JP2022078487A - 複層塗膜形成方法 - Google Patents
複層塗膜形成方法 Download PDFInfo
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- JP2022078487A JP2022078487A JP2020189187A JP2020189187A JP2022078487A JP 2022078487 A JP2022078487 A JP 2022078487A JP 2020189187 A JP2020189187 A JP 2020189187A JP 2020189187 A JP2020189187 A JP 2020189187A JP 2022078487 A JP2022078487 A JP 2022078487A
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- 229910052708 sodium Inorganic materials 0.000 description 2
- 125000004079 stearyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- 229920001285 xanthan gum Polymers 0.000 description 2
- 235000010493 xanthan gum Nutrition 0.000 description 2
- 239000000230 xanthan gum Substances 0.000 description 2
- 229940082509 xanthan gum Drugs 0.000 description 2
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- KCZQSKKNAGZQSZ-UHFFFAOYSA-N 1,3,5-tris(6-isocyanatohexyl)-1,3,5-triazin-2,4,6-trione Chemical compound O=C=NCCCCCCN1C(=O)N(CCCCCCN=C=O)C(=O)N(CCCCCCN=C=O)C1=O KCZQSKKNAGZQSZ-UHFFFAOYSA-N 0.000 description 1
- UNJNXIFNZQRBBV-UHFFFAOYSA-N 1-methylperoxypropan-2-yl acetate Chemical compound COOCC(C)OC(C)=O UNJNXIFNZQRBBV-UHFFFAOYSA-N 0.000 description 1
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- BTOVVHWKPVSLBI-UHFFFAOYSA-N 2-methylprop-1-enylbenzene Chemical compound CC(C)=CC1=CC=CC=C1 BTOVVHWKPVSLBI-UHFFFAOYSA-N 0.000 description 1
- OELQSSWXRGADDE-UHFFFAOYSA-N 2-methylprop-2-eneperoxoic acid Chemical compound CC(=C)C(=O)OO OELQSSWXRGADDE-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 241000951471 Citrus junos Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
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- C08F220/10—Esters
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Abstract
Description
クリヤー塗料組成物は、主剤(A)と、硬化剤(B)とを混合することにより得られ、
主剤(A)は、
主体樹脂としての水酸基含有アクリル樹脂(A-1)と、
水酸基含有アクリル樹脂(A-1)の固形分質量に対して、0.01~3.0質量%の表面調整剤(A-2)と、を含み、
水酸基含有アクリル樹脂(A-1)は、水酸基価80~250mgKOH/g、質量平均分子量1,000~30,000、SP値9.0~12.0であり、
表面調整剤(A-2)は、アクリル樹脂(A-2-i)と、樹脂(A-2-ii)をグラフトすることにより得られた質量平均分子量が3,000~100,000の重合物であり、
アクリル樹脂(A-2-i)のSP値は、8.5~10.0の範囲にあり、
樹脂(A-2-ii)のSP値は、アクリル樹脂(A-2-i)のSP値よりも2.0以上高いことを特徴とする複層塗膜形成方法を提供するものである。
本発明に用いるクリヤー塗料組成物は、主剤(A)と、硬化剤(B)とを混合することにより得らる。主剤(A)は、水酸基価80~250mgKOH/g、質量平均分子量1,000~30,000g/mol、SP値9.0~12.0である水酸基含有アクリル樹脂(A-1)を主体樹脂として含有する。
具体的には、例えば、ゲルパーミェーションクロマトグラフとして、市販品の「HLC8120GPC」(商品名、東ソー(株)製)を使用し、カラムとして、市販品の「TSKgel G2000HXL」、「TSKgel G3000HXL」、「TSKgel G4000HXL」、「TSKgel G5000HXL」(商品名、いずれも東ソー(株)製)の4本のカラムを使用し、溶離液;テトラヒドロフラン、測定温度;40℃、流速;1ml/分、検出器;示差屈折計(RI検出器)の条件で、分子量を測定することができる。
δ=( Vml 1/2δml+Vmh 1/2δmh)/(Vml 1/2+Vmh 1/2)
Vml=V1V2/(φ1V2+φ2V1)
Vmh=V1V3/(φ1V3+φ3V1)
δml=φ1δ1+φ2δ2
δmh=φ1δ1+φ3δ3
Vi:溶媒の分子容( ml/mol)
[ V1、V2、V3はそれぞれ溶媒1、2、3の分子容(本明細書では溶媒1、2、3はそれぞれ、アセトン、ヘキサン、イオン交換水である。下記δも同様。) ]
φi:濁点における各溶媒の体積分率
δi:溶媒のSP値
[δ1、δ2、δ3はそれぞれ溶媒1、2、3のSP値]
ml:低SP値貧溶媒混合系
mh:高SP値貧溶媒混合系
反応水の分離管が付属した還流冷却管、窒素ガス導入装置、温度計、攪拌装置を装備した反応容器に、ダイマー酸(商品名「PRIPOL1017」、CRODA社製、炭素数36)54.0部、ネオペンチルグリコール8.0部、イソフタル酸17.76部、1,6-ヘキサンジオール19.41部、トリメチロールプロパン0.81部を仕込み、120℃まで昇温させて原料を溶解した後、攪拌しながら160℃まで昇温させた。160℃のまま1時間保持した後、5時間かけて230℃まで徐々に昇温させた。230℃を保持して反応を続け、樹脂酸価が4mgKOH/gになったら、80℃以下まで冷却した後に、メチルエチルケトン31.6部を加え、樹脂固形分74.6%、樹脂水酸基価62mgKOH/g、樹脂酸価4mgKOH/g、質量平均分子量3,200の特性値を有するポリエステル樹脂ワニスを得た。
窒素ガス導入装置、温度計、攪拌装置を装備した反応容器に、製造例1により得られたポリエステル樹脂ワニスを78.9部、ジメチロールプロピオン酸7.8部、ネオペンチルグリコール1.5部、メチルエチルケトン40.0部を仕込み、攪拌しながら80℃まで昇温させた後、イソホロンジイソシアネート27.8部を仕込み、80℃を保持したまま各成分を反応させた。イソシアネート価が0.43meq/gになったところでネオペンチルグリコール4.0部を加え、そのまま80℃で反応を継続させた。そして、イソシアネート価が0.01meq/gになったところでブチルセロソルブ33.3部を加えて反応を終了させた。その後、100℃まで昇温させ、減圧下でメチルエチルケトンを除去した。さらに、50℃まで降温させ、ジメチルエタノールアミンを4.0部加えて酸基を中和し、その後に脱イオン水147.9部を加えて、樹脂固形分35.0%、樹脂水酸基価21mgKOH/g、樹脂酸価35mgKOH/g、質量平均分子量7,800の特性値を有するポリウレタン樹脂を得た。
窒素ガス導入装置、温度計、滴下ロート、攪拌装置を装備した反応容器に、製造例2により得られたポリウレタン樹脂を46.4部、脱イオン水33.1部を仕込み、攪拌しながら85℃まで昇温させた後、滴下成分として、スチレン4.92部、メチルメタクリレート5.5部、n-ブチルアクリレート4.02部、2-ヒドロキシエチルメタクリレート1.62部、アクリル酸0.21部、プロピレングリコールモノメチルエーテル3.9部、重合開始剤であるt-ブチルパーオキシ-2-エチルヘキサノエート0.2部の均一混合液を、3.5時間かけて滴下ロートを用いて等速滴下した。滴下終了後、85℃で1時間保持した後、追加触媒として、重合開始剤であるt-ブチルパーオキシ-2-エチルヘキサノエート0.03部をプロピレングリコールモノメチルエーテル0.11部に溶解させた重合開始剤溶液を添加し、さらに85℃で1時間保持したところで反応を終了し、アクリル樹脂/ウレタン樹脂比=50/50、樹脂固形分32.5%、樹脂水酸基価32mgKOH/g、樹脂酸価23mgKOH/gの特性値を有するコア/シェル型アクリルウレタン樹脂を得た。
製造例2により得られたポリウレタン樹脂36.12部に、二酸化チタン(商品名「タイピュア R706」、デュポン社製)29.29部及びカーボンブラック(商品名「MA-100」、三菱ケミカル(株)製)0.3部を加え、モーターミルで分散し、顔料ペーストを作製した。
製造例2により得られたポリウレタン樹脂50.5部に、カーボンブラック(商品名「MA-100」、三菱ケミカル(株)製)1.55部を加え、モーターミルで分散して、顔料ペーストを作製した。
温度計、還流冷却器、攪拌機、滴下ロート及び窒素ガス吹き込み口を備えたフラスコにキシレンを27.0部、プロピレングリコールモノメトキシエーテルアセテートを9.0部仕込み、窒素ガス導入下、攪拌しながら加熱し130℃を保った。次に、130℃の温度で、スチレン6.0部、アクリル酸0.8部、2-ヒドロキシエチルメタクリレート16.7部、n-ブチルメタクリレート36.6部のラジカル重合性モノマーと、重合開始剤としてt-ブチルパーオキシ-2-エチルヘキサノエート1.0部とを均一に混合し、3時間かけて滴下ロートより等速滴下した。滴下終了後、130℃の温度を1時間保った後、反応温度を110℃に下げた。
表1に記載したように原料の仕込み量に変えた以外は、A-1-1と同様の製造方法に従って、水酸基含有アクリル樹脂ワニスA-1-2を得た。
表2に樹脂(A-2-ii)の一部(基礎構造)を構成するモノマー組成、すなわちアクリロニトリル15部、メチルメタクリレート15部より、片末端にメタクリロイル基を有するアクリロニトリル/メチルメタクリレート共重合体のマクロモノマー(A-2-ii)(質量平均分子量4,000)を、以下の方法で作成した。
表面調整剤 A-2-aの製造と同様に、表2に示した樹脂(A-2-ii)の各モノマー組成より、片末端にメタクリロイル基を有するマクロモノマー(A-2-ii)を作成し、各マクロモノマーと、表2に示したアクリル樹脂(A-2-i)のモノマーとを、t-ブチルパーオキシ-2-エチルヘキサノエートを重合開始剤として、キシレン中で共重合し、表2に示した特性値を持つ表面調整剤(A-2-b~A-2-g)の溶液を製造した。
表3に記載した主剤の原料を順次混合して均一になるように攪拌し、同表に示すように主剤、硬化剤を組み合わせてなる、二液型クリヤー塗料組成物を作成した。
1)チヌビン384-2:商品名、BASFジャパン(株)製、ベンゾトリアゾール系紫外線吸収剤(固形分95質量%)
2)チヌビン292:商品名、BASFジャパン(株)製、光安定剤
3)BYK-300:商品名、ビックケミー・ジャパン(株)製、シリコン系表面調整剤(固形分52質量%)
4)ソルベッソ100:商品名、エクソンモービル社製、芳香族炭化水素系溶剤
5)スミジュールN3300:商品名、住化コベストロウレタン(株)製、1,6-ヘキサメチレンジイソシアネートのイソシアヌレートタイプ樹脂(固形分100質量%、NCO含有率21.8質量%)
リン酸亜鉛処理軟鋼板に、カチオン電着塗料(商品名「カソガードNo.500」、BASFコーティングス社製)で、乾燥膜厚が20μmとなるように電着塗装を行い、175℃で25分間焼き付けて、本評価に使用する電着塗膜板とした(以下、「電着板」とする)。
脱脂処理を施した70×150×3mmのポリプロピレン板にプライマー塗料(商品名「プライマックNo.1501」、BASFコーティングス社製)を、乾燥膜厚が10μmとなるようにスプレー塗装を行い、本評価に使用する樹脂塗膜板とした(以下、「樹脂板」とする)。
得られた評価板1および2について、それぞれ以下の塗膜性能評価を行った。
得られた評価板の塗膜外観を、目視観察により、次の基準に従い評価した。なお、評価結果は評価者20人の観察結果の平均である。
◎:塗膜に蛍光灯を映すと、蛍光灯がかなり鮮明に映る。
○:塗膜に蛍光灯を映すと、蛍光灯が少し鮮明に映る。
△:塗膜に蛍光灯を映すと、蛍光灯の周囲(輪郭)がぼやける。
×:塗膜に蛍光灯を映すと、蛍光灯の周囲(輪郭)が著しくぼやける。
評価板を作成した後1週間室温で放置し、その後、40℃の純水に浸漬させ、240時間放置した。浸漬後の塗膜を目視観察により、次の基準に従い評価した。なお、評価結果は評価者20人の観察結果の平均である。
○:白濁が認められない。
△:やや白濁が認められる。
×:はっきりと白濁が認められる。
試験板を無鉛レギュラーガソリン(JIS K2202 2号記載)に20℃で24時間浸漬し、外観を目視で観察し、次に示す基準に従い評価した。なお、評価結果は評価者20人の観察結果の平均である。
○:異常が認められない。
△:わずかに黄変、フクレなどの異常が認められた。
×:黄変、フクレなどの異常が認められた。
粘着剤がアクリル系である両面テープとして、スリーエムジャパン株式会社製アクリルフォームテープGT5912を用い、30mm×30mmのサイズにカットした。厚さ1mm、幅30mm、長さ80mmのステンレス製鋼板を上から30mmの部位で90度に折り曲げたL型治具の上面、すなわち30mm×30mmの部位に、上記のようにカットした両面テープを、上面全体を覆うように貼り付けた。次いで、70mm×150mmの寸法としたの評価板1、2の中央に、L型治具の上面を、評価板と上面との間に一切隙間やテープのズレが生じないことを確認しながら貼り付けた。評価板からL型治具が下に貼りついた向きにして、評価板を両端付近で支え、L型治具に2kgまたは3kgの重りをかけて、室温で7日間まで放置した。次の基準に従い評価した。
◎:3kgの重りをかけて、7日間以上両面テープが剥がれなかった。
○:2kgの重りをかけて、7日間以上両面テープが剥がれなかった。
△:2kgの重りをかけて、2日間以上7日間未満で両面テープが剥がれた。
×:2kgの重りをかけて、2日間未満で両面テープが剥がれた。
Claims (9)
- 電着塗料が塗装され、形成された電着塗膜の焼付けが完了した自動車車体用の金属上に、中塗り塗料組成物、ベース塗料組成物、クリヤー塗料組成物を順次塗装し、加熱硬化させて複層塗膜を形成する方法であって、
前記クリヤー塗料組成物は、主剤(A)と、硬化剤(B)とを混合することにより得られ、
前記主剤(A)は、
主体樹脂としての水酸基含有アクリル樹脂(A-1)と、
前記水酸基含有アクリル樹脂(A-1)の固形分質量に対して、0.01~3.0質量%の表面調整剤(A-2)と、を含み、
前記水酸基含有アクリル樹脂(A-1)は、水酸基価80~250mgKOH/g、質量平均分子量1,000~30,000、SP値9.0~12.0であり、
前記表面調整剤(A-2)は、アクリル樹脂(A-2-i)と、樹脂(A-2-ii)をグラフトすることにより得られた質量平均分子量が3,000~100,000の重合物であり、
前記アクリル樹脂(A-2-i)のSP値は、8.5~10.0の範囲にあり、
前記樹脂(A-2-ii)のSP値は、前記アクリル樹脂(A-2-i)のSP値よりも2.0以上高いことを特徴とする複層塗膜形成方法。 - 自動車外装用の樹脂素材上に、中塗り塗料組成物、ベース塗料組成物、クリヤー塗料組成物を順次塗装し、加熱硬化させて複層塗膜を形成する方法であって、
前記クリヤー塗料組成物は、主剤(A)と、硬化剤(B)とを混合することにより得られ、
前記主剤(A)は、
主体樹脂としての水酸基含有アクリル樹脂(A-1)と、
前記水酸基含有アクリル樹脂(A-1)の固形分質量に対して、0.01~3.0質量%の表面調整剤(A-2)と、を含み、
前記水酸基含有アクリル樹脂(A-1)は、水酸基価80~250mgKOH/g、質量平均分子量1,000~30,000、SP値9.0~12.0であり、
前記表面調整剤(A-2)は、アクリル樹脂(A-2-i)と、樹脂(A-2-ii)をグラフトすることにより得られた質量平均分子量が3,000~100,000の重合物であり、
前記アクリル樹脂(A-2-i)のSP値は、8.5~10.0の範囲にあり、
前記樹脂(A-2-ii)のSP値は、前記アクリル樹脂(A-2-i)のSP値よりも2.0以上高いことを特徴とする複層塗膜形成方法。 - 前記水酸基含有アクリル樹脂(A-1)が、水酸基含有モノ(メタ)アクリレートと、他のビニル系単量体の共重合物からなることを特徴とする請求項1または請求項2記載の複層塗膜形成方法。
- 前記アクリル樹脂(A-2-i)が、複数種類のビニル系単量体の共重合物からなることを特徴とする請求項1~請求項3のいずれか1項に記載の複層塗膜形成方法。
- 前記樹脂(A-2-ii)がアクリル樹脂、ポリウレタン樹脂、エチレンオキシド単位を含む一価のポリアルキレンオキシドのいずれか1種以上からなることを特徴とする請求項1~請求項4のいずれか1項に記載の複層塗膜形成方法。
- 前記表面調整剤(A-2)が、前記アクリル樹脂(A-2-i)/前記樹脂(A-2-ii)=90/10~50/50の質量割合でのグラフト重合体であることを特徴とする請求項1~請求項5のいずれか1項に記載の複層塗膜形成方法。
- 前記中塗り塗料組成物が、主剤中に水酸基価20~40mgKOH/g、酸価20~40mgKOH/gであるアクリルウレタン樹脂を主剤樹脂固形分中20~60質量%含有し、1分子当たり2モル以上のカルボジイミド基を持つカルボジイミド化合物を硬化剤として含有し、主剤樹脂が含有するカルボン酸基の当量に対するカルボジイミド基の当量の比が0.8~1.2である水性二液型中塗り塗料組成物であることを特徴とする請求項1~請求項6のいずれか1項に記載の複層塗膜形成方法。
- 前記ベース塗料組成物が、水酸基価20~40mgKOH/g、酸価20~40mgKOH/gであるアクリルウレタン樹脂を樹脂固形分中20~60質量%含有する水性ベース塗料組成物であることを特徴とする請求項1~請求項7のいずれか1項に記載の複層塗膜形成方法。
- 前記加熱硬化の焼付温度が75~100℃であることを特徴とする請求項1~請求項8のいずれか1項に記載の複層塗膜形成方法。
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