JPS63137973A - Aqueous coating composition containing cationic gel fine particles - Google Patents
Aqueous coating composition containing cationic gel fine particlesInfo
- Publication number
- JPS63137973A JPS63137973A JP61285771A JP28577186A JPS63137973A JP S63137973 A JPS63137973 A JP S63137973A JP 61285771 A JP61285771 A JP 61285771A JP 28577186 A JP28577186 A JP 28577186A JP S63137973 A JPS63137973 A JP S63137973A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- water
- coating composition
- aqueous
- composition according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 27
- 239000008199 coating composition Substances 0.000 title claims description 16
- 239000010419 fine particle Substances 0.000 title abstract description 4
- 229920005989 resin Polymers 0.000 claims abstract description 49
- 239000011347 resin Substances 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000839 emulsion Substances 0.000 claims abstract description 23
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 21
- 238000004070 electrodeposition Methods 0.000 claims abstract description 19
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 15
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 13
- 238000000576 coating method Methods 0.000 claims abstract description 13
- 238000004132 cross linking Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000012736 aqueous medium Substances 0.000 claims abstract description 8
- CQRYARSYNCAZFO-UHFFFAOYSA-N salicyl alcohol Chemical compound OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 5
- 239000011342 resin composition Substances 0.000 claims abstract description 4
- 239000007863 gel particle Substances 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- -1 ether compound Chemical class 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 claims description 3
- 238000007259 addition reaction Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 238000006482 condensation reaction Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 5
- 230000001804 emulsifying effect Effects 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 10
- 239000003973 paint Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- 239000000049 pigment Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 5
- 229960000583 acetic acid Drugs 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000012362 glacial acetic acid Substances 0.000 description 4
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 3
- JSGVZVOGOQILFM-UHFFFAOYSA-N 3-methoxy-1-butanol Chemical compound COC(C)CCO JSGVZVOGOQILFM-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 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 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- CABDEMAGSHRORS-UHFFFAOYSA-N oxirane;hydrate Chemical compound O.C1CO1 CABDEMAGSHRORS-UHFFFAOYSA-N 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 description 1
- QBDAFARLDLCWAT-UHFFFAOYSA-N 2,3-dihydropyran-6-one Chemical compound O=C1OCCC=C1 QBDAFARLDLCWAT-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- MEEKGULDSDXFCN-UHFFFAOYSA-N 2-pentylphenol Chemical compound CCCCCC1=CC=CC=C1O MEEKGULDSDXFCN-UHFFFAOYSA-N 0.000 description 1
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 1
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical compound CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 description 1
- KOKPBCHLPVDQTK-UHFFFAOYSA-N 4-methoxy-4-methylpentan-2-one Chemical compound COC(C)(C)CC(C)=O KOKPBCHLPVDQTK-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 235000010582 Pisum sativum Nutrition 0.000 description 1
- 240000004713 Pisum sativum Species 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical compound NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000004664 distearyldimethylammonium chloride (DHTDMAC) Substances 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- CJMZLCRLBNZJQR-UHFFFAOYSA-N ethyl 2-amino-4-(4-fluorophenyl)thiophene-3-carboxylate Chemical compound CCOC(=O)C1=C(N)SC=C1C1=CC=C(F)C=C1 CJMZLCRLBNZJQR-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000011134 resol-type phenolic resin Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 125000003198 secondary alcohol group Chemical group 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- NVKTUNLPFJHLCG-UHFFFAOYSA-N strontium chromate Chemical compound [Sr+2].[O-][Cr]([O-])(=O)=O NVKTUNLPFJHLCG-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
Hの 〜および一
本発明は、カチオン性ゲル微粒子を含む水性塗料組成物
、特に艶消しカチオン電着塗料組成物に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an aqueous coating composition containing cationic gel particles, particularly a matte cationic electrodeposition coating composition.
従来、電着塗料に内部架橋したエチレン性不飽和単量体
の重合体よりなる微小樹脂粒子(ミクロゲル)を添加す
ることは公知である。特開昭58−93762および同
56−49766参照。これらはミクロゲルの添加によ
り塗膜表面に凹凸をつくり、光の乱反射によって艶消し
効果を得ようとするものである。It is conventionally known to add minute resin particles (microgel) made of internally crosslinked polymers of ethylenically unsaturated monomers to electrodeposition paints. See JP-A-58-93762 and JP-A-56-49766. These methods create irregularities on the surface of the coating film by adding microgel, and aim to achieve a matting effect by diffusely reflecting light.
しかしながらこれらミクロゲルは、電着に必要な電荷を
持たず、かつ水性媒体に不溶であり、塗膜の焼付温度に
おいて熱融合しないため、単独では電着塗装することが
できず、水溶性または水分散性の電着に必要な電荷を持
った水性樹脂と併用しなければならない。しかしながら
その場合ミクロゲルは前記性質のため塗料貯蔵中ミクロ
ゲルが沈降する傾向を有し、かつ充分な艶消し効果が得
られる量で添加すると電着作業性を害する傾向がみられ
る。However, these microgels do not have the charge necessary for electrodeposition, are insoluble in aqueous media, and do not thermally fuse at the baking temperature of the coating film, so they cannot be electrodeposited alone; It must be used in conjunction with a water-based resin that has the necessary charge for electrocoating. However, in this case, due to the above-mentioned properties of the microgel, the microgel tends to settle during storage of the paint, and if added in an amount sufficient to obtain a sufficient matting effect, there is a tendency to impair the workability of electrodeposition.
特開昭61−31199には、α、β−エチレン性不飽
和ポリカルボン酸樹脂とアルコキシル化メチロールメラ
ミンとの加熱反応生成物を中和し、水性分散液とした艶
消し電着塗料が開示されている。この塗料は架橋した樹
脂ゲル微粒子を艶消し剤として使用するものではないの
で十分な艶消し効果が得られにくく、また樹脂全体が均
一に乳化前に加熱されるのであまり加熱を進めると高分
子となり樹脂の水溶化が困難となる。JP-A-61-31199 discloses a matte electrodeposition paint in which a heated reaction product of α,β-ethylenically unsaturated polycarboxylic acid resin and alkoxylated methylolmelamine is neutralized and made into an aqueous dispersion. ing. This paint does not use cross-linked resin gel particles as a matting agent, so it is difficult to obtain a sufficient matting effect, and the entire resin is uniformly heated before emulsification, so if you heat it too much, it will become a polymer. It becomes difficult to make the resin water-soluble.
そこで本発明は、コアは塗膜の焼付時に不溶不融である
が、シェルは電着に必要な正の電荷を持ち、かつ電着て
被塗物に付着し電着塗膜を形成する水性樹脂よりなる、
カチオン性ゲル微粒子を含む水性塗料組成物を提供する
。Therefore, in the present invention, the core is insoluble and infusible when the coating film is baked, but the shell has a positive charge necessary for electrodeposition, and is an aqueous base that is electrodeposited and adheres to the object to be coated to form an electrodeposited coating film. Made of resin,
An aqueous coating composition containing cationic gel particles is provided.
荒夾1抜
本発明は、
固形分として、
(A)水中において正の電荷を有するフィルム形成性水
性樹脂100重量部、および
(B)縮合や付加反応により自己架橋および/または前
記水性樹脂(A)と架橋する水不溶性の熱硬化性架橋剤
10〜250重量部を含む樹脂組成物を水性媒体中にお
いて乳化し、得られるエマルジョンを前記架橋剤(B)
の架橋温度以上の温度において加熱して得られるカチオ
ン性ゲル微粒子を含有することを特徴とする水性塗料組
成物を提供する。In the present invention, the solid content is (A) 100 parts by weight of a film-forming aqueous resin having a positive charge in water, and (B) self-crosslinking and/or the above aqueous resin (A) by condensation or addition reaction. A resin composition containing 10 to 250 parts by weight of a water-insoluble thermosetting crosslinking agent crosslinked with the crosslinking agent (B) is emulsified in an aqueous medium, and the resulting emulsion is mixed with the crosslinking agent (B).
Provided is an aqueous coating composition characterized by containing cationic gel particles obtained by heating at a temperature equal to or higher than the crosslinking temperature.
本発明のカチオン性ゲル微粒子は、粒子自体が電着可能
な正の電荷を持っており、かつ親水性の水性樹脂がシェ
ルとなってコアを覆っているため、これを含む電着塗料
の電着作業性が損なわれることがなく、また塗料の貯蔵
安定性も害されない。The cationic gel particles of the present invention have a positive charge that can be electrodeposited by themselves, and a hydrophilic water-based resin forms a shell and covers the core. The wearability is not impaired, and the storage stability of the paint is not impaired either.
またシェルは電着て被塗物へ付着し、電着塗膜を形成し
、コアは塗膜の焼付時に流動化することなく塗膜に微細
な凹凸を形成するので、すぐれた艶消し効果を発揮する
。本発明のカチオン性ゲル微粒子を含む水性塗料は、電
着のみならず、ディップ、スプレー等によって塗装し、
艶消し塗膜を形成することもできる。In addition, the shell is electrodeposited and adheres to the object to be coated, forming an electrodeposited coating, while the core does not fluidize when the coating is baked, forming fine irregularities on the coating, resulting in an excellent matting effect. Demonstrate. The water-based paint containing cationic gel particles of the present invention can be applied not only by electrodeposition but also by dipping, spraying, etc.
It is also possible to form a matte coating.
好圭互公爽施五謙
水中において正の電荷を有するフィルム形成性水性樹脂
(A)は、カチオン型電着塗料の製造において皮膜形成
性樹脂として使用されている。それらは樹脂中に正の電
荷と親水性を与えるアミノ基のようなカチオン性官能基
を持っている。種々のタイプのこのような樹脂が知られ
ており、本発明において使用できるが、好ましい典型的
な水性樹脂はアミン化ポリブタジェン樹脂である。The film-forming aqueous resin (A) having a positive charge in water is used as a film-forming resin in the production of cationic electrodeposition paints. They have cationic functional groups such as amino groups that give the resin a positive charge and hydrophilicity. Although various types of such resins are known and can be used in the present invention, a typical preferred water-based resin is an aminated polybutadiene resin.
この樹脂は、例えば分子量500〜5000の液状ポリ
ブタジェンを過酸化物によりオキシラン酸素含有量3〜
12重量%となるように部分的にエポキシ化し、これに
100g当たり30〜3゜Oミリモルの1級または2級
アミンを反応させることによって得られる。このものは
酸で中和し、水で希釈することにより水溶液または分散
液をつくる。This resin is produced by, for example, converting liquid polybutadiene with a molecular weight of 500 to 5,000 into an oxirane with an oxygen content of 3 to 5000 by using peroxide.
It is obtained by partially epoxidizing it to 12% by weight and reacting it with 30 to 3 mmol of primary or secondary amine per 100 g. This product is neutralized with acid and diluted with water to create an aqueous solution or dispersion.
縮合や付加反応により自己架橋および/または前記水性
樹脂と架橋する水不溶性の熱硬化型架橋剤(B)の典型
例は、エーテル化したメチロールフェノール類であり、
より好ましくはβ−ヒドロキシフェノールエーテル化合
物である。またアミン化ポリブタジェン樹脂にオキシラ
ン酸素が残存している場合テトラブロモビスフェノール
Aを併用して使用することができる。Typical examples of water-insoluble thermosetting crosslinking agents (B) that self-crosslink and/or crosslink with the aqueous resin through condensation or addition reactions are etherified methylolphenols,
More preferred is a β-hydroxyphenol ether compound. Further, when oxirane oxygen remains in the aminated polybutadiene resin, tetrabromobisphenol A can be used in combination.
メチロールフェノール類は、フェノール、p−クレゾー
ル、p−t−ブチルフェノール、アミルフェノール、p
−フェニルフェノール、ビスフェノールAなどのフェノ
ール類と、ホルムアルデヒドとをアルカリ触媒の存在下
で反応させて得られるもので、エーテル化したメチロー
ルフェノール類は、そのメチロールフェノール類のフェ
ノール性OH基を適当なエーテル化剤、例えばRX(R
等、Xはハロゲン)や、モノエポキシ化合物で一部また
は全部エーテル化することによって得ることができる。Methylolphenols include phenol, p-cresol, p-t-butylphenol, amylphenol, and p-cresol.
- Etherified methylolphenols are obtained by reacting phenols such as phenylphenol and bisphenol A with formaldehyde in the presence of an alkali catalyst. oxidizing agent, such as RX(R
etc., X is halogen) or by partially or completely etherifying with a monoepoxy compound.
エーテル化剤がモノエポキシ化合物である場合エーテル
化したメチロールフェノール類はβ−ヒドロキシフェノ
ールエーテル化合物であり高反応性なため好ましい。When the etherification agent is a monoepoxy compound, the etherified methylolphenol is a β-hydroxyphenol ether compound and is highly reactive, so it is preferable.
架橋剤(B)は、水中で架橋反応を行うので、常圧で反
応させる場合は100℃以下の温度で架橋するものでな
ければならない。しかしながら反応をオートクレーブ中
加圧下で行う場合には、100℃以上の温度で反応する
架橋剤も使用することができる。Since the crosslinking agent (B) performs the crosslinking reaction in water, it must be capable of crosslinking at a temperature of 100° C. or lower when the reaction is carried out at normal pressure. However, if the reaction is carried out under pressure in an autoclave, crosslinking agents which react at temperatures above 100° C. can also be used.
水性樹脂(A)や架橋剤(B)は粘度を下げ、エマルジ
ョン形成を容易にする為有機溶剤を含むことができる。The aqueous resin (A) and crosslinking agent (B) can contain an organic solvent in order to lower the viscosity and facilitate emulsion formation.
そのような溶剤の例には、エチルセロソルブ、プロピル
セロソルブ、ブチルセロソルブ、メタノール、エタノー
ル、イソプロピルアルコール、n−7’タノール、イソ
ブタノール、エチレングリコールジメチルエーテル、ジ
アセトンアルコール、4−メトキシ−4−メチルペンタ
ノン−2,アセトン、メチルエチルケトン、メトキシブ
タノール、ジオキサン、エチレングリコールモノエチル
エーテルアセテート等の水混和性の有機溶剤やキシレン
、トルエン、メチルイソブチルケトン、ヘキサン、四塩
化炭素、2−エチルヘキサノール、イソホロン、シクロ
ヘキサン、ベンゼン等の水不混和性の有機溶剤がある。Examples of such solvents include ethyl cellosolve, propyl cellosolve, butyl cellosolve, methanol, ethanol, isopropyl alcohol, n-7'tanol, isobutanol, ethylene glycol dimethyl ether, diacetone alcohol, 4-methoxy-4-methylpentanone -2, water-miscible organic solvents such as acetone, methyl ethyl ketone, methoxybutanol, dioxane, ethylene glycol monoethyl ether acetate, xylene, toluene, methyl isobutyl ketone, hexane, carbon tetrachloride, 2-ethylhexanol, isophorone, cyclohexane, There are water-immiscible organic solvents such as benzene.
水性樹脂(A)や架橋剤(B)は架橋剤の反応を促進す
る為触媒を含むことができる。架橋剤がβ−ヒドロキシ
フェノールエーテル化合物の場合触媒としてジノニルナ
フタレンスルフォン酸、ジノニルナツタレンジスルフォ
ン酸などがある。The aqueous resin (A) and the crosslinking agent (B) can contain a catalyst to promote the reaction of the crosslinking agent. When the crosslinking agent is a β-hydroxyphenol ether compound, examples of the catalyst include dinonylnaphthalenesulfonic acid and dinonylnaphthalene disulfonic acid.
水性樹脂(A)と架橋剤(B)とを含む樹脂組成物を水
性媒体中において乳化し、エマルジョンを調製するには
、水性樹脂(A)中のアミノ基の少なくとも20モル%
を酸で中和し、架橋剤(B)と、水性媒体とを加え乳化
すればよい。水性樹脂(A)と架橋剤(B)の割合は、
固形分換算で前者100重量部あたり、後者10〜25
0重量部である。To prepare an emulsion by emulsifying a resin composition containing an aqueous resin (A) and a crosslinking agent (B) in an aqueous medium, at least 20 mol% of the amino groups in the aqueous resin (A)
What is necessary is to neutralize it with an acid, add the crosslinking agent (B) and an aqueous medium, and emulsify it. The ratio of aqueous resin (A) and crosslinking agent (B) is
The former per 100 parts by weight in terms of solid content, the latter 10-25
It is 0 parts by weight.
水性樹脂(A)を中和する酸としては、酢酸。The acid that neutralizes the aqueous resin (A) is acetic acid.
プロピオン酸、乳酸などが好ましい。Propionic acid, lactic acid, etc. are preferred.
水性媒体は水であり、乳化を促進させる為界面活性剤を
含むことができる。ノニオン系界面活性剤の例には、ポ
リエチレングリコールアルキルフェニルエーテル、ポリ
エチレングリコールアルキルエーテル、ポリオキシアル
キレンアルキルエーテル、ポリエチレングリコールソル
ビタンモノステアレート、ポリプロピレングリコールポ
リエチレングリコールエーテル等がある。カチオン系界
面活性剤の例には、ラウリルトリメチルアンモニウムク
ロライド、ジステアリルジメチルアンモニウムクロライ
ド、アルキルピコリニウムクロライド等が挙げられる。The aqueous medium is water and can contain a surfactant to promote emulsification. Examples of nonionic surfactants include polyethylene glycol alkylphenyl ether, polyethylene glycol alkyl ether, polyoxyalkylene alkyl ether, polyethylene glycol sorbitan monostearate, polypropylene glycol polyethylene glycol ether, and the like. Examples of cationic surfactants include lauryltrimethylammonium chloride, distearyldimethylammonium chloride, alkylpicolinium chloride, and the like.
エマルジョン中の溶剤はエマルジョンをtll製後加熱
前に共沸などによって除去することが望ましい。これに
よって架橋反応が促進される。It is desirable to remove the solvent in the emulsion by azeotropic distillation or the like after the emulsion is produced and before heating. This accelerates the crosslinking reaction.
このようにして得られたエマルジョンは、架橋剤(B)
の架橋温度に応じ、常圧または加圧下、架橋温度以上の
温度において加熱すれば、目的とするコア/シェル構造
のカチオン性ゲル微粒子の水分散液が得られる。The emulsion thus obtained contains the crosslinking agent (B)
By heating at a temperature equal to or higher than the crosslinking temperature under normal pressure or increased pressure depending on the crosslinking temperature, an aqueous dispersion of cationic gel particles having the desired core/shell structure can be obtained.
本発明のコア/シェル型のエマルジョンは、同じ符号の
電荷の反撥力により水中に安定して分散しているため熱
安定性が良く、そのためエマルジョンの形において架橋
剤(B)の熱架橋反応が進行する。このようなエマルジ
ョンの形における架橋反応は、加熱前後のエマルジョン
へテトラヒドロフランのような樹脂をとかす溶剤を多量
に加えることによって確かめることができる。架橋して
いなければエマルジョンは溶媒中に透明に熔解し、架橋
していれば不溶性となり、溶剤が白濁する。The core/shell type emulsion of the present invention has good thermal stability because it is stably dispersed in water due to the repulsive force of charges of the same sign, and therefore the thermal crosslinking reaction of the crosslinking agent (B) in the emulsion form is stable. proceed. The crosslinking reaction in the form of such an emulsion can be confirmed by adding a large amount of a resin-dissolving solvent, such as tetrahydrofuran, to the emulsion before and after heating. If the emulsion is not cross-linked, it will dissolve transparently in the solvent; if it is cross-linked, it will be insoluble and the solvent will become cloudy.
また、カチオン性ゲル微粒子の水分散液は風乾し、減圧
乾燥の後電子顕微鏡でその粒子を観察することができる
。Further, the aqueous dispersion of cationic gel particles is air-dried, and after drying under reduced pressure, the particles can be observed with an electron microscope.
このようにして得られたカチオン性ゲル微粒子分散液は
、水性塗料、特にカチオン電着塗料として使用すること
ができる。塗料組成物は所望により水溶性または水分散
性のカチオン性フィルム形成樹脂を含むことができ、ま
た必要に応じ、そのカチオン性フィルム形成樹脂に二酸
化チタン、ベンガラ、カーボンブランク等の着色顔料、
ケイ酸アルミニウム、沈降性硫酸バリウム等の体質顔料
、およびリンモリブデン酸アルミニウム、クロム酸スト
ロンチウム、塩基性ケイ酸鉛、クロム酸鉛等の防錆顔料
を添加することもできる。The cationic gel particle dispersion thus obtained can be used as an aqueous paint, especially a cationic electrodeposition paint. The coating composition may optionally contain a water-soluble or water-dispersible cationic film-forming resin, and if necessary, a coloring pigment such as titanium dioxide, red iron oxide, or carbon blank may be added to the cationic film-forming resin.
Extender pigments such as aluminum silicate and precipitated barium sulfate, and antirust pigments such as aluminum phosphomolybdate, strontium chromate, basic lead silicate, and lead chromate may also be added.
塗料組成物は、不揮発分を10〜20%程度に調節し、
乾燥膜厚15〜30μに電着し、焼付けることにより硬
化させることができる。The coating composition has a non-volatile content adjusted to about 10 to 20%,
It can be electrodeposited to a dry film thickness of 15 to 30 microns and cured by baking.
以下に本発明の製造例、実施例および比較例を示す。こ
れらにおいて部および%は重量基準による。Production examples, examples and comparative examples of the present invention are shown below. In these, parts and percentages are based on weight.
製造例1
ミン ポ1ブ ジエン
日石ポリブタジェンB−2000(数平均分子量2,0
00゜1.2結合65%)を過酢酸を用いてエポキシ化
し、オキシラン酸素含有量6.4%のエポキシ化ポリブ
タジェンを製造した。Production example 1 Minpo1butadiene Nisseki polybutadiene B-2000 (number average molecular weight 2,0
00°1.2 bonds (65%) was epoxidized using peracetic acid to produce epoxidized polybutadiene with an oxirane oxygen content of 6.4%.
このエポキシ化ポリブタジェン1000gおよびエチル
セロソルブ354gを2I!、オートクレーブに仕込ん
だ後、ジメチルアミン62.1 gを加え、150℃で
5時間反応させた。未反応アミンを留去してアミン化ポ
リブタジェン樹脂溶液を製造した。このもののアミン価
は120ミリモル/100g(固形分)であった。不揮
発分75%製造例2
一ヒ゛ロキシフェノールエー−ル へ
タマノール722*1)60 部
ブチルグリシジルエーテル *2)23Mn−ブタノー
ル 10 部メトキシブタノール
10 部ジメチルベンジルアミン
0.4部*1)荒用化学工業側製、レゾ
ール型フェノール樹脂
*2)東部化成■製、モノエポキシ化合物反応容器にタ
マノール722を60部仕込み、n−ブタノール10部
とメトキシブタノール10部とを加え、さらにブチルグ
リシジルエーテル23部を加える。これを均一にかきま
ぜながら100℃まで昇温したところで、ジメチルベン
ジルアミン0.4gを添加する。発熱に注意しながら1
00℃に保温し、十分な攪拌状態で3時間経過した後、
反応生成物のグリシジル基含有量を測定したところ、仕
込み量に対して5%以下となっていたので冷却した。得
られた化合物の分析の結果フェノール性OH基が消失し
、メチロール基と2級アルコール基を有するβ−ヒドロ
キシフェノールエーテル化合物を得た。1000g of this epoxidized polybutadiene and 354g of ethyl cellosolve were mixed into 2I! After charging the mixture into an autoclave, 62.1 g of dimethylamine was added, and the mixture was reacted at 150°C for 5 hours. Unreacted amine was distilled off to produce an aminated polybutadiene resin solution. The amine value of this product was 120 mmol/100 g (solid content). Nonvolatile content 75% Production Example 2 Monohydroxyphenol ether Hetamanol 722*1) 60 parts Butyl glycidyl ether *2) 23Mn-Butanol 10 parts Methoxybutanol 10 parts Dimethylbenzylamine
0.4 parts *1) Resol type phenolic resin manufactured by Arayo Kagaku Kogyo *2) Monoepoxy compound manufactured by Tobu Kasei ■ 60 parts of Tamanol 722 was charged in a reaction vessel, and 10 parts of n-butanol and 10 parts of methoxybutanol were added. and then 23 parts of butyl glycidyl ether. When the temperature was raised to 100° C. while stirring uniformly, 0.4 g of dimethylbenzylamine was added. While being careful about fever 1
After keeping the temperature at 00°C for 3 hours with sufficient stirring,
When the glycidyl group content of the reaction product was measured, it was found to be 5% or less based on the amount charged, so it was cooled. As a result of analysis of the obtained compound, the phenolic OH group disappeared, and a β-hydroxyphenol ether compound having a methylol group and a secondary alcohol group was obtained.
実施例1
エマルジ ンA
アミン化ポリブタジェン樹脂 66.7 50氷酢
酸 1.8脱イオン水
369
製造例1のアミン化ポリブタジェン66.7部へ、製造
例2のβ−ヒドロキシフェノールエーテル化合物62.
5部、さらに氷酢酸1.8部を加え、十分に攪拌する。Example 1 Emulgin A Aminated polybutadiene resin 66.7 50 Glacial acetic acid 1.8 Deionized water
369 To 66.7 parts of the aminated polybutadiene of Production Example 1, 62.7 parts of the β-hydroxyphenol ether compound of Production Example 2 was added.
Add 5 parts and 1.8 parts of glacial acetic acid and stir thoroughly.
これに脱イオン水を加えて乳化し、さらに脱イオン水を
追加しながら減圧下で溶剤を除去し、樹脂エマルジョン
Aを得た。その一部をとり、100倍量のテトラヒドロ
フランへ加えたところ透明に溶解した。Deionized water was added to this to emulsify it, and the solvent was removed under reduced pressure while adding deionized water to obtain resin emulsion A. A portion of the solution was taken and added to 100 times the amount of tetrahydrofuran, and the solution was dissolved transparently.
次に樹脂エマルジョンAを55℃で7日間保温し、冷却
してカチオン性ゲル微粒子分散液を得た。Next, resin emulsion A was kept at 55° C. for 7 days and cooled to obtain a cationic gel particle dispersion.
このものはテトラヒドロフラン中に透明に溶解せず、白
濁した。This product did not dissolve transparently in tetrahydrofuran, but became cloudy.
次に不揮発分10%のゲル微粒子分散液にブリキ板をデ
ィップし、風乾し、室温で減圧乾燥後電子顕微鏡で観察
したところ、1100n以下の粒径の微粒子が観察され
た。Next, a tin plate was dipped in a gel particle dispersion containing 10% non-volatile content, air-dried, and after drying under reduced pressure at room temperature, it was observed under an electron microscope, and fine particles with a particle size of 1100 nm or less were observed.
上で得たカチオン性ゲル微粒子分散液を、被塗物を陰極
としてカチオン電着塗装を行い、170℃で20分焼付
けし、20μのクリヤー塗板を得た。テスト結果を表−
■に示す。The cationic gel particle dispersion obtained above was subjected to cationic electrodeposition using the object to be coated as a cathode, and baked at 170° C. for 20 minutes to obtain a 20 μm clear coated plate. Display test results -
Shown in ■.
実施例2
アミン化ポリブタジェン樹脂 66.7 50テト
ラブロモビスフエノールA3050キシレン
10
ブチルセロソルブ 5
エチルセロソルブ 5
氷酢酸 1.8脱イオン水
361.5製造例1のアミン化ポリブ
タジェン樹脂66.7部に、テトラブロモビスフェノー
ルA50部、キシレン10部、ブチルセロソルブ5部、
エチルセ0ソルブ5部、氷酢酸1.8部を加えて十分に
攪拌する。これに脱イオン水を徐々に加えて乳化し、さ
らに脱イオン水を追加しながら減圧下で溶剤を除去し、
樹脂エマルジョンBを得た。このものはテトラヒドロフ
ランに透明に熔解する。Example 2 Aminated polybutadiene resin 66.7 50 Tetrabromobisphenol A3050 Xylene
10 Butyl cellosolve 5 Ethyl cellosolve 5 Glacial acetic acid 1.8 Deionized water
361.5 66.7 parts of the aminated polybutadiene resin of Production Example 1, 50 parts of tetrabromobisphenol A, 10 parts of xylene, 5 parts of butyl cellosolve,
Add 5 parts of ethylcetate and 1.8 parts of glacial acetic acid and stir thoroughly. Deionized water is gradually added to this to emulsify it, and the solvent is removed under reduced pressure while adding deionized water.
Resin emulsion B was obtained. This material dissolves transparently in tetrahydrofuran.
次に樹脂エマルジョンBを55℃で7日間保温し、冷却
してカチオン性ゲル微粒子分散液を得た。Next, resin emulsion B was kept at 55° C. for 7 days and cooled to obtain a cationic gel particle dispersion.
このものはテトラヒドロフランに透明に熔解せず白濁し
た。This product did not dissolve transparently in tetrahydrofuran but became cloudy.
上で得たカチオン性ゲル微粒子分散液を、被塗物を陰極
としてカチオン電着塗装を行い、170℃で20分焼付
けし、20μのクリヤー塗膜を得た。テスト結果を表−
■に示す。The cationic gel particle dispersion obtained above was subjected to cationic electrodeposition using the object to be coated as a cathode, and baked at 170° C. for 20 minutes to obtain a 20 μm clear coating film. Display test results -
Shown in ■.
製造例3 4 アンモニウム E 1800−6.5 (日本石油化学側部。Manufacturing example 3 4 Ammonium E 1800-6.5 (Japan Petrochemicals side.
エポキシ化ポリブタジェン) 1000gブ
チルセロソルブ 349gジメチル
アミン 46g50%乳酸
138g脱イオン水
473gフェニルグリシジルエーテ
ル 117gエポキシ化ポリブタジェン818
00−6.5およびブチルセロソルブをオートクレーブ
に仕込んだ後、ジメチルアミンを加え150℃で5時間
反応させた、。未反応アミンを留去した後、60 ”c
まで冷却し、50%乳酸と脱イオン水の混合液を添加し
た後80℃で30分間攪拌保温する。この後フェニルグ
リシジルエーテルを加え、110 ”cまで昇温し、攪
拌保温しながら内容物の酸価をフェノールフタレンを指
示薬としてアルコール性K OHを規定液とする通常の
方法で測定し、酸価0.1以下を確認するまで反応させ
た後製造を終了する。不揮発分55%
顯耗さ二囚上
第4級アンモニウム樹脂フェス 231g脱イオ
ン水 315gカーボンブラッ
ク 16g二酸化チタン
92gカオリン
220g塩基性ケイ酸鉛
58g脱イオン水 16
33g第4級アンモニウム樹脂に脱イオン水315gを
加えて熔解した後、顔料を加えてディスパーで約1時間
攪拌混合する。この混合物にガラスピーズを加えた後サ
ンドミルで粒度20μ以下に分散し、脱イオン水163
3gを追加してガラスピーズを0別した後製造を終了す
る。不揮発分20%実施例3
製造例1の樹脂エマルジョンA400gと、製造例3の
顔料ペースト100gを混合して55℃で7部間保温し
て冷却した。(epoxidized polybutadiene) 1000g butyl cellosolve 349g dimethylamine 46g 50% lactic acid
138g deionized water
473g phenyl glycidyl ether 117g epoxidized polybutadiene 818
After charging 00-6.5 and butyl cellosolve into an autoclave, dimethylamine was added and reacted at 150°C for 5 hours. After distilling off unreacted amine, 60”c
After adding a mixture of 50% lactic acid and deionized water, the mixture was stirred and kept at 80° C. for 30 minutes. After that, phenylglycidyl ether was added, the temperature was raised to 110"C, and while stirring and keeping warm, the acid value of the contents was measured by the usual method using phenolphthalene as an indicator and alcoholic KOH as a normal solution. After reacting until confirmation of 0.1 or less, production is terminated. Non-volatile content 55% Aged quaternary ammonium resin face 231g Deionized water 315g Carbon black 16g Titanium dioxide
92g kaolin
220g basic lead silicate
58g deionized water 16
After adding 315 g of deionized water to 33 g of quaternary ammonium resin and melting it, the pigment was added and mixed with stirring using a disper for about 1 hour. After adding glass peas to this mixture, they were dispersed in a sand mill to a particle size of 20μ or less, and deionized water was added at 163 °C.
After adding 3g and zeroing out the glass beads, the production is finished. Non-volatile content 20% Example 3 400 g of the resin emulsion A of Production Example 1 and 100 g of the pigment paste of Production Example 3 were mixed and cooled by keeping at 55° C. for 7 parts.
このものを、被塗物を陰極としてカチオン電着塗装を行
い、170℃で20分間焼付けし、20μの塗板を得た
。テスト結果を表−■に示す。This product was subjected to cationic electrodeposition using the object to be coated as a cathode, and baked at 170° C. for 20 minutes to obtain a 20 μm coated plate. The test results are shown in Table-■.
比較例1
樹脂エマルジョンAを加熱しないで用いるほかは実施例
1に同じ。Comparative Example 1 Same as Example 1 except that resin emulsion A was used without heating.
比較例2
樹脂エマルジョンBを加熱しないで用いるはかは実施例
2に同じ。Comparative Example 2 The resin emulsion B was used in the same manner as in Example 2 without being heated.
比較例3
製造例1の樹脂エマルジョンA400gに、製造例3の
顔料ペース)100gを加え、加熱することなく被塗物
を陰極としてカチオン電着塗装を行い、170℃で20
分焼付けして20μの塗膜を得た。テスト結果を表−■
に示す。Comparative Example 3 100 g of the pigment paste of Production Example 3 was added to 400 g of the resin emulsion A of Production Example 1, and cationic electrodeposition was performed without heating using the object to be coated as a cathode.
A coating film of 20 μm was obtained by baking. Table of test results -■
Shown below.
表−■
注)脱脂したミガキ鋼板に膜厚20μになる条件で電着
塗装し、所定条件で焼付けた後、入射光60°の条件で
光沢を測定する。Table - ■ Note) Electrodeposition coating is applied to a degreased polished steel plate to a film thickness of 20 μm, and after baking under specified conditions, the gloss is measured under the condition of incident light of 60°.
Claims (9)
性樹脂100重量部、および (B)縮合や付加反応により自己架橋および/または前
記水性樹脂(A)と架橋する水不溶性の熱硬化性架橋剤
10〜250重量部を含む樹脂組成物を水性媒体中にお
いて乳化し、得られるエマルジョンを前記架橋剤(B)
の架橋温度以上の温度において加熱して得られるカチオ
ン性ゲル微粒子を含有することを特徴とする水性塗料組
成物。(1) As a solid content, (A) 100 parts by weight of a film-forming aqueous resin having a positive charge in water, and (B) water that self-crosslinks and/or crosslinks with the aqueous resin (A) through condensation or addition reaction. A resin composition containing 10 to 250 parts by weight of an insoluble thermosetting crosslinking agent is emulsified in an aqueous medium, and the resulting emulsion is mixed with the crosslinking agent (B).
An aqueous coating composition characterized by containing cationic gel particles obtained by heating at a temperature equal to or higher than the crosslinking temperature.
1項の水性塗料組成物。(2) The aqueous coating composition according to item 1, wherein the emulsion is heated at normal pressure.
水性塗料組成物。(3) The aqueous coating composition according to item 1, wherein the emulsion is heated under pressure.
機溶剤を除去する工程を含む第1項ないし第3項のいず
れかの水性塗料組成物。(4) The water-based coating composition according to any one of Items 1 to 3, wherein the Elmudgeon contains an organic solvent and includes a step of removing the organic solvent before heating.
脂である第1項ないし第4項のいずれかの水性塗料組成
物。(5) The water-based coating composition according to any one of items 1 to 4, wherein the water-based resin (A) is an aminated polybutadiene resin.
ェノール類である第1項ないし第5項のいずかの水性塗
料組成物。(6) The aqueous coating composition according to any one of items 1 to 5, wherein the crosslinking agent (B) is an etherified methylolphenol.
Aである第5項の水性塗料組成物。(7) The aqueous coating composition according to item 5, wherein the crosslinking agent (B) is tetrabromobisphenol A.
ドロキシフェノールエーテル化合物である第6項の水性
塗料組成物。(8) The aqueous coating composition according to item 6, wherein the etherified methylolphenol is a β-hydroxyphenol ether compound.
項ないし第8項のいずれかの組成物。(9) The first aqueous coating composition is for cationic electrodeposition coating.
The composition according to any one of Items 1 to 8.
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61285771A JPH0619058B2 (en) | 1986-11-28 | 1986-11-28 | Aqueous coating composition containing cationic gel particles |
EP87117595A EP0272500B1 (en) | 1986-11-28 | 1987-11-27 | Cationic micro gel praticle dispersion and a coating composition therefrom |
DE87117595T DE3785732T2 (en) | 1986-11-28 | 1987-11-27 | Dispersion of cationic microgel particles and coating composition thereof. |
CA000552992A CA1301393C (en) | 1986-11-28 | 1987-11-27 | Cationic micro gel particle dispersion and a coating composition therefrom |
KR1019870013491A KR950009546B1 (en) | 1986-11-28 | 1987-11-28 | Cationic micro gel particle dispersion and a coating composition therefrom |
US07/126,963 US4788246A (en) | 1986-11-28 | 1987-11-30 | Cationic micro gel particle dispersion and a coating composition therefrom |
AU81913/87A AU595659B2 (en) | 1986-11-28 | 1987-11-30 | Cationic micro gel particle dispersion and a coating composition therefrom |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61285771A JPH0619058B2 (en) | 1986-11-28 | 1986-11-28 | Aqueous coating composition containing cationic gel particles |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS63137973A true JPS63137973A (en) | 1988-06-09 |
JPH0619058B2 JPH0619058B2 (en) | 1994-03-16 |
Family
ID=17695845
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP61285771A Expired - Lifetime JPH0619058B2 (en) | 1986-11-28 | 1986-11-28 | Aqueous coating composition containing cationic gel particles |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0619058B2 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5141685A (en) * | 1989-12-27 | 1992-08-25 | Eastman Kodak Company | Forming shaped articles from orientable polymers and polymer microbeads |
US5143765A (en) * | 1989-12-27 | 1992-09-01 | Eastman Kodak Company | Shaped articles from orientable polymers and polymer microbeads |
US5223383A (en) * | 1989-12-27 | 1993-06-29 | Eastman Kodak Company | Photographic elements containing reflective or diffusely transmissive supports |
USRE34742E (en) * | 1989-12-27 | 1994-09-27 | Eastman Kodak Company | Shaped articles from orientable polymers and polymer microbeads |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS53127545A (en) * | 1977-04-13 | 1978-11-07 | Ota Toshuki | Method of making crosslinked resin particulate dispersion |
JPS5497632A (en) * | 1978-01-19 | 1979-08-01 | Nippon Paint Co Ltd | Coating composition for cathode electrodeposition |
JPS5857422A (en) * | 1981-09-14 | 1983-04-05 | ピ−ピ−ジ−・インダストリ−ズ・インコ−ポレイテツド | Manufacture of cation resin |
JPS5893762A (en) * | 1981-11-30 | 1983-06-03 | Mitsui Toatsu Chem Inc | Matte-finishing electrodepositing paint composition |
JPS58129066A (en) * | 1982-01-27 | 1983-08-01 | Nippon Paint Co Ltd | Coating material composition |
-
1986
- 1986-11-28 JP JP61285771A patent/JPH0619058B2/en not_active Expired - Lifetime
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS53127545A (en) * | 1977-04-13 | 1978-11-07 | Ota Toshuki | Method of making crosslinked resin particulate dispersion |
JPS5497632A (en) * | 1978-01-19 | 1979-08-01 | Nippon Paint Co Ltd | Coating composition for cathode electrodeposition |
JPS5857422A (en) * | 1981-09-14 | 1983-04-05 | ピ−ピ−ジ−・インダストリ−ズ・インコ−ポレイテツド | Manufacture of cation resin |
JPS5893762A (en) * | 1981-11-30 | 1983-06-03 | Mitsui Toatsu Chem Inc | Matte-finishing electrodepositing paint composition |
JPS58129066A (en) * | 1982-01-27 | 1983-08-01 | Nippon Paint Co Ltd | Coating material composition |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5141685A (en) * | 1989-12-27 | 1992-08-25 | Eastman Kodak Company | Forming shaped articles from orientable polymers and polymer microbeads |
US5143765A (en) * | 1989-12-27 | 1992-09-01 | Eastman Kodak Company | Shaped articles from orientable polymers and polymer microbeads |
US5223383A (en) * | 1989-12-27 | 1993-06-29 | Eastman Kodak Company | Photographic elements containing reflective or diffusely transmissive supports |
US5275854A (en) * | 1989-12-27 | 1994-01-04 | Eastman Kodak Company | Shaped articles from orientable polymers and polymer microbeads |
USRE34742E (en) * | 1989-12-27 | 1994-09-27 | Eastman Kodak Company | Shaped articles from orientable polymers and polymer microbeads |
Also Published As
Publication number | Publication date |
---|---|
JPH0619058B2 (en) | 1994-03-16 |
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