JP2013516503A - マルチコート塗装系の機能層のための塗料材料としての無水組成物 - Google Patents
マルチコート塗装系の機能層のための塗料材料としての無水組成物 Download PDFInfo
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- JP2013516503A JP2013516503A JP2012546435A JP2012546435A JP2013516503A JP 2013516503 A JP2013516503 A JP 2013516503A JP 2012546435 A JP2012546435 A JP 2012546435A JP 2012546435 A JP2012546435 A JP 2012546435A JP 2013516503 A JP2013516503 A JP 2013516503A
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
- B05D7/53—Base coat plus clear coat type
- B05D7/532—Base coat plus clear coat type the two layers being cured or baked together, i.e. wet on wet
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/56—Three layers or more
- B05D7/57—Three layers or more the last layer being a clear coat
- B05D7/572—Three layers or more the last layer being a clear coat all layers being cured or baked together
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4291—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from polyester forming components containing monoepoxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
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Abstract
Description
本発明は、無水組成物、塗料材料としての該無水組成物の使用、該組成物を含有するマルチコート塗装系、マルチコート塗装系の製造法ならびに該マルチコート塗装系の使用に関する。更に、本発明は、前記組成物またはマルチコート塗装系で被覆された基体に関する。
現在では、自動車量産塗装の範囲で使用されるマルチコート塗装系は、一般に、腐蝕およびストーンチッピングから保護する、電気泳動的に施されるプライマーとその後の、ストーンチッピングから保護しかつ表面を平滑にするサーフェイサーコートとからなる。この場合、このサーフェイサーコートは、通常、既に焼き付けられたプライマー上に施され、かつ硬化される。しかし、プライマーおよびサーフェイサーコートを一緒に硬化させることも可能である。硬化されたサーフェイサーコート上には、引続き、それぞれの色調に依存して1つ以上のスプレー通路で塗装される、色付与および/または効果付与するベースコートおよびその上にウェット・オン・ウェット法で塗装される防護クリヤコートから、ワンコート塗装または装飾ツーコート塗装が施される。引続き、ワンコート塗装は、硬化されるかまたは単数または複数のベースコートおよびクリヤラッカー層は、一緒に硬化される。最後に記載された"ウェット・オン・ウェット"法の順序は、"ツーウェット(2−Wet)"、"ツーコートワンベイク(2−Coats−1−Bake)"または"ツーシーワンビー(2C1B)"とも呼称される。
従って、本発明は、塗料材料として機能する機能層を少なくとも3つの塗装系を有するマルチコート塗装系(3C1Bマルチコート塗装系)中に中間乾燥なしに形成し、かつ公知技術水準の欠点を有しない組成物を提供するという課題に基づくものであった。この場合、機能層は、公知技術水準の3C1Bマルチコート塗装系のプライマーサーフェイサーコートと置き換えられるはずであった。
意外なことに、公知技術水準の欠点を有しない組成物が見出された。むしろ、3C1Bマルチコート塗装系において、特に良好な被膜間密着、ストーンチッピングに対する高い耐性および高い透明板ガラス接着付着力を有する機能層塗装系を形成する組成物が見出された。
a.結合剤としての少なくとも1つの飽和または不飽和のエポキシ変性されたポリエステル、
b.他の結合剤としての少なくとも1つのアクリレート−またはポリウレタンポリマー、
c.ポリマーミクロ粒子、
d.架橋剤としての、ブロック化されたイソシアネートおよびアミノプラスト樹脂からなる官能基を含有する、少なくとも1つのポリマー、
e.少なくとも1つの顔料、
f.少なくとも1つの有機溶剤および
g.少なくとも1つの助剤または添加剤を含有し、
この場合この組成物の固体は、少なくとも50質量%であり、およびこの組成物は、無水である。
a.結合剤としての少なくとも1つの飽和または不飽和のエポキシ変性されたポリエステル5〜20質量%、
b.他の結合剤としての少なくとも1つのアクリレート−またはポリウレタンポリマー5〜30質量%、
c.ポリマーミクロ粒子5〜20質量%、
d.架橋剤としての、ブロック化されたイソシアネートおよびアミノプラスト樹脂からなる官能基を含有する、少なくとも1つのポリマー5〜15質量%、
e.少なくとも1つの顔料5〜49.5質量%、
f.少なくとも1つの有機溶剤30〜50質量%および
g.少なくとも1つの助剤または添加剤0.5〜40質量%
を含有する。
エポキシ変性されたポリエステル結合剤(PE)は、グリシジルエステル含有単位で変性されたポリエステル樹脂である。
本発明による組成物は、少なくとも1つのアクリレートポリマーまたはポリウレタンポリマーを他の結合剤(BM)として含有する。特に、組成物の全質量に対して5〜30質量%の割合を有する他の結合剤は、本発明による組成物中に含有されている。
本発明による組成物は、ポリマーミクロ粒子を含有する。特に、それぞれ組成物の全質量に対して5.0〜20.0質量%、有利に8.0〜15.0質量%が含有されている。
(a)1分子当たり唯一のエチレン系不飽和基を含有するエチレン系不飽和モノマーまたはこのようなモノマーからなる混合物および
(b)1分子当たり少なくとも2つのエチレン系不飽和基を含有するエチレン系不飽和モノマーまたはこのようなモノマーからなる混合物からの混合物を、
水相中で場合によっては乳化剤の存在下または場合によってはキャリヤー樹脂の存在下で重合し、引続きこうして得られた水性ポリマーミクロ粒子分散液を有機溶剤中または有機溶剤からなる混合物中に移すことにより、得られる。
(c)1分子当たり少なくとも1個の反応性基(G1)を含有するエチレン系不飽和モノマー(M1)またはこのようなモノマー(M1)からなる混合物および
(d)1分子当たり少なくとも1個の、(G1)とは異なる反応性基(G2)を含有するエチレン系不飽和モノマー(M2)またはこのようなモノマー(M2)からなる混合物および
(e)場合によっては他のエチレン系不飽和モノマー(M3)またはこのようなモノマー(M3)からなる混合物からの混合物を、
有機溶剤中で場合によってはキャリヤー樹脂の存在下で重合に掛けることにより、得られる。
本発明による組成物は、この組成物の全質量に対して特に5〜15質量%の、ブロック化されたイソシアネートおよびアミノプラスト樹脂の群から選択される少なくとも1つのポリマーを含有する。
本発明による組成物は、この組成物の全質量に対して特に5〜49.5質量%の少なくとも1つの顔料(P)を含有する。顔料8〜40質量%を含有する組成物は、好ましい。
本発明による組成物は、この組成物の全質量に対して特に30〜50質量%の少なくとも1つの有機溶剤(L)を含有する。
本発明による組成物は、この組成物の全質量に対して特に0.5〜40質量%の少なくとも1つの助剤または添加剤(Z)を含有する。
更に、本発明の対象は、本発明による組成物を製造するための方法である。この場合、この組成物は、前記成分を混合および均質化によって製造されうる。
a.本発明による組成物から得られた、少なくとも1つの機能層A、
b.少なくとも1つのベースコート材料の少なくとも1つのベースコートBおよび
c.少なくとも1つのクリヤコート材料の少なくとも1つのクリヤコートC
を含む。
a.本発明による組成物から得られた、少なくとも1つの機能層A、
b.少なくとも1つのベースコート材料の少なくとも1つのベースコートBおよび
c.少なくとも1つのクリヤコート材料の少なくとも1つのクリヤコートCからなるマルチコート塗装系である。
以下、百分率の記載は、質量%として説明する。
攪拌機、抵抗加熱ヒーター、温度計、ポールリング(Pall−Ring)が充填された充填塔を有し、頭上温度計、蒸留ブリッジ、凝縮用冷却器および受器を装備した、2 lの四口フラスコ中に、1,6−ヘキサンジオール81.0質量部、ネオペンチルグリコール108.0質量部、グリセリン28.0質量部、トリメチロールプロパン38,0質量部、アジピン酸99.0質量部、無水フタル酸157.0質量部およびイソフタル酸125.0質量部を計量供給する。この反応混合物を攪拌しながら急速に160℃に加熱し、160℃で30分間維持する。前記塔の頭上温度が103℃を上廻らないように、温度を1.5時間で160℃から190℃に上昇させる。次に、150℃に冷却し、Cardura E 10 P 63,0質量部およびキシレン7.0質量部を添加し、引続き加熱し、165℃で1時間維持する。次に、230℃に加熱し、および酸価が10mg KOH/gの値を下廻るようになるまで230℃で維持する。エポキシ変性されたポリエステルをさらに冷却し、ソルベントナフサ 155/185 238.0質量部、1−メトキシプロピルアセテート24.0質量部およびエチルエトキシプロピオネート35.0質量部の混合物で溶解する。濃度65%の結合剤溶液が生じる。
反応器中で二量体脂肪酸29.1質量部、1,6−ヘキサンジオール28.5質量部、イソフタル酸8.4質量部およびトルエン1.2質量部からなる混合物を窒素雰囲気下で徐々に154℃に加熱する。引続き、この混合物を40分間、193℃に加熱する。この場合、反応経過は、水分離器を用いて追跡される。酸価10mg KOH/gの達成後に、反応混合物を149℃に冷却する。引続き、無水トリメリット酸11.2質量部を、滴下漏斗を使用しながら徐々に添加する。
実験室用ミル(Getzmann Labormuehle SL 25;粉砕媒体:SAZ 0.6〜0.8mm;エネルギー投入量:100Wh/kg)中に、ドイツ連邦共和国特許出願公開第2006053776号明細書A1、製造例1.1、第17頁、第156節に記載されたアクリレート結合剤40.0質量部、ソルベッソ(Solvesso) 100 42.0質量部、ブタノール8.0質量部、エロジル R972 10.0質量部(Degussa社の市販の珪酸)からなる練り顔料100.0gを石英砂200.0質量部(粒径0.7〜1mm)と一緒に計量供給し、水冷却しながら30分間微粉砕する。引続き、石英砂を分離除去する。
実験室用ミル(上記参照)中に、ドイツ連邦共和国特許出願公開第2006053776号明細書A1、製造例1.1、第17頁、第156節に記載されたアクリレート結合剤19.5質量部、ソルベントナフサ 160/180 10.7質量部(Exxon Mobile社)、ベントン(Bentone) 34 0.6質量部(Elementis Specialeties)、エタノール0.2質量部、Blanc Fixe Micro65.0質量部(Sachtleben社の市販の硫酸バリウム)および酢酸ブチル4.0質量部からなる練り顔料100.0gを石英砂200.0質量部(粒径0.7〜1mm)と一緒に計量供給し、水冷却しながら30分間微粉砕する。引続き、石英砂を分離除去する。
実験室用ミル(上記参照)中に、ドイツ連邦共和国特許出願公開第2006053776号明細書A1、製造例1.1、第17頁、第156節に記載されたアクリレート結合剤152.0質量部、ペンチルプロピオネート33.6質量部、ベントン(Bentone) 34 6.4質量部およびTiPure(登録商標)R902 528.0質量部(Du Pont de Nemours and Company社の市販の二酸化チタン)からなる練り顔料800.0gを石英砂1100.0質量部(粒径0.7〜1mm)と一緒に計量供給し、水冷却しながら30分間微粉砕する。引続き、石英砂を分離除去する。
実験室用ミル(上記参照)中に、ドイツ連邦共和国特許出願公開第2006053776号明細書A1、製造例1.1、第17頁、第156節に記載されたアクリレート結合剤81.6質量部、ペンチルプロピオネート44.8質量部、ソルベッソ(Solvesso) 100 401.6質量部、市販の分散添加剤136.8質量部、市販の顔料相乗剤15.2質量部およびMonarch(登録商標) 900 120.0質量部(Cabot Corp.社の市販のカーボンブラック)からなる練り顔料800.0gを石英砂1100.0質量部(粒径0.7〜1mm)と一緒に計量供給し、水冷却しながら30分間微粉砕する。引続き、石英砂を分離除去する。
スラリーを、11μmの平均粒径を有するコーンフレーク型の市販のノンリーフィングタイプのアルミニウム効果顔料ペースト40.0質量部(Toyal社のAlpate 88037)および酢酸ブチル60.0質量部から、攪拌しながら製造する。
機能層F−1〜F−4を次の成分(質量%で)の混合および均質化によって製造する:
1 ドイツ連邦共和国特許出願公開第2006053776号明細書A1、製造例1.2/1.3、第17頁、第157/158節の記載のミクロゲル
2 Ineos Melamines社のResimene 755
3 Ineos Melamines社のResimene 747
4 Tinuvin 384−2、BASF SE社の95%メトキシ−2−プロピルアセテート(MPA)
5 BASF SE社のTinuvin 123
6 Lindau Chemicals社のLindron 22
7 ドイツ連邦共和国特許出願公開第2006053776号明細書A1、製造例1.1、第17頁、第156節に記載のアクリレート結合剤
8 Desmodul PL 350、Bayer AG社の75%1−メトキシ−2−プロピルアセテート(MPA)/ソルベントナフサ(SN) 160/180
9 Nacure(登録商標) 5225、King Industries,Inc.社のドデシルベンジルスルホン酸(DDBSA)。
技術的性質の試験のために、23μmの乾燥塗膜厚を有する機能層F−1〜F−4を、通常の公知の陰極電着および焼き付けによる電着塗膜で被覆された鋼製基体(車体パネル)からなる試験パネル上に施し(BASF Coatings社のCathoguard(登録商標)500、乾燥塗膜厚20μm)、室温で5分間のフラッシング後に、市販の銀色のハイソリッドベースコート(BASF Coatings社のColorClass HS、乾燥塗膜厚18μm)で上塗りした。引続き、第1の2つの層を5分間フラッシュし、市販のハイソリッド1K(一成分系)クリヤコート(BASF Coatings社のUreGloss、乾燥塗膜厚45μm)で上塗りした。その後に、得られた3C1Bマルチコート塗装系3W−1〜3W−4を140℃のパネル温度で20分間焼き付けた。
Claims (16)
- 無水組成物であって。
a.結合剤としての少なくとも1つの飽和または不飽和のエポキシ変性されたポリエステル、
b.他の結合剤としての少なくとも1つのアクリレート−またはポリウレタンポリマー、
c.ポリマーミクロ粒子、
d.架橋剤としての、ブロック化されたイソシアネートおよびアミノプラスト樹脂からなる官能基を含有する、少なくとも1つのポリマー、
e.少なくとも1つの顔料、
f.少なくとも1つの有機溶剤および
g.少なくとも1つの助剤または添加剤を含有し、
この場合この組成物の固体は、少なくとも50質量%である、上記無水組成物。 - ポリエステルが前記組成物の全質量に対して5〜20質量%の割合で含有されており、この場合全ての成分の質量割合は、総計で100質量%となる、請求項1記載の組成物。
- 前記組成物が、それぞれ組成物の全質量に対して、
a.他の結合剤としての少なくとも1つのアクリレート−またはポリウレタンポリマー5〜30質量%、
b.ポリマーミクロ粒子5〜20質量%、
c.架橋剤としての、ブロック化されたイソシアネートおよびアミノプラスト樹脂からなる官能基を含有する、少なくとも1つのポリマー5〜15質量%、
d.少なくとも1つの顔料5〜49.5質量%、
e.少なくとも1つの有機溶剤30〜50質量%および
f.少なくとも1つの助剤または添加剤0.5〜40質量%を含有する、請求項2記載の組成物。 - ポリエステルが5000〜20000g/molの質量平均分子量を有する、請求項1から3までのいずれか1項に記載の組成物。
- ポリエステル中のエポキシ基の割合は、ポリエステルの全質量に対して5〜15質量%である、請求項1から4までのいずれか1項に記載の組成物。
- 粘度が23℃で、フォードNo.4カップからの24秒〜30秒の流出時間に相当する、請求項1から5までのいずれか1項に記載の組成物。
- 塗料材料としての請求項1から6までのいずれか1項に記載の無水組成物の使用。
- 塗料材料は、マルチコート塗装系における機能層の形成に使用され、この場合このマルチコート塗装系は、
a.請求項1から6までのいずれか1項に記載の組成物から得られる、少なくとも1つの機能層A、
b.少なくとも1つのベースコート材料の少なくとも1つのベースコートBおよび
c.少なくとも1つのクリヤコート材料の少なくとも1つのクリヤコートCを含む、請求項7記載の使用。 - マルチコート塗装系であって、
a.請求項1から6までのいずれか1項に記載の組成物から得られる、少なくとも1つの機能層A、
b.少なくとも1つのベースコート材料の少なくとも1つのベースコートBおよび
c.少なくとも1つのクリヤコート材料の少なくとも1つのクリヤコートCからなるマルチコート塗装系。 - 順次に最初に層A、次に層B、引続き層Cが基体上に施され、引続きA、BおよびCが共通に硬化される、請求項9記載のマルチコート塗装系。
- 最初に層Aが基体上に施され、および硬化され、その後にB、最後にCが基体上に施され、引続きBおよびCが共通に硬化される、請求項9記載のマルチコート塗装系。
- 請求項9から11までのいずれか1項に記載のマルチコート塗装系を製造するための方法において、請求項1から6までのいずれか1項に記載の少なくとも1つの組成物を基体上に塗装し、引続き少なくとも1つのベースコート材料を塗装し、引続き少なくとも1つのクリヤコート材料を塗装することを特徴とする、請求項9から11までのいずれか1項に記載のマルチコート塗装系を製造するための方法。
- 前記組成物ならびにベースコート材料およびクリヤコート材料を共通に硬化させる、請求項12記載の方法。
- 基体を被覆するための、請求項9から11までのいずれか1項に記載のマルチコート塗装系の使用。
- 請求項1から6までのいずれか1項に記載の組成物で被覆された基体。
- 請求項9から11までのいずれか1項に記載のマルチコート塗装系で被覆された基体。
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JP5194465B2 (ja) * | 2006-03-08 | 2013-05-08 | Jfeスチール株式会社 | 塗装鋼板、加工品および薄型テレビ用パネルならびに塗装鋼板の製造方法 |
US7807743B2 (en) | 2006-09-22 | 2010-10-05 | Basf Corporation | Coating composition and film system therefrom |
DE102006053776A1 (de) | 2006-11-15 | 2008-05-21 | Basf Coatings Ag | Lösemittelhaltige, pigmentierte Beschichtungsmittel und ihre Verwendung zur Herstellung von Mehrschichtlackierungen sowie Verfahren zur Verbesserung des Flops von effektgebenden Lackierungen |
CN101289594A (zh) * | 2007-04-18 | 2008-10-22 | 宝山钢铁股份有限公司 | 夹心板、单板双用途彩涂钢板用涂料及其使用方法 |
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Also Published As
Publication number | Publication date |
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US9359525B2 (en) | 2016-06-07 |
JP2016028149A (ja) | 2016-02-25 |
CN102656241B (zh) | 2015-12-02 |
DE102009060803A1 (de) | 2011-07-07 |
KR20120111737A (ko) | 2012-10-10 |
EP2519593A1 (de) | 2012-11-07 |
CN102656241A (zh) | 2012-09-05 |
KR101806580B1 (ko) | 2017-12-07 |
EP2519593B1 (de) | 2016-04-27 |
US20130071668A1 (en) | 2013-03-21 |
JP5933452B2 (ja) | 2016-06-08 |
WO2011080268A1 (de) | 2011-07-07 |
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