JP2019127618A - 溶接鋼管用防錆処理液、溶接鋼管の化成処理方法、溶接鋼管および溶接鋼管の成形加工品 - Google Patents
溶接鋼管用防錆処理液、溶接鋼管の化成処理方法、溶接鋼管および溶接鋼管の成形加工品 Download PDFInfo
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- JP2019127618A JP2019127618A JP2018009508A JP2018009508A JP2019127618A JP 2019127618 A JP2019127618 A JP 2019127618A JP 2018009508 A JP2018009508 A JP 2018009508A JP 2018009508 A JP2018009508 A JP 2018009508A JP 2019127618 A JP2019127618 A JP 2019127618A
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- welded steel
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- chemical conversion
- steel pipe
- film
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Abstract
Description
上記防錆処理液は、フッ素樹脂を含む有機樹脂、第4族元素を含む化合物または第4族元素のイオンおよび上記結合促進剤を含む。上記防錆処理液は、エッチング剤などのその他の成分をさらに含んでもよい。
有機樹脂は、フッ素樹脂を含む有機樹脂である。フッ素樹脂は、化成処理皮膜の耐候性(耐紫外線性および耐光性など)および耐食性(赤錆の防止など)を高めることができる。なお、有機樹脂は、化成処理皮膜の耐候性および耐食性を顕著に低下させない限りにおいて、フッ素樹脂以外の樹脂を含んでもよい。
第4族元素を含む化合物または第4族元素のイオンは、フッ素樹脂、特には水系フッ素樹脂中のカルボキシル基やスルホン酸基などの官能基と反応しやすく、水系フッ素樹脂の硬化または架橋反応を促進する。そのため、第4族元素を含む化合物または第4族元素のイオンは、フッ素樹脂の密着性を高め、かつ、低温乾燥でも化成処理皮膜の耐水性を向上させることができる。
結合促進剤は、防錆処理液中に存在するフッ素樹脂を軟質化することができる。上記結合促進剤によって軟質化したフッ素樹脂は、エマルションを構成する粒子同士がより密に融着しやすくなり、より水を浸透しにくい化成処理皮膜を形成する。そのため、結合促進剤を含む上記防錆処理液から形成された化成処理皮膜は赤錆を発生させにくくなり、化成処理皮膜の耐食性がより高まると考えられる。また、結合促進剤は、フッ素樹脂を軟質化してエマルションを構成する粒子同士をより密に融着しやすくすることにより、より紫外線などの光によって分解しにくい化成処理皮膜を形成する。そのため、結合促進剤を含む上記防錆処理液から形成された化成処理皮膜は、耐候性もより高まると考えられる。
エッチング剤は、基材鋼板の表面を均一化および活性化して、化成処理皮膜の密着性をより高め、化成処理皮膜から鋼板またはめっき鋼板への水の浸透を抑制する。そのため、結合促進剤を含む上記防錆処理液から形成された化成処理皮膜は赤錆を発生させにくくなり、化成処理皮膜の耐食性がより高まると考えられる。
顔料は、化成処理鋼管の光沢および経時的な変色の抑制に寄与する。顔料は、一種でもそれ以上でもよい。顔料は、無機顔料および有機顔料のいずれでもよい。無機顔料の例には、カーボンブラック、シリカ、チタニアおよびアルミナが含まれる。有機顔料の例には、アクリルなどの樹脂粒子が含まれる。なお、「チタニア」は、4A金属であるチタンを含むが、変色抑制効果に優れていることから、本明細書では顔料に分類される。
ワックスは、化成処理鋼管の加工性の向上に寄与する。所期の加工性を得る観点から、ワックスの融点は、80〜150℃であることが好ましい。当該ワックスの例には、フッ素系ワックス、ポリエチレン系ワックスおよびスチレン系ワックスが含まれる。
防錆処理液は、その他の成分として、上述以外の無機化合物、シランカップリング剤などの有機潤滑剤、無機潤滑剤、無機顔料、有機顔料、および染料などを必要に応じて添加してもよい。Mg、Ca、Sr、V、W、Mn、B、Si、Snなどの無機化合物(酸化物、リン酸塩など)は、化成処理皮膜を緻密化して耐水性を向上させる。フッ素系、ポリエチレン系、およびスチレン系などの有機潤滑剤、ならびに二硫化モリブデンおよびタルクなどの無機潤滑剤は、化成処理皮膜の潤滑性を向上させる。また、無機顔料、有機顔料、および染料などを配合することで、化成処理皮膜に所定の色調を付与することができる。
防錆処理液は、水などの溶媒を除く固形分の含有量(固形分濃度)が、防錆処理液の全質量に対して20質量%以上であることが好ましい。固形分の含有量が20質量%以上であると、十分な膜厚を有し、十分な耐候性を有する化成処理皮膜を形成できる。なお、固形分の含有量の上限は処理液安定性の面から、40質量%以下であることが好ましい。
上述した防錆処理液は、溶接鋼管の化成処理に用いることができる。具体的には、上述した防錆処理液を、溶接鋼管の溶接部の表面またはめっきされた溶接鋼管の溶接部の表面に付与し、乾燥させて、化成処理皮膜を形成することができる。
2−1−1.下地鋼
溶接鋼管の下地鋼の種類は、特に限定されない。たとえば、下地鋼は、低炭素鋼、中炭素鋼および高炭素鋼などを含む炭素鋼でもよいし、Mn、Cr、Si、Niなどを含有する合金鋼でもよい。また、下地鋼は、Alキルド鋼などを含むキルド鋼でもよいし、リムド鋼でもよい。良好なプレス成形性が必要とされる場合は、低炭素Ti添加鋼および低炭素Nb添加鋼などを含む深絞り用鋼板が下地鋼として好ましい。また、P、Si、Mnなどの量を特定の値に調整した高強度鋼板を下地鋼として用いてもよい。下地板の板厚は、特に限定されないが、0.8〜3.5mmの範囲内が好ましい。
下地鋼が溶接された溶接鋼管の、溶接部の表面には、耐食性および密着性を向上させる下地化成処理皮膜が形成されていてもよい。下地化成処理皮膜を形成することで、下地鋼またはめっきされた下地鋼の耐食性および密着性を向上させることができる。たとえば、下地鋼またはめっきされた下地鋼を製造してから造管するまでの間に輸送または保存しなければならない場合、下地鋼またはめっきされた下地鋼の表面に腐食が発生するおそれがある。このような場合、下地鋼またはめっきされた下地鋼の表面に予め下地化成処理皮膜を形成しておくと、下地鋼またはめっきされた下地鋼の表面における腐食の発生を防止することができる。
めっきされた下地鋼板から製造された溶接鋼管(以下、単に「溶接めっき鋼管」ともいう。)の溶接部およびその近傍には、溶射補修層が形成されていることが好ましい。溶接めっき鋼管の製造工程では、多くの場合、溶接部から突出したビード突出部が切削され、溶接めっき鋼管の外周面が平滑化される(ビードカット)。ビードカットをする際には、ビード突出部だけでなく、その周囲のめっき層も除去されるため、下地鋼が露出してしまい、耐食性の低下の原因となる。そこで、溶接部およびその近傍の耐食性を回復させるため、下地鋼が露出した部位に溶射補修層を形成することが好ましい。
上述した防錆処理液は、下地鋼、各種めっき層、下地化成処理皮膜および溶射補修層のいずれにも密着性が高い化成処理皮膜を形成できるため、溶接鋼管のうち、成形加工などにより基材鋼板が露出した部位、または溶射補修層が形成された部位に付与し、乾燥させて、化成処理皮膜を形成させることができる。具体的には、上記防錆処理液は、溶接鋼管の表面と、溶接部または溶接部を覆う溶射補修層と、の両方の上に付与される。さらには、上記防錆処理液は、溶接部の溶射補修層の表面のみならず、鋼板またはめっき鋼板の表面または下地化成処理皮膜の上と、その周囲の下地鋼、めっき層または下地化成処理皮膜と、の双方に接するように付与されることが好ましい。化成処理皮膜の形成を容易にし、かつ形成される化成処理皮膜の密着性をより高める観点からは、上述した防錆処理液は、溶接鋼管の溶接部を含む全周に付与されることが好ましい。
上述の防錆処理液から形成された化成処理皮膜を有する溶接鋼管は、溶接鋼管と、上記溶接鋼管の表面に形成された上記化成処理皮膜と、を有する。上記溶接鋼管は、成形加工品であってもよい。成形加工の方法は特に限定されず、公知の方法から選択することができる。上記化成処理皮膜は、溶接鋼管の溶接部に形成される。上記化成処理皮膜は、溶接鋼管の表面と、溶接部または溶接部を覆う溶射補修層と、の両方の上に形成されることが好ましい。さらには、上記化成処理皮膜は、溶接部の溶射補修層の表面のみならず、鋼板またはめっき鋼板の表面または下地化成処理皮膜の上と、その周囲の下地鋼、めっき層または下地化成処理皮膜と、の双方に接するように形成されることが好ましい。化成処理皮膜の形成を容易にし、かつ形成される化成処理皮膜の密着性をより高める観点からは、上記化成処理皮膜は、溶接鋼管の溶接部を含む全周に形成されることが好ましい。
各成分を混合して、表1に示す防錆処理液1〜防錆処理液20を調製した。
板厚1.2mmの鋼板の表面に、表2に示すめっきを施して、めっき材Aおよびめっき材Bとした。めっき材Aおよびめっき材Bの表面に、表3に示す組成の下地水性処理液を塗布し、到達板温140℃で加熱乾燥して下地化成処理皮膜を形成した。形成された下地化成処理皮膜中のバルブメタルの付着量および下地化成処理皮膜の組成を表4に示す。
防錆処理液1〜防錆処理液20から形成した皮膜の耐候性および溶射部耐食性を、以下の基準で評価した。
JIS K 5600−7−7:2008に準拠して促進耐候性試験(キセノンランプ法)を実施した。本試験法では、キセノンアーク灯の光を120分間照射する間に18分間水を噴霧する工程を1サイクル(2時間)として200cyc試験行った。試験前後における化成処理皮膜の厚さ比(TR)に応じて、以下の基準にて皮膜の耐候性を評価した。
A 化成処理皮膜の厚さ比TRは80%以上だった
B 化成処理皮膜の厚さ比TRは60%以上80%未満だった
C 化成処理皮膜の厚さ比TRは40%以上60%未満だった
D 化成処理皮膜の厚さ比TRは20%以上40%未満だった
E 化成処理皮膜の厚さ比TRは20%未満だった
試験片の端面をシールし、上記対候性の評価と同様の手順による促進耐候性試験を200cyc試験行った。その後、35℃の環境下で5%NaCl含有塩水を2時間噴射し、60℃かつ相対湿度30%の環境下で4時間かけて強制乾燥させ、その後、50℃かつ相対湿度95%の環境下で2時間湿潤処理を行う工程を1サイクル(8時間)とする複合サイクル腐食試験を300cyc行った。試験後に溶射部に発生した赤錆発生面積率(WR)に応じて、以下の基準にて皮膜の溶射部耐食性を評価した。
A 赤錆発生面積率(WR)は10%以下だった
B 赤錆発生面積率(WR)は10%超20%以下だった
C 赤錆発生面積率(WR)は20%超50%以下だった
D 赤錆発生面積率(WR)は50超80%以下だった
E 赤錆発生面積率(WR)は80%超だった
各防錆処理液を密閉容器内で常温で180日間保管した。フォードカップ#4からの流下時間を保管前後で比較し、増粘を評価した。
A 保管後の流下時間の増加は4秒未満だった
B 保管後の流下時間の増加は4秒以上だった
110 下地鋼板
120 Al含有Zn系合金めっき層
130 地化成処理皮膜
140 溶接金属
150 ビードカット部
160 溶射補修層
170 化成処理皮膜
Claims (16)
- フッ素樹脂を含む有機樹脂と、
第4族元素を含む化合物または第4族元素のイオンと、
アジピン酸またはフタル酸と炭素数1以上3以下のアルコールとのエステル化合物およびn−メチル−2−ピロリドンからなる群から選択される1以上の結合促進剤を、を含み、
前記第4族元素を含む化合物または第4族元素のイオンの含有量は、金属換算で0.5g/L以上6g/L以下であり、
前記第4族元素を含む化合物または第4族元素のイオンの金属換算した含有量と前記結合促進剤の含有量の合計は、20g/L以下である、
溶接鋼管用防錆処理液。 - 前記フッ素樹脂は、前記フッ素樹脂の全質量に対して6質量%以上のフッ素原子を含む、請求項1に記載の溶接鋼管用防錆処理液。
- 前記第4族元素を含む化合物または第4族元素のイオンの含有量は、金属換算で2g/L以上である、請求項1または2に記載の溶接鋼管用防錆処理液。
- 前記結合促進剤の含有量は0.5g/L以上50g/L以下である、請求項1〜3のいずれか1項に記載の溶接鋼管用防錆処理液。
- リン酸およびリン酸塩、ならびにアンモニアおよびアンモニウム塩、からなる群から選択されるエッチング剤をさらに含む、請求項1〜4のいずれか1項に記載の溶接鋼管用防錆処理液。
- 前記エッチング剤は、リン酸またはリン酸塩と、アンモニアまたはアンモニウム塩と、をいずれも含む、請求項5に記載の溶接鋼管用防錆処理液。
- 前記リン酸またはリン酸塩の含有量は、リン酸アニオン(PO4 3−)換算で1g/L以上であり、かつ、前記アンモニアまたはアンモニウム塩の含有量は、第四級アンモニウムカチオン(NH4 +)換算で1g/L以上である、請求項6に記載の溶接鋼管用防錆処理液。
- 固形分の含有量は20%以上である、請求項1〜7のいずれか1項に記載の溶接鋼管用防錆処理液。
- pHは7.0以上9.5以下である、請求項1〜8のいずれか1項に記載の溶接鋼管用防錆処理液。
- 顔料をさらに含有する、請求項1〜9のいずれか1項に記載の溶接鋼管用防錆処理液。
- ワックスをさらに含有する、請求項1〜10のいずれか1項に記載の溶接鋼管用防錆処理液。
- 溶接鋼管の表面と、溶接部または溶接部を覆う溶射補修層と、の両方に、請求項1〜11のいずれか1項に記載の溶接鋼管用防錆処理液を付与する工程を含む、
溶接鋼管の化成処理方法。 - 前記溶接鋼管用防錆処理液は、溶接鋼管の全周に付与される、請求項12に記載の溶接鋼管の化成処理方法。
- 前記溶接鋼管用防錆処理液は、膜厚0.5μm以上10μm以下の膜厚で付与される、請求項12または13に記載の溶接鋼管の化成処理方法。
- 溶接鋼管の表面と、溶接部または溶接部を覆う溶射補修層と、の両方の上に、化成処理皮膜を有する溶接鋼管であって、
前記化成処理皮膜は、
フッ素樹脂を含む有機樹脂と、
第4族元素を含む化合物または第4族元素のイオンと、
アジピン酸またはフタル酸と炭素数1以上3以下のアルコールとのエステル化合物およびn−メチル−2−ピロリドンからなる群から選択される1以上の結合促進剤と、
を含む、溶接鋼管。 - 溶接鋼管の成形加工によって作製された溶接鋼管の成形加工品であって、
前記溶接鋼管の成形加工品は、溶接鋼管の表面と、溶接部または溶接部を覆う溶射補修層と、の両方の上に化成処理皮膜を有し、
前記化成処理皮膜は、
フッ素樹脂を含む有機樹脂と、
第4族元素を含む化合物または第4族元素のイオンと、
アジピン酸またはフタル酸と炭素数1以上3以下のアルコールとのエステル化合物およびn−メチル−2−ピロリドンからなる群から選択される1以上の結合促進剤と、
を含む、溶接鋼管の成形加工品。
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