JPH0575024B2 - - Google Patents
Info
- Publication number
- JPH0575024B2 JPH0575024B2 JP22268787A JP22268787A JPH0575024B2 JP H0575024 B2 JPH0575024 B2 JP H0575024B2 JP 22268787 A JP22268787 A JP 22268787A JP 22268787 A JP22268787 A JP 22268787A JP H0575024 B2 JPH0575024 B2 JP H0575024B2
- Authority
- JP
- Japan
- Prior art keywords
- aqueous
- resin
- weight
- cationic
- producing
- 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.)
- Expired - Fee Related
Links
- 229920005989 resin Polymers 0.000 claims description 45
- 239000011347 resin Substances 0.000 claims description 45
- 239000000839 emulsion Substances 0.000 claims description 25
- 125000002091 cationic group Chemical group 0.000 claims description 22
- 239000006185 dispersion Substances 0.000 claims description 21
- 239000005062 Polybutadiene Substances 0.000 claims description 19
- 229920002857 polybutadiene Polymers 0.000 claims description 19
- 239000007863 gel particle Substances 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000003822 epoxy resin Substances 0.000 claims description 10
- 229920000647 polyepoxide Polymers 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 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 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000011342 resin composition Substances 0.000 claims description 5
- CQRYARSYNCAZFO-UHFFFAOYSA-N salicyl alcohol Chemical class OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 3
- 230000001804 emulsifying effect Effects 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 3
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- NZNQMPZXPUKVSQ-UHFFFAOYSA-N [O].C1CO1 Chemical group [O].C1CO1 NZNQMPZXPUKVSQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012736 aqueous medium Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229920003986 novolac Polymers 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims 3
- 229930185605 Bisphenol Natural products 0.000 claims 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims 1
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 238000004070 electrodeposition Methods 0.000 description 12
- 239000003431 cross linking reagent Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 150000001412 amines Chemical class 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 229960000583 acetic acid Drugs 0.000 description 7
- 239000003973 paint Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000012362 glacial acetic acid Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 239000010419 fine particle Substances 0.000 description 5
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 239000002609 medium Substances 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 239000005028 tinplate Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000003141 primary amines Chemical class 0.000 description 3
- 239000011134 resol-type phenolic resin Substances 0.000 description 3
- 150000003335 secondary amines Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-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
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-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
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000003054 catalyst 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
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 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
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- CABDEMAGSHRORS-UHFFFAOYSA-N oxirane;hydrate Chemical compound O.C1CO1 CABDEMAGSHRORS-UHFFFAOYSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-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
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 1
- JSGVZVOGOQILFM-UHFFFAOYSA-N 3-methoxy-1-butanol Chemical compound COC(C)CCO JSGVZVOGOQILFM-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
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 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
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 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
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 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
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical class C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- -1 pt-butylphenol Chemical compound 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
- 239000002994 raw material Substances 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Description
本発明の背景および課題
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)を添加し、艶消し塗膜を得ることは公知で
ある。特開昭58−93762および特開昭56−49766参
照。ミクロゲルを電着塗料へ添加することは、艶
消しの目的ばかりでなく、塗膜性能およびつきま
わり性などにも有効である。
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つた水性樹脂と併用
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の貯蔵安定性や、電
着作業性を害し、多量に添加することができな
い。
そこで本発明は、コアは熱硬化性の架橋樹脂よ
りなり、シエルは電着に必要な正の電荷と親水基
を持つている水性樹脂よりなる、コア/シエル構
造の新しいタイプのカチオン性ゲル微粒子の水分
散液の製造方法を提供する。
解決方法
本発明は、
(A) エポキシ樹脂または部分エポキシ化ポリブタ
シエン系樹脂をアミンで変性して得られるカチ
オン性フイルム形成性水性樹脂を固形分換算
100重量部、および
(B) フエノール類のホルムアルデヒドとを反応さ
せて得られるメチロールフエノール類を固形分
換算10〜250重量部含む樹脂組成物を前記水性
樹脂(A)を中和する酸を含む水性媒体中に乳化
し、得られるエマルジヨンを前記メチロールフ
エノール類の反応温度以上の温度において加熱
することを特徴とするカチオン性ゲル微粒子水
分散液の製造方法を提供する。
本発明のカチオン性ゲル微粒子の水分散液は、
粒子自体が電着可能な正の電荷を持つており、か
つ親水性の水性樹脂がシエルとなつて不溶性の熱
硬化型の架橋樹脂のコアを覆つているため、これ
をカチオン電着塗料へ添加した場合、電着作業性
や塗膜性能を害することがなく、また塗料の貯蔵
安定性に悪影響することもない。
好ましい実施態様
カチオン性フイ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。それらは樹脂へ正の電液と
親水性を与えるアミノ基のようなカチオン性官能
基を持つている。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水性
樹脂はアミン変性エポキシ樹脂およびアミン化ポ
リブタジエン樹脂である。
アミン変性エポキシ樹脂はポリグリシジル化合
物に1級または2級アミンを反応させて製造する
ことができる。ポリグリシジル化合物とは分子内
に2個以上のグリシジル基を有するエポキシ化合
物のことであり、芳香族または脂肪族多価アルコ
ールにエピクロルヒドリンを反応させることによ
り得られる。その具体例としては、ビスフエノー
ルA系であるエポトートYD−011(東都化成(株)
製)、脂肪族系であるデナコールEX−212(ナガセ
化成(株)製)およびPG−207(東都化成(株)製)、フエ
ノールノボラツク系であるエポトートYDPN−
638(東都化成(株)製)などがある。
これらのポリグリシジル化合物に付加する1級
または2級アミンとしては、モノメチルアミン、
モノエチルアミン、n−ブチルアミン、モノエタ
ノールアミン等の1級アミンや、ジメチルアミ
ン、ジエチルアミン、ジイソプロピルアミン、N
−メチルエタノールアミン、N−エチルエタノー
ルアミン、ジエタノールアミン等の2級アミン、
およびジエチレントリアミンとメチルイソブチル
ケトンの脱水反応で得られるジケチミンなどがあ
る。これらのアミンはポリグリシジル化合物のエ
ポキシ当量に対しほぼ当量比で反応せしめられ
る。
アミン化ポリブタジエン樹脂とは、
(1) 500〜5000の分子量で50〜500のヨウ素価の炭
素−炭素二重結合およびオキシラン酸素を3〜
12重量%有するエポキシ化ポリブタジエン系高
分子化合物に
(2) 該高分子化合物100g当たり30〜300ミリモル
の、一般式
Background and Problems of the Present Invention Conventionally, it has been known to add minute resin particles (microgel) made of a polymer of internally crosslinked ethylenically unsaturated monomers to electrodeposition paints to obtain a matte coating film. See JP-A-58-93762 and JP-A-56-49766. Adding microgel to electrodeposition paints is effective not only for the purpose of matting, but also for improving coating film performance and throwing power. 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, the microgel cannot be added in large amounts because it impairs the storage stability of the paint and the workability of electrodeposition due to the above-mentioned properties. Therefore, the present invention provides a new type of cationic gel fine particles with a core/shell structure, in which the core is made of a thermosetting crosslinked resin and the shell is made of an aqueous resin that has a positive charge and hydrophilic groups necessary for electrodeposition. Provided is a method for producing an aqueous dispersion of. Solution The present invention provides (A) a cationic film-forming aqueous resin obtained by modifying an epoxy resin or a partially epoxidized polybutadiene resin with an amine in terms of solid content;
100 parts by weight, and (B) a resin composition containing 10 to 250 parts by weight in terms of solid content of methylolphenols obtained by reacting phenols with formaldehyde, and an aqueous resin composition containing an acid that neutralizes the aqueous resin (A). Provided is a method for producing an aqueous dispersion of cationic gel particles, which comprises emulsifying the present invention in a medium and heating the resulting emulsion at a temperature equal to or higher than the reaction temperature of the methylolphenols. The aqueous dispersion of cationic gel particles of the present invention is
The particles themselves have a positive charge that can be electrodeposited, and the hydrophilic water-based resin forms a shell that covers the insoluble thermosetting cross-linked resin core, so this is added to cationic electrodeposition paints. In this case, the electrodeposition workability and coating performance are not impaired, and the storage stability of the paint is not adversely affected. Preferred Embodiments The cationic film-forming aqueous resin (A) 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 electrolyte and hydrophilic properties. Various types of such resins are known, and water-based resins that can be used in the present invention include amine-modified epoxy resins and aminated polybutadiene resins. Amine-modified epoxy resin can be produced by reacting a polyglycidyl compound with a primary or secondary amine. A polyglycidyl compound is an epoxy compound having two or more glycidyl groups in the molecule, and is obtained by reacting an aromatic or aliphatic polyhydric alcohol with epichlorohydrin. A specific example is Epotote YD-011 (manufactured by Toto Kasei Co., Ltd.), which is a bisphenol A type.
), aliphatic Denacol EX-212 (manufactured by Nagase Kasei Co., Ltd.) and PG-207 (manufactured by Toto Kasei Co., Ltd.), and phenol novolac type Epotote YDPN-
638 (manufactured by Toto Kasei Co., Ltd.). The primary or secondary amines added to these polyglycidyl compounds include monomethylamine,
Primary amines such as monoethylamine, n-butylamine, monoethanolamine, dimethylamine, diethylamine, diisopropylamine, N
- Secondary amines such as methylethanolamine, N-ethylethanolamine, diethanolamine,
and diketimine obtained by the dehydration reaction of diethylenetriamine and methyl isobutyl ketone. These amines are reacted in approximately equivalent ratios to the epoxy equivalents of the polyglycidyl compound. Aminated polybutadiene resin is (1) a carbon-carbon double bond with a molecular weight of 500 to 5000 and an iodine value of 50 to 500, and 3 to oxirane oxygen atoms.
(2) 30 to 300 mmol per 100 g of the polymer compound having the general formula
【式】
(式中、R1およびR2はヒドロキシル基で置換
されても良い炭素数1〜20の炭化水素基を表す
か、またはR1とR2は窒素および場合により他の
ヘテロ原子を含む環構造を表す。)
で表されるアミン化合物を反応させ、さらに
(3) 前記(1)の高分子化合物100g当たり0〜200ミ
リモルの、一般式[Formula] (In the formula, R 1 and R 2 represent a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydroxyl group, or R 1 and R 2 represent nitrogen and optionally other heteroatoms. (represents a ring structure containing), and further reacts (3) 0 to 200 mmol of the general formula per 100 g of the polymer compound of (1) above.
【式】
(式中R3は水素原子およびR4は水素原子また
はメチル基を表す。)で表されるα,β不飽和カ
ルボン酸あるいは分子量100〜350で炭素−炭素共
役二重結合を10重量%以上含む不飽和脂肪酸ある
いはそれらの混合物を反応させて得られる反応生
成物をいう。
例えば分子量500〜5000の液状ブタジエンを過
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100
gあたり30〜300ミリモルの前述した1級または
2級アミンを反応させ、場合によりさらに液状ポ
リブタジエン100gあたり200ミリモルまでのアク
リル酸またはメタクリル酸を反応させることによ
つて得られる。
これら樹脂は酸で中和し、水で希釈することに
より水溶液または分散液をつくる。
フエ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メチロールフ
エノール類は、自己架橋および/または前記水性
樹脂と架橋する架橋剤である。これらはレゾール
型フエノール樹脂初期縮合物として良く知られて
おり、フエノール、p−クレゾール、p−t−ブ
チルフエノール、p−アミノフエノール、p−フ
エニルフエノール、ビスフエノールAなどを原料
として製造される。
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。
水性樹脂(A)や架橋剤(B)は粘度を下げ、エマルジ
ヨン形成を容易にするため、有機溶剤を含むこと
ができる。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−ブタノール、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。
水性樹脂(A)や架橋剤(B)は架橋剤の反応を促進す
るためジノニルナフタレンスルフオン酸、ジノニ
ルナフタレンジスルフオン酸などのような触媒を
含むことができる。
水性樹脂(A)と架橋剤(B)とを含む樹脂組成物を水
性樹媒体中において乳化し、エマルジヨンを調製
するには、水性樹脂(A)中のアミノ基の少なくとも
20重量%を酸で中和し、架橋剤(B)と、水性樹媒体
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10〜250重量部である。
水性樹脂(A)を中和する酸としては、酢酸、プロ
ピオン酸、乳酸などが好ましい。
水性樹媒体は水であり、乳化を促進するため界
面活性剤を含むことができる。ノニオン界面活性
剤の例には、ポリエチレングリコールアルキルフ
エニルエーテル、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。
エマルジヨン中の溶剤はエマルジヨンを調製後
加熱前に共沸などによつて除去することが望まし
い。これによつて架橋反応が促進される。
このようにして得られたエマルジヨンは、架橋
剤(B)の反応温度に応じ、常圧または加圧下、反応
温度以上の温度において加熱すれば、目的とする
コア/シエル構造のカチオン性ゲル微粒子の水分
散液が得られる。
本発明のコア/シエル型のエマルジヨンは、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
ヨ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ヨンの形における架橋反
応は、加熱前のエマルジヨンヘテトラヒドロフラ
ンのような樹脂をとかす溶剤を多量に加えること
によつて確かめることができる。架橋していなけ
ればエマルジヨンは溶媒中に透明に溶解し、架橋
していれば不溶性となり、溶剤が白濁する。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。
本発明によつて得られるカチオン性ゲル微粒子
の水分散液は、艶消し、電着塗膜の性能向上など
の目的で公知のカチオン性電着塗料へ添加するこ
とができる。その場合比較的多量に加えても、電
着作業性、塗膜性能、貯蔵安定性等が低下しな
い。また上記分散液は、同様な目的で一般の水性
塗料組成物へ加えることもできる。
以下に本発明の製造例および実施例を示す。こ
れにおいて部および%は重量基準による。
製造例 1
アミン化ポリブタジエンA
日石ポリブタジエンB−2000(数平均分子量
2000、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
化ポリブタジエンを製造した。
このエポキシ化ポリブタジエン1000gおよびエ
チルセロソルブ354gを2オートクレーブに仕
込んだ後、ジメチルアミン62.1g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
ミン化ポリブタジエ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)であつた。不揮発分75%
製造例 2
アミン化ポリブタジエンB
日石ポリブタジエンB−2000(数平均分子量
2000、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
化ポリブタジエンを製造した。
このエポキシ化ポリブタジエン1000gおよびエ
チルセロソルブ354gを2オートクレーブに仕
込んだ後、ジメチルアミン62.1g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、120℃まで冷却しアクリル酸79.3g、ハイド
ロキノン7.6gおよびエチルセロソルブ26.4gの
混合物を添加し、さらに120℃で3時間45分反応
させた。
このもののアミン価は85.2ミリモル/100g、
酸価は10.0ミリモル/100g、そして固形分濃度
は75.4%であつた。
製造例 3
アミン化エポキシ樹脂
固形分
重量部 (%)
エポトートYD−012 *2) 700 700
ブチルセロソルブ 227
ジエチルアミン 73
*2)東都化成(株)製のエポキシ樹脂
エポトートYD−012 700部とブチルセロソル
ブ227部を2オートクレーブに仕込み溶解させ
る。ジブチルアミン73部を仕込み、100℃に上昇
し、90分保温して反応させた。未反応アミンを留
去してアミン化エポキシ樹脂溶液を製造した。
このもののアミン価は128ミリモル/100g(固
形分)であつた。不揮発分70.5%
実施例 1
樹脂エマルジヨンA
固形分
重量部 (%)
アミン化ポリブタジエン樹脂A 100 75
タマノール722 *1) 33.3 25
氷酢酸 2.8
脱イオン水 363.9
*1)荒川化学工業(株)製、レゾール型フエノー
ル樹脂
製造例1のアミン化ポリブタジエン100部へタ
マノール722 33.3部、さらに氷酢酸2.8部を加え、
十分に撹拌する。これに脱イオン水363.9部を加
えて乳化し、樹脂エマルジヨン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。
脱イオン水を追加しながら減圧下で溶剤を除去
し、次に樹脂エマルジヨンAを95℃で6時間保温
し、冷却してカチオン性ゲル微粒子分散液を得
た。
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。
次に不揮発分10%のゲル微粒子分散液にブリキ
板をデイツプし、風乾し、室温で減圧乾燥後電子
顕微鏡で観察したところ、100nm以下の粒径の微
粒子が観察された。
実施例 1
樹脂エマルジヨンB
固形分
重量部 (%)
アミン化ポリブタジエン樹脂B 100 75
タマノール722 *1) 33.3 25
氷酢酸 2.8
脱イオン水 363.9
*1)荒川化学工業(株)製、レゾール型フエノー
ル樹脂
製造例1のアミン化ポリブタジエン100部へ、
タマノール722 33.3部、さらに氷酢酸2.8部を加
え、十分に撹拌する。これに脱イオン水363.9部
を加えて乳化し、樹脂エマルジヨンB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。
脱イオン水を追加しながら減圧下で溶剤を除去
し、次に樹脂エマルジヨンBを95℃で6時間保温
し、冷却してカチオン性ゲル微粒子分散液を得
た。
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。
次に不揮発分10%のゲル微粒子分散液にブリキ
板をデイツプし、風乾し、室温で減圧乾燥後電子
顕微鏡で観察したところ、100nm以下の粒径の微
粒子が観察された。
実施例 3
樹脂エマルジヨンC
固形分
重量部 (%)
アミン化エポキシ樹脂 107 75
タマノール722 *1) 33.3 25
氷酢酸 2.6
脱イオン水 357.1
*1)荒川化学工業(株)製、レゾール型フエノー
ル樹脂
製造例3のアミン化エポキシ樹脂107部へ、タ
マノール722 33.3部、さらに氷酢酸2.6部を加え
て十分に撹拌する。これに脱イオン水357.1部を
加えて乳化し、樹脂エマルジヨンC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。脱イオン水を追加し
ながら減圧下で溶剤を除去し、次に樹脂エマルジ
ヨンC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。
このものはテトラヒドロフラン中に透明に容解
せず、白濁した。
次に不揮発分10%のゲル微粒子分散液にブリキ
板をデイツプし、風乾し、室温で減圧乾燥後電子
顕微鏡で観察したところ、100nm以下の粒径の微
粒子が観察された。
実施例 4
樹脂エマルジヨンD
実施例1において、樹脂エマルジヨンAを95℃
で6時間保温する代わりに、オートクレーブ中
110℃で5時間保温し、冷却してカチオン性ゲル
微粒子分散液を得た。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。
次に不揮発分10%のゲル微粒子分散液にブリキ
板をデイツプし、風乾し、室温で減圧乾燥後電子
顕微鏡で観察したところ、100nm以下の粒径の微
粒子が観察された。[Formula] (In the formula, R 3 is a hydrogen atom and R 4 is a hydrogen atom or a methyl group.) A reaction product obtained by reacting unsaturated fatty acids or a mixture thereof containing % by weight or more. For example, liquid butadiene with a molecular weight of 500 to 5000 is treated with peroxide to reduce the oxygen content of oxirane to 3 to 12% by weight.
Partially epoxidized so that 100
It is obtained by reacting 30 to 300 mmol per g of the aforementioned primary or secondary amine and optionally further reacting up to 200 mmol acrylic acid or methacrylic acid per 100 g of liquid polybutadiene. These resins are neutralized with acid and diluted with water to create an aqueous solution or dispersion. Methylolphenols obtained by reacting phenols and formaldehyde in the presence of an alkali catalyst are crosslinking agents that self-crosslink and/or crosslink with the aqueous resin. These are well known as resol type phenolic resin initial condensates, and are manufactured using phenol, p-cresol, pt-butylphenol, p-aminophenol, p-phenylphenol, bisphenol A, etc. as raw materials. . 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 that react at temperatures above 100° C. can also be used. The aqueous resin (A) and crosslinking agent (B) can contain an organic solvent in order to lower the viscosity and facilitate emulsion formation. Examples of such solvents include ethyl cellosolve, propyl cellosolve, butyl cellosolve, methanol, ethanol, isopropyl alcohol, n-butanol, 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, benzene, etc. water-immiscible organic solvents. The aqueous resin (A) and crosslinking agent (B) can contain a catalyst such as dinonylnaphthalenesulfonic acid, dinonylnaphthalene disulfonic acid, etc. to promote the reaction of the crosslinking agent. In order to prepare an emulsion by emulsifying a resin composition containing an aqueous resin (A) and a crosslinking agent (B) in an aqueous resin medium, at least one of the amino groups in the aqueous resin (A) must be
What is necessary is to neutralize 20% by weight with an acid, add the crosslinking agent (B) and an aqueous resin medium, and emulsify it. Water-based resin (A) and crosslinking agent (B)
The ratio is per 100 parts by weight of the former in terms of solid content,
The latter is 10 to 250 parts by weight. Preferred acids for neutralizing the aqueous resin (A) include acetic acid, propionic acid, and lactic acid. The aqueous tree medium is water and can contain surfactants to promote emulsification. Examples of nonionic surfactants include polyethylene glycol alkyl phenyl 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. It is desirable to remove the solvent in the emulsion by azeotropic distillation or the like after preparing the emulsion and before heating it. This accelerates the crosslinking reaction. Depending on the reaction temperature of the crosslinking agent (B), the emulsion thus obtained can be heated at a temperature above the reaction temperature under normal pressure or increased pressure to form cationic gel particles with the desired core/shell structure. An aqueous dispersion is obtained. 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) is carried out in the emulsion form. proceed. Such a crosslinking reaction in the form of an emulsion can be confirmed by adding a large amount of a resin-dissolving solvent, such as tetrahydrofuran, to the emulsion before heating. If it is not crosslinked, the emulsion will dissolve transparently in the solvent; if it is crosslinked, it will be insoluble and the solvent will become cloudy. In addition, the aqueous dispersion of cationic gel particles was air-dried,
After drying under reduced pressure, the particles can be observed under an electron microscope. The aqueous dispersion of cationic gel particles obtained by the present invention can be added to known cationic electrodeposition paints for the purpose of matting, improving the performance of electrodeposition coatings, and the like. In that case, even if a relatively large amount is added, electrodeposition workability, coating film performance, storage stability, etc. will not deteriorate. The above dispersion can also be added to general aqueous coating compositions for the same purpose. Production examples and examples of the present invention are shown below. Parts and percentages herein are by weight. Production example 1 Aminated polybutadiene A Nisseki polybutadiene B-2000 (number average molecular weight
2000, 1,2 bonds (65%) was epoxidized using peracetic acid to produce epoxidized polybutadiene with an oxirane oxygen content of 6.4%. After charging 1000 g of this epoxidized polybutadiene and 354 g of ethyl cellosolve into two autoclaves, 62.1 g of dimethylamine was added, and the mixture was heated to 150°C.
The reaction was carried out 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). Non-volatile content 75% Production example 2 Aminated polybutadiene B Nisseki polybutadiene B-2000 (number average molecular weight
2000, 1,2 bonds (65%) was epoxidized using peracetic acid to produce epoxidized polybutadiene with an oxirane oxygen content of 6.4%. After charging 1000 g of this epoxidized polybutadiene and 354 g of ethyl cellosolve into two autoclaves, 62.1 g of dimethylamine was added, and the mixture was heated to 150°C.
The reaction was carried out for 5 hours. After distilling off the unreacted amine, the mixture was cooled to 120°C, a mixture of 79.3 g of acrylic acid, 7.6 g of hydroquinone and 26.4 g of ethyl cellosolve was added, and the mixture was further reacted at 120°C for 3 hours and 45 minutes. The amine value of this product is 85.2 mmol/100g.
The acid value was 10.0 mmol/100 g, and the solids concentration was 75.4%. Production example 3 Aminated epoxy resin Solid content weight part (%) Epotote YD-012 *2) 700 700 Butyl cellosolve 227 Diethylamine 73 *2) 700 parts of epoxy resin Epotote YD-012 manufactured by Toto Kasei Co., Ltd. and 227 parts of butyl cellosolve. 2.Pour into an autoclave and dissolve. 73 parts of dibutylamine was charged, the temperature was raised to 100°C, and the temperature was kept for 90 minutes to react. Unreacted amine was distilled off to produce an aminated epoxy resin solution. The amine value of this product was 128 mmol/100 g (solid content). Non-volatile content 70.5% Example 1 Resin emulsion A Solid content weight part (%) Aminated polybutadiene resin A 100 75 Tamanol 722 *1) 33.3 25 Glacial acetic acid 2.8 Deionized water 363.9 *1) Resol manufactured by Arakawa Chemical Co., Ltd. type phenolic resin To 100 parts of the aminated polybutadiene of Production Example 1, add 33.3 parts of Tamanol 722 and further 2.8 parts of glacial acetic acid,
Stir thoroughly. 363.9 parts of deionized water was added to this and emulsified to obtain resin emulsion A. When a portion of it was added to 100 times the amount of tetrahydrofuran, it dissolved transparently. The solvent was removed under reduced pressure while adding deionized water, and then resin emulsion A was kept at 95° C. for 6 hours and cooled to obtain a cationic gel particle dispersion. This product did not dissolve transparently in tetrahydrofuran, but became cloudy. Next, a tin plate was dipped in a gel particle dispersion containing 10% nonvolatile content, air-dried, and dried under reduced pressure at room temperature. When observed under an electron microscope, fine particles with a particle size of 100 nm or less were observed. Example 1 Resin emulsion B Solid content weight part (%) Aminated polybutadiene resin B 100 75 Tamanol 722 *1) 33.3 25 Glacial acetic acid 2.8 Deionized water 363.9 *1) Manufactured by Arakawa Chemical Co., Ltd., resol type phenolic resin to 100 parts of the aminated polybutadiene of Example 1;
Add 33.3 parts of Tamanol 722 and 2.8 parts of glacial acetic acid, and stir thoroughly. 363.9 parts of deionized water was added to this and emulsified to obtain resin emulsion B. When a portion of it was added to 100 times the amount of tetrahydrofuran, it dissolved transparently. The solvent was removed under reduced pressure while adding deionized water, and then resin emulsion B was kept at 95° C. for 6 hours and cooled to obtain a cationic gel particle dispersion. This product did not dissolve transparently in tetrahydrofuran, but became cloudy. Next, a tin plate was dipped in a gel particle dispersion containing 10% nonvolatile content, air-dried, and dried under reduced pressure at room temperature. When observed under an electron microscope, fine particles with a particle size of 100 nm or less were observed. Example 3 Resin emulsion C Solid content weight part (%) Aminated epoxy resin 107 75 Tamanol 722 *1) 33.3 25 Glacial acetic acid 2.6 Deionized water 357.1 *1) Manufactured by Arakawa Chemical Co., Ltd., resol type phenolic resin Production example 33.3 parts of Tamanol 722 and 2.6 parts of glacial acetic acid were added to 107 parts of the aminated epoxy resin No. 3, and the mixture was thoroughly stirred. 357.1 parts of deionized water was added to this and emulsified to obtain resin emulsion C. When a portion of it was added to 100 times the amount of tetrahydrofuran, it dissolved transparently. The solvent was removed under reduced pressure while adding deionized water, and then the resin emulsion C was kept at 55° C. for 7 days and cooled to obtain a cationic gel particle dispersion. This product did not dissolve transparently in tetrahydrofuran and became cloudy. Next, a tin plate was dipped in a gel particle dispersion containing 10% nonvolatile content, air-dried, and dried under reduced pressure at room temperature. When observed under an electron microscope, fine particles with a particle size of 100 nm or less were observed. Example 4 Resin emulsion D In Example 1, resin emulsion A was heated to 95°C.
Instead of keeping warm for 6 hours, autoclave
The mixture was kept at 110° C. for 5 hours and cooled to obtain a cationic gel particle dispersion. This product did not dissolve transparently in tetrahydrofuran, but became cloudy. Next, a tin plate was dipped in a gel particle dispersion containing 10% nonvolatile content, air-dried, and dried under reduced pressure at room temperature. When observed under an electron microscope, fine particles with a particle size of 100 nm or less were observed.
Claims (1)
級アミンを付加して得られるアミン変性エポキ
シ樹脂、または(ii)部分エポキシ化ポリブタジエ
ン系高分子化合物に2級アミンを付加し、場合
によりさらに(メタ)アクリル酸もしくは不飽
和脂肪酸を反応させて得られるアミン化ポリブ
タジエン樹脂より選ばれたカチオン性フイルム
形成性水性樹脂を固形分換算100重量部、およ
び (B) フエノール類とホルムアルデヒドとを反応さ
せて得られるメチロールフエノール類を固形分
換算10〜250重量含む樹脂組成物を前記水性樹
脂(A)を中和する酸を含む水性媒体中に乳化し、
得られるエマルジヨンを前記メチロールフエノ
ールの反応温度以上の温度において加熱するこ
とを特徴とするカチオン性ゲル微粒子水分散液
の製造方法。 2 前記エマルジヨンの加熱が加圧下で行われる
第1項記載のカチオン性ゲル微粒子水分散液の製
造方法。 3 前記エマルジヨンが有機溶剤を含み、前記加
熱前に有機溶剤を除去する工程を含む第1項また
は第2項に記載のカチオン性ゲル微粒子水分散液
の製造方法。 4 前記水性樹脂(A)が、ビスフエノール系、脂肪
族系またはフエノールノボラツク系エポキシ樹脂
に1級または2級アミンを付加して得られるアミ
ン変性エポキシ樹脂である第1項ないし第3項の
いずれかに記載のカチオン性ゲル微粒子水分散液
の製造方法。 5 前記水性樹脂(A)が、 (1) 500〜5000の分子量で50〜500のヨウ素価の炭
素−炭素二重結合およびオキシラン酸素を3〜
12重量%有するエポキシ化ポリブタジエン系高
分子化合物に (2) 該高分子化合物100g当たり30〜300ミリモル
の、一般式 【式】 (式中、R1およびR2はヒドロキシル基で置換
されても良い炭素数1〜20の炭化水素基を表す
か、またはR1とR2は窒素および場合により他の
ヘテロ原子を含む環構造を表す。) で表されるアミン化合物を反応させ、さらに (3) 前記(1)の高分子化合物100g当たり0〜200ミ
リモルの、一般式 【式】 (式中R3は水素原子およびR4は水素原子また
はメチル基を表す。)で表されるα,β不飽和カ
ルボン酸あるいは分子量100〜350で炭素−炭素共
役二重結合を10重量%以上含む不飽和脂肪酸ある
いはそれらの混合物を反応させて得られる反応生
成物である第1項ないし第3項のいずれかに記載
のカチオン性ゲル微粒子水分散液の製造方法。[Scope of Claims] 1 (A) (i) Primary or secondary polyglycidyl compound
An amine-modified epoxy resin obtained by adding a secondary amine, or (ii) a partially epoxidized polybutadiene polymer compound obtained by adding a secondary amine and optionally further reacting with (meth)acrylic acid or unsaturated fatty acid. 100 parts by weight of a cationic film-forming aqueous resin selected from aminated polybutadiene resins, and (B) 10 to 250 parts by weight of methylolphenols obtained by reacting phenols with formaldehyde. emulsifying the resin composition containing the resin composition in an aqueous medium containing an acid that neutralizes the aqueous resin (A),
A method for producing an aqueous dispersion of cationic gel particles, which comprises heating the resulting emulsion at a temperature equal to or higher than the reaction temperature of the methylolphenol. 2. The method for producing an aqueous cationic gel particle dispersion according to item 1, wherein the emulsion is heated under pressure. 3. The method for producing an aqueous cationic gel particle dispersion according to item 1 or 2, wherein the emulsion contains an organic solvent and includes a step of removing the organic solvent before the heating. 4. Items 1 to 3, wherein the aqueous resin (A) is an amine-modified epoxy resin obtained by adding a primary or secondary amine to a bisphenol, aliphatic, or phenol novolak epoxy resin. Any method for producing an aqueous dispersion of cationic gel particles. 5 The aqueous resin (A) has (1) a carbon-carbon double bond with a molecular weight of 500 to 5000 and an iodine value of 50 to 500 and 3 to oxirane oxygen atoms;
(2) 30 to 300 mmol per 100 g of the polymer compound having 12% by weight of the general formula [Formula] (wherein R 1 and R 2 may be substituted with a hydroxyl group) (represents a hydrocarbon group having 1 to 20 carbon atoms, or R 1 and R 2 represent a ring structure containing nitrogen and optionally other heteroatoms), and further (3) 0 to 200 mmol per 100 g of the polymer compound of (1) above, an α,β amorphous compound represented by the general formula [formula] (wherein R 3 is a hydrogen atom and R 4 is a hydrogen atom or a methyl group). Any of Items 1 to 3, which is a reaction product obtained by reacting a saturated carboxylic acid, an unsaturated fatty acid having a molecular weight of 100 to 350 and containing 10% by weight or more of carbon-carbon conjugated double bonds, or a mixture thereof. A method for producing an aqueous dispersion of cationic gel particles as described in .
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62222687A JPS6465173A (en) | 1987-09-04 | 1987-09-04 | Preparation of aqueous dispersion of fine cationic gel particle |
EP87117595A EP0272500B1 (en) | 1986-11-28 | 1987-11-27 | Cationic micro gel praticle dispersion and a coating composition therefrom |
CA000552992A CA1301393C (en) | 1986-11-28 | 1987-11-27 | Cationic micro gel particle dispersion and a coating composition therefrom |
DE87117595T DE3785732T2 (en) | 1986-11-28 | 1987-11-27 | Dispersion of cationic microgel particles and coating composition thereof. |
KR1019870013491A KR950009546B1 (en) | 1986-11-28 | 1987-11-28 | 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 |
US07/126,963 US4788246A (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 |
---|---|---|---|
JP62222687A JPS6465173A (en) | 1987-09-04 | 1987-09-04 | Preparation of aqueous dispersion of fine cationic gel particle |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6465173A JPS6465173A (en) | 1989-03-10 |
JPH0575024B2 true JPH0575024B2 (en) | 1993-10-19 |
Family
ID=16786339
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP62222687A Granted JPS6465173A (en) | 1986-11-28 | 1987-09-04 | Preparation of aqueous dispersion of fine cationic gel particle |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6465173A (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5096556A (en) * | 1990-06-25 | 1992-03-17 | Ppg Industries, Inc. | Cationic microgels and their use in electrodeposition |
JP4735538B2 (en) * | 2004-05-17 | 2011-07-27 | 日本電気株式会社 | Electronics |
-
1987
- 1987-09-04 JP JP62222687A patent/JPS6465173A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS6465173A (en) | 1989-03-10 |
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