JPH0481474A - Production of cationic electrodeposition coating - Google Patents
Production of cationic electrodeposition coatingInfo
- Publication number
- JPH0481474A JPH0481474A JP19665390A JP19665390A JPH0481474A JP H0481474 A JPH0481474 A JP H0481474A JP 19665390 A JP19665390 A JP 19665390A JP 19665390 A JP19665390 A JP 19665390A JP H0481474 A JPH0481474 A JP H0481474A
- Authority
- JP
- Japan
- Prior art keywords
- group
- cationic
- epoxy
- resin
- weight
- 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.)
- Pending
Links
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 52
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 238000000576 coating method Methods 0.000 title abstract description 31
- 239000011248 coating agent Substances 0.000 title abstract description 29
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 59
- 239000010419 fine particle Substances 0.000 claims abstract description 36
- 239000006185 dispersion Substances 0.000 claims abstract description 32
- 229920000642 polymer Polymers 0.000 claims abstract description 29
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 27
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 25
- 125000000524 functional group Chemical group 0.000 claims abstract description 25
- 229920005989 resin Polymers 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 24
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 23
- 239000011342 resin composition Substances 0.000 claims abstract description 23
- 239000003822 epoxy resin Substances 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims description 29
- 239000003973 paint Substances 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 34
- 239000003795 chemical substances by application Substances 0.000 abstract description 13
- 238000001723 curing Methods 0.000 abstract description 11
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 3
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 238000013035 low temperature curing Methods 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 description 37
- -1 alkylene imine Chemical class 0.000 description 36
- 239000002245 particle Substances 0.000 description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 24
- 239000000203 mixture Substances 0.000 description 23
- 239000000047 product Substances 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000004593 Epoxy Substances 0.000 description 17
- 125000004432 carbon atom Chemical group C* 0.000 description 17
- 238000000034 method Methods 0.000 description 17
- 150000001334 alicyclic compounds Chemical class 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 12
- 239000002253 acid Substances 0.000 description 12
- 239000000049 pigment Substances 0.000 description 11
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 9
- 150000007513 acids Chemical class 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 229920002554 vinyl polymer Polymers 0.000 description 9
- 235000011054 acetic acid Nutrition 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 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
- 238000004132 cross linking Methods 0.000 description 8
- 239000003995 emulsifying agent Substances 0.000 description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 229920006243 acrylic copolymer Polymers 0.000 description 7
- 150000001298 alcohols Chemical class 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 7
- 239000008119 colloidal silica Substances 0.000 description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 6
- 238000006735 epoxidation reaction Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 150000002430 hydrocarbons Chemical group 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
- 229920005862 polyol Polymers 0.000 description 6
- 150000003839 salts Chemical group 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229920001228 polyisocyanate Polymers 0.000 description 5
- 239000005056 polyisocyanate Substances 0.000 description 5
- 150000003077 polyols Chemical class 0.000 description 5
- 235000013824 polyphenols Nutrition 0.000 description 5
- 238000007142 ring opening reaction Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 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
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 235000019253 formic acid Nutrition 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920000768 polyamine Polymers 0.000 description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 150000001735 carboxylic acids Chemical class 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
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- WGYKZJWCGVVSQN-UHFFFAOYSA-N mono-n-propyl amine Natural products CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 235000019260 propionic acid Nutrition 0.000 description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- ZKALVNREMFLWAN-VOTSOKGWSA-N (ne)-n-(4-methylpentan-2-ylidene)hydroxylamine Chemical compound CC(C)C\C(C)=N\O ZKALVNREMFLWAN-VOTSOKGWSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-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
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-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
- 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
- NPFYZDNDJHZQKY-UHFFFAOYSA-N 4-Hydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 NPFYZDNDJHZQKY-UHFFFAOYSA-N 0.000 description 2
- VXASQTMYWZHWMX-UHFFFAOYSA-N 4-ethoxybutyl 2-methylprop-2-enoate Chemical compound CCOCCCCOC(=O)C(C)=C VXASQTMYWZHWMX-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 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
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-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
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical class [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- LJSQFQKUNVCTIA-UHFFFAOYSA-N diethyl sulfide Chemical compound CCSCC LJSQFQKUNVCTIA-UHFFFAOYSA-N 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- WVFLGSMUPMVNTQ-UHFFFAOYSA-N n-(2-hydroxyethyl)-2-[[1-(2-hydroxyethylamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCO WVFLGSMUPMVNTQ-UHFFFAOYSA-N 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
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- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- DPUXQWOMYBMHRN-UHFFFAOYSA-N hexa-2,3-diene Chemical compound CCC=C=CC DPUXQWOMYBMHRN-UHFFFAOYSA-N 0.000 description 1
- VUNCWTMEJYMOOR-UHFFFAOYSA-N hexachlorocyclopentadiene Chemical compound ClC1=C(Cl)C(Cl)(Cl)C(Cl)=C1Cl VUNCWTMEJYMOOR-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 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
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 125000002950 monocyclic group Chemical group 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
- SCZVXVGZMZRGRU-UHFFFAOYSA-N n'-ethylethane-1,2-diamine Chemical compound CCNCCN SCZVXVGZMZRGRU-UHFFFAOYSA-N 0.000 description 1
- QHJABUZHRJTCAR-UHFFFAOYSA-N n'-methylpropane-1,3-diamine Chemical compound CNCCCN QHJABUZHRJTCAR-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 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
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 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
- PMJHHCWVYXUKFD-UHFFFAOYSA-N penta-1,3-diene Chemical compound CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 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
- 238000011056 performance test Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000005011 phenolic resin Substances 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
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 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
- 150000003141 primary amines Chemical group 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 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
- 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
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 229940080818 propionamide Drugs 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
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 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
- 150000003242 quaternary ammonium salts 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
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000004819 silanols Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- UQMGAWUIVYDWBP-UHFFFAOYSA-N silyl acetate Chemical class CC(=O)O[SiH3] UQMGAWUIVYDWBP-UHFFFAOYSA-N 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229930006978 terpinene Natural products 0.000 description 1
- 150000003507 terpinene derivatives Chemical class 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
- 150000003573 thiols Chemical class 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 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
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
[産業上の利用分野コ
本発明は塗膜形成方法に関し、さらに詳しくは、硬化剤
としてのブロックポリイソシアネートや硬化触媒として
の有機錫化合物を用いることなく、硬化性、塗膜の付着
性、耐候性、防食性および低温硬化性等の性能に優れ、
さらに被塗物鋭角部(エツジ部)の被覆性(エツジカバ
ー性)が改良された塗膜を形成し得るカチオン電着塗料
の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for forming a coating film, and more specifically, the present invention relates to a method for forming a coating film. Excellent performance in terms of coating film adhesion, weather resistance, corrosion resistance, and low-temperature curing properties.
Furthermore, the present invention relates to a method for producing a cationic electrodeposition paint that can form a coating film with improved edge coverage of the acute corners (edges) of the object to be coated.
[従来の技術とその課題]
従来、カチオン電@塗料用樹脂組成物として、アミン付
加エポキシ樹脂のようなポリアミン樹脂とアルコール類
などでブロックした芳香族ポリイソシアネート化合物(
硬化剤)とを主成分とするものが最も多く使用され、塗
膜の防食性に関して優れた評価を得ている。しかしなが
ら、この塗料用樹脂組成物は本質的な問題点として、硬
化開始温度が高い(170°C以上)、また、硬化開始
c都度を低くするために硬化触媒として有機錫化合物を
用いると、該錫化合物が焼付炉の排気燃焼触媒を被毒さ
せることがある:さらに、塗膜を硬化させるために高温
加熱すると、ブロックポリイソシアネートが熱分解して
ヤニ、ススを生成し、しかも上塗塗膜に黄変、ブリード
、硬化阻害等を引き起こすと共に該上塗塗膜の耐候性が
著しく低下し、白化しやすいなどの重大な欠点を有して
おり、その改良が強く望まれていた。[Prior art and its problems] Conventionally, as a resin composition for cationic electrolyte paint, aromatic polyisocyanate compounds blocked with polyamine resins such as amine-added epoxy resins and alcohols, etc.
Curing agents) are the most commonly used, and have received excellent reviews regarding the anticorrosion properties of coatings. However, the essential problem with this resin composition for coatings is that the curing initiation temperature is high (170°C or higher), and when an organotin compound is used as a curing catalyst to reduce the curing initiation temperature. Tin compounds can poison the firing furnace exhaust combustion catalyst; furthermore, when heated to high temperatures to harden the coating, the block polyisocyanate decomposes, producing tar and soot, and even damaging the topcoat. It has serious drawbacks such as causing yellowing, bleeding, curing inhibition, etc., as well as significantly lowering the weather resistance of the top coat and being susceptible to whitening, and there has been a strong desire for improvement.
このため本出願人は、先に、ブロックポリイソシアネー
ト化合物や有機錫化合物を使用しないでイソシアネート
硬化タイプの優れた長所を有し、且つこれらを用いたこ
とによって生ずる上記大声、を解消したカチオン電着塗
料用樹脂組成物として、水酸基およびカチオン性基を含
有する樹脂(A)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
(B)とを主成分として含有することを特徴とするカチ
オン電着塗料用樹脂組成物を提案した。For this reason, the present applicant has developed a cationic electrodeposition method that has the excellent advantages of an isocyanate curing type without using blocked polyisocyanate compounds or organic tin compounds, and eliminates the above-mentioned loudness caused by the use of these compounds. As a resin composition for paint, one molecule of a resin (A) 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. In this paper, we have proposed a resin composition for cationic electrodeposition paint, which is characterized by containing as a main component an epoxy resin (B) having an average of two or more epoxy resins.
該組成物は、錫触媒を用いなくても160°C辺下の低
温で硬化させることができる:さら(二フロックイソシ
アネート化合物又はその誘導体を使用することがないの
でこれらを用いたことによる前記した種々の欠陥を解消
できる:熱分解による体積収縮が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ので、耐候性を損なうことが少
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。The composition can be cured at temperatures as low as 160°C without the use of a tin catalyst; Can eliminate various defects: No volume shrinkage due to thermal decomposition and exhibits good adhesion: No aromatic urethane bonds or aromatic urea bonds are introduced during cross-linking, so weather resistance is less impaired. It has various excellent advantages such as excellent corrosion resistance and hardening properties of the deposited coating and good stability of the electrodeposition bath.
しかしながら、本発明者等はさらに研究を行なった結果
、上記組成物はエツジカバー性能が不充分であることが
判明した。However, as a result of further research by the present inventors, it was found that the above composition had insufficient edge covering performance.
そこで、本発明者等は上記組成物の利点を損なうことな
く、エツジカバー性を改良することを目的に鋭意研究を
行なった結果、上記樹脂(A)及びエポキシ樹脂(B)
を主な樹脂成分として含有する硬化性樹脂組成物をカチ
オン電着性ゲル化微粒子重合体の水分散化液で水性化し
てなる塗料な用いることによってその目的を達成するこ
とができることを見い出し、本発明を完成した。Therefore, the present inventors conducted intensive research with the aim of improving the edge coverage without impairing the advantages of the above compositions, and as a result, the above resin (A) and epoxy resin (B)
We have discovered that this objective can be achieved by using a curable resin composition containing as the main resin component, which is made water-based with an aqueous dispersion of a cationically electrodepositable gelatinized fine particle polymer. Completed the invention.
かくして、本発明によれば、水酸基およびカチオン性基
を含有する樹脂(A)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
(B)とを主な樹脂成分として含有する硬化性樹脂組成
物をカチオン電着性ゲル化微粒子重合体の水分散液で水
性化してなることを特徴とするカチオン電着塗料の製造
方法が提供される。Thus, according to the present invention, one molecule contains an epoxy group-containing functional group formed by bonding the resin (A) containing a hydroxyl group and a cationic group and an epoxy group to an alicyclic skeleton and/or a bridged alicyclic skeleton. A cationic compound characterized in that it is made by aqueousizing a curable resin composition containing as a main resin component an epoxy resin (B) having an average of two or more particles per epoxy resin with an aqueous dispersion of a cationically electrodepositable gelling fine particle polymer. A method of manufacturing an electrodeposition paint is provided.
本発明で使用するカチオンi電着塗料の硬化性樹脂組成
物(以下、「本組成物」と略称することがある)は、上
記(A)成分と(B)成分とを主成分とする組成物であ
る。The curable resin composition of the cationic electrodeposition paint used in the present invention (hereinafter sometimes abbreviated as "the present composition") is a composition containing the above-mentioned (A) component and (B) component as main components. It is a thing.
本組成物を用いて形成される?i@塗膜は約250℃以
下の温度で硬化しうる。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℃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(B)に含まれるエポキシ基が開環して、
樹脂(A)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(B)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
ものと推察される。Formed using this composition? The i@coating can be cured at temperatures below about 250°C. and especially lead, zirconium, cobalt, aluminum, manganese, copper, zinc, iron,
When one or more compounds containing metals such as chromium and nickel are blended as a catalyst, curing can be achieved even by heating at a low temperature of about 0°C to about 160°C. These cures occur when the epoxy group contained in the epoxy resin (B) opens the ring,
Reacts with the hydroxyl groups (preferably primary ones) in the resin (A), and further reacts with the epoxy groups in the resin (B) to form ether bonds and crosslink and cure. It is inferred.
以下、本組成物の生成分である(A)およびCB)成分
についてさらに詳細に説明する。Components (A) and CB), which are the product components of the present composition, will be explained in more detail below.
」Δ二戒公二
(B)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
性基を同一分子中に有する任意の樹脂が包含される。し
かして、(A)成分としては例えば次のものが挙げられ
る。” Any resin that contains a hydroxyl group that reacts with the epoxy group of component (B) and has a sufficient number of cationic groups in the same molecule to form a stable aqueous dispersion is included. be done. Examples of component (A) 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。(1) A reaction product obtained by reacting a polyepoxy resin and a cationizing agent.
(11)ポリカルボン酸とポリアミンとの重縮合物(米
国特許第2.450.940号明細書参昭)を酸でプロ
トン化したもの
(顧)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
(IV)水酸基ならびにアミノ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、特公昭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(米国特許節3.403.
088号明細書参照):等。(11) Polycondensates of polycarboxylic acids and polyamines (see US Pat. No. 2,450,940), protonated with acids (see) Polyadditions of polyisocyanates and polyols with mono- or polyamines Products protonated with acids (IV) Copolymers of acrylic or vinyl monomers containing hydroxyl groups and amino groups protonated with acids (
Special Publication No. 45-12395, Special Publication No. 45-1239
(Refer to Publication No. 6) (V) An adduct of polycarboxylic acid resin and alkylene imine protonated with acid (U.S. Patent Section 3.403.
088 specification): etc.
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、
米国特許節2.450.940号明細書、米国特許節3
.403.088号明細書、米国特許節3.891.5
29号明細書、米国特許節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
て詳細な記述に代える。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 Section 2.450.940, U.S. Patent Section 3
.. No. 403.088, U.S. Patent Section 3.891.5
No. 29, US Pat.
本発明における(A)成分として特に望ましいのは、前
記(i)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 component (A) in the present invention is a polyepoxide compound 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 (i). It is a reactive product.
前記ポリエポキシド化合物は、エポキシ基を]分子中に
2個以上有する化合物で、一般に少なくとも200、好
ましくは400〜4.000、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−シ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 a compound having two or more epoxy groups in the molecule, and generally has an epoxy group of at least 200, preferably 400 to 4,000, and more preferably 800.
Those having a number average molecular weight within the range of ˜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-hydroxybenzophenone, and bis(4-hydroxyphenyl)-2,2-propane.
-hydroxyphenyl)-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、(A)成分の製
造に特に適当なものは、数平均分子量が少な(とも約3
80、より好適には約800〜約2.0OO1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
シア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 above-mentioned polyepoxide compounds, those particularly suitable for the production of component (A) have a low number average molecular weight (approximately 3
80, more preferably about 800 to about 2.0OO1 and an epoxy equivalent weight of 190 to 2.000, preferably 400 to 1.000.
It is a polyglycidyl ether of a polyphenol compound within the range of 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, polyisocyanate, 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、ジ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、エチルアミノエチル
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
(2) Secondary amines such as diethylamine, jetanolamine, di-n- or lso-propaturamine, N-methylethanolamine, N-ethylethanolamine; 3) Polyamines such as ethylene diamine, diethylene triamine, hydroxyethylamine ethylamine, ethylaminoethylamine, 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級アミン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
させてもよい。Among these, alkanolamines having a hydroxyl group are preferred. Alternatively, the primary amine 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、ヒドロキシエチルヒドラジン
、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、グツコール、乳酸などの水溶性有機カルボン
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, hydroxyethylhydrazine, 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-soluble organic carboxylic acid such as formic acid, acetic acid, gutucol 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、アミン化合物以外に、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順とホウ酸、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 amine compounds, salts of sulfides such as diethyl sulfide, diphenyl sulfide, tetramethylene sulfide, and thiogetanol and boric acid, carbonic acid, organic monocarboxylic acids, etc. can be reacted with epoxy groups to form tertiary compounds.
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
ェイン、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.
本発明で用いる(A)成分の水酸基としては、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:などがあげられる。この
うち、アルカノールアミンによる導入される第1級水酸
基は(B)成分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 of component (A) used in the present invention include:
The alkanolamine in the above cationizing agent, the ring-opened product of caprolactone that may be introduced into the epoxide compound, the primary hydroxyl group that can be introduced from polyol, etc.:
Examples include secondary hydroxyl groups in epoxy resins. Among these, primary hydroxyl groups introduced by alkanolamine are preferred because they have excellent crosslinking and curing reactivity with component (B). As such alkanolamines, those exemplified as the cationizing agent are preferable.
(A)成分における水酸基の含有量は、(B)成分に含
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100〜1.000
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(A)成分を安定に分散しつる
必要な最低限以上が好ましく、K OH(mg/g固形
分)(アミン価)換算で一般に3〜200、特にlO〜
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未漢の場合であっても、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 component (A) is 20 to 5.000, particularly 100 to 1.000 in terms of hydroxyl equivalent, in terms of crosslinking and curing reactivity with the epoxy group contained in component (B).
It is preferable that the primary hydroxyl equivalent is within the range of 200 to 200.
It is desirable that it be within the range of 1.000. The content of the cationic group is preferably at least the minimum necessary to stably disperse the component (A), and is generally 3 to 200 in terms of KOH (mg/g solid content) (amine value), particularly lO~
It is preferably within the range of 80. However, even if the content of cationic groups is less than 3, it is possible to use aqueous dispersion using a surfactant, but in this case, the aqueous dispersion composition pH is usually 4-9
It is desirable to adjust the cationic group so that the number is more preferably 6 to 7.
本発明で用いる(A)成分は、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。Component (A) used in the present invention has a hydroxyl group and a cationic group, and preferably does not contain free epoxy groups in principle.
工l几瓜旦二
上記(A)成分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。A curing agent for forming a crosslinked cured coating film mainly through the etherification reaction with the above component (A), which contains a specific "epoxy group-containing functional group" on average per molecule. It has two or more, preferably three or more.
すなわち、(B)成分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貝の飽和炭素環式環または該環が2側辺上編合
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C3〜6 (好ましくはC1〜4)
アルキレン基[例えば−CHw−−CH2CH2−1−
CH(CH,)−−CH(CH,)CH2−1−C(C
H,+2−−CH(C2H5)C1−1,−など]の橋
にンドメチレン、ニンドエチレンなど)が結合した環を
含有するものである。That is, the epoxy group-containing functional group in component (B) consists of an alicyclic skeleton and/or a bridged alicyclic skeleton and an epoxy group, and the alicyclic skeleton has 4 to 10 members, preferably 5 to 10 members. The bridged alicyclic skeleton contains six saturated carbocyclic rings or a condensed ring in which the rings are fused on two sides, and the bridged alicyclic skeleton has two carbon atoms constituting the above cyclic or polycyclic ring. A linear or branched C3-6 (preferably C1-4) between
Alkylene group [e.g. -CHw--CH2CH2-1-
CH(CH,)--CH(CH,)CH2-1-C(C
H, +2--CH(C2H5)C1-1,-, etc.] contains a ring in which indomethylene, nidoethylene, etc.) are bonded.
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(m)、(TV)参照〕ことが重要である。It is important that two adjacent carbon atoms are common [see, for example, formulas (m) and (TV) 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(I)〜(IV)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 (I) to (IV).
ボキシ基中の炭素原子の]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ている[例え
ば、下記式(I)、(II)参照〕か、或いは該エポキ
シ基の2個の炭素原子と上記脂環式骨格または有橋脂環
式骨格中の唄を構成す式中、R,、R,、R3、RS、
R,、R1、Rlo及びR11はそれぞれH,CH,ま
たはCH,を表わし、そしてR4、R8及びReはそれ
ぞれHまたはCHa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 [see, for example, formulas (I) and (II) below], or In the formula constituting the two carbon atoms of the epoxy group and the above alicyclic skeleton or bridged alicyclic skeleton, R,, R,, R3, RS,
R,, R1, Rlo and R11 each represent H, CH, or CH, and R4, R8 and Re each represent H or CHa.
(B)成分は、上記式(I)〜(TV)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(1)または(II)で示される
エポキシ基含有官能基を少なくとも1種石することがで
き、或いは式(m)または(IV)で示されるエポキシ
基含有官能基を少なくとも1種石することができる。さ
らにまた、エポキシ樹脂(B)は、式(I)または(I
I)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(nI)または(IV)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できる。Component (B) 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 (I) to (TV), such as At least one type of epoxy group-containing functional group represented by formula (1) or (II) can be formed, or at least one type of epoxy group-containing functional group represented by formula (m) or (IV) can be formed. I can do it. Furthermore, the epoxy resin (B) has the formula (I) or (I
It is also possible to have at least one epoxy group-containing functional group represented by I) and at least one epoxy group-containing functional group represented by formula (nI) or (IV) in the same molecule or in different molecules. .
上記のうち、式(I)及び(III)で示されるエポキ
シ基含有基が好ましく、殊に下記式(V)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 (I) and (III) are preferred, and epoxy group-containing functional groups represented by the following formula (V) and epoxy group-containing functional groups represented by the following formula are particularly preferred. suitable.
また、(B)成分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
物の用途等に応じて変えることができるが、−船釣に言
えば、エポキシ当量は通常、100〜2.000、好ま
しくは150〜500、さらに好ましくは150〜25
0の範囲内にあることができ、また、数平均分子量は通
常400〜100.000好ましくは700〜50,0
00、さらに好ましくは700〜30.000の範囲内
にあるのが適当である。In addition, the epoxy equivalent and molecular weight of component (B) are not strictly limited and can be changed depending on the manufacturing method and the use of the final resin composition. The equivalent weight is usually 100 to 2.000, preferably 150 to 500, more preferably 150 to 25
0, and the number average molecular weight is usually 400 to 100,000, preferably 700 to 50,000.
00, more preferably within the range of 700 to 30.000.
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(B)成分は、例えば、特公昭56−8016号
公報、特開昭57−47365号公報、特開昭60−1
66675号公報、特開昭63−221121号公報、
特開昭63−234028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。Component (B) having two or more such epoxy group-containing functional groups in one molecule is disclosed in, for example, Japanese Patent Publication No. 56-8016, Japanese Patent Application Laid-open No. 57-47365, and Japanese Patent Application Laid-open No. 60-1.
No. 66675, Japanese Patent Application Laid-open No. 63-221121,
It is described in documents such as Japanese Unexamined Patent Publication No. 63-234028, and any known one can be used.
或いはまた、上記エポキシ基含有官能基を有する(B)
成分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, (B) having the above epoxy group-containing functional group
The components are obtained by methods known per se, and 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(X)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、
その重合体に残る該二重結合
をエポキシ化する方法。First production method - After partially epoxidizing a portion of the double bonds of the alicyclic compound (X) having two or more carbon-carbon double bonds in one molecule, and ring-opening polymerization of the epoxy group, A method of epoxidizing the double bonds remaining in the polymer.
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
(Y)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。Second production method: A method in which an alicyclic compound (Y) 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、同一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(Z)を重合
する方法。A third production method, a method of polymerizing a compound (Z) having an epoxy group-containing functional group and a polymerizable unsaturated bond in the same 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.
!1旦4ムE乙汰二
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(X)」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1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(B)成分を得る。! One 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 (X)") After that, a ring-opened polymer of the partially epoxidized product is obtained by epoxidizing the epoxy group (partially epoxidized product), and then a ring-opened polymer of the partially epoxidized product is obtained by 1-polymerization of the epoxy group, and then part or all of the double bonds remaining in the polymer are removed. Component (B) is obtained by epoxidation.
脂環化合物(X)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
本骨格とし、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く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 (X) has a basic skeleton of the alicyclic ring or bridged alicyclic ring structure described above for the alicyclic skeleton or bridged alicyclic skeleton, and further includes a double bond and an adjacent alicyclic ring structure constituting the ring. It is a compound that exists between two carbon atoms, or contains at least two or more double bonds based on other carbon atoms that are directly bonded to the carbon atoms constituting the ring structure.
脂環化合物(X)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
脂肪族または脂環式の化合物が適しており、具体的には
、ブクシェン、イソプレン、ビリレン、1.3−ヘキサ
ジエン、2.4−ヘキサジエン、2.4−ペンタジェン
、2−メチル−6−メチレン−2,7−オクタジエン、
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
−メチルシクロペンタジェン、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、1.2.4−1リフエニルシクロペンタシ
エン、14−ジフェニルシクロペンタジェン、1.3−
オクタクロルペンタジェン、ヘキサクロルシクロペンク
ジエン、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
タクロルシクロペンタジェン、1.2.34−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−シクロオクタンジエン、1.3.5−シクロ
オクタトリエン、1.3.6−シクロオクタトリエン、
シクロオフクチトラエン、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
リデンシク口ベンタシエンなどがあげられ、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。The alicyclic compound (X) 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, such as buxene, isoprene, birylene, 1.3-hexadiene, 2.4 -hexadiene, 2,4-pentadiene, 2-methyl-6-methylene-2,7-octadiene,
2.6-dimethyl-1.5.7-octatriene, cyclopentadiene, cyclohexadiene, 4-ethyl-2
-Methylcyclopentadiene, 3-isopropyl-1-
Methylcyclopentadiene, 5-isopropylcyclopentadiene, 1.2.3.4-tetraphenylcyclopentadiene, 1.2.4-1 rifhenylcyclopentadiene, 14-diphenylcyclopentadiene, 1.3-
Octachlorpentadiene, hexachlorcyclopentadiene, 5.5-jethoxy-1,2,3,4-tetrachlorocyclopentadiene, 1.2.3.4.5-pentachlorcyclopentadiene, 1.2 .34-tetrachlorocyclopentadiene, 1.3-cyclopentadiene, 1.3-cyclooctanediene, 1.3.5-cyclooctatriene, 1.3.6-cyclooctatriene,
Examples include cycloofcutitraene, chlorocyclooctatetraene, bromocyclooctatetraene, and 5-cyclohexylidenebentashiene, and each of 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(X)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(X)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, an alicyclic compound (X) 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 (X) obtained in this manner 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
クロヘキサンジエン、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(
X)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, cyclohexane diene, 4-ethyl-2-methylcyclopentadiene, sylvestrene, 2.8 (9)-p-menthadene, vilonene, etc. , 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 X), it can be used as it is without being subjected to the above thermal reaction.
まず、脂環化合物(X)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C
部分エポキシ化)。部分エポキシ化物は、前記脂環化合
物(X)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, C
partial epoxidation). The partially epoxidized product is obtained by modifying some of the double bonds contained in the alicyclic compound (X) 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
在するかもしくは該璋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 the ring, or that a double bond based on another carbon atom is bonded to the carbon atom.
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(X)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
ある(B)成分の末端には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、チオール類等があげ
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ールのいずれであっても
よく、具体的には例えば、メタノール、エタノール、プ
ロパツール、ブタノール、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、
ジブロゴ1/ングリコール、1.3−ブタンジオール、
1.4−ブタンジオール、ペンクンジオール、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 (X). It is preferable to use an initiator in this ring-opening polymerization, and a residue X caused by the initiator component may be bonded to the terminal of component (B), which is the final product. Here, X is a residue of an organic compound having active hydrogen, and examples of the precursor of the organic compound having active hydrogen include alcohols, phenols, carboxylic acids, amines, and thiols. . Among these, the alcohols may be monohydric alcohols or polyhydric alcohols of dihydric or higher hydration, and specific examples include methanol, ethanol, propatool, butanol, pentanol, hexanol, octatool, etc. Aliphatic monohydric alcohols: Aromatic monohydric alcohols such as benzyl alcohol: ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol,
Dibrogo 1/glycol, 1,3-butanediol,
1.4-butanediol, pencundiol, 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、クレゾールノ
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, and cresol novolac resin.
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)−t−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−インプロ
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
シ化合物としては、エポキシ基を有するものであればい
かなるものでもよいが、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)-t-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-inpropanyl-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. Any other epoxy compound that can be copolymerized may be used as long as it has an epoxy group, but preferred examples include oxides 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, 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単独もしくは必
要に応じてその他のエポキシ化合物を併存させて、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じて任意に選ぶ
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(I)〜(rV)のいずれか1種
又は複数種を平均2個以上、好ましくは平均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 alone or in the presence of 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
An average of 2 or more of any one or more of the above structural formulas (I) to (rV) per molecule, preferably an average of 3 or more,
More preferably, it is desirable to select within the range of 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 400-100.000, particularly 700-50.000.
000, more preferably within the range of 700 to 30.000.
開環重合反応には、一般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BP、、
ZnCff 2、AffCff 、、5nCff 、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]−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 generally preferably carried out in the presence of a catalyst, and examples of the catalyst used include amines such as methylamine, ethylamine, propylamine, and piperazine, and organic bases such as pyridines and imidazoles. Types: 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; Alkali acids such as KOH and NaOH BP;
Examples include Lewis acids such as ZnCff 2 , AffCff , 5nCff , and their complexes, and 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01〜5重I%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°C1好ましくは約−30°C
〜約100″Cの範囲内である。反応は溶媒を用いで行
なうことができ、?8媒としては活性水素を有していな
い通常の有機、・各課を使用することが好ましい。These catalysts can be used generally in an amount of 0.001-10% by weight, preferably 0.1-5% by weight, 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. The reaction can be carried out using a solvent, and it is preferable to use an ordinary organic solvent having no active hydrogen as the solvent.
開環重合体には脂環化合物(X)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(B)成分が得られる。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。エポキシ化反
応の際の溶媒使用の有無や反応温度は、用いる製雪や原
料物性に応じて適宜調整することができる。エポキシ化
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
、(B)成分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 ring-opening polymer contains a double bond based on the alicyclic compound (X), and component (B) 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. Whether or not a solvent is used during the epoxidation reaction and the reaction temperature can be adjusted as appropriate depending on the snowmaking used and the physical properties of the raw materials. Depending on the conditions of the epoxidation reaction, a side reaction may occur simultaneously with the epoxidation of the double bond in the raw ring-opening polymer, and a modified substituent may be included in the skeleton of component (B). 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.
このようにして得られる(B)成分のエポキシ当量は一
般に100〜2.000、特に15o〜500、さらに
150〜250の範囲内であることが好ましい。The epoxy equivalent of component (B) thus obtained is generally in the range of 100 to 2.000, particularly 150 to 500, and more preferably 150 to 250.
このような(B)成分としては市販品も使用可能であり
、例えばEHPE−3150,EHPE3100、EH
PE−1150[ダイセル化学工業■製商品名]等があ
げられ、これは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。Commercially available products can also be used as such component (B), such as EHPE-3150, EHPE3100, EH
Examples include PE-1150 [trade name manufactured by Daicel Chemical Industries, Ltd.], which is an epoxy resin having the following structural formula and having a cyclohexane skeleton using 4-vinylcyclohexene-1-oxide.
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.
11匹製童方盈二
例えば、前記脂環化合物(X)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。For example, it can be obtained by epoxidizing at least two of the double bonds contained in the alicyclic compound (X), and then carrying out 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脂
環化合物(Y)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 alicyclic compound (Y) having an average of two or more epoxy groups per molecule, the following monocyclic or condensed ring compounds are representative.
具体的には、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、必要に応じ開始剤、
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(B)
成分を得る。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。この製造方
法においても前記化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。Specifically, one or more of the above-mentioned epoxides are prepared in the same manner as described in the first manufacturing method, and if necessary, an initiator,
(B) By performing a ring-opening polymerization reaction using a catalyst and stopping the reaction at a predetermined reaction point where an epoxy group remains.
Get the ingredients. To stop the reaction, dilution with a solvent,
Any means such as cooling can be used. In this manufacturing method as well, the epoxy compound described above may be copolymerized in the same manner as in the first manufacturing method.
こうして得られる(B)成分は、前記式(I)または(
II)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(III )または(IV )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 component (B) obtained in this way is represented by the formula (I) or (
At least one of the epoxy group-containing functional groups represented by II)
It can also be an epoxy resin having the species and at least one epoxy group-containing functional group represented by the formula (III) or (IV) in the same molecule or in different molecules.
このようにして得られる開環重合体(B)成分の数平均
分子量は一般に400〜100.000、特に700〜
50.000の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100〜2.000、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 number average molecular weight of the ring-opened polymer (B) component obtained in this way is generally from 400 to 100.000, particularly from 700 to
50.000, and the epoxy equivalent generally ranges from 100 to 2.000, particularly from 150 to 2.000.
500, preferably in the range 150-250.
11匁に1万迭二
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(Z)と
しては、例えば以下の一般式■〜■に示すものが挙げら
れる。Examples of compounds (Z) having at least one epoxy group-containing functional group and at least one polymerizable unsaturated bond in the molecule include those shown in the following general formulas Can be mentioned.
■
R,,0
上記−数式中、R12は水素原子又はメチル基を表わし
、R13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+aは炭素数1〜10の2価の炭化水素基
を表わす。■ R,,0 In the above formula, R12 represents a hydrogen atom or a methyl group, R13 represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R+a represents a divalent saturated hydrocarbon group having 1 to 10 carbon atoms. represents a hydrocarbon group.
上記化合物(Z)において、R13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で
きる。またR+□によって表わされる炭素数1〜10の
2価の炭化水素基としては、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、ポリメ上記一般式■〜@
で示される化合物(Z)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。これらの市販品として、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(I)また
は(II )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
キサイドも化合物(Z)として使用できる。In the above compound (Z), the divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms represented by R13 is a linear or branched alkylene group, such as methylene, ethylene, propylene, tetramethylene, ethyl ethylene,
Examples include pentamethylene and hexamethylene groups. Further, the divalent hydrocarbon group having 1 to 10 carbon atoms represented by R+□ includes, for example, methylene, ethylene, propylene, tetramethylene, ethyl ethylene, pentamethylene, hexamethylene, and polymethylene, which has the above general formulas ■ to @
Specific examples of the compound (Z) represented by include 3.4-epoxycyclohexylmethyl acrylate and 3.4-epoxycyclohexylmethylacrylate.
-Epoxycyclohexylmethyl methacrylate and the like. Examples of these commercially available products include METHB and AETHB (both trade names) manufactured by Daicel Chemical Industries, Ltd., both of which have an epoxy group-containing functional group represented by the above formula (I) or (II). This is what we are doing. Furthermore, 4-vinylcyclohexene oxide can also be used as compound (Z).
化合物(Z)から選ばれる1種もしくは2種以上を重合
することによって(B)成分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。Component (B) can be produced by polymerizing one or more selected from compound (Z), but it is also possible to copolymerize a polymerizable unsaturated monomer in its position.
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し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、メタクリル酸へキシル、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、メタクリル酸エトキシブチル
、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ル−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, such as 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, ethoxybutyl methacrylate , acrylic acid or methacrylic acid having 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 acids such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate; or C3-C18 alkenyloxyalkyl esters of acrylic acid or methacrylic acid, such as hydroxyalkyl esters of methacrylic acid having 2-8 carbon atoms, allyloxyethyl acrylate, and allyloxymethacrylate.
(b)ビニル芳香族化合物9例えば、スチしン、a−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 9 For example, styrene, a-methylstyrene, vinyltoluene, p-chlorostyrene.
(C)ポリオレフィン系化合物 例えば、ブタシシエン
、イソプレン、クロロブレン。(C) Polyolefin compound For example, butashicyene, isoprene, chlorobrene.
(d)その他 アクリロニトリル、メタクリロニトリル
、メチルイソプロペニルケトン、酢酸ビニルベオバモノ
マ−(シェル化学製品)、ビニルプロピオネート、ビニ
ルとバレート、ポリカプロラクトン鎖をもつビニル化合
物(例えば、FM3Xモノマー ダイセル化学工業製商
品名)。(d) Others Acrylonitrile, methacrylonitrile, methyl isopropenyl ketone, vinyl acetate beoba monomer (Shell Chemicals), vinyl propionate, vinyl and barate, vinyl compounds with polycaprolactone chains (e.g. FM3X monomer Daicel Chemical Industrial product name).
化合物(Z)と他の重合性不飽和モノマーとの構成比率
は、目的に応じ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(B)成分の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(B
)成分の固形分中化合物(Z)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 compound (Z) and other polymerizable unsaturated monomers can be arbitrarily selected depending on the purpose, and the component (B) obtained by these copolymerization reactions contains an epoxy group per molecule. The functional group can be selected within the range of containing at least 2 functional groups on average, preferably 3 or more on average, more preferably 4 or more on average, but in order to be used as a functional group that imparts sufficient curability, , especially the (B
It is preferable that the content of the compound (Z) in the solid content of component () is in the range of 5 to 100% by weight, more preferably 20 to 100% by weight.
上記第3の製造方法によって得られる(B)成分は、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。反応時間は通
常1〜10時間程度とすることができる。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、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−プチルパオ
キシー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、アゾビスジ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。The component (B) obtained by the third production method 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. . The reaction time can usually be about 1 to 10 hours. Further, as the organic solvent, alcohol solvents, ether solvents, ester solvents, 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 peroxides such as benzoyl peroxide and t-butylpaoxy-2-ethylhexanoate, and azo compounds such as azoisobutylnitrile and azobisdimethylvaleronitrile.
上記第3の製造例の(B)成分は、数平均分子量カ一般
ニ約3.000〜約100.OOoの範囲内にあるもの
が好ましく、特に4.000〜10.000の範囲内に
あるものがより好ましい。Component (B) in the third production example has a number average molecular weight of generally about 3.000 to about 100. It is preferably within the range of OOo, and particularly preferably within the range of 4.000 to 10.000.
上記した(B)成分の中で、自動車ポデー用に使用され
るカチオン’visa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10
0〜2.000、より好ましくは150〜500、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7
00〜50.000、特に好ましくは700〜30.0
00の範囲内にあるものである。Among the above-mentioned components (B), those containing a functional epoxy group per molecule are suitable for use in applications that require high performance, such as cationic visa materials used for automobile podiums. It has an average of 3 or more groups, more preferably an average of 4 or more, and most preferably an average of 5 or more groups, and has an epoxy equivalent of preferably 10.
0 to 2.000, more preferably 150 to 500, especially 150 to 250, and the number average molecular weight is preferably 400 to 100.000, more preferably 7
00-50.000, particularly preferably 700-30.0
It is within the range of 00.
(B)成分の使用量は、用いる(A)成分の種類に応じ
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′r!i@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(B
)成分の(A)成分に対する固形分の重量比が02〜1
.0、特に0.25〜0.85、さらに望ましくはo、
25〜0.65の範囲内となるように選択するのが好ま
しい8
本組成物では、(B)成分の一部が(A)成分にあらか
じめ付加したものが含まれていてもさしつかえない。The amount of component (B) to be used varies depending on the type of component (A) used, ranging from the minimum amount necessary for heat curing of the resulting coating film to the amount of cation 'r! i@ The amount can be changed as appropriate within the maximum amount that does not impair the stability of the paint, but in general (B
The weight ratio of the solid content of component ) to component (A) is 02 to 1.
.. 0, especially 0.25 to 0.85, more preferably o,
It is preferable to select it within the range of 25 to 0.65.8 In the present composition, there is no problem even if a part of the component (B) is added to the component (A) in advance.
本発明において、上記硬化性樹脂組成物を水性化するの
に用いるカチオン電着性ゲル化微粒子重合体の水分散液
(以下、単に[ゲル化微粒子水分散液」ということもあ
る)は、本出願人の出願である特開平2−47173号
公報及び特開平2−64169号公報で提案されている
ものを使用することができる。In the present invention, the aqueous dispersion of the cationically electrodepositable gelling fine particle polymer used to make the curable resin composition aqueous (hereinafter also simply referred to as "gelling fine particle aqueous dispersion") is the present invention. It is possible to use those proposed in Japanese Patent Application Laid-Open Nos. 2-47173 and 2-64169 filed by the applicant.
例えば、
(a)ビニル性二重結合と加水分解性アルコキシシラン
基を含有する重合性不飽和ビニルシランモノマーと、
(b)分子内に少なくとも2個のラジカル重合可能な不
飽和基を含有する重合性モノマーと、(c)ビニル性二
重結合と水酸基を含有する重合性不飽和モノマー及び
(d)その他の重合性不飽和モノマー
を分子内にアリル基を含有するカチオン性反応性乳化剤
を用いて乳化重合せしめでなるゲル化微粒子水分散液及
び
加水分解性アルコキシシラン基及びカチオン性基を含有
するアクリル系共重合体とカチオン性酸性型コロイグル
シリ力との混合物を水分散化し、粒子的架橋させたコロ
イダルシリカ含有ゲル化微粒子水分散液を挙げることが
できる。For example, (a) a polymerizable unsaturated vinyl silane monomer containing a vinyl double bond and a hydrolyzable alkoxysilane group, and (b) a polymerizable unsaturated vinyl silane monomer containing at least two radically polymerizable unsaturated groups in the molecule. A monomer, (c) a polymerizable unsaturated monomer containing a vinyl double bond and a hydroxyl group, and (d) another polymerizable unsaturated monomer are emulsified using a cationic reactive emulsifier containing an allyl group in the molecule. A colloidal obtained by dispersing in water a mixture of an aqueous dispersion of gelled microparticles formed by polymerization, an acrylic copolymer containing a hydrolyzable alkoxysilane group and a cationic group, and a cationic acidic colloidal colloid, and crosslinking the particles in a particulate manner. Mention may be made of a silica-containing gelled fine particle aqueous dispersion.
前者のゲル化微粒子を形成する前記(a)のビニルシラ
ンモノマーとしてはビニルトリメトキシシラン、ビニル
トリエトキシシラン、ビニルトリス(2−メトキシエト
キシ)シラン、γ−メタクノルオキシブロビルトリメト
キシシラン、ビニルトリアセトオキシシラン類があるが
、これらのうち好ましいのはγ−メタクリルオキシプロ
ピルトリメトキシシランである。The vinyl silane monomers (a) that form the former gelled particles include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, γ-methacnoloxybrobyltrimethoxysilane, and vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, γ-methacnoloxybrobyltrimethoxysilane, and vinyltris(2-methoxyethoxy)silane. There are acetoxysilanes, and among these, γ-methacryloxypropyltrimethoxysilane is preferred.
前記(b)の重合性子ツマ−としては、多価アルコール
の重合性不飽和モノカルボン酸エステル、多塩基酸の重
合性不飽和アルコールエステル及び2個以上のビニル基
で置換された芳香族化合物などがあり、それらの例とし
ては、エチレングリコールジ(メタ)アクリレート、1
.6−ヘキサンジオールジアクリレート、ジアリルフタ
レート、ジビニルベンゼン等を挙げることができる。Examples of the polymerizable polymer in (b) include polymerizable unsaturated monocarboxylic acid esters of polyhydric alcohols, polymerizable unsaturated alcohol esters of polybasic acids, and aromatic compounds substituted with two or more vinyl groups. Examples include ethylene glycol di(meth)acrylate, 1
.. Examples include 6-hexanediol diacrylate, diallyl phthalate, and divinylbenzene.
前記(c)のビニル性二重結合と水酸基を含有する重合
性不飽和モノマーは、ゲル化微粒子重合体中に水酸基を
導入するモノマー成分であり、水酸基はゲル化微粒子重
合体を製造するときの親木基もしくは分散粒子間の架橋
反応の官能基の働きをする。該不飽和モノマーの例とし
ては2−ヒドロキシエチル(メタ)アクリレート、ヒド
ロキシプロピル(メタ)アクリレートなどが挙げられる
。The polymerizable unsaturated monomer containing a vinyl double bond and a hydroxyl group (c) above is a monomer component that introduces a hydroxyl group into the gelled fine particle polymer, and the hydroxyl group is used in the production of the gelled fine particle polymer. It acts as a parent group or a functional group for crosslinking reaction between dispersed particles. Examples of the unsaturated monomer include 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and the like.
前記(d)のその他の重合性不飽和モノマーはゲル化微
粒子重合体を構成する残りの成分であり、例えば、メチ
ル(メタ)アクリレート、エチル(メタ)アクリレート
、プロピル(メタ)アクル−トなどの(メタ)アクリル
酸のアルキル(C,〜Cl8)エステル、スチレン、α
−メチルスチレン、ビニルトルエンなどのビニル芳香族
子ツマ−; (メタ)アクリル酸のアミド化合物(メタ
)アクリロニトリル、などの通常のアクリル樹脂の合成
に用いられる公知のモノマーを使用することができる。The other polymerizable unsaturated monomers (d) are the remaining components constituting the gelling fine particle polymer, and include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, etc. Alkyl (C, ~Cl8) ester of (meth)acrylic acid, styrene, α
-Vinyl aromatic molecules such as methylstyrene and vinyltoluene; Known monomers commonly used in the synthesis of acrylic resins, such as (meth)acrylic acid amide compound (meth)acrylonitrile, can be used.
ゲル化微粒子を構成する前記モノマー(a)〜(d)の
配合割合は、
(a)モノマー:1〜30重量%、好ましくは3〜20
重量%
(b)モノマー・1〜30重量%、好ましくは3〜20
重量%
(C)モノマー:1〜30重量%、好ましくは3〜20
重量%
(d)千ツマ−・10〜97重量%、好ましくは40〜
91重量%
の範囲である。The blending ratio of the monomers (a) to (d) constituting the gelled fine particles is as follows: (a) Monomer: 1 to 30% by weight, preferably 3 to 20% by weight
Weight% (b) Monomer・1 to 30% by weight, preferably 3 to 20% by weight
Weight% (C) Monomer: 1-30% by weight, preferably 3-20
Weight% (d) 1,000 to 97% by weight, preferably 40 to 97% by weight
It is in the range of 91% by weight.
また、分子内にアリル基を含有するカチオン性反応性乳
化剤としては、代表的なものとして次式R16RIg
Xe・R,6−N”−CH2−CH−CH2−0−CH
2−C=CH2(I )R,、OH
(式中、R36は置換基を有してもよい炭素数8〜22
の炭化水素基を、RI6およびR17は炭素数1〜3の
アルキル基を、R18は水素原子またはメチル基を示し
、xeは1価の陰イオンを示す。)
で表わされる第四級アンモニウム塩を含有する反応性乳
化剤がある。このものは公知であり(特開昭60−78
947号公報)、ラテムルに180(商品名、花王株式
会社製)として市販されている。In addition, as a representative cationic reactive emulsifier containing an allyl group in the molecule, the following formula R16RIg Xe・R,6-N"-CH2-CH-CH2-0-CH
2-C=CH2(I)R,,OH (wherein, R36 has 8 to 22 carbon atoms which may have a substituent)
RI6 and R17 are alkyl groups having 1 to 3 carbon atoms, R18 is a hydrogen atom or a methyl group, and xe is a monovalent anion. ) There is a reactive emulsifier containing a quaternary ammonium salt represented by: This is publicly known (Japanese Patent Application Laid-Open No. 60-78
No. 947) and Latemul 180 (trade name, manufactured by Kao Corporation).
アリル基を含有するカチオン性反応性乳化剤の使用量は
通常ゲル化微粒子の固形分100重量部に対して0.1
〜30重■%好ましくは05〜5重量%の範囲で用いる
のがよい。The amount of the cationic reactive emulsifier containing an allyl group used is usually 0.1 parts by weight per 100 parts by weight of the solid content of the gelled fine particles.
It is preferable to use it in a range of 30% by weight, preferably 05 to 5% by weight.
上記(a)〜(d)の不飽和モノマーの共重合は、アク
リル共重合体を製造するためのそれ自体公知の方法であ
る乳化重合法によって行なうことができる。上記のモノ
マー混合物を水媒体中でアリル基を含有するカチオン性
反応性乳化剤及び水溶性アゾアミド化合物重合開始剤の
存在下に通常約50〜約100’Cの反応温度において
約1〜約20時間反応を続けることにより行なうことが
できる。The copolymerization of the unsaturated monomers (a) to (d) above can be carried out by emulsion polymerization, which is a method known per se for producing acrylic copolymers. The above monomer mixture is reacted in an aqueous medium in the presence of a cationic reactive emulsifier containing an allyl group and a water-soluble azoamide compound polymerization initiator at a reaction temperature of usually about 50 to about 100'C for about 1 to about 20 hours. This can be done by continuing.
ゲル化微粒子は、通常その水分散液は総重量に基づいて
約10〜40重量%の樹脂固形分含量を有する。ゲル化
微粒子の粒径は、500 nm1J下、好ましくはlO
〜300nm、より好ましくは50〜1100nである
。粒径の調整は分子内にアリル基を含有するカチオン性
反応性乳化剤の量を調節することによって1T′なうこ
とができ、容易に所望の範囲のものを得ることができる
。Gelled microparticles typically have a resin solids content of about 10-40% by weight of the aqueous dispersion, based on total weight. The particle size of the gelling fine particles is 500 nm 1J, preferably 1O
-300nm, more preferably 50-1100n. The particle size can be adjusted to 1T' by adjusting the amount of the cationic reactive emulsifier containing an allyl group in the molecule, and a desired range can be easily obtained.
また、コロイダルシリカ含有ゲル化微粒子は、前記(a
)モノマー、(c)モノマー及び(d)モノマーの他に
、ビニル性二重結合とカチオン性基を含有する重合性不
飽和モノマー(e)[例えば、ジメチルアミノプロピル
(メタ)アクリレト、ジエチルアミノエチル(メタ)ア
クリレートなどのジアルキル(C,〜6)アミノアルキ
ル(C,〜6)(メタ)アクリレート1を以下に述べる
配合割合:
(a)モノマー:1〜30重量%、好ましくは3〜20
重量%
(e)モノマー・5〜30重量%、好ましくは5〜25
重量%
(C)モノマー・0〜30重量%、好ましくは5〜20
重量%
(d)モノマー二lO〜94重量%、好ましくは35〜
82重量%
て共重合して得られるアクリル系共重合体とカチオン性
酸性型コロイダルシリカとを混合し、水分散化して粒子
的架橋せしめてなるものである。Further, the colloidal silica-containing gelled fine particles described above (a
) monomer, (c) monomer and (d) monomer, as well as polymerizable unsaturated monomer (e) containing a vinylic double bond and a cationic group [for example, dimethylaminopropyl (meth)acrylate, diethylaminoethyl ( Dialkyl (C, ~6) aminoalkyl (C, ~6) (meth)acrylate 1 such as meth)acrylate is blended in the following proportions: (a) Monomer: 1 to 30% by weight, preferably 3 to 20% by weight.
Weight% (e) Monomer - 5-30% by weight, preferably 5-25
Weight% (C) Monomer・0-30% by weight, preferably 5-20
% by weight (d) Monomer 20 to 94% by weight, preferably from 35 to 94% by weight
It is made by mixing an acrylic copolymer obtained by copolymerizing 82% by weight with cationic acidic colloidal silica, dispersing it in water, and crosslinking it in particles.
アクリル系共重合体は、−8父に、約10〜約100、
好ましくは約15〜約80のアミン価:0〜約200、
好ましくは約30〜約130の水酸基価、及び約5.0
00〜約100.000、好ましくは約7.000〜約
30.000の数平均分子量を有することが望ましい。The acrylic copolymer has -8 to about 10 to about 100,
Amine number: 0 to about 200, preferably about 15 to about 80;
Preferably a hydroxyl value of about 30 to about 130, and about 5.0
It is desirable to have a number average molecular weight of from 0.00 to about 100.000, preferably from about 7.000 to about 30.000.
カチオン性酸性型コロイダルシリカの市販品としては、
例えば[アプライドCT−300Jおよび[アプライド
CT−400J(旭電化工業殊製品)、「スノーテック
スO」 (日産化学工業株製品)、「カフロイドSNJ
(触媒化成工業■製品)などを挙げることができ、
5in2を基本単位とする水中分散体であって、特に0
004〜01−の範囲内の平均粒子径を有するものが包
含される。Commercially available cationic acidic colloidal silica products include:
For example, [Applied CT-300J and [Applied CT-400J (Asahi Denka Special Products), "Snowtex O" (Nissan Chemical Industries, Ltd. product), "Cafroid SNJ
(Catalyst Chemical Industry ■Products), etc.
An aqueous dispersion having a basic unit of 5in2, especially 0
Those having an average particle diameter within the range of 004 to 01- are included.
上記アクリル系共重合体とコロイダルシリカとの混合比
率は厳密に制限されるものではないが−Mには、固形分
比でアクリル系共重合体100重量部に対してコロイダ
ルシリカ1〜50重量部の範囲が好ましく、さらには5
〜20重量部の範囲にあることがより好ましい。Although the mixing ratio of the acrylic copolymer and colloidal silica is not strictly limited, -M includes 1 to 50 parts by weight of colloidal silica per 100 parts by weight of the acrylic copolymer in terms of solid content. is preferably in the range of , more preferably 5
More preferably, the amount is in the range of 20 parts by weight.
このようにして製造されるコロイダルシリカ含有ゲル化
微粒子水分散液は、分散粒子の平均粒子径が一般に1胛
以下、好ましくは001〜0、 3F+、より好ましく
は0.05〜0.2Pの範囲内である。粒径の調整はア
クリル系共重合体中のカチオン性基の量およびコロイダ
ルシリカの種類および量を調節することによって行なう
ことができ、容易に所望の範囲のものを得ることができ
る。In the aqueous dispersion of gelled fine particles containing colloidal silica produced in this way, the average particle diameter of the dispersed particles is generally 1 or less, preferably in the range of 001 to 0.3F+, more preferably in the range of 0.05 to 0.2P. It is within. The particle size can be adjusted by adjusting the amount of cationic groups and the type and amount of colloidal silica in the acrylic copolymer, and a desired range can be easily obtained.
本発明において、上記硬化性樹脂組成物をゲル化微粒子
水分散液で水性化する方法は、硬化性樹脂組成物の有機
溶剤溶液を酸性化合物で中和し、中和樹脂組成物有機溶
液を得たのち、このものに該ゲル化微粒子水分散液を徐
々に添加して水分散化を行なうのが特に好ましい。該酸
性化合物としては、例えば塩酸、リン酸、ギ酸、酢酸、
プロピオン酸、酪酸、乳酸、ヒドロキシ酢酸などの無機
及び有機酸が使用できる。中和は通常最終的に得られる
カチオン電着塗料のpnが3〜9、好ましくは5〜8の
範囲になるように配合するのが望ましい。また、有機溶
剤は硬化性樹脂組成物を溶解もしくは分散できるもので
あれば特に制限なしに使用できるが、好ましくは水混和
性の有機溶剤を主成分とするものが望ましい。水混和性
の有機溶剤の代表的な例としてはプロパツール、ダイア
七トンアルコール、 5eC−ブタノール、tert−
ブタノールなどのアルコール類、エチレングリコール、
ブチルセロソルブ、エチルセロソルブ、プロピレングリ
コール千ツメチルエーテル、ジエチレングリコールなど
のエーテルアルコール類及びその化アセトン、カルピト
ールアセテートなどが挙げられる。また、上記以外にも
、例えばキシレン、トルエンなどの芳香族炭化水素類、
酢酸ブチルなどのエステル類、メチルエチルケトンなど
のケトン類、n−ブタノールなどのアルコール類などの
水混和性の乏しい有機溶剤も併用して使用できる。中和
樹脂組成物有機溶液に添加する際のゲル化微粒子水分散
液の固形分は、約20重量%以下、好ましくは約15重
量%以下、更に好ましくは約10重量%以下の範囲で行
なうことが望ましい。固形分が約20重I%より高くな
ると水性化物の粒子径が大きくなり塗料貯蔵安定性や塗
面平滑性などが低下する恐れがあるので好ましくない。In the present invention, the method of aqueousizing the curable resin composition with an aqueous dispersion of gelled fine particles involves neutralizing a solution of the curable resin composition in an organic solvent with an acidic compound to obtain a neutralized organic solution of the resin composition. It is particularly preferable to then gradually add the gelled fine particle aqueous dispersion to this material to effect water dispersion. Examples of the acidic compound include hydrochloric acid, phosphoric acid, formic acid, acetic acid,
Inorganic and organic acids such as propionic acid, butyric acid, lactic acid, hydroxyacetic acid can be used. Neutralization is usually carried out so that the final cationic electrodeposition coating has a pn of 3 to 9, preferably 5 to 8. Further, the organic solvent can be used without any particular restriction as long as it can dissolve or disperse the curable resin composition, but it is preferable to use a water-miscible organic solvent as the main component. Typical examples of water-miscible organic solvents include propatool, dia-7ton alcohol, 5eC-butanol, and tert-
Alcohols such as butanol, ethylene glycol,
Examples include ether alcohols such as butyl cellosolve, ethyl cellosolve, propylene glycol methyl ether, and diethylene glycol, and their derivatives, such as acetone and carpitol acetate. In addition to the above, aromatic hydrocarbons such as xylene and toluene,
Organic solvents with poor water miscibility such as esters such as butyl acetate, ketones such as methyl ethyl ketone, and alcohols such as n-butanol can also be used in combination. The solid content of the gelled fine particle aqueous dispersion when added to the neutralized resin composition organic solution should be in the range of about 20% by weight or less, preferably about 15% by weight or less, more preferably about 10% by weight or less. is desirable. If the solid content is higher than about 20% by weight, the particle size of the aqueous compound will become large and the storage stability of the paint and the smoothness of the painted surface may deteriorate, which is not preferable.
ゲル化微粒子水分散液の配合割合は、固形分換算でゲル
化微粒子及び硬化性樹脂組成物の総合計量でゲル化微粒
子が約1〜35重量%、好ましくは約4〜20重量%、
硬化性樹脂組成物が約99〜65重量%、好ましくは約
96〜80重量%の範囲で配合できる。ゲル化微粒子の
割合が約1重量%より少ないとエツジ部に対する塗膜被
覆性が低下し、他方、約35重量%より多くなると塗面
平滑性が低下するので好ましくない。中和樹脂組成物有
機溶液の水性化は、所望される電着塗料の固形分、通常
、約10〜70重量%になるまで、ゲル化微粒子水分散
液単独もしくはゲル化微粒子水分散液と脱イオン水を組
合わせて水性化を行なうことができる。ゲル化微粒子水
分散液と脱イオン水を組合わせて用いる場合には、硬化
性樹脂組成物が油相から水相に相転換するまでに部もし
くは全部のゲル化微粒子水分散液を用いることが望まし
い。水性化は、特に制限されず従来から知られた、例え
ばデシルバー、ホモミキサなどの分散機を用いて実施で
きる。The blending ratio of the gelled fine particle aqueous dispersion is about 1 to 35% by weight, preferably about 4 to 20% by weight of the gelled fine particles, based on the total amount of the gelled fine particles and the curable resin composition in terms of solid content.
The curable resin composition can be blended in an amount of about 99 to 65% by weight, preferably about 96 to 80% by weight. If the proportion of the gelled fine particles is less than about 1% by weight, the coatability of the coating film on the edge portion will decrease, while if it exceeds about 35% by weight, the smoothness of the coated surface will decrease, which is not preferable. The neutralized resin composition organic solution is made into an aqueous solution by decomposition with the gelled fine particle aqueous dispersion alone or with the gelled fine particle aqueous dispersion until the desired solids content of the electrodeposition paint is reached, usually about 10 to 70% by weight. Aqueous formation can be achieved by combining with ionized water. When using a combination of a gelled fine particle aqueous dispersion and deionized water, it is possible to use part or all of the gelled fine particle aqueous dispersion before the curable resin composition undergoes a phase transformation from an oil phase to an aqueous phase. desirable. Aqueousization can be carried out using a conventionally known dispersing machine such as a desilver or a homomixer without any particular limitation.
また、本発明において、カチオン電着塗料には、従来か
ら使用されている着色顔料、体質顔料、防錆顔料等を配
合することができる。Furthermore, in the present invention, conventionally used coloring pigments, extender pigments, antirust pigments, and the like can be blended into the cationic electrodeposition paint.
本発明において、被塗装物にカチオン電@塗料(I)を
1it@塗装する方法としては、特に限定されるもので
はないが、例えばカチオン電@塗利(I)を固形分濃度
が約5〜40重量%、好ましくは約10〜30重量%と
なるように脱イオン水などで希釈し、さらにpHを約5
,5〜90、好ましくは約58〜70の範囲内に調整し
た塗料を電着浴とし、浴温的15〜35°Cに調整し、
該浴中に被塗装物を浸漬したのも被塗装物と対極との間
で電圧的50〜400■を印加し約1〜5分間の条件で
電着塗装を行なうことにより実施できる。電着塗装の膜
厚は、通常、約10〜70胛、好ましくは約15〜50
P(乾燥膜厚)である。In the present invention, the method of applying cationic electrolyte (I) to the object to be coated is not particularly limited; Dilute with deionized water etc. to 40% by weight, preferably about 10 to 30% by weight, and further adjust the pH to about 5%.
, 5 to 90, preferably about 58 to 70, as an electrodeposition bath, and the bath temperature is adjusted to 15 to 35 °C,
The object to be coated can be immersed in the bath by electrodeposition by applying a voltage of 50 to 400 cm between the object and the counter electrode for about 1 to 5 minutes. The film thickness of the electrodeposition coating is usually about 10 to 70 mm, preferably about 15 to 50 mm.
P (dry film thickness).
本発明において、電着塗装後、水洗を行なった方が好ま
しい。水洗は、通常、脱イオン水、上水塗料の限外濾過
液または逆浸透l濾過液を用いて行なわれる。In the present invention, it is preferable to wash with water after electrodeposition coating. Water washing is usually carried out using deionized water, ultrafiltrate of water-based paints or reverse osmosis filtrate.
また、カチオン電着塗膜は、約100〜180°Cで焼
付は硬化される。Further, the cationic electrodeposition coating film is cured by baking at about 100 to 180°C.
かくして形成される塗装塗膜には、該塗膜の焼付前もし
くは焼付後に、必要に応じて更に上塗り塗料を適宜塗り
重ねて仕上げることができる。The paint film thus formed can be finished by further applying an appropriate top coat as necessary before or after baking the paint film.
[作用及び発明の効果]
以上述べた如く、本発明は、水酸基とエポキシ基との反
応を利用して硬化させるカチオン電着塗料であることか
ら、従来の水酸基とブロック化されたイソシアネート基
とを有機錫化合物の存在下で硬化させたものと比較して
、硬化性、耐候性、耐変色性などの性能が優れる。[Function and Effects of the Invention] As described above, the present invention is a cationic electrodeposition coating that is cured by utilizing the reaction between a hydroxyl group and an epoxy group, and therefore it is possible to cure the cationic electrodeposition coating by using a reaction between a hydroxyl group and a blocked isocyanate group. Compared to those cured in the presence of organotin compounds, it has superior properties such as curability, weather resistance, and discoloration resistance.
また、本発明によって得られるカチオン電着塗料は、添
加されるゲル化微粒子が凝集、異常電着、沈降などの問
題をおこすことなく共電着され、焼付時にゲル化微粒子
に存在するアルコキシシラン基の加水分解によって生成
したシラノール基が該シラノール基同志および水酸基と
縮合して粒子間架橋およびベース樹脂との架橋が行なわ
れる効果と、ゲル化微粒子自身の体積効果の両方により
塗膜の溶融粘度の低下を制御できるので、塗膜の平滑性
とエツジ部の塗膜形成性を容易に維持することができる
。In addition, the cationic electrodeposition paint obtained by the present invention has the advantage that the gelled fine particles added can be co-electrodeposited without causing problems such as agglomeration, abnormal electrodeposition, or sedimentation, and the alkoxysilane groups present in the gelled fine particles during baking. The melt viscosity of the coating film decreases due to both the effect of the silanol groups generated by hydrolysis of the silanol groups condensing with each other and hydroxyl groups, resulting in interparticle crosslinking and crosslinking with the base resin, and the volume effect of the gelled fine particles themselves. Since the deterioration can be controlled, the smoothness of the coating film and the coating film forming properties at the edges can be easily maintained.
更に、本発明によって得られるカチオン電着塗料は、硬
化性樹脂組成物及びゲル化微粒子成分が水中に均一に分
散しておりしかも分散粒子の粒子径が比較的細かいので
貯蔵安定性、塗面平滑性及びエツジ部の塗膜形成性など
の性能のバランスに優れた効果が発揮される。Furthermore, the cationic electrodeposition paint obtained by the present invention has a curable resin composition and a gelled fine particle component uniformly dispersed in water, and the particle size of the dispersed particles is relatively small, resulting in good storage stability and smooth coating surface. It exhibits an excellent balance of performance such as hardness and edge film forming properties.
以下実施例および比較例を挙げて本発明を具体的に説明
する。「部」および「%」は「重量部」および「重量%
」を意味する。The present invention will be specifically explained below with reference to Examples and Comparative Examples. "Parts" and "%" are "parts by weight" and "% by weight"
” means.
■、製造例
ユA工」しか1毀】
(A−1)
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1004J、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80〜100″Cて滴下後
100°Cで2時間保持して固形分68%、第1級水酸
基当量528、アミン価53をもつ(A−1)を得た。(A-1) 1900 parts of a bisphenol A type epoxy resin with an epoxy equivalent of 950 [trade name [Epicoat 1004J, manufactured by Shell Chemical ■] was dissolved in 993 parts of butyl cellosolve, and After dropping 210 parts of amine at 80-100''C, the mixture was maintained at 100°C for 2 hours to obtain (A-1) having a solid content of 68%, a primary hydroxyl equivalent of 528, and an amine value of 53.
(A−2)
エポキシ当量190のビスフェノールAジグリシジェル
エーテル950部、エポキシ当量330のエポキシ樹脂
XB−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
グリコールモツプチルエーテル489部で希釈、冷却し
たのち、温度を90°Cに保ちなからジェタノールアミ
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−メチルアミノエタノル185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592、アミ2価55の(A−2)を得た。(A-2) 950 parts of bisphenol A diglycidel ether with an epoxy equivalent of 190, 330 parts of epoxy resin XB-4122 (trade name manufactured by Ciba Geigy) with an epoxy equivalent of 330,
456 parts of bisphenol A and 21 parts of jetanolamine
The temperature was raised to 120°C, and the epoxy value was 1.
.. After reacting until the concentration was 0.2 mmol/g, diluting with 489 parts of ethylene glycol motsubutyl ether and cooling, the temperature was maintained at 90°C. 535 parts of monoethanolamine adduct and 185 parts of N-methylaminoethanol were added, and the reaction was carried out until the viscosity increase stopped. ) was obtained.
工旦−り滅1凶臥1
EHPE3150 [エポキシ当N175〜195、ダ
イセル化学工業■製コ326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(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。EHPE3150 [Epoxy N175-195, manufactured by Daicel Chemical Industries, Ltd. 326 parts and 82 parts of propylene glycol monomethyl ether were heated and dissolved at 100°C,
(B-1) 40. Solid content 80%, epoxy equivalent 190.
I got 8 copies. The number average molecular weight of the resin was approximately 1.500.
ゲルイ 1 重A 1の製造
撹拌装置、温度計、冷却管及び加熱マントルを備えたI
J2のフラスコに、脱イオン水3507部及び乳化剤(
ラテムに−180、正正社製、25%水溶液第4級アン
モニウム塩素アリル基含有カチオン性反応性乳化剤)8
0部を加え、撹拌しながら90℃まで昇温した。これに
重合開始剤(VA−086、和光紬薬社製、2.2′−
アゾビス[2−メチル−N−(2ヒドロキシエチル)−
プロピオンアミド])12.5部を脱イオン水500部
に溶解した水溶液を加えた。15分後にモノマー混合物
(スチレン/n−ブチルアクリレート/1,6−ヘキサ
ンジオールジアクリレート=470/470/60部)
を加えた。重合は90°Cで7時間おこなって、脱イオ
ン水で希釈し固形分10%、平均粒子径70nm(コー
ルタ−カウンター社ナノサイザーN−4で測定)のゲル
化微粒子重合体■を得た。Gelui 1 heavy A 1 production I equipped with stirring device, thermometer, cooling tube and heating mantle
In a J2 flask, add 3507 parts of deionized water and an emulsifier (
Latemni-180, manufactured by Seiseisha, 25% aqueous solution Quaternary ammonium chloride allyl group-containing cationic reactive emulsifier) 8
0 part was added, and the temperature was raised to 90°C while stirring. A polymerization initiator (VA-086, manufactured by Wako Tsumugi Co., Ltd., 2.2'-
Azobis[2-methyl-N-(2hydroxyethyl)-
An aqueous solution of 12.5 parts of propionamide]) dissolved in 500 parts of deionized water was added. After 15 minutes, a monomer mixture (styrene/n-butyl acrylate/1,6-hexanediol diacrylate = 470/470/60 parts)
added. Polymerization was carried out at 90 DEG C. for 7 hours and diluted with deionized water to obtain a gelled fine particle polymer (2) having a solid content of 10% and an average particle size of 70 nm (measured with Coulter Counter's Nanosizer N-4).
ゲルイ徹亘 重A 2の製゛告
撹拌機、空気導入管、冷却管、温度制御装置を備えたフ
ラスコに、イソホロンジイソシアネート222部及びメ
チルイソブチルケトン50部を仕込み、乾燥空気を液相
に吹き込みながら撹拌して70℃まで昇温した。これに
ジブチルスズジラウレート03部を加え、次いで2−ヒ
ドロキシエチルアクリレート116部を1時間で滴下し
、滴下終了後もさらに1時間70°Cに保った。続いて
メチルイソブチルケトキシム115部を1時間で滴下し
た。滴下終了後も加熱して70’Cに保ち、反応混合物
を経時的に採取して−NCOの吸収をIRで確認し、−
NGOの吸収がなくなった時点を反応終点とした。か(
して90%インホロンジイソシアネート/2−ヒドロキ
シエチルアクリレート/メチルイソブチルケトキシムブ
ロック体溶液のインシアネート化合物を得た。222 parts of isophorone diisocyanate and 50 parts of methyl isobutyl ketone were charged into a flask equipped with a stirrer, an air introduction pipe, a cooling pipe, and a temperature control device, and while blowing dry air into the liquid phase. The mixture was stirred and heated to 70°C. To this was added 03 parts of dibutyltin dilaurate, then 116 parts of 2-hydroxyethyl acrylate was added dropwise over 1 hour, and the temperature was maintained at 70°C for another 1 hour after the dropwise addition was completed. Subsequently, 115 parts of methyl isobutyl ketoxime was added dropwise over 1 hour. After the completion of the dropwise addition, the mixture was heated and maintained at 70'C, and the reaction mixture was sampled over time to confirm absorption of -NCO by IR.
The end point of the reaction was defined as the point at which the absorption of NGO ceased. mosquito(
Thus, an incyanate compound having a 90% inphorone diisocyanate/2-hydroxyethyl acrylate/methyl isobutyl ketoxime block solution was obtained.
次に撹拌装置、温度計、冷却管及び加熱マン+−ルを備
えた1f2.のフラスコに、脱イオン水700部及び前
記と同様のラテムに−180162部を入れ、撹拌しな
がら90℃まで昇温した。これに重合開始剤である前記
と同様のVA−0862部を脱イオン水100部に溶解
した水溶液を加えた。15分後に下記モノマー混合物を
加えた。Next, 1f2. equipped with a stirrer, thermometer, cooling tube and heating mantle. 700 parts of deionized water and -180162 parts of the same lame as above were placed in a flask, and the temperature was raised to 90° C. with stirring. To this was added an aqueous solution prepared by dissolving 2 parts of the same VA-086 as the polymerization initiator in 100 parts of deionized water. After 15 minutes, the following monomer mixture was added.
スチレン 32部n−ブチ
ルアクリレート 32部1.6−ヘキサン
ジオール 30部ジアクリレート
2−ヒドロキシエチルアクリレート 4部KBM−
503× 2部×γ−メタクリロキシ
ブロビルトリメトキシシラン(信越化学工業社製)
重合は90°Cて6時間おこなった。次にこのものに下
記モノマー混合物を滴下した。Styrene 32 parts n-butyl acrylate 32 parts 1,6-hexanediol 30 parts diacrylate 2-hydroxyethyl acrylate 4 parts KBM-
503 x 2 parts x γ-methacryloxybrobyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) Polymerization was carried out at 90°C for 6 hours. Next, the following monomer mixture was added dropwise to this mixture.
スチレン 38部n−ブチ
ルアクリレート 38部2−ヒドロキシエ
チルアクリレート 4部上記製造で得たインシアネ
ート化合物 22部重合は90″Cで2時間おこなった
。Styrene 38 parts n-butyl acrylate 38 parts 2-hydroxyethyl acrylate 4 parts Incyanate compound obtained in the above production 22 parts Polymerization was carried out at 90''C for 2 hours.
次に脱イオン水で希釈し固形分10%、平均粒子径74
nm(コールタ−社ナノサイザーN−4で測定)のゲル
化微粒子重合体■を得た。Next, dilute with deionized water to obtain a solid content of 10% and an average particle size of 74.
A gelled fine particle polymer (2) with a particle diameter of 1.5 nm (measured with Coulter Nanosizer N-4) was obtained.
級社二ニス上」
上記(A−1)成分7部、オスチックス鉛3部、酸化チ
タン19部、精製クレー5部、カーボンブラック1部、
酢酸0.25部、脱イオン水37.7部をペブルミルで
分散を行なって固形分43%の顔料ペーストを得た。7 parts of the above (A-1) component, 3 parts of Ostix lead, 19 parts of titanium oxide, 5 parts of purified clay, 1 part of carbon black,
A pigment paste with a solid content of 43% was obtained by dispersing 0.25 parts of acetic acid and 37.7 parts of deionized water using a Pebble Mill.
1社へニス上Ω
上記顔料ペースト■製造例において、(A−1)ワニス
に代えて(A−2)ワニスを用いた以外は顔料ペースト
■の製造例と同様にして固形分43%の顔料ペーストを
得た。Ω on varnish to one company Ω Pigment with a solid content of 43% in the same manner as in the production example of pigment paste ■, except that (A-2) varnish was used instead of (A-1) varnish in the above pigment paste ■ production example. Got the paste.
、Ll−里主
実施例1
前記(A−1)成分103部、(B)成分31部及び酢
酸との中和混合物をデシルバーで攪拌を行ないながら、
このものに固形分10%のゲル化機粒子重合体■150
部を徐々に添加し固形分40%の水分散液を得た。続い
て得られた水分散液に脱イオン水366部及び顔料ペー
ス1070部を配合して固形分20%のカチオン電着塗
料を得た。, Ll-Rinushi Example 1 A neutralized mixture of 103 parts of the component (A-1), 31 parts of the component (B), and acetic acid was stirred with a desilver,
Add gelling machine particle polymer ■150 to this product with a solid content of 10%.
1 part was gradually added to obtain an aqueous dispersion with a solid content of 40%. Subsequently, 366 parts of deionized water and 1070 parts of pigment paste were added to the obtained aqueous dispersion to obtain a cationic electrodeposition paint having a solid content of 20%.
実施例2
実施例1において、固形分10%のゲル化微粒子重合体
■の代わりに固形分10%のゲル化微粒子重合体■を使
用する以外は、同様の方法で固形分20%のカチオン電
着塗料を得た。Example 2 A cationic electrolyte with a solid content of 20% was prepared in the same manner as in Example 1, except that gelled fine particle polymer ■ with a solid content of 10% was used instead of gelled fine particle polymer ■ with a solid content of 10%. Obtained paint.
実施例3
実施例1において固形分10%のゲル化機粒子重合体■
150部に代えて脱イオン水を減量して固形分20%に
調製したゲル化機粒子重合体■75部及び脱イオン水3
66部を441部とした以外は実施例1と同様の方法で
固形分20%の電@塗料を得た。Example 3 Gelling machine particle polymer ■ with solid content of 10% in Example 1
75 parts of gelling machine particle polymer prepared by reducing the amount of deionized water to 20% solids instead of 150 parts and 3 parts of deionized water
An electric paint having a solid content of 20% was obtained in the same manner as in Example 1 except that 441 parts were changed from 66 parts.
実施例4
実施例1において、(A−1)成分を(A2)成分に、
そして、顔料ペースト■を■に代えた以外は実施例1と
同様にして実施例4のカチオン電着塗料を得た。Example 4 In Example 1, component (A-1) was changed to component (A2),
Then, a cationic electrodeposition paint of Example 4 was obtained in the same manner as in Example 1 except that the pigment paste (■) was replaced with (2).
比較例1
ニレクロン#9400 (関西ペイント社製、商品名、
エポキシ系ポリアミド樹脂、固形分20%、グレー)の
塗料を用いた。Comparative Example 1 Nirekron #9400 (manufactured by Kansai Paint Co., Ltd., trade name,
A paint made of epoxy polyamide resin, solid content 20%, gray) was used.
比較例2
(A−1)成分103部、(B)成分31部及び酢酸と
の混合物をデシルバーで撹拌を行ないながら、脱イオン
水441部を徐々に添加し、続いて顔料ペースト070
部を配合して固形分20%の水分散化物を得た。次に該
水分散化物650部に20%のゲル化機粒子重合体■7
5部をデシルバーで混合して固形分20%のカチオン電
着塗料を得た。Comparative Example 2 441 parts of deionized water was gradually added to a mixture of 103 parts of component (A-1), 31 parts of component (B), and acetic acid while stirring with a Desilver, and then 441 parts of deionized water was added, followed by pigment paste 070.
A water dispersion with a solid content of 20% was obtained. Next, add 20% gelling particle polymer (7) to 650 parts of the water dispersion.
5 parts were mixed in DeSilver to obtain a cationic electrodeposition paint with a solid content of 20%.
実施例及び比較例のものを表−1塗装条件で塗膜を得た
。得られた塗膜の性能を表−2に示す。Coating films of Examples and Comparative Examples were obtained under the coating conditions shown in Table-1. The performance of the obtained coating film is shown in Table-2.
表−
[性能試験方法]
(*1)塗膜溶融粘度
焼付時の電着塗膜店融粘度を転球式粘度測定法(J I
5−Z−0237に準する)との対比により引っかき
傷跡の熱流動外観から評価した。数値は最低時の粘度(
センチポイズ)を示す。Table - [Performance test method] (*1) Coating film melt viscosity Measure the melt viscosity of the electrodeposited film during baking using the rolling ball viscosity measurement method (JI
5-Z-0237) was evaluated based on the thermal fluid appearance of the scratch marks. The value is the lowest viscosity (
centipoise).
(*2)端面被覆性
平坦部の硬化膜厚が20−となる条件て、工・ンジ部角
度約20”のカッターナイフの替刃(オルファ製LB−
10〜PB#3020処理)に電着塗装し、所定の焼付
条件で硬化させて試験板を作成する。試験板のエツジ部
が垂直になる様にツルトスプレー装置にセットし、JI
S 22371塩水フンム試験により168時間後の
エツジ部の防食性を評価する。(*2) Under the condition that the cured film thickness of the flat part of the end face coverage is 20", the replacement blade of the cutter knife with an angle of about 20" (Olfa LB-
10 to PB#3020 treatment) and cured under predetermined baking conditions to prepare a test plate. Set the test plate in the Tsuruto spray device so that the edge part is vertical, and apply the JI
S22371 Salt water hum test evaluates the corrosion resistance of the edge after 168 hours.
Oサビ発生全くなし ○−サビわずかに発生 × サビ著しく発生 (*3)塗面平滑性 電@塗面の仕上り性を目視て評価する。No rust at all ○ - Slight rust occurrence × Significant rust occurs (*3) Painted surface smoothness Visually evaluate the finish of the painted surface.
○良好
■はぼ良好
△やや不良
(*4)耐衝撃性
JIS K5400−1979 6. 133B法に
準して、20°Cの雰囲気下において行なう。重さ50
0g、撃心の尖端直径坏インチの条件で塗膜損傷を生じ
ない最大高さを示す(cm)。50cmを最高値とした
。○ Good ■ Very good △ Slightly poor (*4) Impact resistance JIS K5400-1979 6. It is carried out in an atmosphere at 20°C according to the 133B method. weight 50
0g and the point diameter of the center of impact is 1 inch (cm). The maximum value was 50 cm.
(*5)耐塩水噴霧性
素地に達するように電着塗膜にナイフでクロスカッ1−
キズを入れ、これをJIS 22371によって1.
000時間塩水噴霧試験を行ない、ナイフ傷からの錆、
フクレ巾を測定する。(*5) Cross-cut the electrodeposited coating with a knife to reach the salt water spray resistant substrate.
A scratch is made and this is 1. according to JIS 22371.
000 hour salt spray test to eliminate rust from knife scratches,
Measure the blister width.
(*6)2コート耐候性
焼付電着塗板上に、さらにアミノアルキド樹脂系塗料ア
ミラッククリヤー(関西ペイント社製)を35F塗装し
、140°C115分焼付りた。この塗板を20時間サ
ンシャインウエザオメータにかけ、40°Cの水中に2
0時間浸漬した後 塗板にクロスカットを入れて、セロ
ファン粘着テープで剥離試験を行なう。この試験を繰り
返し行なう。(*6) On the 2-coat weather-resistant baked electrodeposition coated plate, amino alkyd resin paint Amirac Clear (manufactured by Kansai Paint Co., Ltd.) was further applied at 35F and baked at 140°C for 115 minutes. This coated plate was placed in a sunshine weatherometer for 20 hours, and then placed in water at 40°C for 2 hours.
After immersion for 0 hours, crosscuts are made on the coated plate and a peel test is performed using cellophane adhesive tape. Repeat this test.
また、実施例1〜4及び比較例2において頷月ペースト
を全く配合しない以外は実施例1〜4及び比較例2に記
載の方法と同様にして製造を行なって顔料成分を有さな
い実施例1〜4及び比較例2の水分散液を得た。これら
の水分散液は、それぞれ実施例1は平均粒子径02−以
下、貯蔵安定性良好であり、実施例2は平均粒子径02
−以下、貯蔵安定性良好であり、実施例3は平均粒子径
0.2P以上、貯蔵安定性若干沈降物が見られ、比較例
は平均粒子径05P以上、貯蔵安定性沈降物、凝集物が
見られた。貯蔵安定性は30°C7日間放置したのち沈
降物、凝集物を観察した。In addition, Examples 1 to 4 and Comparative Example 2 were produced in the same manner as in Examples 1 to 4 and Comparative Example 2, except that Nodzuki paste was not blended at all, and Examples 1 to 4 and Comparative Example 2 did not contain pigment components. Aqueous dispersions of Examples 1 to 4 and Comparative Example 2 were obtained. Each of these aqueous dispersions in Example 1 had an average particle size of 02- or less and had good storage stability, and in Example 2 had an average particle size of 02- or less.
- The following shows good storage stability: Example 3 has an average particle size of 0.2P or more, with some storage stability sediments, and Comparative Example has an average particle size of 05P or more, with no storage stability sediments or aggregates. It was seen. Storage stability was determined by observing sediments and aggregates after standing at 30°C for 7 days.
Claims (2)
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(B)とを主な樹脂成
分として含有する硬化性樹脂組成物を、カチオン電着性
ゲル化微粒子重合体の水分散液で水性化してなることを
特徴とするカチオン電着塗料の製造方法。(1) Resin containing hydroxyl group and cationic group (A)
and an epoxy resin (B) having an average of two or more epoxy group-containing functional groups per molecule formed by bonding an epoxy group to an alicyclic skeleton and/or a bridged alicyclic skeleton as the main resin component. 1. A method for producing a cationic electrodeposition paint, which comprises aqueousizing a curable resin composition with an aqueous dispersion of a cationically electrodepositable gelling fine particle polymer.
が固形分10重量%以下である請求項1記載のカチオン
電着塗料の製造方法。(2) The method for producing a cationic electrodeposition paint according to claim 1, wherein the aqueous dispersion of the cationic electrodepositable gelling fine particle polymer has a solid content of 10% by weight or less.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP19665390A JPH0481474A (en) | 1990-07-25 | 1990-07-25 | Production of cationic electrodeposition coating |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP19665390A JPH0481474A (en) | 1990-07-25 | 1990-07-25 | Production of cationic electrodeposition coating |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0481474A true JPH0481474A (en) | 1992-03-16 |
Family
ID=16361360
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP19665390A Pending JPH0481474A (en) | 1990-07-25 | 1990-07-25 | Production of cationic electrodeposition coating |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0481474A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010508396A (en) * | 2006-10-26 | 2010-03-18 | ビー・エイ・エス・エフ、コーポレーション | Film-forming material coordinated with metal |
JP2010508398A (en) * | 2006-10-26 | 2010-03-18 | ビー・エイ・エス・エフ、コーポレーション | Method for producing a coating containing a film-forming material coordinated with a metal |
JP2010508397A (en) * | 2006-10-26 | 2010-03-18 | ビー・エイ・エス・エフ、コーポレーション | Film-forming material coordinated with metal |
-
1990
- 1990-07-25 JP JP19665390A patent/JPH0481474A/en active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010508396A (en) * | 2006-10-26 | 2010-03-18 | ビー・エイ・エス・エフ、コーポレーション | Film-forming material coordinated with metal |
JP2010508398A (en) * | 2006-10-26 | 2010-03-18 | ビー・エイ・エス・エフ、コーポレーション | Method for producing a coating containing a film-forming material coordinated with a metal |
JP2010508397A (en) * | 2006-10-26 | 2010-03-18 | ビー・エイ・エス・エフ、コーポレーション | Film-forming material coordinated with metal |
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