JP4443276B2 - 塗膜形成方法 - Google Patents
塗膜形成方法 Download PDFInfo
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- JP4443276B2 JP4443276B2 JP2004087678A JP2004087678A JP4443276B2 JP 4443276 B2 JP4443276 B2 JP 4443276B2 JP 2004087678 A JP2004087678 A JP 2004087678A JP 2004087678 A JP2004087678 A JP 2004087678A JP 4443276 B2 JP4443276 B2 JP 4443276B2
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- meth
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- monomer
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- 238000000576 coating method Methods 0.000 title claims description 49
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 77
- 239000003973 paint Substances 0.000 claims description 72
- 239000000178 monomer Substances 0.000 claims description 57
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 54
- 150000001875 compounds Chemical class 0.000 claims description 50
- 239000011248 coating agent Substances 0.000 claims description 45
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- 229920000178 Acrylic resin Polymers 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 39
- -1 2-hydroxypropyl Chemical group 0.000 claims description 32
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- 125000003700 epoxy group Chemical group 0.000 claims description 21
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 17
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 14
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- 239000002253 acid Substances 0.000 claims description 11
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
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- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
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- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 claims description 4
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 6
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- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 4
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- 238000010422 painting Methods 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 229920001225 polyester resin Polymers 0.000 description 4
- 239000004645 polyester resin Substances 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
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- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- ZHHKVLCBIBQGKO-UHFFFAOYSA-H naphthol green B Chemical compound [Na+].[Na+].[Na+].[Fe+3].[O-]S(=O)(=O)C1=CC=C2C(=N[O-])C(=O)C=CC2=C1.[O-]S(=O)(=O)C1=CC=C2C(=N[O-])C(=O)C=CC2=C1.[O-]S(=O)(=O)C1=CC=C2C(=N[O-])C(=O)C=CC2=C1 ZHHKVLCBIBQGKO-UHFFFAOYSA-H 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- PFENPVAFZTUOOM-UHFFFAOYSA-N phenyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OC1=CC=CC=C1 PFENPVAFZTUOOM-UHFFFAOYSA-N 0.000 description 1
- 239000012994 photoredox catalyst Substances 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- GVIIRWAJDFKJMJ-UHFFFAOYSA-N propan-2-yl 3-oxobutanoate Chemical compound CC(C)OC(=O)CC(C)=O GVIIRWAJDFKJMJ-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- DHGFMVMDBNLMKT-UHFFFAOYSA-N propyl 3-oxobutanoate Chemical compound CCCOC(=O)CC(C)=O DHGFMVMDBNLMKT-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 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 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
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- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- NQISDOIAJWWPGA-UHFFFAOYSA-N triethyl(3-hydroxypropyl)azanium Chemical compound CC[N+](CC)(CC)CCCO NQISDOIAJWWPGA-UHFFFAOYSA-N 0.000 description 1
- GZBUMTPCIKCWFW-UHFFFAOYSA-N triethylcholine Chemical compound CC[N+](CC)(CC)CCO GZBUMTPCIKCWFW-UHFFFAOYSA-N 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
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- JBCJMTUHAXHILC-UHFFFAOYSA-N zinc;octanoic acid Chemical compound [Zn+2].CCCCCCCC(O)=O JBCJMTUHAXHILC-UHFFFAOYSA-N 0.000 description 1
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Description
以下、本発明の方法についてさらに詳細に説明する。
本発明の方法が適用対象とする被塗物は、自動車用のドアミラー、ホイルキャップ、ドアハンドル、エアロパーツなどに用いられている、アクリロニトリルブタジエンスチレン樹脂(ABS樹脂)やポリカーボネート樹脂(PC樹脂)などの硬質樹脂製の部品である。
着色ベース塗料
着色ベース塗料は、クリヤ塗料に先立って、硬質樹脂製部品上に塗装される塗料であり、硬質樹脂に対する付着性が良好なそれ自体既知の着色ベース塗料を使用することができる。具体的には、例えば、水酸基価が40〜120のポリエステルポリオールと、ヒドロキシ化合物で変性したイソシアヌレート型ポリイソシアネートをマロン酸ジアルキルエステル及びアセト酢酸エステルでブロックした脂肪族及び/又は脂環式ブロックポリイソシアネートとを含んでなる1液型の着色ベース塗料を使用することができる。
クリヤ塗料
本発明の方法に従い着色ベース塗料の塗装面に適用されるクリヤ塗料は、水酸基含有アクリル樹脂(A)及び硬化剤(B)を必須成分とし、且つさらに好ましくは、オリゴマー(C)を含んでなるものである。以下、これらの成分についてさらに詳しく説明する。
水酸基含有アクリル樹脂(A):
水酸基含有アクリル樹脂(A)は、
(a)4−ヒドロキシブチル(メタ)アクリレートモノマー、及びヒドロキシアルキル(メタ)アクリレートにε−カプロラクトンを開環重合させることにより得られるε−カプロラクトン変性ビニルモノマーより選ばれる1級水酸基含有モノマー 8〜30重量%、
(b)2級水酸基含有モノマー 10〜40重量%、及び
(c)その他の重合性不飽和モノマー 30〜82重量%
をラジカル共重合することにより得られる水酸基価が80〜160mgKOH/gのアクリル樹脂である。
CH2=C(R1)−COO−R2−O(COC5H10O)nH (I)
式中、
R1は水素原子又はメチル基であり、
R2は炭素数2〜6,特に2もしくは3のアルキレン基であり、
nは1〜10、好ましくは1〜5の整数である、
で示されるものが包含され、中でも特に、上記式(I)において、R1が水素原子であり、R2がエチレン基であるものが好適である。そのようなε−カプロラクトン変性ビニルモノマーはそれ自体既知のものであり、市販品として、例えば、「プラクセルFA−1」、「プラクセルFA−2」、「プラクセルFA−3」、「プラクセルFA−4」、「プラクセルFA−5」、「プラクセルFM−1」、「プラクセルFM−2」、「プラクセルFM−3」、「プラクセルFM−4」、「プラクセルFM−5」(以上、いずれもダイセル化学(株)製、商品名)などをあげることができる。
15〜20重量%、
モノマー(b):10〜40重量%、好ましくは15〜35重量%、さらに好ましくは
20〜30重量%、
モノマー(c):30〜82重量%、好ましくは40〜75重量%、さらに好ましくは
50〜65重量%。
本発明においてクリヤ塗料に使用される硬化剤(B)は、以上に述べた水酸基含有アクリル樹脂(A)中の水酸基と反応して該アクリル樹脂(A)を硬化させることができるものであり、好適には、ポリイソシアネート化合物を使用することができる。
本発明に従い前述の着色ベース塗料の塗膜上に適用されるクリヤ塗料は、以上に述べた水酸基含有アクリル樹脂(A)と硬化剤(B)を含んでなるものであり、アクリル樹脂(A)と硬化剤(B)の配合比率は、これら両成分の合計固形分を基準にして、アクリル樹脂(A)は60〜90重量%、好ましくは65〜85重量%、さらに好ましくは70〜80重量%の範囲内、そして硬化剤(B)は10〜40重量%、好ましくは15〜35重量%、さらに好ましくは20〜30重量%の範囲内とすることができる。
製造例1:アクリル樹脂No.1の製造
攪拌器、冷却器、温度制御装置、窒素導入管及び滴下ロートを備えた反応装置に有機溶剤45部を仕込み、反応容器内を窒素で置換し、加熱攪拌して容器内が130℃に達したら、下記組成のモノマー混合物を3時間かけて滴下した。
ε−カプロラクトン変性ビニルモノマー 15部
2−ヒドロキシプロピルアクリレート 5部
2−ヒドロキシプロピルメタアクリレート 15部
スチレン 25部
メチルメタアクリレート 10部
イソブチルメタアクリレート 18部
n−ブチルアクリレート 5部
アクリル酸 2部
ジ−tert−ブチルハイドロパーオキサイド 8部
滴下終了後、130℃で30分間熟成し、酸価16mgKOH/g、水酸基価122mgKOH/g、重量平均分子量12,000及び固形分60%のアクリル樹脂No.1を得た。
表1に示す組成のモノマー混合物を使用する以外は、製造例1と同様にして、アクリル樹脂No.2〜No.7を得た。
製造例8:オリゴマーNo.1の製造
攪拌器、冷却器、温度制御器、窒素導入管及び滴下ロートを備えた反応装置にジメチロールブタン酸296部を仕込み、反応容器内を窒素で置換し、120℃に加熱した。それに「カージュラE10」490部を2時間かけて滴下し、120℃の温度を保持し、酸価が9以下になった時点で反応を終了させた。得られたオリゴマーNo.1は、固形分98%、ガードナー粘度(20℃)Z6Z7、水酸基価428mgKOH/g、数平均分子量600、重量平均分子量610であった。
実施例1:クリヤ塗料No.1の製造
アクリル樹脂No.1 60部(固形分)及びデスモジュールN3300(注2)40部(固形分)及びオリゴマーNo.1 10部を混合し、粘度をフォードカップ#4/20℃で50秒に調整してクリヤ塗料No.1を得た。
実施例2及び3:クリヤ塗料No.2〜3の製造
表2に示す配合内容とする以外は、実施例1と同様にして、クリヤ塗料No.2および3を得た。
比較例1〜4:クリヤ塗料No.4〜7の製造
表2に示す配合内容とする以外は、実施例1と同様にして、クリヤ塗料No.4〜7を得た。
試験板の作製:
脱脂したABS樹脂の平板(70×150×3mm)の上に、ソフレックス
#400(関西ペイント社製、商品名、メタリックベース塗料)を15μmの膜厚で塗装し、7分間室温にてセッテングを行った。次に、クリヤ塗料No.1〜No.7を塗装し、70℃−20分間の条件下に焼き付け硬化を行い、試験板No.1〜No.7を得た。
試験は下記の条件下に行った。その結果を表3に示す。
×:塗膜異常がみられる。
(注4)ゲル分率:クリヤ塗料No.1〜No.7を膜厚が40μmになるように塗装し、70℃−20分間焼き付けした。次に、アマルガム法を用いて塗膜を剥離し、一定の大きさ(5×5cm)にカットした後、塗膜の重量(W1)を測定した。次に、有機溶剤(アセトン)に24時間(20℃)浸漬した後、風乾し、溶剤抽出後の塗膜重量(W2)を測定した。ゲル分率(%)を以下の式に従って求めた。
(注5)塗膜の鉛筆硬度:着色ベース塗料及び各クリヤ塗料を塗装した試験板について、JIS K 5400 8.4.2に記載の方法に従い鉛筆硬度を測定した。
(注6)塗膜のタック性:表面のタックの度合いを指触で評価した。
△:わずかにタックがあるが、指紋の跡は付かない
×:タックがあり、指紋の跡がつく。
(注7)付着性:JIS K 5400 8.5.2に記載の方法に従い1mm×1mmのゴバン目テープ付着試験を行った。
△:一部剥離あり
×:全面に剥離あり。
(注8)仕上がり性:目視により下記の基準で評価した。
△:ラウンド感や光沢のムラがある
×:ラウンド感や肌荒れが著しい。
Claims (16)
- 硬質樹脂製部品上に、着色ベ−ス塗料、次いでクリヤ塗料を塗装し、両塗膜を硬化させることからなる塗膜形成方法において、クリヤ塗料として、
(a)4−ヒドロキシブチル(メタ)アクリレートモノマー、及びヒドロキシアルキル(メタ)アクリレートにε−カプロラクトンを開環重合させることにより得られるε−カプロラクトン変性ビニルモノマーより選ばれる1級水酸基含有モノマー 8〜30重量%、(b)2級水酸基含有モノマー 10〜40重量%及び(c)その他の重合性不飽和モノマー 30〜82重量%をラジカル共重合することにより得られる、水酸基価が80〜160mgKOH/gであり且つ重量平均分子量が5,000〜20,000の範囲内にある水酸基含有アクリル樹脂(A)、
硬化剤(B)、ならびに
カルボキシル基含有化合物のカルボキシル基とエポキシ基含有化合物のエポキシ基との間の開環エステル化反応生成物であって、少なくとも該開環エステル化反応により生成する水酸基を有する、水酸基価が200〜800mgKOH/gの範囲内にあり且つ重量平均分子量が1,000以下である水酸基含有オリゴマー(C)
を、アクリル樹脂(A)と硬化剤(B)との合計固形分を基準にして、アクリル樹脂(A)を60〜90重量%、硬化剤(B)を10〜40重量%、及び水酸基含有オリゴマー(C)を1〜20重量%の割合で含んでなるクリヤ塗料を使用することを特徴とする塗膜形成方法。 - 着色ベ−ス塗料が、水酸基価が40〜120のポリエステルポリオールと、ヒドロキシ化合物で変性したイソシアヌレート型ポリイソシアネートをマロン酸ジアルキルエステル及びアセト酢酸エステルでブロックした脂肪族及び/又は脂環式ブロックポリイソシアネートとを含んでなる1液型の着色ベース塗料である請求項1に記載の方法。
- 水酸基含有アクリル樹脂(A)が100〜140mgKOH/gの範囲内の水酸基価を有する請求項1又は2に記載の方法。
- 水酸基含有アクリル樹脂(A)が0〜40mgKOH/gの範囲内の酸価を有する請求項1〜3のいずれかに記載の方法。
- ε−カプロラクトン変性ビニルモノマーが下記式(I)
CH2=C(R1)−COO−R2−O(COC5H10O)nH (I)
式中、
R1は水素原子又はメチル基であり、
R2は炭素数2〜6のアルキレン基であり、
nは1〜10の整数である、
で示されるものである請求項1〜4のいずれかに記載の方法。 - R1が水素原子であり、R2がエチレン基である請求項5に記載の方法。
- 2級水酸基含有モノマー(b)が2−ヒドロキシプロピル(メタ)アクリレート、2−ヒドロキシブチル(メタ)アクリレート、3−ヒドロキシブチル(メタ)アクリレート、及び(メタ)アクリル酸とエポキシ基含有化合物の付加物よりなる群から選ばれる請求項1〜6のいずれかに記載の方法。
- 2級水酸基含有モノマー(b)が2−ヒドロキシプロピル(メタ)アクリレートである請求項1〜7のいずれかに記載の方法。
- その他の重合性不飽和モノマー(c)がスチレン、(メタ)アクリル酸のアルキルエステル及び(メタ)アクリル酸よりなる群から選ばれる請求項1〜8のいずれかに記載の方法。
- 水酸基含有アクリル樹脂(A)がモノマー(a)10〜25重量%、モノマー(b)15〜35重量%およびモノマー(c)40〜75重量%をラジカル共重合することにより得られるものである請求項1〜9のいずれかに記載の方法。
- 硬化剤(B)がブロック化されていてもよいポリイソシアネート化合物である請求項1〜10のいずれかに記載の方法。
- クリヤ塗料が、アクリル樹脂(A)及び硬化剤(B)を、両者の合計固形分を基準にして、アクリル樹脂(A)65〜85重量%及び硬化剤(B)15〜35重量%の割合で含んでなる請求項1〜11のいずれかに記載の方法。
- 着色ベ−ス塗料及びクリヤ塗料の両塗膜の硬化を2コート1ベーク方式又は2コート2ベーク方式によって行う請求項1〜12のいずれかに記載の方法。
- 硬化を60〜70℃の温度で行う請求項1〜13のいずれかに記載の方法。
- (a)4−ヒドロキシブチル(メタ)アクリレートモノマー、及びヒドロキシアルキル(メタ)アクリレートにε−カプロラクトンを開環重合させることにより得られるε−カプロラクトン変性ビニルモノマーより選ばれる1級水酸基含有モノマー 8〜30重量%、(b)2級水酸基含有モノマー 10〜40重量%及び(c)その他の重合性不飽和モノマー 30〜82重量%をラジカル共重合することにより得られる水酸基価が80〜160mgKOH/gの水酸基含有アクリル樹脂(A)、硬化剤(B)、ならびにカルボキシル基含有化合物のカルボキシル基とエポキシ基含有化合物のエポキシ基との間の開環エステル化反応生成物であって、少なくとも該開環エステル化反応により生成する水酸基を有する、水酸基価が200〜800mgKOH/gの範囲内にあり且つ重量平均分子量が1,000以下である水酸基含有オリゴマー(C)を、アクリル樹脂(A)と硬化剤(B)との合計固形分を基準にして、アクリル樹脂(A)を60〜90重量%、硬化剤(B)を10〜40重量%、及び水酸基含有オリゴマー(C)を1〜20重量%の割合で含んでなるクリヤ塗料。
- 請求項1〜14のいずれかに記載の方法によって得られる塗装物品。
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JP4296178B2 (ja) * | 2003-12-08 | 2009-07-15 | ナトコ株式会社 | 塗料組成物及びそれを塗工してなる塗装物 |
JP4872247B2 (ja) | 2005-06-16 | 2012-02-08 | Basfコーティングスジャパン株式会社 | 熱硬化性塗料組成物 |
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