JP2005254106A - Method for rustproofing end face of surface-treated steel plate and end face rustproofing liquid - Google Patents
Method for rustproofing end face of surface-treated steel plate and end face rustproofing liquid Download PDFInfo
- Publication number
- JP2005254106A JP2005254106A JP2004067539A JP2004067539A JP2005254106A JP 2005254106 A JP2005254106 A JP 2005254106A JP 2004067539 A JP2004067539 A JP 2004067539A JP 2004067539 A JP2004067539 A JP 2004067539A JP 2005254106 A JP2005254106 A JP 2005254106A
- Authority
- JP
- Japan
- Prior art keywords
- face
- coupling agent
- exposure test
- treated steel
- titanate coupling
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Images
Abstract
Description
本発明は、表面処理鋼板の端面防錆方法および端面防錆処理液に関する技術分野に属するものであり、特には、コイル状やシート状で供給される建材、家電等向けめっき鋼板、表面処理鋼板、プレコート鋼板を需要家が切断または打ち抜き加工により製品化する際に生じる鋼板端面を防錆するための端面防錆方法に関する。 The present invention belongs to a technical field related to an end face rust prevention method and an end face rust prevention treatment liquid for a surface treated steel sheet. The present invention relates to an end surface rust prevention method for rust prevention of a steel plate end surface produced when a customer manufactures a precoated steel sheet by cutting or punching.
鋼板の耐食性を高めるために、各種亜鉛系めっきが施され、更にその上に塗装が行われることもある。しかし、切断または打ち抜き加工で生じた鋼板の端面は、鉄と亜鉛系めっきが露出しているため、耐食性に劣ることが問題となっている。従来は、このような端面の防錆として、ジンクリッチペイント等の防錆塗料、シリコーン樹脂、フッ素樹脂、エポキシ樹脂やアクリル樹脂等のワニス（樹脂溶液）のディッピング、スプレーなどの処理が行われてきた。 In order to improve the corrosion resistance of the steel sheet, various types of zinc plating are applied, and further, coating may be performed thereon. However, the end face of the steel plate produced by cutting or punching is inferior in corrosion resistance because iron and zinc-based plating are exposed. Conventionally, rust prevention paint such as zinc rich paint, varnish (resin solution) such as silicone resin, fluororesin, epoxy resin and acrylic resin, dipping and spraying have been performed as rust prevention for such end faces. It was.
このような処理以外の端面防錆方法として、下記(1) 〜(4) のものがある。 There are the following (1) to (4) as end face rust prevention methods other than such treatment.
(1) 特開平3-6387号公報記載のもの：
これは、めっき鋼板の防錆方法に関するものであり、「りん酸塩（リン酸亜鉛等）皮膜処理を端面に施す」というものである。しかし、無機塩のため鋼板との接着性が不良であり、水には容易に洗い流されるため、建材など屋外に暴露される用途には不適当である。
(1) Those described in JP-A-3-6387:
This relates to a rust prevention method for a plated steel sheet, and is “applying a phosphate (such as zinc phosphate) coating to the end face”. However, since it is an inorganic salt, its adhesion to the steel sheet is poor and it is easily washed away with water, so it is not suitable for applications such as building materials exposed to the outdoors.
(2) 特公平7-116617号公報記載のもの：
これは、表面処理鋼板の露出地鉄端面防錆方法に関するものであり、「Ni錯化合物を含むアルカリ脱脂液、もしくは、キレート化合物を含むアルカリ脱脂液、もしくは、縮合リン酸化合物と２価以上の金属イオンとからなる縮合リン酸塩化合物を含むアルカリ脱脂液、もしくは、硝酸塩、亜硝酸塩化合物を含むアルカリ脱脂液で処理し、脱脂と同時に、露出地鉄端面に防錆皮膜を形成させる」というものである。しかし、生成するのは無機皮膜であるため、上記(1) の場合と同様、建材等屋外に暴露される用途には不適当である。
(2) Those described in Japanese Examined Patent Publication No.7-116617:
This relates to a method for preventing rust of exposed steel from the surface-treated steel sheet. “An alkaline degreasing solution containing a Ni complex compound, an alkaline degreasing solution containing a chelate compound, or a condensed phosphate compound and a divalent or higher valence. It is treated with an alkaline degreasing solution containing a condensed phosphate compound composed of metal ions or an alkaline degreasing solution containing a nitrate or nitrite compound, and at the same time as degreasing, a rust-preventive film is formed on the exposed end surface of the steel. It is. However, since it produces an inorganic film, it is not suitable for applications such as building materials that are exposed outdoors, as in the case of (1) above.
(3) 特開平4-280986号公報記載のもの：
これは、塗装鋼板の端面防錆方法に関するものであり、「Al3+及びCl- の両イオンを含有する水溶液に、端面を接触させ、乾燥させる」というものである。この公報では、「端面防錆性の機構としてAlの酸化物、水酸化物等のAl化合物からなる緻密な耐食性に優れた被膜が端面に形成されたためと推測される」としている。しかし、生成するのは無機皮膜のため、上記(1) や(2) の場合と同様、建材等屋外に暴露される用途には不適当である。
(3) Those described in JP-A-4-280986:
This relates to a method for preventing rusting of coated steel sheets, and is “to make an end surface contact with an aqueous solution containing both ions of Al 3+ and Cl − and to dry”. In this publication, it is assumed that “a fine anti-corrosion film made of an Al compound such as an oxide or hydroxide of Al is formed on the end face as the end face anti-rust mechanism”. However, since it produces an inorganic film, it is unsuitable for applications such as building materials that are exposed outdoors, as in (1) and (2) above.
(4) 文献「Application of Silane Technology to Prevent Corrosion of Metals and Improve Paint Adhesion，Trans IMF, 1999, 77(2)) 」には、シランカップリング剤が端面防錆に有効であることが記載されている。しかし、端面にシランカップリング剤皮膜を作製させるためには、高濃度のシランカップリング剤溶液が必要となる。
前記従来の端面防錆方法である塗料やワニスによる処理は、端面防錆に効果があるが、溶剤としてシンナー系が使用されているため、乾燥に時間がかかり、また、常温で硬化させる必要があるものもあり、通常は養生に１日程度かかる。また、現場施工のため、溶剤の臭気が問題になる。このように、塗料やワニスによる処理は手間がかかる作業で、工程が煩雑であり、大量生産品の処理には不適当である。 Treatment with paint or varnish, which is the conventional end face rust prevention method, is effective for end face rust prevention, but since a thinner system is used as a solvent, it takes time to dry and it is necessary to cure at room temperature. There are some, and it usually takes about a day to cure. In addition, because of construction on site, the odor of the solvent becomes a problem. As described above, the treatment with paint or varnish is a time-consuming operation, the process is complicated, and it is inappropriate for the treatment of mass-produced products.
前記(1) 〜(3) の公報記載の無機物での端面被覆は、接着性、耐水性に劣り、屋外使用にとっては不適当である。 The end face coating with inorganic materials described in the above-mentioned publications (1) to (3) is inferior in adhesion and water resistance and is unsuitable for outdoor use.
前記(4) の文献記載のシランカップリング剤を適用する方法に関しては、シランカップリング剤皮膜を作製させるためには高濃度のシランカップリング剤溶液が必要となり、このためコスト面より現実的でない。 Regarding the method of applying the silane coupling agent described in the literature of (4), a high concentration silane coupling agent solution is required to produce a silane coupling agent film, which is not practical from the viewpoint of cost. .
本発明はこのような事情に着目してなされたものであって、その目的は、塗料やワニスによる処理の場合に比べて処理が簡単であると共に、前記(1) 〜(3) の公報記載の無機物での端面被覆の場合に比べて屋外での端面耐食性を向上することができる表面処理鋼板の端面防錆方法および端面防錆処理液を提供しようとするものである。 The present invention has been made paying attention to such circumstances, and its purpose is that the treatment is simpler than the treatment with paint or varnish, and the description in the above-mentioned publications (1) to (3). It is an object of the present invention to provide an end face rust prevention method and end face rust prevention treatment liquid for a surface-treated steel sheet capable of improving the end face corrosion resistance outdoors as compared with the case of end face covering with an inorganic substance.
本発明者らは、上記目的を達成するため、鋭意研究を行なった結果、本発明を完成するに至った。本発明によれば上記目的を達成することができる。 In order to achieve the above object, the present inventors have intensively studied, and as a result, completed the present invention. According to the present invention, the above object can be achieved.
このようにして完成され上記目的を達成することができた本発明は、表面処理鋼板の端面防錆方法および端面防錆処理液に係わり、特許請求の範囲の請求項１〜３記載の表面処理鋼板の端面防錆方法（第１〜３発明に係る表面処理鋼板の端面防錆方法）、請求項４記載の表面処理鋼板の端面防錆処理液（第４発明に係る表面処理鋼板の端面防錆処理液）であり、それは次のような構成としたものである。 The present invention completed as described above and capable of achieving the above object relates to an end face rust prevention method and an end face rust prevention treatment liquid for a surface-treated steel sheet, and the surface treatment according to claims 1 to 3 of the claims. End face rust prevention method for steel sheets (end face rust prevention method for surface-treated steel sheets according to first to third inventions), end face rust prevention liquid for surface-treated steel sheets according to claim 4 (end face prevention for surface-treated steel sheets according to fourth invention) Rust treatment liquid), which has the following configuration.
即ち、請求項１記載の表面処理鋼板の端面防錆方法は、表面処理鋼板の端面に、炭素数が５以上の疎水基を３個以上有するチタネート系カップリング剤を含む溶液を塗布することを特徴とする表面処理鋼板の端面防錆方法である〔第１発明〕。 That is, the end surface rust prevention method for the surface-treated steel sheet according to claim 1 is to apply a solution containing a titanate coupling agent having three or more hydrophobic groups having 5 or more carbon atoms to the end surface of the surface-treated steel sheet. A feature of the present invention is an end surface rust prevention method for a surface-treated steel sheet [first invention].
請求項２記載の表面処理鋼板の端面防錆方法は、前記溶液のチタネート系カップリング剤濃度が0.5 〜20質量％である請求項１記載の表面処理鋼板の端面防錆方法である〔第２発明〕。 The end surface rust prevention method for the surface-treated steel sheet according to claim 2 is the end surface rust prevention method for the surface-treated steel sheet according to claim 1, wherein the titanate coupling agent concentration of the solution is 0.5 to 20% by mass. invention〕.
請求項３記載の表面処理鋼板の端面防錆方法は、前記端面のチタネート系カップリング剤の塗布量が、Ti量で５μg/m2〜50μg/m2である請求項１または２記載の表面処理鋼板の端面防錆方法である〔第３発明〕。 The end face rust-preventive method for the surface treated steel sheet according to claim 3, wherein the coating amount of the titanate coupling agent of the end surface, according to claim 1 or 2 surface described in Ti content is 5μg / m 2 ~50μg / m 2 This is an end surface rust prevention method for the treated steel sheet [third invention].
請求項４記載の表面処理鋼板の端面防錆処理液は、炭素数が５以上の疎水基を３個以上有するチタネート系カップリング剤を0.5 〜20質量％含有することを特徴とする表面処理鋼板の端面防錆処理液である〔第４発明〕。 5. The surface-treated steel sheet according to claim 4, wherein the surface-treated steel sheet contains 0.5 to 20 mass% of a titanate coupling agent having 3 or more hydrophobic groups having 5 or more carbon atoms. [4th invention].
本発明に係る表面処理鋼板の端面防錆方法によれば、従来の塗料やワニスによる処理の場合に比べて処理が簡単になると共に、従来の無機物での端面被覆（特開平3-6387号、特公平7-116617号、特開平4-280986号公報記載のもの）の場合に比べて屋外での端面耐食性を向上することができる。本発明に係る表面処理鋼板の端面防錆処理液は、表面処理鋼板の端面防錆方法に好適に用いることができる。 According to the end face rust prevention method of the surface-treated steel sheet according to the present invention, the treatment becomes simpler than the case of the treatment with the conventional paint or varnish, and the end face coating with a conventional inorganic substance (Japanese Patent Laid-Open No. 3-6387, Compared to the cases described in Japanese Patent Publication No.7-116617 and JP-A-4-280986, the end face corrosion resistance outdoors can be improved. The end surface rust prevention liquid of the surface-treated steel sheet according to the present invention can be suitably used for the end surface rust prevention method of the surface-treated steel sheet.
本発明者らは前記目的を達成すべく鋭意研究を重ねた。その結果、シランカップリング剤よりチタネートカップリング剤のほうが優れた端面防錆効果を示すことが分かった。 The inventors of the present invention have made extensive studies to achieve the above object. As a result, it was found that the titanate coupling agent had a superior end face rust prevention effect than the silane coupling agent.
チタネート系カップリング剤は、シランカップリング剤と同様に、１分子中に疎水基と親水基を有しているため、親水基が鋼板表面の水酸基と反応することで、良好な接着性を保持すると共に、鋼板表面に存在する疎水基が水等の腐食を引き起こす物質の浸入を防ぐ作用を有する。 The titanate coupling agent has a hydrophobic group and a hydrophilic group in one molecule, like the silane coupling agent, so that the hydrophilic group reacts with the hydroxyl group on the surface of the steel sheet to maintain good adhesion. At the same time, the hydrophobic group present on the surface of the steel sheet has an action of preventing the entry of substances that cause corrosion such as water.
シランカップリング剤は疎水基数の多いもの、長い疎水基を有するものが得られないため、防錆効果が不十分である。一方、チタネート系カップリング剤は、シランカップリング剤に比べて、疎水基の鎖が長く、疎水基数も多いため、鋼板表面を広い面積で覆うことができる（例えば図１〜２参照）。従って、チタネート系カップリング剤は、水等の腐食を引き起こす物質の浸入を防ぐことが可能となり、シランカップリング剤より、良好な防錆効果を示す。 Since a silane coupling agent having a large number of hydrophobic groups or a long hydrophobic group cannot be obtained, the rust prevention effect is insufficient. On the other hand, the titanate coupling agent has a longer chain of hydrophobic groups and a larger number of hydrophobic groups than the silane coupling agent, so that the steel plate surface can be covered with a wide area (see, for example, FIGS. 1 and 2). Therefore, the titanate coupling agent can prevent the entry of substances that cause corrosion such as water, and exhibits a better antirust effect than the silane coupling agent.
チタネート系カップリング剤の防錆効果は疎水基数と疎水基長さに依存し、あまり少なく、且つ短いと防錆効果が不十分であるため、疎水基数は３個以上で、炭素数は５以上である必要がある。 The rust prevention effect of titanate coupling agents depends on the number of hydrophobic groups and the length of the hydrophobic group, and if it is too small and short, the rust prevention effect is insufficient, so the number of hydrophobic groups is 3 or more, and the number of carbons is 5 or more. Need to be.
そこで、本発明に係る表面処理鋼板の端面防錆方法は、表面処理鋼板の端面に、炭素数が５以上の疎水基を３個以上有するチタネート系カップリング剤を含む溶液を塗布することを特徴とすることとしている。 Then, the end surface rust prevention method of the surface-treated steel sheet according to the present invention is characterized in that a solution containing a titanate coupling agent having three or more hydrophobic groups having 5 or more carbon atoms is applied to the end surface of the surface-treated steel sheet. It is supposed to be.
この表面処理鋼板の端面防錆方法によれば、従来の塗料やワニスによる処理の場合に比べて処理が簡単になると共に、従来の無機物での端面被覆（特開平3-6387号、特公平7-116617号、特開平4-280986号公報記載のもの）の場合に比べて屋外での端面耐食性を向上することができる。更に、シランカップリング剤による場合よりも、屋外での端面耐食性を向上することもできる。しかも、シランカップリング剤による場合のように高濃度溶液が必要となることは必ずしもなく、経済性に優れている。 According to the method of preventing rust of the surface-treated steel sheet, the treatment becomes simpler than the conventional treatment with paint or varnish, and the end face coating with a conventional inorganic substance (Japanese Patent Laid-Open No. 3-6387, JP-B-7) -116617 and JP-A-4-280986), the end face corrosion resistance outdoors can be improved. Furthermore, outdoor end face corrosion resistance can also be improved rather than the case where it is based on a silane coupling agent. In addition, a high-concentration solution is not always required as in the case of using a silane coupling agent, and the economy is excellent.
ここで、チタネート系カップリング剤とは、加水分解可能なアルコキシ基（ＲＯ−）と有機官能基（疎水基）（Ｘ）を１分子中に持つ化合物である。本発明に係るチタネート系カップリング剤は、炭素数：５以上の疎水基（Ｘ）を３個以上有するものである。これは、例えば下記式（１）で示されるような化合物である。なお、式（１）において、ＲＯ−は、具体的にはCH3O−、 C2H5O−、 CH3OC2H4O−等を表し、加水分解後はチタノール基を生成する。また、Ｘ−は、Ｃ（炭素）が５個以上の炭素鎖を有する官能基を表している。疎水基（Ｘ）の数は３個である。 Here, the titanate coupling agent is a compound having a hydrolyzable alkoxy group (RO-) and an organic functional group (hydrophobic group) (X) in one molecule. The titanate coupling agent according to the present invention has three or more hydrophobic groups (X) having 5 or more carbon atoms. This is, for example, a compound represented by the following formula (1). In formula (1), RO— specifically represents CH 3 O—, C 2 H 5 O—, CH 3 OC 2 H 4 O—, etc., and produces a titanol group after hydrolysis. X- represents a functional group in which C (carbon) has 5 or more carbon chains. The number of hydrophobic groups (X) is three.
本発明に係るチタネート系カップリング剤は、鋼材表面の水酸基に結合する親水基を含み、鋼材表面に広がって防錆効果を発揮する疎水基を３個以上有し、その疎水基の炭素数が５以上のものである。かかるチタネート系カップリング剤としては、例えば、味の素ファインテクノ社がチタネート系カップリング剤プレンアクトの商品名で提供する製品群、即ち、ＫＲ−ＴＴＳ、ＫＲ−４６Ｂ、ＫＲ−５５、ＫＲ−４１Ｂ、ＫＲ−３８Ｓ、ＫＲ−１３８Ｓ、ＫＲ−２３８Ｓ、３３８Ｘ、ＫＲ９ＳＡ（品番）が挙げられる。疎水基の個数および疎水基の炭素数の上限は特に定めないが、通常は疎水基数９個、炭素数は30個程度である。 The titanate coupling agent according to the present invention includes a hydrophilic group that binds to a hydroxyl group on the surface of a steel material, has three or more hydrophobic groups that spread on the surface of the steel material and exhibit a rust prevention effect, and the number of carbons of the hydrophobic group is 5 or more. As such titanate coupling agents, for example, Ajinomoto Fine Techno Co., Ltd., a product group provided under the trade name of titanate coupling agent Preneact, namely, KR-TTS, KR-46B, KR-55, KR-41B, KR -38S, KR-138S, KR-238S, 338X, KR9SA (product number). The upper limit of the number of hydrophobic groups and the number of carbon atoms of the hydrophobic group is not particularly limited, but is usually about 9 hydrophobic groups and about 30 carbon atoms.
チタネート系カップリング剤は、水等の溶媒に溶解して溶液とする。溶液濃度は、低すぎると１回の塗布で十分な防錆効果が得られないため、0.5 質量％（重量％）以上であることが好ましい。また、濃すぎても効果が飽和することから、上限を20質量％とすることが好ましい〔第２発明〕。 The titanate coupling agent is dissolved in a solvent such as water to form a solution. If the solution concentration is too low, a sufficient rust prevention effect cannot be obtained by a single application, and therefore it is preferably 0.5% by mass (% by weight) or more. Moreover, since an effect is saturated even if it is too thick, it is preferable to make an upper limit into 20 mass% [2nd invention].
チタネート系カップリング剤の端面付着量（塗布量）は、Ti量で５μg/m2〜50μg/m2であることが好ましい〔第３発明〕。５μg/m2未満では、端面がTi化合物で覆われない部分が残るため、防錆性に劣る。一方、50μg/m2を超えても効果に差がなく、また、吸湿の問題が生じる可能性がある。 End surface adhesion amount titanate coupling agent (coating amount) is preferably 5μg / m 2 ~50μg / m 2 in Ti amount [Third Invention]. If it is less than 5 μg / m 2 , the end face is not covered with the Ti compound, so that the rust resistance is poor. On the other hand, even if it exceeds 50 μg / m 2 , there is no difference in effect, and there is a possibility that a problem of moisture absorption occurs.
端面の塗布されたチタネート系カップリング剤の検出については、その塗布された個所を溶剤（水やアルコール等）に浸漬または溶剤で洗浄し、それにより得られた液（浸漬液または洗浄液）を濃縮した後、 FT-IR（フーリェ変換赤外分光法）でチタネートカップリング剤であることの確認、 GC-MS（ガスクロマトグラフ質量分析法）、 NMR（核磁気共鳴法による分析法）等で構造の同定を行うことができる。なお、チタネート系カップリング剤の市販品が容易に入手できるので、これをリファレンスとして用いて比較することも可能である。 For detection of the titanate coupling agent applied to the end face, the applied part is immersed in a solvent (water, alcohol, etc.) or washed with a solvent, and the resulting liquid (immersion liquid or cleaning liquid) is concentrated. After confirming that it is a titanate coupling agent by FT-IR (Fourier transform infrared spectroscopy), GC-MS (gas chromatograph mass spectrometry), NMR (analysis method by nuclear magnetic resonance method), etc. Identification can be performed. In addition, since the commercial item of a titanate coupling agent can be obtained easily, it can also be compared using this as a reference.
本発明に係る端面防錆処理は、溶融亜鉛めっき鋼板(GI)、電気亜鉛めっき鋼板(EG)、合金化亜鉛めっき鋼板(GA)、溶融亜鉛−アルミ合金メッキ鋼板、樹脂被覆溶融亜鉛−アルミ合金めっき鋼板などの端面防錆に使用できる。本発明の適用範囲はこれらの表面処理鋼板に限定されず、これら以外の表面処理鋼板、例えばメッキ鋼板に化成処理を施した化成処理鋼板や塗装を施したプレコート鋼板（塗装鋼板）等の端面防錆に適用可能である。 End face rust prevention treatment according to the present invention includes hot dip galvanized steel sheet (GI), electrogalvanized steel sheet (EG), alloyed galvanized steel sheet (GA), hot dip galvanized aluminum plated steel sheet, resin-coated hot dip galvanized aluminum alloy. Can be used for rust prevention of plated steel sheets. The scope of application of the present invention is not limited to these surface-treated steel plates, but other surface-treated steel plates, for example, end face preventions such as chemical-treated steel plates that have been subjected to chemical conversion treatment on coated steel plates or pre-coated steel plates that have been coated (painted steel plates). Applicable to rust.
本発明に係る表面処理鋼板の端面防錆処理液は、前述のように、炭素数が５以上の疎水基を３個以上有するチタネート系カップリング剤を0.5 〜20質量％含有することを特徴とするものである〔第４発明〕。この端面防錆処理液によれば、１回の塗布で十分な防錆効果が得られる。なお、上記チタネート系カップリング剤の含有量（濃度）が0.5 質量％未満の場合、１回の塗布で十分な防錆効果を得ることが難しくなる。また、この濃度が20質量％超の場合、防錆効果が飽和し、ひいては経済性の低下を招く。 As described above, the end surface antirust treatment liquid for the surface-treated steel sheet according to the present invention contains 0.5 to 20% by mass of a titanate coupling agent having 3 or more hydrophobic groups having 5 or more carbon atoms. [4th invention]. According to this end face antirust treatment liquid, a sufficient antirust effect can be obtained by a single application. In addition, when content (concentration) of the said titanate coupling agent is less than 0.5 mass%, it will become difficult to acquire sufficient rust prevention effect by one application | coating. Moreover, when this density | concentration exceeds 20 mass%, a rust prevention effect will be saturated and it will cause the fall of economical efficiency by extension.
本発明の実施例および比較例について、以下説明する。なお、本発明はこの実施例に限定されるものではなく、本発明の趣旨に適合し得る範囲で適当に変更を加えて実施することも可能であり、それらはいずれも本発明の技術的範囲に含まれる。 Examples of the present invention and comparative examples will be described below. The present invention is not limited to this embodiment, and can be implemented with appropriate modifications within a range that can be adapted to the gist of the present invention, all of which are within the technical scope of the present invention. include.
〔例１〕
チタネートカップリング剤としてＫＲＴＴＳ（商品名：品番）（味の素ファインテクノ社製）（イソプロピルトリイソステアロイルチタネート）を用い、これを水で濃度１質量％（重量％）に希釈して、端面防錆処理液を得た。なお、このチタネート系カップリング剤は、炭素数が１７の疎水基を３個有するものである。
[Example 1]
As a titanate coupling agent, KRTTS (trade name: product number) (manufactured by Ajinomoto Fine Techno Co., Ltd.) (isopropyl triisostearoyl titanate) is diluted with water to a concentration of 1% by mass (weight%), and end face rust prevention treatment is performed. A liquid was obtained. This titanate coupling agent has three hydrophobic groups having 17 carbon atoms.
溶融亜鉛メッキ鋼板(GI)（角鋼板の厚さ：1.6mm ）を短冊状（50mm×150mm)に切断し、試験片を得た。 A hot-dip galvanized steel sheet (GI) (square steel plate thickness: 1.6 mm) was cut into strips (50 mm x 150 mm) to obtain test pieces.
上記試験片を有機溶媒で脱脂処理した後、試験片の端面（長手方向、両側）を前記端面防錆処理液に浸漬し、風乾し、暴露試験用サンプルを得た。なお、浸漬しなかった端面はテープでシールした。前記端面防錆処理液の浸漬、風乾は１回行った。即ち、端面防錆処理液の塗布は１回行った。 After degreasing the test piece with an organic solvent, the end face (longitudinal direction, both sides) of the test piece was immersed in the end face antirust treatment solution and air-dried to obtain a sample for an exposure test. The end face that was not immersed was sealed with tape. The end face antirust treatment liquid was immersed and air-dried once. That is, the end face anti-rust treatment liquid was applied once.
暴露試験用サンプルのTi付着量は、アルカリ性水溶液で、端面に付着したチタネート系カップリング剤を溶解させ、TiをICP-MS（誘導結合プラズマ質量分析法）で定量分析して求めた。 The amount of Ti attached to the sample for the exposure test was determined by dissolving the titanate coupling agent adhering to the end face with an alkaline aqueous solution and quantitatively analyzing Ti by ICP-MS (inductively coupled plasma mass spectrometry).
上記のようにして得られた暴露試験用サンプルについて、恒温恒湿槽（温度：50℃、相対湿度（ＲＨ）：98％）暴露試験、屋外暴露試験を各１ヶ月実施した。 The exposure test samples obtained as described above were subjected to a constant temperature and humidity chamber (temperature: 50 ° C., relative humidity (RH): 98%) exposure test and outdoor exposure test for one month each.
屋外暴露試験は、兵庫県の神戸製鋼所加古川製鉄所内で行った。このとき、サンプルを載置する暴露台の高さは約１ｍ、暴露台の傾斜角度は約30度である。 The outdoor exposure test was conducted at the Kakogawa Works in Kobe Steel, Hyogo Prefecture. At this time, the height of the exposure table on which the sample is placed is about 1 m, and the inclination angle of the exposure table is about 30 degrees.
暴露試験終了後、端面防錆効果の程度（端面耐食性）を評価した。この評価は次のようにして行った。即ち、暴露試験終了後の端面の写真を撮って拡大し、目視によって赤錆発生率を求め、下記(1) 、(2) の基準で評価を行った。なお、赤錆発生率は、端面の面積に対する赤錆発生の認められた個所の面積の割合（％）である。 After the exposure test was completed, the degree of end surface rust prevention effect (end surface corrosion resistance) was evaluated. This evaluation was performed as follows. That is, a photograph of the end face after the exposure test was taken and enlarged, the red rust occurrence rate was obtained by visual observation, and the evaluation was performed according to the following criteria (1) and (2). The red rust occurrence rate is the ratio (%) of the area where red rust occurrence is recognized to the end face area.
(1) 恒温恒湿槽暴露試験の場合は、赤錆発生率：０〜0.5 ％のものを○（良好）、赤錆発生率：0.5 〜1.0 ％のものを△、赤錆発生率：1.0 ％以上のものを×（不良）とした。 (2) 屋外暴露試験の場合は、赤錆発生率：０〜10％のものを○（良好）、赤錆発生率：10〜20％のものを△、赤錆発生率：20％以上のものを×（不良）とした。 (1) In the constant temperature and humidity chamber exposure test, red rust incidence: 0 to 0.5% ○ (good), red rust incidence: 0.5 to 1.0% △, red rust incidence: 1.0% or more The thing was made into x (defect). (2) For outdoor exposure tests, red rust incidence: 0-10% ○ (good), red rust incidence: 10-20% △, red rust incidence: 20% or more × (Defect).
〔例２〕
チタネートカップリング剤として、前記ＫＲＴＴＳに代えてＫＲ−４６Ｂ（商品名：品番）（味の素ファインテクノ社製）（テトラオクチルビス（ジトリデシルホスファイト）チタネート）を用いた。なお、このチタネート系カップリング剤は、炭素数が１３の疎水基を４個有するものである。
[Example 2]
As a titanate coupling agent, KR-46B (trade name: product number) (manufactured by Ajinomoto Fine Techno Co.) (tetraoctyl bis (ditridecyl phosphite) titanate) was used in place of the KRTTS. This titanate coupling agent has 4 hydrophobic groups having 13 carbon atoms.
この点を除き前記例１の場合と同様の試験等を行った。即ち、上記チタネートカップリング剤（ＫＲ−４６Ｂ）を水で濃度１質量％（重量％）に希釈して端面防錆処理液を得、これを前記例１の場合と同様の試験片の端面に同様の方法により塗布して暴露試験用サンプルを得、この暴露試験用サンプルについて前記例１の場合と同様の方法によりTi付着量を求め、前記例１の場合と同様の方法により恒温恒湿槽暴露試験、屋外暴露試験を実施し、前記例１の場合と同様の方法により端面防錆効果の程度（端面耐食性）を評価した。 Except for this point, the same tests as in Example 1 were performed. That is, the titanate coupling agent (KR-46B) was diluted with water to a concentration of 1% by mass (weight%) to obtain an end face antirust treatment liquid, which was applied to the end face of the test piece as in Example 1 above. A sample for exposure test was obtained by applying in the same manner, and the amount of Ti adhesion was determined for the sample for exposure test by the same method as in Example 1, and the constant temperature and humidity chamber was obtained by the same method as in Example 1. An exposure test and an outdoor exposure test were carried out, and the degree of end surface rust prevention effect (end surface corrosion resistance) was evaluated by the same method as in Example 1.
〔例３〕
チタネートカップリング剤として、ＫＲ３８Ｓ（商品名：品番）（味の素ファインテクノ社製）（イソプロピルトリス（ジオクチルピロフォスフェ−ト）チタネート）を使用した。なお、このチタネート系カップリング剤は、炭素数が８の疎水基を６個有するものである。
[Example 3]
As a titanate coupling agent, KR38S (trade name: product number) (manufactured by Ajinomoto Fine Techno Co.) (isopropyl tris (dioctyl pyrophosphate) titanate) was used. This titanate coupling agent has 6 hydrophobic groups having 8 carbon atoms.
この点を除き前記例１の場合と同様の試験等を行った。即ち、上記チタネートカップリング剤（ＫＲ３８Ｓ）を水で濃度１質量％に希釈して端面防錆処理液を得、これを前記例１の場合と同様の試験片の端面に同様の方法により塗布して暴露試験用サンプルを得、この暴露試験用サンプルについて前記例１の場合と同様の方法によりTi付着量を求め、同様の方法により恒温恒湿槽暴露試験、屋外暴露試験を実施し、同様の方法により端面防錆効果の程度（端面耐食性）を評価した。 Except for this point, the same tests as in Example 1 were performed. That is, the titanate coupling agent (KR38S) was diluted with water to a concentration of 1% by mass to obtain an end face antirust treatment liquid, which was applied to the end face of the same test piece as in Example 1 by the same method. A sample for an exposure test was obtained, and the amount of Ti adhesion was obtained for the sample for the exposure test by the same method as in Example 1, and a constant temperature and humidity chamber exposure test and an outdoor exposure test were conducted by the same method. The degree of end surface rust prevention effect (end surface corrosion resistance) was evaluated by the method.
〔例４〕
チタネートカップリング剤として、ＫＲ９ＳＡ（商品名：品番）（味の素ファインテクノ社製）（イソプロピルトリ−ｎ−ドデシルベンゼンスルフォニルチタネート）を使用した。なお、このチタネート系カップリング剤は、炭素数が１２の疎水基を３個有するものである。
[Example 4]
As a titanate coupling agent, KR9SA (trade name: product number) (manufactured by Ajinomoto Fine Techno Co.) (isopropyl tri-n-dodecylbenzenesulfonyl titanate) was used. The titanate coupling agent has three hydrophobic groups having 12 carbon atoms.
この点を除き前記例１の場合と同様の試験等を行った。即ち、上記チタネートカップリング剤（ＫＲ９ＳＡ）を水で濃度１質量％に希釈して端面防錆処理液を得、これを前記例１の場合と同様の試験片の端面に同様の方法により塗布して暴露試験用サンプルを得、この暴露試験用サンプルについて前記例１の場合と同様の方法によりTi付着量を求め、同様の方法により恒温恒湿槽暴露試験、屋外暴露試験を実施し、同様の方法により端面防錆効果の程度（端面耐食性）を評価した。 Except for this point, the same tests as in Example 1 were performed. That is, the titanate coupling agent (KR9SA) was diluted with water to a concentration of 1% by mass to obtain an end face antirust treatment liquid, which was applied to the end face of the test piece similar to that in Example 1 by the same method. A sample for an exposure test was obtained, and the amount of Ti adhesion was obtained for the sample for the exposure test by the same method as in Example 1, and a constant temperature and humidity chamber exposure test and an outdoor exposure test were conducted by the same method. The degree of end surface rust prevention effect (end surface corrosion resistance) was evaluated by the method.
〔例５〕
チタネートカップリング剤に代えてシランカップリング剤KBM-903 （商品名：品番）（信越化学製）（γ−アミノプロピルトリメトキシシラン）を用いた。
[Example 5]
Instead of the titanate coupling agent, a silane coupling agent KBM-903 (trade name: product number) (manufactured by Shin-Etsu Chemical) (γ-aminopropyltrimethoxysilane) was used.
この点を除き前記例１の場合と同様の試験等を行った。即ち、上記シランカップリング剤（KBM-903 ）を水で濃度１質量％に希釈して端面防錆処理液を得、これを前記例１の場合と同様の試験片の端面に同様の方法により塗布して暴露試験用サンプルを得、この暴露試験用サンプルについて前記例１の場合と同様の方法により恒温恒湿槽暴露試験、屋外暴露試験を実施し、同様の方法により端面防錆効果の程度（端面耐食性）を評価した。 Except for this point, the same tests as in Example 1 were performed. That is, the silane coupling agent (KBM-903) was diluted with water to a concentration of 1% by mass to obtain an end face antirust treatment liquid, which was applied to the end face of the test piece as in Example 1 by the same method. A sample for exposure test was obtained by coating, and the exposure test sample was subjected to a constant temperature and humidity chamber exposure test and an outdoor exposure test by the same method as in Example 1 above, and the degree of end face rust prevention effect by the same method. (End surface corrosion resistance) was evaluated.
〔例６〕
チタネートカップリング剤に代えてシランカップリング剤KBM-1003（商品名：品番）（信越化学製）（ビニルトリメトキシシラン）を用いた。この点を除き前記例１の場合と同様の試験等を行った。即ち、上記シランカップリング剤（KBM-1003）を水で濃度１質量％に希釈して端面防錆処理液を得、これを前記例１の場合と同様の試験片の端面に同様の方法により塗布して暴露試験用サンプルを得、この暴露試験用サンプルについて前記例１の場合と同様の方法により恒温恒湿槽暴露試験、屋外暴露試験を実施し、同様の方法により端面防錆効果の程度（端面耐食性）を評価した。
[Example 6]
Instead of the titanate coupling agent, a silane coupling agent KBM-1003 (trade name: product number) (manufactured by Shin-Etsu Chemical) (vinyltrimethoxysilane) was used. Except for this point, the same tests as in Example 1 were performed. That is, the silane coupling agent (KBM-1003) was diluted with water to a concentration of 1% by mass to obtain an end face antirust treatment liquid, which was applied to the end face of the same test piece as in Example 1 by the same method. A sample for exposure test was obtained by coating, and the exposure test sample was subjected to a constant temperature and humidity chamber exposure test and an outdoor exposure test by the same method as in Example 1 above, and the degree of end face rust prevention effect by the same method. (End surface corrosion resistance) was evaluated.
〔例７〕
チタネートカップリング剤に代えてシランカップリング剤KBM-403 （商品名：品番）（信越化学製）（γ−グリシドキシプロピルトリメトキシシラン）を用いた。この点を除き前記例１の場合と同様の試験等を行った。即ち、上記シランカップリング剤（KBM-403)を水で濃度１質量％に希釈して端面防錆処理液を得、これを前記例１の場合と同様の試験片の端面に同様の方法により塗布して暴露試験用サンプルを得、この暴露試験用サンプルについて前記例１の場合と同様の方法により恒温恒湿槽暴露試験、屋外暴露試験を実施し、同様の方法により端面防錆効果の程度（端面耐食性）を評価した。
[Example 7]
Instead of the titanate coupling agent, a silane coupling agent KBM-403 (trade name: product number) (manufactured by Shin-Etsu Chemical) (γ-glycidoxypropyltrimethoxysilane) was used. Except for this point, the same tests as in Example 1 were performed. That is, the silane coupling agent (KBM-403) was diluted with water to a concentration of 1% by mass to obtain an end face antirust treatment liquid, which was applied to the end face of the test piece similar to that in Example 1 by the same method. A sample for exposure test was obtained by coating, and the exposure test sample was subjected to a constant temperature and humidity chamber exposure test and an outdoor exposure test by the same method as in Example 1 above, and the degree of end face rust prevention effect by the same method. (End surface corrosion resistance) was evaluated.
〔例８〕
チタネートカップリング剤に代えてシランカップリング剤KBM-803 （商品名：品番）（信越化学製）（γ−メルカプトプロピルトリメトキシシラン）を用いた。この点を除き前記例１の場合と同様の試験等を行った。即ち、上記シランカップリング剤（KBM-803)を水で濃度１質量％に希釈して端面防錆処理液を得、これを前記例１の場合と同様の試験片の端面に同様の方法により塗布して暴露試験用サンプルを得、この暴露試験用サンプルについて前記例１の場合と同様の方法により恒温恒湿槽暴露試験、屋外暴露試験を実施し、同様の方法により端面防錆効果の程度（端面耐食性）を評価した。
[Example 8]
Instead of the titanate coupling agent, a silane coupling agent KBM-803 (trade name: product number) (manufactured by Shin-Etsu Chemical) (γ-mercaptopropyltrimethoxysilane) was used. Except for this point, the same tests as in Example 1 were performed. That is, the silane coupling agent (KBM-803) was diluted with water to a concentration of 1% by mass to obtain an end face antirust treatment liquid, and this was applied to the end face of the same test piece as in Example 1 by the same method. A sample for exposure test was obtained by coating, and the exposure test sample was subjected to a constant temperature and humidity chamber exposure test and an outdoor exposure test in the same manner as in Example 1, and the degree of antirust effect on the end face by the same method. (End surface corrosion resistance) was evaluated.
〔例９〕
チタネートカップリング剤として、ＫＲ４４（商品名：品番）（味の素ファインテクノ社製）（イソプロピルトリ（Ｎ−アミノエチル−アミノエチル）チタネート）を用いた。なお、上記チタネート系カップリング剤は、疎水基の数が３個、その疎水基の炭素数が４である（炭素数が５以上の疎水基を３個以上有するという条件を満たすものではない）。
[Example 9]
As a titanate coupling agent, KR44 (trade name: product number) (manufactured by Ajinomoto Fine Techno Co., Ltd.) (isopropyl tri (N-aminoethyl-aminoethyl) titanate) was used. The titanate coupling agent has 3 hydrophobic groups and 4 carbon atoms in the hydrophobic group (it does not satisfy the condition that it has 3 or more hydrophobic groups having 5 or more carbon atoms). .
この点を除き前記例１の場合と同様の試験等を行った。即ち、上記チタネートカップリング剤（ＫＲ４４）を水で濃度１質量％に希釈して端面防錆処理液を得、これを前記例１の場合と同様の試験片の端面に同様の方法により塗布して暴露試験用サンプルを得、この暴露試験用サンプルについて前記例１の場合と同様の方法により恒温恒湿槽暴露試験、屋外暴露試験を実施し、同様の方法により端面防錆効果の程度（端面耐食性）を評価した。 Except for this point, the same tests as in Example 1 were performed. That is, the titanate coupling agent (KR44) was diluted with water to a concentration of 1% by mass to obtain an end face antirust treatment liquid, which was applied to the end face of the same test piece as in Example 1 by the same method. The exposure test sample was obtained, and the exposure test sample was subjected to a constant temperature and humidity chamber exposure test and an outdoor exposure test in the same manner as in Example 1 above. Corrosion resistance) was evaluated.
〔例１０〕
チタネートカップリング剤の濃度を0.05質量％とした。即ち、チタネートカップリング剤ＫＲＴＴＳを水で濃度0.05質量％に希釈して端面防錆処理液を得た。
[Example 10]
The concentration of the titanate coupling agent was 0.05% by mass. That is, the titanate coupling agent KRTTS was diluted with water to a concentration of 0.05% by mass to obtain an end face antirust treatment liquid.
この点を除き前記例１の場合と同様の試験等を行った。即ち、上記端面防錆処理液を前記例１の場合と同様の試験片の端面に同様の方法により塗布して暴露試験用サンプルを得、この暴露試験用サンプルについて前記例１の場合と同様の方法によりTi付着量を求め、同様の方法により恒温恒湿槽暴露試験、屋外暴露試験を実施し、同様の方法により端面防錆効果の程度（端面耐食性）を評価した。 Except for this point, the same tests as in Example 1 were performed. That is, the end face antirust treatment liquid is applied to the end face of the test piece similar to that in Example 1 by the same method to obtain an exposure test sample, and this exposure test sample is the same as in Example 1 above. Ti adhesion amount was calculated | required by the method, the constant temperature / humidity tank exposure test and the outdoor exposure test were implemented by the same method, and the grade (end surface corrosion resistance) of the end surface rust prevention effect was evaluated by the same method.
〔例１１〕
チタネートカップリング剤の濃度を0.2 質量％とした。即ち、チタネートカップリング剤ＫＲＴＴＳを水で濃度0.2 質量％に希釈して端面防錆処理液を得た。
[Example 11]
The concentration of the titanate coupling agent was 0.2% by mass. That is, the titanate coupling agent KRTTS was diluted with water to a concentration of 0.2% by mass to obtain an end face antirust treatment liquid.
この点を除き前記例１の場合と同様の試験等を行った。即ち、上記端面防錆処理液を前記例１の場合と同様の試験片の端面に同様の方法により塗布して暴露試験用サンプルを得、この暴露試験用サンプルについて前記例１の場合と同様の方法によりTi付着量を求め、同様の方法により恒温恒湿槽暴露試験、屋外暴露試験を実施し、同様の方法により端面防錆効果の程度（端面耐食性）を評価した。 Except for this point, the same tests as in Example 1 were performed. That is, the end face antirust treatment liquid is applied to the end face of the test piece similar to that in Example 1 by the same method to obtain an exposure test sample, and this exposure test sample is the same as in Example 1 above. Ti adhesion amount was calculated | required by the method, the constant temperature / humidity tank exposure test and the outdoor exposure test were implemented by the same method, and the grade (end surface corrosion resistance) of the end surface rust prevention effect was evaluated by the same method.
〔例１２〕
溶融亜鉛メッキ鋼板(GI)（角鋼板の厚さ：1.6mm ）を短冊状（50mm×150mm)に切断し、試験片を得た。これを暴露試験用サンプルとし、前記例１の場合と同様の方法により恒温恒湿槽暴露試験、屋外暴露試験を実施し、同様の方法により端面耐食性を評価した。
[Example 12]
A hot-dip galvanized steel sheet (GI) (square steel plate thickness: 1.6 mm) was cut into strips (50 mm x 150 mm) to obtain test pieces. Using this as a sample for an exposure test, a constant temperature and humidity chamber exposure test and an outdoor exposure test were performed by the same method as in Example 1, and the end face corrosion resistance was evaluated by the same method.
〔例１３〕
エポキシ樹脂防錆剤（MSクリア（商品名）、神東塗料製）を固形分濃度10％に希釈して端面防錆処理液を得た。
[Example 13]
An epoxy resin rust inhibitor (MS Clear (trade name), manufactured by Shinto Paint) was diluted to a solid content concentration of 10% to obtain an end face rust preventive solution.
この点を除き前記例１の場合と同様の試験等を行った。即ち、上記端面防錆処理液を前記例１の場合と同様の試験片の端面に同様の方法により塗布して暴露試験用サンプルを得、この暴露試験用サンプルについて前記例１の場合と同様の方法によりTi付着量を求め、同様の方法により恒温恒湿槽暴露試験、屋外暴露試験を実施し、同様の方法により端面防錆効果の程度（端面耐食性）を評価した。 Except for this point, the same tests as in Example 1 were performed. That is, the end face antirust treatment liquid is applied to the end face of the test piece similar to that in Example 1 by the same method to obtain an exposure test sample, and this exposure test sample is the same as in Example 1 above. Ti adhesion amount was calculated | required by the method, the constant temperature / humidity tank exposure test and the outdoor exposure test were implemented by the same method, and the grade (end surface corrosion resistance) of the end surface rust prevention effect was evaluated by the same method.
用いられたチタネート系カップリング剤についての疎水基の数および１分子中のTi数と共に暴露試験用サンプルのTi付着量を表１に示す。恒温恒湿槽暴露試験結果および屋外暴露試験結果を表２に示す。 Table 1 shows the Ti adhesion amount of the sample for the exposure test together with the number of hydrophobic groups and the number of Ti in one molecule for the titanate coupling agent used. Table 2 shows the results of the constant temperature and humidity chamber exposure test and the outdoor exposure test.
例５〜８の場合には、端面防錆処理液としてシランカップリング剤を含む溶液を用いており、恒温恒湿槽暴露試験での赤錆発生率が×（不良）あるいは△であり、屋外暴露試験での赤錆発生率が×（不良）である。 In the case of Examples 5 to 8, a solution containing a silane coupling agent is used as the end face anti-rust treatment solution, the occurrence rate of red rust in the constant temperature and humidity chamber exposure test is x (defect) or Δ, and it is exposed outdoors. The occurrence rate of red rust in the test is x (defect).
例９の場合には、端面防錆処理液として疎水基の数が３個、その疎水基の炭素数が４のチタネート系カップリング剤（炭素数が５以上の疎水基を３個以上有するという条件を満たしていない）を含む溶液を用いており、恒温恒湿槽暴露試験での赤錆発生率が×（不良）であり、屋外暴露試験での赤錆発生率が×（不良）である。 In the case of Example 9, the titanate coupling agent (having 3 or more hydrophobic groups having 5 or more carbon atoms) having 3 hydrophobic groups and 4 carbon atoms in the hydrophobic group as the end face antirust treatment liquid. Solution that does not satisfy the conditions), the occurrence rate of red rust in the constant temperature and humidity chamber exposure test is x (defect), and the occurrence rate of red rust in the outdoor exposure test is x (defect).
これらに対し、例１〜４の場合には、端面防錆処理液として炭素数が８〜１８の疎水基を３〜６個有するチタネート系カップリング剤（炭素数が５以上の疎水基を３個以上有するという条件を満たしている）を１質量％含む溶液を用いており、エポキシ樹脂防錆剤を含む溶液を用いた場合と同様、恒温恒湿槽暴露試験での赤錆発生率が○（良好）であると共に、屋外暴露試験での赤錆発生率が○（良好）である。なお、例10〜11の場合、チタネート系カップリング剤の濃度が0.05〜0.2 質量％であるため、恒温恒湿槽暴露試験での赤錆発生率も屋外暴露試験での赤錆発生率も×（不良）であるので、１回の塗布では十分な防錆効果が得られないことになるが、数回塗布すれば恒温恒湿槽暴露試験での赤錆発生率も屋外暴露試験での赤錆発生率も○（良好）となる。 On the other hand, in Examples 1-4, titanate coupling agents having 3 to 6 hydrophobic groups having 8 to 18 carbon atoms (3 hydrophobic groups having 5 or more carbon atoms as the end surface antirust treatment liquid). As in the case of using a solution containing an epoxy resin rust inhibitor, the red rust occurrence rate in the constant temperature and humidity chamber exposure test is ○ ( Good) and the occurrence rate of red rust in the outdoor exposure test is good (good). In Examples 10 to 11, since the concentration of the titanate coupling agent is 0.05 to 0.2% by mass, the red rust occurrence rate in the constant temperature and humidity chamber exposure test and the red rust occurrence rate in the outdoor exposure test are x (defects). However, if it is applied once, the red rust occurrence rate in the constant temperature and humidity chamber exposure test and the red rust occurrence rate in the outdoor exposure test will not be obtained. ○ (Good).
例１〜４の場合のチタネート系カップリング剤の鋼板表面の分子構造モデルを模式図で示すと、例えば図１のようになる。例９の場合のチタネート系カップリング剤および例５〜８の場合のシランカップリング剤の鋼板表面の分子構造モデルを模式図で示すと、例えば図２のようになる。
本発明に係る表面処理鋼板の端面防錆方法は、従来の塗料やワニスによる処理の場合に比べて処理が簡単であると共に従来の無機物での端面被覆（特開平3-6387号、特公平7-116617号、特開平4-280986号公報記載のもの）の場合に比べて屋外での端面耐食性を向上させることができるので、コイル状やシート状で供給される建材、家電等向けめっき鋼板、表面処理鋼板、プレコート鋼板を需要家が切断または打ち抜き加工により製品化する際に生じる鋼板端面を防錆するための端面防錆方法として、好適に用いることができ、それらの端面耐食性を向上することができる。 The end surface rust prevention method for the surface-treated steel sheet according to the present invention is simpler than the conventional treatment with paint or varnish, and the conventional end face coating with an inorganic substance (Japanese Patent Laid-Open No. 3-6387, Japanese Patent Publication No. 7). -116617, JP-A-4-280986, etc.) can improve the end face corrosion resistance outdoors, so that the coated steel sheet for building materials, home appliances, etc. supplied in coil form or sheet form, It can be used suitably as an end face rust prevention method for preventing rust on the end faces of steel sheets that are produced when customers make surface-treated steel sheets and pre-coated steel sheets by cutting or punching, and to improve the corrosion resistance of the end faces. Can do.
Claims (4)
An end surface antirust treatment liquid for a surface-treated steel sheet, comprising 0.5 to 20% by mass of a titanate coupling agent having 3 or more hydrophobic groups having 5 or more carbon atoms.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004067539A JP2005254106A (en) | 2004-03-10 | 2004-03-10 | Method for rustproofing end face of surface-treated steel plate and end face rustproofing liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004067539A JP2005254106A (en) | 2004-03-10 | 2004-03-10 | Method for rustproofing end face of surface-treated steel plate and end face rustproofing liquid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2005254106A true JP2005254106A (en) | 2005-09-22 |
Family
ID=35080366
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004067539A Withdrawn JP2005254106A (en) | 2004-03-10 | 2004-03-10 | Method for rustproofing end face of surface-treated steel plate and end face rustproofing liquid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2005254106A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010029934A1 (en) * | 2008-09-12 | 2010-03-18 | コニカミノルタホールディングス株式会社 | Substrate and process for forming electroconductive pattern |
| WO2018198384A1 (en) | 2017-04-26 | 2018-11-01 | 日新製鋼株式会社 | Water-based treatment solution, chemical conversion treatment method, and chemical-conversion-treated steel sheet |
-
2004
- 2004-03-10 JP JP2004067539A patent/JP2005254106A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010029934A1 (en) * | 2008-09-12 | 2010-03-18 | コニカミノルタホールディングス株式会社 | Substrate and process for forming electroconductive pattern |
| WO2018198384A1 (en) | 2017-04-26 | 2018-11-01 | 日新製鋼株式会社 | Water-based treatment solution, chemical conversion treatment method, and chemical-conversion-treated steel sheet |
| KR20190139905A (en) | 2017-04-26 | 2019-12-18 | 닛테츠 닛신 세이코 가부시키가이샤 | Aqueous treatment liquid, chemical treatment method and chemically treated steel sheet |
| US11280004B2 (en) | 2017-04-26 | 2022-03-22 | Nippon Steel Nisshin Co., Ltd. | Water-based treatment solution, chemical conversion treatment method, and chemical-conversion-treated steel sheet |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Prosek et al. | Corrosion performance of Zn–Al–Mg coatings in open and confined zones in conditions simulating automotive applications | |
| Nam et al. | The behaviour of praseodymium 4-hydroxycinnamate as an inhibitor for carbon dioxide corrosion and oxygen corrosion of steel in NaCl solutions | |
| RAJA et al. | Inhibitory effect of kopsia singapurensis extract on the corrosion behavior ofmild steel in acidmedia | |
| Rocca et al. | Inhibition treatment of the corrosion of lead artefacts in atmospheric conditions and by acetic acid vapour: use of sodium decanoate | |
| de Azevedo Alvarenga et al. | Atmospheric corrosion evaluation of electrogalvanized, hot-dip galvanized and galvannealed interstitial free steels using accelerated field and cyclic tests | |
| Gao et al. | Effect of anti-corrosive performance, roughness and chemical composition of pre-treatment layer on the overall performance of the paint system on cold-rolled steel | |
| US7625439B1 (en) | Bath composition for converting surface of ferrous metal to mixed oxides and organometallic compounds of aluminum and iron | |
| Fedel et al. | Sebacic acid as corrosion inhibitor for hot‐dip galvanized (HDG) steel in 0.1 M NaCl | |
| Telegdi et al. | Coatings against corrosion and microbial adhesion | |
| JP2001522941A (en) | Corrosion protection of galvanized steel sheet or galvanized steel sheet | |
| Zapponi et al. | Prohesion and outdoors tests on corrosion products developed over painted galvanized steel sheets with and without Cr (VI) species | |
| Aramaki | An attempt to prepare nonchromate, self-healing protective films containing molybdate on iron | |
| JP2005254106A (en) | Method for rustproofing end face of surface-treated steel plate and end face rustproofing liquid | |
| Bierwagen | Corrosion and its control by coatings | |
| LeBozec et al. | A new accelerated corrosion test for marine paint systems used for ship's topsides and superstructures | |
| JP2015163731A (en) | Metal surface treatment agent | |
| Bano et al. | Spatial evaluation of preservability of mild steel by coal tar epoxy coatings via spectroscopic and microscopic techniques | |
| Hajar et al. | Corrosion performance of coating thickness in marine environment | |
| JP6052521B2 (en) | Process for manufacturing corrosion-resistant metal member coating and process for manufacturing corrosion-resistant metal member | |
| Cristoforetti et al. | Influence of deposition parameters on the behavior of nitro-cobalt-based and Ti-hexafluoride-based pretreatments | |
| Wu et al. | Rapid corrosion testing of polymer coated steel using a constant voltage | |
| Tepe et al. | Evaluation of environmentally friendly Zr based nano structured conversion coating for HRS (Hot Rolled Steel) in powder coating | |
| Sheikholeslami | Long-Term Field Performance of Waterborne Coatings | |
| JP5742259B2 (en) | Coated steel for marine / river environment and manufacturing method thereof | |
| Ryabova et al. | Environmentally Friendly Corrosion Protection |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Effective date: 20060925 Free format text: JAPANESE INTERMEDIATE CODE: A621 |
|
| A761 | Written withdrawal of application |
Effective date: 20081016 Free format text: JAPANESE INTERMEDIATE CODE: A761 |