JP6323952B2 - 基材の被膜形成方法 - Google Patents
基材の被膜形成方法 Download PDFInfo
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- JP6323952B2 JP6323952B2 JP2014170394A JP2014170394A JP6323952B2 JP 6323952 B2 JP6323952 B2 JP 6323952B2 JP 2014170394 A JP2014170394 A JP 2014170394A JP 2014170394 A JP2014170394 A JP 2014170394A JP 6323952 B2 JP6323952 B2 JP 6323952B2
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- Japan
- Prior art keywords
- group
- polymerizable unsaturated
- meth
- isocyanate
- acrylate
- Prior art date
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- 239000002346 layers by function Substances 0.000 claims description 17
- 230000009477 glass transition Effects 0.000 claims description 14
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- 238000001721 transfer moulding Methods 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- FGKCGMMQJOWMFW-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;bromide Chemical compound [Br-].CC(=C)C(=O)OCC[N+](C)(C)C FGKCGMMQJOWMFW-UHFFFAOYSA-M 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- FUSUHKVFWTUUBE-UHFFFAOYSA-N vinyl methyl ketone Natural products CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- PIMBTRGLTHJJRV-UHFFFAOYSA-L zinc;2-methylprop-2-enoate Chemical compound [Zn+2].CC(=C)C([O-])=O.CC(=C)C([O-])=O PIMBTRGLTHJJRV-UHFFFAOYSA-L 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
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Description
工程(1):イソシアネート反応性基を有する樹脂(A)及びイソシアネート基含有重合性不飽和化合物(B)を含有する組成物(1)を使用して、下塗り塗膜層を形成する工程、
工程(2):前記工程(1)で下塗り塗膜層が形成された基材上に、機能性付与基含有重合性不飽和化合物及び熱重合開始剤を含有する組成物(2)を使用して、機能性付与層を形成する工程、及び
工程(3):前記工程(1)及び(2)により、下塗り塗膜層及び機能性付与層が形成された基材を加熱する工程、
を順次行うことを特徴とする基材上への被膜形成方法。
基材上に、
工程(1):イソシアネート反応性基を有する樹脂(A)及びイソシアネート基含有重合性不飽和化合物(B)を含有する組成物(1)を使用して、下塗り塗膜層を形成する工程、
工程(2):前記工程(1)で下塗り塗膜層が形成された基材上に、機能性付与基含有重合性不飽和化合物及び熱重合開始剤を含有する組成物(2)を使用して、機能性付与層を形成する工程、及び
工程(3):前記工程(1)及び(2)により、下塗り塗膜層及び機能性付与層が形成された基材を加熱する工程、を順次行うことを特徴とするものである。
本発明において、基材は表面を改質して機能性を付与する対象となる。基材としては、特に制限はなく、有機材料、無機材料、或いは、有機と無機とのハイブリッド材料のいずれであってもよい。本発明における基材としては、有機材料、有機と無機とのハイブリッド材料等の有機高分子化合物を含む基材であることが好ましい。
本発明の被膜形成方法において、必須工程である工程(1)の前に、表面を改質して機能性を付与する対象となる基材に対し、プラズマ処理、コロナ放電処理、活性エネルギー線処理、火炎処理、研磨処理、ブラスト処理などから選択された少なくとも1種の物理的方法による処理(物理的処理)を行うことができる。これらの物理的処理は必要に応じて2種以上を併用して行うこともできる。
工程(1)では、基材上に、イソシアネート反応性基を有する樹脂(A)及びイソシアネート基含有重合性不飽和化合物(B)を含有する組成物(1)を使用して、下塗り塗膜層を形成する。工程(1)に先立ち、前記工程(0)の物理的処理及び/又は前記化学的処理を行う場合は、該物理的処理及び/又は化学的処理が施された基材上に、下塗り塗膜層を形成する。
イソシアネート反応性基を有する樹脂(A)は、1分子中に少なくとも1個のイソシアネート反応性基を有する樹脂である。
(i) アルキル又はシクロアルキル(メタ)アクリレート:例えば、メチル(メタ)アクリレート、エチル(メタ)アクリレート、n−プロピル(メタ)アクリレート、イソプロピル(メタ)アクリレート、n−ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、tert−ブチル(メタ)アクリレート、n−ヘキシル(メタ)アクリレート、n−オクチル(メタ)アクリレート、2−エチルヘキシル(メタ)アクリレート、ノニル(メタ)アクリレート、トリデシル(メタ)アクリレート、ラウリル(メタ)アクリレート、ステアリル(メタ)アクリレート、イソステアリル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、メチルシクロヘキシル(メタ)アクリレート、t−ブチルシクロヘキシル(メタ)アクリレート、シクロドデシル(メタ)アクリレート、トリシクロデカニル(メタ)アクリレート等。
(ii) イソボルニル基を有する重合性不飽和モノマー:イソボルニル(メタ)アクリレート等。
(iii) アダマンチル基を有する重合性不飽和モノマー:アダマンチル(メタ)アクリレート等。
(iv) トリシクロデセニル基を有する重合性不飽和モノマー:トリシクロデセニル(メタ)アクリレート等。
(v) 芳香環含有重合性不飽和モノマー:ベンジル(メタ)アクリレート、スチレン、α−メチルスチレン、ビニルトルエン等。
(vi) アルコキシシリル基を有する重合性不飽和モノマー:ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス(2−メトキシエトキシ)シラン、γ−(メタ)アクリロイルオキシプロピルトリメトキシシラン、γ−(メタ)アクリロイルオキシプロピルトリエトキシシラン等。
(vii) フッ素化アルキル基を有する重合性不飽和モノマー:パーフルオロブチルエチル(メタ)アクリレート、パーフルオロオクチルエチル(メタ)アクリレート等のパーフルオロアルキル(メタ)アクリレート;フルオロオレフィン等。
(viii) マレイミド基等の光重合性官能基を有する重合性不飽和モノマー。
(ix) ビニル化合物:N−ビニルピロリドン、エチレン、ブタジエン、クロロプレン、プロピオン酸ビニル、酢酸ビニル等。
(x) カルボキシル基含有重合性不飽和モノマー:(メタ)アクリル酸、マレイン酸、クロトン酸、β−カルボキシエチル(メタ)アクリレート等。
(xi) 含窒素重合性不飽和モノマー:(メタ)アクリロニトリル、(メタ)アクリルアミド、N,N−ジメチルアミノエチル(メタ)アクリレート、N,N−ジエチルアミノエチル(メタ)アクリレート、N,N−ジメチルアミノプロピル(メタ)アクリルアミド、メチレンビス(メタ)アクリルアミド、エチレンビス(メタ)アクリルアミド、グリシジル(メタ)アクリレートとアミン化合物との付加物等。
(xii) 重合性不飽和基を1分子中に2個以上有する重合性不飽和モノマー:アリル(メタ)アクリレート、エチレングリコールジ(メタ)アクリレート、1,4−ブタンジオールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、1,6−ヘキサンジオールジ(メタ)アクリレート等。
(xiii) エポキシ基含有重合性不飽和モノマー:グリシジル(メタ)アクリレート、β−メチルグリシジル(メタ)アクリレート、3,4−エポキシシクロヘキシルメチル(メタ)アクリレート、3,4−エポキシシクロヘキシルエチル(メタ)アクリレート、3,4−エポキシシクロヘキシルプロピル(メタ)アクリレート、アリルグリシジルエーテル等。
(xiv) 分子末端がアルコキシ基であるポリオキシエチレン鎖を有する(メタ)アクリレート。
(xv) スルホン酸基を有する重合性不飽和モノマー:2−アクリルアミド−2−メチルプロパンスルホン酸、2−スルホエチル(メタ)アクリレート、アリルスルホン酸、4−スチレンスルホン酸等;これらスルホン酸のナトリウム塩及びアンモニウム塩等。
(xvi) リン酸基を有する重合性不飽和モノマー:アシッドホスホオキシエチル(メタ)アクリレート、アシッドホスホオキシプロピル(メタ)アクリレート、アシッドホスホオキシポリ(オキシエチレン)グリコール(メタ)アクリレート、アシッドホスホオキシポリ(オキシプロピレン)グリコール(メタ)アクリレート等。
(xvii) 紫外線吸収性官能基を有する重合性不飽和モノマー:2−ヒドロキシ−4(3−メタクリロイルオキシ−2−ヒドロキシプロポキシ)ベンゾフェノン、2−ヒドロキシ−4−(3−アクリロイルオキシ−2−ヒドロキシプロポキシ)ベンゾフェノン、2,2’−ジヒドロキシ−4−(3−メタクリロイルオキシ−2−ヒドロキシプロポキシ)ベンゾフェノン、2,2’−ジヒドロキシ−4−(3−アクリロイルオキシ−2−ヒドロキシプロポキシ)ベンゾフェノン、2−(2’−ヒドロキシ−5'−メタクリロイルオキシエチルフェニル)−2H−ベンゾトリアゾール等。
(xviii) 光安定性重合性不飽和モノマー:4−(メタ)アクリロイルオキシ1,2,2,6,6−ペンタメチルピペリジン、4−(メタ)アクリロイルオキシ−2,2,6,6−テトラメチルピペリジン、4−シアノ−4−(メタ)アクリロイルアミノ−2,2,6,6−テトラメチルピペリジン、1−(メタ)アクリロイル−4−(メタ)アクリロイルアミノ−2,2,6,6−テトラメチルピペリジン、1−(メタ)アクリロイル−4−シアノ−4−(メタ)アクリロイルアミノ−2,2,6,6−テトラメチルピペリジン、4−クロトノイルオキシ−2,2,6,6−テトラメチルピペリジン、4−クロトノイルアミノ−2,2,6,6−テトラメチルピペリジン、1−クロトノイル−4−クロトノイルオキシ−2,2,6,6−テトラメチルピペリジン等。
(xix) カルボニル基を有する重合性不飽和モノマー:アクロレイン、ダイアセトンアクリルアミド、ダイアセトンメタクリルアミド、アセトアセトキシエチルメタクリレート、ホルミルスチロール、4〜7個の炭素原子を有するビニルアルキルケトン(例えば、ビニルメチルケトン、ビニルエチルケトン、ビニルブチルケトン)等。
(xx) 酸無水物基を有する重合性不飽和モノマー:無水マレイン酸、無水イタコン酸、無水シトラコン酸等。
Tg(℃)=Tg(K)−273
式中、W1、W2、・・・Wnは各モノマーの質量分率であり、T1、T2・・・Tnは各モノマーのホモポリマーのガラス転移温度Tg(K)である。
なお、各モノマーのホモポリマーのガラス転移温度は、POLYMER HANDBOOK Fourth Edition,J.Brandrup,E.h.Immergut,E.A.Grulke編(1999年)による値であり、該文献に記載されていないモノマーのガラス転移温度は、該モノマーのホモポリマーを重量平均分子量が50,000程度になるようにして合成したときの静的ガラス転移温度とする。
イソシアネート基含有重合性不飽和化合物(B)は、分子内に1個以上のイソシアネート基及び1個以上の重合性不飽和基を有する化合物である。
工程(2)では、前記工程(1)で基材上に形成された下塗り塗膜層上に、機能性付与基含有重合性不飽和化合物及び熱重合開始剤を含有する組成物(2)を使用して、機能性付与層を形成する。
機能性付与基含有重合性不飽和化合物は、分子内に、1個以上の重合性不飽和基及び1個以上の機能性付与基を有する化合物である。
1)親水性を付与するための、親水性基、
2)撥水性/撥油性を付与するための、撥水性/撥油性基、
3)屈折率変動を付与するための、高い増分または低い増分の屈折を有する官能基、
4)紫外線吸収特性を付与するための、紫外線吸収性を有する官能基、
5)光安定性を付与するための、光安定性を有する官能基、
6)生物特性を付与するための、生物特性を有する官能基、
7)難燃性を付与するための、難燃性基、
8)帯電防止性を付与するための、帯電防止性基、
等を挙げることができる。
ポリオキシエチレン基、ポリオキシプロピレン基、オキシエチレン基とオキシプロピレン基との両方を含むポリオキシアルキレン基等のポリオキシアルキレン基;
水酸基、アミド;
3級アミノ基、4級アンモニウム塩等を挙げることができる。
〔式中、R1は水素原子又はメチル基、R2は−CPH2P−、−C(CPH2P+1)H−、−CH2C(CPH2P+1)H−又は−CH2CH2O−、Rfは−CnF2n+1、−(CF2)nH、−CnF2n−CF3、−(CF2)pOCnF2nCjH2j+1、−(CF2)pOCmH2mCiH2iH、−N(CPH2P+1)COCnF2n+1、−N(CPH2P+1)SO2CnF2n+1である。但し、pは1〜10、nは1〜16、mは0〜10、iは0〜16、jは0〜10の整数である。〕
CF2=CFORg ・・・(II)
(式中Rgは炭素数1〜20のフルオロアルキル基を表わす。)
CH2=CHRg・・・(III)
(式中Rgは炭素数1〜20のフルオロアルキル基を表わす。)
CH2=CR3COOR5RjR6OCOCR4=CH2 ・・・(IV)
〔式中、R3、R4は水素原子又はメチル基、R5、R6は−CqH2q−、−C(CqH2q+1)H−、−CH2C(CqH2q+1)H−又は−CH2CH2O−、Rjは−CtF2tである。但し、qは1〜10、tは1〜16の整数である。〕
CH2=CHR7COOCH2(CH2Rk)CHOCOCR8=CH2・・・(V)
(式中、R7、R8は水素原子又はメチル基、Rkは−CyF2y+1である。但し、yは1〜16の整数である。)
上記のフッ素含有重合性不飽和化合物としては、以下の具体例を挙げることができる。
熱重合開始剤は、加熱により、フリーラジカル(中間体の形態でも)を発生する化合物の全て又は化合物の混合物である。
工程(2)の後、下塗り塗膜層及び機能性付与層が形成された基材を加熱することにより、基材、下塗り塗膜層及び機能性付与層が一体となって強固に結合した、表面が改質され新たに機能性が付与された塗装物品を得ることができる。
製造例1
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、酢酸ブチル45部を仕込み、窒素ガスを吹き込みながら115℃で攪拌し、この中に2−ヒドロキシエチルメタクリレート24部、2−ヒドロキシエチルアクリレート3部、スチレン20部、シクロヘキシルメタクリレート30部、n−ブチルアクリレート23部、酢酸ブチル10部及び2,2’−アゾビスイソブチロニトリル2部からなるモノマー混合物を4時間かけて均一速度で滴下し、さらに同温度で1時間熟成した。その後さらに酢酸ブチル15部及び2,2’−アゾビスイソブチロニトリル1.0部の混合物を3時間かけて反応容器に滴下し、滴下終了後1時間熟成させたのち、酢酸ブチルで希釈し、固形分50%の水酸基含有アクリル樹脂(A−1)溶液を得た。
製造例1において、モノマー混合物の配合組成及び反応温度を表1に示すものとする以外は、製造例1と同様にして、固形分50%の水酸基含有アクリル樹脂(A−2)〜(A−11)溶液を得た。各水酸基含有アクリル樹脂の水酸基価、重量平均分子量、ガラス転移温度ならびに芳香族重合性不飽和モノマー及び脂環族重合性不飽和モノマーの合計含有量を表1にあわせて示す。
製造例12
製造例1で得られた水酸基含有アクリル樹脂(A−1)溶液200部(固形分100部)、イソシアネート基含有重合性不飽和化合物(B−1)(注1)34部(固形分34部)、「スミジュールN−3300」(商品名、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環付加物、固形分含有率100%)30部、ジブチル錫ジアセテート0.001部及び「TINUVIN123」(商品名、BASF社製、光安定剤、固形分含有率100%)0.1部を均一に混合し、さらに固形分が30%になるように酢酸ブチルで希釈攪拌して、組成物(1−1)を得た。
製造例12において、配合組成を表2に示すものとする以外は、製造例12と同様にして、固形分30%の組成物(1−2)〜(1−22)を得た。なお表2に示す配合組成は、各成分の固形分質量による。
製造例34
メタクリロイルオキシエチル−N,N−ジメチルアンモニウム−α−メチルカルボキシベタイン10部、「V−50」(商品名、和光純薬工業社製、熱重合開始剤)0.5部、エタノール65部及び脱イオン水25部を混合して組成物(2−1)を得た。
ビニルスルホン酸10部、「V−50」0.5部、エタノール65部及び脱イオン水25部を混合して組成物(2−2)を得た。
ビニルスルホン酸10部、「V−50」0.5部、エタノール65部、脱イオン水10部及び20%水酸化ナトリウム水溶液18.5部を混合して組成物(2−3)を得た。
2−アクリルアミド−2−メチルプロパンスルホン酸10部、「V−50」0.5部、エタノール65部及び脱イオン水25部を混合して組成物(2−4)を得た。
2−アクリルアミド−2−メチルプロパンスルホン酸10部、「V−50」0.5部、エタノール65部、脱イオン水17部及び20%水酸化ナトリウム水溶液9.7部を混合して組成物(2−5)を得た。
2−アクリルアミド−2−メチルプロパンスルホン酸10部、「V−50」0.5部、エタノール65部、脱イオン水14部及び20%水酸化カリウム水溶液13.5部を混合して組成物(2−6)を得た。
2−アクリルアミド−2−メチルプロパンスルホン酸10部、過硫酸アンモニウム0.5部、エタノール65部、脱イオン水17部及び20%水酸化ナトリウム水溶液9.7部を混合して組成物(2−7)を得た。
「フルオレスター」(商品名、東ソーエフテック社製、2,2,2−トリフルオロエチルメタクリレート、分子量168、固形分100%)10部、「V−65」(商品名、和光純薬工業社製、熱重合開始剤)0.5部及び「スワゾール1000」(商品名、丸善石油化学社製、石油系炭化水素溶剤)90部を混合して組成物(2−8)を得た。
「サイラプレーンFM−0711」(商品名、JNC社製、α−ブチル−ω−(3−メタクリロキシプロピル)ポリジメチルシロキサン、重量平均分子量1,000、固形分100%)10部、「V−65」0.5部及び「スワゾール1000」90部を混合して組成物(2−9)を得た。
「サイラプレーンFM−0711」8部、「ライトアクリレートMPD−A」(商品名、共栄社化学社製、3−メチル−1,5−ペンタンジオールジアクリレート、固形分100%)2部、「V−65」0.5部及び「スワゾール1000」90部を混合して組成物(2−10)を得た。
基材
(ABS基材)
100mm×150mm×3.0mmのアクリロニトリル−ブタジエン−スチレン板の表面をイソプロピルアルコールで脱脂して基材とした。
100mm×150mm×3.0mmのアクリロニトリル−ブタジエン−スチレン板の表面をイソプロピルアルコールで脱脂した。その後、「レタンPGハイブリッドエコ サンメタリック塗料」(商品名、関西ペイント社製)を膜厚15μmになるように塗装し、80℃で5分乾燥したものを基材とした。
ABS基材上に、製造例12で得た組成物(1−1)を、エアスプレーを用いて膜厚が20μmとなるように塗装し、常温で10分間セッティングを行った後、80℃で30分間加熱して硬化塗膜を得た。次に、該硬化塗膜上に、製造例34で得た組成物(2−1)を、マイクロワイプを用いて塗り伸ばした後、別の清浄なクロスでむらがなくなるまでふき取った。次に、90℃で30分間加熱を行った。最後に、被膜が形成された面を水洗し、室温で自然乾燥させて、被膜形成基材を得た。
基材、組成物(1)及び組成物(2)として、表3に記載のものを使用し、組成物(1)の膜厚を表3に記載のとおりに変更する以外は、実施例1と同様にして、各被膜形成基材を得た。なお、組成物(2)として組成物(2−1)〜(2−7)を用いた実施例1〜27及び31〜57は、親水性付与被膜形成基材の製造例であり、組成物(2)として組成物(2−8)〜(2−10)を用いた実施例28〜30及び58〜60は、撥水性付与被膜形成基材の製造例である。
得られた各被膜形成基材について、各種試験を行った。評価結果を表3に示す。
平滑性:各被膜形成基材について、平滑性を下記基準にて評価した
◎:非常に滑らかで非常に良い
○:滑らかで良い
△:やや粗く少し悪い
×:粗く悪い。
◎:試験前の被膜に対して、全く外観の変化のないもの
○:試験前の被膜に対して、わずかにツヤびけ、ふくれ又は変色が見られるが、製品とした時に問題の無いレベル
△:試験前の被膜に対して、若干、ツヤびけ、ふくれ又は変色が見られる
×:試験前の被膜に対して、著しく、ツヤびけ、ふくれ又は変色が見られる。
各被膜形成基材の被膜面にJIS K 5600−5−6(1990)に準じて2mm×2mmのゴバン目100個を作り、その面に粘着テープを貼着し、急激に剥がした後に、被膜面に残ったゴバン目塗膜の数を評価した。
◎:残存個数/全体個数=100個/100個で縁欠けなし
○:残存個数/全体個数=100個/100個で縁欠けあり
△:残存個数/全体個数=99個〜90個/100個
×:残存個数/全体個数=89個以下/100個。
Claims (12)
- 基材上に、
工程(1):イソシアネート反応性基を有する樹脂(A)及びイソシアネート基含有重合性不飽和化合物(B)を含有する組成物(1)を使用して、下塗り塗膜層を形成する工程、
工程(2):前記工程(1)で下塗り塗膜層が形成された基材上に、機能性付与基含有重合性不飽和化合物及び熱重合開始剤を含有する組成物(2)を使用して、機能性付与層を形成する工程、及び
工程(3):前記工程(1)及び(2)により、下塗り塗膜層及び機能性付与層が形成された基材を加熱する工程、
を順次行うことを特徴とする基材上への被膜形成方法。 - イソシアネート反応性基を有する樹脂(A)の重量平均分子量が、3,000〜100,000である請求項1に記載の被膜形成方法。
- イソシアネート反応性基を有する樹脂(A)のガラス転移温度が、10〜100℃である請求項1又は2に記載の被膜形成方法。
- イソシアネート反応性基を有する樹脂(A)が水酸基含有樹脂(A1)である請求項1〜3のいずれか1項に記載の被膜形成方法。
- 水酸基含有樹脂(A1)の水酸基価が、15〜240mgKOH/gである請求項4に記載の被膜形成方法。
- 水酸基含有樹脂(A1)が水酸基含有アクリル樹脂である請求項4又は5に記載の被膜形成方法。
- 水酸基含有アクリル樹脂が、共重合モノマー成分として、芳香族重合性不飽和モノマー及び/又は脂環族重合性不飽和モノマーを含有し、該芳香族重合性不飽和モノマー及び脂環族重合性不飽和モノマーの合計含有量が、モノマー成分の総量に対して10〜90質量%である混合物を重合して得られる水酸基含有アクリル樹脂である、請求項6に記載の被膜形成方法。
- イソシアネート基含有重合性不飽和化合物(B)の重量平均分子量が、200〜4,000である、請求項1〜7のいずれか1項に記載の被膜形成方法。
- イソシアネート基含有重合性不飽和化合物(B)が、分子内にイソシアネート基を2個以上有する化合物であることを特徴とする請求項1〜8のいずれか1項に記載の被膜形成方法。
- 組成物(1)が、さらに、イソシアネート基含有重合性不飽和化合物(B)以外の、ブロックされていてもよいポリイソシアネート化合物を含有することを特徴とする請求項1〜9のいずれか1項に記載の被膜形成方法。
- 組成物(1)が、さらに、イソシアネート基含有重合性不飽和化合物(B)以外の重合性不飽和化合物を含有することを特徴とする請求項1〜10のいずれか1項に記載の被膜形成方法。
- 基材上に、請求項1〜11のいずれか1項に記載の被膜形成方法により被膜が形成された塗装物品。
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