JP5909891B2 - High corrosion resistant black skin steel - Google Patents
High corrosion resistant black skin steel Download PDFInfo
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- JP5909891B2 JP5909891B2 JP2011142499A JP2011142499A JP5909891B2 JP 5909891 B2 JP5909891 B2 JP 5909891B2 JP 2011142499 A JP2011142499 A JP 2011142499A JP 2011142499 A JP2011142499 A JP 2011142499A JP 5909891 B2 JP5909891 B2 JP 5909891B2
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- oxide layer
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- 229910000831 Steel Inorganic materials 0.000 title claims description 62
- 239000010959 steel Substances 0.000 title claims description 62
- 230000007797 corrosion Effects 0.000 title claims description 38
- 238000005260 corrosion Methods 0.000 title claims description 38
- 239000000463 material Substances 0.000 claims description 49
- 229920005989 resin Polymers 0.000 claims description 46
- 239000011347 resin Substances 0.000 claims description 46
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 22
- 238000000576 coating method Methods 0.000 claims description 21
- 239000011248 coating agent Substances 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 230000009477 glass transition Effects 0.000 claims description 8
- -1 polyethylene Polymers 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229920005992 thermoplastic resin Polymers 0.000 claims description 5
- 229920001187 thermosetting polymer Polymers 0.000 claims description 4
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 239000004640 Melamine resin Substances 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920002857 polybutadiene Polymers 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 29
- 238000011156 evaluation Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005098 hot rolling Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000005422 blasting Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 230000003449 preventive effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004834 spray adhesive Substances 0.000 description 2
- 241000405961 Scomberomorus regalis Species 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 229920006334 epoxy coating Polymers 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007591 painting process Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Description
本発明は、鉄鋼材料、特に、熱間圧延ままで表面が酸化物層（以下「表面スケール」と呼ぶ）によって覆われている鉄鋼材料（以下「黒皮鋼材」と呼ぶ）であって、耐食性を向上するための耐食性向上処理がなされた高耐食黒皮鋼材に関する。なお、本発明における黒皮鋼材とは、形鋼、棒鋼、鋼管、鋼板等を含むものである。 The present invention is a steel material, in particular, a steel material (hereinafter referred to as “black skin steel”) whose surface is covered with an oxide layer (hereinafter referred to as “surface scale”) as it is hot-rolled, and has corrosion resistance. The present invention relates to a highly corrosion resistant black skin steel material that has been subjected to a corrosion resistance improving treatment for improving the resistance. In addition, the black skin steel material in this invention contains a shape steel, a bar steel, a steel pipe, a steel plate, etc.
従来、建築、土木用途などに用いられる黒皮鋼材は、１次保管時、倉庫など屋根のある場所で一部は保管されるものの、屋外で野積みされることが多い。特に、屋外で保管される黒皮鋼材は赤錆や黄錆が発生し、著しく外観を損なう上、無塗装でコンクリート中に埋めて使用する場合には、コンクリートとの密着性が低下したりする。このような赤錆や黄錆発生による外観劣化は、屋内で長期保管される場合にも生じる。 Conventionally, black skin steel materials used for construction, civil engineering and the like are often piled outdoors, although some are stored in a place with a roof such as a warehouse during primary storage. In particular, black rust steel materials stored outdoors generate red rust and yellow rust, which remarkably deteriorates the appearance, and when used without being painted in concrete, adhesion to the concrete is reduced. Such deterioration of appearance due to the occurrence of red rust and yellow rust also occurs when stored indoors for a long time.
一方、塗装して使用する場合には、塗装密着性ならびに塗装後耐食性を向上させる目的で塗装前処理としてショットブラスト等でケレンして黒皮除去処理を行う。黒皮鋼材保管時の腐食環境がマイルドな場合や保管期間が短い場合には赤錆や黄錆の発生は少なく、ショットブラストなどの黒皮除去処理で簡単に赤錆や黄錆も落とすことができるので、外観劣化が問題になることは少ない。 On the other hand, when used after coating, black skin removal treatment is performed by shot blasting or the like as pre-coating treatment for the purpose of improving paint adhesion and post-coating corrosion resistance. When the corrosive environment when storing black skin steel is mild or when the storage period is short, the occurrence of red rust and yellow rust is small, and it is easy to remove red rust and yellow rust by black skin removal treatment such as shot blasting. , Appearance degradation is rarely a problem.
しかし、黒皮鋼材保管時の腐食環境や保管期間などの影響で、著しく赤錆や黄錆が発生した黒皮鋼材では、錆落し工程に時間がかかるとともに、赤錆や黄錆発生による部分的な板厚減少により、塗装後の外観不良となることがある。さらに、板厚の減少が著しく大きくなると、所定の板厚より薄くなる部分が発生する場合もある。 However, in the case of black skin steel material, where the red rust and yellow rust have remarkably occurred due to the corrosive environment and storage period during storage of black skin steel material, the rust removal process takes time and a partial plate due to the occurrence of red rust and yellow rust. Reduced thickness may cause poor appearance after painting. Furthermore, when the reduction of the plate thickness is remarkably increased, a portion that is thinner than a predetermined plate thickness may occur.
上記した問題を改善する方法として特許文献１では、黒皮鋼材の表面をリン酸塩を含む水溶液で処理して、表面の酸化物層における亀裂部にリン酸塩皮膜を形成させることにより、耐食性と電着塗装やコンクリ−トとの密着性に優れた鋼材が開示されている。 In Patent Document 1, as a method for improving the above-described problem, the surface of a black skin steel material is treated with an aqueous solution containing a phosphate, and a phosphate film is formed at a crack portion in the oxide layer on the surface, thereby providing corrosion resistance. Steel materials excellent in adhesion between the electrodeposition coating and the concrete are disclosed.
しかしながら、特許文献１に記載の方法では、リン酸塩皮膜が部分的に厚くなって、鋼材の表面が白くなったり、粉末となって剥がれ落ちたりする場合がある。 However, in the method described in Patent Document 1, the phosphate film may be partially thick, and the surface of the steel material may be whitened or peeled off as a powder.
本発明は、上記した問題を解決するため、黒皮鋼材における赤錆や黄錆発生による密着不良や外観不良を防止し、スケール除去工程や塗装工程でのトラブルをなくすため、所望の耐食性を奏する高耐食黒皮鋼材を提供することを目的とする。 In order to solve the above-mentioned problems, the present invention prevents adhesion failure and appearance failure due to occurrence of red rust and yellow rust in black skin steel material, and eliminates troubles in the scale removal process and painting process. An object is to provide a corrosion-resistant black skin steel material.
本発明の要旨は、次の通りである。 The gist of the present invention is as follows.
第一の発明は、表面が鉄を主成分とする酸化物層で覆われた鋼材において、その鉄系酸化物層が樹脂を含有する物質で被覆されていることを特徴とする高耐食黒皮鋼材である。 A first invention is a high corrosion-resistant black skin characterized in that a steel material whose surface is covered with an oxide layer mainly composed of iron, the iron-based oxide layer being coated with a resin-containing substance It is a steel material.
第二の発明は、前記樹脂が、熱硬化性樹脂および／またはガラス転移点１０℃以上の熱可塑性樹脂であることを特徴とする第一の発明に記載の高耐食黒皮鋼材である。 A second invention is the highly corrosion-resistant black skin steel material according to the first invention, wherein the resin is a thermosetting resin and / or a thermoplastic resin having a glass transition point of 10 ° C. or higher.
第三の発明は、前記樹脂を含有する物質の平均付着量が０．０１〜２０ｇ／ｍ２であることを特徴とする第一または第二の発明に記載の高耐食黒皮鋼材である。 A third invention is the highly corrosion-resistant black skin steel material according to the first or second invention, wherein an average adhesion amount of the substance containing the resin is 0.01 to 20 g / m 2 .
第四の発明は、前記表面が鉄を主成分とする酸化物層で覆われた鋼材において、その鉄系酸化物層を樹脂を含有する塗布物で被覆し、乾燥させることを特徴とする第一乃至第三の発明の何れかの発明に記載の高耐食黒皮鋼材の製造方法である。 According to a fourth aspect of the present invention, in the steel material whose surface is covered with an oxide layer containing iron as a main component, the iron-based oxide layer is coated with a coating containing a resin and dried. A method for producing a highly corrosion-resistant black skin steel material according to any one of the first to third inventions.
第五の発明は、前記樹脂を含有する塗布物の粘度を１０００ｃＰ未満とすることを特徴とする第四の発明に記載の高耐食黒皮鋼材の製造方法。 5th invention makes the viscosity of the coating material containing the said resin less than 1000 cP, The manufacturing method of the highly corrosion-resistant black skin steel material as described in 4th invention characterized by the above-mentioned.
本発明の高耐食黒皮鋼材は、黒皮鋼材の表面が樹脂を含有する物質で覆われているので、表面スケールに生じる亀裂部や剥離部が被覆され、亀裂部や剥離部からの鋼素地への腐食因子の侵入が抑制され、黒皮鋼材の耐食性が向上する。また、ワックスや粘性のある防錆油などによる防錆処理ではない為、黒皮鋼材表面のべとつきなどの作業性劣化がなく、実際の施工においては、屋外長期保管しても赤錆の発生が飛躍的に抑えられ、錆発生によるコンクリートとの密着性低下が抑制されるため、前処理なし、または軽いケレンなどでの対応が可能となり、前処理工数の増加や塗装外観不良などの問題がなくなる。 Since the surface of the black skin steel material is covered with a resin-containing substance, the high corrosion resistance black skin steel material of the present invention is coated with cracks and peeling portions generated on the surface scale, and the steel substrate from the crack portions and peeling portions is covered. Invasion of corrosion factors into the steel is suppressed, and the corrosion resistance of the black skin steel material is improved. In addition, since it is not rust-proofing with wax or viscous rust-proof oil, there is no deterioration in workability such as stickiness of the surface of the black skin steel material. Therefore, it is possible to cope with no pre-treatment or light keren, and problems such as an increase in the number of pre-treatment steps and poor coating appearance are eliminated.
本発明の実施形態に係る高耐食黒皮鋼材は、熱間圧延または熱間圧延後に冷間矯正された黒皮鋼材を用いる。黒皮鋼材の表面スケールは、種々の酸化物（酸化性や導電性を具備または不備のもの等）から成り、それぞれ温度に対する線膨張係数が異なっている。このため、熱間圧延後の冷却過程や冷間矯正などの工程において、黒皮鋼材の表面スケールには亀裂や剥離が発生する。本発明は、このような黒皮鋼材の表面を、樹脂を含有する物質で被覆処理して製造される。 As the highly corrosion-resistant black skin steel material according to the embodiment of the present invention, a black skin steel material cold-corrected after hot rolling or hot rolling is used. The surface scale of the black skin steel material is made of various oxides (having or lacking oxidation property or conductivity, etc.), and has different linear expansion coefficients with respect to temperature. For this reason, cracks and delamination occur on the surface scale of the black skin steel material in processes such as the cooling process after hot rolling and cold straightening. The present invention is manufactured by coating the surface of such a black leather material with a substance containing a resin.
被覆処理の方法は特に限定するものではなく、各種の塗装方法（浸漬、スプレーコーター、ロールコーター、フローコーター、バーコーター、刷毛塗り、電着塗装、粉体塗装等）が適用可能であるが、微細な亀裂部や剥離部にも塗装を施す観点からは、樹脂を含有する物質を溶液としてから塗装することが好ましい。溶液とすることにより、微細な亀裂部や剥離部に前記溶液が侵入し、乾燥する事により処理液中の樹脂成分などが亀裂部や剥離部を均一に覆うことが可能となる。 The method of coating treatment is not particularly limited, and various coating methods (immersion, spray coater, roll coater, flow coater, bar coater, brush coating, electrodeposition coating, powder coating, etc.) can be applied. From the viewpoint of coating fine cracked portions and peeled portions, it is preferable to apply the resin-containing substance as a solution. By using the solution, the solution enters the fine cracked part or the peeled part, and the resin component in the treatment liquid can uniformly cover the cracked part or the peeled part by drying.
なお、ここで使用する樹脂の種類は、特に限定するものではなく、種々の成分が適用可能である。例えば、エポキシ樹脂、フェノール樹脂、メラミン樹脂、ポリエステル、ポリエチレン、ポリプロピレン、ウレタン樹脂、アクリル樹脂、ブタジエン樹脂、また、２種以上の樹脂を共重合した樹脂等があげられる。 In addition, the kind of resin used here is not specifically limited, A various component is applicable. For example, an epoxy resin, a phenol resin, a melamine resin, a polyester, a polyethylene, a polypropylene, a urethane resin, an acrylic resin, a butadiene resin, a resin obtained by copolymerizing two or more kinds of resins, and the like can be given.
熱可塑性樹脂でも熱硬化性樹脂でも適用可能であるが、熱可塑性樹脂の場合は、ガラス転移点は１０℃以上が好ましい。ガラス転移点の低すぎる樹脂の場合、作業雰囲気温度によってはべとついて作業性が劣化する場合があるからである。このような観点から、ガラス転移点が低い樹脂を使用する場合は、硬化剤を用いたり、他の樹脂と共重合してガラス転移点をあげることが好ましい。 Either a thermoplastic resin or a thermosetting resin is applicable, but in the case of a thermoplastic resin, the glass transition point is preferably 10 ° C. or higher. This is because, in the case of a resin having a glass transition point that is too low, workability may deteriorate depending on the working atmosphere temperature. From such a viewpoint, when using a resin having a low glass transition point, it is preferable to use a curing agent or to copolymerize with other resins to increase the glass transition point.
また、樹脂の形態も特に限定するものではなく、水系でも有機溶剤系でも粉状でも適用可能であるが、作業環境の観点からは、エマルション、ディスパージョン、水溶性等の水系樹脂が好ましい。ただし、水系樹脂の場合は、水と接することによる赤錆の発生を抑えるため、迅速に乾燥させることが好ましい。また、被覆する樹脂を含有する物質は、樹脂以外の成分を含有してもよいが、被膜に亀裂が出ないようにするために、樹脂の含有比率は多い方が好ましく、５０重量％以上が好ましい。樹脂以外の成分として、無機成分等を造膜を阻害しない範囲で添加してもよい。 Also, the form of the resin is not particularly limited, and it can be applied in an aqueous system, an organic solvent system, or a powder form, but an aqueous resin such as an emulsion, a dispersion, and a water-soluble resin is preferable from the viewpoint of the working environment. However, in the case of water-based resin, it is preferable to dry quickly in order to suppress generation of red rust caused by contact with water. Further, the substance containing the resin to be coated may contain components other than the resin. However, in order to prevent the coating from cracking, it is preferable that the content ratio of the resin is large, and 50% by weight or more. preferable. As a component other than the resin, an inorganic component or the like may be added within a range not inhibiting the film formation.
この様にして、黒皮鋼材の表面に樹脂を含有する物質が被覆されることになる。すなわち、表面スケールの亀裂部や剥離部の地鉄表面および亀裂部内部が樹脂を含有する物質で被覆されることにより、地鉄の露出が大幅に減少するので、地鉄への腐食因子の侵入が効果的に防止され、黒皮鋼材の耐食性が格段に向上する。また、亀裂部や剥離部以外の黒皮皮膜部に樹脂を含有する物質が形成されることにより黒皮の耐食性よりも優れた耐食性が確保できる。 In this way, the surface of the black skin steel material is coated with the substance containing the resin. In other words, the surface scale cracks and the peeled part of the iron surface and the inside of the crack are covered with a resin-containing substance, so that the exposure of the iron is greatly reduced. Is effectively prevented, and the corrosion resistance of the black skin steel material is remarkably improved. Moreover, the corrosion resistance superior to the corrosion resistance of a black skin is securable by forming the substance containing resin in the black skin film part other than a crack part and a peeling part.
樹脂を含有する物質の平均付着量は、０．０１ｇ／ｍ２以上２０ｇ／ｍ２以下とする。
０．０１ｇ／ｍ２未満では亀裂部や剥離部が多い場合に耐食性向上効果が不十分であり、２０ｇ／ｍ２超えでは鋼材表面への付着が多くなり塗装時に簡単なケレンなどで充分に落とすことが難しくなり、塗膜の密着性不良を起こす場合があるからである。より好適な付着量は、０．１ｇ／ｍ２以上１．５ｇ／ｍ２以下である。
The average adhesion amount of the substance containing the resin is 0.01 g / m 2 or more and 20 g / m 2 or less.
If it is less than 0.01 g / m 2 , the effect of improving the corrosion resistance is insufficient when there are many cracks and peeled parts, and if it exceeds 20 g / m 2 , the adhesion to the steel surface increases, and it can be sufficiently removed with simple kelen during coating. This is because it becomes difficult to cause poor adhesion of the coating film. A more preferable adhesion amount is 0.1 g / m 2 or more and 1.5 g / m 2 or less.
また、樹脂塗布時の塗布物の粘度は、１０００ｃＰ未満とする。黒皮には、上述したように、クラックや欠陥部が多く、この中へ十分な樹脂が供給されることで耐食性が向上する。１０００ｃＰ以上では、細かい黒皮部のクラックや欠陥部に樹脂が供給されないまま被覆されるので、相対的に耐食性が劣る。更により好適な粘度範囲は、より樹脂の付きまわり性の向上する１００ｃＰ以下が良い。 Moreover, the viscosity of the coated material at the time of resin coating shall be less than 1000 cP. As described above, the black skin has many cracks and defective portions, and sufficient corrosion resistance is improved by supplying sufficient resin therein. If it is 1000 cP or more, the cracks and defects in fine black skin portions are coated without being supplied with resin, so that the corrosion resistance is relatively inferior. Further, a more preferable viscosity range is 100 cP or less which improves the throwing power of the resin.
上述した黒皮鋼材の耐食性の格段の向上によって、赤錆や黄錆の発生が抑えられるので、黒皮鋼材を黒皮ままで使用した場合であってもコンクリートとの密着性が低下することがない。 Due to the marked improvement in the corrosion resistance of the black skin steel material described above, the occurrence of red rust and yellow rust can be suppressed, so even if the black skin steel material is used as it is, the adhesion with concrete will not be reduced. .
本発明の実施形態に係る黒皮鋼材における耐食性向上効果を確認するために、熱間圧延した１１ｍｍ厚の黒皮鋼材から３０ｍｍ×２００ｍｍサイズのサンプルを採取し、３点曲げによって黒皮鋼材に最大で３％の歪を与え、黒皮に亀裂を形成した。その後、表１に示す処理液、処理条件により黒皮鋼材表面を処理した後、耐食性評価試験、作業性評価試験、塗装性評価試験を実施した。 In order to confirm the effect of improving the corrosion resistance of the black skin steel material according to the embodiment of the present invention, a sample of 30 mm × 200 mm size is taken from the hot rolled 11 mm thick black skin steel material, and the maximum strength of the black skin steel material by three-point bending. 3% strain was applied, and cracks were formed in the black skin. Thereafter, the surface of the black skin steel material was treated with the treatment liquid and treatment conditions shown in Table 1, followed by a corrosion resistance evaluation test, a workability evaluation test, and a paintability evaluation test.
塗布物の粘度は、溶剤、水などの溶媒に溶解したものは、Ｂ型粘度計で測定し、粉体塗装に供するものは、メルトフローメーター（溶融粘度計）で、対象とする温度における粘度を測定した。 The viscosity of the coated material is measured with a B-type viscometer when it is dissolved in a solvent such as solvent or water, and the viscosity at the target temperature is measured with a melt flow meter (melt viscometer) for powder coating. Was measured.
耐食性評価試験は、６０日間の屋外暴露（岡山県倉敷市にて、海岸線より約５００ｍ離れた場所）後の表面状況を観察して判断した。 The corrosion resistance evaluation test was judged by observing the surface condition after 60 days of outdoor exposure (in Kurashiki City, Okayama Prefecture, about 500 m away from the coastline).
◎：赤錆および黄錆の発生がほとんどなくて試験前の状態が残っているもの
○：赤錆および黄錆発生面積１０％以下
△：赤錆および黄錆発生面積率１０％超え３０％以下
×：赤錆および黄錆発生面積が３０％超え
作業性評価試験は、鋼材表面に貼るシ−ルの粘着性で評価した。
◎: Red rust and yellow rust are hardly generated and the state before the test remains ○: Red rust and yellow rust generation area 10% or less △: Red rust and yellow rust generation area ratio exceeds 10% and 30% or less ×: Red rust And the yellow rust generation area exceeded 30%, and the workability evaluation test was evaluated by the adhesiveness of the seal applied to the steel material surface.
シール：５０ｍｍ×５０ｍｍの上質紙にスプレー接着剤を１０ｃｍ離れた位置から２秒間スプレー（スプレー接着剤：住友スリーエム製 ニューダクトスプレー１．５）
粘着性評価方法：前記シールを鋼板表面に貼り付け、常温にて１日後にシールの粘着状況を調査した。
Seal: Spray the spray adhesive on a high-quality paper of 50 mm x 50 mm from a position 10 cm away for 2 seconds (spray adhesive: Sumitomo 3M New Duct Spray 1.5)
Adhesive evaluation method: The above-mentioned seal was affixed to the steel sheet surface, and the adhesive state of the seal was investigated after 1 day at room temperature.
◎：１日後にシ−ルが全く剥離せず
○：１日後にシ−ルの２０％以下が剥離
△：１日後にシールの２０％超え５０％以下が剥離
×：１日後にシ−ルの５０％超えが剥離
塗装性評価試験は、鋼材表面をかるくブラシでケレンしたのち、スプレ−にてエポキシ塗装を施し、常温にて１日経過後に、ＮＴカッターでエポキシ塗装の表面に、２ｍｍ間隔で１１本の地鉄に達する直線傷を入れ、さらにこれらと直交する方向に同様の直線傷を入れて、１００マスの格子パターンとした後、ニチバン（株）のセロテ−プ（登録商標）を格子の部分に接着した後、セロテープ（登録商標）を一気に引きはがし、１００マスの格子部分でのエポキシ塗膜残存面積率で評価した。
◎: Seal does not peel at all after 1 day ○: 20% or less of seal peels after 1 day △: After 20 days, seal exceeds 20% and 50% or less ×: Seal after 1 day In the paintability evaluation test, the steel surface was cleansed with a light brush, then epoxy was applied with a spray, and after 1 day at room temperature, the surface of the epoxy was coated with an NT cutter at intervals of 2 mm. After making straight flaws that reach 11 pieces of iron and making similar straight flaws in a direction perpendicular to these to make a grid pattern of 100 squares, Nichiban Co., Ltd.'s Cero Tape (registered trademark) After adhering to the lattice portion, cellotape (registered trademark) was peeled off at a stretch, and the epoxy coating residual area ratio at the lattice portion of 100 squares was evaluated.
◎：塗装膜剥離がないもの、または塗装膜残存面積率が９０％以上
○：塗装膜残存面積率が７５％以上９０％未満
△：塗装膜残存面積率が５０％以上７５％未満
×：塗装膜残存面積率が５０％未満
試験結果を表１に示す。
◎: No paint film peeling or paint film remaining area ratio 90% or more ○: Paint film remaining area ratio 75% or more and less than 90% △: Paint film remaining area ratio 50% or more and less than 75% ×: Painting The film remaining area ratio is less than 50%.
発明例である樹脂を含む処理剤で処理したＮｏ．１〜Ｎｏ．２８は、耐食性向上効果が認められ、さらに作業性や塗装性にも優れていた。 No. processed with the processing agent containing resin which is the invention example. 1-No. No. 28 was found to have an effect of improving corrosion resistance, and was also excellent in workability and paintability.
このうち、Ｎｏ．２は、付着させる物質の付着量が多いため、塗装性が若干劣り、Ｎｏ．５は、付着させる物質の付着量が少ないために、耐食性が若干劣る傾向であり、ガラス転移点が−１０℃と低い樹脂を用いたＮｏ．７は、常温では被膜が若干べたついているため、作業性及び塗装性が劣化傾向であり、Ｎｏ．２６、２７、２８は、いずれも黒皮面への塗布時の粘度が高いため、耐食性が相対的に低下していたが、いずれも無処理のＮｏ．３３より優れた耐食性を示した。 Of these, No. No. 2 is slightly inferior in paintability due to the large amount of substances to be adhered. No. 5 has a tendency to be slightly inferior in corrosion resistance due to a small amount of the substance to be adhered, and No. 5 using a resin having a low glass transition point of −10 ° C. No. 7 has a tendency to deteriorate workability and paintability because the film is slightly sticky at room temperature. Nos. 26, 27, and 28 all had a relatively low corrosion resistance due to their high viscosity when applied to the black skin surface. Corrosion resistance superior to 33 was exhibited.
比較例であるＮｏ．２９は、ワックスで処理したが、耐食性は向上したものの、ワックスを除去しない状態では作業性及び塗装性が実用に耐えないレベルであった。同じく、比較例であるＮｏ．３０は、さび止め油で処理したが、耐食性の向上は無く、止め油を除去しない状態では作業性及び塗装性が実用に耐えないレベルであった。 No. which is a comparative example. Although No. 29 was treated with wax, the corrosion resistance was improved, but the workability and paintability were at a level that could not withstand practical use without removing the wax. Similarly, No. 1 as a comparative example. No. 30 was treated with rust-preventing oil, but there was no improvement in corrosion resistance, and the workability and paintability were at a level that could not withstand practical use without removing the stopping oil.
比較例であるＮｏ．３１、Ｎｏ．３２は、防錆剤を付着させたが、屋外暴露で降雨により防錆剤が洗い流されたためと思われ、耐食性の向上効果が認められなかった。 No. which is a comparative example. 31, no. In No. 32, the rust preventive agent was adhered, but it was thought that the rust preventive agent was washed away by rain during outdoor exposure, and the effect of improving the corrosion resistance was not recognized.
本発明の黒皮鋼材は表面スケールに生じている亀裂部剥離部が樹脂を含有する物質で被覆されているので、優れた防錆効果を有し、形鋼、棒鋼、鋼管、鋼板等の各種形態の高耐食黒皮鋼材として広く利用することができる。 The black skin steel material of the present invention has an excellent rust-preventing effect because the crack part peeled portion generated on the surface scale is coated with a resin-containing substance, and various types of steel such as shaped steel, bar steel, steel pipe, steel plate, etc. It can be widely used as a highly corrosion resistant black skin steel material.
Claims (3)
前記樹脂を含有する物質は、熱硬化性樹脂および／またはガラス転移点１０℃以上の熱可塑性樹脂を５０重量％以上含み、かつ、平均付着量が０．０１〜２０ｇ／ｍ２であり、
前記熱硬化性樹脂および／またはガラス転移点１０℃以上の熱可塑性樹脂は、エポキシ樹脂、フェノール樹脂、メラミン樹脂、ポリエステル、ポリエチレン、ポリプロピレン、ウレタン樹脂、アクリル樹脂、ブタジエン樹脂、および、これらの樹脂の内２種以上の樹脂を共重合した樹脂の内から選ばれることを特徴とする高耐食黒皮鋼材。 In the steel material whose surface is covered with an oxide layer mainly composed of iron, the iron-based oxide layer is coated with a substance containing a resin,
Material containing the resin, a thermosetting resin and / or glass transition point of 10 ° C. or more thermoplastic resins comprising 50 wt% or more, and an average coating weight of Ri 0.01 to 20 g / m 2 der,
The thermosetting resin and / or the thermoplastic resin having a glass transition point of 10 ° C. or higher are epoxy resin, phenol resin, melamine resin, polyester, polyethylene, polypropylene, urethane resin, acrylic resin, butadiene resin, and those resins. high corrosion mill scale steel, wherein Rukoto selected inner two or more resins from among the copolymerized resin.
表面が鉄を主成分とする酸化物層で覆われた鋼材の前記鉄系酸化物層を、エポキシ樹脂、フェノール樹脂、メラミン樹脂、ポリエステル、ポリエチレン、ポリプロピレン、ウレタン樹脂、アクリル樹脂、ブタジエン樹脂、および、これらの樹脂の内２種以上の樹脂を共重合した樹脂の内から選ばれた樹脂を固形分中５０重量％以上含有する塗布物で被覆し、乾燥させることを特徴とする高耐食黒皮鋼材の製造方法。 It is a manufacturing method of the highly corrosion-resistant black skin steel material according to claim 1 ,
The iron-based oxide layer of the steel material whose surface is covered with an oxide layer mainly composed of iron, epoxy resin, phenol resin, melamine resin, polyester, polyethylene, polypropylene, urethane resin, acrylic resin, butadiene resin, and A highly corrosion-resistant black skin characterized in that a resin selected from among resins obtained by copolymerizing two or more of these resins is coated with a coating containing 50% by weight or more of the solid content and dried. Steel manufacturing method.
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