JP2017154089A - 複層塗膜形成方法 - Google Patents
複層塗膜形成方法 Download PDFInfo
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- JP2017154089A JP2017154089A JP2016040180A JP2016040180A JP2017154089A JP 2017154089 A JP2017154089 A JP 2017154089A JP 2016040180 A JP2016040180 A JP 2016040180A JP 2016040180 A JP2016040180 A JP 2016040180A JP 2017154089 A JP2017154089 A JP 2017154089A
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- coating film
- pigment
- acid
- resin
- coating
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Abstract
【解決手段】中塗り塗料、水性ベース塗料並びに水酸基含有アクリル樹脂及びポリイソシアネート化合物を含有するクリヤー塗料を順次塗装して、中塗り塗膜、ベース塗膜及びクリヤー塗膜からなる複層塗膜を形成し、さらにクリヤー塗膜上に接着剤層を形成する複層塗膜形成方法において、中塗り塗料が、水酸基含有ポリエステル樹脂、メラミン樹脂、ピラゾールブロックポリイソシアネート化合物、顔料及び有機溶剤を含有し、中塗り塗料中に含まれる顔料の濃度が特定範囲内であり、中塗り塗料による形成塗膜の20℃における破断伸び率、ヤング率、及びツーコン硬度がそれぞれ特定範囲内である複層塗膜形成方法とする。
【選択図】なし
Description
しかしながら、耐チッピング性のレベルアップを、例えば中塗り塗膜の軟質化により図ろうとすると中塗り塗膜の凝集力が低下することにより、ガラス部材等の部材との接着部の複層塗膜が凝集破壊を起こしたり、電着塗膜と中塗り塗膜界面との間でハガレが生じたりすることにより、部材との接着性が不良となる問題が起こる場合があった。
しかしながら、特許文献1の塗膜形成方法及び特許文献2の複層塗膜では、耐チッピング性が不十分となる場合があった。
電着塗装された自動車車体の一部に、下記工程(1)〜(5)を順次行なう複層塗膜形成方法であって、
工程(1):電着塗膜上に、中塗り塗料(X)を塗装して中塗り塗膜を形成する工程
工程(2):前記工程(1)で形成された中塗り塗膜上に、水性ベース塗料(Y)を塗装してベース塗膜を形成する工程
工程(3):前記工程(2)で形成されたベース塗膜上に、水酸基含有アクリル樹脂及びポリイソシアネート化合物を含有するクリヤー塗料(Z)を塗装してクリヤー塗膜を形成する工程
工程(4):前記工程(1)〜(3)で形成された中塗り塗膜、ベース塗膜及びクリヤー塗膜を加熱硬化する工程
工程(5):クリヤー塗膜上に接着剤層を形成する工程
前記中塗り塗料(X)が、(A)水酸基含有ポリエステル樹脂、(B)メラミン樹脂、(C)ピラゾールブロックポリイソシアネート化合物、(D)顔料、及び(E)有機溶剤を含有し、前記メラミン樹脂(B)及び前記ピラゾールブロックポリイソシアネート化合物(C)の含有量の比(B/C)が固形分比で5/35〜20/15であり、且つ顔料(D)の濃度(PWC)が40〜60%であり、
前記中塗り塗膜の加熱硬化後の硬化塗膜の20℃における破断伸び率が40〜90%であり、ヤング率が600〜1600MPaであり、ツーコン硬度が3〜9であることを特徴とする複層塗膜形成方法、に係るものである。
工程(1):電着塗膜上に、中塗り塗料(X)を塗装して中塗り塗膜を形成する工程
工程(2):前記工程(1)で形成された中塗り塗膜上に、水性ベース塗料(Y)を塗装してベース塗膜を形成する工程
工程(3):前記工程(2)で形成されたベース塗膜上に、水酸基含有アクリル樹脂及びポリイソシアネート化合物を含有するクリヤー塗料(Z)を塗装してクリヤー塗膜を形成する工程
工程(4):前記工程(1)〜(3)で形成された中塗り塗膜、ベース塗膜及びクリヤー塗膜を加熱硬化する工程
工程(5):クリヤー塗膜上に接着剤層を形成する工程
カチオン電着塗料による場合、具体的には例えば、固形分質量濃度が約5〜約40質量%の範囲内になるように脱イオン水等で希釈し、pHを5.5〜8.0の範囲内に保持して常法により電着塗装することができる。塗膜は約140〜約210℃の温度、好ましくは150〜180℃の温度で、10〜60分間、好ましくは20〜30分間加熱して硬化せしめることができる。また、塗装膜厚は、硬化塗膜に基づいて約10〜約60μm、特に15〜30μmの範囲内であることが好ましい。
本発明の方法によれば、まず、工程(1)として、電着塗装された自動車車体の一部である電着塗膜上に、中塗り塗料(X)が塗装され、中塗り塗膜が形成される。一般に、中塗り塗料は、下塗り塗膜と上塗り塗膜の間に中塗り塗膜層を形成させ、複層塗膜層間の付着性向上に寄与し、被塗物表面の粗度隠蔽による仕上がり外観、及び耐チッピング性向上等の目的で塗装される塗料である。
本発明の方法において、中塗り塗料(X)は、(A)水酸基含有ポリエステル樹脂、(B)メラミン樹脂、(C)ピラゾールブロックポリイソシアネート化合物、(D)顔料、及び(E)有機溶剤を含有する塗料組成物である。
水酸基含有ポリエステル樹脂(A)は、既知の方法で、常法に従い、多塩基酸と多価アルコ−ルとをエステル化反応させることによって合成することができる。
水酸基含有ポリエステル樹脂(A)は、カルボキシル基等の酸基を有しているものが好ましい。
ポリエステル樹脂へカルボキシル基を導入する場合、例えば、水酸基含有ポリエステル樹脂に無水酸を付加し、ハーフエステル化することで導入することもできる。
本発明において、中塗り塗料(X)の架橋剤成分として、メラミン樹脂(B)を含有する。
また、上記メチロール化メラミン樹脂のメチロール基を、適当なアルコールによって、部分的に又は完全にエーテル化したものも使用することができる。エーテル化に用いられるアルコールとしては、例えば、メチルアルコール、エチルアルコール、n−プロピルアルコール、i−プロピルアルコール、n−ブチルアルコール、i−ブチルアルコール、2−エチル−1−ブタノール、2−エチル−1−ヘキサノール等を挙げることができる。
本発明において、中塗り塗料(X)の架橋剤成分として、さらに、ピラゾールブロックポリイソシアネート化合物(C)を含有する。
ブロックポリイソシアネート化合物は、例えば、100℃以上、好ましくは130℃以上に加熱することにより、イソシアネート基が再生し、反応性基と容易に反応することができる。
ポリイソシアネート化合物としては、例えば、具体的には、脂肪族ポリイソシアネート、脂環族ポリイソシアネート、芳香脂肪族ポリイソシアネート、芳香族ポリイソシアネート及びこれらポリイソシアネートの誘導体等を挙げることができる。
含有量の比(B/C)が20/15の比率を超えてピラゾールブロックポリイソシアネート化合物の割合が少ないと、架橋反応により生成するウレタン結合が少ないために耐チッピング性が不良となる場合がある。
また、含有量の比(B/C)が5/35を超えた比率でピラゾールブロックポリイソシアネート化合物の割合が多いと、架橋反応により生成するウレタン結合が多くなることにより軟質な塗膜となるので、塗膜の凝集力が低下することにより、ガラス部材等の部材を接着する際の接着強度が低下する場合がある。
顔料(D)としては、通常、塗料に用いられる顔料を使用することができる。具体的には、二酸化チタン、亜鉛華、カーボンブラック、フタロシアニンブルー、プルシアンブルー、コバルトブルー、アゾ顔料、フタロシアニン顔料、キナクリドン顔料、イソインドリン顔料、スレン系顔料、ペリレン顔料等の着色顔料;クレー、カオリン、バリタ、硫酸バリウム、炭酸バリウム、炭酸カルシウム、シリカ、アルミナホワイト、タルク等の体質顔料;アルミニウムフレーク、雲母フレーク等の光輝性顔料等を好適に使用することができる。
有機溶剤(E)としては、例えばヘキサン、ヘプタン、キシレン、トルエン等の炭化水素系;酢酸エチル、酢酸ブチル等のエステル類;エチレングリコールモノメチルエーテル等のエーテル系;エタノール、プロパノール、2−エチルヘキシルアルコール等のアルコール系;メチルエチルケトン、メチルイソブチルケトン等のケトン系;スワゾール310、スワゾール1000(コスモ石油株式会社製)等の芳香族炭化水素系;脂肪族炭化水素系、脂環族炭化水素系、アミド系等の溶剤を挙げることができる。これらの有機溶剤は単独でもしくは2種以上を併用して使用することができる。
上記架橋剤成分のうち、ピラゾールブロックポリイソシアネート化合物(C)に対しては、有機錫化合物等の有機金属化合物を使用することができる。
中塗り塗料(X)は、前述の成分を混合分散せしめることによって調製することができる。塗装時の固形分含有率は、45〜75質量%、特に50〜70質量%の範囲に調整しておくことが好ましい。
破断伸び率は、破断した時点での長さ増分の、元の試験前の長さに対する割合である。ヤング率はストレス−ストレイン曲線の立ち上がり時の曲線の傾きである。
本発明の方法によれば、次に、工程(1)で形成された中塗り塗膜上に、水性ベース塗料(Y)が塗装され、ベース塗膜が形成される。水性ベース塗料(Y)は、本発明により形成される複層塗膜の意匠性の付与、中塗り塗膜との積層による意匠性及び深み感を向上させる塗料である。
平均粒子径が前記上限値を超えると得られる塗膜の粒子感が過剰になって意匠的に好ましくない場合があり、下限値未満では粒子感が不十分になる場合がある。
光干渉性顔料としては、具体的には天然マイカ、人工マイカ、アルミナフレーク、シリカフレーク、ガラスフレーク等の半透明の基材を金属酸化物で被覆した顔料を使用することができる。
ガラスフレークを基材とする光干渉性顔料の場合は、塗膜の粒子感の点から平均粒子径が15〜100μm、特に17〜45μmの範囲内のものを好適に使用することができる。
上記光干渉性顔料の厚さは、0.05〜7.0μm、特に0.1〜3μmの範囲内のものを使用することが好ましい。
ここでいう粒子径及び厚さは、マイクロトラック粒度分布測定装置 MT3300(商品名、日機装株式会社製)を用いてレーザー回折散乱法によって測定した体積基準粒度分布のメジアン径を意味する。
本発明の方法によれば、上記の如くして水性ベース塗料(Y)を塗装して得られたベース塗膜上に、クリヤー塗料(Z)を塗装して、クリヤー塗膜を形成する。
本発明の方法において、クリヤー塗料(Z)は、水酸基含有アクリル樹脂及びポリイソシアネート化合物を含有するクリヤー塗料である。
水酸基含有アクリル樹脂は、水酸基含有不飽和単量体(M−1)及びその他の共重合可能な不飽和単量体(M−2)を常法により共重合せしめることによって製造することができる。
水酸基含有不飽和単量体(M−1)の配合割合が20質量%未満となると、硬化塗膜の架橋が不十分となって、所定の耐擦り傷性が得られにくくなる場合がある。一方、50質量%を超えると、その他の共重合可能な不飽和単量体(M−2)との相溶性や共重合反応性が低下し、さらに得られた水酸基含有アクリル樹脂及びポリイソシアネート化合物(B)との相溶性が低下することにより、塗膜の仕上り外観が低下する場合がある。
上記単量体混合物を共重合して水酸基含有アクリル樹脂を得るための共重合方法は、特に限定されるものではなく、それ自体既知の共重合方法を用いることができるが、なかでも有機溶剤中にて、重合開始剤の存在下で重合を行なう溶液重合法を好適に使用することができる。
紫外線吸収剤を使用する場合、紫外線吸収剤のクリヤー塗料(Z)中の含有量としては、通常、樹脂固形分総合計量100質量部に対して0〜10質量部、特に0.2〜5質量部、さらに特に0.3〜2質量部の範囲内であることが耐侯性、耐黄変性の面から好ましい。
光安定剤を使用する場合、光安定剤のクリヤー塗料(Z)中の含有量としては、通常、樹脂固形分総合計量100質量部に対して0〜10質量部、特に0.2〜5質量部、さらに特に0.3〜2質量部の範囲内であることが耐侯性、耐黄変性の面から好ましい。
本発明の複層塗膜形成方法においては、上記工程(1)〜(3)で形成される中塗り塗膜、ベース塗膜及びクリヤー塗膜が加熱硬化される。
クリヤー塗料(Z)を塗装してなるクリヤー塗膜は、通常、未硬化のベースコート塗膜と一度に加熱硬化される。
本発明の方法によれば、自動車車体本体とガラス部材等の接着のため、クリヤー塗膜上に、一般に、固定されるガラス部材の形状に相応する枠状に、接着剤層が形成される。
また、樹脂の数平均分子量は、ゲル浸透クロマトグラフィー(GPC)によって標準ポリスチレンの検量線を用いて測定したものである。
(製造例1〜11)
表1に示す組成の各原材料((A)水酸基含有ポリエステル樹脂、(B)メラミン樹脂、(C)ピラゾールブロックポリイソシアネート化合物、(D)顔料及び(E)有機溶剤)を混合、攪拌することにより、20℃におけるフォードカップNo.4による粘度30秒の各中塗り塗料(X1)〜(X11)を得た。なお、各成分の配合量は固形分量である(有機溶剤(E)を除く)。
なお、中塗り塗料(X7)〜(X11)は、比較例用の中塗り塗料である。
水酸基含有ポリエステル樹脂(A−1):トリメチロールプロパン、シクロヘキサンジメタノール、イソフタル酸およびアジピン酸を用いて常法によりエステル化反応せしめた。数平均分子量4500、水酸基価120、酸価10。
水酸基含有ポリエステル樹脂(A−2):トリメチロールプロパン、シクロヘキサンジメタノール、イソフタル酸およびアジピン酸を用いて常法によりエステル化反応せしめた。数平均分子量5000、水酸基価90、酸価6。
メラミン樹脂(B−1):重量平均分子量1200、イミノ基含有メチルブチル混合エーテル化メラミン。
メラミン樹脂(B−2):数平均分子量1500、イミノ基含有ブチルエーテル化メラミン。
ブロックポリイソシアネート化合物(C−1):ヘキサメチレンジイソシアネ−トを3,5−ジメチルピラゾールでフルブロックした化合物。
ブロックポリイソシアネート化合物(C−2):ヘキサメチレンジイソシアネ−トをメチルエチルケトオキシムでフルブロックした化合物。
顔料(D−1):二酸化チタン、平均粒径0.25μm
顔料(D−2):硫酸バリウム、平均粒径0.7μm
顔料(D−3):カーボンブラック、平均粒径0.02μm
有機溶剤(E−1):酢酸ブチル
(製造例12)
水酸基含有アクリル樹脂分散液(i)100部(固形分30部)、水酸基含有水溶性アクリル樹脂(ii)73部(固形分40部)、メチル−ブチル混合エーテル化メラミン樹脂(固形分60%、重量平均分子量2,000)50部(固形分30部)、アルミニウム顔料ペースト「GX−40A」(旭化成メタルズ社製、金属含有量74%)11部、及びアルミニウム顔料ペースト「MH−8805」(旭化成メタルズ社製、金属含有量68%)10部を配合して、ASE−60(アルカリ膨潤型増粘剤、商品名、ロームアンドハース社製)、2−(ジメチルアミノ)エタノール及び脱イオン水を添加して調整、攪拌混合し、塗装に適正な粘度に希釈して、pH8.0、塗料固形分23%の水性ベース塗料(Y1)を得た。
温度計、サーモスタット、撹拌装置、還流冷却器、窒素導入管及び滴下装置を備えた反応容器に脱イオン水130部、「アクアロンKH−10」(商品名、第一工業製薬株式会社製、ポリオキシエチレンアルキルエーテル硫酸塩エステルアンモニウム塩、有効成分97%)0.52部を仕込み、窒素気流中で撹拌混合し、80℃に昇温した。次いで下記のモノマー乳化物(1)のうちの全量の1%量及び6%過硫酸アンモニウム水溶液5.3部を反応容器内に導入し80℃で15分間保持した。次いで、残りのモノマー乳化物(1)を3時間かけて、同温度に保持した反応容器内に滴下した。滴下終了後、1時間熟成した。
次いで、下記のモノマー乳化物(2)を1時間かけて滴下した。1時間熟成した後、5% 2−(ジメチルアミノ)エタノール水溶液40部を反応容器に徐々に加えながら30℃まで冷却し、100メッシュのナイロンクロスで濾過することにより、濾液として、平均粒子径120nm(サブミクロン粒度分布測定装置「COULTER N4型」(ベックマン・コールター社製)を用いて、脱イオン水で希釈して20℃で測定した。)、固形分濃度30%の水酸基含有アクリル樹脂分散液(i)を得た。得られた水酸基含有アクリル樹脂分散液(i)の酸価は33mgKOH/g、水酸基価は25mgKOH/gであった。
モノマー乳化物(1):脱イオン水42部、「アクアロンKH−10」0.72部、メチレンビスアクリルアミド2.1部、スチレン2.8部、メチルメタクリレート16.1部、エチルアクリレート28部及びn−ブチルアクリレート21部を混合攪拌して、モノマー乳化物(1)を得た。
モノマー乳化物(2):脱イオン水18部、「アクアロンKH−10」0.31部、過硫酸アンモニウム0.03部、メタクリル酸5.1部、2−ヒドロキシエチルアクリレート5.1部、スチレン3部、メチルメタクリレート6部、エチルアクリレート1.8部及びn−ブチルアクリレート9部を混合攪拌して、モノマー乳化物(2)を得た。
フラスコにプロピレングリコールモノプロピルエーテル35部を仕込み85℃に昇温後、メチルメタクリレート30部、2−エチルヘキシルアクリレート20部、n−ブチルアクリレート29部、ヒドロキシエチルアクリレート15部、アクリル酸6部、プロピレングリコールモノプロピルエーテル15部及び2,2’−アゾビス(2,4−ジメチルバレロニトリル)2.3部の混合物を4時間かけてフラスコに滴下し、滴下終了後1時間熟成した。その後さらにプロピレングリコールモノプロピルエーテル10部及び2,2’−アゾビス(2,4−ジメチルバレロニトリル)1部の混合物を1時間かけてフラスコに滴下し、滴下終了後1時間熟成した。さらにジエタノールアミン7.4部を加え、固形分濃度55%、酸価47mgKOH/g、水酸基価72mgKOH/gの水酸基含有水溶性アクリル樹脂(ii)を得た。
(製造例13)
水酸基含有アクリル樹脂(iii)64部、UV1164(チバガイギー社製、紫外線吸収剤)2部、及びHALS292(チバガイギー社製、光安定剤)2部からなる主剤を酢酸エチルに溶解させた主剤と、硬化剤N−3300(住化バイエルウレタン社製、ヘキサメチレンジイソシアネートのイソシアヌレート、固形分100%、NCO含有率21.8%)36部とをディスパーを用いて攪拌して混合し、酢酸エチル及び酢酸ブチルの混合溶剤(質量比1/1)で希釈してフォードカップ#No.4を用いて20℃で17秒の粘度に調整することによりクリヤー塗料(Z1)を得た。
水酸基含有アクリル樹脂(iii):モノマー組成がスチレン/シクロヘキシルメタクリレート/2−エチルヘキシルアクリレート/2−ヒドロキシエチルアクリレート/アクリル酸=20/26/19/34/1のモノマー組成物を準備し、該モノマー組成物100部に対して重合開始剤ジt−アミルパーオキサイド1部を用いて重合し、水酸基含有アクリル樹脂(iii)を得た。固形分60質量%(希釈溶剤:エトキシエチルプロピオネート)、重量平均分子量10000、水酸基価164mgKOH/g、酸価8mgKOH/g)であった。
(試験用被塗物の作製)
リン酸亜鉛処理された冷延鋼板に「エレクロンGT−10」(商品名、関西ペイント株式会社製、熱硬化性エポキシ樹脂系カチオン電着塗料)を膜厚20μmとなるように電着塗装し、170℃で30分間加熱して硬化させて試験用被塗物とした。
1)試験用被塗物に、前記製造例1で得た中塗り塗料(X1)をハンドスプレーガンで硬化塗膜15μmになるように塗装し、7分間放置後、140℃で30分間焼付した。
次いで、該中塗り塗膜上に前記製造例12で得た水性ベース塗料(Y1)をハンドスプレーガンで硬化膜厚10μmとなるように塗装し、5分間放置後、80℃で3分間プレヒートを行なった。
次いで、該未硬化のベース塗膜上に製造例13で作成したクリヤー塗料(Z1)を硬化膜厚10〜15μmとなるようにハンドスプレーガン塗装し、7分間放置した後、140℃で30分間加熱して該複層塗膜をすべて加熱硬化させることにより試験板を作製した。
上記試験板にさらにウレタン系接着剤(商品名「3740」、サンスター株式会社製、自動車用ウインドシールド剤)を、塗布形状が幅20mm、厚さ3mm、長さ100mm以上となるように塗布し、離型紙を被せた後、平板で均一に押さえつけた。平板を取り除いた後、温度23±2℃、湿度50±5%で72時間放置して硬化させた。その後、離型紙を剥がして、WDB(ガラス接着性)試験用の試験板Aを作製した。
次いで、該中塗り塗膜上に前記製造例12で得た水性ベース塗料(Y1)をハンドスプレーガンで硬化膜厚15μmとなるように塗装し、5分間放置後、80℃で3分間プレヒートを行なった。
次いで、該未硬化のベース塗膜上に製造例13で作成したクリヤー塗料(Z1)を硬化膜厚35μmとなるようにハンドスプレーガンで塗装し、7分間放置した後、140℃で30分間加熱して該複層塗膜をすべて加熱硬化させることにより、仕上がり外観(平滑性)及び耐チッピング試験用の試験板Bを作製した。
実施例1において、中塗り塗料(X1)を中塗り塗料(X2)〜(X11)のいずれかに変更する以外は、実施例1と同様にして各試験板(2種類)を作製した。
上記作製した各試験板Aを40℃に設定した恒温水槽中に240時間浸漬させ、その後、23℃の水中に1時間浸漬させて冷却した後、以下の剥離試験を行った。
硬化した接着剤層を塗膜に対して90度以上の方向に手で引っ張りながら2〜3mm間隔で、塗膜に対して約60度の角度で塗膜表面に達するところまでカッターナイフでカットを入れる。接着剤層を剥がした後の剥離状態を以下の「◎」、「○」、「△」、「×」の基準により評価した。
◎:接着剤層の剥れが認められず、塗膜の露出も認められない。
○:塗膜は破壊されず、接着剤層のみが凝集破壊を起こして剥れるが、塗膜と接着剤層の付着はほぼ保たれている。
△:塗膜が凝集破壊を起こして剥れる。
×:塗膜と接着剤層との界面で剥れが認められる。
上記作製した各試験板Bの複層塗膜表面の平滑性について、以下の「◎」、「○」、「△」、「×」の基準に従い、目視評価を実施した。
◎:良好
○:やや良好
△:やや劣る
×:劣る
スガ試験機株式会社製の飛石試験機JA−400型(チッピング試験装置)の試片保持台に上記作製した各試験板Bを設置し、−20℃において、35cmの距離から0.5MPaの圧縮空気により、6号砕石300gを試験板に対して90度の角度で衝突させた。その後、得られた試験板Bを水洗して、乾燥し、塗面に布粘着テープ(ニチバン株式会社製)を貼着して、それを剥離した後、塗膜のキズの発生程度等を目視で観察し、以下の「◎」、「○」、「△」、「×」の基準により評価した。
◎:キズの大きさが極めて小さく(1.2mm以下)、素地の鋼板が露出していない。
○:キズの大きさが小さく(1.2mmを超えて2.0mm未満)、素地の鋼板が露出していない。
△:キズの大きさは小さいが(1.2mmを超えて2.0mm未満)、素地の鋼板が露出している。
×:キズの大きさは大きく(2.0mm以上)、素地の鋼板も大きく露出している。
Claims (1)
- 電着塗装された自動車車体の一部に、下記工程(1)〜(5)を順次行なう複層塗膜形成方法であって、
工程(1):電着塗膜上に、中塗り塗料(X)を塗装して中塗り塗膜を形成する工程
工程(2):前記工程(1)で形成された中塗り塗膜上に、水性ベース塗料(Y)を塗装してベース塗膜を形成する工程
工程(3):前記工程(2)で形成されたベース塗膜上に、水酸基含有アクリル樹脂及びポリイソシアネート化合物を含有するクリヤー塗料(Z)を塗装してクリヤー塗膜を形成する工程
工程(4):前記工程(1)〜(3)で形成された中塗り塗膜、ベース塗膜及びクリヤー塗膜を加熱硬化する工程
工程(5):クリヤー塗膜上に接着剤層を形成する工程
前記中塗り塗料(X)が、(A)水酸基含有ポリエステル樹脂、(B)メラミン樹脂、(C)ピラゾールブロックポリイソシアネート化合物、(D)顔料、及び(E)有機溶剤を含有し、前記メラミン樹脂(B)及び前記ピラゾールブロックポリイソシアネート化合物(C)含有量の比(B/C)が固形分比で5/35〜20/15であり、且つ顔料(D)の濃度(PWC)が40〜60%であり、
前記中塗り塗膜の加熱硬化後の硬化塗膜の20℃における破断伸び率が40〜90%であり、ヤング率が600〜1600MPaであり、ツーコン硬度が3〜9であることを特徴とする複層塗膜形成方法。
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