JPH01149864A - Room temperature curing emulsion coating - Google Patents
Room temperature curing emulsion coatingInfo
- Publication number
- JPH01149864A JPH01149864A JP30917787A JP30917787A JPH01149864A JP H01149864 A JPH01149864 A JP H01149864A JP 30917787 A JP30917787 A JP 30917787A JP 30917787 A JP30917787 A JP 30917787A JP H01149864 A JPH01149864 A JP H01149864A
- Authority
- JP
- Japan
- Prior art keywords
- emulsion
- polymer
- ethylenically unsaturated
- epoxy resin
- water
- 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
- 239000000839 emulsion Substances 0.000 title claims abstract description 105
- 239000011248 coating agent Substances 0.000 title abstract description 45
- 238000000576 coating method Methods 0.000 title abstract description 45
- 229920000642 polymer Polymers 0.000 claims abstract description 79
- 239000000178 monomer Substances 0.000 claims abstract description 52
- 239000003822 epoxy resin Substances 0.000 claims abstract description 46
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 46
- 239000002245 particle Substances 0.000 claims abstract description 31
- 125000003277 amino group Chemical group 0.000 claims abstract description 12
- 239000003973 paint Substances 0.000 claims description 61
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 35
- 239000004908 Emulsion polymer Substances 0.000 claims description 25
- 238000004132 cross linking Methods 0.000 abstract description 19
- 238000003860 storage Methods 0.000 abstract description 9
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 abstract description 4
- 230000000379 polymerizing effect Effects 0.000 abstract description 4
- 229920001577 copolymer Polymers 0.000 abstract description 3
- 239000004844 aliphatic epoxy resin Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 50
- 239000000203 mixture Substances 0.000 description 47
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- 230000000052 comparative effect Effects 0.000 description 28
- 238000000034 method Methods 0.000 description 23
- 238000012360 testing method Methods 0.000 description 22
- 238000001035 drying Methods 0.000 description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 13
- 238000001723 curing Methods 0.000 description 13
- 239000003995 emulsifying agent Substances 0.000 description 12
- 230000000704 physical effect Effects 0.000 description 12
- 238000010998 test method Methods 0.000 description 12
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 239000000049 pigment Substances 0.000 description 11
- 238000009472 formulation Methods 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 9
- -1 amino compound Chemical class 0.000 description 9
- 230000007423 decrease Effects 0.000 description 9
- 239000003999 initiator Substances 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 239000003513 alkali Substances 0.000 description 8
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000002585 base Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 5
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 4
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- 239000004923 Acrylic lacquer Substances 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000003282 alkyl amino group Chemical group 0.000 description 3
- 239000010425 asbestos Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052895 riebeckite Inorganic materials 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 239000004846 water-soluble epoxy resin Substances 0.000 description 3
- 230000002087 whitening effect Effects 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- DWKNOLCXIFYNFV-HSZRJFAPSA-N 2-[[(2r)-1-[1-[(4-chloro-3-methylphenyl)methyl]piperidin-4-yl]-5-oxopyrrolidine-2-carbonyl]amino]-n,n,6-trimethylpyridine-4-carboxamide Chemical compound CN(C)C(=O)C1=CC(C)=NC(NC(=O)[C@@H]2N(C(=O)CC2)C2CCN(CC=3C=C(C)C(Cl)=CC=3)CC2)=C1 DWKNOLCXIFYNFV-HSZRJFAPSA-N 0.000 description 2
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical group OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 108010039491 Ricin Proteins 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- 229920003180 amino resin Polymers 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 239000006115 industrial coating Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- BIIBYWQGRFWQKM-JVVROLKMSA-N (2S)-N-[4-(cyclopropylamino)-3,4-dioxo-1-[(3S)-2-oxopyrrolidin-3-yl]butan-2-yl]-2-[[(E)-3-(2,4-dichlorophenyl)prop-2-enoyl]amino]-4,4-dimethylpentanamide Chemical compound CC(C)(C)C[C@@H](C(NC(C[C@H](CCN1)C1=O)C(C(NC1CC1)=O)=O)=O)NC(/C=C/C(C=CC(Cl)=C1)=C1Cl)=O BIIBYWQGRFWQKM-JVVROLKMSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-NMQOAUCRSA-N 1,2-dideuteriooxyethane Chemical compound [2H]OCCO[2H] LYCAIKOWRPUZTN-NMQOAUCRSA-N 0.000 description 1
- JLPULHDHAOZNQI-ZTIMHPMXSA-N 1-hexadecanoyl-2-(9Z,12Z-octadecadienoyl)-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCCCCCC\C=C/C\C=C/CCCCC JLPULHDHAOZNQI-ZTIMHPMXSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- ULEVTQHCVWIDPC-UHFFFAOYSA-N 2-(methylamino)ethyl prop-2-enoate Chemical compound CNCCOC(=O)C=C ULEVTQHCVWIDPC-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- JWCDUUFOAZFFMX-UHFFFAOYSA-N 2-ethenoxy-n,n-dimethylethanamine Chemical compound CN(C)CCOC=C JWCDUUFOAZFFMX-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical group OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical class C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 1
- RSIWALKZYXPAGW-NSHDSACASA-N 6-(3-fluorophenyl)-3-methyl-7-[(1s)-1-(7h-purin-6-ylamino)ethyl]-[1,3]thiazolo[3,2-a]pyrimidin-5-one Chemical compound C=1([C@@H](NC=2C=3N=CNC=3N=CN=2)C)N=C2SC=C(C)N2C(=O)C=1C1=CC=CC(F)=C1 RSIWALKZYXPAGW-NSHDSACASA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- PPKRCJXSSVFUAJ-UHFFFAOYSA-N C(C(=C)CC(=O)O)(=O)O.S(O)(O)(=O)=O Chemical compound C(C(=C)CC(=O)O)(=O)O.S(O)(O)(=O)=O PPKRCJXSSVFUAJ-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- MWHHJYUHCZWSLS-UHFFFAOYSA-N FC=1C=C(C=CC1C1=C2CNC(C2=C(C=C1)C=1NC(=CN1)C)=O)NC(=O)NC1=C(C=C(C=C1F)F)F Chemical compound FC=1C=C(C=CC1C1=C2CNC(C2=C(C=C1)C=1NC(=CN1)C)=O)NC(=O)NC1=C(C=C(C=C1F)F)F MWHHJYUHCZWSLS-UHFFFAOYSA-N 0.000 description 1
- 241000425362 Hydrium Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
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- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012615 aggregate Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 239000012874 anionic emulsifier Substances 0.000 description 1
- 239000007798 antifreeze agent Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 150000001674 calcium compounds Chemical class 0.000 description 1
- 239000011083 cement mortar Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- FSQQTNAZHBEJLS-UPHRSURJSA-N maleamic acid Chemical compound NC(=O)\C=C/C(O)=O FSQQTNAZHBEJLS-UPHRSURJSA-N 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 150000004027 organic amino compounds Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical compound C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229940083466 soybean lecithin Drugs 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はエポキシ樹脂を粒子内部に含み、且つ、粒子外
層にこのエポキシ樹脂の架橋促進剤或は架橋点ともなシ
得るアミノ基を有する共重合体を含む、常温で架橋する
重合体エマルジョンをビヒクルとするエマルジョン塗料
に関する。Detailed Description of the Invention [Industrial Field of Application] The present invention is directed to a copolymer containing an epoxy resin inside the particles and having an amino group in the outer layer of the particles that can act as a crosslinking accelerator or a crosslinking point for the epoxy resin. The present invention relates to an emulsion paint whose vehicle is a polymer-containing polymer emulsion that crosslinks at room temperature.
現在、糧々の重合体エマルジョンがエマルジョン塗料の
ビヒクルとして用いられており、ビヒクルとして用いら
れる重合体エマルジョンを何らかの方法で架橋すること
Kよって、塗膜の耐久性をよシ向上させることも周知で
、既に種々の架橋の方法が提唱され、一部は実用的に行
われている。Currently, many polymer emulsions are used as vehicles for emulsion paints, and it is well known that the durability of paint films can be improved by crosslinking the polymer emulsions used as vehicles by some method. Various cross-linking methods have already been proposed, and some have already been put into practical use.
これらの架橋方法として最もよく知られ、また実用化さ
れているものにN−メチロールアクリルアミド、アクリ
ルアミド、β−ヒドロキシエチルアクリレートなどの各
種反応基を持った単量体を共重合した重合体エマルジョ
ンにメラミン樹脂の如きアミノプラストを配合して架橋
するものがある。The most well-known and practically used crosslinking method is to add melamine to a polymer emulsion made by copolymerizing monomers with various reactive groups such as N-methylol acrylamide, acrylamide, and β-hydroxyethyl acrylate. There are some that are crosslinked by blending aminoplasts such as resins.
しかし、この場合は常温での乾燥では殆んど架橋が行な
われないので、加熱乾燥が可能な工業塗装などの用途に
使用が限定されている。ところでエマルジョン塗料が最
も多く用いられる建築塗料では常温乾燥で塗装されるが
、常温で架橋できるものとして、カルボキシル基含有単
量体を共重合したカル?キシル化重合体エマルジョ/に
亜鉛華などの多価金属塩を加えて、カルボキシル基と金
属イオンとをイオン架橋する方法が比較的よく行われて
いる。しかしながら、この場合は、水、アルカリなどに
よって加水分解し易い欠点があシ、このため一般にエマ
ルジョン塗料がよく用いられるモルタル、コンクリート
などの基材への塗装では充分な効果が発揮されず、むし
ろアルカリで加水分解し7て塗膜の剥離可能な性質を利
用するフロア−・ポリッシュなどに供されている。However, in this case, almost no crosslinking occurs when drying at room temperature, so its use is limited to applications such as industrial coatings that can be dried by heating. By the way, emulsion paints are the most commonly used architectural paints and are applied by drying at room temperature, but carboxyl group-containing monomers are copolymerized with carboxyl group-containing monomers, which can be crosslinked at room temperature. A relatively common method is to add a polyvalent metal salt such as zinc white to a xylated polymer emulsion to ionically crosslink carboxyl groups and metal ions. However, in this case, it has the disadvantage that it is easily hydrolyzed by water, alkali, etc., and for this reason, it is not sufficiently effective when applied to base materials such as mortar and concrete, for which emulsion paints are often used; It is hydrolyzed and used in floor polishes and other products that take advantage of the removable properties of the paint film.
これに対し、カルボキシル化重合体エマルジョンにエポ
キシ樹脂の乳化分散体あるいは水溶性エポキシ樹脂を混
合配合して架橋する方法も行なわれておシ、エポキシ樹
脂のグリシジル基と重合体中のカルボキシル基が有機ア
ミノ化合物を促進剤として架橋反応することが知られて
いる。On the other hand, a method of crosslinking by mixing and blending an emulsified dispersion of epoxy resin or a water-soluble epoxy resin with a carboxylated polymer emulsion has been carried out, in which the glycidyl groups of the epoxy resin and the carboxyl groups in the polymer It is known that a crosslinking reaction can be carried out using an amino compound as a promoter.
ところが上記の如きエポキシ樹脂の乳化分散体あるいは
水溶性エポキシ樹脂とカル?キシル化乳化重合体の併用
による架橋方法も、配合物の安定性に制限があり、いわ
ゆるポット・ライフが問題となる。このため、一般にエ
ポキシ樹脂および/または架橋促進剤を使用時に添加、
混合して用いる二液型となっておシ、使用時の作業性が
劣るという欠点がある。However, if the emulsified dispersion of epoxy resin or water-soluble epoxy resin and Cal? A crosslinking method using a xylated emulsion polymer in combination also has limitations in the stability of the formulation, and poses a problem of so-called pot life. For this reason, epoxy resins and/or crosslinking accelerators are generally added at the time of use.
It is a two-component type that is mixed and used, but it has the disadvantage of poor workability during use.
また、エポキシ樹脂の乳化分散体を用いる場合は、エポ
キシ樹脂およびカルボキシル化重合体が、それぞれ別の
粒子となっているため、粒子表面に吸着して分散粒子を
安定化させている乳化剤層などの影響によシ充分な架橋
が行われないことがあシ、一方、水溶性のエポキシ樹脂
を用いた場合は、このような問題が少ないかわシに配合
物の安定性が低下し、ポット・ライフが短くなシ、取扱
い上、問題点がある。In addition, when using an emulsified dispersion of epoxy resin, the epoxy resin and carboxylated polymer are separate particles, so an emulsifier layer that stabilizes the dispersed particles by adsorbing to the particle surface is used. On the other hand, when a water-soluble epoxy resin is used, this problem is less likely to occur, but the stability of the formulation decreases and the pot life is shortened. There are problems in handling as the length is short.
このような問題点を解決する方法として、例えば特公昭
59−52188号公報に、工2キシ化合物の存在下に
、特に、エチレンと酢酸ビニルを乳化共重合して工?キ
シ樹脂含有エチレンー酢酸ビニル共重合体エマルジョン
を製造し、これを顔料分散液と配合し、次いで通常使用
前に有機アミノ化合物の硬化促進剤を加えて塗料として
用いると良いことが述べられている。この場合、分散状
態にあるエチレン−酢酸ビニル共重合体粒子にエポキシ
化合物が均一に存在し、しかも粒子中のエポキシ化合物
がエチレン−酢酸ビニル共重合体によって保護されてい
ることによシ硬化促進剤を加えてもポットライフが長く
、且つ、良好な塗膜性能が得られるであろうことも示さ
れている。しかしながら、この方法においても硬化促進
剤を使用前に添加して使用しなければならないという、
いわゆる二液型塗料となるため、塗装現場での二液の混
合という作業の繁雑さがあシ、又、水不溶性のアミノ樹
脂を水分散型とした硬化促進剤を用いた場合、特に、エ
ポキシ樹脂含有重合体エマルジョンと水分散型硬化促進
剤との粒子状態での混合となるため、重合体と硬化促進
剤との相溶性が充分でないと塗膜性能が不充分となる可
能性があシ、更に、水溶性である低分子量アミノ化合物
の硬化促進剤を用いた場合は、セメントモルタル、コン
クリートなどの多孔質基材へ塗料を塗装した場合に水の
基材への浸透に伴い、水に溶解している硬化剤も一緒に
浸透してしまったり、又、低分子量のものであれば乾燥
時に蒸発して失われることもあシ、充分な性能を発揮し
得ない欠点がある。As a method for solving such problems, for example, Japanese Patent Publication No. 59-52188 discloses a method of emulsion copolymerizing ethylene and vinyl acetate in the presence of a polyvinyloxy compound. It is stated that it is good to produce an ethylene-vinyl acetate copolymer emulsion containing a xyl resin, blend it with a pigment dispersion, and then add a curing accelerator of an organic amino compound before use as a paint. In this case, the epoxy compound exists uniformly in the ethylene-vinyl acetate copolymer particles in a dispersed state, and the epoxy compound in the particles is protected by the ethylene-vinyl acetate copolymer. It has also been shown that the pot life will be longer and better coating performance will be obtained even if . However, even in this method, a curing accelerator must be added before use.
Since it is a so-called two-component paint, the work of mixing the two components at the painting site is complicated, and when a curing accelerator made of water-insoluble amino resin is used, it is especially difficult to use epoxy resin. Since the resin-containing polymer emulsion and the water-dispersed curing accelerator are mixed in the form of particles, there is a risk that the coating film performance will be insufficient if the polymer and curing accelerator are not sufficiently compatible. Furthermore, when a water-soluble low molecular weight amino compound curing accelerator is used, when a paint is applied to a porous base material such as cement mortar or concrete, water permeates into the base material and Dissolved curing agents may permeate along with the curing agent, and if it has a low molecular weight, it may evaporate and be lost during drying, resulting in the disadvantage that sufficient performance cannot be achieved.
本発明はとのような問題を解決すべくなされたものであ
シ、−液型で用いることができ、安定で、貯蔵安定性に
優れ、かつ常温でも良好な架橋塗膜が得られる常温硬化
性エマルジョン塗料を提供することを目的とする。The present invention was made to solve the following problems: - A room-temperature curing method that can be used in liquid form, is stable, has excellent storage stability, and provides a good crosslinked coating film even at room temperature. The purpose of the present invention is to provide emulsion paints with high compatibility.
本発明は、(IL)アミノ基を分子中に含まないエチレ
ン性不飽和単量体を水不溶性のエポキシ樹脂の存在下に
乳化重合させて種粒子たる乳化重合体を製造し、次いで
(b)前記乳化重合体の存在下で、アミノ基を含有する
エチレン性不飽和単量体およびこれと共重合可能な他の
エチレン性不飽和単量体を乳化重合させて得られる重合
体エマルジ璽ンをビヒクルとする常温硬化性エマルジョ
ン塗料である。In the present invention, (IL) an ethylenically unsaturated monomer that does not contain an amino group in its molecule is emulsion polymerized in the presence of a water-insoluble epoxy resin to produce an emulsion polymer as seed particles, and then (b) A polymer emulsion obtained by emulsion polymerizing an ethylenically unsaturated monomer containing an amino group and another ethylenically unsaturated monomer copolymerizable therewith in the presence of the emulsion polymer. It is an emulsion paint that cures at room temperature as a vehicle.
本発明において用いる重合体エマルジョンは前記の(a
) 、 (b)工程によって得られることから同一の乳
化微粒子内K、架橋剤である水不溶性エポキシ樹脂を含
有する部分と、架橋促進剤或いは架橋点ともな)得るア
ミノ基含有エチレン性不飽和単量体を構成単位として含
有する部分とを層構造として含むことを特徴とするもの
であ)、この層構造によって一液型で使用可能で、かつ
安定な乳化重合体が提供される。The polymer emulsion used in the present invention is the above-mentioned (a)
) and (b) are obtained in the same emulsified fine particles, the part containing the water-insoluble epoxy resin as a crosslinking agent, and the amino group-containing ethylenically unsaturated monomer (which also serves as a crosslinking accelerator or crosslinking point). This layered structure provides a stable emulsion polymer that can be used in one-component form.
以下に本発明で用いる重合体エマルジョンの構成を更に
詳細に説明する。The structure of the polymer emulsion used in the present invention will be explained in more detail below.
重合体エマルジョンの製造において種粒子として用いら
れる、水不溶性エポキシ樹脂含有乳化重合体は、水不溶
性エポキシ樹脂を乳化重合に用いるエチレン性不飽和単
量体に溶解した後、公知の方法で乳化重合することによ
シ容易に得られる。The water-insoluble epoxy resin-containing emulsion polymer used as seed particles in the production of a polymer emulsion is obtained by dissolving the water-insoluble epoxy resin in an ethylenically unsaturated monomer used for emulsion polymerization, and then emulsion polymerizing it by a known method. In particular, it is easily obtained.
他の方法としては乳化剤を含む水相中に水不溶性のエポ
キシ樹脂を加えて分散した後、エチレン性不飽和単量体
を加えつつ乳化重合することもできる。Another method is to add and disperse a water-insoluble epoxy resin in an aqueous phase containing an emulsifier, and then perform emulsion polymerization while adding an ethylenically unsaturated monomer.
ここで、エチレン性不飽和単量体と水不溶性エポキシ樹
脂の重量比率は100:100〜100:5が望ましく
、エポキシ樹脂がこれ以上多くなると、乳化重合体粒子
中にとり込まれないエポキシ樹脂が多くなシ、生成した
乳化重合体の安定性が低下し、また乳化重合中の凝集物
の発生も多くなるという問題を生ずる。一方、エポキシ
樹脂の比率が少なくなると、最終エマルジョン中のエポ
キシ樹脂、含量も当然少なくなるので、充分な架橋効果
が得られなくなる。Here, the weight ratio of the ethylenically unsaturated monomer and the water-insoluble epoxy resin is preferably 100:100 to 100:5; if the epoxy resin exceeds this value, a large amount of the epoxy resin will not be incorporated into the emulsion polymer particles. Otherwise, problems arise in that the stability of the produced emulsion polymer decreases and the occurrence of aggregates increases during emulsion polymerization. On the other hand, if the ratio of the epoxy resin decreases, the content of the epoxy resin in the final emulsion will naturally decrease, making it impossible to obtain a sufficient crosslinking effect.
水不溶性のエポキシ樹脂としては市販品の主要タイプで
あるエピクロルヒドリン−ビスフェノールA型エポキシ
樹脂が最も有用であるが、グリシジル基を2個以上有し
、かつ、水に不溶ないしは難溶性で、エチレン性不飽和
単量体のいずれかに可溶であれば使用することができ、
これらとしては脂肪族系エポキシ樹脂、エポキシ化ウレ
タン樹脂なども有用である。The most useful water-insoluble epoxy resin is epichlorohydrin-bisphenol A type epoxy resin, which is the main type of commercially available epoxy resin. Can be used if it is soluble in any of the saturated monomers,
As these, aliphatic epoxy resins and epoxidized urethane resins are also useful.
水溶性ないしは親水性の大なるエポキシ樹脂は、本発明
では乳化重合体粒子中にとシ込まれ難く、水相中に存在
するか、重合体粒子表面に存在し易くなるので使用でき
ない。Epoxy resins that are highly water-soluble or hydrophilic cannot be used in the present invention because they are difficult to penetrate into the emulsion polymer particles and tend to exist in the aqueous phase or on the surface of the polymer particles.
次に、(b)工程である第2段目の乳化重合で用いられ
るアミノ基含有エチレン性不飽和単量体としてはN−メ
チルアミノエチルアクリレートまたはメタクリレート、
ジメチルアミノエチルアクリレートまたはメタクリレー
トなどのアクリル酸またはメタクリル酸のアルキルアミ
ノエステル類、ビニルピリジンの如きモノビニルピリジ
ン類、ジメチルアミノエチルビニルエーテルの如きアル
キルアミノ基を有するビニルエーテル類、N−(2−ジ
メチルアミノエチル)アクリルアミドまたはメタクリル
アミドの如きアルキルアミノ基を有する不飽和アミド類
などかあシ、これらのうち、特にジメチルアミノエチル
アクリレートまたはメタクリレートが、他のエチレン性
不飽和単量体との共重合には有用である。Next, as the amino group-containing ethylenically unsaturated monomer used in the second stage emulsion polymerization, which is step (b), N-methylaminoethyl acrylate or methacrylate,
Alkylamino esters of acrylic acid or methacrylic acid such as dimethylaminoethyl acrylate or methacrylate, monovinylpyridines such as vinylpyridine, vinyl ethers having an alkylamino group such as dimethylaminoethyl vinyl ether, N-(2-dimethylaminoethyl) Among these, dimethylaminoethyl acrylate or methacrylate are particularly useful for copolymerization with other ethylenically unsaturated monomers, such as unsaturated amides having an alkylamino group such as acrylamide or methacrylamide. be.
これらのアミノ基含有エチレン性不飽和単量体は第2段
目の乳化重合において用いられるエチレン性不飽和単量
体中に1〜25重量%の比率で用いるが、これよ多少な
い共重合量では架橋促進剤としての作用が不充分であシ
、一方、これよシ多い使用量では、これらのアミノ基含
有エチレン性不飽和単量体が親水性が強いため、共重合
体の親水性も大となり、得られる乳化重合体皮膜の耐水
性が低下するという欠点を生ずる。These amino group-containing ethylenically unsaturated monomers are used at a ratio of 1 to 25% by weight in the ethylenically unsaturated monomers used in the second stage emulsion polymerization, but the amount of copolymerization is less than this. On the other hand, when used in a larger amount, these amino group-containing ethylenically unsaturated monomers have strong hydrophilic properties, so the hydrophilicity of the copolymer also decreases. This results in a drawback that the water resistance of the resulting emulsion polymer film decreases.
エチレン性不飽和単量体の一部としてエチレン性不飽和
カルボン酸を用いて共重合することは後述する理由から
も重要であるが、エチレン性不飽和カルボン酸はこの種
粒子製造の段階(、)で用いてもよいし、次の乳化重合
の段階(b)で用いてもよく、さらに両方に用いてもよ
い。Copolymerization using ethylenically unsaturated carboxylic acid as part of the ethylenically unsaturated monomer is important for the reasons described below, but ethylenically unsaturated carboxylic acid is ), it may be used in the next emulsion polymerization step (b), or it may be used in both.
このように(a)工程および/または(b)工程のエチ
レン性不飽和単量体中に重要成分として用いられるエチ
レン性不飽和カルボン酸としては、アクリル酸、メタク
リル酸、クロトン酸の如きエチレン性不飽和−塩基性カ
ルポン酸、イタコン酸、マレイン酸、フマル酸の如きエ
チレン性不飽和二塩基性カルぎン醸があシ、これらの一
種または二種以上が用いられる。iた、エチレン性不飽
和二塩基性カルデン酸のモノアルキルエステルも使用す
ることができる。As described above, the ethylenically unsaturated carboxylic acids used as important components in the ethylenically unsaturated monomer in step (a) and/or (b) include ethylenic acids such as acrylic acid, methacrylic acid, and crotonic acid. Ethylenically unsaturated dibasic carboxylic acids such as unsaturated-basic carboxylic acid, itaconic acid, maleic acid, and fumaric acid, and one or more of these are used. Additionally, monoalkyl esters of ethylenically unsaturated dibasic caldic acids can also be used.
これらのエチレン性不飽和カルボン酸の使用はエポキシ
樹脂との架橋点となる他、周知の如く乳化重合体の機械
的安定性の向上にも効果があシ、一方、前記のアミノ基
も一部エポキシ樹脂との架橋点ともなシ得るので、使用
量は必ずしもエポキシ樹脂の反応基と当量関係にある必
要はないが、種粒子の乳化重合工程(、)および次段階
の乳化重合工程(b)における各エチレン性不飽和単量
体の合計量の1〜10重量係であシ、これよシ少ない量
では、良好な架橋効果が得られず、またこれよシ多くな
ると生成乳化重合体皮膜の耐水性、耐アルカリ性が低下
するので好ましくない、また、これらのエチレン性不飽
和カル?ン酸は本発明では種粒子の乳化重合時または次
段階の乳化重合時あるいはその両方で用いられる。The use of these ethylenically unsaturated carboxylic acids not only serves as a crosslinking point with the epoxy resin, but also has the effect of improving the mechanical stability of emulsion polymers, as is well known. Since the crosslinking point with the epoxy resin is also available, the amount used does not necessarily have to be in an equivalent relationship with the reactive group of the epoxy resin, but the amount used is not necessarily in an equivalent relationship with the reactive group of the epoxy resin. If the amount is less than 1 to 10% by weight of the total amount of each ethylenically unsaturated monomer in These ethylenically unsaturated calcium compounds are undesirable because they reduce water resistance and alkali resistance. In the present invention, phosphoric acid is used during the emulsion polymerization of seed particles and/or during the subsequent emulsion polymerization.
本発明の重合体エマルジョンに用いられるその他のエチ
レン性不飽和単量体としてはアクリル酸メチル、アクリ
ル酸エチル、アクリル酸ブチル等のアクリル酸エステル
類;メタクリル酸メチル、メタクリル酸エチル等のメタ
クリル酸エステル類;マレイン酸、フマル酸、4タコン
酸ノ各エステル類;酢酸ビニル、ゾロピオン酸ビニル、
第3級カルボン酸ビニル等のビニルエステル類;スチレ
ン、ビニルトルエンの如き芳香族ビニル化合物、ビニル
ピロリドンの如き複素環式ビニル化合物;塩化ビニル、
アクリロニトリル、ビニルエーテル、ビニルケトン、ビ
ニルアミド等;塩化ビニリデン、フッ化ビニリデン等ハ
ロゲン化ビニリデン化合物;エチレン、プロピレン等の
α−オレフィン類;ブタジェンの如きジエン類などかあ
シ、また、所望によジアクリルアミド、メタクリルアミ
ド、マレイン酸アミド等のα、β−エチレン性不飽和酸
のアミド類;N−メチロールアクリルアミドまたはメタ
クリルアミド、ジアセトンアクリルアミド等の不飽和カ
ルデン酸の置換アミド;ジアリルフタレー)、ジビニル
ベンゼン、アリルアクlJL/−)、トリメチロールプ
ロノぐントリメタクリレートの如き1分子中に2個以上
の不飽和結合を有する単量体なども用いることができる
。さらに、ビニルスルホン酸、スチレンスルホン酸、ア
リルアルキルイタコネート硫酸エステルなどの不飽和基
とスルホン酸基、サルフェート基を有するものおよびこ
れらのアルカリ塩も使用することができる。Other ethylenically unsaturated monomers used in the polymer emulsion of the present invention include acrylic esters such as methyl acrylate, ethyl acrylate, and butyl acrylate; methacrylic esters such as methyl methacrylate and ethyl methacrylate. esters of maleic acid, fumaric acid, and tetraconic acid; vinyl acetate, vinyl zolopionate,
Vinyl esters such as tertiary vinyl carboxylate; aromatic vinyl compounds such as styrene and vinyltoluene; heterocyclic vinyl compounds such as vinylpyrrolidone; vinyl chloride;
Acrylonitrile, vinyl ether, vinyl ketone, vinylamide, etc.; halogenated vinylidene compounds such as vinylidene chloride, vinylidene fluoride; α-olefins such as ethylene and propylene; dienes such as butadiene, etc. Amides of α, β-ethylenically unsaturated acids such as amide and maleic acid amide; substituted amides of unsaturated caldenic acids such as N-methylol acrylamide or methacrylamide, diacetone acrylamide; diallylphthale), divinylbenzene, allyl acrylate Monomers having two or more unsaturated bonds in one molecule, such as trimethylolpronotrimethacrylate, etc., can also be used. Furthermore, those having an unsaturated group, a sulfonic acid group, a sulfate group, such as vinyl sulfonic acid, styrene sulfonic acid, allyl alkyl itaconate sulfate, and alkali salts thereof can also be used.
次に本発明に用いられる重合体エマルジョンの乳化重合
方法について述べる。Next, a method for emulsion polymerization of the polymer emulsion used in the present invention will be described.
種粒子となる水不溶性のエポキシ樹脂を含む乳化重合体
は水中で乳化剤の存在下、エポキシ樹脂を溶解したエチ
レン性不飽和単量体混合物からラジカル生成開始剤を用
いて公知の乳化重合方法で製造する。また、他の方法と
して乳化剤を溶解した水相中にエポキシ樹脂を加えて乳
化分散後、エチレン性不飽和単量体混合物およびラジカ
ル生成開始剤を加えて公知の方法で乳化重合してもよい
。An emulsion polymer containing a water-insoluble epoxy resin serving as seed particles is produced by a known emulsion polymerization method using a radical generation initiator from an ethylenically unsaturated monomer mixture in which an epoxy resin is dissolved in water in the presence of an emulsifier. do. Alternatively, an epoxy resin may be added to an aqueous phase in which an emulsifier is dissolved, and after emulsion dispersion, an ethylenically unsaturated monomer mixture and a radical generation initiator may be added, and emulsion polymerization may be carried out by a known method.
次いで、前記で得られた乳化重合体を水相に加え、″同
様にエチレン性不飽和単量体混合物およびラジカル生成
開始剤を加えて公知の方法で乳化重合することによシ重
合体エマルジョンが製造される。この場合、乳化重合中
の凝集物の生成の防止など、重合系の安定化のために種
粒子の乳化重合体に加えて乳化剤をさらに追加して加え
てもよい。Next, the emulsion polymer obtained above is added to the aqueous phase, an ethylenically unsaturated monomer mixture and a radical generation initiator are added in the same manner, and emulsion polymerization is carried out by a known method to form a polymer emulsion. In this case, an additional emulsifier may be added in addition to the emulsion polymer of the seed particles to stabilize the polymerization system, such as to prevent the formation of aggregates during emulsion polymerization.
上記は種粒子を別途製造し、それを用いて次段階にて乳
化重合する方法であるが、この他、同一反応装置内で種
粒子に相当する乳化重合体を製造し、続けて、その系内
へ次段階の乳化重合で用いるエチレン性不飽和単量体混
合物およびラジカル生成開始剤を加えて乳化重合する方
法にて製造することもできる。即ち、乳化剤を溶解した
水相中で、種粒子となるエチレン性不飽和単量体混合物
をエポキシ樹脂の存在下、ラジカル生成開始剤を用いて
乳化重合した後、次段階のエチレン性不飽和単量体混合
物およびラジカル生成開始剤を加えて乳化重合して本発
明に用いられる重合体エマルジョンが得られる。The above method is a method in which seed particles are separately produced and used for emulsion polymerization in the next step. It can also be produced by emulsion polymerization by adding an ethylenically unsaturated monomer mixture and a radical generation initiator to be used in the next step of emulsion polymerization. That is, in an aqueous phase in which an emulsifier is dissolved, an ethylenically unsaturated monomer mixture serving as seed particles is emulsion polymerized using a radical generation initiator in the presence of an epoxy resin, and then the ethylenically unsaturated monomer mixture in the next step is polymerized using a radical generation initiator. A polymer emulsion used in the present invention is obtained by adding a polymer mixture and a radical generation initiator and carrying out emulsion polymerization.
水不溶性のエポキシ樹脂二種粒子の製造工程(、)と後
段乳化重合工程(b)における全エチレン性不飽和単量
体の重量比率は2:100〜50〜100とする必要が
ある。エポキシ樹脂が2:100より少ないと充分な架
橋効果が得られず、また、50:100よシ多くなると
生成乳化重合体の安定性が低下したシ、未反応のエポキ
シ樹脂の残存によシ、乳化重合体よシ得られたフィルム
が過剰に柔かくなるという欠点を生ずる。The weight ratio of all ethylenically unsaturated monomers in the water-insoluble epoxy resin second particle production process (2) and the latter stage emulsion polymerization process (b) needs to be 2:100 to 50 to 100. When the ratio of epoxy resin is less than 2:100, a sufficient crosslinking effect cannot be obtained, and when the ratio is more than 50:100, the stability of the resulting emulsion polymer decreases, and unreacted epoxy resin remains. Emulsion polymers have the disadvantage that the resulting film is excessively soft.
本発明で用いる重合体エマルジョンの製造時に乳化剤と
して用いられるものとしては、アルキルベンゼンスルホ
ン酸ソーダ、2ウリル硫酸ソーダ、ナトリウムジオクチ
ルスルホサクシネート、アルキルフェニルポリオキシエ
チレンサル7エートソーダ塩またはアンモニウム塩など
のアニオン性乳化剤、ホリオキシエチレンアルキルフェ
ニルエーテル、ポリオキシエチレンアルキルエーテル、
ポリオキシエチレン−4リオキシプロピレンブロツク共
重合体など通常乳化重合に用いられているものがあげら
れる。乳化剤の使用量は種粒子となる乳化重合体の乳化
重合工程(、)においては水不溶性エポキシ樹脂とエチ
レン性不飽和単量体の合計重量に対して0.5〜15重
量%の範囲て使用するのが好ましい、乳化剤量がこれよ
シ多くなると最終重合体エマルジョンの耐水性の低下を
もたらす場合があるので好ましくなく、またこれよシ少
ない乳化剤量では乳化重合時の安定性、生成乳化重合体
の安定性が低下する場合がある。さらに、次段の乳化重
合工程(b)における乳化剤の追加使用量は、種粒子の
乳化重合体固形分重量に対し10重量%以下にすること
が、新たな別粒子の生成を少なくする点から望ましい。Examples of emulsifiers used in the production of the polymer emulsion used in the present invention include anionic compounds such as sodium alkylbenzene sulfonate, sodium diuryl sulfate, sodium dioctyl sulfosuccinate, and alkylphenyl polyoxyethylene sulfate sodium salt or ammonium salt. Emulsifier, phoroxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether,
Examples include those commonly used in emulsion polymerization, such as polyoxyethylene-4-lioxypropylene block copolymers. The amount of emulsifier used is in the range of 0.5 to 15% by weight based on the total weight of the water-insoluble epoxy resin and ethylenically unsaturated monomer in the emulsion polymerization process (,) of the emulsion polymer that becomes the seed particles. It is preferable to use a larger amount of emulsifier, since this may result in a decrease in the water resistance of the final polymer emulsion, and a smaller amount of emulsifier may result in poor stability during emulsion polymerization and poor stability of the resulting emulsion polymer. stability may decrease. Furthermore, the additional amount of emulsifier used in the next emulsion polymerization step (b) should be 10% by weight or less based on the solid weight of the emulsion polymer in the seed particles, in order to reduce the generation of new particles. desirable.
また重合体エマルジョンを得るための乳化重合において
用いられるラジカル生成開始剤としては、通常の乳化重
合に用いられているもの艇使用されるが、これらとして
は過硫酸カリウム、過硫酸アンモニウム、アゾビスイソ
ブチルニトリルおよびその゛塩酸塩などがあげられ、ま
たクメンハイドロA?−オキサイド、t@rt−ブチル
ハイドロパーオキサイドなどの有機過酸化物も必要に応
じて使用することができる。さらに、これらの過硫酸塩
または過酸化物と鉄イオンなどの金属イオンおよびナト
リウムスルホオキシレートホルムアルデヒド、ピロ亜硫
酸ソーダ、L−アスコルビン酸などの還元剤を組合わせ
て用いる公知のレドックス系開始剤も用いることができ
る。In addition, as the radical generation initiator used in emulsion polymerization to obtain a polymer emulsion, those used in ordinary emulsion polymerization are used, and these include potassium persulfate, ammonium persulfate, and azobisisobutylnitrile. and its hydrochloride, and cumene hydro A? -oxide, t@rt-butyl hydroperoxide, and other organic peroxides can also be used if necessary. Furthermore, a known redox initiator is also used in which these persulfates or peroxides are used in combination with metal ions such as iron ions and reducing agents such as sodium sulfooxylate formaldehyde, sodium pyrosulfite, and L-ascorbic acid. be able to.
乳化重合時の濃度は、実用的な観点よシ、最終エマルジ
ョンが25〜65重量%の固形分濃度となるようにする
のがよく、また反応系へのエチレン性不飽和単量体およ
びラジカル生成開始剤は一括仕込み、連続滴下、分割添
加など公知のいずれの方法でも行うことがモきる。From a practical point of view, the concentration during emulsion polymerization is preferably such that the final emulsion has a solid content concentration of 25 to 65% by weight, and also to prevent the formation of ethylenically unsaturated monomers and radicals in the reaction system. The initiator can be added by any known method such as batch charging, continuous dropwise addition, and divided addition.
乳化重合時の温度も、公知の乳化重合で行われている範
囲でよく、また乳化重合は常圧下、またはガス状のエチ
レン性不飽和単量体を使用するときは加圧下で行われる
。The temperature during emulsion polymerization may be within the range used in known emulsion polymerizations, and the emulsion polymerization is performed under normal pressure or under pressure when a gaseous ethylenically unsaturated monomer is used.
本発明の常温硬化性エマルジョン塗料は、上記に特定し
た重合体エマルジョンをビヒクルとして通常のエマルジ
、ン塗料の製造と全く同様にして製造される。即ち、顔
料、充填剤、骨材、分散剤、湿潤剤、増粘剤及び/又は
レオロジーコントロール剤、消泡剤、可塑剤、造膜助剤
、有機溶剤、防腐剤、防パイ剤、−調節剤、防錆剤など
それぞれの目的に応じて選択、組み合わされ、通常の方
法で塗料とされる。The room temperature curable emulsion paint of the present invention is produced in exactly the same manner as in the production of conventional emulsion paints using the above-specified polymer emulsion as a vehicle. i.e. pigments, fillers, aggregates, dispersants, wetting agents, thickeners and/or rheology control agents, defoamers, plasticizers, coalescents, organic solvents, preservatives, anti-padding agents, -modifiers. They are selected and combined according to their purpose, such as anti-corrosion agents and anti-corrosion agents, and are made into paints using normal methods.
このようにして得られた本発明の塗料は貯蔵安定性が良
好で、塗装作業時のポット・ライフの心配がなく、従来
のエマルジョン塗料と同様に塗装し、常温乾燥のみで優
れた耐久性を有する塗膜をもたらす、尚、当然のことな
がら、本発明の常温硬化性エマルジョン塗料は、加熱乾
燥工程でも、もちろん使用可能であシ、これによっても
良好な架橋塗膜が得られるので、現場塗装の他、工場で
の各種工業塗装においても省エネルギー型(低温硬化型
)塗料としても有用である。The paint of the present invention thus obtained has good storage stability, there is no need to worry about pot life during painting work, it can be applied in the same way as conventional emulsion paints, and it has excellent durability by simply drying at room temperature. Of course, the room-temperature-curing emulsion paint of the present invention can also be used in a heating drying process, and a good cross-linked paint film can also be obtained by this, so it is suitable for on-site painting. In addition, it is useful as an energy-saving (low-temperature curing) paint in various industrial coatings in factories.
以下に例を挙げ本発明をよシ詳細に説明するが、本発明
は以下の実施例のみに限定されるものではない、なお、
以下の部およびチはいずれも重量に基づく値である。The present invention will be explained in more detail with reference to examples below, but the present invention is not limited only to the following examples.
All parts and parts below are based on weight.
実施例1.比較例1.比較例2
攪拌機、還流コンデンサー、滴下漏斗および温度計を取
シつけた1、5tの反応容器に下記の原料を仕込み溶解
した。Example 1. Comparative example 1. Comparative Example 2 The following raw materials were charged and dissolved in a 1.5 t reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer.
脱イオン水 324.0部エマ
ルグン931 (花王■製品:
ノニオン乳化剤) 16.0部
ネオダンR(第一工業製薬■製品:
アニオン乳化剤)4,0部
rlQ)
次いで、下記の混合物を滴下漏斗に入れた。Deionized water 324.0 parts Emulgun 931 (Kao product: nonionic emulsifier) 16.0 parts Neodan R (Daiichi Kogyo Seiyaku product: anionic emulsifier) 4.0 parts rlQ) Next, put the following mixture into the dropping funnel. Ta.
エビクロン850(大日本インキ化学工業■製品:エポ
キシ樹脂) 40.0部アクリル酸ブチル
200.0部メタクリル酸メチル
192.0部アクリル酸
8.0部窒素ガスを送入しつつ、攪拌下に、反応装置
内温を60℃に昇温し、脱イオン水に溶解した2%濃度
の過硫酸カリウム水溶液を40部添加し、次いで滴下漏
斗に入れたエポキシ樹脂と単量体の混合物の20%を加
えた。重合熱による温度上昇をウォーター・パスによシ
制御し、内温を80’Cに保ちつつ、続いてエポキシ樹
脂/単量体混合物の残シと2%過硫酸カリウム水溶液8
0部を2時間かけて滴下し、重合した。さらに80℃で
2時間保持した後、室温まで冷却して200メツシユ濾
布で濾過し、取出して種粒子となる乳化重合体を得た。Ebicuron 850 (Dainippon Ink & Chemicals ■Product: epoxy resin) 40.0 parts Butyl acrylate
200.0 parts methyl methacrylate
192.0 parts acrylic acid
While feeding 8.0 parts of nitrogen gas and stirring, the internal temperature of the reactor was raised to 60°C, 40 parts of a 2% potassium persulfate aqueous solution dissolved in deionized water was added, and then added dropwise. Added 20% of the epoxy resin and monomer mixture in the funnel. While controlling the temperature rise due to polymerization heat using a water pass and maintaining the internal temperature at 80'C, the remaining epoxy resin/monomer mixture and 2% potassium persulfate aqueous solution 8
0 part was added dropwise over 2 hours to polymerize. After further holding at 80° C. for 2 hours, the mixture was cooled to room temperature, filtered through a 200-mesh filter cloth, and taken out to obtain an emulsion polymer serving as seed particles.
このものは不揮発分濃度50.3%、pH2,8であっ
た。This product had a nonvolatile content concentration of 50.3% and a pH of 2.8.
同様な1.5tの反応装置に上記で得た乳化重合体45
2部および水125部を仕込んだ。次に下記のエチレン
性不飽和単量体混合液を調整し滴下漏斗に入れた。The emulsion polymer 45 obtained above was placed in a similar 1.5 t reactor.
2 parts and 125 parts water. Next, the following ethylenically unsaturated monomer mixture was prepared and placed in the dropping funnel.
アクリル酸エチル 120.0部メ
タクリル酸メチル 74.0部ジメ
チルアミノエチルメタクリレート 4.0部
アクリル酸 2.0部窒素ガ
スを送入しつつ、攪拌しながら反応装置内温を70℃に
昇温し、別の滴下漏斗に準備した2チ過硫酸カリウム水
溶液60部すよび上記単量体混合液を滴下して重合した
。これらの滴下は内温を70℃に保ちつつ2時間で行っ
た。さらに、同温度で2時間保持後、室温に冷却して2
00メツシユ濾布で濾過し、本発明に用いる重合体エマ
ルジョン(E−1)を得た。得られた重合体エマルジョ
ン(E−1)は不揮発分濃度50.2チ、声5.9、粘
度120 cps (B M型回転粘度計、p−ターA
2、回転数6 Orpm。で25℃にて測定)であった
。次に、このエマルジョンをそのtま、および−をアン
モニア水で9.5に調整したものを、それぞれ50℃で
1チ月間保存したところ、いずれも凝集などの変化がな
く安定であった。また声調整前および調整後のそれぞれ
のエマルジョンを3ミルアプリケーターでガラス板上に
塗布し、48時間、約25℃の室温で乾燥した後、表面
をトルエンを含ませた布でラビングテストを行った結果
、いずれも50回のラビングで表面に若干の損傷が認め
られたが、溶解して消滅することがなく良好な耐溶剤性
を示し、架橋皮膜が形成されていることが認められた。Ethyl acrylate 120.0 parts Methyl methacrylate 74.0 parts Dimethylaminoethyl methacrylate 4.0 parts Acrylic acid 2.0 parts While feeding nitrogen gas and stirring, the internal temperature of the reactor was raised to 70°C. Then, 60 parts of a prepared aqueous solution of potassium dithipersulfate and the above monomer mixture were added dropwise to a separate dropping funnel for polymerization. These drops were carried out for 2 hours while maintaining the internal temperature at 70°C. Furthermore, after holding at the same temperature for 2 hours, it was cooled to room temperature for 2 hours.
The mixture was filtered through a 00 mesh filter cloth to obtain a polymer emulsion (E-1) used in the present invention. The obtained polymer emulsion (E-1) had a nonvolatile content concentration of 50.2 cm, a voice of 5.9, and a viscosity of 120 cps (BM type rotational viscometer, p-tar A
2. Number of revolutions: 6 Orpm. (measured at 25°C). Next, when this emulsion was adjusted to 9.5 with aqueous ammonia and stored at 50° C. for 1 month, both were stable without any changes such as aggregation. In addition, each emulsion before and after voice adjustment was applied onto a glass plate using a 3 mil applicator, and after drying at room temperature of approximately 25°C for 48 hours, a rubbing test was performed on the surface with a cloth soaked in toluene. As a result, although some damage was observed on the surface after 50 rubbings, it was found that the coatings did not dissolve and disappear, showing good solvent resistance, and that a crosslinked film was formed.
一方、比較例1として上記実施例1と同じ組成となるよ
うエポキシ樹脂および種粒子に用いたエチレン性不飽和
単量体および第2段目の重合で用いたエチレン性不飽和
単量体を混合して用いて、種粒子で行った如き乳化重合
条件で乳化重合して、重合体エマルジョン(RE−1)
を得た。得られた重合体エマルジョン(RE−1)は不
揮発分濃度50.2%、pH5,8、粘度180 cP
sであった。これを実施例1と同様に、そのままのもの
と−を9.5に調整したものを用いて皮膜のトルエンラ
ビングテス)>よび50℃で保存試験を行った結果、皮
膜の耐溶剤性は共に良好であったがpH5,8のものは
50℃で2週間保存後、またpH9,5のものは50℃
で3日後に凝集し、安定性が不良であった。On the other hand, as Comparative Example 1, the epoxy resin, the ethylenically unsaturated monomer used in the seed particles, and the ethylenically unsaturated monomer used in the second stage polymerization were mixed to have the same composition as in Example 1. A polymer emulsion (RE-1) is obtained by carrying out emulsion polymerization under the same emulsion polymerization conditions as with the seed particles.
I got it. The obtained polymer emulsion (RE-1) had a nonvolatile content of 50.2%, a pH of 5.8, and a viscosity of 180 cP.
It was s. As in Example 1, we performed a toluene rubbing test (toluene rubbing test) on the film and a storage test at 50°C using the film as it was and the film with - adjusted to 9.5. As a result, the solvent resistance of the film was both It was good, but the one with pH 5.8 was stored at 50℃ for 2 weeks, and the one with pH 9.5 was stored at 50℃.
After 3 days, the mixture agglomerated and had poor stability.
さらに、比較例2として、比較何重からエポキシ樹脂を
除いて同様に乳化重合して重合体エマルジョン(RE−
2)を得た。但し、この場合不揮発分濃度を50チとす
るため脱イオン水の仕込み量も、これに相当する量減量
して乳化重合した。得られた重合体エマルジョン(RE
−2)は不揮発分濃度50.0 %、pH6,0、粘度
150 cPaであった。Furthermore, as Comparative Example 2, a polymer emulsion (RE-
2) was obtained. However, in this case, in order to set the nonvolatile content concentration to 50%, the amount of deionized water charged was also reduced by a corresponding amount for emulsion polymerization. The resulting polymer emulsion (RE
-2) had a nonvolatile content concentration of 50.0%, a pH of 6.0, and a viscosity of 150 cPa.
このものの声未調整のもの及びpH9,5に調整のもの
の安定性は50℃、1チ月後も共に良好であったが、皮
膜のトルエンラビングテストでは皮膜が溶解し損失した
。The stability of the unadjusted product and the product adjusted to pH 9.5 was good even after 1 month at 50°C, but the film was dissolved and lost in the toluene rubbing test.
上記で得た各重合体エマルジ、/を用いて、下記の配合
によシエマルジョン塗料を製造した。Using each of the polymer emulsions obtained above, emulsion paints were produced according to the following formulations.
水 10
0部水分散性大豆レシチン(分散剤)
3zエチレングリコール(凍結防止剤) 2
01ジブチルフタレート(可塑剤) 11N
重合体エマルジョン 3201不揮発分濃
度:58%
顔料容積濃度=50%
各々の塗料及び塗膜性能のテスト結果は表−1の如くで
あった。water 10
0 parts water-dispersible soybean lecithin (dispersant)
3z ethylene glycol (antifreeze agent) 2
01 Dibutyl phthalate (plasticizer) 11N
Polymer emulsion 3201 Non-volatile content concentration: 58% Pigment volume concentration = 50% The test results of each paint and coating performance are as shown in Table-1.
表−1
〔試験方法〕
基 材:市販セメント・アスベスト板塗料塗布方法
:刷毛二度塗シ
塗布量’、200fi7/d
乾 燥=23℃、60チRHで7日間塗料粘度:ス
トマー型粘度計による。測定温度25℃。Table 1 [Test method] Base material: Commercially available cement/asbestos board Paint application method: Two coats with a brush, 200fi7/d Drying = 23°C, 7 days at 60°RH Paint viscosity: Stomer type viscometer by. Measurement temperature: 25°C.
耐 水 性:水中に2週間浸漬(約20℃)。Water resistance: Soaked in water for 2 weeks (approximately 20°C).
耐アルカリ性:2%NaOHy Ca (OH) 2飽
和水溶液に2週間浸漬(約20℃)。Alkali resistance: Immersed in 2% NaOHy Ca (OH) 2 saturated aqueous solution for 2 weeks (approximately 20°C).
耐溶剤性: トルエンを含浸させた脱脂綿を用いて、手
で100回塗膜面を摩擦。Solvent resistance: Rub the coated surface 100 times by hand using absorbent cotton impregnated with toluene.
耐 候 性:サンシャイン・ウェザ−・メーターで1.
000時間曝露。Weather resistance: 1. on the Sunshine Weather Meter.
000 hours exposure.
実施例1の塗料は安定性、塗膜性能とも良好であったが
、比較例1の塗料は塗膜性能に優れるものの、安定性に
劣シ、一方、比較例2の塗料は安定性が良好なるものの
、塗膜性能に劣るものでちった。The paint of Example 1 had good stability and film performance, but the paint of Comparative Example 1 had excellent film performance but poor stability, while the paint of Comparative Example 2 had good stability. However, the coating performance was poor.
実施例2.比較例3
実施例1と同様の反応装置に下記の原料を仕込んで溶解
した。Example 2. Comparative Example 3 The following raw materials were charged into the same reaction apparatus as in Example 1 and dissolved.
脱イオン水 332.0部エマ
ルダン931 16.0部ノイff
yEA−1204,0部
ハイテノールN−082,0部
次に窒素ガスを送入しつつ、攪拌下に下記のあらかじめ
溶解したエポキシ樹脂/単量体混合物を仕込んだ。Deionized water 332.0 parts Emuldan 931 16.0 parts Neuff
yEA-1204, 0 parts Hytenol N-082, 0 parts Next, while introducing nitrogen gas and stirring, the following pre-dissolved epoxy resin/monomer mixture was charged.
エピクロン1050(犬日本インキ化学工業■製品:エ
デキシ樹脂) 24.0部アクリル酸ブチル
50.0部メタクリル酸メチル
47.0部メタクリル酸
3.0部次いで、内温を30℃に調節した後、1
チF@ C15・6H20水溶液0.5部を加え、さら
に2チ過硫酸アンモニウム水溶液50部および2チビロ
亜硫酸ソ一ダ水溶液50部を加えた。これKよ多重合が
開始され、発熱し、種粒子となる乳化重合体を生成した
0発熱停止後1時間保持した後内温を50℃に保ち、次
に、あらかじめ調整した下記の単量体混合物および2チ
過硫酸アンモニウム水溶液50部と2%ピロ亜硫酸ソー
ダ水溶液50部を2時間で滴下して重合させた。Epicron 1050 (Inu Nippon Ink Chemical Industry Product: Edexy resin) 24.0 parts Butyl acrylate
50.0 parts methyl methacrylate
47.0 parts methacrylic acid
3.0 parts Then, after adjusting the internal temperature to 30°C, 1
0.5 parts of an aqueous solution of TiF@C15.6H20 was added, and further 50 parts of an aqueous solution of ammonium di-thipersulfate and 50 parts of an aqueous solution of sodium di-thibirosulfite were added. Multipolymerization started at K, generating heat and producing an emulsion polymer that became seed particles. After the heat generation stopped, the internal temperature was maintained at 50°C for 1 hour, and then the following monomers prepared in advance were added. The mixture, 50 parts of an aqueous ammonium dithipersulfate solution, and 50 parts of a 2% aqueous sodium pyrosulfite solution were added dropwise over 2 hours to polymerize.
アクリル酸ブチル 80.0部アク
リル酸エチル 79.0部メタクリ
ル酸メチル 129.0部ジメチルアミ
ノエチルメタクリレート9.0部メタクリル酸
3.0部さらに、50℃で2時間保持
した後、室温に冷却して、アンモニア水で−Iを8.5
に調節後、200メツシユ濾布で濾過し、取出して本発
明に用いる重合体エマルジョン(E−2)を得た。この
ものは不揮発分濃度45.3チ、粘度100 ePaで
、50℃での保存安定性は1チ月間良好であった。Butyl acrylate 80.0 parts Ethyl acrylate 79.0 parts Methyl methacrylate 129.0 parts Dimethylaminoethyl methacrylate 9.0 parts Methacrylic acid
3.0 parts After further holding at 50°C for 2 hours, it was cooled to room temperature, and -I was diluted with 8.5 parts of ammonia water.
After adjusting the temperature, it was filtered through a 200 mesh filter cloth and taken out to obtain a polymer emulsion (E-2) used in the present invention. This product had a nonvolatile content concentration of 45.3 cm, a viscosity of 100 ePa, and good storage stability at 50° C. for 1 month.
一方、比較例3として上記よジェポキシ樹脂を除いたも
のを上記と同様にして乳化重合して、重合体エマルジョ
ン(RE−3)を得た。このものは不揮発分濃度44.
0%、粘度70 cPs (B M型回転粘度計、ロー
ターA1、回転数6 Orpm、で25℃にて測定)で
あシ、−を同様に8.5に調節した。On the other hand, as Comparative Example 3, the same as above but excluding the jepoxy resin was subjected to emulsion polymerization in the same manner as above to obtain a polymer emulsion (RE-3). This one has a non-volatile content of 44.
0%, viscosity 70 cPs (measured at 25° C. using a BM rotational viscometer, rotor A1, rotation speed 6 Orpm), and - was similarly adjusted to 8.5.
本実施例の重合体エマルジョン(E−2)と比較のため
に得たエポキシ樹脂を含まない重合体エマルジョン(R
E−3)とをそれぞれ実施例1と同様にしてガラス板に
塗布し、皮膜を形成せしめた。The polymer emulsion (E-2) of this example and the polymer emulsion (R
E-3) was applied to a glass plate in the same manner as in Example 1 to form a film.
次いで、実施例1と同様なトルエンラビングテストを行
ったところ、本実施例の重合体エマルジョン(E−2)
はトルエンラビングによる皮膜の損傷は僅かであったが
、比較の重合体エマルジョン(RE−3)は、これによ
シ皮膜のラビング部の大部分が溶解し損失した。また、
同様に作成した皮膜を25℃の水中に48時間浸漬して
、状態変化を観察したところ、本実施例の重合体エマル
ジョン(E−2)の皮膜は白化、膨潤が極めて少なく、
良好な耐水性を示したが、比較の重合体エマルジョン(
RE−3)の皮膜は白化、膨潤共に著しく、耐水性に劣
った。Next, a toluene rubbing test similar to that in Example 1 was conducted, and the result was that the polymer emulsion (E-2) of this example
The coating was slightly damaged by toluene rubbing, but in the comparative polymer emulsion (RE-3), most of the rubbed portion of the coating was dissolved and lost due to this. Also,
A similarly prepared film was immersed in water at 25°C for 48 hours and changes in state were observed. The film of the polymer emulsion (E-2) of this example showed extremely little whitening and swelling.
It showed good water resistance, but the comparative polymer emulsion (
The film of RE-3) showed significant whitening and swelling and was poor in water resistance.
上記の各重合体エマルジョンを用いて実施例1と同様の
配合で塗料化した。塗料及び塗膜性能のテスト結果は表
−2の如くであった。Each of the above polymer emulsions was used to form a paint in the same formulation as in Example 1. The test results for paint and coating performance are shown in Table 2.
表−2
〔試験方法は表−1と同様。〕
実施例2の塗料は塗料安定、塗膜性能ともに良好であっ
た。Table-2 [Test method is the same as Table-1. ] The paint of Example 2 was good in both paint stability and film performance.
実施例1と同様の反応装置に下記の原料を仕込み溶解し
た。The following raw materials were charged and dissolved in the same reaction apparatus as in Example 1.
脱イオン水 500.0部エマル
ダン931 30.0部ハイテノール
N−081,0部
窒素ガスを送入しつつ、攪拌しながら温度を(9q)
60℃に昇温し、次にエビクロン850をioo、。Deionized water 500.0 parts Emuldan 931 30.0 parts Hitenol N-081.0 parts While feeding nitrogen gas and stirring, raise the temperature to (9q) 60°C, then add Evicron 850 to ioo ,.
部とノイグンEA−12010,0部とを混合した混合
物を30分間で徐々に加え、さらに1時間攪拌しエポキ
シ樹脂を分散させた。続いて、下記単量体混合物を加え
た。A mixture of 0 parts and 10 parts of Noigun EA-120 was gradually added over 30 minutes, and the mixture was further stirred for 1 hour to disperse the epoxy resin. Subsequently, the following monomer mixture was added.
アクリル酸ブチル 50.0部スチレン
45,0部メタクリル酸
5.0部上記単量体混合物を添加後
、2%過硫酸カリウム水溶液25部を加え、温度を適宜
冷却または加熱して70℃に保ちつつ、4時間保持し反
応させた。Butyl acrylate 50.0 parts Styrene 45.0 parts Methacrylic acid
After adding 5.0 parts of the above monomer mixture, 25 parts of a 2% potassium persulfate aqueous solution was added, and while the temperature was maintained at 70° C. by cooling or heating as appropriate, the mixture was maintained for 4 hours to react.
次に下記の単量体混合物および2q6過硫酸力リウム水
溶液50部を2時間で滴下して重合した。Next, the following monomer mixture and 50 parts of 2q6 hydrium persulfate aqueous solution were added dropwise over 2 hours to polymerize.
アクリル酸ブチル iio、o部メタクリ
ル酸メチル 75.0部ジメチルアミノエ
チルアクリレート 10,0部メタクリル酸
5.0部さらに、70℃にて2時
間保持後、室温まで冷却し、200メツシユ濾布で濾過
し取出した。得られた重合体エマルジョン(E−3)は
不揮発分濃度43.0%、pH6,7、粘度80 eP
sであった。このエマルジョンは50℃の保存安定性は
1ケ月後も良好であシ、また実施例1と同様に25℃で
ガラス板上に塗布した皮膜の耐トルエン性も良好であっ
た。Butyl acrylate iio, o parts Methyl methacrylate 75.0 parts Dimethylaminoethyl acrylate 10.0 parts Methacrylic acid
5.0 parts The mixture was further maintained at 70° C. for 2 hours, cooled to room temperature, filtered through a 200 mesh filter cloth, and taken out. The obtained polymer emulsion (E-3) had a nonvolatile content concentration of 43.0%, a pH of 6.7, and a viscosity of 80 eP.
It was s. This emulsion had good storage stability at 50°C even after one month, and as in Example 1, the toluene resistance of the film coated on a glass plate at 25°C was also good.
次に、比較例4として、上記よシエピクロン850を除
き、且つ、重合体エマルジョンの不揮発分濃度を43チ
とするために脱イオン水の仕込み量を132部減量し、
その他は同様にして重合体エマルジョン(RE−4)を
合成し、この重合体エマルジョン(RE−4)100部
に対し、市販エポキシ樹脂エマルジョン(エピクロン8
5−75W:大日本インキ化学工業KK製品)15部を
加えて混合した。得られた配合物は不揮発分濃度47,
0%pH6,7、粘度120 ePsであった。このも
のは50℃、2日間後に凝集を起し、又、上記と同様の
方法による皮膜の耐トルエン性試験の結果、−部溶解、
膨潤による損傷が認められた。Next, as Comparative Example 4, Ciepiclon 850 was removed from the above, and the amount of deionized water was reduced by 132 parts in order to set the nonvolatile content concentration of the polymer emulsion to 43 parts.
Other than that, a polymer emulsion (RE-4) was synthesized in the same manner, and a commercially available epoxy resin emulsion (Epiclon 8
5-75W: 15 parts of Dainippon Ink Chemicals KK product) were added and mixed. The resulting formulation had a non-volatile content of 47,
0% pH 6.7, viscosity 120 ePs. This material agglomerated after 2 days at 50°C, and as a result of the toluene resistance test of the film by the same method as above, -partial dissolution,
Damage due to swelling was observed.
上記の両者を、実施例1と同様の塗料配合によシ塗料化
して、塗料及び塗膜物性を試験した結果は表−3の如く
であった。Both of the above were made into a paint using the same paint formulation as in Example 1, and the physical properties of the paint and the paint film were tested, and the results are as shown in Table 3.
表−3
〔試験方法は、下記を除き表−1と同様〕0耐洗浄性;
ガードナー型洗浄機によシ、マルセル石鹸1.5%とミ
ガキ砂10%混合水溶液にて1000回塗膜面を摩耗。Table-3 [Test method is the same as Table-1 except for the following] 0 Washing resistance;
A Gardner-type washer was used to abrade the painted surface 1000 times using a mixed aqueous solution of 1.5% Marcel soap and 10% polishing sand.
実施例3の塗料は安定性、塗膜物性とも良好であったが
、比較例4の塗料は安定性、塗膜物性ともに劣った。The coating material of Example 3 had good stability and physical properties of the coating film, but the coating material of Comparative Example 4 had poor stability and physical properties of the coating film.
実施例2で合成した重合体エマルジョン(E−2)及び
比較例3の重合体エマルジ、ン(RE−3)をそれぞれ
用いて下記の配合によシ塗料を調製した。Using the polymer emulsion (E-2) synthesized in Example 2 and the polymer emulsion (RE-3) of Comparative Example 3, paints were prepared according to the following formulation.
タモ−ルア31(25%)(分散剤) 7.2
7.2 7.2エチレングリコール 1
5 15 15重合体エマルジョン(E−2)
451 − −重合体エマルジョン(RE−
3) −465−同 上 −
−459アンモニア水(28チ) 7 7
7不揮発分濃度;51チ
顔料重量濃度(PWC) : 55%
上記塗料の安定性及び磨軟鋼板に塗布した塗膜の物性は
表−4の如くであった。Tamorure 31 (25%) (dispersant) 7.2
7.2 7.2 Ethylene glycol 1
5 15 15 polymer emulsion (E-2)
451--Polymer emulsion (RE-
3) -465-same as above-
-459 Ammonia water (28ch) 7 7
7 Non-volatile content concentration: 51 Pigment weight concentration (PWC): 55% The stability of the above coating material and the physical properties of the coating film applied to the polished mild steel plate were as shown in Table 4.
表−4 判定;◎優秀、○良、△やや劣る。x不良。Table-4 Judgment: ◎Excellent, ○Good, △Slightly inferior. x Defective.
〔試験方法〕
基 材:磨軟鋼板
塗布量:25μ(パーコーター460による)乾 燥:
23℃、5日間
試片の調製:乾燥後試片の裏面及び側面を、アクリル系
ラッカー(クリヤー)にてシールした後供試。[Test method] Base material: Polished mild steel plate Coating amount: 25μ (by Percoater 460) Drying:
23°C for 5 days Preparation of specimen: After drying, the back and sides of the specimen were sealed with acrylic lacquer (clear) and then tested.
付着性: 10m+aX 10zrnの広さに1mm間
隙でナイフでゴパン目を入れ、市販セロテープによシ、
セロテープ剥離テスト。Adhesiveness: Make a hole with a knife with a 1mm gap in an area of 10m+aX 10zrn, and use commercially available sellotape.
Sellotape peel test.
耐水性:クロスカットを入れた試片を水中に1週間浸漬
して塗膜2発錆、フクレ、その他状態変化観察。Water resistance: A cross-cut specimen was immersed in water for one week, and two coats of rust, blisters, and other changes in condition were observed.
耐塩水性:同様に5%食垣水中に1週間浸漬。Salt water resistance: Similarly immersed in 5% food water for one week.
耐塩水噴霧性:同様試片を塩水噴霧試験機中で96時間
曝露。Salt water spray resistance: A similar specimen was exposed in a salt water spray tester for 96 hours.
実施例2においてエポキシ樹脂をエビクロン1050か
らエビクロン850に変えて、使用量を20部とし、又
、メタクリル酸メチルをスチレンに置換した他は同じに
して重合体エマルジョン(E−4)を合成した。次にこ
の重合体エマルジ。A polymer emulsion (E-4) was synthesized in the same manner as in Example 2 except that the epoxy resin was changed from Eviclon 1050 to Eviclon 850, the amount used was 20 parts, and styrene was substituted for methyl methacrylate. Next is this polymer emulsion.
ン(E−4)と、市販の吹付タイル用アクリル−スチレ
ン系エマルジョン、ポンコー)5410(大日本インキ
化学工業KK 、製品)をそれぞれ用いて下記の如く吹
付タイルポデー・コート配合を行りた。A sprayed tile pode coat was prepared as follows using a commercially available acrylic-styrene emulsion for sprayed tiles, Ponko 5410 (manufactured by Dainippon Ink & Chemicals KK).
実施例5 比較例7
トリポリリン酸カリ(5q6水溶液) 4
6.0 46.0エチレングリコール
4.0 4.0重合体エマルジョン(E−4
)(45チ)152.5 −市販品ポンコー)54
10(50%) −137,2アンモニア水
(28チ) 1.5 1.5不
揮発分濃度=85%
顔料重量濃度=92%
市販セメント・アスベスト板に、市販塩化ビニル−酢酸
ビニルコポリマー溶液をシーラーとして刷毛塗シし、乾
燥後、上記塗料をタイル・ガンを用いて吹付圧力2.5
kg/aiにて塗布量2ゆ/?程度となるよう玉吹き
した。室温にて24時間乾燥後、市販アクリル系ラッカ
ー・エナメルをトップコートして(塗布量:2oog/
m’)、さらに室温で5日間乾□燥した。Example 5 Comparative Example 7 Potassium tripolyphosphate (5q6 aqueous solution) 4
6.0 46.0 Ethylene glycol
4.0 4.0 Polymer emulsion (E-4
) (45chi) 152.5 - Commercial product Ponko) 54
10 (50%) -137.2 Ammonia water (28%) 1.5 1.5 Non-volatile content concentration = 85% Pigment weight concentration = 92% A commercially available vinyl chloride-vinyl acetate copolymer solution was applied as a sealer to a commercially available cement/asbestos board. After drying, spray the above paint using a tile gun at a pressure of 2.5.
Application amount 2yu/? in kg/ai? I sprayed the ball so that it was just the right amount. After drying at room temperature for 24 hours, top coat with commercially available acrylic lacquer/enamel (coating amount: 2oog/
m'), and was further dried at room temperature for 5 days.
上記にて得た各塗装板につき、塗膜物性を試験の結果は
表−5の如くであった。The results of testing the physical properties of the coating film for each of the coated plates obtained above were as shown in Table 5.
表−5 東付着性: JIS−A−6910による。Table-5 East adhesion: According to JIS-A-6910.
実施例5は付着性に優れ、耐久性も良好であった。Example 5 had excellent adhesion and good durability.
実施例1及び比較例2並びに3の塗料に、それぞれ同量
の寒水石5厘及び3厘のに1混合物を加えて混和し、実
施例6.比較例8.比較例9のリシン塗料を得た。To the paints of Example 1 and Comparative Examples 2 and 3, the same amount of 5 liters of Kansui stone and 1 mixture of 3 liters, respectively, were added and mixed. Comparative example 8. A ricin paint of Comparative Example 9 was obtained.
市販セメント・アスベスト板にリシン・ガンにて塗布量
1 kg/n?となるようそれぞれのりシン塗料を吹付
塗装し、室温で5日間乾燥した。Apply amount 1 kg/n to commercially available cement/asbestos board with ricin gun? Each piece was spray-painted with glue paint so that it would look like this, and then dried at room temperature for 5 days.
それぞれの塗膜の性能を比較したところ、表−6の如く
であった。When the performance of each coating film was compared, the results were as shown in Table 6.
表−6
実施例6は塗料安定性、塗膜性能ともに良好であった0
単量体組成を、
(種粒子となる乳化重合体の組成)
エピクロン850 40.0部アクリ
ル酸2−エチルヘキシル 42,0スチレン
40.0メタクリル酸メチル
15,0メタクリル酸
3,0(第二段目の単量体組成)
アクリル酸2−エチルヘキシル 126.0部メタ
クリル酸メチル 157.5ジメチルアミノ
エチルメタクリレート 12.0アクリル酸
4.5の如く変えたほかは実施例
2の重合体エマルジ冒ンの合成と同じにして重合し、重
合体エマルジ盲ン(E−5)を得た。得られた重合体エ
マルジョン(E−5)にさらに水を加えて、不揮発分濃
度を45.0%に調節した。このものの粘度は120e
Psで、50℃での保存安定性は1ケ月後も良好であっ
た。Table 6 Example 6 had good paint stability and film performance. Monomer composition: (Composition of emulsion polymer serving as seed particles) Epicron 850 40.0 parts 2-ethylhexyl acrylate 42, 0 styrene
40.0 Methyl methacrylate
15,0 methacrylic acid
3,0 (second stage monomer composition) 2-ethylhexyl acrylate 126.0 parts Methyl methacrylate 157.5 Dimethylaminoethyl methacrylate 12.0 Acrylic acid
Polymerization was carried out in the same manner as in the synthesis of the polymer emulsion binder in Example 2, except for the changes described in 4.5, to obtain a polymer emulsion binder (E-5). Water was further added to the obtained polymer emulsion (E-5) to adjust the nonvolatile content concentration to 45.0%. The viscosity of this product is 120e
Ps had good storage stability at 50°C even after one month.
一方、比較例10として上記よジェポキシ樹脂を除いた
ものを同様に合成した。得られた重合体エマルジョン(
RE−5)は不揮発分濃度44. O% 。On the other hand, as Comparative Example 10, a product similar to the above but excluding the jepoxy resin was synthesized in the same manner. The obtained polymer emulsion (
RE-5) has a nonvolatile content of 44. O%.
粘度100 cPg t p’ 8.5であった。 、
それぞれの重合体エマルジョンを用いて下記配合にて水
性グロスイイントを調製した。The viscosity was 100 cPg t p' 8.5. ,
Aqueous gloss ints were prepared using the respective polymer emulsions according to the following formulations.
水
10.0部エチレングリコール 2.
6ノイダンEA−1200,3
ペストサイドFX O
,01JR−60OA(酸化チタン:帝国化工KK製品
)36.0アンモニア水(28チ)
0.15重合体エマルジョン(44チ)
113.6テキサノール 7.0
8N−デフォ−マー121
0.3セロサイズQP−4400(3%)9.2不揮発
分濃度 :47チ
顔料容積濃度(PVC): 20チ
それぞれの塗料及び塗膜物性試験の結果は表−7の如く
であった。water
10.0 parts ethylene glycol 2.
6 Noidan EA-1200, 3 Pestside FX O
, 01JR-60OA (Titanium oxide: Teikoku Kako KK product) 36.0 Ammonia water (28T)
0.15 polymer emulsion (44)
113.6 Texanol 7.0
8N-Deformer 121
0.3 Cellosize QP-4400 (3%) 9.2 Non-volatile content concentration: 47 cm Pigment volume concentration (PVC): 20 cm The results of the physical property tests for each paint and coating film were as shown in Table 7.
塗料粘度:ストマー型粘度計による。測定温度25℃
光 沢:塗料を3m11アプリケーターにてガラス
板上に塗布し、1日乾燥後村上式光
沢計にて入射角/反射角==60°/60゜で光沢を測
定。Paint viscosity: Based on a stormer type viscometer. Measurement temperature: 25°C Gloss: Paint was applied onto a glass plate using a 3m11 applicator, and after drying for one day, the gloss was measured using a Murakami gloss meter at angle of incidence/angle of reflection ==60°/60°.
耐 水 性:フレキシブル板に刷毛で塗料を2度塗シし
1日間乾燥後水中に96時間浸漬
(裏面アクリル・ウレタンでシール)
耐アルカリ性:上記と同様の試片をCa (OH) 2
飽和水溶液中に浸漬、(裏面アクリル−ウレタ
ンでシール)
促進耐湿熱性:溶剤型アクリルでシールしたフレキシブ
ル板に塗料を約1+1ulHの厚さに塗布、7日間乾燥
後裏面が水に浸潤した状態で上部50mよシ赤外線ラン
プを照射7日後に塗膜の状態を判定。Water resistance: Paint the flexible board twice with a brush, dry for one day, and then immerse in water for 96 hours (sealed with acrylic/urethane on the back) Alkali resistance: A sample similar to the above was coated with Ca (OH) 2
Immersed in a saturated aqueous solution (sealed with acrylic-urethane on the back side) Accelerated heat and humidity resistance: Paint was applied to a thickness of approximately 1+1 ulH on a flexible board sealed with solvent-based acrylic, and after drying for 7 days, the upper side was wetted with water. The condition of the paint film was determined 7 days after irradiation with an infrared lamp at a distance of 50 m.
耐溶剤性:耐水、耐アルカリ性試験と同様の試片の表面
をトルエンを含浸させた脱脂綿を用い、手で100回摩
擦。Solvent resistance: The surface of the same specimen as in the water and alkali resistance tests was rubbed 100 times by hand using absorbent cotton impregnated with toluene.
耐 候 性:サンシャイン・ウニデーメーターで1.0
00時間曝露。Weather resistance: 1.0 on the Sunshine Uniday Meter
00 hours exposure.
上記の如く、実施例70グロスペイントは良好な光沢、
塗膜耐久性を示した。As mentioned above, the Example 70 gloss paint has good gloss,
It showed the durability of the coating film.
上記した実施例7において、エピクロン850をエビク
ロン1050に置換したほかは同様にして重合体エマル
ジョン(E−6)を得た。得られた重合体エマルジョン
(E−6)及び比較例10で用いたエポキシ樹脂を含ま
ない重合体エマルジョン(RE−5)をそれぞれ用いて
下記塗料を調製した。A polymer emulsion (E-6) was obtained in the same manner as in Example 7, except that Epiclon 850 was replaced with Eviclon 1050. The following paints were prepared using the obtained polymer emulsion (E-6) and the epoxy resin-free polymer emulsion (RE-5) used in Comparative Example 10, respectively.
実施例8 比較例11
重合体エマルジョン(E−6) 89部 −
重合体エマルジョン(RE−5) 9
1部テキサノール 22
水 2
−顔料重量濃度: 3チ
不揮発分濃度=40チ
それぞれの塗料及び塗膜物性試験結果は表−8の如くで
あった。Example 8 Comparative Example 11 Polymer emulsion (E-6) 89 parts -
Polymer emulsion (RE-5) 9
1 part Texanol 22 Water 2
- Pigment weight concentration: Non-volatile matter concentration of 3 pieces = 40 pieces The results of the physical property test for each paint and coating film are as shown in Table 8.
表−8
〔試験方法〕
基 材:未処理ダル鋼板(JIS−G−3141−D)
、トルエンにて脱脂して使用。Table-8 [Test method] Base material: Untreated dull steel plate (JIS-G-3141-D)
, used after degreasing with toluene.
塗 布:パーコーターにて膜厚20μ(ドライ)となる
よう塗布。Application: Apply to a film thickness of 20μ (dry) using a percoater.
乾 燥:室温3日。Drying: 3 days at room temperature.
光 沢:塗料を3ミルアゾリケーターにてガラス板上に
塗布し、1日乾燥後村上式光沢計にて入射角/反射角=
60°760°で測定。Gloss: Paint is applied on a glass plate using a 3 mil asolicator, and after drying for one day, the incident angle/reflection angle is measured using a Murakami gloss meter.
Measured at 60°760°.
耐水性二上記条件で塗装した試片をアクリル・ラッカー
にて、裏面及び側面をシール塗装抜水中に48時間浸漬
。Water Resistance 2 The specimen painted under the above conditions was coated with acrylic lacquer and immersed in water for 48 hours to seal the back and sides.
耐塩水噴霧性 :同様試片の塗面にクロス・カットをほ
どこした後、塩水噴霧試験機に入れ、48時間曝露。Salt water spray resistance: After making a cross cut on the painted surface of a similar specimen, it was placed in a salt water spray tester and exposed for 48 hours.
耐溶剤性:塗装試片(未シール)をガソリン中に24時
間浸漬。Solvent resistance: Painted specimen (unsealed) immersed in gasoline for 24 hours.
付着性=10酊X10m扉で1mmX1龍間隔にてゴパ
ン目力、トをほどこした後、市販セロテープを貼付し、
次いでセロテープを剥離し、カット部の残存数測定。Adhesiveness = 10mm x 10m door with 1mm x 1mm spacing, then apply commercially available sellotape.
Next, remove the cellophane tape and measure the number of pieces remaining in the cut area.
実施例8の塗料は安定で、光沢、塗膜耐久性に優れるこ
とが認められた。The paint of Example 8 was found to be stable and excellent in gloss and film durability.
実施例2に用いた重合体エマルジョンにおいて、種粒子
となる乳化重合体の組成を下記の如くに変え、又、脱イ
オン水を158部とした。In the polymer emulsion used in Example 2, the composition of the emulsion polymer serving as the seed particles was changed as follows, and the amount of deionized water was changed to 158 parts.
エビクロン850 24.0部アクリ
ル酸ブチル 40.0アクリル酸エチル
20.0メタクリル酸メチル
38.0メタクリル酸 2
.0更に、第二段の滴下重合の単量体組成もアクリル酸
エチル 120.0部アクリル酸ブチル
150.0メタクリル酸メチル
21.0ジメチルアミノエチルメタクリレート6
.0メタクリル酸 3,0の如く
変えた。Evicron 850 24.0 parts Butyl acrylate 40.0 Ethyl acrylate 20.0 Methyl methacrylate
38.0 Methacrylic acid 2
.. Furthermore, the monomer composition for the second stage dropwise polymerization is ethyl acrylate 120.0 parts butyl acrylate 150.0 methyl methacrylate
21.0 Dimethylaminoethyl methacrylate 6
.. 0 methacrylic acid 3,0.
その他は同じKして乳化重合して得た重合体エマルジョ
ン(K−7)は不揮発分55.2チ、pH8,5、粘度
600 eP@、であった。又、比較例12として上記
よジェポキシ樹脂を除いたものを同様に乳化重合した。A polymer emulsion (K-7) obtained by emulsion polymerization using the same K except for the above had a nonvolatile content of 55.2%, a pH of 8.5, and a viscosity of 600 eP@. Moreover, as Comparative Example 12, the same emulsion polymerization as above except for the jepoxy resin was carried out.
得られた重合体エマルジョン(RE−6)は不揮発分5
4.0%、PH8,5、粘度480 egg。The obtained polymer emulsion (RE-6) had a nonvolatile content of 5
4.0%, PH8.5, viscosity 480 egg.
であった、 ・
それぞれ得られた重合体エマルジョンを用いて、下記の
塗料配合を行い複層伸長型塗装剤の主剤(ポデー・コー
ト)を調製した。・Using each of the obtained polymer emulsions, the following coating composition was carried out to prepare a main ingredient (Podey Coat) for a multilayer elongated coating agent.
重合体エマルジョン(E−7) 371.8
部 −重合体エマルジョン(RE−6)
−37B、7部デモールEP(分散剤、花王KK製品)
7.7 7.7エチレングリコール
5.5 5.5セルトップHP−10
35,55,5
炭力ルMS−100312,4312,4タイベークR
−5507,77,7
5%ハイ・メトローズ90SH−1500036,53
6,5合計 1,102.51,109.4NY
(不揮発分濃度)% 78.6 78.1p
vc(顔料容積濃度)チ 50.0 50.O
pwc(顔料重量濃度)チ 70.2 70.
2上記配合物の塗膜物性をJIS−A−6021K準拠
しテストした結果は表−9の如くであった。Polymer emulsion (E-7) 371.8
Part - Polymer emulsion (RE-6)
-37B, 7 parts Demol EP (dispersant, Kao KK product)
7.7 7.7 Ethylene glycol
5.5 5.5 Cell Top HP-10
35,55,5 Charcoal MS-100312,4312,4 Thai Bake R
-5507,77,7 5% High Metrose 90SH-1500036,53
6.5 total 1,102.51,109.4NY
(Non-volatile content concentration)% 78.6 78.1p
vc (pigment volume concentration) 50.0 50. O
pwc (pigment weight concentration) 70.2 70.
2 The physical properties of the coating film of the above formulation were tested in accordance with JIS-A-6021K, and the results were as shown in Table 9.
表−9
〔試験方法〕
顛作成条件 :塗 膜 厚・・・約1 zx (ドライ
)乾 燥・・・室温30日
打 抜 き・・・3号ダンベル
引張試験条件 : (JIS A−6021準拠)
測 定 !・・・テンシロン
引張速度・−・200關/−h
測定温度・・・−20℃、−10℃。Table 9 [Test method] Screen preparation conditions: Coating film thickness: approx. 1 zx (dry) drying: 30 days at room temperature Punching: No. 3 dumbbell tensile test conditions: (based on JIS A-6021) )
measurement ! ...Tensilon tensile speed: -200 speeds/-h Measurement temperature: -20°C, -10°C.
20℃、60℃
処理試片:加熱処理・・・80℃×7日アルカリ処理・
・・0.1%NaOH。20°C, 60°C treated specimen: Heat treatment...80°C x 7 days alkali treatment.
...0.1% NaOH.
飽和Ca (OH) 2 X 78
注) −20,−10,60℃の伸度はチャック間、2
0℃は標線間を表示
実施例9の塗膜は強伸度ともに優れ、耐熱性。Saturated Ca (OH) 2
0°C indicates between the marked lines. The coating film of Example 9 has excellent strength and elongation, and is heat resistant.
耐アルカリ性も良好であった。Alkali resistance was also good.
実施例1.比較例1.比較例2に用いたそれぞれの重合
体エマルジョン(E−1)、(RE−1)9(RE−2
)を用いて、下記の配合によシ、各々、実施例10.比
較例13.比較例14の単層弾性塗料を得た。Example 1. Comparative example 1. Each polymer emulsion (E-1), (RE-1) 9 (RE-2) used in Comparative Example 2
) according to the following formulations, respectively, Example 10. Comparative example 13. A single layer elastic paint of Comparative Example 14 was obtained.
トリポリリン酸カリ(5q6水溶液)
4.54ノイダンEA−1202,27
エチレングリコール 22.72
水 7
9.96アデカネー)B−1903,64
重合体エマルジョン(50%) 69
2.95テキサノール 12.4
9キシレン 3.187デ
力ノールuw−42o/水=y25.22合 計
1,063.00不揮発分濃
度(NY) 54.596顔料容積濃度(PVC)
15.2%顔料重量濃度(PWC) 39.6%
それぞれの塗料、塗膜物性試験結果は表−10の如くで
あった。Potassium tripolyphosphate (5q6 aqueous solution)
4.54 Noidan EA-1202,27 Ethylene Glycol 22.72
water 7
9.96 Adekane) B-1903,64 Polymer emulsion (50%) 69
2.95 Texanol 12.4
9 xylene 3.187 detonol uw-42o/water = y25.22 total
1,063.00 Non-volatile concentration (NY) 54.596 Pigment volume concentration (PVC)
15.2% Pigment Weight Concentration (PWC) 39.6%
The physical property test results for each paint and coating film were as shown in Table 10.
/
/
7/
/
/
7/
表−10
〔試験方法〕
塗料粘度=BH型4 rpmの塗料粘度(cp−)塗膜
光沢ニガラス板に3m1lアプリケーターにて塗布し、
1日乾燥後に60°反射率を測定。/ / 7/ / / 7/ Table 10 [Test method] Paint viscosity = BH type 4 rpm Paint viscosity (CP-) Paint film was applied to a glossy glass plate with a 3ml applicator,
Measure the 60° reflectance after drying for one day.
JIS A6910 :
伸 び 率・・・塗膜厚がドライで約1訂になる様に試
片を作成しその後
JIS伸長性試験方法に従っ
て養生し2号ダンベルにて打
抜いたものを試験片とした。JIS A6910: Elongation rate: A test piece was prepared so that the coating film thickness was approximately 1st grade when dry, then cured according to the JIS elongation test method, and punched out with a No. 2 dumbbell. .
(塗布→7日間養生→裏面7
日間養生→打抜)
伸び時の劣化・・・上記の試片を1号ダンベルにて打抜
き試験片とした。(Coating → Curing for 7 days → Curing for 7 days on the back side → Punching) Deterioration during elongation: The above specimen was punched out using a No. 1 dumbbell as a test piece.
付着強さ・・・下塗シ剤としてアクリデイ。Adhesion strength: Acryday as an undercoat agent.
り53−448を塗布し3時間 乾燥後、試料を試験方法に従 って塗布し、14日間養生後 共訳、浸水後の付着強さに用 いる試験体の四側面は養生終 了3日前に塩化ビニル樹脂塗 料で塗シ込んだ。接着剤は2 液凰エポキシ接着剤を使用し た。Apply 53-448 for 3 hours. After drying, test the sample according to the test method. After applying and curing for 14 days Co-translated, used for adhesion strength after immersion in water The four sides of the specimen Painted with vinyl chloride resin 3 days before completion I painted it with paint. Adhesive is 2 Using liquid epoxy adhesive Ta.
温冷繰返し作用に対する抵抗性:
(20±2℃水中18Hrs−+
一20±3℃X3Hrs−+
50±3℃X3Hrs)X10サイクル透 水 性(−
)・・・JIS伸長性試験方法に準拠耐衝撃性 ・・・
l
耐候性 ・・・ l
塗膜強度: JIS A6910伸び率を測定した時点
での塗膜強度を表示。Resistance to repeated heating and cooling: (18Hrs-+ in 20±2℃ water - 20±3℃X3Hrs-+ 50±3℃X3Hrs)×10 cycles Water permeability (-
)...Conforms to JIS extensibility test method Impact resistance...
l Weather resistance...l Coating film strength: Displays the coating film strength at the time of measuring the JIS A6910 elongation rate.
促進耐候性:伸び率を測定したものと同様の塗膜をスタ
ンダードウェザ−メーターに500時間照射した後の2
0℃に於ける塗膜強伸度を測定
実施例10の塗料は安定性良好で、表−10の如く塗膜
物性も良好であった。比較例13は塗膜物性は比較的良
好であったが、塗料安定性に劣シ、50℃、2週間の貯
蔵安定性テストで凝集した。Accelerated weathering resistance: 2 after irradiating a coating similar to the one whose elongation rate was measured using a standard weather meter for 500 hours.
Measurement of strength and elongation of the coating film at 0°C. The coating of Example 10 had good stability, and the physical properties of the coating film were also good as shown in Table 10. Comparative Example 13 had relatively good physical properties of the coating film, but had poor coating stability, and agglomerated during a two-week storage stability test at 50°C.
実施例−7で用いた重合体エマルジョン(E−5)及び
、比較例−10で用いた重合体エマルジョン(RE−5
)をそれぞれ用いて下記の塗料を配合した。The polymer emulsion (E-5) used in Example-7 and the polymer emulsion (RE-5) used in Comparative Example-10
) were used to formulate the following paints.
実施例−11比較例−15
重合体エマルジョン(E−5) 100.0部
−重合体エマルジョン(RE−5)
102.3部ブチルセロソルブ
3.5 3.5テキサノール
1.5 1.5上記配合め各塗料を市販フ
レキシブル板に乾燥膜厚40ミクロンとなるようスプレ
ー塗装し、次いで70℃、20分間乾燥し、塗装板を得
た。これらの塗膜物性試験結果は表−11の如くであっ
た。Example-11 Comparative Example-15 Polymer emulsion (E-5) 100.0 parts - Polymer emulsion (RE-5)
102.3 parts Butyl cellosolve
3.5 3.5 Texanol
1.5 1.5 Each of the above-mentioned paints was spray-coated onto a commercially available flexible board to a dry film thickness of 40 microns, and then dried at 70°C for 20 minutes to obtain a coated board. The physical property test results of these coating films were as shown in Table 11.
表−11
〔試験方法〕
常態密着性;塗面上にカミソリ刃を用いて2酩ゴパン目
10XIO個を作り、セロテ
ープハクリテストを行なう。Table 11 [Test method] Normal adhesion: 10×10 pieces of 2 goblets are made on the coated surface using a razor blade, and a sellotape peeling test is performed.
(塗膜)耐水性;20℃水中圧試片を1ケ月浸漬し塗面
のツヤ引け、白化フクレ等をみる。(Coating film) Water resistance: A pressure test specimen was immersed in water at 20°C for one month to observe loss of gloss, whitening, blisters, etc. on the painted surface.
耐アルカリ性;20℃5チカ性ソーダ液中に7日間浸漬
し、塗面の状態変化をみる。Alkali resistance: Immerse in 5-strong soda solution at 20°C for 7 days and observe changes in the state of the coated surface.
耐湿熱性;50℃、98%RH以上の条件下に1ケ月放
置後の塗面状態変化をみる。Humid and heat resistance: Changes in the condition of the coated surface after being left for one month under conditions of 50°C and 98% RH or higher.
耐温水サイクルテスト; 試片を70℃温水中に2時間
浸漬後、50℃乾燥機内で2時間乾
燥する。この操作を10回くシかえ
し塗面の変化を観察する。Hot water cycle test: The specimen is immersed in hot water at 70°C for 2 hours and then dried in a dryer at 50°C for 2 hours. Repeat this operation 10 times and observe changes in the coating surface.
耐沸水性;沸騰水中に2時間浸漬し塗面の状態” をみ
る。Boiling water resistance: immerse in boiling water for 2 hours and check the condition of the painted surface.
凍結融解サイクル;試片を20〜30℃水中に2時間浸
漬し、直ちに一20℃下で凍結さ
せるこの操作を10回くシかえし、
塗面のクラックハガレフクレ等をみ
る。Freeze-thaw cycle: Immerse the specimen in water at 20-30°C for 2 hours and immediately freeze at -20°C. Repeat this process 10 times to check for cracks, peeling, etc. on the painted surface.
実施例−11の塗膜は極めて良好な耐久性を示し、70
℃、20分の乾燥の如き低温処理でも架橋性が良好なる
ことが認められた。The coating film of Example-11 showed extremely good durability, with a rating of 70
It was found that even low-temperature treatment such as drying at 20 minutes at 0.degree. C. resulted in good crosslinking properties.
新規な架橋性重合体エマルジョンをビヒクルとして用い
る本発明のエマルジョン塗料は、−抜型でかつ常温で硬
化できまた、貯蔵安定性に優れるほか耐久性の良好な硬
化塗膜が得られる。The emulsion coating material of the present invention using a novel crosslinkable polymer emulsion as a vehicle can be cured by mold cutting and at room temperature, and provides a cured coating film with excellent storage stability and good durability.
Claims (1)
飽和単量体を水不溶性のエポキシ樹脂の存在下に乳化重
合させて種粒子たる乳化重合体を製造し、次いで(b)
前記乳化重合体の存在下で、アミノ基を含有するエチレ
ン性不飽和単量体およびこれと共重合可能な他のエチレ
ン性不飽和単量体を乳化重合させて得られる重合体エマ
ルジョンをビヒクルとする常温硬化性エマルジョン塗料
。(1) (a) An ethylenically unsaturated monomer that does not contain an amino group in its molecule is subjected to emulsion polymerization in the presence of a water-insoluble epoxy resin to produce an emulsion polymer as seed particles, and then (b)
In the presence of the emulsion polymer, a polymer emulsion obtained by emulsion polymerization of an ethylenically unsaturated monomer containing an amino group and another ethylenically unsaturated monomer copolymerizable therewith is used as a vehicle. Room-temperature curing emulsion paint.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP30917787A JP2606244B2 (en) | 1987-12-07 | 1987-12-07 | Room temperature curable emulsion paint |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP30917787A JP2606244B2 (en) | 1987-12-07 | 1987-12-07 | Room temperature curable emulsion paint |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH01149864A true JPH01149864A (en) | 1989-06-12 |
JP2606244B2 JP2606244B2 (en) | 1997-04-30 |
Family
ID=17989859
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP30917787A Expired - Fee Related JP2606244B2 (en) | 1987-12-07 | 1987-12-07 | Room temperature curable emulsion paint |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2606244B2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002146275A (en) * | 2000-11-16 | 2002-05-22 | Daicel Chem Ind Ltd | Aqueous coating agent for inorganic building material and aqueous coating material composition for inorganic building material |
JP2019094458A (en) * | 2017-11-27 | 2019-06-20 | 藤倉化成株式会社 | Water-based sealer |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4221399B2 (en) | 2005-07-29 | 2009-02-12 | 株式会社シマノ | Bicycle hub cover |
-
1987
- 1987-12-07 JP JP30917787A patent/JP2606244B2/en not_active Expired - Fee Related
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002146275A (en) * | 2000-11-16 | 2002-05-22 | Daicel Chem Ind Ltd | Aqueous coating agent for inorganic building material and aqueous coating material composition for inorganic building material |
JP2019094458A (en) * | 2017-11-27 | 2019-06-20 | 藤倉化成株式会社 | Water-based sealer |
Also Published As
Publication number | Publication date |
---|---|
JP2606244B2 (en) | 1997-04-30 |
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