JP5675941B2 - ポリマーを含有する水性組成物を用いた金属表面の被覆方法、水性組成物、及び被覆基材の使用 - Google Patents
ポリマーを含有する水性組成物を用いた金属表面の被覆方法、水性組成物、及び被覆基材の使用 Download PDFInfo
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- JP5675941B2 JP5675941B2 JP2013256999A JP2013256999A JP5675941B2 JP 5675941 B2 JP5675941 B2 JP 5675941B2 JP 2013256999 A JP2013256999 A JP 2013256999A JP 2013256999 A JP2013256999 A JP 2013256999A JP 5675941 B2 JP5675941 B2 JP 5675941B2
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Classifications
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Description
1.特に高湿度の雰囲気(例えばクロスハッチ付着性試験による試験、及びDIN EN ISO 6270−2CHによる交互の湿度及び空気温度の凝縮試験雰囲気内の保存後の円錘マンドレル上の曲げ)において付着問題が生じ得るような、例えば粉体皮膜、溶媒に基づく塗料又は水性塗料によるポリマー表面の不十分な塗装性。
2.ポリマー表面の光沢の著しい低下、黄色、茶色又は/及び無煙炭色への変化、又は/及びチョーキング効果(=皮膜が形成された又は/及び化学的に架橋されたポリマー/コポリマーが破壊され、皮膜が粒子として洗い落とされ得、且つ、粉体として除去され得る、紫外線への曝露の際のポリマー皮膜の分解)が0.5〜1.5年の屋外曝露期間の後に生じるような、屋外曝露に対する不十分な長期耐性(例えば、Frankfurt am Mainにおける直射日光への直接的な曝露による屋外における0.5〜2年間の耐久試験)。
3.特に0.5〜2μmの範囲の皮膜厚さにおける不十分な耐食性(例えばDIN EN ISO 7253に対する塩水噴霧試験による試験)。
4.結果として、多くの場合、コイル被覆ラインに応じて50〜150℃の範囲内の被覆帯の温度によって、ポリマー皮膜は、当該被覆が接触する帯の次の層に付着する場合があり、それにより巻戻しの間にポリマー皮膜の破壊が容易に生じ得、それ故に被覆帯の耐食性の悪化が生じ得る、特に被覆鋼帯の場合におけるコイル内への金属帯の傷に対する不十分な耐ブロッキング性(Chemetallの内部のガイドラインに従う耐ブロッキング性試験であって、ここで市販の家庭用アルミニウム箔を水性組成物で処理し、塗布された未乾燥塗膜を特定の方法で乾燥し、正常状態下でのレスト時間後にその箔を約10の層に積層し、次いで2kg/cm2超の荷重下で圧縮し、この積層物を例えば60℃で2時間荷重下で保存し、次いで積層物をその個々の層に分離して、被覆箔面を評価した結果、箔層は、許容できる小さな模様のみを残して造作なく分離することが可能でなければならない)。
5.特に前記帯の長手方向分割中の特にコイル皮膜ラインにおける金属帯への有機皮膜の塗布の直後のポリマー皮膜の不十分な耐磨耗性であって、ここで前記帯板は、例えば単一圧延板の製造中、特に板の切断及び積層中又は/及びロール成形、深絞り又は/及びトリミングのように特別に成形された機械加工部品を作製するための成形による更なる処理中に、従来、多くの場合約400m/分の領域でのライン速度で超高圧下で押圧されて高速での前記帯の機械加工及び制御が可能になる(Chemetallの内部のガイドラインに従う耐磨耗性試験であって、それにより、水性組成物で被覆して乾燥した標本板は、200g/cm2の荷重の印加下で共に押圧され、前後に50回曲げられ;次いで機械的に荷重を加えた皮膜による塵成形が評価される)。
a)有機塗膜形成剤中の含有率の70〜100質量%がポリカーボネート、ポリウレタン、アイオノマー、ポリ(メタ)アクリレート、ポリエステル、ポリエーテル又は/及びポリスチレンからなる群から選択される合成樹脂に基づくポリマー、コポリマー、ブロックコポリマー又は/及びグラフトコポリマーの形態の少なくとも1種の水溶性又は/及び水分散合成樹脂を含み、ポリカーボネート及びポリウレタン含有率が各々少なくとも10質量%である、主成分としての少なくとも1種の合成樹脂からなる有機塗膜形成剤、
b)有機塗膜形成剤用塗膜形成補助剤としての少なくとも1種の長鎖アルコール、
c)少なくとも1種の架橋剤、
d)少なくとも1種の潤滑剤、及び
e)A)シラン、シラノール又は/及びシロキサンに基づく少なくとも1種の物質、又は/及び、B)走査型電子顕微鏡で測定して平均粒径が0.005〜0.3μmの範囲である粒子形態の少なくとも1種の無機化合物、及び
f)場合により、少なくとも1種の有機腐食防止剤、少なくとも1種の有機溶媒又は/及び少なくとも1種の添加剤
を含有することを特徴とし、ここで金属表面は水性組成物に接触し、有機塗膜は実質的に金属表面上に形成され、次いで乾燥され、場合により硬化され、ここで乾燥及び場合により硬化もされた塗膜は、硬化塗膜の限定領域を分離してそれを秤量することによって決定される0.01〜10μmの範囲の膜厚を有する。
a)主成分として、少なくとも1種の合成樹脂、即ち、ポリカーボネート及びポリウレタンの含有率がそれぞれ少なくとも10質量%であるポリカーボネート、ポリウレタン、アイオノマー、ポリ(メタ)アクリレート、ポリエステル、ポリエーテル又は/及びポリスチレンからなる群から選択される合成樹脂に基づくポリマー、コポリマー、ブロックコポリマー又は/及びグラフトコポリマーの形態の少なくとも1種の水溶性合成樹脂又は/及び水分散性合成樹脂を含む有機塗膜形成剤において70〜100質量%の含有率の合成樹脂からなる有機塗膜形成剤、
b)有機塗膜形成剤のための塗膜形成補助剤としての少なくとも1種の長鎖アルコール、
c)少なくとも1種の架橋剤、
d)少なくとも1種の潤滑剤、及び
e)A)シラン、シラノール又は/及びシロキサンに基づく少なくとも1種の物質又は/及びB)走査型電子顕微鏡で測定される平均粒径が0.005〜0.3μmの範囲である粒子形態の少なくとも1種の無機化合物、及び
f)場合により少なくとも1種の有機腐食防止剤、少なくとも1種の有機溶媒又は/及び少なくとも1種の添加剤、を含有することを特徴とする。
以下に記載する実施例及び比較例は、更に詳細に本発明の内容を例示することを意図したものである。所定の濃度及び組成物は、研究機関において使用される通りの浴組成物自体に関するものであって、場合により使用されるより高く濃縮されたバッチ溶液に関するものではない。市販の帯板加工ライン上で、対応する水性組成物の濃度は、塗布及びラインに応じて、従来、大部分が研究機関の2〜4倍高い。全ての所定の濃度は、活性成分を含む固体含有率であると理解されるべきであり、換言すれば、濃度は、使用する原料が例えば水性溶液又は/及び分散液として希釈された形態にあったかどうかに関係なく、活性成分の比率に関する。例えば、添加剤の総量を増加させるか、又は例えば消泡剤又は/及び流れ調整剤(例えばポリシロキサン等)の量を増加させるかのいずれかのために、以下に記載される組成物の他に、他の添加剤を添加すること又は/及び従って量を調整することは、商業活動において必要又は所望であり得る。
本発明による実施例B1〜B31及び比較例VB1〜VB12:
例えば55%AlZn(Galvalume(登録商標))を有する、商業的な、冷間圧延され、その後合金亜鉛メッキされた鋼帯から得られ、保護のために保存中に注油された鋼板を、まずアルカリスプレークリーナにおいて脱脂し、水で洗浄し、高温で乾燥した。成分を共に混合し、次いでアンモニア溶液を用いて水性分散液のpHを8.2に調整した。浴組成物は、第1表に記載の水性組成物からなった。次いで、約10mL/m2の未乾燥塗膜厚が達成されるような方法でロールコータを使用して定義量の水性組成物を塗布した。次いで未乾燥塗膜を約70℃、約100℃又は約150℃PMTの温度で乾燥し、塗膜に作製し、いくぶん硬化した。乾燥中のみ、加熱を行った。しかるに架橋は実質的に乾燥の際、および引き続き後架橋として生じたのみである。次いで、この方法で処理された鋼板を、その防食性、その機械的性質及びその他の性能についてテストした。24時間の保存時間後、全ての試験を実施した。
第1表の水性組成物は、ポリマー皮膜に容易に加工することが可能だった。乾燥ポリマー皮膜は、各々約1.2μm又は約1.7μmの範囲の膜厚を有した。全ての皮膜は、透明で無色であり、金属表面の光学性が事実上変化なしに更に顕著となり得るほどの淡い絹の光沢を有していた。
本発明による実施例B41〜B60、及び比較例VB21〜VB32:
商業的な、冷間圧延され、その後溶融亜鉛メッキされた鋼帯から得られ、保護のために保存中に注油された鋼板を、まずアルカリスプレークリーナにおいて脱脂し、水で水洗し、高温で乾燥した。水性組成物の成分を共に混合し、次いでアンモニア溶液を用いて水性分散液のpHを8.2に調整した。浴組成物は、第2表に記載の水性組成物からなった。次いで、約10mL/m2の未乾燥塗膜厚が達成されるような方法でロールコータを使用して定義量の水性組成物を塗布した。次いで未乾燥塗膜を約100℃又は約150℃PMTの温度で乾燥し、塗膜に作製し、いくぶん硬化した。乾燥中のみ、加熱を行った。しかるに架橋は実質的に乾燥中にのみ生じ、その後の架橋後として生じた。次いで、この方法で処理された鋼板を、その防食性、その機械的性質及びその他の性能についてテストした。24時間の保存時間後、全ての試験を実施した。
第2表の水性組成物は、ポリマー皮膜に容易に加工することが可能だった。乾燥ポリマー皮膜は、各々約1.2μmの範囲の膜厚を有した。全ての皮膜は、透明で無色であり、金属表面の光学性が事実上変化なしに更に顕著となり得るほどの淡い絹の光沢を有していた。
Claims (32)
- 金属表面を被覆する前に前処理するための、又は金属表面を処理するための水性組成物において、前記組成物が、水の他に、
a)有機塗膜形成剤中の合成樹脂の含有率の70〜100質量%がポリカーボネート、ポリウレタン、アイオノマー、ポリ(メタ)アクリレート、ポリエステル、ポリエーテル又は/及びポリスチレンからなる群から選択される合成樹脂に基づくポリマー、コポリマー、ブロックコポリマー又は/及びグラフトコポリマーの形態の少なくとも1種の水溶性又は/及び水分散合成樹脂を含み、ポリカーボネート及びポリウレタン含有率が各々少なくとも10質量%である、主成分としての少なくとも1種の合成樹脂からなる有機塗膜形成剤、その際、前記有機塗膜形成剤は、陽イオン的、陰イオン的又は/及び立体的に安定している合成樹脂又は/及びその溶液/分散液であってよく、
b)有機塗膜形成剤用塗膜形成補助剤としての少なくとも1種の長鎖アルコール、その際、前記長鎖アルコールは、6〜16個のC原子を有するものであり、
c)少なくとも1種の架橋剤、
d)少なくとも1種の潤滑剤、
e)A)シラン、シラノール又は/及びシロキサンに基づく少なくとも1種の物質、又は/及び、B)走査型電子顕微鏡で測定して平均粒径が0.005〜0.3μmの範囲である粒子形態の少なくとも1種の無機化合物、及び
f)場合により、少なくとも1種の有機腐食防止剤、少なくとも1種の有機溶媒又は/及び少なくとも1種の添加剤
を含有することを特徴とする水性組成物。 - 有機塗膜形成剤が、合成樹脂混合物である、又は/及び尿素ホルムアルデヒド、メラミンホルムアルデヒド、(メタ)アクリレート、ポリアクリル酸、ポリエーテル、ポリエチレン、ポリエチレンイミン、ポリスチレン、ポリビニル又は/及びポリビニルフェノールに基づく合成樹脂を含有する少なくとも1種の混合ポリマーを含有することを特徴とする、請求項1に記載の水性組成物。
- 有機塗膜形成剤が、(メタ)アクリレート、エチレン(メタ)アクリレート又は/及びスチレン(メタ)アクリレートに基づく少なくとも1種のポリマー、コポリマー、ブロックコポリマー又は/及びグラフトコポリマーの形態の合成樹脂を含有することを特徴とする、請求項1又は2に記載の水性組成物。
- 有機塗膜形成剤が、有機塗膜形成剤の全含有率の10〜70質量%の範囲のポリカーボネートに基づく少なくとも1種のポリマー、コポリマー、ブロックコポリマー又は/及びグラフトコポリマーの形態の合成樹脂を含有することを特徴とする、請求項1から3までのいずれか1項に記載の水性組成物。
- 有機塗膜形成剤が、有機塗膜形成剤の全含有率の10〜70質量%の範囲のポリウレタンに基づく少なくとも1種のポリマー、コポリマー、ブロックコポリマー又は/及びグラフトコポリマーの形態の合成樹脂を含有することを特徴とする、請求項1から4までのいずれか1項に記載の水性組成物。
- 有機塗膜形成剤が、有機塗膜形成剤の全含有率の1〜40質量%の範囲のポリエステルに基づく少なくとも1種のポリマー、コポリマー、ブロックコポリマー又は/及びグラフトコポリマーの形態の合成樹脂を含有することを特徴とする、請求項1から5までのいずれか1項に記載の水性組成物。
- 更なる化合物を添加することなく水性組成物中における有機塗膜形成剤のpHが6.5〜11であることを特徴とする、請求項1から6までのいずれか1項に記載の水性組成物。
- 水性組成物が、活性成分を含む固体に基づいて2〜600g/Lの含有率の有機塗膜形成剤を含むことを特徴とする、請求項1から7までのいずれか1項に記載の水性組成物。
- 水性組成物が、活性成分を含む固体に基づいて0.01〜50g/Lの含有率で有機塗膜形成剤のための塗膜形成補助剤として少なくとも1種の長鎖アルコールを含むことを特徴とする、請求項1から8までのいずれか1項に記載の水性組成物。
- ほとんど又は全く均質の有機膜は、水及び他の揮発成分の除去中又は/及び除去後に少なくとも1種の塗膜形成補助剤と共に有機塗膜形成剤から塗膜形成により形成されることを特徴とする、請求項1から9までのいずれか1項に記載の水性組成物。
- 少なくとも1種の非加水分解シラン、部分的に加水分解されたシラン又は/及び完全に加水分解されたシラン、又は/及び少なくとも1種の対応するシラノール又は/及びシロキサンが水性組成物に添加されることを特徴とする、請求項1から10までのいずれか1項に記載の水性組成物。
- 水性組成物が、少なくとも1種の部分的に加水分解されたシラン又は/及び完全に加水分解されたシラン、又は/及び少なくとも1種の対応するシラノール又は/及びシロキサンを含有することを特徴とする、請求項1から11までのいずれか1項に記載の水性組成物。
- 少なくとも1種のアシルオキシシラン、アルキルシラン、アミノシラン、ビス−シリルシラン、エポキシシラン、フルオロアルキルシラン、イソシアナートシラン、メルカプトシラン、(メタ)アクリラトシラン、モノシリルシラン、ポリシリルシラン、ウレイドシラン、ビニルシラン、又は/及び少なくとも1種の対応するシラノール又は/及びシロキサンが含まれることを特徴とする、請求項1から12までのいずれか1項に記載の水性組成物。
- 活性成分を含む固体に基づいて0.1〜50g/Lの範囲でシランとして算出される少なくとも1種のシラン、シラノール又は/及びシロキサンの含有率が水性組成物に添加されていることを特徴とする、請求項1から13までのいずれか1項に記載の水性組成物。
- 水性組成物が、それぞれアジリジン、アゾ化合物、ジアミン、ジイミド、ホルムアルデヒド、イミダゾール、イソシアネート、イソシアヌレート、メラミン、過酸化物、トリアジン又は/及びトリアゾールに基づく少なくとも1種の架橋剤を含有することを特徴とする、請求項1から14までのいずれか1項に記載の水性組成物。
- 水性組成物が、ホウ素含有化合物又は塩基性化合物に基づく少なくとも1種の無機架橋剤を含有することを特徴とする、請求項1から15までのいずれか1項に記載の水性組成物。
- 無機架橋剤が、チタン、ハフニウム又は/及びジルコニウムに基づく又は/及びカーボネート又は炭酸アンモニウムに基づくものであることを特徴とする、請求項16記載の水性組成物。
- 活性成分を含む固体に基づいて0.01〜50g/Lの範囲の少なくとも1種の架橋剤の含有率が水性組成物に添加されることを特徴とする、請求項1から17までのいずれか1項に記載の水性組成物。
- パラフィン、ポリエチレン及びポリプロピレンからなる群から選択される少なくとも1種のワックスが、潤滑剤として使用されることを特徴とする、請求項1から18までのいずれか1項に記載の水性組成物。
- 少なくとも1種の酸化ワックス又は/及び少なくとも1種の微結晶ワックスが潤滑剤として使用されることを特徴とする、請求項19に記載の水性組成物。
- 潤滑剤として使用されるワックスの融点が40〜160℃の範囲であることを特徴とする、請求項19または20に記載の水性組成物。
- 顕著に異なる性質を有する少なくとも2種の潤滑剤が含まれることを特徴とする、請求項19から21までのいずれか1項に記載の水性組成物。
- 微粉、分散液又は/及び懸濁液を、粒子形態の無機化合物として含有していることを特徴とする、請求項1から22までのいずれか1項に記載の水性組成物。
- 無色、白色又は/及びほぼ無着色の粒子が粒子形態の無機化合物として使用されることを特徴とする、請求項1から23までのいずれか1項に記載の水性組成物。
- 水性組成物が、活性成分を含む固体に基づいて粒子形態において0.1〜500g/Lの少なくとも1種の無機化合物を含有することを特徴とする、請求項1から24までのいずれか1項に記載の水性組成物。
- 水性組成物が、アミン、アルカノールアミン、アルキルアミノエタノール、コハク酸誘導体、導電性ポリマー又は/及びチオールに基づく少なくとも1種の有機腐食防止剤を含有することを特徴とする、請求項1から25までのいずれか1項に記載の水性組成物。
- 使用される合成樹脂の内の少なくとも1種が放射線硬化性樹脂であり、更に少なくとも1種の光重合開始剤が含まれており、化学線による照射による架橋が可能であることを特徴とする、請求項1から26までのいずれか1項に記載の水性組成物。
- 水性組成物が、少なくとも1種の殺生物剤、消泡剤、湿潤剤又は/及び塗料添加剤を含有することを特徴とする、請求項1から27までのいずれか1項に記載の水性組成物。
- 水性組成物が、Cr3+に基づいた少なくとも1種のクロム化合物を含有することを特徴とする、請求項1から28までのいずれか1項に記載の水性組成物。
- 6.5〜11の範囲のpHを有することを特徴とする、請求項1から29までのいずれか1項に記載の水性組成物。
- ローラー塗り、流し塗り、ブレード塗り、スパッタリング、吹付け塗り、刷毛塗り又は浸漬、場合によりローラーによる次のスクィージングにより塗布されることを特徴とする、請求項1から30までのいずれか1項に記載の水性組成物。
- 被覆される金属表面が、アルミニウム、鉄、銅、マグネシウム、ニッケル、チタン、スズ、亜鉛、又は/及びアルミニウム又は/及び鉄、銅、マグネシウム、ニッケル、チタン、スズ又は/及び亜鉛を含有する合金からなる群から選択されるものであることを特徴とする、請求項1から31までのいずれか1項に記載の水性組成物。
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ZA200906528B (en) | 2010-11-24 |
JP2014087796A (ja) | 2014-05-15 |
CA2680242C (en) | 2015-12-15 |
CA2680242A1 (en) | 2008-09-18 |
KR20090125175A (ko) | 2009-12-03 |
BRPI0808680A2 (pt) | 2015-06-16 |
EP2131964A1 (de) | 2009-12-16 |
WO2008110480A1 (de) | 2008-09-18 |
US20100062200A1 (en) | 2010-03-11 |
AU2008225914A1 (en) | 2008-09-18 |
AU2008225914B2 (en) | 2011-12-22 |
AR065646A1 (es) | 2009-06-24 |
US20140134368A1 (en) | 2014-05-15 |
CN101678397A (zh) | 2010-03-24 |
JP5553617B2 (ja) | 2014-07-16 |
JP2010520808A (ja) | 2010-06-17 |
US8936836B2 (en) | 2015-01-20 |
KR101597300B1 (ko) | 2016-02-25 |
DE102007011553A1 (de) | 2008-09-11 |
CN101678397B (zh) | 2021-12-03 |
BRPI0808680B1 (pt) | 2019-12-17 |
MX2009009558A (es) | 2009-10-28 |
CN104162504A (zh) | 2014-11-26 |
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