JP4408924B2 - Composition for UV-curable cationic electrodeposition coating and coating film thereof - Google Patents
Composition for UV-curable cationic electrodeposition coating and coating film thereof Download PDFInfo
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- JP4408924B2 JP4408924B2 JP2007248430A JP2007248430A JP4408924B2 JP 4408924 B2 JP4408924 B2 JP 4408924B2 JP 2007248430 A JP2007248430 A JP 2007248430A JP 2007248430 A JP2007248430 A JP 2007248430A JP 4408924 B2 JP4408924 B2 JP 4408924B2
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- 238000004070 electrodeposition Methods 0.000 title claims description 62
- 238000000576 coating method Methods 0.000 title claims description 54
- 239000011248 coating agent Substances 0.000 title claims description 49
- 125000002091 cationic group Chemical group 0.000 title claims description 16
- 239000000203 mixture Substances 0.000 title description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 229920006163 vinyl copolymer Polymers 0.000 claims description 29
- 239000003999 initiator Substances 0.000 claims description 27
- PCKZAVNWRLEHIP-UHFFFAOYSA-N 2-hydroxy-1-[4-[[4-(2-hydroxy-2-methylpropanoyl)phenyl]methyl]phenyl]-2-methylpropan-1-one Chemical compound C1=CC(C(=O)C(C)(O)C)=CC=C1CC1=CC=C(C(=O)C(C)(C)O)C=C1 PCKZAVNWRLEHIP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 17
- 238000010521 absorption reaction Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 229920002554 vinyl polymer Polymers 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 14
- 239000012986 chain transfer agent Substances 0.000 claims description 9
- 238000003776 cleavage reaction Methods 0.000 claims description 8
- 239000008199 coating composition Substances 0.000 claims description 8
- 125000004103 aminoalkyl group Chemical group 0.000 claims description 7
- 238000004090 dissolution Methods 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- ZOKCNEIWFQCSCM-UHFFFAOYSA-N (2-methyl-4-phenylpent-4-en-2-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(C)CC(=C)C1=CC=CC=C1 ZOKCNEIWFQCSCM-UHFFFAOYSA-N 0.000 claims description 6
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 claims description 5
- JZKPKNSYAHAKJY-UHFFFAOYSA-N 1-[4-(4-benzoylphenyl)sulfanylphenyl]-2-methyl-2-(4-methylphenyl)sulfonylpropan-1-one Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C)(C)C(=O)C(C=C1)=CC=C1SC1=CC=C(C(=O)C=2C=CC=CC=2)C=C1 JZKPKNSYAHAKJY-UHFFFAOYSA-N 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
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- 239000003973 paint Substances 0.000 description 24
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- 239000000126 substance Substances 0.000 description 17
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- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 15
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- 239000002585 base Substances 0.000 description 10
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
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- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- -1 methacryloyl ester Chemical class 0.000 description 6
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- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
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- 239000003795 chemical substances by application Substances 0.000 description 4
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- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical compound CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004264 Petrolatum Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 2
- 125000003282 alkyl amino group Chemical group 0.000 description 2
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- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
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- RWXMAAYKJDQVTF-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl prop-2-enoate Chemical compound OCCOCCOC(=O)C=C RWXMAAYKJDQVTF-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
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- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
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- 238000007796 conventional method Methods 0.000 description 1
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- CQAZHDHHROTUHL-UHFFFAOYSA-N cyclohexane;methanol;prop-2-enoic acid Chemical compound OC.OC.OC(=O)C=C.C1CCCCC1 CQAZHDHHROTUHL-UHFFFAOYSA-N 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
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- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- VPASWAQPISSKJP-UHFFFAOYSA-N ethyl prop-2-enoate;isocyanic acid Chemical compound N=C=O.CCOC(=O)C=C VPASWAQPISSKJP-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- MDNFYIAABKQDML-UHFFFAOYSA-N heptyl 2-methylprop-2-enoate Chemical compound CCCCCCCOC(=O)C(C)=C MDNFYIAABKQDML-UHFFFAOYSA-N 0.000 description 1
- SCFQUKBBGYTJNC-UHFFFAOYSA-N heptyl prop-2-enoate Chemical compound CCCCCCCOC(=O)C=C SCFQUKBBGYTJNC-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- KCTMTGOHHMRJHZ-UHFFFAOYSA-N n-(2-methylpropoxymethyl)prop-2-enamide Chemical compound CC(C)COCNC(=O)C=C KCTMTGOHHMRJHZ-UHFFFAOYSA-N 0.000 description 1
- ADGJZVKOKVENDN-UHFFFAOYSA-N n-(butoxymethyl)-2-methylprop-2-enamide Chemical compound CCCCOCNC(=O)C(C)=C ADGJZVKOKVENDN-UHFFFAOYSA-N 0.000 description 1
- UTSYWKJYFPPRAP-UHFFFAOYSA-N n-(butoxymethyl)prop-2-enamide Chemical compound CCCCOCNC(=O)C=C UTSYWKJYFPPRAP-UHFFFAOYSA-N 0.000 description 1
- YGRMNBNGHHDGCX-UHFFFAOYSA-N n-(ethoxymethyl)-2-methylprop-2-enamide Chemical compound CCOCNC(=O)C(C)=C YGRMNBNGHHDGCX-UHFFFAOYSA-N 0.000 description 1
- LSWADWIFYOAQRZ-UHFFFAOYSA-N n-(ethoxymethyl)prop-2-enamide Chemical compound CCOCNC(=O)C=C LSWADWIFYOAQRZ-UHFFFAOYSA-N 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- YOZHLACIXDCHPV-UHFFFAOYSA-N n-(methoxymethyl)-2-methylprop-2-enamide Chemical compound COCNC(=O)C(C)=C YOZHLACIXDCHPV-UHFFFAOYSA-N 0.000 description 1
- ULYOZOPEFCQZHH-UHFFFAOYSA-N n-(methoxymethyl)prop-2-enamide Chemical compound COCNC(=O)C=C ULYOZOPEFCQZHH-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000002088 tosyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])S(*)(=O)=O 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Description
本発明は、液経時安定性が良好で、高感度であり、熱に弱いメッキ基材に対し、良好な表面硬化性、付着性、耐食性、耐候性、耐薬品性を付与する紫外線硬化型カチオン電着塗料用組成物、及び、それを用いて得られる塗膜に関するものである。 The present invention is a UV curable cation that provides good surface hardening, adhesion, corrosion resistance, weather resistance, and chemical resistance to a plating base material that has good liquid aging stability, high sensitivity, and heat resistance. The present invention relates to an electrodeposition coating composition and a coating film obtained by using the composition.
近年、クロムメッキは、６価クロムの規制により、３価クロムによるクロムメッキが検討されている。しかし、３価クロムにより作製したクロムメッキの耐食性は、６価クロムにより作製したものより劣るため、塗装による耐食性の改善が求められており、耐食性、及び、塗装効率が良好である電着塗装への要望が高まっている。
しかし、一般的なメッキ上の電着塗料は熱硬化型であるため、熱変形に弱いプラスチックメッキや熱変色しやすい銀メッキ等の上には使用できなかった。
そこで、その対策として熱硬化型ではなく紫外線硬化型電着塗料が考えられ、その提案は古くからなされてきている（特許文献１〜６）。
In recent years, chromium plating with trivalent chromium has been studied in accordance with the regulation of hexavalent chromium. However, since the corrosion resistance of chromium plating produced with trivalent chromium is inferior to that produced with hexavalent chromium, there is a need for improved corrosion resistance by painting. Toward electrodeposition coating with good corrosion resistance and painting efficiency The demand is growing.
However, since the general electrodeposition paint on plating is a thermosetting type, it could not be used on plastic plating which is vulnerable to thermal deformation or silver plating which is easily subject to thermal discoloration.
Therefore, as a countermeasure, an ultraviolet curable electrodeposition paint is considered instead of a thermosetting type, and the proposal has been made for a long time (Patent Documents 1 to 6).
水溶性又は水分散性の重合性不飽和樹脂を含む成分と非水溶性光重合開始剤を主成分としてからなるアニオン電着性光硬化性組成物が提案されている（特許文献１）。これらの組成物は、光硬化性組成物を複雑な形状の被塗物に均一に塗布する効果はあるが、アニオン型であるので電着時に被塗物の溶出が起こり、メッキ素材の変色を起こすため、基材が限定される問題があった。
カチオン型としては、水溶性又は水分散性樹脂のバインダーの一部にエポキシ化ポリブタジエンを使用した紫外線硬化型カチオン電着性組成物が提案されている（特許文献２）。これらの組成物では、塗膜の黄変が起こるため意匠性が要求される用途に使用はできない。
An anionic electrodepositable photocurable composition comprising a component containing a water-soluble or water-dispersible polymerizable unsaturated resin and a water-insoluble photopolymerization initiator as main components has been proposed (Patent Document 1). These compositions have the effect of uniformly applying a photocurable composition to a complex-shaped object to be coated, but because of the anion type, the object to be coated is eluted during electrodeposition, and the plating material is discolored. This causes a problem that the base material is limited.
As the cationic type, an ultraviolet curable cationic electrodepositable composition using epoxidized polybutadiene as a part of a binder of a water-soluble or water-dispersible resin has been proposed (Patent Document 2). These compositions cannot be used for applications requiring design properties because yellowing of the coating occurs.
紫外線硬化電着塗料として、電着フォトレジスト、例えば、カチオン性の水溶性又は水分散性の（メタ）アクリル樹脂、多官能（メタ）アクリル樹脂、光重合開始剤等からなる組成物が提案されている（例えば特許文献３）。これらの電着フォトレジストは、エッチング、めっきマスク、プリント配線板の微細加工用途に使用されており、最終的な塗膜としては残存しない。そのため組成物をメッキ素材上に適用しようとした場合、紫外線照射時の硬化塗膜性能として基材への密着性や耐候性に劣り、また、経時での塗膜黄変、剥離が発生するため耐食性の要求されるメッキ素材上には使用できない。 As an ultraviolet curable electrodeposition coating composition, an electrodeposition photoresist, for example, a composition comprising a cationic water-soluble or water-dispersible (meth) acrylic resin, a polyfunctional (meth) acrylic resin, a photopolymerization initiator, etc. has been proposed. (For example, Patent Document 3). These electrodeposition photoresists are used for fine processing of etching, plating masks, and printed wiring boards, and do not remain as final coatings. Therefore, when trying to apply the composition on a plating material, the cured coating film performance at the time of ultraviolet irradiation is inferior in adhesion to the substrate and weather resistance, and the coating film yellows and peels over time. It cannot be used on plating materials that require corrosion resistance.
メッキ素材用にカチオン電着性を有する平均分子量２０００〜３００００の樹脂と分子中に３個以上のアクリロイル基を有する多官能アクリレートを使用する方法（特許文献４）が開示されている。しかしながら、これらの組成物では、所定の性能を得るのに非常に多くの光照射量が必要であり、そのためメッキ基材が紫外線硬化ランプ光源から発せられる赤外光を吸収し、ＡＢＳ樹脂のような耐熱温度の低い基材では熱変形を起こすという問題があった。 A method using a resin having an average molecular weight of 2000 to 30000 having cationic electrodeposition for a plating material and a polyfunctional acrylate having three or more acryloyl groups in the molecule is disclosed (Patent Document 4). However, in these compositions, a very large amount of light irradiation is required to obtain a predetermined performance. Therefore, the plating base material absorbs infrared light emitted from an ultraviolet curing lamp light source, and it is like ABS resin. There is a problem that a base material having a low heat-resistant temperature causes thermal deformation.
上記組成物で耐熱性の低いメッキ基材を熱変形させないためには、高感度化（光照射量を下げる）が必要であるが、光重合開始剤として、アルコール系溶剤が存在すると水層に移行しやすいものを使用しているため、光重合開始剤の量を必要以上に増やさないといけなく、光重合開始剤を増やすと基材との密着性低下や、塗膜中に残存して塗膜の経時劣化を促進する原因となるため問題があった。
また、電着塗料は、通常のスプレー塗料のごとく使い切りではなく、使用した塗料固形分を補給して使用するために経時安定性が特に重要であるが、これらの組成物では硬化剤
の加水分解が起こるため経時安定性が悪く、電着塗料液を定期的に全量更新することが必要であった。
In order to prevent thermal deformation of a plating base material having low heat resistance with the above composition, it is necessary to increase sensitivity (reduce the amount of light irradiation), but in the presence of an alcohol solvent as a photopolymerization initiator, Because it is easy to migrate, the amount of photopolymerization initiator must be increased more than necessary, and if the photopolymerization initiator is increased, the adhesion to the substrate will be reduced and it will remain in the coating film. There is a problem because it causes the deterioration of the coating film over time.
In addition, electrodeposition paints are not used up like normal spray paints, but stability over time is particularly important for replenishing the used paint solids. However, in these compositions, hydrolysis of the curing agent is important. Therefore, the stability over time was poor, and it was necessary to periodically update the entire amount of the electrodeposition coating liquid.
水層への光重合開始剤の移行性を改良する方法として、水酸基を有する光重合開始剤、水酸基を有するメタアクリロイルエステル、及び、アルカノールアミンとトリイソシアネートの反応物からなる、水分散性光重合開始剤を使用する方法（特許文献５）も考えられるが、水分散性光重合開始剤自体がカチオン電着性を有するので、基体樹脂との電着析出性に差異が生じるため、安定した塗膜性能が得がたく、水分散性光重合開始剤の合成も煩雑である。 Water dispersible photopolymerization comprising a photopolymerization initiator having a hydroxyl group, a methacryloyl ester having a hydroxyl group, and a reaction product of alkanolamine and triisocyanate as a method for improving the migration of the photopolymerization initiator to the aqueous layer A method using an initiator (Patent Document 5) is also conceivable. However, since the water-dispersible photopolymerization initiator itself has cationic electrodeposition, a difference in electrodeposition with the base resin occurs, so that stable coating is possible. The film performance is difficult to obtain, and the synthesis of the water-dispersible photopolymerization initiator is complicated.
また感度を上げる方法として、側鎖に不飽和結合を導入する方法が提案されている（特許文献６）。この方法では、一分子中に不飽和結合と水酸基を有する化合物とジイソシアネートの反応から合成された一分子中に不飽和基とイソシアネート基を有する化合物に基体樹脂の水酸基を反応させるが、反応工程が複雑であり、また、イソシアネートエチルアクリレートのごとき一分子中に不飽和基とイソシアネート基を有する化合物を使用しても良いが、製造コストが上昇し、電着塗料として使用する場合は、側鎖の不飽和基が硬化剤と反応して凝集物を生じ、塗料の経時安定性が良好でなかった。
以上のようにプラスチックメッキ素材上の紫外線硬化型カチオン電着塗料として、液経時安定性が良好であり、且つ、高感度で十分な塗膜性能を満たすものはこれまで得られていなかった。
As a method for increasing sensitivity, a method of introducing an unsaturated bond into a side chain has been proposed (Patent Document 6). In this method, the hydroxyl group of the base resin is reacted with a compound having an unsaturated group and an isocyanate group in one molecule synthesized from the reaction of a compound having an unsaturated bond and a hydroxyl group in one molecule and a diisocyanate. It may be complicated, and a compound having an unsaturated group and an isocyanate group in one molecule such as isocyanate ethyl acrylate may be used. However, when the production cost is increased and it is used as an electrodeposition coating, The unsaturated group reacted with the curing agent to form an aggregate, and the aging stability of the paint was not good.
As described above, no UV-curable cationic electrodeposition coating on a plastic plating material has been obtained so far that has good liquid-time stability and high sensitivity and sufficient coating performance.
本発明は、前記したような従来技術における問題を解決し、液経時安定性が良好であり、高感度で、且つ、表面硬化性、付着性、耐食性、耐候性、耐薬品性が良好な紫外線硬化型カチオン電着塗料用組成物を提供することを目的とする。 The present invention solves the problems in the prior art as described above, has good liquid aging stability, high sensitivity, and has excellent surface curability, adhesion, corrosion resistance, weather resistance, and chemical resistance. It is an object of the present invention to provide a curable cationic electrodeposition coating composition.
上記課題を解決するために、本願発明者らは、特定の水溶性又は水分散性ビニル系共重合体、一分子中に３個以上の不飽和基を有する化合物、さらに、特定の光重合開始剤を含有することを特徴とする紫外線硬化型カチオン電着塗料用組成物を用いて、電着塗装を行なうことで克服できることを見出し、本願発明にいたった。
すなわち本発明は、
（Ａ） 以下の（ａ）〜（ｃ）成分を用いて共重合することにより得られる、一部の主鎖末端に不飽和基を有する水溶性又は水分散性ビニル系共重合体 ５０〜８０重量部、
（ａ）置換基として３級アミノアルキル基を有する共重合性ビニル系単量体 ４〜１５重量部
（ｂ）（ａ）以外の共重合性ビニル系単量体 ８５〜９６重量部
（ｃ）付加開裂型連鎖移動剤 共重合性ビニル系単量体（ａ）と（ｂ）の合計１００重量部に対し、０．０５〜２０重量部
（Ｂ） 一分子中に３個以上の不飽和基を有する化合物 ２０〜５０重量部、
（Ｃ） アルコール系溶剤を３％含む水１００ｇに対する２５℃での溶解量が０．０２ｇ未満、且つ、２００ｎｍ〜４００ｎｍにおける極大吸収のモル吸光係数εが１０，０００
Ｌ／ｍｏｌ・ｃｍ以上である光重合開始剤 （Ａ）と（Ｂ）の合計１００重量部に対して、０．１〜８重量部
を含有することを特徴とする紫外線硬化型カチオン電着塗料用組成物、を要旨とするものである。
In order to solve the above-mentioned problems, the present inventors have developed a specific water-soluble or water-dispersible vinyl copolymer, a compound having three or more unsaturated groups in one molecule, and a specific photopolymerization start. It has been found that this can be overcome by performing electrodeposition coating using a composition for ultraviolet curable cationic electrodeposition coatings characterized by containing an agent.
That is, the present invention
(A) A water-soluble or water-dispersible vinyl copolymer having an unsaturated group at the end of the main chain, obtained by copolymerization using the following components (a) to (c): 50 to 80 Parts by weight,
(A) Copolymerizable vinyl monomer having a tertiary aminoalkyl group as a substituent 4 to 15 parts by weight (b) Copolymerizable vinyl monomer other than (a) 85 to 96 parts by weight (c) Addition-cleavage type chain transfer agent 0.05 to 20 parts by weight (B) 3 or more unsaturated groups per molecule with respect to 100 parts by weight of the total copolymerizable vinyl monomers (a) and (b) 20 to 50 parts by weight of a compound having
(C) The amount of dissolution at 25 ° C. in 100 g of water containing 3% of an alcohol solvent is less than 0.02 g, and the molar absorption coefficient ε of the maximum absorption at 200 nm to 400 nm is 10,000.
An ultraviolet curable cationic electrodeposition coating composition containing 0.1 to 8 parts by weight with respect to a total of 100 parts by weight of the photopolymerization initiator (A) and (B) which is L / mol · cm or more. The gist of the composition.
本発明は以上説明したように構成されているから、本発明の紫外線硬化型カチオン電着塗料用組成物を使用することで照射光量が低くなるためプラスチックメッキ基材の変形がなく、経時で安定した塗膜性能が得られ、また、当該電着塗料用組成物を用いて形成された電着塗膜は、良好な表面硬化性、付着性、耐食性、耐候性、耐薬品性を有しており、産業上極めて有用である。 Since the present invention is configured as described above, the amount of irradiation light is reduced by using the composition for ultraviolet curable cationic electrodeposition coating of the present invention, so the plastic plating base material is not deformed and stable over time. The electrodeposition coating film formed using the electrodeposition coating composition has good surface curability, adhesion, corrosion resistance, weather resistance, and chemical resistance. It is extremely useful in industry.
本発明の構成と作用を説明する。本発明においては、一部の主鎖末端に不飽和基を有する水溶性又は水分散性ビニル系共重合体（Ａ）、一分子中に３個以上の不飽和基を有する化合物（Ｂ）、アルコール系溶剤を３％含む水１００ｇに対する２５℃での溶解量が０．０２ｇ未満、且つ、２００ｎｍ〜４００ｎｍにおける極大吸収のモル吸光係数εが１０，０００Ｌ／ｍｏｌ・ｃｍ以上である光重合開始剤（Ｃ）の各成分は、紫外線硬化型カチオン電着塗料用組成物を得るための必須構成成分である。 The configuration and operation of the present invention will be described. In the present invention, a water-soluble or water-dispersible vinyl copolymer (A) having an unsaturated group at a part of the main chain terminal, a compound (B) having three or more unsaturated groups in one molecule, Photopolymerization initiator having a dissolution amount at 25 ° C. of less than 0.02 g in 100 g of water containing 3% of an alcohol solvent and a molar absorption coefficient ε of maximum absorption at 200 nm to 400 nm of 10,000 L / mol · cm or more. Each component of (C) is an essential component for obtaining a composition for an ultraviolet curable cationic electrodeposition coating.
（Ａ）成分の水溶性又は水分散性のビニル系共重合体を構成する、置換基として３級アミノアルキル基を有する共重合性ビニル系単量体（ａ）としては、ジメチルアミノエチルアクリレート、ジメチルアミノエチルメタクリレート、ジエチルアミノエチルアクリレート、ジエチルアミノエチルメタクリレート、ジメチルアミノプロピルアクリルアミド等のアクリル系カチオン電着塗料に一般的に使用されるものを用いられるがこれらに限定されない。なかでもジエチルアミノエチルアクリレート、ジエチルアミノエチルメタクリレートを用いるのが望ましい。 As the copolymerizable vinyl monomer (a) having a tertiary aminoalkyl group as a substituent constituting the water-soluble or water-dispersible vinyl copolymer of the component (A), dimethylaminoethyl acrylate, Although what is generally used for acrylic cationic electrodeposition paints, such as dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylamide, etc. is used, it is not limited to these. Of these, it is desirable to use diethylaminoethyl acrylate or diethylaminoethyl methacrylate.
また本発明において置換基としてアミノアルキル基を有する共重合性ビニル系単量体は、これまでのアクリルカチオン電着における水分散性や電気泳動性の効果だけでなく、置換基のアミノアルキル基に紫外線硬化時の酸素による硬化障害の原因となるパーオキシラジカルが連鎖移動することで、パーオキシラジカルを失活させ、且つ、重合開始する効果があり、塗膜表面の硬化性を向上させる。 In the present invention, the copolymerizable vinyl monomer having an aminoalkyl group as a substituent has not only the water dispersibility and electrophoretic effects in the conventional acrylic cation electrodeposition, but also the aminoalkyl group of the substituent. The chain transfer of peroxy radicals that cause curing failure due to oxygen during UV curing has the effect of deactivating the peroxy radicals and initiating polymerization, thereby improving the curability of the coating film surface.
（Ａ）成分の一部の主鎖末端に不飽和基を有する水溶性又は水分散性ビニル系共重合体を構成する、その他のビニル系単量体（ｂ）としては、メチルアクリレート、メチルメタクリレート、エチルアクリレート、エチルメタクリレート、ｎ−プロピルアクリレート、ｎ−プロピルメタクリレート、イソプロピルアクリレート、イソプロピルメタクリレート、ノルマルブチルアクリレート、ノルマルブチルメタクリレート、ノルマルヘキシルアクリレート、ノルマルヘキシルメタクリレート、ノルマルヘプチルアクリレート、ノルマルヘプチルメタクリレート、２−エチルヘキシルアクリレート、２−エチルヘキシルメタクリレート、ノルマルラウリルアクリレート、ラウリルメタクリレート、ステアリルアクリレート、ステアリルメタクリレート等の炭素数約２０までのアルキル基を有する同様な共重合性ビニルエステルやシクロヘキシルアクリレート、シクロヘキシルメタクリレート、イソボルニルアクリレート、イソボルニルメタクリレートなどの側鎖に脂環式炭化水素基を有する共重合性ビニルエステル系単量体、２−ヒドロキシエチルアクリレート、２−ヒドロキシエチルメタクリレート、２−ヒドロキシプロピルアクリレート、２−ヒドロキシプロピルメタクリレート、３−ヒドロキシプロピルアクリレート、３−ヒドロキシプロピルメタクリレート、４−ヒドロキシブチルアクリレート、４−ヒドロキシブチルメタクリレート、ジエチレングリコールモノアクリレート、シクロヘキサンジメタノールモノアク
リレート等の水酸基含有単量体、及び、スチレン、α−メチルスチレン、α−クロロスチレン、ビニルトルエン等の芳香族基を有するビニル系単量体が使用できる。さらにアクリルアミド、Ｎ−メチロールアクリルアミド、Ｎ−メトキシメチルアクリルアミド、Ｎ−エトキシメチルアクリルアミド、Ｎ−イソブトキシメチルアクリルアミド、Ｎ−ブトキシメチルアクリルアミド、メタクリルアミド、Ｎ−メチロールメタクリルアミド、Ｎ−メトキシメチルメタクリルアミド、Ｎ−エトキシメチルメタクリルアミド、Ｎ−イソブトキシメチルメタクリルアミド、Ｎ−ブトキシメチルメタクリルアミド等の（メタ）アクリルアミド類やアクリロニトリル、酢酸ビニル等を使用することも出来る。
As the other vinyl monomer (b) constituting the water-soluble or water-dispersible vinyl copolymer having an unsaturated group at the end of the main chain of part of the component (A), methyl acrylate, methyl methacrylate , Ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, normal butyl acrylate, normal butyl methacrylate, normal hexyl acrylate, normal hexyl methacrylate, normal heptyl acrylate, normal heptyl methacrylate, 2-ethylhexyl Acrylate, 2-ethylhexyl methacrylate, normal lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate Copolymers having an alicyclic hydrocarbon group in the side chain, such as a similar copolymerizable vinyl ester having an alkyl group of up to about 20 carbon atoms such as cyclohexyl, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate and isobornyl methacrylate. Polymerizable vinyl ester monomer, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate , 4-hydroxybutyl methacrylate, hydroxyl group-containing monomers such as diethylene glycol monoacrylate, cyclohexane dimethanol monoacrylate, and styrene, α-methyl Vinyl monomers having an aromatic group such as styrene, α-chlorostyrene and vinyl toluene can be used. Further, acrylamide, N-methylol acrylamide, N-methoxymethyl acrylamide, N-ethoxymethyl acrylamide, N-isobutoxymethyl acrylamide, N-butoxymethyl acrylamide, methacrylamide, N-methylol methacrylamide, N-methoxymethyl methacrylamide, N (Meth) acrylamides such as ethoxymethyl methacrylamide, N-isobutoxymethyl methacrylamide, N-butoxymethyl methacrylamide, acrylonitrile, vinyl acetate and the like can also be used.
（Ａ）成分の一部の主鎖末端に不飽和基を有する水溶性又は水分散性ビニル系共重合体を構成する付加開裂型連鎖移動剤（ｃ）は、開始剤により発生した開始ラジカルや成長ラジカルが付加開裂型連鎖移動剤に付加反応することでω末端が開裂し、新たに、ラジカルを生成して、その生成ラジカルが重合開始するタイプの連鎖移動剤であり、その開裂の際にポリマー末端に不飽和結合を形成することで、マクロモノマーの合成に利用される。 (A) The addition-cleavage chain transfer agent (c) constituting the water-soluble or water-dispersible vinyl copolymer having an unsaturated group at the end of the main chain of the component is an initiating radical generated by the initiator, This is a type of chain transfer agent in which the ω terminal is cleaved by the addition reaction of the growing radical to the addition-cleavage type chain transfer agent, and a new radical is generated, and the generated radical starts polymerization. By forming an unsaturated bond at the polymer terminal, it is used for the synthesis of a macromonomer.
本発明における付加開裂型連鎖移動剤の効果としては、水溶性、または、水分散性ビニル系共重合体の一部の主鎖末端に不飽和結合を導入できる。そのため一分子中に３個以上の不飽和基を有する化合物との相溶性がきわめて優れ、一分子中に３個以上の不飽和基を有する化合物をコアとしたコアシェル型エマルジョンを形成するので、一分子中に３個以上の不飽和基を有する化合物の加水分解が抑制されるため液安定性が良好である。また紫外線硬化時には、マクロモノマーとして、架橋ネットワークに組み込まれることで、硬化収縮を低減して、メッキ基材との密着性を向上させる効果もある。
具体的には、２，４−ジフェニル−４−メチル−１−ペンテン（αメチルスチレンダイマー）、α−ブロモメチルアクリル酸メチル、α−ベンジルオキシメチルアクリル酸エチル、α−ベンジルオキシメチルスチレン等が上げられるが、２，４−ジフェニル−４−メチル−１−ペンテンが好ましい。
As an effect of the addition-cleavage type chain transfer agent in the present invention, an unsaturated bond can be introduced into a part of the main chain terminal of the water-soluble or water-dispersible vinyl copolymer. Therefore, the compatibility with a compound having three or more unsaturated groups in one molecule is extremely excellent, and a core-shell type emulsion having a compound having three or more unsaturated groups in one molecule as a core is formed. Since the hydrolysis of a compound having 3 or more unsaturated groups in the molecule is suppressed, the liquid stability is good. Moreover, at the time of ultraviolet curing, by incorporating it as a macromonomer into the cross-linked network, there is an effect of reducing curing shrinkage and improving the adhesion to the plating substrate.
Specifically, 2,4-diphenyl-4-methyl-1-pentene (α methyl styrene dimer), methyl α-bromomethyl acrylate, ethyl α-benzyloxymethyl acrylate, α-benzyloxymethyl styrene, etc. 2,4-diphenyl-4-methyl-1-pentene is preferred.
（Ａ）成分の一部の主鎖末端に不飽和基を有する水溶性又は水分散性ビニル系共重合体を重合する際に使用される溶剤は、イソプロピルアルコール、ノルマルブタノール、イソブタノール等のアルコール類、エチレングリコールモノブチルエーテル、エチレングリコールモノターシャリーブチルエーテル等のセロソルブ類、プロピレングリコールモノメチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル等のプロピレングリコールエーテル類が望ましい。
（Ａ）成分の一部の主鎖末端に不飽和基を有する水溶性又は水分散性ビニル系共重合体を重合する際に使用される重合開始剤は、アゾビスイソブチロニトリル、２，２‘−アゾビス（２，４−ジメチルバレロニトリル）等のアゾ系開始剤、過酸化ベンゾイル、２，５−ジメチル−２，５−ジ（ｔ−ブチルペルオキシ）ヘキサン等の過酸化物等が使用できる。
The solvent used when polymerizing the water-soluble or water-dispersible vinyl copolymer having an unsaturated group at the end of the main chain of a part of the component (A) is an alcohol such as isopropyl alcohol, normal butanol, and isobutanol. And cellosolves such as ethylene glycol monobutyl ether and ethylene glycol monotertiary butyl ether, and propylene glycol ethers such as propylene glycol monomethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether are desirable.
(A) The polymerization initiator used when polymerizing the water-soluble or water-dispersible vinyl copolymer having an unsaturated group at the end of the main chain of the component is azobisisobutyronitrile, 2, Used are azo initiators such as 2'-azobis (2,4-dimethylvaleronitrile), peroxides such as benzoyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, etc. it can.
さらに（Ｂ）成分の一分子中に３個以上の不飽和基を有する化合物としては、トリメチロールプロパントリアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ジトリメチロールプロパンテトラアクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールヘキサアクリレート等のポリオール誘導体の多官能（メタ）アクリレート類、ペンタエリスリトールトリアリレート、ペンタエリスリトールテトラアリレート、トリメチロールプロパントリアリレート等の多官能アリレート類、ポリエステル（メタ）アクリレート類、市販品としてはアロニックスＭ−７１００、Ｍ−８０３０、Ｍ−８０６０（いずれも東亞合成（株）製）、ウレタンアクリレート、デンドリティックアクリレート、ポリエーテルアクリレート等が用いることが出来るがこれらに限定されない。また、上記の一分子中に３個以上の不飽和基を有する化合物は、１種単独又は２種以上を組み合
わせて使用することができる。
本発明における一部の主鎖末端に不飽和基を有する水溶性又は水分散性ビニル系共重合体（Ａ）のアルキルアミノ基を中和するのに用いることのできる酸としては、ギ酸、酢酸、乳酸等が挙げられる。酸は、（Ａ）成分中の３級アルキルアミノ基に対して、モル比が０．３〜０．９となるように添加すればよい。
Furthermore, as a compound having three or more unsaturated groups in one molecule of component (B), trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, Polyfunctional (meth) acrylates of polyol derivatives such as dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, polyfunctional arylates such as pentaerythritol triarylate, pentaerythritol tetraarylate and trimethylolpropane triarylate, polyester (meth) As acrylates and commercially available products, Aronix M-7100, M-8030, M-8060 (all manufactured by Toagosei Co., Ltd.) , Urethane acrylates, dendritic acrylates, but can be polyether acrylate used without limitation. Moreover, the compound which has 3 or more unsaturated groups in said 1 molecule can be used individually by 1 type or in combination of 2 or more types.
Examples of the acid that can be used to neutralize the alkylamino group of the water-soluble or water-dispersible vinyl copolymer (A) having an unsaturated group at the end of the main chain in the present invention include formic acid, acetic acid And lactic acid. The acid may be added so that the molar ratio is 0.3 to 0.9 with respect to the tertiary alkylamino group in the component (A).
次に、（Ｃ）成分のアルコール系溶剤を３％含む水１００ｇに対する２５℃での溶解量が０．０２ｇ未満、且つ、２００ｎｍ〜４００ｎｍにおける極大吸収のモル吸光係数εが１０，０００Ｌ／ｍｏｌ・ｃｍ以上である光重合開始剤について詳細を示す。
通常の塗布型水系紫外線硬化塗膜においては特に問題とはならないが、紫外線硬化型電着塗料では、光重合開始剤の塗膜中への共進性が非常に重要な要件である。これまで、疎水性や非水溶性の光重合開始剤を使用すれば電着塗料に使用できると特許等の文献に多数示されているが、今回本願発明者らは、実際のところアルコール系溶剤を使用している場合、水に溶けない光重合開始剤もアルコール系溶剤を介し、水中に溶け出していることを見出した。アルコール系溶剤（イソプロピルアルコール１ｇ、プロピレングリコールモノメチルエーテル２ｇ）に光重合開始剤を溶かし、脱イオン水で総量を１００ｇにしたときに、液が完全に透明な場合を溶解していると判断した。その主な結果を表１に示す。
Next, the dissolved amount at 25 ° C. in 100 g of water containing 3% of the alcohol solvent of component (C) is less than 0.02 g, and the molar absorption coefficient ε of the maximum absorption at 200 nm to 400 nm is 10,000 L / mol · Details of the photopolymerization initiator that is cm or more will be described.
Although there is no particular problem with ordinary coating-type water-based UV curable coatings, co-propagation of the photopolymerization initiator into the coating film is a very important requirement for UV curable electrodeposition coatings. So far, it has been shown in literatures such as patents that a hydrophobic or water-insoluble photopolymerization initiator can be used for electrodeposition paints. It has been found that a photopolymerization initiator that is not soluble in water is also dissolved in water via an alcohol solvent. When the photopolymerization initiator was dissolved in an alcohol solvent (isopropyl alcohol 1 g, propylene glycol monomethyl ether 2 g) and the total amount was made 100 g with deionized water, it was judged that the solution was completely transparent. The main results are shown in Table 1.
イソプロピルアルコールやプロピレングリコールモノメチルエーテルは、水溶性又は水分散性のビニル系共重合体を合成する際に一般的に使用されるが、水に容易に溶解するた
めに、水溶性または水分散性のビニル系共重合体を中和し、乳化転相した後に、樹脂中に存在するものも水層に移行する傾向にある。
その際に、アルコール系溶剤を３％含む水１００ｇに対する２５℃での溶解量が０．０２ｇ以上の光重合開始剤は、例えば、電着塗料が加熱残分１０％に対し、１％光重合開始剤を使用している場合、塗膜中に存在する光重合開始剤の２０％以上が水層に移行する可能性があることを示している。
Isopropyl alcohol and propylene glycol monomethyl ether are generally used in the synthesis of water-soluble or water-dispersible vinyl copolymers, but are easily soluble in water. After the vinyl copolymer is neutralized and subjected to emulsion phase inversion, what is present in the resin also tends to migrate to the aqueous layer.
At that time, a photopolymerization initiator having a dissolution amount at 25 ° C. in 100 g of water containing 3% of an alcohol solvent of 0.02 g or more is, for example, 1% photopolymerization with respect to a heating residue of 10%. When the initiator is used, it has shown that 20% or more of the photoinitiator which exists in a coating film may transfer to a water layer.
その結果、水層に移行する量が多くなり、電着時に塗料樹脂とともに析出する光重合開始剤の量が低下することとなり、さらに、塗膜表面のムラをなくす目的で電着後に析出塗膜表面の不安定層を除去する水洗工程においても、塗膜表面に存在する光重合開始剤が水洗水中に溶解するために塗膜の硬化性がさらに低くなる。
しかしながら、アルコール系溶剤を３％含む水１００ｇに対する２５℃での溶解量が０．０２ｇ以上の光重合開始剤を使用しても良好な表面硬化性が出ない場合がある。
そこで、さらに鋭意研究した結果、理論的な機構は解明していないが、分光光度計にて測定した２００ｎｍ〜４００ｎｍにおける極大吸収のモル吸光係数εが１０，０００Ｌ／ｍｏｌ・ｃｍ以上である光重合開始剤（Ｃ）を使用することで良好な表面硬化性が得られることを見出した。
As a result, the amount transferred to the water layer increases, the amount of photopolymerization initiator deposited together with the coating resin during electrodeposition decreases, and the coating film deposited after electrodeposition for the purpose of eliminating unevenness of the coating film surface Even in the washing step for removing the unstable layer on the surface, the photopolymerization initiator existing on the surface of the coating film is dissolved in the washing water, so that the curability of the coating film is further lowered.
However, even when a photopolymerization initiator having a dissolution amount at 25 ° C. in 100 g of water containing 3% of an alcohol solvent of 0.02 g or more is used, good surface curability may not be obtained.
Therefore, as a result of further earnest research, the theoretical mechanism has not been elucidated, but photopolymerization having a molar absorption coefficient ε of the maximum absorption at 200 nm to 400 nm measured by a spectrophotometer is 10,000 L / mol · cm or more. It has been found that good surface curability can be obtained by using the initiator (C).
本発明に使用できるアルコール系溶剤を３％含む水１００ｇに対する２５℃での溶解量が０．０２ｇ未満、且つ、２００ｎｍ〜４００ｎｍにおける極大吸収のモル吸光係数εが１０，０００Ｌ／ｍｏｌ・ｃｍ以上である光重合開始剤（Ｃ）として、２−メチル−１−［４−（メチルチオ）フェニル］−２−（４−モルフォリニル）−１−プロパノン、２−（４−メチル）ベンジル−２−（ジメチルアミノ）−１−［４−（４−モルフォリニル）フェニル］−１−ブタノン、２−ベンジル−２−（ジメチルアミノ）−１−［４−（４−モルフォリニル）フェニル］−１−ブタノンなどのα−アミノケトン類、２−ヒドロキシ−１−｛４−［４−（２−ヒドロキシ−２−メチルプロピオニル）−ベンジル］フェニル｝−２−メチルプロパン−１−オン、オリゴ ２−ヒドロキシ−２−メチル−１−［４−（１−メチルビニル）フェニル］プロパノン（商品名：ＥｓａｃｕｒｅＫＩＰ１５０、ＥｓａｃｕｒｅＯＮＥ等Ｌａｍｂｅｒｔｉ社製）等の分子量３００以上のα−ヒドロキシケトン類、２，４−ジエチルチオキサントン、高分子チオキサントン（商品名：ＧＥＮＯＰＯＬ ＴＸ、ＲＡＨＮ社製）等のチオキサントン類、１−［４−（４−ベンゾイルフェニルスルファニル）フェニル］−２−メチル−２−［（４−メチルフェニル）スルフォニル］プロパン−１−オン等のケトスルフォン類が使用できる。 The amount of dissolution at 25 ° C. in 100 g of water containing 3% of an alcohol solvent that can be used in the present invention is less than 0.02 g, and the molar absorption coefficient ε of the maximum absorption at 200 nm to 400 nm is 10,000 L / mol · cm or more. As a certain photoinitiator (C), 2-methyl-1- [4- (methylthio) phenyl] -2- (4-morpholinyl) -1-propanone, 2- (4-methyl) benzyl-2- (dimethyl) Α) such as amino) -1- [4- (4-morpholinyl) phenyl] -1-butanone and 2-benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1-butanone -Aminoketones, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] phenyl} -2-methylpropane-1-o Α-hydroxy ketones having a molecular weight of 300 or more, such as 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone (trade name: Esacure KIP150, EsacureONE, etc., manufactured by Lamberti) , 4-diethylthioxanthone, polymeric thioxanthone (trade name: GENOPOL TX, manufactured by RAHN), and the like, 1- [4- (4-benzoylphenylsulfanyl) phenyl] -2-methyl-2-[(4- Ketosulfones such as methylphenyl) sulfonyl] propan-1-one can be used.
なかでも、２−メチル−１−［４−（メチルチオ）フェニル］−２−（４−モルフォリニル）−１−プロパノン、２−（４−メチル）ベンジル−２−（ジメチルアミノ）−１−［４−（４−モルフォリニル）フェニル］−１−ブタノン、２−ベンジル−２−（ジメチルアミノ）−１−［４−（４−モルフォリニル）フェニル］−１−ブタノンなどのα−アミノケトン類、２−ヒドロキシ−１−｛４−［４−（２−ヒドロキシ−２−メチルプロピオニル）−ベンジル］フェニル｝−２−メチルプロパン−１−オン、オリゴ ２−ヒドロキシ−２−メチル−１−［４−（１−メチルビニル）フェニル］プロパノン（商品名：ＥｓａｃｕｒｅＫＩＰ１５０、ＥｓａｃｕｒｅＯＮＥ等Ｌａｍｂｅｒｔｉ社製）等の分子量３００以上のα−ヒドロキシケトン類、１−［４−（４−ベンゾイルフェニルスルファニル）フェニル］−２−メチル−２−［（４−メチルフェニル）スルフォニル］プロパン−１−オン等のケトスルフォン類が好ましい。
上記の光重合開始剤においては、１種、または、２種以上組み合わせて使用することができる。また、黄変しない程度にアミン等の光増感剤を併用することもできる。
Among them, 2-methyl-1- [4- (methylthio) phenyl] -2- (4-morpholinyl) -1-propanone, 2- (4-methyl) benzyl-2- (dimethylamino) -1- [4 Α-aminoketones such as-(4-morpholinyl) phenyl] -1-butanone and 2-benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2-hydroxy -1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] phenyl} -2-methylpropan-1-one, oligo 2-hydroxy-2-methyl-1- [4- (1 -Methylvinyl) phenyl] propanone (trade name: Esacure KIP150, Esacure ONE, etc., manufactured by Lamberti), etc. α-hydroxyketo having a molecular weight of 300 or more S, 1- [4- (4-benzoyl) phenyl] -2-methyl-2 - [(4-methylphenyl) sulfonyl] Ketosurufon such propan-1-one and the like are preferable.
In said photoinitiator, it can be used 1 type or in combination of 2 or more types. Further, a photosensitizer such as amine can be used in combination to such an extent that yellowing does not occur.
本発明における一部の主鎖末端に不飽和基を有する水溶性、または、水分散性ビニル系共重合体（Ａ）により得られた電着塗膜は、プラスチックメッキ基材への優れた密着性を
有し、置換基としてアミノアルキル基を有する共重合性ビニル系単量体（ａ）４〜１５重量部、好ましくは６〜１２重量部、（ａ）以外の共重合性ビニル系単量体（ｂ）が８５〜９６重量部、好ましくは８８〜９４重量部、共重合性ビニル系単量体（ａ）と（ｂ）の合計１００重量部に対し、付加開裂型連鎖移動剤（ｃ）０．０５〜２０重量部、好ましくは０．５重量部〜５重量部を重合し作製した一部の主鎖末端に不飽和基を有する水溶性、または、水分散性ビニル系共重合体により得られた電着樹脂組成物は、水分散性が特に良好であり、それにより得られた電着塗膜は、塗膜性能に優れている。
The electrodeposition coating film obtained from the water-soluble or water-dispersible vinyl copolymer (A) having an unsaturated group at the end of the main chain in the present invention has excellent adhesion to a plastic plating substrate. And a copolymerizable vinyl monomer having an aminoalkyl group as a substituent (a) 4 to 15 parts by weight, preferably 6 to 12 parts by weight, and a copolymerizable vinyl monomer other than (a) The body (b) is 85 to 96 parts by weight, preferably 88 to 94 parts by weight, and the addition-cleavage chain transfer agent (c) for 100 parts by weight of the total of the copolymerizable vinyl monomers (a) and (b). ) A water-soluble or water-dispersible vinyl copolymer having an unsaturated group at the end of the main chain produced by polymerizing 0.05 to 20 parts by weight, preferably 0.5 to 5 parts by weight. The electrodeposition resin composition obtained by the above has particularly good water dispersibility, and the electrodeposition resin obtained thereby. The coatings have excellent film performance.
本発明の一部の主鎖末端に不飽和基を有する水溶性又は水分散性ビニル系共重合体（Ａ）の構成である置換基としてアミノアルキル基を有する共重合性ビニル系単量体（ａ）が４重量部未満である電着樹脂組成物は液安定性が悪く、１５重量部を超えると得られた塗膜の耐水性、耐薬品性が悪く、また、増感作用が大きくなるため黄変、基材との密着性が悪くなる。
共重合性ビニル系単量体（ａ）と（ｂ）の合計１００重量部に対し、付加開裂型連鎖移動剤（ｃ）が０．０５重量部未満であると液安定性が低下し、また硬化収縮が大きくなるので基材との密着性が悪くなり、２０重量部を超えると未反応の付加開裂型連鎖移動剤が残存して硬化不足を生じる。
A copolymerizable vinyl monomer having an aminoalkyl group as a substituent which is a constitution of the water-soluble or water-dispersible vinyl copolymer (A) having an unsaturated group at the end of the main chain of the present invention ( An electrodeposition resin composition having a) of less than 4 parts by weight has poor liquid stability, and if it exceeds 15 parts by weight, the resulting coating film has poor water resistance and chemical resistance, and has an increased sensitizing action. Therefore, yellowing and adhesiveness with a base material worsen.
If the addition-cleavage chain transfer agent (c) is less than 0.05 parts by weight with respect to a total of 100 parts by weight of the copolymerizable vinyl monomers (a) and (b), the liquid stability decreases. Since the curing shrinkage increases, the adhesion to the substrate is deteriorated, and when it exceeds 20 parts by weight, an unreacted addition-cleavage chain transfer agent remains and insufficient curing occurs.
本発明の一部の主鎖末端に不飽和基を有する水溶性又は水分散性ビニル系共重合体（Ａ）５０〜８０重量部、好ましくは、６０〜７５重量部、一分子中に３個以上の不飽和基を有する化合物（Ｂ）２０〜５０重量部、好ましくは、２５〜４０重量部で用いる。水溶性又は水分散性ビニル系共重合体（Ａ）の割合が５０重量部未満では、十分な水分散性が得られず液安定性が悪く沈降を生じやすくなり、８０重量部を超えると十分な塗膜性能が得られない。
一分子中に３個以上の不飽和基を有する化合物（Ｂ）の割合が、２０重量部未満では、十分な塗膜性能が得られず（耐薬品性、塗膜硬度）、５０重量部以上では、十分な水分散性が得られず、また、製造コストも上昇する。
The water-soluble or water-dispersible vinyl copolymer (A) having an unsaturated group at the end of a part of the main chain of the present invention (50) to 80 parts by weight, preferably 60 to 75 parts by weight, 3 in one molecule The compound (B) having the above unsaturated group is used in an amount of 20 to 50 parts by weight, preferably 25 to 40 parts by weight. If the proportion of the water-soluble or water-dispersible vinyl copolymer (A) is less than 50 parts by weight, sufficient water dispersibility cannot be obtained, the liquid stability is poor, and precipitation tends to occur. Film performance is not obtained.
If the ratio of the compound (B) having 3 or more unsaturated groups in one molecule is less than 20 parts by weight, sufficient film performance cannot be obtained (chemical resistance, film hardness), 50 parts by weight or more. However, sufficient water dispersibility cannot be obtained, and the production cost also increases.
さらに（Ａ）と（Ｂ）の合計１００重量部に対して、アルコール系溶剤を３％含む水１００ｇに対する２５℃での溶解量が０．０２ｇ未満、且つ、２００ｎｍ〜４００ｎｍにおける極大吸収のモル吸光係数εが１０，０００Ｌ／ｍｏｌ・ｃｍ以上である光重合開始剤（Ｃ）は、０．１〜８重量部、好ましくは、０．５〜５重量部で使用し、０．１重量部未満では、十分な塗膜性能（耐溶剤性、耐薬品性、塗膜硬度等）が得られず、８重量部を超えると硬化塗膜のメッキ基材との密着性の低下、黄変、さらに製造コストが上昇する。 Furthermore, with respect to a total of 100 parts by weight of (A) and (B), the amount of dissolution at 25 ° C. in 100 g of water containing 3% of an alcohol solvent is less than 0.02 g, and the molar absorption of the maximum absorption at 200 nm to 400 nm. The photopolymerization initiator (C) having a coefficient ε of 10,000 L / mol · cm or more is used in an amount of 0.1 to 8 parts by weight, preferably 0.5 to 5 parts by weight, and less than 0.1 parts by weight. However, sufficient film performance (solvent resistance, chemical resistance, film hardness, etc.) cannot be obtained, and if it exceeds 8 parts by weight, the adhesiveness of the cured film to the plating substrate is reduced, yellowing, Manufacturing cost increases.
本発明により構成される紫外線硬化型カチオン電着樹脂組成物を用いた電着条件としては、通電工程において印加される電圧は１０〜４００Ｖ、好ましくは４０〜１５０Ｖであり、通電時間は０．５分〜５分、好ましくは１〜４分である。電圧が高いほど通電時間は短く、電圧が低ければ通電時間を長くする。印加電圧は通電と同時に設定電圧をかけるハードスタート、あるいは徐々に設定電圧まで電圧を上げていくソフトスタートのいずれでもかまわない。
電着塗装された被塗装物は、水洗され、次いで６０℃で１０分間程度加熱し、塗装膜中の水分を乾燥したのちに紫外線硬化装置を用い、積算光量２００ｍＪ／ｃｍ２〜２，０００ｍＪ／ｃｍ２を照射して硬化塗膜を得る。
As the electrodeposition conditions using the ultraviolet curable cationic electrodeposition resin composition constituted according to the present invention, the voltage applied in the energization step is 10 to 400 V, preferably 40 to 150 V, and the energization time is 0.5. Minutes to 5 minutes, preferably 1 to 4 minutes. The higher the voltage, the shorter the energization time, and the lower the voltage, the longer the energization time. The applied voltage may be either a hard start in which a set voltage is applied simultaneously with energization, or a soft start in which the voltage is gradually raised to the set voltage.
The electrodeposition-coated object is washed with water and then heated at 60 ° C. for about 10 minutes to dry the moisture in the coating film, and then an ultraviolet curing device is used, and an integrated light quantity of 200 mJ / cm 2 to 2,000 mJ / Irradiate cm 2 to obtain a cured coating film.
以下に本発明の実施例および比較例を挙げてさらに具体的に説明するが、これによって本発明が限定されるものではない。なお、実施例、比較例中の部は、特に断りのない限り重量部である。
製造例１
攪拌装置、還流冷却器および窒素導入管を備えた３リットルの４つ口フラスコにイソプロパノール１０．０部、プロピレングリコールモノメチルエーテル１０．０部を仕込み、９０℃に昇温した。別にイソプロパノール５部、プロピレングリコールモノメチルエーテル１３部、ジエチルアミノエチルメタクリレート８部、２−ヒドロキシエチルアクリレート１０部、スチレン１０部、ｎ−ブチルアクリレート２０部、メチルメタクリレート５２部、アゾビスイソブチロニトリル１．５部、２，４−ジフェニル−４−メチル−１−ペンテン１部の混合液を滴下ロートに仕込み、前記フラスコ内に１２０分かけて滴下した。滴下終了後、さらにプロピレングリコールモノメチルエーテル０．４部、アゾビスイソブチロニトリル０．２部を、３０分毎に３回添加したのちに、さらに９０℃で９０分反応を続けた。それにより得られた共重合体は、アミン価２３．５ｍｇＫＯＨ／ｇ−ｒｅｓｉｎの一部の主鎖末端に不飽和基を有する水分散性ビニル共重合体（固形分７２．５％）であった。
Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited thereto. In addition, the part in an Example and a comparative example is a weight part unless there is particular notice.
Production Example 1
10.0 parts of isopropanol and 10.0 parts of propylene glycol monomethyl ether were charged into a 3 liter four-necked flask equipped with a stirrer, a reflux condenser and a nitrogen introduction tube, and the temperature was raised to 90 ° C. Separately, 5 parts of isopropanol, 13 parts of propylene glycol monomethyl ether, 8 parts of diethylaminoethyl methacrylate, 10 parts of 2-hydroxyethyl acrylate, 10 parts of styrene, 20 parts of n-butyl acrylate, 52 parts of methyl methacrylate, azobisisobutyronitrile A mixed solution of 5 parts and 1 part of 2,4-diphenyl-4-methyl-1-pentene was charged into a dropping funnel and dropped into the flask over 120 minutes. After completion of the dropwise addition, 0.4 part of propylene glycol monomethyl ether and 0.2 part of azobisisobutyronitrile were added three times every 30 minutes, and the reaction was further continued at 90 ° C. for 90 minutes. The copolymer thus obtained was a water-dispersible vinyl copolymer (solid content: 72.5%) having an unsaturated group at the end of the main chain with an amine value of 23.5 mg KOH / g-resin. .
製造例２
攪拌装置、還流冷却器および窒素導入管を備えた３リットルの４つ口フラスコにイソプロパノール１０．０部、プロピレングリコールモノメチルエーテル１０．０部を仕込み、９０℃に昇温した。別にイソプロパノール５部、プロピレングリコールモノメチルエーテル１３部、ジエチルアミノエチルメタクリレート１０部、２−ヒドロキシエチルアクリレート１０部、スチレン１０部、ｎ−ブチルアクリレート２０部、メチルメタクリレート５０部、アゾビスイソブチロニトリル１．５部、２，４−ジフェニル−４−メチル−１−ペンテン１部の混合液を滴下ロートに仕込み、前記フラスコ内に１２０分かけて滴下した。滴下終了後、さらにプロピレングリコールモノメチルエーテル０．４部、アゾビスイソブチロニトリル０．２部を、３０分毎に３回添加したのちに、さらに９０℃で９０分反応を続けた。それにより得られた共重合体は、アミン価２９．４ｍｇＫＯＨ／ｇ−ｒｅｓｉｎの一部の主鎖末端に不飽和基を有する水分散性ビニル共重合体（固形分７２．５％）であった。
Production Example 2
10.0 parts of isopropanol and 10.0 parts of propylene glycol monomethyl ether were charged into a 3 liter four-necked flask equipped with a stirrer, a reflux condenser and a nitrogen introduction tube, and the temperature was raised to 90 ° C. Separately, 5 parts of isopropanol, 13 parts of propylene glycol monomethyl ether, 10 parts of diethylaminoethyl methacrylate, 10 parts of 2-hydroxyethyl acrylate, 10 parts of styrene, 20 parts of n-butyl acrylate, 50 parts of methyl methacrylate, azobisisobutyronitrile A mixed solution of 5 parts and 1 part of 2,4-diphenyl-4-methyl-1-pentene was charged into a dropping funnel and dropped into the flask over 120 minutes. After completion of the dropwise addition, 0.4 part of propylene glycol monomethyl ether and 0.2 part of azobisisobutyronitrile were added three times every 30 minutes, and the reaction was further continued at 90 ° C. for 90 minutes. The copolymer thus obtained was a water-dispersible vinyl copolymer having an amine value of 29.4 mg KOH / g-resin and an unsaturated group at the end of the main chain (solid content: 72.5%). .
製造例３
攪拌装置、還流冷却器および窒素導入管を備えた３リットルの４つ口フラスコにイソプロパノール１０．０部、プロピレングリコールモノメチルエーテル１０．０部を仕込み、９０℃に昇温した。別にイソプロパノール５部、プロピレングリコールモノメチルエーテル１３部、ジエチルアミノエチルメタクリレート１０部、２−ヒドロキシエチルアクリレート１０部、スチレン１０部、２−エチルヘキシルアクリレート１０部、ｎ−ブチルアクリレート２０部、メチルメタクリレート４０部、アゾビスイソブチロニトリル１．５部、２，４−ジフェニル−４−メチル−１−ペンテン１部の混合液を滴下ロートに仕込み、前記フラスコ内に１２０分かけて滴下した。滴下終了後、さらにプロピレングリコールモノメチルエーテル０．４部、アゾビスイソブチロニトリル０．２部を、３０分毎に３回添加したのちに、さらに９０℃で９０分反応を続けた。それにより得られた共重合体は、アミン価２９．４ｍｇＫＯＨ／ｇ−ｒｅｓｉｎの一部の主鎖末端に不飽和基を有する水分散性ビニル共重合体（固形分７２．５％）であった。
Production Example 3
10.0 parts of isopropanol and 10.0 parts of propylene glycol monomethyl ether were charged into a 3 liter four-necked flask equipped with a stirrer, a reflux condenser and a nitrogen introduction tube, and the temperature was raised to 90 ° C. Separately, 5 parts isopropanol, 13 parts propylene glycol monomethyl ether, 10 parts diethylaminoethyl methacrylate, 10 parts 2-hydroxyethyl acrylate, 10 parts styrene, 10 parts 2-ethylhexyl acrylate, 20 parts n-butyl acrylate, 40 parts methyl methacrylate, azo A mixed solution of 1.5 parts of bisisobutyronitrile and 1 part of 2,4-diphenyl-4-methyl-1-pentene was charged into a dropping funnel and dropped into the flask over 120 minutes. After completion of the dropwise addition, 0.4 part of propylene glycol monomethyl ether and 0.2 part of azobisisobutyronitrile were added three times every 30 minutes, and the reaction was further continued at 90 ° C. for 90 minutes. The copolymer thus obtained was a water-dispersible vinyl copolymer having an amine value of 29.4 mg KOH / g-resin and an unsaturated group at the end of the main chain (solid content: 72.5%). .
製造例４
攪拌装置、還流冷却器および窒素導入管を備えた３リットルの４つ口フラスコにイソプロパノール１０．０部、プロピレングリコールモノメチルエーテル１０．０部を仕込み、９０℃に昇温した。別にイソプロパノール５部、プロピレングリコールモノメチルエーテル１３部、ジエチルアミノエチルメタクリレート１０部、２−ヒドロキシエチルアクリレート１０部、スチレン１０部、ｎ−ブチルアクリレート２０部、メチルメタクリレート５０部、アゾビスイソブチロニトリル１．５部の混合液を滴下ロートに仕込み、前記フラスコ内に１２０分かけて滴下した。滴下終了後、さらにプロピレングリコールモノメチルエーテル０．４部、アゾビスイソブチロニトリル０．２部を、３０分毎に３回添加したのち
に、さらに９０℃で９０分反応を続けた。
それにより得られた共重合体は、アミン価２９．６ｍｇＫＯＨ／ｇ−ｒｅｓｉｎの水分散性ビニル共重合体（固形分７２．３％）であった。
Production Example 4
10.0 parts of isopropanol and 10.0 parts of propylene glycol monomethyl ether were charged into a 3 liter four-necked flask equipped with a stirrer, a reflux condenser and a nitrogen introduction tube, and the temperature was raised to 90 ° C. Separately, 5 parts of isopropanol, 13 parts of propylene glycol monomethyl ether, 10 parts of diethylaminoethyl methacrylate, 10 parts of 2-hydroxyethyl acrylate, 10 parts of styrene, 20 parts of n-butyl acrylate, 50 parts of methyl methacrylate, azobisisobutyronitrile 5 parts of the mixed solution was charged into a dropping funnel and dropped into the flask over 120 minutes. After completion of the dropwise addition, 0.4 part of propylene glycol monomethyl ether and 0.2 part of azobisisobutyronitrile were added three times every 30 minutes, and the reaction was further continued at 90 ° C. for 90 minutes.
The copolymer thus obtained was an aqueous dispersible vinyl copolymer (solid content: 72.3%) having an amine value of 29.6 mgKOH / g-resin.
［実施例１］
製造例１で得られたビニル系共重合体９６．６部とペンタエリスリトールテトラアクリレート３０部を混合し、乳酸１．５部を混合し、さらに２−ヒドロキシ−１−｛４−［４−（２−ヒドロキシ−２−メチルプロピオニル）−ベンジル］フェニル｝−２−メチルプロパン−１−オン（商品名：Ｉｒｇａｃｕｒｅ１２７、チバスペシャルティケミカルズ社製）２部を添加混合した。攪拌を続けながら、脱イオン水を２０９．９部加えて転相乳化を行ない、電着塗料用原液を得た。別の容器に脱イオン水を６６６．１部仕込み、攪拌しながら前記電着塗料用原液３３３．３部を投入し、次に乳酸を０．６部添加し電着塗料を得た。
[Example 1]
96.6 parts of the vinyl copolymer obtained in Production Example 1 and 30 parts of pentaerythritol tetraacrylate were mixed, 1.5 parts of lactic acid was mixed, and 2-hydroxy-1- {4- [4- ( 2-hydroxy-2-methylpropionyl) -benzyl] phenyl} -2-methylpropan-1-one (trade name: Irgacure 127, manufactured by Ciba Specialty Chemicals) was added and mixed. While continuing to stir, 209.9 parts of deionized water was added to perform phase inversion emulsification to obtain a stock solution for electrodeposition paint. 666.1 parts of deionized water was charged into another container, 333.3 parts of the stock solution for electrodeposition paint was added with stirring, and then 0.6 parts of lactic acid was added to obtain an electrodeposition paint.
［実施例２］
製造例２で得られたビニル系共重合体９６．６部とペンタエリスリトールテトラアクリレート３０部を混合し、乳酸１．８部を混合し、さらに２−ヒドロキシ−１−｛４−［４−（２−ヒドロキシ−２−メチルプロピオニル）−ベンジル］フェニル｝−２−メチルプロパン−１−オン（商品名：Ｉｒｇａｃｕｒｅ１２７、チバスペシャルティケミカルズ社製）２部を添加混合した。攪拌を続けながら、脱イオン水を２０９．６部加えて転相乳化を行ない、電着塗料用原液を得た。別の容器に脱イオン水を６６５．９部仕込み、攪拌しながら前記電着塗料用原液３３３．３部を投入し、次に乳酸を０．８部添加し電着塗料を得た。
[Example 2]
96.6 parts of the vinyl copolymer obtained in Production Example 2 and 30 parts of pentaerythritol tetraacrylate were mixed, 1.8 parts of lactic acid was mixed, and 2-hydroxy-1- {4- [4- ( 2-hydroxy-2-methylpropionyl) -benzyl] phenyl} -2-methylpropan-1-one (trade name: Irgacure 127, manufactured by Ciba Specialty Chemicals) was added and mixed. While continuing to stir, 209.6 parts of deionized water was added to perform phase inversion emulsification to obtain a stock solution for electrodeposition paint. In a separate container, 665.9 parts of deionized water was charged, 333.3 parts of the stock solution for electrodeposition paint was added while stirring, and then 0.8 parts of lactic acid was added to obtain an electrodeposition paint.
［実施例３］
製造例２で得られたビニル系共重合体を使う代わりに製造例３で得られたビニル系共重合体を使う以外は、実施例２と同様な方法で電着塗料を作製した。
［実施例４］
２−ヒドロキシ−１−｛４−［４−（２−ヒドロキシ−２−メチルプロピオニル）−ベンジル］フェニル｝−２−メチルプロパン−１−オン（商品名：Ｉｒｇａｃｕｒｅ１２７、チバスペシャルティケミカルズ社製））を使う代わりに１−［４−（４−ベンゾイルフェニルスルファニル）フェニル］−２−メチル−２−［（４−メチルフェニル）スルフォニル］プロパン−１−オン（商品名：Ｅｓａｃｕｒｅ１００１Ｍ、Ｌａｍｂｅｒｔｉ社製）を使う以外は、実施例２と同様な方法で電着塗料を作製した。
［実施例５］
２−ヒドロキシ−１−｛４−［４−（２−ヒドロキシ−２−メチルプロピオニル）−ベンジル］フェニル｝−２−メチルプロパン−１−オン（商品名：Ｉｒｇａｃｕｒｅ１２７、チバスペシャルティケミカルズ社製）を使う代わりに２−メチル−１−［４−（メチルチオ）フェニル］−２−（４−モルフォリニル）−１−プロパノン（商品名：Ｉｒｇａｃｕｒｅ９０７、チバスペシャルティケミカルズ社製）を使う以外は、実施例２と同様な方法で電着塗料を作製した。
［実施例６］
２−ヒドロキシ−１−｛４−［４−（２−ヒドロキシ−２−メチルプロピオニル）−ベンジル］フェニル｝−２−メチルプロパン−１−オン（商品名：Ｉｒｇａｃｕｒｅ１２７、チバスペシャルティケミカルズ社製））を使う代わりにオリゴ ２−ヒドロキシ−２−メチル−１−［４−（１−メチルビニル）フェニル］プロパノン（商品名：ＥｓａｃｕｒｅＫＩＰ１５０、Ｌａｍｂｅｒｔｉ社製）を使う以外は、実施例２と同様な方法で電着塗料を作製した。
[Example 3]
An electrodeposition paint was prepared in the same manner as in Example 2, except that the vinyl copolymer obtained in Production Example 3 was used instead of the vinyl copolymer obtained in Production Example 2.
[Example 4]
2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] phenyl} -2-methylpropan-1-one (trade name: Irgacure 127, manufactured by Ciba Specialty Chemicals)). Instead of using 1- [4- (4-benzoylphenylsulfanyl) phenyl] -2-methyl-2-[(4-methylphenyl) sulfonyl] propan-1-one (trade name: Esacure 1001M, manufactured by Lamberti) Except for the above, an electrodeposition paint was prepared in the same manner as in Example 2.
[Example 5]
2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] phenyl} -2-methylpropan-1-one (trade name: Irgacure 127, manufactured by Ciba Specialty Chemicals) is used. Instead of 2-methyl-1- [4- (methylthio) phenyl] -2- (4-morpholinyl) -1-propanone (trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals), it was the same as Example 2. An electrodeposition paint was prepared by various methods.
[Example 6]
2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] phenyl} -2-methylpropan-1-one (trade name: Irgacure 127, manufactured by Ciba Specialty Chemicals)). Instead of using oligo 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone (trade name: Esacure KIP150, manufactured by Lamberti), the battery was charged in the same manner as in Example 2. A coating was made.
［比較例１］
製造例４で得られたビニル系共重合体９６．８部とペンタエリスリトールテトラアクリレート３０部を混合し、乳酸１．９部を混合し、さらに２−ヒドロキシ−１−｛４−［４−（２−ヒドロキシ−２−メチルプロピオニル）−ベンジル］フェニル｝−２−メチルプロパン−１−オン（商品名：Ｉｒｇａｃｕｒｅ１２７、チバスペシャルティケミカルズ社製）２部を添加混合した。攪拌を続けながら、脱イオン水を２０９．３部加えて転相乳化を行ない、電着塗料用原液を得た。別の容器に脱イオン水を６６５．９部仕込み、攪拌しながら前記電着塗料用原液３３３．３部を投入し、次に乳酸を０．８部添加し電着塗料を得た。
[Comparative Example 1]
96.8 parts of the vinyl copolymer obtained in Production Example 4 and 30 parts of pentaerythritol tetraacrylate were mixed, 1.9 parts of lactic acid were mixed, and 2-hydroxy-1- {4- [4- ( 2-hydroxy-2-methylpropionyl) -benzyl] phenyl} -2-methylpropan-1-one (trade name: Irgacure 127, manufactured by Ciba Specialty Chemicals) was added and mixed. While continuing stirring, 209.3 parts of deionized water was added to carry out phase inversion emulsification to obtain a stock solution for electrodeposition paint. In a separate container, 665.9 parts of deionized water was charged, 333.3 parts of the stock solution for electrodeposition paint was added while stirring, and then 0.8 parts of lactic acid was added to obtain an electrodeposition paint.
［比較例２］
２−ヒドロキシ−１−｛４−［４−（２−ヒドロキシ−２−メチルプロピオニル）−ベンジル］フェニル｝−２−メチルプロパン−１−オン（商品名：Ｉｒｇａｃｕｒｅ１２７、チバスペシャルティケミカルズ社製）を使う代わりに１−ヒドロキシシクロヘキシルフェニルケトン（商品名：Ｉｒｇａｃｕｒｅ１８４、チバスペシャルティケミカルズ社製）を使う以外は、実施例２と同様な方法で電着塗料を作製した。
[Comparative Example 2]
2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] phenyl} -2-methylpropan-1-one (trade name: Irgacure 127, manufactured by Ciba Specialty Chemicals) is used. Instead, an electrodeposition paint was prepared in the same manner as in Example 2 except that 1-hydroxycyclohexyl phenyl ketone (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals) was used.
［比較例３］
２−ヒドロキシ−１−｛４−［４−（２−ヒドロキシ−２−メチルプロピオニル）−ベンジル］フェニル｝−２−メチルプロパン−１−オン（商品名：Ｉｒｇａｃｕｒｅ１２７、チバスペシャルティケミカルズ社製）を使う代わりにベンゾインイソプロピルエーテルを使う以外は、実施例２と同様な方法で電着塗料を作製した。
前記実施例１〜５および比較例１〜３の電着塗料用原液および電着塗料液の成分を総括して表２に示す。
[Comparative Example 3]
2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] phenyl} -2-methylpropan-1-one (trade name: Irgacure 127, manufactured by Ciba Specialty Chemicals) is used. An electrodeposition paint was prepared in the same manner as in Example 2 except that benzoin isopropyl ether was used instead.
The components of the electrodeposition paint stock solution and the electrodeposition paint solution of Examples 1 to 5 and Comparative Examples 1 to 3 are summarized in Table 2.
樹脂組成物の評価 実施例１〜４、比較例１〜３で調整した電着塗料液を使用し、常法に従って陰極に各３価クロム液を用いニッケルクロムメッキを施したＡＢＳ樹脂板（５ｃ
ｍ×１０ｃｍ）を、陽極にＳＵＳ３０４板を用いて、１０μｍの塗膜厚が得られる条件で電着塗装を実施した。次いで電着塗装されたニッケルクロムメッキ処理したＡＢＳ樹脂板を取り出して充分に水洗したのち、６０℃の温度で１０分間乾燥して、水分、溶剤分を乾燥し、高圧水銀灯にて積算光量１，０００ｍＪ／ｃｍ２を照射して塗膜を硬化させた。ニッケルクロムメッキ処理されたＡＢＳ樹脂板上に形成された電着塗膜の特性は表３に示すとおりであった。
Evaluation of Resin Composition ABS resin plate (5c) using the electrodeposition coating liquid prepared in Examples 1 to 4 and Comparative Examples 1 to 3 and nickel chrome plating using each trivalent chromium liquid on the cathode according to a conventional method
m × 10 cm) was subjected to electrodeposition coating using a SUS304 plate as the anode under the condition that a coating thickness of 10 μm was obtained. Next, the nickel chrome plated ABS resin plate coated with electrodeposition is taken out and washed thoroughly with water, and then dried at a temperature of 60 ° C. for 10 minutes to dry the moisture and solvent. The coated film was cured by irradiation with 000 mJ / cm 2 . Table 3 shows the characteristics of the electrodeposition coating film formed on the nickel chromium plated ABS resin plate.
実施例において、一部の主鎖末端に不飽和基を有する水溶性又は水分散性ビニル系共重合体を使用しているため、硬化剤との相溶性が向上するため液安定性が良好であり、一部の主鎖末端に不飽和基を有する水溶性又は水分散性ビニル系共重合体がマクロモノマーとしても機能し、硬化反応時に硬化収縮を低減することで付着性も良好になる。また、分光光度計にて測定した２００ｎｍ〜４００ｎｍにおける極大吸収のモル吸光係数εが１０，０００Ｌ／ｍｏｌ・ｃｍ以上である光重合開始剤を使用しているので優れた表面硬化性を有する。 In the examples, since a water-soluble or water-dispersible vinyl copolymer having an unsaturated group at a part of the main chain ends is used, the compatibility with the curing agent is improved, so that the liquid stability is good. A water-soluble or water-dispersible vinyl copolymer having an unsaturated group at a part of the main chain also functions as a macromonomer, and adhesion is improved by reducing curing shrinkage during the curing reaction. Moreover, since the photoinitiator whose molar absorption coefficient (epsilon) of the maximum absorption in 200 nm-400 nm measured with the spectrophotometer is 10,000 L / mol * cm or more is used, it has the outstanding surface curability.
評価方法
（１）肌感 目視判定で◎：良好 ○：やや不足 ×：不足をそれぞれ示す。
（２）鉛筆硬度 ＪＩＳ Ｋ ５６００−５−４ に従って評価した。
（３）付着性：ＪＩＳ Ｋ ５６００−５−６ に従って評価、◎：１００／１００で塗膜剥離なし、○：１００／１００でクロスカット交点での塗膜剥離が１５％未満、×：１００／１００以下でクロスカット交点での塗膜剥離が１５％以上。
（４）表面硬化性：脱脂綿にエタノールを染み込ませ、１ｋｇの荷重で１００回往復した後の塗膜厚残存率で評価：◎：９０％以上、○：９０〜８０％、×：８０％未満
（５）耐候性：サンシャインウェザーオーメーター２００時間後の外観で評価。
◎：異常なし、○：塗膜表面に少し荒れがある、×：塗膜表面全面が荒れる。
Evaluation method (1) Skin feeling ◎: Good by visual judgment ○: Slightly insufficient ×: Indicates insufficient.
(2) Pencil hardness It evaluated according to JISK5600-5-4.
(3) Adhesiveness: evaluated according to JIS K 5600-5-6, ◎: No coating peeling at 100/100, ○: Coating peeling at cross cut at less than 15% at 100/100, ×: 100/100 Less than 100, coating film peeling at cross-cut intersection is 15% or more.
(4) Surface curability: Evaluated by coating film thickness residual ratio after impregnating absorbent cotton with ethanol and reciprocating 100 times with a load of 1 kg: A: 90% or more, B: 90-80%, X: less than 80% (5) Weather resistance: Evaluated by appearance after 200 hours of sunshine weatherometer.
A: No abnormality, B: Slight roughness on the coating surface, X: Roughness on the entire coating surface.
（６）耐食性：中性塩水噴霧試験は、ＪＩＳ Ｋ ５６００−７−１に従い実施し、塗膜にクロスカットを入れ、７２時間後のブリスターの幅で評価、◎：０ｍｍ、○：３ｍｍ未満、×：３ｍｍ以上。
（７）耐酸性：内径３２ｍｍ、高さ３０ｍｍのリングをワセリンで塗膜表面に接触させ、リングの高さ１／２まで５％硫酸水溶液を入れ、２０℃で１２０時間後の外観状態をＲ．Ｎ．で評価：◎：Ｒ．Ｎ．９．８以上、○：Ｒ．Ｎ．９〜９．５、×：Ｒ．Ｎ．９未満。（８）耐アルカリ性：内径３２ｍｍ、高さ３０ｍｍのリングをワセリンで塗膜表面に接触させ、リングの高さ１／２まで５％水酸化ナトリウム水溶液を入れ、２０℃で４８時間後の外観状態をＲ．Ｎ．で評価：◎：Ｒ．Ｎ．９．８以上、○：Ｒ．Ｎ．９〜９．５、×：Ｒ．Ｎ．９未満。
（９）液経時安定性 液調整した後１ヶ月遮光容器中にて保存後、再電着した時の電着塗膜外観（ピンホール）で評価。◎：なし、○：少しある、×：多い。
(6) Corrosion resistance: Neutral salt spray test was conducted according to JIS K 5600-7-1, put a crosscut into the coating film, and evaluated by the width of the blister after 72 hours, ◎: 0 mm, ◯: less than 3 mm, X: 3 mm or more.
(7) Acid resistance: A ring with an inner diameter of 32 mm and a height of 30 mm was brought into contact with the surface of the coating film with petrolatum, 5% sulfuric acid aqueous solution was added to the height of the ring, and the appearance after 120 hours at 20 ° C was R. . N. Evaluation: A: R.D. N. 9.8 or more, O: R.I. N. 9-9.5, x: R.I. N. Less than 9. (8) Alkali resistance: A ring with an inner diameter of 32 mm and a height of 30 mm is brought into contact with the surface of the coating film with petrolatum, a 5% aqueous sodium hydroxide solution is added to the height of the ring, and the appearance after 48 hours at 20 ° C. R. N. Evaluation: A: R.D. N. 9.8 or more, O: R.I. N. 9-9.5, x: R.I. N. Less than 9.
(9) Stability over time of liquid Evaluation was made on the appearance of the electrodeposition coating film (pinhole) when re-deposited after storage in a light-shielding container for 1 month after liquid adjustment. A: None, B: Some, X: Many.
本発明の紫外線硬化型カチオン電着塗料用組成物を使用することで照射光量が低くなるためプラスチックメッキ基材の変形がなく、経時で安定した塗膜性能が得られ、また、当該電着塗料用組成物を用いて形成された電着塗膜は、良好な表面硬化性、付着性、耐食性、耐候性、耐薬品性を有しており、産業上極めて有用である。 By using the ultraviolet curable cationic electrodeposition coating composition of the present invention, the amount of irradiation light is reduced, so that the plastic plating base material is not deformed, and a stable coating performance can be obtained over time. The electrodeposition coating film formed using the composition for coating has excellent surface curability, adhesion, corrosion resistance, weather resistance, and chemical resistance, and is extremely useful industrially.
Claims (2)
（ａ）置換基として３級アミノアルキル基を有する共重合性ビニル系単量体 ４
〜１５重量部
（ｂ）（ａ）以外の共重合性ビニル系単量体 ８５〜９６重量部
（ｃ）２，４−ジフェニル−４−メチル−１−ペンテンである付加開裂型連鎖移動剤
共重合性ビニル系単量体（ａ）と（ｂ）の合計１００重量部に対し、０．０
５〜２０重量部
（Ｂ） 一分子中に３個以上の不飽和基を有する化合物 ２０〜５０重量部、
（Ｃ） アルコール系溶剤を３％含む水１００ｇに対する２５℃での溶解量が０．０２ｇ未満、且つ、２００ｎｍ〜４００ｎｍにおける極大吸収のモル吸光係数εが１０，０００Ｌ／ｍｏｌ・ｃｍ以上である２−ヒドロキシ−１−｛４−［４−（２−ヒドロキシ−２−メチルプロピオニル）−ベンジル］フェニル｝−２−メチルプロパン−１−オン、２−メチル−１−［４−（メチルチオ）フェニル］−２−（４−モルフォリニル）−１−プロパノン、及び、１−［４−（４−ベンゾイルフェニルスルファニル）フェニル］−２−メチル−２−［（４−メチルフェニル）スルフォニル］プロパン−１−オンから選ばれる１種又は２種以上の光重合開始剤 （Ａ）と（Ｂ）の合計１００重量部に対して、０．１〜８重量部
を含有することを特徴とする紫外線硬化型カチオン電着塗料用組成物。 (A) A water-soluble or water-dispersible vinyl copolymer having an unsaturated group at the end of the main chain, obtained by copolymerization using the following components (a) to (c): 50 to 80 Parts by weight,
(A) Copolymerizable vinyl monomer having a tertiary aminoalkyl group as a substituent 4
-15 parts by weight (b) 85-96 parts by weight of a copolymerizable vinyl monomer other than (a)
(C) Addition-cleavage chain transfer agent which is 2,4-diphenyl-4-methyl-1-pentene
For a total of 100 parts by weight of copolymerizable vinyl monomers (a) and (b), 0.0%
5-20 parts by weight
(B) 20-50 parts by weight of a compound having 3 or more unsaturated groups in one molecule,
(C) The amount of dissolution at 25 ° C. in 100 g of water containing 3% of an alcohol solvent is less than 0.02 g, and the molar absorption coefficient ε of the maximum absorption at 200 nm to 400 nm is 10,000 L / mol · cm 2 -Hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] phenyl} -2-methylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] 2- (4-morpholinyl) -1-propanone and 1- [4- (4-benzoylphenylsulfanyl) phenyl] -2-methyl-2-[(4-methylphenyl) sulfonyl] propan-1-one 100 parts by weight of the total of one or two or more photopolymerization initiators selected from the (a) (B), and characterized in that it contains 0.1 to 8 parts by weight UV curable cationic electrodeposition coating composition that.
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| CN 200810130393 CN101397470B (en) | 2007-09-26 | 2008-07-16 | Composite for ultraviolet ray curable cation electrodeposition coating and film thereof |
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