has been completed as a result of further study of a one-pack type high corrosion resistance coating composition that effectively suppresses the progress of rust in the depth direction of the steel material on the basis of the above knowledge. The following (1) It has the structure of (3).
(1) A one-component high corrosion resistance coating composition used on the surface of steel structures or steel pipes made of ordinary steel or weathering steel, wherein the coating composition is (A) an oxidation having an unsaturated bond Polymeric resin, (B) stannous sulfate, (C) rust preventive pigment, (D) extender pigment, and (E) colored pigment, and (B) stannous sulfate content is a coating composition 2.0 to 8.0 parts by weight with respect to 100 parts by weight of (C), and (C) the content of the anticorrosive pigment is (A) with respect to 100 parts by weight of the oxidizable polymerizable resin having an unsaturated bond. 10 to 20 parts by weight, and (D) the extender pigment contains at least one pigment selected from the group consisting of sericite pigments, silicon dioxide pigments, hydrous magnesium silicate pigments, and calcium carbonate pigments The pigment volume concentration in the formed coating film is in the range of 30 to 40%. One-high corrosion resistance coating composition characterized in that it.
(2) The surface of a steel structure or a steel pipe so that the one-pack type highly corrosion-resistant coating composition described in (1) is used as an undercoat coating (I) so that the cured film thickness per time is 35 to 70 μm. Is then applied several times, and then a top coating (II) selected from the group consisting of a long oil phthalate resin paint and a medium oil phthalate resin paint is applied to the surface so that the cured film thickness is 20 to 50 μm. A painting method characterized by that.
(3) A steel structure or a steel pipe made of ordinary steel or weathering steel, which is coated by the coating method described in (2).
本発明によれば、腐食性の高い過酷な高飛来塩化物環境下にある普通鋼または耐候性鋼材からなる鋼構造物や鋼製配管等の表面の深さ方向に進行する錆を効果的に防止することができる１液型高耐食性塗料組成物を提供することができる。 According to the present invention, rust that progresses in the depth direction of the surface of a steel structure or a steel pipe made of ordinary steel or weathering steel in a highly corrosive and severe high-fly chloride environment is effectively prevented. A one-component high corrosion resistance coating composition that can be prevented can be provided.
本発明の１液型高耐食性塗料組成物は、普通鋼材または耐候性鋼材からなる鋼構造物または鋼製配管等の表面に使用されるものであり、（Ａ）不飽和結合を有する酸化重合性樹脂、（Ｂ）硫酸第一スズ、（Ｃ）防錆顔料、（Ｄ）体質顔料、及び（Ｅ）着色顔料を含有する。 The one-pack type high corrosion resistance coating composition of the present invention is used on the surface of steel structures or steel pipes made of ordinary steel or weathering steel, and (A) oxidation-polymerizable having an unsaturated bond. Resin, (B) stannous sulfate, (C) rust preventive pigment, (D) extender pigment, and (E) colored pigment.
基剤樹脂としては、１液型塗料用樹脂として使用されている、ウレタン樹脂、アクリル樹脂、アルキド樹脂、エポキシ樹脂、および、それらの混合物、グラフト重合物、ブロック重合物を使用することができるが、本発明では、作業性と性能のバランスから、（Ａ）不飽和結合を有する酸化重合性樹脂を使用することが好ましい。 As the base resin, urethane resins, acrylic resins, alkyd resins, epoxy resins, and mixtures thereof, graft polymers, and block polymers, which are used as one-component paint resins, can be used. In the present invention, from the balance between workability and performance, it is preferable to use (A) an oxidation polymerizable resin having an unsaturated bond.
（Ａ）不飽和結合を有する酸化重合性樹脂としては、不飽和基含有アルキド樹脂、不飽和基含有エポキシ変性アルキド樹脂、不飽和基含有ポリエステル樹脂、および、それらと他の樹脂との混合物が好適に使用できる。（Ａ）不飽和結合を有する酸化重合性樹脂は、塗料組成物１００重量部に対して２０〜４０重量部配合されることが好ましい。 (A) As an oxidative polymerizable resin having an unsaturated bond, an unsaturated group-containing alkyd resin, an unsaturated group-containing epoxy-modified alkyd resin, an unsaturated group-containing polyester resin, and a mixture thereof with other resins are suitable. Can be used for (A) It is preferable that 20-40 weight part of oxidatively polymerizable resin which has an unsaturated bond is mix | blended with respect to 100 weight part of coating compositions.
（Ｂ）硫酸第一スズは、深さ方向の錆の進行を抑制するために使用されるものであり、塗料組成物の１００重量部に対して２．０〜８．０重量部、好ましくは４．０〜８．０重量部配合される。（Ｂ）硫酸第一スズの配合が上記割合より少ない場合には、深さ方向の錆を抑制する効果が得られず、また、上記割合より多い場合には、塗膜が長期間水につけられた場合に膨れが生じやすくなるので好ましくない。 (B) stannous sulfate is used to suppress the progress of rust in the depth direction, and is preferably 2.0 to 8.0 parts by weight, preferably 100 parts by weight of the coating composition. 4.0 to 8.0 parts by weight are blended. (B) If the stannous sulfate content is less than the above ratio, the effect of suppressing rust in the depth direction cannot be obtained, and if it is greater than the above ratio, the coating film is immersed in water for a long period of time. In such a case, swelling is likely to occur.
本発明の塗料組成物には、通常の防食用途の１液型塗料に使用される各種の顔料として（Ｃ）防錆顔料、（Ｄ）体質顔料、（Ｅ）着色顔料が使用される。 In the coating composition of the present invention, (C) an anticorrosive pigment, (D) an extender pigment, and (E) a colored pigment are used as various pigments used in a one-component paint for ordinary anticorrosion applications.
（Ｃ）防錆顔料としては、縮合リン酸アルミニウム系、カルシウム系、リン酸亜鉛系、モリブデン酸亜鉛系、メタホウ酸バリウム系等が挙げられる。（Ｃ）防錆顔料の配合量は、（Ａ）不飽和結合を有する酸化重合性樹脂の固形分１００重量部に対して１０〜２０重量部、好ましくは１１〜１９重量部である。（Ｃ）防錆顔料の配合が上記割合より少ない場合には、塗膜の傷からの錆の発生を抑制する効果が不十分となり、また、上記割合を超えて配合してもそれ以上の効果は認められない。 (C) Examples of the rust preventive pigment include condensed aluminum phosphate, calcium, zinc phosphate, zinc molybdate, and barium metaborate. (C) The compounding quantity of a rust preventive pigment is 10-20 weight part with respect to 100 weight part of solid content of the oxidation polymerizable resin which has (A) unsaturated bond, Preferably it is 11-19 weight part. (C) When the proportion of the rust preventive pigment is less than the above proportion, the effect of suppressing the generation of rust from the scratches on the coating film becomes insufficient, and even if the proportion exceeds the above proportion, the effect is higher. It is not allowed.
（Ｄ）体質顔料は、塗料の性状を調整するために用いられる。一般に１液型塗料においては、硫酸バリウム、カオリン、マイカ、クレー系、セリサイト系、二酸化ケイ素系、含水ケイ酸マグネシウム系などの体質顔料が用いられるが、本発明の塗料組成物は、セリサイト系顔料、二酸化ケイ素系顔料、含水ケイ酸マグネシウム系顔料、及び炭酸カルシウム系顔料からなる群から選ばれる少なくとも１種の体質顔料が使用される。これらの体質顔料の配合量は、塗料組成物中の顔料の全重量の５０重量％以上であることが好ましい。５０重量％より少ない場合には十分な充填効果が得られず、塗膜強度が得られない可能性がある。 (D) The extender pigment is used to adjust the properties of the paint. In general, in one-pack type paints, extender pigments such as barium sulfate, kaolin, mica, clay, sericite, silicon dioxide, and hydrous magnesium silicate are used. At least one extender selected from the group consisting of pigments based on pigments, silicon dioxide pigments, hydrous magnesium silicate pigments, and calcium carbonate pigments is used. The amount of these extender pigments is preferably 50% by weight or more of the total weight of the pigments in the coating composition. When the amount is less than 50% by weight, a sufficient filling effect cannot be obtained, and the coating film strength may not be obtained.
（Ｅ）着色顔料は、塗料を彩色するためのものであり、通常の１液型塗料に使用される着色顔料が使用される。このような着色顔料としては、二酸化チタン、カーボンブラック、フタロシアニンブルー、ベンガラ、有機系黄色顔料、有機系赤顔料などが挙げられるが、これらに限定されるものではない。 (E) The color pigment is for coloring the paint, and a color pigment used in a normal one-component paint is used. Examples of such a colored pigment include, but are not limited to, titanium dioxide, carbon black, phthalocyanine blue, red rose, organic yellow pigment, and organic red pigment.
本発明の塗料組成物では、形成される塗膜における硫酸第一スズ、防錆顔料、体質顔料、着色顔料からなる顔料体積濃度は３０〜４０％の範囲にあり、好ましくは３１〜３９％の範囲にある。ここで「顔料体積濃度」は、塗料中の全樹脂分と全顔料との合計固形分に占めるその顔料分の体積割合である。顔料の体積は、顔料の重量と密度から計算することができる。顔料体積濃度が上記下限より小さい場合には、塗膜が長期間浸漬されたときに膨れが生じやすくなり、一方上記上限より大きい場合には、塗膜が長期間浸漬されたときに点錆が生じやすくなる。 In the coating composition of the present invention, the pigment volume concentration composed of stannous sulfate, rust preventive pigment, extender pigment, and colored pigment in the formed coating film is in the range of 30 to 40%, preferably 31 to 39%. Is in range. Here, the “pigment volume concentration” is a volume ratio of the pigment content in the total solid content of the total resin content and the total pigment content in the paint. The pigment volume can be calculated from the pigment weight and density. When the pigment volume concentration is less than the above lower limit, swelling tends to occur when the coating film is immersed for a long period of time, while when it is larger than the above upper limit, spot rust occurs when the coating film is immersed for a long period of time. It tends to occur.
本発明の塗料組成物は、上記の（Ａ）〜（Ｅ）の成分以外に、通常の１液型塗料に用いられるタレ止め剤、消泡剤、レベリング剤、カップリング剤、金属ドライヤー等の添加剤をそのまま使用することができる。 In addition to the components (A) to (E) described above, the coating composition of the present invention includes a sagging inhibitor, an antifoaming agent, a leveling agent, a coupling agent, a metal dryer, and the like that are used in ordinary one-component paints. The additive can be used as it is.
本発明の塗料組成物は、単独で複数回、例えば２〜３回塗り重ねて使用されることができるが、周囲と色調を合わせたり長期間変退色を抑制する必要がある場合には、本発明の塗料組成物を下塗り塗料（Ｉ）とし、他の適当な上塗り塗料（ＩＩ）を併用することができる。本発明の塗料組成物を下塗り塗料（Ｉ）として使用する場合には、１回あたりの硬化膜厚が３５〜７０μｍとなるようにして、鋼構造物または鋼製配管等の表面に塗装され、この表面にさらに上塗り塗料（ＩＩ）が塗装される。 The coating composition of the present invention can be used by being applied a plurality of times, for example, 2 to 3 times, but if it is necessary to match the color tone with the surroundings or to suppress discoloration for a long time, The coating composition of the invention can be used as the undercoat paint (I), and other appropriate topcoat paint (II) can be used in combination. When the coating composition of the present invention is used as the undercoat paint (I), it is applied to the surface of a steel structure or a steel pipe so that the cured film thickness per time is 35 to 70 μm, The top coat (II) is further applied to this surface.
上塗り塗料（ＩＩ）は、例えば長油性フタル酸樹脂系塗料及び中油性フタル酸樹脂系塗料のような合成樹脂調合ペイントから選ばれ、その膜厚としては、２０〜５０μｍが好適である。上述のように、下塗り塗料（Ｉ）及び上塗り塗料（ＩＩ）を塗布した場合、複層塗膜のＳＡＥ Ｊ２３３４（ＳＡＥ：Ｓｏｃｉｅｔｙ Ａｕｔｏｍｏｔｉｖｅ Ｅｎｇｉｎｅｅｒｓ）試験５０サイクルにおける剥離面積率が３％未満、好ましくは１．５％未満であり、最大腐食深さが０．２５ｍｍ未満、好ましくは０．２ｍｍ未満であることができる。 The top coating material (II) is selected from synthetic resin-prepared paints such as long oil phthalic acid resin-based paints and medium oil phthalic acid resin-based paints, and the film thickness is preferably 20 to 50 μm. As described above, when the undercoat paint (I) and the top coat paint (II) are applied, the peeled area ratio in the 50 cycles of the SAE J2334 (SAE: Society Automotive Engineers) test of the multilayer coating film is less than 3%, preferably 1 .5% and the maximum corrosion depth can be less than 0.25 mm, preferably less than 0.2 mm.
本発明の塗料組成物を使用して塗装することにより、製鉄所や化学プラント、海洋構造物等における鋼構造物や鋼製配管では、塗膜に鋼材に達するような傷が入っても深さ方向への錆の進行が効果的に抑制されるので、補修が容易であり、設備を長期間稼働することが可能になる。 By painting using the coating composition of the present invention, in steel structures and steel pipes in steelworks, chemical plants, marine structures, etc., even if scratches that reach the steel material enter the coating film, the depth Since the progress of rust in the direction is effectively suppressed, the repair is easy and the facility can be operated for a long time.
補修塗装においては、構造上の制約や危険物が存在する等の周辺環境の制約のため、粉塵が多量に発生するブラスト処理や火花が生じるディスクサンダー処理といった有効性の高いケレン処理作業が行えない場合が殆どである。その場合はワイヤーブラシ処理やスクレーパー等の手工具でのケレン処理作業となり錆や塩化物等が残存する。本発明の塗料組成物を使用して塗装することにより、鋼材の深さ方向への錆の進行が抑制される。本発明の塗料組成物の塗装対象となる鋼材としては、普通鋼材のみならず、Ｓｎ，Ｃｕ，Ｃｒ，Ｎｉ等の耐食性改善元素が添加されている耐候性鋼材でもよく、寧ろ好適である。 In repair painting, due to structural restrictions and restrictions on the surrounding environment such as the presence of dangerous materials, highly effective kelen processing such as blasting that generates a large amount of dust and disc sandering that generates sparks cannot be performed. Most of the cases. In that case, it becomes a kelen treatment work with a hand tool such as a wire brush treatment or a scraper, and rust, chloride, etc. remain. By applying the coating composition of the present invention, the progress of rust in the depth direction of the steel material is suppressed. The steel material to be coated with the coating composition of the present invention is not only a normal steel material but also a weathering steel material to which a corrosion resistance improving element such as Sn, Cu, Cr, Ni or the like is added.
表１に示す材料及び配合の（Ａ）不飽和結合を有する酸化重合性樹脂、（Ｂ）硫酸第一スズ、（Ｃ）防錆顔料、（Ｄ）体質顔料、（Ｅ）着色顔料等に粘度３０〜７０ｄＰａ・Ｓになるように適量の溶剤を加えて、均一な状態となるように攪拌することにより下塗り塗料を作成した。表中の各成分の含有量は重量部を表わす。 Viscosity to (A) oxidation polymerizable resin having unsaturated bond, (B) stannous sulfate, (C) antirust pigment, (D) extender pigment, (E) colored pigment, etc. An undercoat paint was prepared by adding an appropriate amount of solvent so as to be 30 to 70 dPa · S, and stirring the mixture so as to be in a uniform state. The content of each component in the table represents parts by weight.
作成した下塗り塗料を、普通鋼材から作成したブラスト板またはワイヤーブラシ処理で浮き錆を除去した錆鋼板の全面に、所定の乾燥膜厚が得られるよう１回あたり５０μｍになるようにエアースプレーで１日１回塗りで２回塗装した。また、上塗り塗料については、下塗り塗料の塗装後に１回塗りで２５μｍとなるようエアースプレーで塗装した。塗装終了後は２３℃で７日間乾燥して、試験板上に防錆塗膜を形成させた。なお、錆鋼板は、同様のブラスト板をＳＡＥ Ｊ２３３４で１０サイクル試験して作成したものを使用した。 Apply the prepared undercoat paint to the entire surface of a blasted plate made from plain steel or from a rusted steel plate from which rust has been removed by wire brush treatment, and air spray so that a predetermined dry film thickness can be obtained at 50 μm per time. Painted twice a day. In addition, the top coat was applied by air spray so that the final coat was 25 μm after the undercoat was applied. After the completion of coating, the coating was dried at 23 ° C. for 7 days to form a rust preventive coating on the test plate. In addition, the rust steel plate used what produced the same blast board by carrying out 10 cycles test by SAE J2334.
こうして作成した供試材をＳＡＥ Ｊ２３３４で５０サイクル試験して、鋼材の最大腐食深さと塗膜の剥離面積率を測定した。上塗り塗膜を塗装した試験板についても同様に、ＳＡＥ Ｊ２３３４で５０サイクル試験して鋼材の最大腐食深さと塗膜の剥離面積率を測定した。 The specimens thus prepared were subjected to a 50-cycle test using SAE J2334, and the maximum corrosion depth of the steel material and the peeled area ratio of the coating film were measured. Similarly, the test plate coated with the top coat film was similarly subjected to a 50 cycle test with SAE J2334, and the maximum corrosion depth of the steel material and the peeled area ratio of the paint film were measured.
ＳＡＥ Ｊ２３３４ 湿潤：５０℃、相対湿度１００％、６時間→塩分付着＊：０．２５時間→乾燥：６０℃、相対湿度５０％、１７．７５時間
＊以下の重量％組成の塩を溶かした水溶液を噴霧する。
０．５％ＮａＣｌ、０．１％ＣａＣｌ２、０．００７５％ＮａＨＣＯ３
製鉄所や海洋構造物等における鋼構造物や鋼製配管等の屋外環境の湿潤状態は、ＳＡＥ Ｊ２３３４に近いと考えられる。
SAE J2334 Wetting: 50 ° C., relative humidity 100%, 6 hours → salt deposition *: 0.25 hour → drying: 60 ° C., relative humidity 50%, 17.75 hours Spray.
0.5% NaCl, 0.1% CaCl 2 , 0.0075% NaHCO 3
It is considered that the wet state of the outdoor environment such as steel structures and steel pipes in steelworks and offshore structures is close to SAE J2334.
表１中、比較例１〜３、実施例１〜３は、（Ｂ）硫酸第一スズの含有量を変化させた例であり、比較例４，５、実施例４，５は、顔料体積濃度を変化させた例であり、比較例６，７、実施例６，７は、（Ｃ）防錆顔料の含有量を変化させた例である。また、実施例８，９は、実施例２の下塗り塗料の上にさらに上塗り塗料を塗装した供試材の例である。 In Table 1, Comparative Examples 1 to 3 and Examples 1 to 3 are examples in which the content of (B) stannous sulfate was changed, and Comparative Examples 4 and 5 and Examples 4 and 5 were pigment volumes. This is an example in which the concentration is changed, and Comparative Examples 6 and 7 and Examples 6 and 7 are examples in which the content of (C) the rust preventive pigment is changed. Examples 8 and 9 are examples of test materials obtained by further applying a top coat onto the undercoat of Example 2.
表１から、混合塗料中の（Ｂ）硫酸第一スズの含有量が本発明の範囲内である実施例１〜３は、（Ｂ）硫酸第一スズの含有量が本発明の範囲外である比較例１〜３と比較して、ブラスト鋼板および錆鋼板の両方において、最大腐食深さおよび剥離面積率が小さいことがわかる。この効果は、（Ｂ）硫酸第一スズの含有量が本発明にとってより好ましい範囲（４．０〜８．０重量部）である実施例２，３において、一層顕著である。また、実施例８，９から、上記効果は、上塗り塗料をさらに塗装した場合でも同様に奏されることがわかる。さらに、実施例４〜７、比較例４〜７から、顔料体積濃度または（Ｃ）防錆顔料の含有量の値が本発明の範囲外になると、（Ｂ）硫酸第一スズの含有量が本発明の範囲内であっても、上記効果に劣ることがわかる。 From Table 1, Examples 1-3 in which the content of (B) stannous sulfate in the mixed paint is within the scope of the present invention are (B) the content of stannous sulfate is outside the scope of the present invention. It can be seen that the maximum corrosion depth and the peeled area ratio are small in both the blast steel plate and the rust steel plate as compared with certain Comparative Examples 1 to 3. This effect is even more remarkable in Examples 2 and 3 where the content of (B) stannous sulfate is in a more preferable range (4.0 to 8.0 parts by weight) for the present invention. In addition, from Examples 8 and 9, it can be seen that the above-described effects can be obtained in the same manner even when a top coat is further applied. Furthermore, from Examples 4-7 and Comparative Examples 4-7, when the value of the pigment volume concentration or the content of the (C) rust preventive pigment is outside the scope of the present invention, the content of (B) stannous sulfate is increased. Even within the scope of the present invention, it can be seen that the above effects are inferior.
本発明の塗料組成物は、製鉄所、化学プラント、海洋構造物等の過酷な環境下にある普通鋼材または耐候性鋼材からなる鋼構造物や鋼製配管等の錆抑制を含む維持補修に極めて有用である。 The coating composition of the present invention is extremely useful for maintenance and repair including rust control of steel structures and steel pipes made of ordinary steel or weather-resistant steel under harsh environments such as steelworks, chemical plants, and marine structures. Useful.
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