JPH0474892A - Formation of coating film - Google Patents
Formation of coating filmInfo
- Publication number
- JPH0474892A JPH0474892A JP18830890A JP18830890A JPH0474892A JP H0474892 A JPH0474892 A JP H0474892A JP 18830890 A JP18830890 A JP 18830890A JP 18830890 A JP18830890 A JP 18830890A JP H0474892 A JPH0474892 A JP H0474892A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- parts
- water
- epoxy
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 118
- 239000011248 coating agent Substances 0.000 title claims abstract description 108
- 230000015572 biosynthetic process Effects 0.000 title description 3
- 239000002253 acid Substances 0.000 claims abstract description 31
- 238000004070 electrodeposition Methods 0.000 claims abstract description 30
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 29
- 229920001225 polyester resin Polymers 0.000 claims abstract description 23
- 239000004645 polyester resin Substances 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 12
- 229920003180 amino resin Polymers 0.000 claims abstract description 5
- 229920001982 poly(ester urethane) Polymers 0.000 claims abstract 2
- 239000003973 paint Substances 0.000 claims description 81
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 64
- 125000002091 cationic group Chemical group 0.000 claims description 45
- 239000000126 substance Substances 0.000 claims description 15
- 229920005862 polyol Polymers 0.000 claims description 11
- 150000003077 polyols Chemical class 0.000 claims description 10
- 238000013007 heat curing Methods 0.000 claims description 9
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 238000009713 electroplating Methods 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 26
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 abstract description 13
- 150000001768 cations Chemical class 0.000 abstract description 4
- 150000005215 alkyl ethers Chemical class 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 105
- 239000011347 resin Substances 0.000 description 105
- 239000010408 film Substances 0.000 description 72
- 238000001723 curing Methods 0.000 description 66
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 57
- -1 isocyanate compounds Chemical class 0.000 description 51
- 125000003700 epoxy group Chemical group 0.000 description 50
- 150000001875 compounds Chemical class 0.000 description 47
- 239000004593 Epoxy Substances 0.000 description 36
- 239000002585 base Substances 0.000 description 33
- 229920000647 polyepoxide Polymers 0.000 description 31
- 239000007787 solid Substances 0.000 description 31
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 25
- 239000003822 epoxy resin Substances 0.000 description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 24
- 125000000524 functional group Chemical group 0.000 description 22
- 239000000047 product Substances 0.000 description 21
- 125000002723 alicyclic group Chemical group 0.000 description 20
- 238000004519 manufacturing process Methods 0.000 description 20
- 239000003795 chemical substances by application Substances 0.000 description 18
- 150000001334 alicyclic compounds Chemical class 0.000 description 17
- 239000000178 monomer Substances 0.000 description 17
- 229920001228 polyisocyanate Polymers 0.000 description 17
- 239000005056 polyisocyanate Substances 0.000 description 17
- 239000002981 blocking agent Substances 0.000 description 16
- 239000000049 pigment Substances 0.000 description 16
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 14
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 13
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 238000004132 cross linking Methods 0.000 description 11
- 239000003960 organic solvent Substances 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 10
- 229920000877 Melamine resin Polymers 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 230000037303 wrinkles Effects 0.000 description 9
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 8
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 8
- 235000011054 acetic acid Nutrition 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 125000005442 diisocyanate group Chemical group 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 238000007665 sagging Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- 150000001298 alcohols Chemical class 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 description 6
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 6
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 6
- 244000028419 Styrax benzoin Species 0.000 description 6
- 235000000126 Styrax benzoin Nutrition 0.000 description 6
- 235000008411 Sumatra benzointree Nutrition 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
- 229960002130 benzoin Drugs 0.000 description 6
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 235000019382 gum benzoic Nutrition 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 6
- 235000013824 polyphenols Nutrition 0.000 description 6
- 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 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 5
- 150000001721 carbon Chemical group 0.000 description 5
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- 238000010422 painting Methods 0.000 description 5
- 238000007142 ring opening reaction Methods 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 4
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 4
- FYYIUODUDSPAJQ-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 2-methylprop-2-enoate Chemical compound C1C(COC(=O)C(=C)C)CCC2OC21 FYYIUODUDSPAJQ-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000006735 epoxidation reaction Methods 0.000 description 4
- 235000019253 formic acid Nutrition 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 238000007592 spray painting technique Methods 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 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 4
- 229910000165 zinc phosphate Inorganic materials 0.000 description 4
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000004359 castor oil Substances 0.000 description 3
- 235000019438 castor oil Nutrition 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 125000001841 imino group Chemical group [H]N=* 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- WGYKZJWCGVVSQN-UHFFFAOYSA-N mono-n-propyl amine Natural products CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 3
- DFENKTCEEGOWLB-UHFFFAOYSA-N n,n-bis(methylamino)-2-methylidenepentanamide Chemical compound CCCC(=C)C(=O)N(NC)NC DFENKTCEEGOWLB-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 150000002923 oximes Chemical class 0.000 description 3
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 150000003839 salts Chemical group 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- PTJXTWSQQDGHHY-UHFFFAOYSA-N 1-ethyl-3-methylcyclopenta-1,3-diene Chemical compound CCC1=CC(C)=CC1 PTJXTWSQQDGHHY-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 2
- ZGHFDIIVVIFNPS-UHFFFAOYSA-N 3-Methyl-3-buten-2-one Chemical compound CC(=C)C(C)=O ZGHFDIIVVIFNPS-UHFFFAOYSA-N 0.000 description 2
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- CVKMDAZAUGXUFX-UHFFFAOYSA-N C1C2(C=C)CCC1C1C2O1 Chemical compound C1C2(C=C)CCC1C1C2O1 CVKMDAZAUGXUFX-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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- 229940057867 methyl lactate Drugs 0.000 description 1
- UJNZOIKQAUQOCN-UHFFFAOYSA-N methyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C)C1=CC=CC=C1 UJNZOIKQAUQOCN-UHFFFAOYSA-N 0.000 description 1
- SOOARYARZPXNAL-UHFFFAOYSA-N methyl-thiophenol Natural products CSC1=CC=CC=C1O SOOARYARZPXNAL-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 description 1
- IONSZLINWCGRRI-UHFFFAOYSA-N n'-hydroxymethanimidamide Chemical compound NC=NO IONSZLINWCGRRI-UHFFFAOYSA-N 0.000 description 1
- QHJABUZHRJTCAR-UHFFFAOYSA-N n'-methylpropane-1,3-diamine Chemical compound CNCCCN QHJABUZHRJTCAR-UHFFFAOYSA-N 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- 230000003533 narcotic effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 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
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 150000003003 phosphines Chemical group 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- WXNYILVTTOXAFR-UHFFFAOYSA-N prop-2-en-1-ol;styrene Chemical compound OCC=C.C=CC1=CC=CC=C1 WXNYILVTTOXAFR-UHFFFAOYSA-N 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-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
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 102220190959 rs577182758 Human genes 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- 235000005713 safflower oil Nutrition 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000004819 silanols Chemical class 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- JLGUDDVSJCOLTN-UHFFFAOYSA-N strontium;oxido-(oxido(dioxo)chromio)oxy-dioxochromium Chemical compound [Sr+2].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JLGUDDVSJCOLTN-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 229930006978 terpinene Natural products 0.000 description 1
- 150000003507 terpinene derivatives Chemical class 0.000 description 1
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- 150000003954 δ-lactams Chemical class 0.000 description 1
Abstract
Description
【発明の詳細な説明】
り鼠上Ω五里豆I
本発明はカチオン電@塗料と水性塗料(非電@)とをウ
ェットオンウェットで塗装し1次いで該両塗膜を加熱に
より同時に硬化せしめる、いわゆる2コ一ト1ベーク方
式による新規な複層塗膜形成法に関する。[Detailed Description of the Invention] The present invention involves coating a cationic electrolyte paint and a water-based paint (non-electrolyte) wet-on-wet, and then curing both coatings simultaneously by heating. , relates to a novel multilayer coating film formation method using a so-called two-coat one-bake method.
′ の 1とその課
カヂオン電着塗料を電着塗装し加熱硬化してから、該塗
面に中塗り塗料もしくは上塗り塗料を塗装し、加熱硬化
することが多く行なわれているい
しかしながら、近年、塗装工程の短縮化、省資源および
公害防止などの観点から、カチオン電着塗膜を加熱硬化
させることなく該塗面に水性の中塗り又は上塗り塗料を
塗装したのち、該両塗膜を加熱により同時に硬化せしめ
る2コ一ト1ベータ方式による塗膜形成法の開発が強く
望まれているが、未だ実用に到っていない6
例えばカチオンWt塗装未硬化塗面に有機溶列形塗料を
塗装したのち、加熱して該両塗膜を同時に硬化させると
、未硬化のカチオン電着塗膜は有機溶剤型塗料中に含ま
れる有機溶剤によって膨潤や侵食を受け、加熱硬化後の
塗膜面に凹凸やシワ、チヂミなどが発生しやすい。1 and its sections It is common practice to electrodeposit cationic electrodeposition paint, heat cure it, and then apply an intermediate coat or top coat to the coated surface and heat cure it.However, in recent years, coating From the viewpoint of shortening the process, saving resources, and preventing pollution, a water-based intermediate coat or top coat is applied to the coated surface without heating and curing the cationic electrodeposition coating, and then both coatings are simultaneously heated. Although there is a strong desire to develop a coating film forming method using a two-coat one-beta method for curing, it has not yet been put to practical use6. When both coating films are simultaneously cured by heating, the uncured cationic electrodeposited coating is swollen and eroded by the organic solvent contained in the organic solvent-based coating, resulting in unevenness and unevenness on the coating surface after heating and curing. Wrinkles and blemishes are likely to occur.
また、上記有機溶列形塗料に代えて、ポリエステル樹脂
およびフルエーテル化メラミン樹脂を主成分とする水性
塗料を用いると、凹凸、シワ、チヂミなとは殆ど発生し
ないが、加熱時に未硬化のカチオン1i@塗膜から揮散
する塩基性物質や、低分子物質が多量上層塗膜に移行し
て該上層塗膜の硬化反応阻害を生し十分硬化しない。さ
らに、該水性塗料自体の塗膜の平滑性や鮮映性が十分で
なく、しかも従来の有機溶剤型塗料に比べて、塗膜硬化
中に揮発成分(例えば水)が突沸じて、いわゆる「ワキ
」が発生しやすく、この現象は30〜40/J711の
膜厚においても肝、ぬられ、仕上がり外観低下の原因と
なっている。このワキによる塗膜欠陥を避けるため、あ
らかじめ低温度(約60℃)で予備加熱を行なって未硬
化塗膜中の水をほとんど揮散させてから、さらに昇温し
で加熱硬化すると、水分が十分揮散する前に未硬化塗膜
の温度が上昇し、従って塗膜粘度が低下して垂直部でタ
レを生じる。また、このタレを防止するため、しオロジ
ーコントロール剤や体質面粗等を配合して構造粘性を大
きくすると、塗着した塗液の流展性が低下し、加熱硬化
後の水性塗料塗膜の平滑性が悪くなる。更に、ワキ対策
のため、カラス転移温度の低い脂肪酸変性ポリエステル
樹脂を基体樹脂として用いると、タレ易くなり、塗膜の
硬度も低下し、該塗面に塗装した塗膜の鮮映性が不足す
る。In addition, if a water-based paint containing polyester resin and full etherified melamine resin as the main components is used instead of the above-mentioned organic solution type paint, unevenness, wrinkles, and stiffness will hardly occur, but uncured cations will form when heated. 1i@ A large amount of basic substances and low-molecular substances volatilized from the coating film migrates to the upper coating film and inhibits the curing reaction of the upper coating film, resulting in insufficient curing. Furthermore, the smoothness and sharpness of the film of the water-based paint itself are not sufficient, and compared to conventional organic solvent-based paints, volatile components (e.g., water) boil out during the curing of the paint film, so-called " This phenomenon is a cause of wetting and deterioration of the finished appearance even in a film thickness of 30 to 40/J711. In order to avoid paint film defects caused by this blistering, preheating is performed at a low temperature (approximately 60°C) to volatilize most of the water in the uncured paint film, and then the temperature is further raised to heat cure to ensure sufficient water content. Before volatilization, the temperature of the uncured coating film increases, and the viscosity of the coating film decreases, causing sag in the vertical portions. In addition, in order to prevent this sagging, if the structural viscosity is increased by adding a hardening agent or surface roughening agent, the flowability of the applied coating liquid will decrease, and the water-based paint film after heat curing will deteriorate. Smoothness deteriorates. Furthermore, when a fatty acid-modified polyester resin with a low glass transition temperature is used as a base resin to prevent underarm spots, it tends to sag, the hardness of the coating film decreases, and the clarity of the coating film applied to the coating surface is insufficient. .
課 ”するための 「
本発明はカチオン電着塗膜および水性塗料を2コ一ト1
ベーク方式で塗装する工程における前記欠陥の解消を目
的としており、鋭意研究の結果、特定された両塗料を用
いることによって目的を達成でき、本発明を完成した。The present invention consists of two coats of a cationic electrodeposition coating and a water-based paint.
The purpose was to eliminate the above-mentioned defects in the baking process, and as a result of intensive research, the purpose was achieved by using both paints specified, and the present invention was completed.
すなわち、本発明は、カチオンを前塗装未硬化塗膜面に
水性塗料を塗装し、加熱して該両塗膜を同時に硬化させ
て複層塗膜を形成するにあたり、該カチオン電11塗料
の電着塗膜の加熱硬化時における塗膜減量が10重量%
以下であり、そして上記水性塗料が、
(a)酸価10〜100および水酸基価20〜300の
ポリエステル樹脂および/またはウレタン変性ポリエス
テル樹脂、
(b)水性アミノ樹脂および
(c)一般式
%式%)
で示されるポリエーテルポリオール
を主成分とし、さらに必要に応して
(d)アルキルエーテル化ベンゾイン
を配合してなる塗料であることを特徴とする塗膜形成法
に関する。That is, the present invention provides a method for forming a multilayer coating by applying a water-based coating onto the uncured surface of a pre-coated cationic coating and curing both coatings simultaneously by heating. Coating film loss during heat curing of deposited film is 10% by weight
and the water-based paint is (a) a polyester resin and/or a urethane-modified polyester resin with an acid value of 10 to 100 and a hydroxyl value of 20 to 300, (b) an aqueous amino resin, and (c) a general formula % formula %. ) The present invention relates to a method for forming a coating film, characterized in that the coating material is a coating material containing as a main component a polyether polyol represented by the following formula, and further containing (d) alkyl etherified benzoin as required.
本発明の方法は、2コ一トlベーク方式であるため、カ
チオン電着塗膜のみを硬化するための加熱乾燥炉が全く
必要でないのでその設備費、用地および炉のランニング
諸経費(燃料費、メンテナンス費その他)がすべて省略
できる。Since the method of the present invention is a two-coat one-baking method, there is no need for a heating drying oven for curing only the cationic electrodeposited coating, and therefore the equipment cost, site, and furnace running expenses (fuel costs, etc.) are not required. , maintenance costs, etc.) can all be omitted.
また、上記両塗料は水を主な溶媒又は分散媒としている
ために、安全衛生、省資源および公害防止に有利である
。Further, since both of the above paints use water as the main solvent or dispersion medium, they are advantageous in terms of safety and health, resource saving, and pollution prevention.
さらに、本発明によって形成される複層塗膜は、前記従
来法に比べて、塗面の平滑性、光沢ならびに鮮映性、塗
膜の付着性、耐湿性、耐チッピング性および硬化性がす
ぐれており、しかも、ワキ、タレ、シワ、チヂミおよび
凹凸などの発生も全く認められないという技術的効果も
有している。Furthermore, the multilayer coating film formed by the present invention has superior coating surface smoothness, gloss, and sharpness, coating adhesion, moisture resistance, chipping resistance, and curing properties compared to the conventional method. Moreover, it also has the technical effect of not showing any occurrence of wrinkles, sagging, wrinkles, sagging, unevenness, etc.
まず、本発明の方法で用いるカチオン電着塗料(以下、
「塗料(A)」と略称することがある)は、そのt@塗
膜の加熱硬化時の塗膜減量が10重量%以下、特に好ま
しくは7重量%以下であることが必要である。10重量
%より大きくなると、その塗面に塗装した水性塗料の塗
面の平滑性や鮮映性などが低下するので好ましくない。First, the cationic electrodeposition paint (hereinafter referred to as
It is necessary for the paint (sometimes abbreviated as "paint (A)") to have a coating loss of 10% by weight or less, particularly preferably 7% by weight or less, during heat curing of the t@coating film. If it exceeds 10% by weight, it is not preferable because the smoothness and sharpness of the water-based paint applied to the painted surface will deteriorate.
本発明において、塗料(A)の電着塗膜の加熱硬化時の
塗膜減量・(X)は、まず、通常の条件でカチオン電着
塗装を行ない、電着浴から引き上げて塗面を水洗し、1
05°Cで3時間加熱して塗膜中の水分のすべてもしく
は殆どを除去してから塗膜重量(Y)を測定し、次いで
、170’cて20分加熱して該塗膜を三次元架橋硬化
した後の塗膜型1 (Z)を測定した。これらの測定値
を次式にあてはめて塗膜減量(X)をもとめた。In the present invention, the coating film loss (X) during heat curing of the electrodeposited coating film of paint (A) is determined by first performing cationic electrodeposition coating under normal conditions, then removing it from the electrodeposition bath and washing the coated surface with water. 1
The coating film weight (Y) was measured after heating at 05°C for 3 hours to remove all or most of the water in the film, and then heating at 170°C for 20 minutes to transform the film into a three-dimensional The coating film type 1 (Z) after crosslinking and curing was measured. These measured values were applied to the following formula to determine the coating film weight loss (X).
塗料Aは、加熱硬化時の塗膜減量が10重量%以下、好
ましくは7重量%以下のカチオン電着塗料であれば制限
を受けないが、特にこれらの条件を有する以下に例示す
るカチオン電着塗料(A−1)および(A−2)が好ま
しい。Coating A is not limited as long as it has a coating film loss of 10% by weight or less, preferably 7% by weight or less during heat curing, but in particular, the following cationic electrodeposition coatings having these conditions: Paints (A-1) and (A-2) are preferred.
塗料(A−1):水酸基およびカチオン性基を含有する
樹脂(I)と、脂環式骨格および/または有橋脂環式骨
格にエポキシ基が結合してなるエポキシ基含有官能基を
1分子あたり平均2個以上有するエポキシ樹脂(II)
とを主成分として含有するカチオン電着塗料。Paint (A-1): One molecule of resin (I) containing a hydroxyl group and a cationic group, and an epoxy group-containing functional group formed by bonding an epoxy group to an alicyclic skeleton and/or a bridged alicyclic skeleton. Epoxy resin (II) having an average of 2 or more per
A cationic electrodeposition paint containing as the main component.
該塗料(A−1)を用いて形成される電着塗膜は約25
0℃以下の温度で硬化する。そして特に、鉛、ジルコニ
ウム、コバルト、アルミニウム、マンガン、銅、亜鉛、
鉄、クロム、ニッケル等の金属を含む化合物の単独又は
複数を触媒として配合すると、約り0℃〜約160°C
という低温加熱でも硬化させることができる。これらの
硬化はエポキシ樹脂(IT)に含まれるエポキシ基が開
環して、樹脂(I)中の水酸基(好ましくは第1級のも
の)と反応して、さらに、該樹脂(II)中のエポキシ
基同士が反応して、それぞれエーテル結合を形成して架
橋硬化するものと推察され、硬化反応時に副生物の発生
が殆どなく、塗膜減量が極めて少ない。The electrodeposited film formed using the paint (A-1) has a thickness of about 25
Cures at temperatures below 0°C. and especially lead, zirconium, cobalt, aluminum, manganese, copper, zinc,
When one or more compounds containing metals such as iron, chromium, and nickel are used as a catalyst, the temperature ranges from about 0°C to about 160°C.
It can also be cured by heating at a low temperature. In these curing processes, the epoxy group contained in the epoxy resin (IT) opens the ring, reacts with the hydroxyl group (preferably primary type) in the resin (I), and then It is presumed that the epoxy groups react with each other to form ether bonds, resulting in crosslinking and curing, and there are almost no by-products generated during the curing reaction, and the weight loss of the coating film is extremely small.
従って、塗料(A−1)は、錫触媒を用いなくても16
0℃以下の低温で硬化させることができる。さらに、ブ
ロックイソシアネート化合物又はその誘導体を使用する
必要がない、熱分解による加熱減量(体積収縮)が少な
く良好な付着性を示す:架橋結合中に芳香族ウレタン結
合又は芳香族尿素結合を持ち込むことがない:電着塗膜
の防食性ならびに硬化性がすぐれている:電着浴の安定
性が良好である:などの種々の優れた利点を有する9
塗料(A−1)に使用される水酸基及びカチオン性基を
有する樹脂(1)(以下このものを「基体樹脂(■)」
ということもある)には、(II)成分のエポキシ基と
反応しつる水酸基を含有し且つ安定な水性分散物を形成
するのに十分な数のカチオン性基を有する任意の樹脂が
包含される。しかして、該基体樹脂(I)としては例え
ば次のものが挙げられる。Therefore, the paint (A-1) can be used without using a tin catalyst.
It can be cured at a low temperature of 0°C or lower. Furthermore, there is no need to use blocked isocyanate compounds or their derivatives, and there is little heating loss (volume shrinkage) due to thermal decomposition, which shows good adhesion: it is possible to introduce aromatic urethane bonds or aromatic urea bonds during crosslinking. 9. Hydroxyl groups used in paint (A-1) and Resin (1) having a cationic group (hereinafter referred to as "base resin (■)")
) includes any resin that contains a hydroxyl group that reacts with the epoxy group of component (II) and has a sufficient number of cationic groups to form a stable aqueous dispersion. . Examples of the base resin (I) include the following.
(1)ポリエポキシ樹脂とカチオン化剤とを反応せしめ
て得られる反応生成物:
(11)ポリカルボン酸とポリアミンとの重縮合物(米
国特許筒2.450.940号明細書参照)を酸でプロ
トン化したもの:
(i)ポリイソシアネート及びポリオールとモノ又はポ
リアミンとの重付加物を酸でプロトン化したもの
(1v)水酸基ならびにアミン基含有アクリル系又はビ
ニル系モノマーの共重合体を酸でプロトン化したもの(
特公昭45−12395号公報、特公開45−1239
6号公報参照);
(V)ポリカルボン酸樹脂とアルキレンイミンとの付加
物を酸でプロトン化したもの(米国特許第3.403.
088号明細書参照)1等。(1) Reaction product obtained by reacting a polyepoxy resin and a cationizing agent: (11) A polycondensate of a polycarboxylic acid and a polyamine (see U.S. Pat. No. 2,450,940). (i) Polyadducts of polyisocyanates and polyols with mono- or polyamines are protonated with acids. (1v) Copolymers of acrylic or vinyl monomers containing hydroxyl groups and amine groups are protonated with acids. Protonated (
Special Publication No. 45-12395, Publication No. 45-1239
(V) An adduct of a polycarboxylic acid resin and an alkylene imine which is protonated with an acid (see US Pat. No. 3.403.
(See specification of No. 088) 1st prize.
これらのカチオン性樹脂の具体例及び製造方法について
は、例えば特公昭45−12395号公報、特公昭45
−12396号公報、特公昭49−23087号公報、
米国特許第2.450.940号明細書、米国特許第3
.403.088号明細書、米国特許第3.891.5
29号明細書、米国特許第3.963.663号明細書
等に記載されているので、ここではこれらの引用を以っ
て詳細な記述に代久る。For specific examples and manufacturing methods of these cationic resins, see, for example, Japanese Patent Publication No. 45-12395,
-12396 Publication, Special Publication No. 49-23087,
U.S. Patent No. 2.450.940, U.S. Patent No. 3
.. No. 403.088, U.S. Pat. No. 3.891.5
No. 29, US Pat. No. 3,963,663, etc., and therefore detailed descriptions thereof will be made by citing these references here.
基体樹脂(I)として特に望ましいのは、前記(1)に
包含される、ポリフェノール化合物とエピクロルヒドリ
ンとから得られる防食性に優れているポリエポキシド化
合物のエポキシ基にカチオン化剤を反応せしめて得られ
る反応性生成物である。Particularly desirable as the base resin (I) is a reaction obtained by reacting a cationizing agent with the epoxy group of a polyepoxide compound with excellent corrosion resistance obtained from a polyphenol compound and epichlorohydrin, which is included in the above (1). It is a sexual product.
前記ポリエポキシド化合物は、エポキシ基る化合物で、
一般に少なくとも200、好ましくは400〜4.00
0、さらに好ましくは800〜2.000の範囲内の数
平均分子量を有するものが適している。そのようなポリ
エポキシド化合物としてはそれ自体公知のものを使用す
ることができ、例えば、ポリフェノール化合物をアルカ
リの存在下にエピクロルヒドリンと反応させることによ
り製造することができるポリフェノール化合物のポリグ
リシジルエーテルが包含される。ここで使用しつるポリ
フェノール化合物としては、例えば、ビス(4−ヒドロ
キシフェニル)−2,2=プロパン、4,4′ジヒドロ
キシベンゾフエノン、ビス(4−ヒドロキシフェニル)
−1,1エタン、ビス=(4−ヒドロキシフェニル)1
.1−イソブタン、ビス(4−ヒドロキシ−tert−
ブチル−フェニル)−2,2−プロパン、ビス(2−ヒ
ドロキシナフチル)メタン、1.5−ジヒドロキシナフ
タレン、ビス(2,4−ジヒドロキシフェニル)メタン
、テトラ(4−ヒドロキシフェニル)−1,1,2,2
−エタン、4.4′−ジヒドロキシジフェニルエーテル
、4.4′−ジヒドロキシジフェニルスルホン、フェノ
ールノボラック、クレゾールノボラック等が挙げられる
。The polyepoxide compound is an epoxy group compound,
Generally at least 200, preferably from 400 to 4.00
Those having a number average molecular weight in the range of 0, more preferably 800 to 2.000 are suitable. As such polyepoxide compounds, those known per se can be used, and include, for example, polyglycidyl ethers of polyphenol compounds that can be produced by reacting polyphenol compounds with epichlorohydrin in the presence of an alkali. . Examples of the polyphenol compounds used here include bis(4-hydroxyphenyl)-2,2=propane, 4,4' dihydroxybenzophenone, and bis(4-hydroxyphenyl)-2,2=propane.
-1,1 ethane, bis=(4-hydroxyphenyl)1
.. 1-isobutane, bis(4-hydroxy-tert-
butyl-phenyl)-2,2-propane, bis(2-hydroxynaphthyl)methane, 1,5-dihydroxynaphthalene, bis(2,4-dihydroxyphenyl)methane, tetra(4-hydroxyphenyl)-1,1, 2,2
-ethane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, phenol novolak, cresol novolak, and the like.
上記したポリエポキシド化合物の中で、基体樹脂(I)
の製造に特に適当なものは、数平均分子量が少なくとも
約380、より好適には約800〜約2.000、及び
エポキシ当量が190〜2.000、好適には400〜
1.000の範囲内のポリフェノール化合物のポリグリ
シジルエーテルであり、殊に下記式
で示されるものである。該ポリエポキシド化合物は、ポ
リオール、ポリエーテルポリオール、ポリエステルポリ
オール、ポリアミドアミン、ポリカルボン酸、ポリイソ
シテネートなどと部分的に反応させてもよく、さらに、
δ−4カプロラクトン、アクリルモノマーなどをグラフ
ト重合させてもよい。Among the polyepoxide compounds described above, base resin (I)
Particularly suitable for the preparation of are those having a number average molecular weight of at least about 380, more preferably from about 800 to about 2.000, and an epoxy equivalent weight of from 190 to 2.000, preferably from 400 to
It is a polyglycidyl ether of a polyphenol compound within the range of 1.000, especially one represented by the following formula. The polyepoxide compound may be partially reacted with a polyol, polyether polyol, polyester polyol, polyamide amine, polycarboxylic acid, polyisocytenate, etc., and further,
Graft polymerization of δ-4 caprolactone, acrylic monomer, etc. may be performed.
一方、上記ポリエポキシド化合物にカチオン性基を導入
するためのカチオン化剤としては、脂肪族または脂環族
または芳香−脂肪族の第1級もしくは第2級アミン、第
3級アミン塩、第2級スルフィド塩、第3級ホスフィン
塩などが挙げられる。これらはエポキシ基と反応してカ
チオン性基を形成する。さらに第3級アミノアルコール
とジイソシアネートの反応によって得られる第3級アミ
ノモノイソシアネートをエポキシ樹脂の水酸基と反応さ
せてカチオン性基とすることもできる。On the other hand, examples of the cationizing agent for introducing a cationic group into the polyepoxide compound include aliphatic, alicyclic, or aromatic-aliphatic primary or secondary amines, tertiary amine salts, secondary Examples include sulfide salts and tertiary phosphine salts. These react with epoxy groups to form cationic groups. Furthermore, a tertiary amino monoisocyanate obtained by the reaction of a tertiary amino alcohol and a diisocyanate can be reacted with a hydroxyl group of an epoxy resin to form a cationic group.
前記カチオン化剤におけるアミン化合物の例としては、
例えば次のものを例示することができる。Examples of the amine compound in the cationizing agent include:
For example, the following can be exemplified.
(1)メチルアミン、エチルアミン、n−又は1so−
プロピルアミン、モノエタノールアミン、n−又は1s
o−プロパツールアミンなどの第1級アミン
(2)ジエチルアミン、ジェタノールアミン、ンn−又
は1so−プロパツールアミン、N−メチルエタノール
アミン、N−エチルエタノールアミンなどの第2級アミ
ン
(3)エチレンジアミン、ジエチレントリアミン、ヒド
ロキシエチルアミンエチルアミン、エチルアミノエヂル
アミン、メチルアミノプロピルアミン、ジメチルアミノ
エチルアミン、ジメチルアミノプロピルアミンなどのポ
リアミン。(1) Methylamine, ethylamine, n- or 1so-
Propylamine, monoethanolamine, n- or 1s
Primary amines such as o-properamine (2) Secondary amines such as diethylamine, jetanolamine, n- or 1so-properamine, N-methylethanolamine, N-ethylethanolamine (3) Polyamines such as ethylene diamine, diethylene triamine, hydroxyethylamine ethylamine, ethylaminoedylamine, methylaminopropylamine, dimethylaminoethylamine, dimethylaminopropylamine.
これらの中で水酸基を有するアルカノールアミン類が好
ましい。また、第1級アミノ基を予めケトンと反応させ
てブロックした後、残りの活性水素でエポキシ基と反応
させでもよい。Among these, alkanolamines having a hydroxyl group are preferred. Alternatively, the primary amino group may be blocked by reacting with a ketone in advance, and then the remaining active hydrogen may be reacted with the epoxy group.
さらに、上記アミン化合物以外にアンモニア、ヒドロキ
シルアミン、ヒドラジン、ヒドロキシエヂルヒドラジン
、N−ヒドロキシエチルイミダシリン化合物などの塩基
性化合物も同様に使用することができる。これらの化合
物を用いて形成される塩基性基は酸、特に好ましくはギ
酸、酢酸、グリコール酸、乳酸などの水滴性有機カルボ
ン酸でプロトン化してカチオン性基とすることができる
。Furthermore, in addition to the above-mentioned amine compounds, basic compounds such as ammonia, hydroxylamine, hydrazine, hydroxyedylhydrazine, and N-hydroxyethylimidacillin compounds can also be used. The basic group formed using these compounds can be protonated to a cationic group with an acid, particularly preferably a water-dropping organic carboxylic acid such as formic acid, acetic acid, glycolic acid, or lactic acid.
さらに、トリエチルアミン、トリエタノールアミン、N
、N−ジメチルエタノールアミン、N−メチルジェタノ
ールアミン、N、N−ジエチルエタノールアミン、N−
エチルジェタノールアミンなどの第3級アミンなども使
用でき、これらは酸で予めプロトン化し、エポキシ基と
反応させて第4級塩にすることができる。Furthermore, triethylamine, triethanolamine, N
, N-dimethylethanolamine, N-methyljetanolamine, N,N-diethylethanolamine, N-
Tertiary amines such as ethyljetanolamine can also be used, and these can be preprotonated with acid and reacted with epoxy groups to form quaternary salts.
また、アミノ化合物以外に、ジエチルスルフィド、ジフ
ェニルスルフィド、テトラメチレンスルフィド、チオジ
ェタノールなどのスルフィド類とホウ酸、炭酸、有機モ
ノカルボン酸などとの塩をエポキシ基と反応させて第3
級スルホニウム塩としてもよい。In addition to amino compounds, salts of sulfides such as diethyl sulfide, diphenyl sulfide, tetramethylene sulfide, and thiogetanol with boric acid, carbonic acid, organic monocarboxylic acids, etc. can be reacted with epoxy groups to form a tertiary compound.
It may also be used as a class sulfonium salt.
更に、トリエチルホスフィン、フエニルジメチルホスフ
ィン、ジフェニルメチルホスフィン、トリフェニルホス
フィンなどのホスフィン類と上記の如き酸との塩をエポ
キシ基と反応させて、第4級ホスホニウム塩としてもよ
い。Furthermore, a salt of a phosphine such as triethylphosphine, phenyldimethylphosphine, diphenylmethylphosphine, or triphenylphosphine and the above-mentioned acid may be reacted with an epoxy group to form a quaternary phosphonium salt.
基体樹脂(I)の水酸基としては、例えば、上記カチオ
ン化剤中のアルカノールアミン、エポキシド化合物中に
導入されることがあるカプロラクトンの開環物およびポ
リオールなどから導入できる第1級水酸基;エポキシ樹
脂中の2級水酸基9などがあげられる。このうち、アル
カノールアミンにより導入される第1級水酸基はエポキ
シ樹脂(II )との架橋硬化反応性がすぐれているの
で好ましい。このようなアルカノールアミンは前記カチ
オン化剤で例示したものが好ましい。Examples of the hydroxyl group in the base resin (I) include alkanolamines in the cationizing agent, primary hydroxyl groups that can be introduced from ring-opened products of caprolactone that may be introduced into epoxide compounds, polyols, etc.; Examples include the secondary hydroxyl group 9 of . Among these, primary hydroxyl groups introduced by alkanolamines are preferred because they have excellent crosslinking and curing reactivity with the epoxy resin (II). As such alkanolamines, those exemplified as the cationizing agent are preferable.
基体樹脂(I)における水酸基の含有量は、エポキシ樹
脂(II)に含まれるエポキシ基との架橋硬化反応性の
点からみて、水酸基当量で20〜5.000、特に10
0〜1.000の範囲内が好ましく、特に第1級水酸基
当量は200〜1.000の範囲内にあることが望まし
い。また、カチオン性基の含有量は、該基体樹脂(1)
を安定に分散しうる必要な最低限以上が好ましく、K
OH(mg/ g固形分)Cアミン価)換算で一般に3
〜200、特に10〜80の範囲内にあることが好まし
い。しかし、カチオン性基の含有量が3以下の場合であ
っても、界面活性剤などを使用して水性分散化して使用
することも可能であるが、この場合には、水性分散組成
物のpHが通常4〜9、より好ましくは6〜7になるよ
うにカチオン性基を調整するのが望ましい。The content of hydroxyl groups in the base resin (I) is 20 to 5.000 in terms of hydroxyl equivalent, especially 10 in terms of crosslinking and curing reactivity with the epoxy groups contained in the epoxy resin (II).
It is preferably within the range of 0 to 1.000, and it is particularly desirable that the primary hydroxyl equivalent is within the range of 200 to 1.000. In addition, the content of cationic groups is based on the base resin (1).
K is preferably at least the minimum necessary to stably disperse K.
Generally 3 in terms of OH (mg/g solid content) C amine value)
-200, particularly preferably in the range of 10-80. However, even if the content of cationic groups is 3 or less, it is possible to use aqueous dispersion using a surfactant, etc., but in this case, the pH of the aqueous dispersion composition It is desirable to adjust the cationic group so that the number is usually 4 to 9, more preferably 6 to 7.
基体樹脂(I)は、水酸基及びカチオン性基を有してお
り、遊離のエポキシ基は原則として含まないことが望ま
しい。The base resin (I) has a hydroxyl group and a cationic group, and preferably does not contain a free epoxy group in principle.
次に上記基体樹脂(I)と混合して使用される硬化剤と
してのエポキシ樹脂(II)について説明する。Next, the epoxy resin (II) as a curing agent used in combination with the base resin (I) will be explained.
該エポキシ樹脂(II)(以下このものを[硬化用樹脂
(II)Jということもある)は、基体樹脂(1)と主
として前記のごとくエーテル化反応などによって架橋硬
化塗膜を形成するための硬化剤であって、特定の「エポ
キシ基含有官能基」を1分子あたり平均2個以上、好ま
しくは3個以上有するものである。The epoxy resin (II) (hereinafter also referred to as "curing resin (II) J") is used to form a crosslinked cured coating film with the base resin (1) mainly through the etherification reaction as described above. A curing agent having an average of 2 or more, preferably 3 or more, specific "epoxy group-containing functional groups" per molecule.
すなわち、硬化用樹脂(II)における該エポキシ基含
有官能基は、脂環式骨格および/または有橋脂環式骨格
とエポキシ基とからなり、脂環式骨格は、4〜10員、
好ましくは5〜6員の飽和炭素環式環または該環が2個
以上縮合した縮合環を含有し、また、有橋脂環式骨格は
、上記環式または多環式環を構成する炭素原子2個の間
に直鎖状もしくは分岐鎖状の01〜6(好ましくは01
〜4)アルキレン基[例えば−CH2−1−CH2−C
H2−。That is, the epoxy group-containing functional group in the curing resin (II) consists of an alicyclic skeleton and/or a bridged alicyclic skeleton and an epoxy group, and the alicyclic skeleton is a 4- to 10-membered,
Preferably, the bridged alicyclic skeleton contains a 5- to 6-membered saturated carbocyclic ring or a condensed ring in which two or more of these rings are condensed, and the bridged alicyclic skeleton contains carbon atoms constituting the above-mentioned cyclic or polycyclic ring. Linear or branched chain 01-6 (preferably 01
~4) Alkylene group [e.g. -CH2-1-CH2-C
H2-.
−CH(CH$)−1−CH2(CH、) CH、−。-CH(CH$)-1-CH2(CH,) CH,-.
−C(CH−1g−1−CH(C2H,)CH2−など
]の橋(エンドメチレン、エンドエチレンなど)が結合
した環を含有するものである。It contains a ring to which a bridge of -C (CH-1g-1-CH(C2H,)CH2-, etc.) (endomethylene, endoethylene, etc.) is bonded.
ている[例えば、下記式(イ)、(ロ)誉照コか、或い
は該エポキシ基の2個の炭素原子と上証脂環式骨格また
は有橋脂環式骨格中の現を構成する隣接する2個の炭素
原子とが共通している[例えば下記式(ハ)、(ニ)参
照]ことが重要である。[For example, the following formulas (a), (b), or the two carbon atoms of the epoxy group and the adjacent alicyclic skeleton or bridged alicyclic skeleton It is important that two carbon atoms are common [see, for example, formulas (c) and (d) below].
そのようなエポキシ基含有官能基の具体例としては、下
記式(イ)〜(ニ)で示されるものが挙げられる。Specific examples of such epoxy group-containing functional groups include those represented by the following formulas (a) to (d).
ボキシ基中の炭素原子の1つが上記脂環式骨格または有
橋脂環式骨格中の環炭素原子に直接結合し式中、R1、
R2、R1、R2、R,、R,、RI。及びRIIはそ
れぞれH,CH,またはCz Hsを表わし、そしてR
4、Re及びR9はそれぞれHまたはCH,を表わす。One of the carbon atoms in the boxy group is directly bonded to a ring carbon atom in the alicyclic skeleton or bridged alicyclic skeleton, and in the formula, R1,
R2, R1, R2, R,, R,, RI. and RII represent H, CH, or Cz Hs, respectively, and R
4, Re and R9 each represent H or CH.
エポキシ樹脂(II)は、上記式(イ)〜(ニ)から選
ばれるエポキシ基含有官能基を1分子あたり平均少なく
とも2個、好ましくは2個以上、より好ましくは4個以
上有することができ、例えば式Cイ)または(ロ)で示
されるエポキシ基含有官能基を少なくとも1種有するこ
とができ、或いは式(ハ)または(ニ)で示されるエポ
キシ基含有官能基を少なくとも1種有することができる
。The epoxy resin (II) can have an average of at least 2, preferably 2 or more, more preferably 4 or more epoxy group-containing functional groups per molecule selected from the above formulas (a) to (d), For example, it can have at least one kind of epoxy group-containing functional group represented by formula C a) or (b), or it can have at least one kind of epoxy group-containing functional group represented by formula (c) or (d). can.
さらにまた、エポキシ樹脂(IT)は、式(イ)または
(ロ)で示されるエポキシ基含有官能基の少なくとも1
種と、式(ハ)または(ニ)で示されるエポキシ基含有
官能基の少なくとも1種とを同じ分子内または異なる分
子内に有することもてきる。Furthermore, the epoxy resin (IT) has at least one epoxy group-containing functional group represented by formula (a) or (b).
The species and at least one kind of epoxy group-containing functional group represented by formula (c) or (d) can be contained in the same molecule or in different molecules.
上記のうち、式(イ)及び(ハ)で示されるエポキシ基
含有基が好ましく、殊に下記式(ホ)で示されるエポキ
シ基含有官能基、及び下記式で示されるエポキシ基含有
官能基が好適である。Among the above, epoxy group-containing groups represented by formulas (a) and (c) are preferred, and in particular, epoxy group-containing functional groups represented by the following formula (e) and epoxy group-containing functional groups represented by the following formula are preferred. suitable.
また、エポキシ樹脂(H)のエポキシ当量及び分子量は
厳密に制限されるものではなく、その製造方法や最終の
樹脂組成物の用途等に応して変えることができるが、−
89的に言えば、エポキシ当量は通常、100〜2.0
00、好ましくは150〜500、さらに好ましくは1
50〜250の範囲内にあることができ、また、数平均
分子量は通常400〜ioo、ooo、好ましくは70
0〜50.000、さらに好ましくは700〜30.0
00の範囲内にあるのが適当である。In addition, the epoxy equivalent and molecular weight of the epoxy resin (H) are not strictly limited, and can be changed depending on the manufacturing method and the use of the final resin composition.
In terms of 89, the epoxy equivalent is usually 100 to 2.0.
00, preferably 150-500, more preferably 1
50 to 250, and the number average molecular weight is usually 400 to ioo, ooo, preferably 70
0 to 50.000, more preferably 700 to 30.0
It is appropriate that the value be within the range of 00.
このようなエポキシ基含有官能基を1分子中に2個以上
有するエポキシ樹脂[硬化用樹脂(II)コは、例えば
、特公昭56−8016号公幸K、特開昭57−473
65号公報、特開昭60−166675号公報、特開昭
63−221’121号公報、特開昭63−23402
8号公報などの文献に記載されており、それ自体既知の
ものを使用することができる。Epoxy resins having two or more such epoxy group-containing functional groups in one molecule [curing resin (II)] are used, for example, in Japanese Patent Publication No. 56-8016 Koyuki K, Japanese Patent Publication No. 57-473
65, JP 60-166675, JP 63-221'121, JP 63-23402
It is described in documents such as Japanese Patent Application No. 8, and those known per se can be used.
或いはまた、上記エポキシ基含有官能基を有するエポキ
シ樹脂(IT)はそれ自体既知の方法によって得られ、
その主な製造法を以下に列挙するが、これらに限定され
るものではない。Alternatively, the epoxy resin (IT) having the epoxy group-containing functional group is obtained by a method known per se,
The main manufacturing methods are listed below, but are not limited to these.
第1の製造方法 1分子中に炭素−炭素二重結合を2個
以上有する脂環化合
物の該二重結合の一部を部分
エポキシ化し、そのエポキシ
基な開環重合した後、重合体
に残る該二重結合をエポキシ
化する方法。First production method Partially epoxidizes a part of the double bonds of an alicyclic compound having two or more carbon-carbon double bonds in one molecule, and after ring-opening polymerization of the epoxy groups, the remaining in the polymer A method of epoxidizing the double bond.
第2の製造方法、同一分子中にエポキシ基を2個以上有
する脂環化合物を該
エポキシ基に基づいて、該エ
ポキシ基のすべてが消去しな
い程度に開環重合する方法。The second production method is a method in which an alicyclic compound having two or more epoxy groups in the same molecule is subjected to ring-opening polymerization based on the epoxy groups to such an extent that all of the epoxy groups are not eliminated.
第3の製造方法二同−分子中にエポキシ基含有官能基と
重合性不飽和結合と
を有する化合物を重合する方
法。Third production method - A method of polymerizing a compound having an epoxy group-containing functional group and a polymerizable unsaturated bond in the molecule.
以下、これらの製造方法についてさらに具体的に説明す
る。Hereinafter, these manufacturing methods will be explained in more detail.
東上二に童男]:
1分子中に炭素−炭素二重結合を2個以上有する脂環化
合物(以下、「脂環化合物(■)」と略称する)に含ま
れる該二重結合の一部をエポキシ化しく部分エポキシ化
物)、次いで該エポキシ基の開環重合によって該部分エ
ポキシ化物の開環重合体を得たのち、該重合体中に残存
する上記二重結合の一部もしくは全部をエポキシ化する
ことによって硬化用樹脂(II)を得る。Higashijo Ni Ni Doan]: A part of the double bonds contained in an alicyclic compound having two or more carbon-carbon double bonds in one molecule (hereinafter abbreviated as "alicyclic compound (■)") (partially epoxidized product), then ring-opening polymerization of the epoxy group to obtain a ring-opening polymer of the partially epoxidized product, and then some or all of the double bonds remaining in the polymer are epoxidized. Curing resin (II) is obtained by converting the resin into a resin.
脂環化合物(1)は、脂環式骨格または有橋脂環式骨格
について前述した脂環式環または有橋脂環式環構造を基
体骨格とし、さらに二重結合を、環を構成する隣接炭素
原子2つの間で存在するか、又は該環構造を構成する炭
素原子に他の炭素原子に基づ(二重結合が直接結合する
状態で少なくとも2個以上含有する化合物である。The alicyclic compound (1) has an alicyclic ring or a bridged alicyclic ring structure as a base skeleton described above for the alicyclic skeleton or a bridged alicyclic skeleton, and further includes a double bond and an adjacent alicyclic ring structure constituting the ring. It is a compound that contains at least two double bonds that exist between two carbon atoms or are directly bonded to a carbon atom that constitutes the ring structure based on another carbon atom.
脂環化合物(I)は、例えば共役ジエン化合物を既知の
方法に基いて加熱することによっても得られる。共役ジ
エン化合物は、1分子中に共役関係にある二重結合を1
対以上、好ましくは1〜5対有する炭素数が4〜30の
脂肪族また脂環式の化合物が適しており、具体的には、
ブタジェン、イソプレン、ビリレン、1.3−へキサジ
エン、2.4−へキサジエン、2,4−へブタジェン、
2−メチル−6−メチレン−2,7−オフクジエン、2
.6−シメチルー1.5.7−オクタトリエン、シクロ
ペンタジェン、シクロへキサジエン、4−エチル−2−
メチルシクロペンクジエン、3−イソプロピル−1−メ
チルシクロペンタジェン、5−イソプロピルシクロペン
クジエン、1.2.3.4−テトラフェニルシクロペン
タジェン、1.2.4−トリフェニルシクロペンタジェ
ン、1.4−ジフェニルシクロペンタジェン、1.3−
オクククロルベンタジエン、ヘキサクロルシクロペンタ
ジェン、5.5−ジェトキシ−1,2,3,4−テトラ
クロルシクロペンタジェン、1.2.3,4.5−ペン
ククロルシクロペンタジエン、1.2,3.4−テトラ
クロルシクロペンタジェン、1,3−シクロペンタジェ
ン、1.3−シクロオクタジエン、l、3.5−シクロ
オクタトリエン、1.3.6−シクロオクタトリエン、
シクロオクタテトラエン、クロルシクロオクタテトラエ
ン、ブロムシクロオクタテトラエン、5−シクロへキシ
リデンシクロペンタジェンなどがあげられ、これらはそ
れぞれ単独でもしくは2種以上組合わせて用いることが
できる。Alicyclic compound (I) can also be obtained, for example, by heating a conjugated diene compound according to a known method. Conjugated diene compounds contain one double bond in a conjugated relationship in one molecule.
Suitable are aliphatic or alicyclic compounds having 4 to 30 carbon atoms, preferably 1 to 5 pairs, and specifically,
Butadiene, isoprene, birylene, 1,3-hexadiene, 2,4-hexadiene, 2,4-hebutadiene,
2-methyl-6-methylene-2,7-ofcudiene, 2
.. 6-dimethyl-1.5.7-octatriene, cyclopentadiene, cyclohexadiene, 4-ethyl-2-
Methylcyclopentadiene, 3-isopropyl-1-methylcyclopentadiene, 5-isopropylcyclopentadiene, 1.2.3.4-tetraphenylcyclopentadiene, 1.2.4-triphenylcyclopentadiene, 1 .4-diphenylcyclopentadiene, 1.3-
occuchlorobentadiene, hexachlorocyclopentadiene, 5.5-jethoxy-1,2,3,4-tetrachlorocyclopentadiene, 1.2.3,4.5-pencuchlorocyclopentadiene, 1.2, 3.4-tetrachlorocyclopentadiene, 1,3-cyclopentadiene, 1.3-cyclooctadiene, 1,3.5-cyclooctatriene, 1.3.6-cyclooctatriene,
Examples include cyclooctatetraene, chlorocyclooctatetraene, bromocyclooctatetraene, and 5-cyclohexylidenecyclopentadiene, and these can be used alone or in combination of two or more.
共役ジエン化合物を必要によりチーグラー触媒を用いて
加熱下で反応を行なわしめると脂環化合物(I)が得ら
れる。この加熱反応はそれ自体既知の方法で行なうこと
ができ、例えば、特開昭49−102643号公報に開
示された方法で行うことができる。このようにして得ら
れる脂環化物(I)の代表例を示せば次のとおりである
。When the conjugated diene compound is reacted under heating using a Ziegler catalyst if necessary, the alicyclic compound (I) is obtained. This heating reaction can be carried out by a method known per se, for example, by the method disclosed in JP-A-49-102643. Representative examples of the alicyclic compound (I) thus obtained are as follows.
上記共役ジエン化合物のうち、シクロペンタジェン、シ
クロへキサジエン、4−エチル−2−メチルシクロペン
タジェンなどの脂環式構造を有する化合物や、シルベス
トレン、2.8 (9) −p−メンタジェン、ビロネ
ン、1.3−ジメチル−1−エチル−3,5−シクロへ
キサジエン、テルピネン、フエランドレン、ジペンテン
、インリモネン、リモネンなどはすでに脂環式化合物(
I)の構造を有しているので、上記熱反応に供すること
なくそのまま使用することができる。Among the above conjugated diene compounds, compounds having an alicyclic structure such as cyclopentadiene, cyclohexadiene, 4-ethyl-2-methylcyclopentadiene, sylvestrene, 2.8 (9) -p-menthadene, Vironene, 1,3-dimethyl-1-ethyl-3,5-cyclohexadiene, terpinene, phelandrene, dipentene, imlimonene, limonene, etc. are already known as alicyclic compounds (
Since it has the structure I), it can be used as it is without being subjected to the above thermal reaction.
まず、脂環化合物(1)に含まれる炭素−炭素二重結合
の一部を過酸化物などによってエポキシ基に変性する(
部分エポキシ化)。部分エポキシ化物は、前記脂環化合
物(I)に含まれる複数の二重結合のうち一部をエポキ
シ基に変性したものであり、その具体例を示せば次のと
おりである。First, a portion of the carbon-carbon double bonds contained in the alicyclic compound (1) are modified into epoxy groups using peroxide or the like (
partial epoxidation). The partially epoxidized product is obtained by modifying some of the double bonds contained in the alicyclic compound (I) into epoxy groups, and specific examples thereof are as follows.
天然に得られるエポキシカレンなども部分エポキシ化物
として使用することができる。Naturally available epoxycarene and the like can also be used as partially epoxidized products.
部分エポキシ化物は1分子中にエポキシ基と炭素−炭素
二重結合とをそれぞれ少なくとも1個ずつ有しており、
該二重結合は環を構成する隣接の炭素原子2個の間に存
在するかもしくは鎖環の炭素原子に他の炭素原子に基づ
く二重結合が結合していることが必要である。The partially epoxidized product has at least one epoxy group and at least one carbon-carbon double bond in one molecule,
It is necessary that the double bond exists between two adjacent carbon atoms constituting a ring, or that a double bond based on another carbon atom is bonded to a carbon atom of a chain ring.
次に、この部分エポキシ化物中のエポキシ基に基いて開
環重合して脂環式化合物(I)の重合体を得る。この開
環重合には開始剤を用いることが好ましく、最終製品で
る硬化用樹脂(TI )の末端に該開始剤成分による残
基Xが結合していてもよい。ここで、Xは活性水素を有
する有機化合物残基であり、その前駆体である活性水素
を有する有機化合物としては、例えば、アルコール類、
フェノール類、カルボン酸類、アミン類、チオール印等
があげられる。このうち、アルコール類としては、1価
アルコール及び2価以上の多価アルコルのいずれであっ
てもよ(、具体的には例えば、メタノール、エタノール
、プロパツール、ブクノール、ペンタノール、ヘキサノ
ール、オクタツール等の脂肪族1価アルコール、ベンジ
ルアルコールのような芳香族1価アルコール:エチレン
グリコール、ジエチレングリコール、トリエチレングリ
コール、ポリエチレングリコール、プロピレングリコー
ル、ジプロピレングリコール、13−ブタンジオール、
1.4−ブタンジオール、ベンタンジオール、1.6−
ヘキサンジオール、ネオペンチルグリコール、オキシピ
バリン酸ネオペンチルグリコールエステル、シクロヘキ
サンジメタツール、グリセリン、ジグリセリン、ポリグ
リセリン、トリメチロールプロパン、トリメチロールエ
タン、ペンタエリスリトール、ジペンタエリスリトール
などの多価アルコール等が例示される。Next, ring-opening polymerization is performed based on the epoxy groups in this partially epoxidized product to obtain a polymer of the alicyclic compound (I). It is preferable to use an initiator in this ring-opening polymerization, and a residue X of the initiator component may be bonded to the end of the curing resin (TI) as the final product. Here, X is a residue of an organic compound having active hydrogen, and examples of the organic compound having active hydrogen, which is a precursor thereof, include alcohols,
Examples include phenols, carboxylic acids, amines, thiol marks, etc. Among these, the alcohols may be monohydric alcohols or polyhydric alcohols of dihydric or higher valence (for example, methanol, ethanol, propatool, bukunol, pentanol, hexanol, octatool). Aliphatic monohydric alcohols such as benzyl alcohol, aromatic monohydric alcohols such as benzyl alcohol: ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 13-butanediol,
1.4-butanediol, bentanediol, 1.6-
Examples include polyhydric alcohols such as hexanediol, neopentyl glycol, neopentyl glycol oxypivalate, cyclohexane dimetatool, glycerin, diglycerin, polyglycerin, trimethylolpropane, trimethylolethane, pentaerythritol, and dipentaerythritol. be done.
フェノール類としては、例えば、フェノール、クレゾー
ル、カテコール、プロガロール、ハイドロキノン、ハイ
ドロキノンモノメチルエーテル、ビスフェノールA、ビ
スフェノールF、4.4′−ジヒドロキシベンゾフェノ
ン、ビスフェノールS、フェノール樹脂、タレゾールノ
ボラック樹脂等が挙げられる。Examples of phenols include phenol, cresol, catechol, progallol, hydroquinone, hydroquinone monomethyl ether, bisphenol A, bisphenol F, 4,4'-dihydroxybenzophenone, bisphenol S, phenol resin, Talezol novolac resin, and the like.
カルボン酸類としては、ギ酸、酢酸、プロピオン酸、酪
酸、動植物油の脂肪酸:フマル酸、マレイン酸、アジピ
ン酸、ドデカン2酸、トリメリット酸、ピロメリット酸
、ポリアクリル酸、フタール酸、イソフタル酸、テレフ
タル酸等を例示することができ、また、乳酸、クエン酸
、オキシカプロン酸等の水酸基とカルボン酸を共に有す
る化合物も使用することができる。Carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, fatty acids from animal and vegetable oils: fumaric acid, maleic acid, adipic acid, dodecanoic acid, trimellitic acid, pyromellitic acid, polyacrylic acid, phthalic acid, isophthalic acid, Examples include terephthalic acid, and compounds having both a hydroxyl group and a carboxylic acid such as lactic acid, citric acid, and oxycaproic acid can also be used.
さらに、その他の活性水素を有する化合物として、テト
ラメチルシリケート、テトラエチルシリケート、メチル
トリメトキシシラン、メチルトリエトキシシラン、ジメ
チルジメトキシシラン、フェニルトリメトキシシラン等
のアルコキシシランと水の混合物又はこれらのシラノー
ル化合物、ポリビニルアルコール、ポリ酢酸ビニル部分
加水分解物、デンプン、セルロース、セルロースアセテ
ート、セルロースアセテートブチレート、ヒドロキシエ
チルセルロース、アクリルポリオール樹脂、スチレン−
アリルアルコール共重合樹脂、スチレン−マレイン酸共
重合樹脂、アルキッド樹脂、ポリエステルポリオール樹
脂、ポリカプロラクトンポリオール樹脂等も使用するこ
とができる。また、活性水素と共に不飽和二重結合を有
していてもよく、さらに該不飽和二重結合がエポキシ化
されたものであっても差し支えない。また、アルコキシ
金属化合物のように触媒と開始剤が同一であってもよい
。Furthermore, other active hydrogen-containing compounds include mixtures of alkoxysilanes such as tetramethylsilicate, tetraethylsilicate, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, and phenyltrimethoxysilane with water, or silanol compounds thereof; Polyvinyl alcohol, polyvinyl acetate partial hydrolyzate, starch, cellulose, cellulose acetate, cellulose acetate butyrate, hydroxyethyl cellulose, acrylic polyol resin, styrene
Allyl alcohol copolymer resin, styrene-maleic acid copolymer resin, alkyd resin, polyester polyol resin, polycaprolactone polyol resin, etc. can also be used. Further, it may have an unsaturated double bond together with active hydrogen, and the unsaturated double bond may be epoxidized. Further, the catalyst and the initiator may be the same as in the case of an alkoxy metal compound.
通常、上記活性水素を有する有機化合物を開始剤にし、
上記部分エポキシ化物、例えば4−ビニルシクロヘキセ
ン−1−オキシト、4−ビニルシクロ[2,2,1]
3−メチル−4(または5)−1−プロペニル−1−シ
クロヘキセンオキシド、2.4−または1.4−ジメチ
ル−4エチニル−1−シクロヘキセンオキシド、4−ビ
ニルシクロ[2,2,1]へブテン−1−オキシト(ビ
ニルノルボルネンオキシド)、2−メチル−4−イソプ
ロパニル−シクロヘキセンオキシドなどを単独または複
数用いて開環重合する。このとき更に上記部分エポキシ
化物に属さない他のエポキシ化合物を併存させて、開環
共重合することも可能である。共重合させ得る他のエポ
キシ化物としては、エポキシ基を有するものであればい
かな冬ものでもよいが、好適な例には、エチレンオキサ
イド、プロピレンオキサイド、ブチレンオキサイド、ス
チレンオキサイド等の不飽和化合物の酸化物;アリルグ
リシジルエーテル、2−エチルへキシルグリシジルエー
テル、メチルグリシジルエーテル、ブチルグリシジルエ
ーテル、フェニルグリシジルエーテル等のグリシジルエ
ーテル化合物アクリル酸、メタクリル酸のような不飽和
有機カルボン酸のグリシジルエステル化合物:3.4−
エポキシシクロヘキシルメチル(メタ)アクリレートな
どの脂環式オキシラン基含有ビニル単量体等があげられ
る。Usually, the above-mentioned organic compound having active hydrogen is used as an initiator,
The above partially epoxidized products, such as 4-vinylcyclohexene-1-oxyto, 4-vinylcyclo[2,2,1]
3-Methyl-4 (or 5)-1-propenyl-1-cyclohexene oxide, 2,4- or 1,4-dimethyl-4ethynyl-1-cyclohexene oxide, 4-vinylcyclo[2,2,1]hebutene Ring-opening polymerization is carried out using one or more of -1-oxyto(vinylnorbornene oxide), 2-methyl-4-isopropanyl-cyclohexene oxide, and the like. At this time, it is also possible to co-exist other epoxy compounds that do not belong to the above-mentioned partially epoxidized products and carry out ring-opening copolymerization. Other epoxides that can be copolymerized may be of any type as long as they have an epoxy group, but suitable examples include oxidation of unsaturated compounds such as ethylene oxide, propylene oxide, butylene oxide, and styrene oxide. Glycidyl ether compounds such as allyl glycidyl ether, 2-ethylhexyl glycidyl ether, methyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, etc. Glycidyl ester compounds of unsaturated organic carboxylic acids such as acrylic acid and methacrylic acid: 3. 4-
Examples include alicyclic oxirane group-containing vinyl monomers such as epoxycyclohexylmethyl (meth)acrylate.
上記開環重合体は、部分エポキシ化物を星独もしくは必
要に応じてその他のエポキシ化合物を併用させて、これ
らに含まれるエポキシ基を開環重合(エーテル結合)さ
せることによって得られる。開環重合体におけるその他
のエポキシ化合物の構成比率は目的に応して任意に選ぶ
ことができるが、具体的には、得られる開環共重合体1
分子あたり前記構造式(イ)〜(ニ)のいずれか1種又
は複数種を平均2個以上、好ましくは3個以上、より好
ましくは4個以上有する範囲内で選ぶことが望ましい。The above-mentioned ring-opening polymer can be obtained by ring-opening polymerization (ether bonding) of the epoxy groups contained in the partially epoxidized product using Seidoku or other epoxy compounds as necessary. The composition ratio of other epoxy compounds in the ring-opening polymer can be arbitrarily selected depending on the purpose, but specifically, the ring-opening copolymer 1 obtained
It is desirable to select one or more of the above structural formulas (a) to (d) per molecule within the range of an average of 2 or more, preferably 3 or more, and more preferably 4 or more.
このようにして得られる該(共)重合体の数平均分子量
は一般に400〜100.000、特に700〜50.
000、さらに700〜30.000の範囲内にあるこ
とが好ましい。The number average molecular weight of the (co)polymer thus obtained is generally from 400 to 100.000, particularly from 700 to 50.000.
000, more preferably within the range of 700 to 30.000.
開環重合反応には、−Mに触媒の存在下に行なうことが
好ましく、使用しつる触媒としては、例えば、メチルア
ミン、エチルアミン、プロピルアミン、ピペラジン等の
アミン類、ピリジン類、イミダゾール類等の有機塩基類
;ギ酸、酢酸、プロピオン酸等の有機酸類、硫酸、塩酸
等の無機酸ナトリウムメチラート等のアルカリ金属アル
コラード類+KOH,NaOH等のアルカリ類9BF3
、Z n C122、AffCR!、5nC12,等の
ルイス酸又はそのコンプレックス類;トリエチルアルミ
ニウム、アルミニウムアセチルアセトナート、チタニウ
ムアセチルアセトナート、ジエチル亜鉛等の有機金属化
合物を挙げることができる。The ring-opening polymerization reaction is preferably carried out in the presence of a catalyst for -M, and examples of the catalysts used include amines such as methylamine, ethylamine, propylamine, and piperazine, pyridines, and imidazoles. Organic bases; organic acids such as formic acid, acetic acid, and propionic acid; inorganic acids such as sulfuric acid and hydrochloric acid; alkali metal alcoholades such as sodium methylate + alkalis such as KOH and NaOH 9BF3
, Z n C122, AffCR! , 5nC12, or complexes thereof; organometallic compounds such as triethylaluminum, aluminum acetylacetonate, titanium acetylacetonate, and diethylzinc.
これらの触媒は反応物に対して一般に
0.001〜10重量%、好ましくはO1〜5重量%の
範囲内で使用することができる。開環重合反応温度は一
般に約−70〜約200°C5好ましくは約−30’C
〜約100°Cの範囲内である。These catalysts can be used generally in an amount of 0.001 to 10% by weight, preferably 1 to 5% by weight of O, based on the reactants. The ring-opening polymerization reaction temperature is generally about -70 to about 200°C, preferably about -30'C.
~about 100°C.
反応は溶媒を用いて行なうことができ、溶媒としては活
性水素を有していない通常の有機溶媒を使用することが
好ましい。The reaction can be carried out using a solvent, and it is preferable to use a conventional organic solvent that does not contain active hydrogen.
開環重合体には脂丁5化合物(I)に基づく二重結合が
存在しており、そのすべてもしくは一部をエポキシ化す
ることによってエポキシ樹脂(II)が得られる。二重
結合のエポキシ化は例えば過酸類、ハイドロパーオキサ
イド類等のエポキシ化剤を用いて行なうことができる。The ring-opening polymer contains a double bond based on the compound (I), and epoxy resin (II) can be obtained by epoxidizing all or part of the double bond. Epoxidation of double bonds can be carried out using, for example, epoxidizing agents such as peracids and hydroperoxides.
エポキシ化反応の際の溶媒使用の有無や反応温度は、用
いる装置や原料物性に応じて適宜調整することができる
6工ポキシ化反応の条件によって、原料開環重合体中の
二重結合のエポキシ化と同時に副反応がおこり、変性さ
れた置換基が、エポキシ樹脂(II)の骨格中に含まれ
ることがある。この変性された置換基としては、例えば
エポキシ化剤として過酢酸を用いる場合には、下記構造
の置換基があげられ、これは生成したエポキシ基と副生
じた酢酸との反応によるものと思われる。The presence or absence of a solvent and the reaction temperature during the epoxidation reaction are determined by the conditions of the six-stage poxidation reaction, which can be adjusted appropriately depending on the equipment used and the physical properties of the raw material. A side reaction may occur at the same time as the reaction, and a modified substituent may be included in the skeleton of the epoxy resin (II). Examples of this modified substituent include, for example, when peracetic acid is used as an epoxidizing agent, the substituent has the following structure, and this is thought to be due to the reaction between the generated epoxy group and the by-produced acetic acid. .
このようにして得られるエポキシ樹脂(TI)のエポキ
シ当量は一般に100〜2.000、特に150〜50
0、さらに150〜250の範囲内であることが好まし
い。The epoxy equivalent of the epoxy resin (TI) obtained in this way is generally 100 to 2.000, particularly 150 to 50.
0, more preferably within the range of 150 to 250.
このようなエポキシ樹脂(TI )としては市販品も使
用可能であり、例えばEHPE−3150、EHPE−
3100、EHPE−1150[ダイセル化学工業■製
簡品名コ等があげられ、これ1ま4−ビニルシクロヘキ
セン−1−オキサイドを用いたシクロヘキサン骨格をも
つ下記構造式のエポキシ樹脂である。Commercial products can also be used as such epoxy resins (TI), such as EHPE-3150 and EHPE-3150.
3100, EHPE-1150 (manufactured by Daicel Chemical Industries, Ltd.), and is an epoxy resin having a cyclohexane skeleton using 4-vinylcyclohexene-1-oxide and having the following structural formula.
これらの変性された置換基が含まれる比率はエポキシ化
剤の種類、エポキシ化剤と不飽和基のモル比、反応条件
によって定まる。The ratio of these modified substituents included is determined by the type of epoxidizing agent, the molar ratio of the epoxidizing agent to the unsaturated group, and the reaction conditions.
式中、nは2以上であり、好ましくは3以上より好まし
くは4以上である。In the formula, n is 2 or more, preferably 3 or more, more preferably 4 or more.
liL製盪方進
例えば、前記脂環化合物(r)に含まれる二重結合のう
ち少なくとも2個をエポキシ化し、次いでエポキシ基が
残存するように開環重合することによって得られる。LiL can be obtained, for example, by epoxidizing at least two of the double bonds contained in the alicyclic compound (r), and then ring-opening polymerization so that the epoxy group remains.
上記1分子あたり平均2個以上のエポキシ基を有するエ
ポキシ化物としては、単環式もしくは縮合環式の下記化
合物が代表的に示される。As the epoxidized product having an average of two or more epoxy groups per molecule, the following monocyclic or condensed ring compounds are representative.
基体的には、上記エポキシ化物の1種以上を前記第1の
製造方法で述べたのと同様にして、必要に応し開始剤、
触媒を使用し、開環重合反応を行ないエポキシ基が残存
している所定の反応点で反応を止めることによりエポキ
シ樹脂(II)を得る。反応を停止させるには、溶剤に
よる希釈、冷却等任意の手段が使用することができる。Basically, one or more of the above epoxides are prepared in the same manner as described in the first manufacturing method, and if necessary, an initiator,
Epoxy resin (II) is obtained by carrying out a ring-opening polymerization reaction using a catalyst and stopping the reaction at a predetermined reaction point where an epoxy group remains. Any means such as dilution with a solvent or cooling can be used to stop the reaction.
この製造方法においても前記他のエポキシ化合物を第1
の製造方法と同様に共重合させてもよい。Also in this manufacturing method, the other epoxy compound is
Copolymerization may be carried out in the same manner as in the production method.
こうして得られる硬化用樹脂(II)は、前記式(イ)
または(ロ)で示されるエポキシ基含有官能基の少なく
とも1種と前記式(ハ)または(ニ)で示されるエポキ
シ基含有官能基の少なくとも1種とを同一分子中または
異なる分子中に有するエポキシ樹脂であることもできる
。The curing resin (II) thus obtained has the formula (a)
or an epoxy containing at least one epoxy group-containing functional group represented by (b) and at least one epoxy group-containing functional group represented by formula (c) or (d) in the same molecule or in different molecules. It can also be a resin.
このようにして得られる開環重合体[硬化用樹脂(II
)]の数平均分子量は一般に400〜10.000、特
iニア00〜50.000(7)範囲内にあることが好
ましく、また、エポキシ当量は一般に100〜2.00
0、特に150〜500、さらに150〜250の範囲
内にあることが好都合である。The ring-opened polymer thus obtained [curing resin (II
)] is generally in the range of 400 to 10.000, particularly preferably in the range of 00 to 50.000 (7), and the epoxy equivalent is generally in the range of 100 to 2.00.
0, especially in the range 150-500, even 150-250.
λ1旦販童方蓬二
同−分子中にエポキシ基含有官能基と重合性不飽和結合
とをそれぞれ少なくとも1個ずつ有する化合物(以下、
「重合性エポキシモノマー」と略称することがある)と
しては、例えば以下の一般式■〜@に示すものがあげら
れる。λ1 Danhan Dohata Hoji Do - A compound having at least one epoxy group-containing functional group and at least one polymerizable unsaturated bond in the molecule (hereinafter referred to as
Examples of the "polymerizable epoxy monomer" (sometimes abbreviated as "polymerizable epoxy monomer") include those shown in the following general formulas (1) to (1).
上記一般式中、RIIは水素原子又はメチル基を表わし
、R1□は炭素数1〜6の2価の脂肪族飽和炭化水素基
を表わし、R+sは炭素数1〜10の2価の炭化水素基
を表わす。In the above general formula, RII represents a hydrogen atom or a methyl group, R1□ represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R+s represents a divalent hydrocarbon group having 1 to 10 carbon atoms. represents.
上記重合性エポキシモノマーにおいて、R1□によって
表わされる炭素数1〜6の2価の脂肪族炭化水素基とし
ては、直鎖状又は分枝鎖状のアルキレン基、例えばメチ
レン、エチレン、プロピレン、テトラメチレン、エチル
エチレン、ペンタメチレン、ヘキサメチレン基等を挙げ
ることがてきる。またR 12によって表わされる炭素
数1〜〕0の2価の炭化水素基としでは、例えばメチレ
ンエチレン、プロピレン、テトラメチレン、エチルエチ
レン、ペンタメチレン、ヘキサメチレン、ボッメチレン
、フェニレン、 XΣ
”−CH* e CH2−基等を挙げることができる。In the above polymerizable epoxy monomer, the divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms represented by R1□ is a linear or branched alkylene group, such as methylene, ethylene, propylene, tetramethylene. , ethylethylene, pentamethylene, hexamethylene groups, etc. Examples of the divalent hydrocarbon group having 1 to 0 carbon atoms represented by R12 include methyleneethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene, bommethylene, phenylene, XΣ''-CH*e Examples include CH2- group.
上記一般式■〜0で示される重合性エポキシモノマーの
具体例としては、3.4−エポキシシクロヘキシルメチ
ルアクリレートおよび3.4−エポキシシクロヘキシル
メチルメタクリレートなどがあげられる。これらの市版
品として、例えば、ダイセル化学工業製のMETHB、
AETHB(いずれも商品名)等があげられ、これらは
いずれも前記式(イ)または(ロ)で示されるエポキシ
基含有官能基を有しているものである。さらに、4−ビ
ニルシクロヘキセンオキサイドも重合性エポキシモノマ
ーとして使用できる。Specific examples of the polymerizable epoxy monomers represented by the above general formulas (1) to (0) include 3.4-epoxycyclohexylmethyl acrylate and 3.4-epoxycyclohexylmethyl methacrylate. Examples of these commercial products include METHB manufactured by Daicel Chemical Industries, Ltd.
Examples include AETHB (all trade names), all of which have an epoxy group-containing functional group represented by formula (a) or (b) above. Furthermore, 4-vinylcyclohexene oxide can also be used as a polymerizable epoxy monomer.
重合性エポキシモノマーから選はれる1種もしくは2種
以上を重合することによってエポキシ樹脂(II)を製
造することができるが、その陣地の重合性不飽和モノマ
ーを共重合させることもできる。Epoxy resin (II) can be produced by polymerizing one or more selected polymerizable epoxy monomers, but it is also possible to copolymerize other polymerizable unsaturated monomers.
上記他の重合性不飽和モノマーとしては、得られる(共
)重合体に望まれる性能に応じて広範に選択することが
でき、その代表例を示せば次のとおりである。The other polymerizable unsaturated monomers mentioned above can be selected from a wide range depending on the desired performance of the resulting (co)polymer, and representative examples thereof are as follows.
(a)アクリル酸又はメタクリル酸のエステル:例えば
、アクリル酸メチル、アクリル酸エチル、アクリル酸プ
ロピル、アクリル酸イソプロピル、アクリル酸ブチル、
アクリル酸ヘキシル、アクリル酸オクチル、アクリル酸
ラウリル、メタクリル酸メチル、メタクリル酸エチル、
メタクリル酸プロピル、メタクリル酸イソプロピル、メ
タクリル酸ブチル、メタクリル酸ヘキシル、メタクリル
酸オクチル、メタクリル酸ラウリル等のアクリル酸又は
メタクリル酸の炭素数1〜18のアルキルエステル:ア
クリル酸メトキシブチル、メタクリル酸メトキシブチル
、アクリル酸メトキシエチル、メタクリル酸メトキシエ
チル、アクリル酸エトキシブチル、メタクリル酸エトキ
シブチル等のアクリル酸又はメタクリル酸の炭素数2〜
18のアルコキシアルキルエステル:アリルアクリレー
ト、アリルメタクリレート等のアクリル酸又はメタクリ
ル酸の炭素数2〜8のアルケニルエステル;ヒドロキシ
エチルアクリレート、ヒドロキシエチルメタクリレート
、ヒドロキシプロピルアクリレート、ヒドロキシプロピ
ルメタクリレート等のアクリル酸又はメタクリル酸の炭
素数2〜8のヒドロキシアルキルエステル:アリルオキ
シエチルアクリレート、アリルオキシメタクリレート等
のアクリル酸又はメタクリル酸の炭素数3〜18のアル
ケニルオキシアルキルエステル。(a) Esters of acrylic acid or methacrylic acid: for example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate,
Hexyl acrylate, octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate,
C1-18 alkyl esters of acrylic acid or methacrylic acid such as propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate: methoxybutyl acrylate, methoxybutyl methacrylate, Acrylic acid or methacrylic acid with 2 or more carbon atoms, such as methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate, and ethoxybutyl methacrylate
18 alkoxyalkyl esters: C2-8 alkenyl esters of acrylic acid or methacrylic acid such as allyl acrylate and allyl methacrylate; acrylic acid or methacrylic acid such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate C2-C8 hydroxyalkyl ester: C3-C18 alkenyloxyalkyl ester of acrylic acid or methacrylic acid such as allyloxyethyl acrylate and allyloxymethacrylate.
(b)ビニル芳香族化合物:例えば、スチレン、α〜メ
チルスチレン、ビニルトルエン、p−クロルスチレン。(b) Vinyl aromatic compounds: for example, styrene, α-methylstyrene, vinyltoluene, p-chlorostyrene.
(C)ポリオレフィン系化合物:例えば、ブタジシエン
、イソプレン、クロロブレン。(C) Polyolefin compound: For example, butadicyene, isoprene, chlorobrene.
(d)その他、アクリロニトリル、メククリロニトリル
、メチルイソプロペニルケトン、酢酸ビニルビバレート
=(シェル化学製品)、ビニルプロピオネート、ビニル
ビバレート、ポリカプロラクトン鎖をもつビニル化合物
(例えば、F M −3xモノマー ダイセル化学工業
製商品名)。(d) In addition, acrylonitrile, meccrylonitrile, methyl isopropenyl ketone, vinyl acetate bivalate (Shell Chemical Products), vinyl propionate, vinyl bivalate, vinyl compounds with polycaprolactone chains (for example, F M -3x Monomer (trade name manufactured by Daicel Chemical Industries).
重合性エポキシモノマーと他の重合性不飽和モノマーと
の構成比率は、目的に応して任意に選択することができ
、これらの共重合反応によって得られるエポキシ樹脂(
H)の1分子中あたりエポキシ基含有官能基が平均少な
くとも2個、好ましくは平均3個以上、より好ましくは
平均4個以上含有するような範囲で選択することができ
るが十分な硬化性を付与する官能基として利用するため
には、特に該エポキシ樹脂(Ii)固形分中重合性エポ
キシモノマー含有率が5〜100重量%、より好ましく
は20〜100重量%の範囲内となるようにするのが好
ましい。The composition ratio of the polymerizable epoxy monomer and other polymerizable unsaturated monomers can be arbitrarily selected depending on the purpose, and the epoxy resin (
H) can be selected within a range such that each molecule contains at least 2 epoxy group-containing functional groups, preferably 3 or more on average, more preferably 4 or more on average, but provides sufficient curability. In order to use it as a functional group, the content of the polymerizable epoxy monomer in the solid content of the epoxy resin (Ii) should be in the range of 5 to 100% by weight, more preferably 20 to 100% by weight. is preferred.
上記第3の製造方法によって得られるエポキシ樹脂(I
I )は、通常のアクリル樹脂やビニル樹脂等の重合性
不飽和結合に基く重合反応と同様の方法、条件を用いて
製造することができる。このような重合反応の一例とし
て、各単量体成分を有機溶剤に溶解もしくは分散せしめ
、ラジカル重合開始剤の存在下で60〜180℃程度の
温度で撹拌しながら加熱する方法を示すことができる。Epoxy resin (I
I) can be produced using the same method and conditions as those for polymerization reactions based on polymerizable unsaturated bonds in ordinary acrylic resins, vinyl resins, and the like. As an example of such a polymerization reaction, there can be shown a method in which each monomer component is dissolved or dispersed in an organic solvent and heated while stirring at a temperature of about 60 to 180°C in the presence of a radical polymerization initiator. .
反応時間は通常1〜10時間程度とすることができる。The reaction time can usually be about 1 to 10 hours.
また、有機溶剤としては、アルコール系溶媒、エーテル
系溶媒、エステル系溶媒1、炭化水素系溶媒等を使用で
きる。炭化水素系溶媒を用いる場合には、溶解性の点か
ら他の溶媒を併用することが好ましい。さらに、ラジカ
ル開始剤として通常用いられているものをいずれも用い
ることができ、その具体例として、過酸化ベンゾイル、
t−ブチルパーオキシ−2−エチルヘキサノエート等の
過酸化物、アゾイソブチルニトリル、アゾビスメチルバ
レロニトリル等のアゾ化合物等を示すことができる。Further, as the organic solvent, alcohol solvents, ether solvents, ester solvents 1, hydrocarbon solvents, etc. can be used. When using a hydrocarbon solvent, it is preferable to use other solvents in view of solubility. Furthermore, any commonly used radical initiator can be used; specific examples include benzoyl peroxide,
Examples include peroxides such as t-butylperoxy-2-ethylhexanoate, azo compounds such as azoisobutylnitrile, and azobismethylvaleronitrile.
上記第3の製造例のエポキシ樹脂(II )は、数平均
分子量が一般に約3.000〜約100.000の範囲
内にあるものが好ましく、特に4.000〜10.00
0の範囲内にあるものがより好ましい。The epoxy resin (II) of the above third production example preferably has a number average molecular weight generally in the range of about 3.000 to about 100.000, particularly 4.000 to 10.00.
Those within the range of 0 are more preferable.
上記した硬化用樹脂(II )の中で、自動車ポデー用
に使用されるカチオン電蓄塗料のような高度の性能が要
求される用途に用いるのに適しているのは、1分子あた
りにエポキシ基含有官能基を平均して3個以上、より好
ましくは平均して4個以上、最も好ましくは平均して5
個以上有するものであり、また、エポキシ当量が好まし
くは10O〜2.000、より好ましくは150〜50
0、特に150〜250の範囲内にあり、そして数平均
分子量が好ましくは400〜100.000、より好ま
しくは700〜50.000、特に好ましくは700〜
30.000の範囲内にあるものである。Among the above-mentioned curing resins (II), those that have an epoxy group per molecule are suitable for use in applications that require high performance, such as cationic electroacoustic paints used for automobile bodies. The number of functional groups contained is 3 or more on average, more preferably 4 or more on average, and most preferably 5 on average.
and an epoxy equivalent of preferably 10 to 2.000, more preferably 150 to 50.
0, especially in the range of 150 to 250, and the number average molecular weight is preferably 400 to 100,000, more preferably 700 to 50,000, particularly preferably 700 to
It is within the range of 30.000.
硬化用樹脂(II)の使用量は、用いる基体樹脂CI)
の種類に応じて、また得られる塗膜が熱硬化するのに必
要な最少量乃至カチオン電蓄塗料の安定性をそこなわな
い最大量の範囲内で適宜変えることができるが、一般に
は硬化用樹脂(TI)の基体樹脂(I)に対する固形分
の重量比が0.2〜10、特に0.25〜0.85、さ
らに望ましくは025〜0.65の範囲内となるように
選択するのが好ましい。The amount of curing resin (II) used depends on the base resin used (CI)
Depending on the type of paint, the amount can be changed as appropriate within the range of the minimum amount required for the resulting coating film to be cured by heat to the maximum amount that does not impair the stability of the cationic storage paint. The weight ratio of the solid content of the resin (TI) to the base resin (I) is selected to be within the range of 0.2 to 10, particularly 0.25 to 0.85, more preferably 0.25 to 0.65. is preferred.
硬化用樹脂(II)の一部が基体樹脂(I)にあらかじ
め付加したものが含まれていてもさしつかえない。There is no problem even if a part of the curing resin (II) is added to the base resin (I) in advance.
かくして基体樹脂(I)と硬化用樹脂(II)からなる
組成物はカチオン電蓄塗料(A−1)として使用するこ
とができる。Thus, the composition consisting of the base resin (I) and the curing resin (II) can be used as a cationic charge storage paint (A-1).
塗料(A−1)を調製するには、例えば、基体樹脂(I
)と硬化用樹脂(II)を混合した後、水中に安定に分
散せしめ、次いで必要に応じて、カーボンブラック、チ
タン白、鉛白、酸化鉛、ベンガラのような着色顔料:ク
レー、タルクのような体質顔料ニクロム酸ストロンチウ
ム、クロム酸鉛、塩基性クロム酸鉛、鉛丹、ケイ酸鉛、
塩基性ケイ酸鉛、リン酸鉛、塩基性リン酸鉛、トリポリ
リン酸鉛、ケイクロム酸鉛、黄鉛、シアナミド鉛、鉛酸
カルシウム、亜鉛化鉛、硫酸鉛、塩基性硫酸鉛等の防食
顔料、或いはさらに他の添加剤を混練することによって
行なわれる。配合し得る他の添加剤としては、例えば、
分散剤又は塗面のハジキ防止剤としての少量の非イオン
系界面活性剤;硬化促進剤等が挙げられる。To prepare the paint (A-1), for example, the base resin (I
) and the curing resin (II), then stably dispersed in water, and then, if necessary, a coloring pigment such as carbon black, titanium white, lead white, lead oxide, red iron oxide, clay, talc, etc. Extending pigments strontium dichromate, lead chromate, basic lead chromate, red lead, lead silicate,
Anticorrosion pigments such as basic lead silicate, lead phosphate, basic lead phosphate, lead tripolyphosphate, lead silichromate, yellow lead, lead cyanamide, calcium leadate, lead zincide, lead sulfate, basic lead sulfate, Alternatively, it may be carried out by further kneading other additives. Other additives that can be blended include, for example,
Examples include a small amount of a nonionic surfactant as a dispersant or an anti-repellent agent for the coated surface; a curing accelerator, and the like.
特に、塗料(A−1)によるii着塗膜を160℃以下
の低温で十分に硬化するようにするには、鉛化合物、ジ
ルコニウム化合物、コバルト化合物、アルミニウム化合
物、マンガン化合物、銅化合物、亜鉛化合物、鉄化合物
、クロム化合物ニッケル化合物などから選ばれる1種も
しくは2種以上の金属化合物を触媒として添加すること
が有効である。これらの金属化合物の具体例としては、
例えば、ジルコニウムアセチルアセトナト、コバルトア
セチルアセトナート、アルミニウムアセチルアセトナー
ト、マンガンアセチルアセトナートなどのキレート化合
物;β−ヒドロキシアミノ構造を有する化合物と酸化鉛
(II)のキレート化反応生成物:2−エチルヘキサン
rli釦、セカノイック鉛、ナフチックス鉛、オクチッ
クス鉛、安息香酸鉛、酢酸鉛、乳酸船、ギ酸鉛、グリコ
ール酸鉛、オクチックスジルコニウムなどのカルボキシ
レートなどが挙げられる。In particular, in order to fully cure the II coating film of paint (A-1) at a low temperature of 160° C. or lower, lead compounds, zirconium compounds, cobalt compounds, aluminum compounds, manganese compounds, copper compounds, zinc compounds, etc. It is effective to add one or more metal compounds selected from , iron compounds, chromium compounds, nickel compounds, etc. as catalysts. Specific examples of these metal compounds include:
For example, chelate compounds such as zirconium acetylacetonate, cobalt acetylacetonate, aluminum acetylacetonate, manganese acetylacetonate; chelation reaction product of a compound having a β-hydroxyamino structure and lead (II) oxide: 2-ethyl Examples include carboxylates such as hexane rli button, secanoic lead, naphthix lead, octix lead, lead benzoate, lead acetate, lactic acid carrier, lead formate, lead glycolate, and octix zirconium.
上記金属化合物は、基体樹脂(I)と硬化用樹脂(II
)との合計固形分重量に対し、金属含有率が一顧に10
重量%以下、好ましくは5重1%以下の量で使用するこ
とができる。The above metal compound is composed of a base resin (I) and a curing resin (II).
) and the total solid weight, the metal content is at a glance 10
It can be used in an amount of up to 5% by weight, preferably up to 1% by weight.
塗料(A−2):水酸基およびカチオン性基を有する樹
脂(I)とブロックポリイソシアネート化合物(TI)
とを主成分として含有するカチオン電着塗料。Paint (A-2): Resin (I) having hydroxyl group and cationic group and blocked polyisocyanate compound (TI)
A cationic electrodeposition paint containing as the main component.
樹脂(I)としては、すでに説明した基体樹脂(I)か
ら選ばれるものが好ましい。The resin (I) is preferably selected from the base resins (I) already described.
ブロックポリイソシアネート化合物(III )は、各
々理論量のポリイソシアネート化合物とインシアネート
ブロック剤との付加及生成物であって樹脂(I)の架橋
剤である。このポリイソシアネート化合物としては、例
えば、トリレンジイソシアネート、キシリレンジイソシ
アネート、フェニレンジイソシアネート、ビス(イソシ
アネートメチル)シクロヘキサン、テトラメチレンジイ
ソシアネート、ヘキサメチレンジイソシアネート、メチ
レンジイソシアネート、インホロンジイソシアネートな
どの芳香族、脂環族、脂肪族のポリイソシアネート化合
物およびこれらのイソシアネト化合物の過剰量にエチレ
ングリコール、プロピレングリコール、トリメチロール
プロパン、ヘキサントリオール、ヒマシ油などの低分子
活性水素含有化合物を反応させて得られる末端イソシア
ネート含有プレポリマーが挙げられる。また、インシア
ネートブロック剤はポリイソシアネート化合物のイソシ
アネート基に付加してブロックするものであり、そして
付加によって生成するブロックポリイソシアネート化合
物は常温において安定で、且つ解III温度以上に加熱
した際、ブロック剤を解離して遊離のインシアネート基
を再生しつるものであることが重要である。Blocked polyisocyanate compounds (III) are addition products of stoichiometric amounts of polyisocyanate compounds and inocyanate blocking agents, and are crosslinking agents for resin (I). Examples of the polyisocyanate compound include aromatic and alicyclic compounds such as tolylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, bis(isocyanatemethyl)cyclohexane, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, and inphorone diisocyanate; A terminal isocyanate-containing prepolymer obtained by reacting an aliphatic polyisocyanate compound and an excess amount of these isocyanate compounds with a low-molecular active hydrogen-containing compound such as ethylene glycol, propylene glycol, trimethylolpropane, hexanetriol, or castor oil is Can be mentioned. In addition, the incyanate blocking agent is added to the isocyanate group of the polyisocyanate compound to block it, and the blocked polyisocyanate compound produced by the addition is stable at room temperature, and when heated above the decomposition III temperature, the blocking agent It is important that the inocyanate group is dissociated to regenerate the free incyanate group.
特に本発明ではカチオン電着塗膜の加熱減量が10重量
%以下でなければならないので、このブロック剤として
は分子量が130以下の低分子化合物な用いることが好
ましい。具体的には、フェノール、クレゾール、キシレ
ノール、り四ロフェノールおよびエチルフェノールなど
のフェノール系ブロック剤:ε−カプロラクタム、δ−
バレロラククム、γ−ブチロラクタムおよびβ−プロピ
オラクタムなどのラクタム系ブロック剤、アセト酢酸エ
チルおよびアセチルアセトンなどの活性メチレン系ブロ
ック剤:メタノール、エタノール、プロパツール、ブク
ノール、アミルアルコール、エチレングリコールモノメ
チルエーテル、エチレングリコールモノエチルエーテル
、エチレングリコールモノブチルエーテル、ジエチレン
グリコールモノメチルエーテル、プロピレングリコール
モノメチルエーテル、ベンジルアルコール、グリコール
酸メチル、グリコール酸ブチル、ジアセトンアルコール
、乳酸メチルおよび乳酸エチルなどのアルコール系ブロ
ック剤、ホルムアミドキシム、アセトアルドキシム、ア
セトキシム、メチルエチルケトキシム、ジアセチルモノ
オキシム、シクロヘキサンオキシムなどのオキシム系フ
゛ロツク剤、ブチルメルカプタン、ヘキシルメルカプタ
ン、t−ブチルメルカプタン、チオフェノール、メチル
チオフェノール、エチルチオフェノールなどのメルカプ
タン系ブロック剤、酢酸アミド、ベンズアミドなどの酸
アミド系ブロック剤:コハク酸イミドおよびマレイン酸
イミドなとのイミド系ブロック剤;キシリジン、アニリ
ン、ブチルアミン、ジブチルアミンなどのアミン系ブロ
ック剤。In particular, in the present invention, since the loss on heating of the cationic electrodeposition coating must be 10% by weight or less, it is preferable to use a low molecular weight compound having a molecular weight of 130 or less as the blocking agent. Specifically, phenolic blocking agents such as phenol, cresol, xylenol, dichlorophenol, and ethylphenol; ε-caprolactam, δ-
Lactam-based blocking agents such as valerolactum, γ-butyrolactam and β-propiolactam, active methylene-based blocking agents such as ethyl acetoacetate and acetylacetone: methanol, ethanol, propatool, buknol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol Alcohol-based blocking agents such as monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl alcohol, methyl glycolate, butyl glycolate, diacetone alcohol, methyl lactate and ethyl lactate, formamidoxime, acetalde Oxime blocking agents such as oxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, cyclohexane oxime, mercaptan blocking agents such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, methylthiophenol, ethylthiophenol, acetamide, Acid amide blocking agents such as benzamide; Imide blocking agents such as succinimide and maleic imide; Amine blocking agents such as xylidine, aniline, butylamine, dibutylamine.
イミダゾール、2−エチルイミダゾールなどのイミダゾ
ール系ブロック剤、エチレンイミンおよびプロピレンイ
ミンなどのイミン系ブロック剤、などをあげることがで
きる。このうち、塗料の安定性や塗膜の硬化性などのバ
ランスから、メチルエチルエトオキシムなどのオキシム
系ブロック用]が特に好適である。Examples include imidazole blocking agents such as imidazole and 2-ethylimidazole, and imine blocking agents such as ethyleneimine and propyleneimine. Among these, oxime-based blocks such as methyl ethyl ethoxime are particularly suitable in view of the balance between paint stability and coating curability.
塗料(A−2)において上記基体樹脂(I)とブロック
ポリイソシアネート化合物(Ill )との比率は特に
制限を受けないが、該同成分の合計固形分量に基いて、
基体樹脂(I)は40〜95重量%、特に60〜90重
量%、ブロックポリイソシアネート化合物(II )は
60〜5重量%、特:二40〜10重量%がそれぞ乙好
ましい。In the paint (A-2), the ratio of the base resin (I) to the blocked polyisocyanate compound (Ill) is not particularly limited, but based on the total solid content of the same components,
The base resin (I) is preferably 40 to 95% by weight, particularly 60 to 90% by weight, and the block polyisocyanate compound (II) is preferably 60 to 5% by weight, particularly 240 to 10% by weight.
上記塗料(A−2)には、(へ−1)に例示巳た体質顔
料および防食顔料を配合することができ、さらに硬化を
促進するために錫触媒などを配合することもできる。The paint (A-2) may contain the extender pigments and anticorrosion pigments exemplified in (F-1), and may also contain tin catalysts and the like to promote curing.
このようにして調製されるカチオン電看塗ヰ4を基体上
に電着させて得られる塗膜の膜厚は厳畜に制限されるも
のではないが、一般には、硬化塗膜に基いて3〜200
LLの範囲内が適しており、また塗膜は、例えば70〜
250℃、好ましくは120’C−160°C間の温度
で加熱硬化させることができる。塗装は、通常のカチオ
ン電着塗装条件を用いて行なうことができる。例えば、
浴濃度(固形分濃度5〜40重量%、好ましくは10〜
25重量%及び浴pH5〜8、好ましくは55〜7の範
囲内のカチオン電着浴を調製する。次し1てこの電着浴
を用い、例えば5cmX l 5cmX 1 cmの大
きさのカーボン板を陽極とし且つ例えば5cmX15c
mX0.7mmの大きさのリン酸亜鉛処理板を陰極とす
る場合、下記の条件下に電着を行なうことができる。The thickness of the coating film obtained by electrodepositing the cationic coating 4 prepared in this manner on a substrate is not strictly limited, but generally, the thickness of the coating film obtained by electrodepositing the cationic coating 4 prepared in this way is based on the cured coating film. ~200
A range of LL is suitable, and the coating film is, for example, 70 to
It can be heat cured at a temperature of 250°C, preferably between 120'C and 160°C. Coating can be performed using normal cationic electrodeposition coating conditions. for example,
Bath concentration (solid content concentration 5-40% by weight, preferably 10-40% by weight)
A cationic electrodeposition bath is prepared with a pH of 25% by weight and a bath pH in the range of 5-8, preferably 55-7. Next, using a 1-lever electrodeposition bath, use a carbon plate with a size of, for example, 5 cm x 1 cm as an anode, and a carbon plate with a size of, for example, 5 cm x 15 cm.
When a zinc phosphate-treated plate with a size of m x 0.7 mm is used as a cathode, electrodeposition can be carried out under the following conditions.
浴温度 20〜35°C1好ましくは25〜30℃、
直流電流
電流密度: 0.005+−2A/am2.好ましくは
O、Ol〜L A/cm2
電 圧:10〜500V、好ましくは100〜300
v
通電時間二0.5〜5分間、好ましくは2〜3分間
本発明の方法は、上記塗料(A)をカチオン電@塗装後
、電着浴から被塗物を引き上げ水洗したのち、1i@塗
膜面の水滴を除去し、さらに好ましくは電着塗膜中に含
まれる水分の殆どもしくは全部を熱風などの乾燥手段で
除去したのち、水性塗料を塗装してから、加熱して該両
塗膜を同時に硬化せしめるところに特徴とする。Bath temperature: 20-35°C, preferably 25-30°C, DC current density: 0.005+-2A/am2. Preferably O, Ol~LA/cm2 Voltage: 10~500V, preferably 100~300
v Current application time: 20.5 to 5 minutes, preferably 2 to 3 minutes In the method of the present invention, after applying the above-mentioned paint (A) with a cationic electrolyte, the object to be coated is pulled up from the electrodeposition bath, washed with water, and then 1i@ After removing water droplets from the coating surface, and more preferably removing most or all of the moisture contained in the electrodeposited coating using a drying method such as hot air, a water-based coating is applied, and then both coatings are heated. The feature is that the film is cured at the same time.
本発明において用いる水性塗料(以下、「塗料B」と略
称することがある)について説明す塗料(B)は
■ 酸価が10〜100で且つ水酸基価が20〜300
のポリエステル樹脂、
■ 水性アミノ樹脂、および
■ 一般式
[ただし、Rは、
nは2〜1oの整数である。コ
で示されるポリエーテルポリオールを主成分とし、さら
に必要に応して、
■ アルキルエーテル化ベンゾイン
を加えてなる水性塗料である。The water-based paint used in the present invention (hereinafter sometimes abbreviated as "Paint B") Paint (B) has an acid value of 10 to 100 and a hydroxyl value of 20 to 300.
(1) Aqueous amino resin, and (2) General formula [wherein R is, n is an integer from 2 to 1o]. This is a water-based paint containing the polyether polyol shown in (2) as a main component, and optionally, (1) alkyl etherified benzoin added thereto.
塗料(B)において、上記■、■および@成分からなる
系でも本発明の目的は十分に達成できるが、■、■、■
および■成分のずべてを含むと、ワキやタレの発生が全
くなく、しかも平滑性や鮮映性などもすぐれているので
より好ましい。In paint (B), the object of the present invention can be fully achieved even with a system consisting of the above-mentioned components ■, ■, and @.
It is more preferable to include all of the components (1) and (2), since no wrinkles or sagging occur at all, and the smoothness and image clarity are also excellent.
塗料CB)の主成分を構成する■〜■成分について具体
的に説明する。Components (1) to (2) constituting the main components of paint CB) will be specifically explained.
@成分 酸価が10〜100で且つ水酸基価が20〜3
00のポリエステル樹脂である。@Ingredients Acid value is 10-100 and hydroxyl value is 20-3
00 polyester resin.
当該ポリエステル樹脂としては、エチレングリコール、
ジエチレングリコール、プロピレングリコール、ブタン
ジオール、ベンタンジオール、2.2−ジメチルプロパ
ンジオール、グリセリン、トリメチロールプロパン、ペ
ンタエリスリトールなどの多価アルコールおよび必要に
応じて併用するm個アルコールまたは分子中に1個のグ
ノシジル基を有するモノエポキシ化合物(たとえば、[
カージュラEJ (商品名、シェル化学■製))をア
ルコール成分とし、無水フタル酸、イソフタル酸、テト
ラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、無
水マレイン酸、無水コハク酸、アジピン酸、セパチン酸
、無水トリメリ・ノ)・酸、無ホビロメリット酸などの
多塩基酸、および必要に応して併用する安、密香酸やt
−ブチル安居香酸なとの一塩基酸を酸成分として、上記
アルコール成分と上記酸成分とを縮合してなるオイルフ
リーポリエステル樹脂、または上記アルコール成分およ
び上記酸成分に加えてヒマシ油、脱水ヒマシ油、桐油、
サフラワー油、大豆油、アマニ油、トール油、ヤシ油な
ど、およびそれらの脂肪酸のうちの1種または2種以上
の混合物である油成分を、上記酸成分およびアルコール
成分に加えて、三者を反応させて得られる油変性ポリエ
ステル樹脂などがあげられる。また、アクリル樹脂やビ
ニル樹脂をグラフト化したポリエステル樹脂も(A)成
分として使用できる。The polyester resin includes ethylene glycol,
Polyhydric alcohols such as diethylene glycol, propylene glycol, butanediol, bentanediol, 2,2-dimethylpropanediol, glycerin, trimethylolpropane, pentaerythritol, and m alcohols used together as necessary or one gnosidyl in the molecule monoepoxy compounds having groups (for example, [
Cardura EJ (trade name, manufactured by Shell Chemical ■)) is used as an alcohol component, including phthalic anhydride, isophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, succinic anhydride, adipic acid, cepatic acid, and trimeric anhydride.・ノ)・Acids, polybasic acids such as anophobylomellitic acid, and ammonium, argentic acid and t, which are used in combination as necessary.
- An oil-free polyester resin obtained by condensing the above alcohol component and the above acid component using a monobasic acid such as butyl andyzoic acid as the acid component, or in addition to the above alcohol component and the above acid component, castor oil, dehydrated castor oil, tung oil,
An oil component such as safflower oil, soybean oil, linseed oil, tall oil, coconut oil, etc., and one or a mixture of two or more of these fatty acids, is added to the above acid component and alcohol component. Examples include oil-modified polyester resins obtained by reacting. Moreover, polyester resin grafted with acrylic resin or vinyl resin can also be used as component (A).
また、■成分としては、ウレタン変性ポリエステル樹脂
を用いると、貯蔵安定性、耐ワキ性、鮮映性および耐チ
・ンビング性などがさらに向上するので好ましい。In addition, it is preferable to use a urethane-modified polyester resin as component (2), since this further improves storage stability, scuffing resistance, sharpness, and scratching resistance.
該樹脂は、上記で例示したアルコール成分と酸成分とを
反応させてなるポリエステル樹脂(オイルフリーが好ま
しい)に、ポリイソシアネート化合物(ジイソシアネー
トが好ましい)を水酸基過剰にして反応させて得られる
。ポリイソシアネート化合物としては、例えばトリレン
ジイソシアネート、4.4′−ジフェニルメタンジイソ
シアネート等の芳香族ポリイソシアネート化合物、キシ
リレンジイソシアネート、メタまたはバラテトラメチル
キシリレンジイソシアネートのような芳香脂肪族ポリイ
ソシアネート化合物、ヘキサメチレンジイソシアネート
、インホロンジイソシアネート、及びこれらのビユレッ
ト化物やインシアヌレート化物、トリメチルへキサメチ
レンジイソシアネート、水素添加キシレンジイソシアネ
ート、水素添加4.4′−ジフェニルメタンジイソシア
ネートなどの脂肪族ポリイソシアネートや脂環族ポリイ
ソシアネート等が挙げられる。このうち、塗料(B)の
貯蔵安定性向上のためにはトリレンジイソシアネート、
キシリレンジイソシアネートおよびインホロンジイソシ
アネートが好ましい。ポリイソシアネート化合物の使用
量は、ポリエステル樹脂に対して1〜40重量%。特に
4〜30重量%が好ましい。The resin is obtained by reacting a polyester resin (preferably oil-free) obtained by reacting the alcohol component and acid component exemplified above with a polyisocyanate compound (preferably diisocyanate) in an excess of hydroxyl groups. Examples of the polyisocyanate compound include aromatic polyisocyanate compounds such as tolylene diisocyanate and 4,4'-diphenylmethane diisocyanate, araliphatic polyisocyanate compounds such as xylylene diisocyanate, meta- or baratetramethyl xylylene diisocyanate, and hexamethylene. Diisocyanate, inphorone diisocyanate, biuret and incyanurate products thereof, aliphatic polyisocyanates and alicyclic polyisocyanates such as trimethylhexamethylene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, etc. can be mentioned. Among these, tolylene diisocyanate,
Xylylene diisocyanate and inphorone diisocyanate are preferred. The amount of polyisocyanate compound used is 1 to 40% by weight based on the polyester resin. Particularly preferred is 4 to 30% by weight.
かかる■成分は、酸価が10〜100、好ましくは15
〜50、水酸基価が20〜300、好ましくは50〜2
30である。酸価が10より小さくなると水性化が不十
分となり、水酸基価が20より小さ(なると塗膜の硬化
性が不十分であり、また酸価が100、水酸基価が30
0を越えると塗膜の耐水性、耐薬品性が低下するのでい
ずれも好ましくない。Such component (1) has an acid value of 10 to 100, preferably 15.
-50, hydroxyl value is 20-300, preferably 50-2
It is 30. If the acid value is less than 10, the aqueousization will be insufficient, and if the hydroxyl value is less than 20, the curability of the coating will be insufficient;
If it exceeds 0, the water resistance and chemical resistance of the coating film will decrease, which is not preferable.
さらに■成分に関し、重量平均分子量は1.000〜2
0.000、特i:3.000〜15.000が適して
いる。Furthermore, regarding the component (■), the weight average molecular weight is 1.000 to 2.
0.000, especially i: 3.000 to 15.000.
これらの■成分に塩基性物質を添加してカルボキシル基
の50%以上を中和して水性とする。ここで用いられる
塩基性物質としては、例えばアンモニア、メチルアミン
、エチルアミン、ジメチルアミン、ジエチルアミン、ト
リメチルアミン、1−ジエチルアミン、ジメチルエタノ
ールアミン、シエタノールアミン、トリエタノールアミ
ンなどがあり、このうち、ジェタノールアミン、ジメチ
ルエタノールアミン、トリエタノールアミンなどが好適
である。A basic substance is added to these components (1) to neutralize at least 50% of the carboxyl groups to make them aqueous. Examples of basic substances used here include ammonia, methylamine, ethylamine, dimethylamine, diethylamine, trimethylamine, 1-diethylamine, dimethylethanolamine, cyethanolamine, triethanolamine, etc. Among these, jetanolamine , dimethylethanolamine, triethanolamine, etc. are suitable.
■成分 水性アミノ樹脂である。■Component: Water-based amino resin.
これは、■成分の架橋剤であって、たとえはシー、トリ
ー、テトラ−、ベンクー、ヘキサ−メチロールメラミン
およびそれらのメチルエーテル化物、尿素−ホルムアル
デヒド縮合物、尿素−メラミン共縮合物などをあげるこ
とができる。This is a crosslinking agent of component (1), such as C, tri, tetra, Benku, hexa-methylol melamine and their methyl ethers, urea-formaldehyde condensates, urea-melamine co-condensates, etc. I can do it.
■成分は、水に溶解するか又は水中に層分離や沈降する
ことなく安定に分散する程度に親水性である。(2) The component is hydrophilic to the extent that it dissolves in water or is stably dispersed in water without layer separation or sedimentation.
■成分としては上記のうちメラミンが好ましい。該メラ
ミンの官能基と塗料(B)の性能との関連は次の通りで
ある。(2) As the component, melamine is preferred among the above. The relationship between the functional groups of the melamine and the performance of the paint (B) is as follows.
(1)メチロール化メラミンの完全エーテル化物を用い
ると、ワキ抵抗性は高くなるが、架橋反応温度が高く、
140〜150°C程度で該塗膜を硬化させるのに、酸
触媒を使用しないと架橋反応が不足となる傾向がある。(1) Using a completely etherified methylolated melamine increases armpit resistance, but the crosslinking reaction temperature is high;
If an acid catalyst is not used to cure the coating film at about 140 to 150°C, the crosslinking reaction tends to be insufficient.
(ll)メチロール基(−CH20H)とアルキルエー
テル基(−CH20R)とが混在するメラミンでは、初
期硬化が速く、酸触媒は不要であるが、塗着塗膜から水
や瀉剤が十分に揮散しないうちに塗膜表面で硬化が始ま
りワキ発生の原因となることがある。(ll) Melamine, which has a mixture of methylol groups (-CH20H) and alkyl ether groups (-CH20R), has a fast initial curing and does not require an acid catalyst, but water and a cleaning agent do not volatilize sufficiently from the applied coating film. Over time, the coating may begin to harden on the surface, causing wrinkles.
(i)イミノ基(>NH)とアルキルエーテル基(−C
H20R)とが混在するメラミンでは、酸触媒なして1
40〜150°C程度で(A)成分と良く架橋反応する
。また、この架橋反応は比較的遅くかつ自己硬化性もメ
チロール基はど速くないので、有機溶剤および水などが
揮散し塗膜が溶融流動してから架橋硬化かはしまるので
平滑性良好でワキのないかつ硬化性のよい塗且莫が得ら
れる。(i) Imino group (>NH) and alkyl ether group (-C
For melamine mixed with H20R), 1
It crosslinks well with component (A) at about 40 to 150°C. In addition, this crosslinking reaction is relatively slow and self-curing is not as fast as the methylol group, so the organic solvent and water are volatilized and the coating melts and flows before it crosslinks and hardens, resulting in good smoothness and smoothness. A coating with good curability and free of stains can be obtained.
本発明において、■成分としては、かかる意味で、(朝
1)イミノ基含有水溶性アミン樹脂が最も適している。In this sense, (Morning 1) imino group-containing water-soluble amine resin is most suitable as component (1) in the present invention.
■成分ニ一般式 %式% [ただし、Rは、 nは2〜10の整数である。] で示されるポリエーテルポリオールである。■General formula of components %formula% [However, R is n is an integer from 2 to 10. ] It is a polyether polyol shown by
ここで、上記式中nが2より小さくなると水溶化が不十
分であり、10より大きくなると塗膜の耐水、性が劣化
するので好ましくない。特に、式中nは2〜5が最も好
ましい。Here, if n in the above formula is smaller than 2, water solubility will be insufficient, and if it is larger than 10, the water resistance and properties of the coating film will deteriorate, which is not preferable. In particular, n in the formula is most preferably 2 to 5.
この■成分を配合することによって、塗装時の不揮発分
含有率が上がり、スプレー塗装などによる霧化が良好と
なり特に、塗着した塗料が流展しやすいためにワキ限界
膜厚が向上するなどの好結果が得られる。By blending this component, the non-volatile content during painting increases, and atomization during spray painting becomes better.In particular, the applied paint spreads more easily, improving the critical underarm film thickness. Good results can be obtained.
■成分:アルキルエーテル化ベンゾインである。■Component: Alkyl etherified benzoin.
これは、ベンゾインのアルキル(炭素数1〜4が好まし
い)エーテル化物で、具体的には、ベンゾインメチルエ
ーテル、ベンゾインエチルエーテル、ベンゾインn−プ
ロピルエーテル、ベンゾイン1so−プロピルエーテル
、ベンゾインn−ブチルエーテル、ベンゾインis○−
ブチルエーテルなどが挙げられる。This is an alkyl (preferably carbon number 1 to 4) etherified product of benzoin, and specifically, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin 1so-propyl ether, benzoin n-butyl ether, benzoin is○-
Examples include butyl ether.
これらは単独もしくは2種以上組合せて使用することが
できる。These can be used alone or in combination of two or more.
■成分の添加方法としては、(1)顔料分散時に添加す
る、(2)■成分の水溶液に常温もしくは加温下で添加
して撹拌混合する、(3)■成分の合成時に添加する等
の方法があり、いずれの添加方法を用いてもワキ改良効
果に影響はないが一般には塗料中の顔料含有量及び■成
分の融点等を考慮して決定される。このうち、(2)の
方法が好ましい。■Addition methods for the component include (1) adding it during pigment dispersion, (2) ■adding it to an aqueous solution of the component at room temperature or under heating and stirring, and (3) adding it during the synthesis of the component. There are several methods of addition, and although there is no effect on the underarm improvement effect, the addition method is generally determined by taking into account the pigment content in the paint and the melting point of component (2). Among these, method (2) is preferred.
■成分を配合することによってワキ発生が抑止されワキ
発生膜厚を大きくするのに有効である。(2) Combining the ingredients is effective in suppressing the occurrence of wrinkles and increasing the thickness of the film that causes wrinkles.
塗料(B)は上記■、■および◎成分を必須としており
、これらの構成比率は目的に応して任意に選択できるが
、■、■および◎成分の合計重量に基いて、■成分が3
0〜85重量%、特に50〜80重量%、■成分は10
〜40重量%、特に15〜30重量%および■成分は5
〜30重■%、特に5〜20重量%がそれぞれ適してい
る。Paint (B) requires the above components ■, ■, and ◎, and the composition ratio of these can be arbitrarily selected depending on the purpose, but based on the total weight of the components ■, ■, and ◎,
0 to 85% by weight, especially 50 to 80% by weight, ■ component is 10
~40% by weight, especially 15-30% by weight, and component 5
~30% by weight, in particular 5-20% by weight, respectively, are suitable.
また、■成分は、■、■および@成分の合計Iに対して
、0.1〜10重量%、特に1〜5重量%が好ましい。Furthermore, the amount of component (1) is preferably 0.1 to 10% by weight, particularly 1 to 5% by weight, based on the total I of components (2), (2), and @components.
塗*4 (B)で用いる■、■、■各成分は、それぞれ
単独でもワキ抵抗性改良効果はあるが、その程度はワキ
限界膜厚で40部m程度(乾燥膜厚で)にすぎず、昨今
の中塗り厚膜指向(例えば45部m以上)の場合では不
十分である。なぜなら、スプレー塗装などにおいて約4
5戸の膜厚に塗装しても、若干タレやタマリなどが生し
てその部分の膜厚が60prmまたはそれ以上になるこ
とがあるので、60F+以上でもワキなどが発生しない
ことが強く望まれており、塗料(B)により、■成分に
■および◎成分、さらに必要に応して■成分を配合する
ことによって、ワキ限界膜厚を60−以上にすることが
可能になった。なお、これらの膜厚は予備加熱せず、塗
装後、架橋硬化のために直ちに加熱した系についてであ
る。Each of the components ■, ■, and ■ used in coating *4 (B) has the effect of improving armpit resistance even when used alone, but the extent of this effect is only about 40 parts m (dry film thickness) at the critical armpit film thickness. However, it is insufficient in the case of the recent thick film oriented intermediate coating (for example, 45 parts m or more). This is because in spray painting etc.
Even if the paint is painted to a film thickness of 5cm, some sagging or sagging may occur and the film thickness in that area may reach 60prm or more, so it is highly desirable that no wrinkles occur even at 60F+ or higher. With the paint (B), by blending the component (■) with the components (■) and (◎), and further, if necessary, the component (■), it became possible to increase the critical underarm film thickness to 60- or more. Note that these film thicknesses are for a system that was not preheated but was heated immediately after coating for crosslinking and curing.
塗料(B)は、上記@、■および@成分を必須成分とす
るが、さらにハジキ防止剤、消泡剤、レベリング剤、た
れ防止剤および硬化促進剤(酸触媒)などの各種の変性
剤、助剤を必要に応して添加することができる。また、
アルコール系、エーテルアルコール系、エステル系、ケ
トン系などの水と自由に混和し得る有機溶剤を配合する
こともでき、その配合量は、樹脂固形分(重量)に対し
20重量%以下の範囲が適している。The paint (B) has the above @, ■, and @ components as essential components, and further contains various modifiers such as anti-cissing agents, antifoaming agents, leveling agents, anti-sagging agents, and curing accelerators (acid catalysts). Auxiliary agents can be added if necessary. Also,
Organic solvents that are freely miscible with water, such as alcohols, ether alcohols, esters, and ketones, can also be blended, and the blending amount is within a range of 20% by weight or less based on the resin solid content (weight). Are suitable.
また、塗膜の膜厚保持性、塗装作業性及び塗膜の物理強
度向上等のため、酸化チタン、硫酸バリウム、炭酸カル
シウム、クレー等の無機顔料や、これに加えて看彩のた
めの各種顔料を上記各成分の合計樹脂固形分100重1
部に対して、1〜200重量部配合することが好ましい
。In addition, inorganic pigments such as titanium oxide, barium sulfate, calcium carbonate, and clay are used to improve the film thickness retention, painting workability, and physical strength of the paint film. The total resin solid content of each of the above components is 100 parts by weight.
It is preferable to add 1 to 200 parts by weight.
塗料(B)は水で塗装適正粘度に調整し、スプレー塗装
、静電塗装によって塗装される。塗装膜厚は平坦部で硬
化塗膜にもとづいて30〜50μmが適している。The paint (B) is adjusted to an appropriate viscosity with water and applied by spray painting or electrostatic painting. The suitable thickness of the coating film is 30 to 50 μm in flat areas, based on the cured coating film.
本発明の方法は、塗料(A)をカチオン電着塗装し、加
熱硬化させることなく、該未硬化塗面に塗料(B)を塗
装したのち、加熱して該両塗膜を同時に硬化させる。両
塗膜を硬化させるための加熱温度は、特に制限を受けな
いが、具体的には、70〜250℃、特に120〜16
0℃の範囲が好ましい。In the method of the present invention, the coating material (A) is cationically electrodeposited, the coating material (B) is coated on the uncured coating surface without heating and curing, and then both coatings are cured simultaneously by heating. The heating temperature for curing both coating films is not particularly limited, but specifically 70 to 250°C, especially 120 to 16°C.
A range of 0°C is preferred.
本発明において、塗料(B)の塗膜は上塗り塗膜として
の機能も有しているので、上記塗料(A)および(B)
を塗装してなる2コート仕上げとして利用できるが、最
も好ましいのは、さらに上塗り塗料(ソリッドカラー又
はメタリック仕上げなど)を塗装し、塗料(B)を中塗
り塗料として利用することである。In the present invention, since the paint film of paint (B) also has a function as a top coat film, the paints (A) and (B) described above
Although it can be used as a two-coat finish, it is most preferable to further apply a top coat (solid color or metallic finish, etc.) and use the paint (B) as an intermediate coat.
次に実施例により本発明を更に具体的に説明する。実施
例中「部」は「重量部」であり、「%」は「重量%」で
ある。Next, the present invention will be explained in more detail with reference to Examples. In the Examples, "parts" are "parts by weight" and "%" are "% by weight".
■製造例
1−1 基体樹脂(1)の製造
■基体樹脂(■−■)
エポキシ当量950のビスフェノールAタイプエポキシ
樹脂[商品名[エピコートl 004、シェル化学■製
] 1900部をブチルセロソルブ993部に溶解し、
ジェタノールアミン210部を反応させて固形分68%
、第1級水酸基当量528、アミン価53をもつ基体樹
脂(■−■)を得た。■Production example 1-1 Production of base resin (1) ■Base resin (■-■) Bisphenol A type epoxy resin with epoxy equivalent weight of 950 [trade name [Epicoat l 004, manufactured by Shell Chemical ■] 1900 parts to 993 parts of butyl cellosolve dissolve,
Reacted with 210 parts of jetanolamine to achieve a solid content of 68%.
, a base resin (■-■) having a primary hydroxyl group equivalent of 528 and an amine value of 53 was obtained.
■基体樹脂(■−■)
モノエタノールアミン39部を反応容器中で60’Cに
保ち、N、N−ジメチルアミノプロピルアクリルアミド
100部を滴下し、60°Cで5時間反応させ、N、N
−ジメチルアミノプロピルアクリルアミドのモノエタノ
ールアミン付加物を得た。■Base resin (■-■) 39 parts of monoethanolamine was maintained at 60'C in a reaction vessel, 100 parts of N,N-dimethylaminopropylacrylamide was added dropwise, and the mixture was reacted at 60°C for 5 hours.
- A monoethanolamine adduct of dimethylaminopropylacrylamide was obtained.
別にエポキシ当量190のビスフェノールAジグリシジ
ルエーテル950部、エポキシ当量340のプロピレン
グリコールジグリシジルニーチル340部、ビスフェノ
ールA456部及びジェタノールアミン21部を仕込み
、120°Cまて昇温し、エポキシ価が1.02ミリモ
ル/gになるまで反応させた後、エチレングリコールモ
ノブチルエーテル479部で希釈、冷却したのち、温度
を100°Cに保ちながら、ジェタノールアミン158
部及び上記N、N−ジメチルアミノプロピルアクリルア
ミドのモノエタノールアミン付加物43部を加え、粘度
上昇が止まるまで反応させ、樹脂固形分80%、第1級
水酸基当量518、アミン価54の基体樹脂(■−■)
を得た。Separately, 950 parts of bisphenol A diglycidyl ether with an epoxy equivalent of 190, 340 parts of propylene glycol diglycidyl nityl with an epoxy equivalent of 340, 456 parts of bisphenol A, and 21 parts of jetanolamine were charged, and the temperature was raised to 120°C to determine the epoxy value. After reacting until the concentration was 1.02 mmol/g, diluted with 479 parts of ethylene glycol monobutyl ether and cooled, 158 parts of jetanolamine was added while maintaining the temperature at 100°C.
1 part and 43 parts of the monoethanolamine adduct of the above N,N-dimethylaminopropylacrylamide were added, and the reaction was continued until the viscosity stopped increasing. ■−■)
I got it.
■基体樹脂(I−■)
エポキシ当量190のビスフェノールAジグリシジルエ
ーテル950部、エポキシ当量330のエポキシ樹脂X
B−4122(チバガイギー社製商品名)330部、ビ
スフェノールA456部及びジェタノールアミン21部
を仕込み、120°Cまで昇温し、エポキシ価が、1.
02ミリモル/gになるまで反応させた後、エチレング
リコールモノブチルエーテル489部で希釈、冷却した
のちジェタノールアミン126部、上記N、N−ジメチ
ルアミノプロピルアクリルアミドのモノエタノールアミ
ン付加物535部及びN−メチルアミンエタノール18
5部を加え、反応させ、樹脂固形分80%、第1級水酸
基当量592、アミン価55の基体樹脂(■−■)を得
た。■Base resin (I-■) 950 parts of bisphenol A diglycidyl ether with an epoxy equivalent of 190, epoxy resin X with an epoxy equivalent of 330
330 parts of B-4122 (trade name manufactured by Ciba Geigy), 456 parts of bisphenol A, and 21 parts of jetanolamine were charged and heated to 120°C until the epoxy value was 1.
After reacting until the concentration was 0.2 mmol/g, diluting with 489 parts of ethylene glycol monobutyl ether and cooling, 126 parts of jetanolamine, 535 parts of the monoethanolamine adduct of the above N,N-dimethylaminopropylacrylamide, and N- Methylamine ethanol 18
5 parts were added and reacted to obtain a base resin (■-■) having a resin solid content of 80%, a primary hydroxyl equivalent of 592, and an amine value of 55.
1−2硬化用樹脂(II)の製造
■硬化用樹脂(II−■)
EHPE3150 [エポキシ当量175〜195、ダ
イセル化学工業■製]32.6部とプロピレングリコー
ルモノメチルエーテル82部を100°Cで加熱溶解し
、固形分80%、エポキシ当量190の硬化用樹脂(B
−1)40,8部を得た。該樹脂の数平均分子量は約1
.500であった。1-2 Production of Curing Resin (II) ■Curing Resin (II-■) 32.6 parts of EHPE3150 [epoxy equivalent 175-195, manufactured by Daicel Chemical Industries, Ltd.] and 82 parts of propylene glycol monomethyl ether were heated at 100°C. Curing resin (B) with solid content of 80% and epoxy equivalent of 190
-1) 40.8 copies were obtained. The number average molecular weight of the resin is approximately 1
.. It was 500.
■硬化用樹脂(TI−■)
ビニルノルボルネンオキシド136部、4−ビニルシク
ロヘキセン−1−オキシト124部及びトリメチロール
プロパン18部にBF3−エーテラートの10%酢酸エ
チル溶液200部を50℃で4時間かけて滴下して開環
重合を行なった。酢酸エチルを加えて水洗し、酢酸エチ
ル層を濃縮してから新に酢酸エチル130部を加えて溶
解し、過酢酸160部を酢酸エチル溶液として50°C
で4時間かけて滴下し、更に50℃で2時間熟成しエポ
キシ化反応を行なった。酢酸、酢酸エチル、過酢酸を除
去後、酢酸エチル500部に40 ’Cて溶解し、つづ
いて250部の蒸留水で4回洗浄後酢酸エチルを除去し
、80°Cで78部のプロピレングリコールモノメチル
エーテルに溶解し、固形分80%、エポキシ当量202
の硬化用樹脂(II−■)を得る。該樹脂の数平均分子
量は約1.300であった。■Curing resin (TI-■) 200 parts of a 10% ethyl acetate solution of BF3-etherate was added to 136 parts of vinylnorbornene oxide, 124 parts of 4-vinylcyclohexene-1-oxide, and 18 parts of trimethylolpropane at 50°C for 4 hours. was added dropwise to perform ring-opening polymerization. Add ethyl acetate and wash with water, concentrate the ethyl acetate layer, add 130 parts of fresh ethyl acetate to dissolve, and prepare 160 parts of peracetic acid as an ethyl acetate solution at 50°C.
The mixture was added dropwise over 4 hours and further aged at 50°C for 2 hours to carry out an epoxidation reaction. After removing acetic acid, ethyl acetate, and peracetic acid, it was dissolved in 500 parts of ethyl acetate at 40'C, then washed 4 times with 250 parts of distilled water, ethyl acetate was removed, and dissolved in 78 parts of propylene glycol at 80°C. Dissolved in monomethyl ether, solids content 80%, epoxy equivalent weight 202
A curing resin (II-■) is obtained. The number average molecular weight of the resin was approximately 1.300.
■硬化用樹脂(II−■)
リモネンの部分エポキシ化物(2−メチル−4−インプ
ロペニル−1−シクロヘキセンオキシド)304部とト
リメチロールプロパン18部に、BF、−エーテラート
の10%酢酸エチル溶液200部を50°Cで4時間か
けて滴下した。以下の操作を硬化用樹脂(H−■)と同
様に行ない、80°Cで80部のエチレングリコールモ
ノフチルエーテルに溶解し、固形分80%、エポキシ当
量205の硬化用樹脂(II−■)を得た。該樹脂の数
平均分子量は約1.000であった。■Curing resin (II-■) 304 parts of partially epoxidized limonene (2-methyl-4-impropenyl-1-cyclohexene oxide) and 18 parts of trimethylolpropane are mixed with 200 parts of a 10% ethyl acetate solution of BF,-etherate. part was added dropwise at 50°C over 4 hours. The following operations were carried out in the same manner as for the curing resin (H-■), and the curing resin (II-■) was dissolved in 80 parts of ethylene glycol monophthyl ether at 80°C, with a solid content of 80% and an epoxy equivalent of 205. I got it. The number average molecular weight of the resin was about 1.000.
■硬化用樹脂(II−■)
2.4−または1,4−ジメチル−4エチニル−1シク
ロヘキセンオキシド304部を用い硬化用樹脂(IT−
■)と同様に行ない、固形分80%、エポキシ当119
9の硬化用樹脂(II−■)を得た。該樹脂の数平均分
子量は約950であった。■ Curing resin (II-■) Curing resin (IT-
■) Proceed in the same manner as above, solid content 80%, epoxy 119%
A curing resin (II-■) of No. 9 was obtained. The number average molecular weight of the resin was approximately 950.
■硬化用樹脂(II−■〕
セル化学■社製商品名コ460部、アルミニウムアセチ
ルアセトナート0.3部及びテトラエトキシシラン5部
に蒸留水O
1部を加え、so’cて
1時間保った後、120°Cて3時間反応後エチし・フ
グリコールモノブチルエーテル116部を加えて、固形
分80%エポキシ当量280部の硬化用樹脂(TI−■
)を得た。該樹脂の数平均分子量は約1.100であっ
た。■Curing resin (II-■) Add 1 part of distilled water O to 460 parts of product name manufactured by Cell Kagaku ■, 0.3 parts of aluminum acetylacetonate, and 5 parts of tetraethoxysilane, and keep it for 1 hour in SO'C. After reaction at 120°C for 3 hours, 116 parts of ethylated fuglycol monobutyl ether was added to form a curing resin (TI-■
) was obtained. The number average molecular weight of the resin was approximately 1.100.
■硬化用樹脂(H−■)
シクロベンクジエンの二量体132部を酢酸エチル70
部に湾解し、過酢酸160部を酢酸エチル溶液として3
5°Cで7時間かけて滴下し、更に40°Cで6時間熟
成した。酢酸、酢酸エチル、過酢酸を除去後、酢酸エチ
ル500部に40°Cて溶解し、つづいて250部の蒸
留水で5回洗浄後酢酸エチルを除去し、80°Cで43
部のメチルイソブチルケトンに溶解し、固形分80%、
エポキシ当1190の化合物(C)を得た。■Curing resin (H-■) 132 parts of cyclobencdiene dimer was added to 70 parts of ethyl acetate.
1 part and 160 parts of peracetic acid as an ethyl acetate solution.
The mixture was added dropwise at 5°C over 7 hours and further aged at 40°C for 6 hours. After removing acetic acid, ethyl acetate, and peracetic acid, it was dissolved in 500 parts of ethyl acetate at 40°C, then washed 5 times with 250 parts of distilled water, the ethyl acetate was removed, and the solution was dissolved at 80°C for 43 hours.
Dissolved in 1 part methyl isobutyl ketone, solid content 80%,
Compound (C) containing 1190 epoxy compounds was obtained.
4−ビニルシクロヘキセン94部を酢酸エチル75部に
溶解し、過酢酸160部を酢酸エチルl容液と1−で5
0°Cで4時間かけて滴下し、更に50°Cて2時間熟
成した。酢酸、酢酸エチル、過酢酸を除去後、酢酸エチ
ル500部に40°Cて(容解し、つづいて250部の
蒸留水で5回洗浄後酢酸エチルを除去し、80°Cで3
2部のメチルイソブチルケトンに箔解し、固形分80%
、エポキシ当量65の化合物(D)を得た。化合物(C
)225部と化合物(D)163部にアルミニウムアセ
チルアセトナート0.2部及びトリメチロールプロパン
10部を加え、100°Cで1時間保った後、150℃
で3時間反応後エチレングリコルモノブチルエーテル6
0部を加えて冷却する。94 parts of 4-vinylcyclohexene were dissolved in 75 parts of ethyl acetate, and 160 parts of peracetic acid was mixed with 1 volume of ethyl acetate by 5 parts.
The mixture was added dropwise at 0°C over 4 hours, and further aged at 50°C for 2 hours. After removing acetic acid, ethyl acetate, and peracetic acid, the solution was dissolved in 500 parts of ethyl acetate at 40°C. After washing 5 times with 250 parts of distilled water, the ethyl acetate was removed, and the solution was dissolved at 80°C for 3
Foil dissolved in 2 parts of methyl isobutyl ketone, solids content 80%
, compound (D) having an epoxy equivalent of 65 was obtained. Compound (C
) and 163 parts of compound (D) were added 0.2 parts of aluminum acetylacetonate and 10 parts of trimethylolpropane, kept at 100°C for 1 hour, and then heated to 150°C.
After reacting for 3 hours with ethylene glycol monobutyl ether 6
Add 0 parts and cool.
固形分70%、エポキシ当量210の硬化用樹脂(II
−■)を得た。該樹脂の数平均分子量は約1.100で
あった。Curing resin (II
−■) was obtained. The number average molecular weight of the resin was approximately 1.100.
■硬化用樹脂(II−■)
METHB (3,4−エポキシシクロヘキシルメチル
メタクリレート)334部にアゾビスジメチルバレロニ
トリル2部を溶解したものを、100°Cに加熱したメ
チルイソブチルケトン10部とブチルセロソルブ10部
との混合溶剤に2時間かけて滴下し、1時間熟成後、1
25℃に昇温しで更に1時間熟成し、固形分60%、エ
ポキシ当量196の硬化用樹脂(+1−■)i@液54
部を得た。該樹脂の数平均分子量は約10.000であ
った。■Curing resin (II-■) A solution of 2 parts of azobisdimethylvaleronitrile dissolved in 334 parts of METHB (3,4-epoxycyclohexylmethyl methacrylate) was heated to 100°C, and then mixed with 10 parts of methyl isobutyl ketone and 10 parts of butyl cellosolve. It was added dropwise over 2 hours to a mixed solvent with 100% of
The temperature was raised to 25°C and further aged for 1 hour to obtain a curing resin (+1-■) i@liquid 54 with a solid content of 60% and an epoxy equivalent of 196.
I got the department. The number average molecular weight of the resin was approximately 10.000.
■硬化用樹脂(II−■)
METHBモノマー32.0部とヒドロキシエチルアク
リレート8.0部を混合したものにアゾビスジメチルバ
レロニトリル2.4部を溶解したものをloO’cに加
熱したブチルセロソルブ24部に2時間かけて滴下し、
1時間熟成した後、125℃に昇温しで更に1時間熟成
し、固形分60%、エポキシ当量245の硬化用樹脂(
Il−■)648部を得た。該樹脂の数平均分子量は約
12.000であった。■Curing resin (II-■) Butyl cellosolve 24 obtained by heating a mixture of 32.0 parts of METHB monomer and 8.0 parts of hydroxyethyl acrylate and 2.4 parts of azobisdimethylvaleronitrile to loO'c. drip onto the area over 2 hours,
After aging for 1 hour, the temperature was raised to 125°C and further aging for 1 hour, resulting in a curing resin (solid content 60%, epoxy equivalent weight 245).
648 parts of Il-■) were obtained. The number average molecular weight of the resin was approximately 12,000.
■硬化用樹脂(II−■)
3.4−エポキシシクロヘキシルメチルアクリレート3
7部とヒドロキシエチルアクリレート3部を混合したも
のにアゾビスジメチルバレロニトリル2.4部を溶解し
、以下硬化用樹脂B−9と同様に処理を行ない、固形分
60%、エポキシ当量200の硬化用樹脂(II−■)
を得た。該樹脂の数平均分子量は約15.000であっ
た。■Curing resin (II-■) 3.4-Epoxycyclohexylmethyl acrylate 3
2.4 parts of azobisdimethylvaleronitrile was dissolved in a mixture of 7 parts of hydroxyethyl acrylate and 3 parts of hydroxyethyl acrylate, and the following treatment was carried out in the same manner as for curing resin B-9 to obtain a solid content of 60% and an epoxy equivalent of 200. Resin (II-■)
I got it. The number average molecular weight of the resin was approximately 15,000.
I−3顔料ペーストの製造
顔料ペースト(P−1)
基体樹脂12.5部に10%ギ酸4,4部を加え、攪拌
しながら脱イオン水15部を加える。更にチク2010
部、クレー10部、カーボン1部、塩基性ケイ酸鉛2部
を加え、ボールミルで24時間分散後説イオン水11部
を加え、固形分50%のペーストを得た。基体樹脂は、
第1表に記載の各実施例と同一のものを用いた。I-3 Preparation of Pigment Paste Pigment Paste (P-1) Add 4.4 parts of 10% formic acid to 12.5 parts of base resin, and add 15 parts of deionized water while stirring. Furthermore Chiku 2010
10 parts of clay, 1 part of carbon, and 2 parts of basic lead silicate were dispersed in a ball mill for 24 hours, and 11 parts of ionized water (described later) was added to obtain a paste with a solid content of 50%. The base resin is
The same material as in each Example described in Table 1 was used.
I−4カチオン電着塗料(A−1)の製造上記の基体樹
脂、硬化用樹脂および顔料ペーストを第1表に示した配
合量に混合して塗料(A−1)を得た。I-4 Production of cationic electrodeposition paint (A-1) The above base resin, curing resin and pigment paste were mixed in the amounts shown in Table 1 to obtain paint (A-1).
第1表において、基体樹脂および硬化用樹脂の配合量は
いずれも樹脂固形分で示してあり、脱イオン水を配合し
て固形分含有率を20%に調製したのち、さらに、前記
顔料ペースト(P−1)を92部および脱イオン水を配
合して固形分含有率20%の電着浴を作成した。In Table 1, the blending amounts of the base resin and curing resin are both shown in resin solid content, and after blending deionized water to adjust the solid content to 20%, the pigment paste ( An electrodeposition bath having a solid content of 20% was prepared by blending 92 parts of P-1) with deionized water.
I−5カチオン電着塗料(A−2)の製造■ 基体樹脂
(■−■)
■ジメチルベンジルアミン酢酸塩
■p−ノニルフェノール
26部
79部
■ジェタノールアミン
■ブチルセロソルブ
■セロソルブ
成分■〜■を一緒にし150°Cて2時間反応せた後、
成分■〜■を配合し、80〜90°Cで3時間反応させ
、固形分75%の基体樹脂(I−■)を得る。I-5 Production of cationic electrodeposition paint (A-2) ■ Base resin (■ - ■) ■ Dimethylbenzylamine acetate ■ 26 parts and 79 parts of p-nonylphenol ■ Jetanolamine ■ Butyl cellosolve ■ Cellosolve components ■ ~ ■ together After reacting at 150°C for 2 hours,
Components (1) to (2) are blended and reacted at 80 to 90°C for 3 hours to obtain a base resin (I-2) with a solid content of 75%.
■ 顔料ペースト
チタン白 14.5 FHI
カーボン 0454部体質顔
料(クレー) 70 部ケイ酸鉛
23 部シフ゛チルナンオキサイド
20 邪説イオン水 2
749部からなる固形分50%の那料ペーストを得た。■ Pigment paste titanium white 14.5 FHI
Carbon 0454 parts Extender pigment (clay) 70 parts Lead silicate
23 Part shifternan oxide 20 Mythical ionized water 2
A narcotic paste containing 749 parts with a solid content of 50% was obtained.
■ カチオン電着塗料(A−2)の製造前記基体樹脂を
用いて固形分32%の2種の水性エマルジョンを作成し
た。組成及び配合量を下記に示す。(2) Production of cationic electrodeposition paint (A-2) Two types of aqueous emulsions each having a solid content of 32% were prepared using the above-mentioned base resin. The composition and blending amount are shown below.
■基体樹脂(II −A )
A−2−■
112部
A−2−■
112部
ンジイソシアネ
ト
ンジイソシアネート
■酢酸鉛 10 10■10%
酢酸 93 93■脱イオン水
179.45 179.45次いで、この
水性エマルジョン318.75部に前記顔料ペースト5
956部及び脱イオン水280.59部を混合し固形分
20%のカチオン電着浴を作成した。■Base resin (II-A) A-2-■ 112 parts A-2-■ 112 parts Diisocyanetone diisocyanate ■ Lead acetate 10 10 ■ 10%
Acetic acid 93 93■Deionized water
179.45 179.45 Next, 5 parts of the pigment paste was added to 318.75 parts of this aqueous emulsion.
A cationic electrodeposition bath having a solid content of 20% was prepared by mixing 956 parts and 280.59 parts of deionized water.
I−6水性塗料(B)の製造
■・ ■成分の製造
■−1
エチレングリコール196部、トリメチロールプロパン
18.5部および無水フタル酸467部を160〜23
0°Cて7時間反応させてなるポリエステル樹脂にトリ
レンジイソシアネート157部を120°Cで反応させ
たのもさらに無水トリメリット酸52部を加えて180
°Cで1時間反応させて、重量平均分子量が6.000
、酸価が40および水酸基価が112のウレタン変性ポ
リ−エステル樹脂■−1を得た。I-6 Manufacture of water-based paint (B) ■・ ■ Manufacture of components ■-1 196 parts of ethylene glycol, 18.5 parts of trimethylolpropane and 467 parts of phthalic anhydride were mixed into 160 to 23 parts of phthalic anhydride.
157 parts of tolylene diisocyanate was reacted at 120°C with a polyester resin obtained by reacting at 0°C for 7 hours, and 52 parts of trimellitic anhydride was further added to give 180 parts of tolylene diisocyanate.
After reacting at °C for 1 hour, the weight average molecular weight was 6.000.
A urethane-modified polyester resin (1) having an acid value of 40 and a hydroxyl value of 112 was obtained.
■−2
エチレングリコール193部、トリメチロールプロパン
182部および無水フタル酸462部を160〜230
°Cて7時間反応させてなるポリエステル樹脂にキシレ
ンジイソシアネート16.8部を120°Cで反応させ
たのち、さらに無水トリメリット酸5.1部を加えて1
80°Cで1時間反応させて、重量平均分子量が6.2
00、酸価が40および水酸基価が110のウレタン変
性ポリエステル樹脂■−2を得た。■-2 193 parts of ethylene glycol, 182 parts of trimethylolpropane, and 462 parts of phthalic anhydride in 160 to 230 parts
After reacting 16.8 parts of xylene diisocyanate at 120°C with the polyester resin obtained by reacting at 120°C for 7 hours, 5.1 parts of trimellitic anhydride was further added.
After reacting at 80°C for 1 hour, the weight average molecular weight was 6.2.
00, a urethane modified polyester resin (2) having an acid value of 40 and a hydroxyl value of 110 was obtained.
■−3
エチレングリコール27.7部、グリセリン10.3部
および無水フタル酸500部を160〜230″Cで7
時間反応させてなるポリエステル樹脂にトリレンジイソ
シアネート9.7部を120’cで反応させたのち、さ
らに無水フタル酸83部を加えて160℃で3時間反応
させて、重量平均分子量が4.500、酸価が50およ
び水酸基価が200のウレタン変性ポリエステル樹脂■
−3を得た。■-3 27.7 parts of ethylene glycol, 10.3 parts of glycerin, and 500 parts of phthalic anhydride at 160 to 230"C.
After reacting the resulting polyester resin with 9.7 parts of tolylene diisocyanate at 120°C, 83 parts of phthalic anhydride was added and reacted at 160°C for 3 hours, resulting in a weight average molecular weight of 4.500. , urethane-modified polyester resin with an acid value of 50 and a hydroxyl value of 200■
I got -3.
■ 水性塗料(B)
上記■成分などを第2表に示した配合量に従って混合分
散して水性塗料(B)とした。(2) Water-based paint (B) The above components (1) and others were mixed and dispersed according to the amounts shown in Table 2 to prepare a water-based paint (B).
第2表において、■〜■成分の配合量は固形分に基づい
ており、B−■の現用の有機溶剤型中塗り塗料は「アミ
ラックシーラー」 (関西ペイント■製ポリエステル樹
脂系、商品名)である。In Table 2, the compounding amounts of components ■ to ■ are based on the solid content, and the current organic solvent-based intermediate coating paint for B-■ is "Amilac Sealer" (polyester resin type manufactured by Kansai Paint ■, trade name). It is.
(°l)■成分名称 ■−1〜3は前記製造例で得たもの。(°l)■Component name (2)-1 to 3 were obtained in the above production example.
(°2)■成分名称
(■−1)、[サイメルフ03J (三井すイアナミ
ド■製品、イミノ基含有メラミン樹脂)(°3)■成分
名称
般式
で示されるポリエーテルポリオールにおいて、(■−1
)・n=3のもの
(■−2):n=4のもの
(*4)■成分名称
(■−1):ベンゾインエチルエーテル(中5)有機溶
剤・ジエチレングリコールモノエチルエーテル。これら
の配合量は、■成分、■成分および@成分の合計固形分
100重量部あたっである。(°2) ■Component name (■-1), [Cymelf 03J (Mitsui Suyanamide ■ product, imino group-containing melamine resin) (°3) ■Component name In the polyether polyol shown by the general formula, (■-1
)・N=3 (■-2): n=4 (*4) ■Component name (■-1): Benzoin ethyl ether (medium 5) Organic solvent/diethylene glycol monoethyl ether. The amount of these ingredients is per 100 parts by weight of the total solid content of component (1), component (2) and component @.
顔料としては■、■および@成分の合計固形分100重
量部あたり、酸化チタン白80部、硫酸バリウム20部
およびカーボンブラック0.3部を配合した。As pigments, 80 parts of titanium oxide white, 20 parts of barium sulfate, and 0.3 parts of carbon black were blended per 100 parts by weight of the total solid content of components (1), (2), and (@).
これら顔料は、■成分の一部及び脱イオン水、消泡剤と
一緒に容器に仕込み、ガラスピーズを分散メジアとして
1時間かけて、ツブゲージで測定した粒子(ツブ)が5
LL以下になるように分散した。These pigments were placed in a container together with a part of the ingredients (1), deionized water, and an antifoaming agent, and were dispersed using glass beads as a dispersion medium for 1 hour.
It was dispersed so that it was below LL.
TI 実施例
浴温30℃に調整したカチオン電着塗料(A−1)およ
び(A−2)にリン酸亜鉛処理鋼板を浸漬し、200〜
300■で3分間型着してから塗板を引き上げ、水洗し
てから、100°Cて10分間水切り乾燥した後、水性
塗料(B)を該未硬化電着塗面に噴霧塗装し、室温で5
分放置してから加熱して該両塗膜を硬化させた。TI Example A zinc phosphate treated steel plate was immersed in cationic electrodeposition paints (A-1) and (A-2) whose bath temperature was adjusted to 30°C.
After molding at 300°C for 3 minutes, remove the coated plate, wash with water, drain and dry at 100°C for 10 minutes, then spray paint the water-based paint (B) on the uncured electrodeposited surface and leave it at room temperature. 5
Both coatings were cured by heating after being allowed to stand for several minutes.
これらの塗装工程および形成した塗膜の性能試験結果を
第3表に示した。Table 3 shows these coating steps and the performance test results of the coating films formed.
第3表において、
1 カチオン電@塗料(A−3)は、前記A2−■にお
けるジブロックイソホロンジイソシアネートのメチルエ
ヂルケトオキシム(ブロック剤)をジフェニルメクンジ
イソシアネートを2エチルへキシルグリコールでジブロ
ックしたものに代えた以夕)はすべてA−2−■と同様
にして製造した。In Table 3, 1. The cationic electrolyte paint (A-3) is obtained by diblocking methyl edyl ketoxime (blocking agent) of diblock isophorone diisocyanate in A2-■ above with diphenylmecund diisocyanate with 2 ethylhexyl glycol. (2) were all produced in the same manner as A-2-■.
24力チオン電着塗膜を水洗後、100°Cて10分間
乾煙すると水分の殆どは揮散し除去できるが、架橋反応
(硬化)は行′なわれていない。After washing the 24-force thione electrodeposited coating with water and drying it at 100°C for 10 minutes, most of the moisture can be volatilized and removed, but no crosslinking reaction (curing) has taken place.
760°Cて30分加熱(焼付)すると架橋硬化する。It is crosslinked and hardened by heating (baking) at 760°C for 30 minutes.
3 上塗り塗料の「アミラック黒」は関西ペイント((
1)製部品名で、メラミン/ポリエステル系有機溶剤型
熱硬化性塗料である。3 The top coat “Amirac Black” is manufactured by Kansai Paint ((
1) The product name is a melamine/polyester organic solvent-based thermosetting paint.
4 性能試験方法
下記のうち、(4)から(b)は、前記のごとくカチオ
ン電着塗第4および水性塗料を塗装し、加熱硬化させて
なる塗板について試験した結果である。また、(7)か
ら(10)は、該水性塗料の硬化塗面にさらにアミラッ
ク興を塗装し、140°Cで30分焼付してなる塗板に
ついて試験した結果ある。4 Performance Test Method Among the following, (4) to (b) are the results of tests on coated plates coated with cationic electrodeposition coating No. 4 and water-based paint as described above and cured by heating. In addition, (7) to (10) are the results of tests on coated plates obtained by further coating the cured surface of the water-based paint with Amirac Ko and baking it at 140°C for 30 minutes.
(1)加熱減量
鋼板の重量をWoとし、この鋼板に30°Cにおいて2
00〜300■で3分間カチオン電着後、電着浴から引
き上げて塗面を水洗し、105℃で3時間加熱して塗膜
中の水分のすべてもしくは殆どを除去してから塗膜重量
(Y)を測定し、次いで、170℃で20分加熱して該
塗膜を三次元架橋硬化した後の塗膜重量(Z)を測定し
た。これらの測定値を次式にあてはめて塗膜減量(X)
をもとめた。(1) The weight of the heat loss steel plate is Wo, and the weight of this steel plate is 2 at 30°C.
After cationic electrodeposition for 3 minutes at 00 to 300 cm, remove the coating from the electrodeposition bath, wash the coated surface with water, heat it at 105℃ for 3 hours to remove all or most of the water in the coating, and then calculate the coating weight ( Y) was measured, and then the coating film weight (Z) after three-dimensionally crosslinking and curing the coating film by heating at 170° C. for 20 minutes was measured. Apply these measured values to the following formula to calculate the coating film weight loss (X)
I asked for.
(2)ワキ限界膜厚
約10cmX 45cmのリン酸亜鉛処理鋼板に第3表
に示した工程でそれぞれカチオン塗装しく硬化塗膜で2
0μ)、水切乾燥後、水性塗料を、薄膜部で約30F+
、厚膜部で約70戸(いずれも水性塗料羊独硬化膜塗膜
に基づく)になるようスプレー塗装で膜厚傾斜塗装し、
塗装ブース(20〜25℃の温度で、70〜75%RH
に調湿)にて塗板を10分間、水平に保持した後、15
0°Cの乾燥機で焼付硬化させる。このときに、ワキの
塗装欠陥のない、最大膜厚(電着塗膜と水性塗料塗膜と
の合計)をもってワキ限界膜厚(単位P)とする。(2) A cationic coating is applied to a zinc phosphate treated steel plate with a critical film thickness of approximately 10 cm x 45 cm using the steps shown in Table 3.
0μ), after draining and drying, apply water-based paint to the thin film area at approximately 30F+
The thickness of the coating was applied by spray painting at an angle to approximately 70 units (all based on water-based cured coatings).
Painting booth (at a temperature of 20-25℃, 70-75% RH)
After holding the coated plate horizontally for 10 minutes at
Bake and harden in a dryer at 0°C. At this time, the maximum film thickness (total of the electrodeposited coating film and the water-based paint film) without coating defects on the armpit is defined as the critical armpit film thickness (unit: P).
(3)タレ限界膜厚
長辺にそって直径10闘の穴を、4cm間隔で空けたリ
ン酸亜鉛処理鋼板(10X45cm)を用いる。*装は
、上記(2)と同様に行う、塗装置後より、セツティン
グ時及び焼付は時共に、塗板は垂直に保持する(穴が横
に並ぶ様に)、このときの穴の周辺のタレ欠陥のない最
大膜厚(両塗膜の合計)をもってタレ限界膜厚(単位・
胛)とする。(3) Sag limit film thickness A zinc phosphate treated steel plate (10 x 45 cm) with holes of 10 mm in diameter made at 4 cm intervals along the long side is used. *The installation is done in the same way as in (2) above. After painting, during setting and baking, hold the coating plate vertically (so that the holes are lined up horizontally). The maximum film thickness without sagging defects (total of both coatings) is the sag limit film thickness (unit:
To be a yakuza).
(4)平滑性
水性塗料塗面の平滑性を目視評価した。ちぢみ、オレン
ジビールおよびへこみなどの発生が全く詔められないも
のを○、少し発生したものを△、多く発生したものを×
とした。(4) Smoothness The smoothness of the surface coated with the water-based paint was visually evaluated. ○ indicates that there is no shrinkage, orange beer or dents, △ indicates that there is a little, and × indicates that there is a lot of denting.
And so.
(5)塗膜硬度
20℃の恒温室で、American Chain &
CableCompany製のTUKON m1cr
ohardness testerにて水性塗料塗面の
硬度を測定した。数値が大きくなるに従って硬質になる
。(5) American Chain &
TUKON m1cr made by Cable Company
The hardness of the surface coated with the water-based paint was measured using an ohardness tester. The larger the number, the harder it becomes.
(6)硬化性
20°Cで、水性塗料塗膜の表面をキジロールを含むガ
ーゼで強く10回こすった後ツヤびけを観察し、硬化性
を評価した。○ 異常なし、△ ツヤひけ発生。(6) Curing properties Curing properties were evaluated by rubbing the surface of the water-based paint film at 20°C vigorously 10 times with gauze containing Kijiroru and observing for gloss loss. ○ No abnormality, △ Shine and sink.
(7)鮮映性
写像性測定器[IMAGE CLA旧TY METER
’:スガ試験機■製]で測定。表中の数字はICM値で
0〜100%の範囲の値をとり、数値の大きい方が鮮映
性(写像性)がよく、ICM値が85以上であれば鮮映
性がすぐれていることを示す6(8)iiitチッピン
グ性
飛石試験機(スガ試験機■、JA−400型)を使用、
同試験機の試料ホルダーに塗装試験板を垂直にとりつけ
50gの7号砕石を、同試験機の圧力計で4 kg/
cm”の空気圧で噴射し、砕石を試験板に対し垂直に衝
突させる。その時のハガレ傷の程度を良好(○)〜劣る
(×)の5段階で判定した。(7) Image clarity measuring device [IMAGE CLA former TY METER]
': Measured using Suga Test Instruments ■. The numbers in the table are ICM values that range from 0 to 100%; the higher the number, the better the image clarity, and if the ICM value is 85 or higher, the image clarity is excellent. Using a 6(8)III chipping stone tester (Suga Test Instruments ■, JA-400 type),
The painted test plate was mounted vertically on the sample holder of the testing machine, and 50g of No. 7 crushed stone was measured using the pressure gauge of the testing machine at 4kg/
cm'' air pressure to collide the crushed stone vertically against the test plate.The degree of peeling damage at that time was judged on a five-point scale from good (◯) to poor (x).
(9)付着性
ゴバン目(1x1mm10O個)セロハン粘着テープテ
ストによった。○は、はがれなしを示す。(9) Adhesiveness Tested with cellophane adhesive tape (100 pieces of 1 x 1 mm). ○ indicates no peeling.
(1D)耐湿性
温度50℃、相対湿度98〜100%RHのブリスター
ボックスに、5日間放置後とり出し、フクレの有無を調
べた。○はフクレなし、△はフクレ発生を示す。(1D) Humidity Resistance After being left in a blister box at a temperature of 50° C. and a relative humidity of 98 to 100% RH for 5 days, the sample was taken out and checked for blisters. ○ indicates no blister, △ indicates occurrence of blister.
Claims (1)
熱して該両塗膜を同時に硬化させて複層塗膜を形成する
にあたり、該カチオン電着塗料の電着塗膜の加熱硬化時
における塗膜減量が10重量%以下であり、そして、上
記水性塗料が、 (a)酸価10〜100および水酸基価20〜300の
ポリエステル樹脂および/またはウレタン変性ポリエス
テル樹脂、 (b)水性アミノ樹脂および (c)一般式、 ▲数式、化学式、表等があります▼ (ただし、Rは、▲数式、化学式、表等があります▼ま
たは ▲数式、化学式、表等があります▼、nおよびmは2〜
10の整 数である) で示されるポリエーテルポリオール を主成分とし、さらに必要に応じて (d)アルキルエーテル化ベンゾイン を配合してなる塗料であることを特徴とする塗膜形成法
。[Scope of Claims] When a water-based paint is applied to the surface of a cured coating film after cationic electrodeposition coating and is heated to simultaneously cure both coatings to form a multilayer coating film, the electroplating of the cationic electrodeposition coating The coating film loss during heat curing of the deposited coating film is 10% by weight or less, and the water-based paint is made of (a) a polyester resin and/or urethane-modified polyester resin having an acid value of 10 to 100 and a hydroxyl value of 20 to 300; , (b) Water-based amino resin and (c) General formula, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, R is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, n and m are 2~
A method for forming a coating film, characterized in that the coating material is a coating material containing as a main component a polyether polyol represented by:
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2188308A JP2975061B2 (en) | 1990-07-17 | 1990-07-17 | Coating method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2188308A JP2975061B2 (en) | 1990-07-17 | 1990-07-17 | Coating method |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0474892A true JPH0474892A (en) | 1992-03-10 |
JP2975061B2 JP2975061B2 (en) | 1999-11-10 |
Family
ID=16221338
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2188308A Expired - Lifetime JP2975061B2 (en) | 1990-07-17 | 1990-07-17 | Coating method |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2975061B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2349643A (en) * | 1999-04-21 | 2000-11-08 | Kansai Paint Co Ltd | Cationic electrodeposition coating composition |
-
1990
- 1990-07-17 JP JP2188308A patent/JP2975061B2/en not_active Expired - Lifetime
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2349643A (en) * | 1999-04-21 | 2000-11-08 | Kansai Paint Co Ltd | Cationic electrodeposition coating composition |
GB2349643B (en) * | 1999-04-21 | 2001-09-05 | Kansai Paint Co Ltd | Cationic electrodeposition coating composition |
US6342546B1 (en) | 1999-04-21 | 2002-01-29 | Kansai Paint Co., Ltd. | Cationic electrodeposition coating composition |
Also Published As
Publication number | Publication date |
---|---|
JP2975061B2 (en) | 1999-11-10 |
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