JPH0280452A - Production of water-dispersible resin powder composition - Google Patents
Production of water-dispersible resin powder compositionInfo
- Publication number
- JPH0280452A JPH0280452A JP63231686A JP23168688A JPH0280452A JP H0280452 A JPH0280452 A JP H0280452A JP 63231686 A JP63231686 A JP 63231686A JP 23168688 A JP23168688 A JP 23168688A JP H0280452 A JPH0280452 A JP H0280452A
- Authority
- JP
- Japan
- Prior art keywords
- water
- parts
- composition
- aqueous dispersion
- resin
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 52
- 239000000843 powder Substances 0.000 title claims abstract description 27
- 229920005989 resin Polymers 0.000 title claims description 22
- 239000011347 resin Substances 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 36
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000006185 dispersion Substances 0.000 claims abstract description 25
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 7
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 230000009477 glass transition Effects 0.000 claims abstract description 5
- 229920000642 polymer Polymers 0.000 claims abstract description 5
- 239000011342 resin composition Substances 0.000 claims description 8
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 4
- 239000000084 colloidal system Substances 0.000 abstract description 6
- 239000003995 emulsifying agent Substances 0.000 abstract description 6
- 230000001681 protective effect Effects 0.000 abstract description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000003505 polymerization initiator Substances 0.000 abstract description 3
- 239000011541 reaction mixture Substances 0.000 abstract description 3
- 239000012736 aqueous medium Substances 0.000 abstract description 2
- 150000001412 amines Chemical class 0.000 abstract 1
- 150000007974 melamines Chemical class 0.000 description 20
- 238000000034 method Methods 0.000 description 20
- 239000004640 Melamine resin Substances 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- -1 2-ethylhexyl Chemical group 0.000 description 10
- 238000009472 formulation Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000001694 spray drying Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000004568 cement Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000004815 dispersion polymer Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 235000019256 formaldehyde Nutrition 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 239000011396 hydraulic cement Substances 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 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
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- XXQBEVHPUKOQEO-UHFFFAOYSA-N potassium superoxide Chemical compound [K+].[K+].[O-][O-] XXQBEVHPUKOQEO-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-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
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- 239000004908 Emulsion polymer Substances 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical compound NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000012874 anionic emulsifier Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- OGVXYCDTRMDYOG-UHFFFAOYSA-N dibutyl 2-methylidenebutanedioate Chemical compound CCCCOC(=O)CC(=C)C(=O)OCCCC OGVXYCDTRMDYOG-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- IEPRKVQEAMIZSS-AATRIKPKSA-N diethyl fumarate Chemical compound CCOC(=O)\C=C\C(=O)OCC IEPRKVQEAMIZSS-AATRIKPKSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- SLPCHCIQXJFYPY-UHFFFAOYSA-N ethenyl phenylmethanesulfonate Chemical compound C=COS(=O)(=O)CC1=CC=CC=C1 SLPCHCIQXJFYPY-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 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
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical compound NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 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
- 239000000025 natural resin Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical class C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 239000011433 polymer cement mortar Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 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
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical class [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は水分散型樹脂粉末組成物の新規にして有用なる
製造法に関するものであり、さらに詳細には、特定の乳
化共重合体分散液と、特定のメラミンスルホン酸塩のホ
ルマリン縮合物とを含んで成る樹脂組成物を乾燥して粉
末化せしめることから成る。水に再分散可能であって、
取り扱いも容易で、しかも応用配合物の物性をも向上さ
せうる、水分散型樹脂粉末組成物の製造法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a new and useful method for producing a water-dispersed resin powder composition, and more particularly, to a method for producing a specific emulsion copolymer dispersion. and a formalin condensate of a specific melamine sulfonate are dried and powdered. redispersible in water,
The present invention relates to a method for producing a water-dispersible resin powder composition that is easy to handle and can also improve the physical properties of applied formulations.
これまでにも、この棟の水に再分散可能な樹脂粉末組成
物、すなわち水分散性の粉末状樹脂組成物は、接着剤と
して、またはセメント系の水硬性物質の混和剤として知
られている。Until now, this water-redispersible resin powder composition, i.e., a water-dispersible powder resin composition, has been known as an adhesive or as an admixture for cement-based hydraulic substances. .
かかる樹脂粉末組成物の製造法としては、主に樹脂分散
液をディスクやノズルを用いて熱風流中で噴霧乾燥せし
めるという方法が用いられている。As a method for producing such a resin powder composition, a method is mainly used in which a resin dispersion is spray-dried in a hot air stream using a disk or a nozzle.
そのさい、噴霧乾燥時における樹脂粒子の融着や、この
融着に伴う再分散性の不良を改善するために１種々の方
法が採られてきた。At this time, various methods have been adopted to improve the fusion of resin particles during spray drying and the poor redispersibility associated with this fusion.
その一つとして、ポリマーの調製時、すなわち重合中と
か、樹脂分散液の噴霧前に、ポリビニルアルコールなど
の保護コロイドを添加するといった方法もあるが、こう
した方法によれば、樹脂の再分散性の向上化は果たし得
るものの、応用配合物の耐水性を著しく悪化させるとい
う不都合のあることは無視できない。One method is to add a protective colloid such as polyvinyl alcohol during the preparation of the polymer, that is, during polymerization or before spraying the resin dispersion. Although improvements can be made, the disadvantage of significantly deteriorating the water resistance of applied formulations cannot be ignored.
また、炭酸カルシウムやタルクなどの無機質充填剤を用
いるという方法によるも、少量の添加では効果を期し得
ないし、逆に、添加蓋を多くすれば、樹脂組成物それ自
体の特性を損う結果になるから、こうした方法もまた１
問題が残るものであると言える。Furthermore, even if inorganic fillers such as calcium carbonate or talc are used, they cannot be expected to be effective if added in small amounts, and conversely, if the amount of fillers added is increased, the properties of the resin composition itself may be impaired. Therefore, this method is also 1.
It can be said that problems remain.
さらに、特公昭５１−４６１２６号公報に開示されてい
るような、メラミンスルホン酸塩のホルマリン縮金物（
以下、スルホン化メラミン樹脂と略記する。）を ＬＪ
ｊ霧する直前に添加するという方法もあるにｆｉあるが
、該スルホン化メラミン樹脂としては、専ら、セメント
や石膏などの分散剤として良く知られていて公知慣用の
、Ｉリエチレングリコールを標準物質とするｒルパーミ
エーショ／・クロマトグラフィー換算の重量平均分子！
（以下同様）が、精々、５，０００〜５０，０００程度
の比較的低分子量領域のものがそのまま転用されている
にすぎないという現状にある。Furthermore, as disclosed in Japanese Patent Publication No. 51-46126, a formalin condensate of melamine sulfonate (
Hereinafter, it will be abbreviated as sulfonated melamine resin. ) to LJ
Although there is a method of adding the sulfonated melamine resin just before spraying, the standard substance used as the sulfonated melamine resin is I-lyethylene glycol, which is well known and commonly used as a dispersant for cement and plaster. Rlupermeation/・Weight average molecule in terms of chromatography!
(The same applies hereafter) However, at present, only those in a relatively low molecular weight range of about 5,000 to 50,000 are being used as is.
したがって、かかるスルホン化メラミン樹脂の添加を噴
霧直前に行なうという上記の方法に従えば、なるほど、
再分散性それ自体は向上するものの、こうした低分子址
のスルホン化メラミン樹脂それ自身が、電解質や凝集剤
としての働きを有するものである処から、必ずしも、水
性分散体との混和性は良くなく、そのために、添加混合
物の安定性も悪く、かつ取り扱いも容易であるとは言え
ない。Therefore, if you follow the above method of adding the sulfonated melamine resin immediately before spraying,
Although the redispersibility itself is improved, since the low molecular weight sulfonated melamine resin itself functions as an electrolyte and a flocculant, its miscibility with an aqueous dispersion is not necessarily good. Therefore, the stability of the additive mixture is poor, and it cannot be said that it is easy to handle.
このように、各種の添加剤を用いるという従来の方法は
、再分散性の向上を専らの目的としているものである処
から、再分散性の向上化を図ると共に、応用配合物の物
性向上化という目的をも果たすことについては何らの示
唆を与えるものではなく、シたがって、こうした広大な
目的のために添加剤を用いるという技術思想は類例を見
ないとも言えるであろうし、換言すれば、添加剤を用い
て所かる広大な目的を達成しようとする試みは何−つと
して為されていないとも言えよう。In this way, the conventional method of using various additives has the sole purpose of improving redispersibility. There is no suggestion whatsoever that this purpose is achieved, and therefore, it can be said that the technical idea of using additives for such a vast purpose is unprecedented.In other words, It can be said that no attempt has been made to use additives to achieve certain broad objectives.
しかるに、杢発明者らは上述した従来技術における。唯
一とも言える長所と種々の欠点との存在に鑑みて、水へ
の再分散化が可能であって、取り扱いも容易であり、か
つ応用配合物の物理的性能および機械的性能などの向上
化をも果たしうるような水分散型樹脂粉末組成物を提供
することを目的として鋭意検討を重ねた結果、Ｉ＃定の
ガラス転移温度を有する。ｄ リマーの乳化共重合体た
る水性樹脂分散体と、特定の分子量を有するスルホン化
メラミン樹脂とを必須の成分とする樹脂組成物を乾燥し
粉末化せしめることから成る製造法が、再分散性はもと
よりのこと、取り扱いの容易さ（取り扱い性）にもすぐ
れた粉末状樹脂組成物を与えるものであることを見い出
し、加えて、水硬性セメントなどに、上記した如き製造
法により得られる水分散型樹脂粉末組成物を添加したさ
いには。However, the inventors of the present invention are concerned with the prior art described above. Considering the unique advantages and various disadvantages, it is possible to redisperse in water, easy to handle, and improve the physical and mechanical performance of applied formulations. As a result of extensive research aimed at providing a water-dispersible resin powder composition that can achieve the same goal, we have found that it has a glass transition temperature of I#. A manufacturing method that consists of drying and powdering a resin composition containing an aqueous resin dispersion that is an emulsion copolymer of d reamer and a sulfonated melamine resin having a specific molecular weight as essential components, has poor redispersibility. It has been discovered that it provides a powdered resin composition that is not only easy to handle, but also provides a water-dispersible resin composition that can be used in hydraulic cement, etc. When adding the resin powder composition.
すぐれた物理的強度ならびに基材付着性などの新たな効
果を発現するものであることをも見い出して１本発明を
完成させるに到った。They have also discovered that it exhibits new effects such as excellent physical strength and adhesion to substrates, leading to the completion of the present invention.
すなわち１本発明は必須の成分として、α、β−エチレ
ン性不飽和単量体を乳化重合させて得られる、ガラス転
移温度が３０℃以下なる？リマーの水性分散体■と１重
量平均分子量が１０万以上なる。スルホン化メラミン樹
脂、つまり、メラミンスルホン酸塩のホルマリン縮金物
（Ｂ）とを、該水性分散体（Ａ）：スルホン化メラミン
樹脂（Ｂ）なる固形分重量比が７５’ ： ２５〜９９
：１となるように含んで成る樹脂組成物を乾燥粉末化せ
しめることから成る。水分散型樹脂粉末組成物の製造方
法を提供しようとするものである。Namely, in the present invention, the glass transition temperature obtained by emulsion polymerization of an α,β-ethylenically unsaturated monomer as an essential component is 30°C or lower. The weight average molecular weight of Rimmer aqueous dispersion (1) is 100,000 or more. The sulfonated melamine resin, that is, the formalin condensate of melamine sulfonate (B), is mixed with the aqueous dispersion (A):sulfonated melamine resin (B) in a solid content weight ratio of 75': 25 to 99.
The method consists of drying and powdering a resin composition comprising: 1. The present invention aims to provide a method for producing a water-dispersed resin powder composition.
ここにおいて、上記α、β−エチレン性不飽和単量体と
して特に代表的なもののみを挙げるに止めれば、（メタ
）アクリル酸メチル、（メタ）アクリル酸エチル、（メ
タ）アクリルｆｌｌ−ｎ−ブチル、（メタ）アクリル酸
イソブチル、（メタ）アクリル酸−２−エチルヘキシル
もしくは（メタ）アクリル酸ラウリルの如き（メタ）ア
クリル酸エステル類；ジエチルマレエート、ジエチルフ
マレ−トもしくはジブチルイタコネートの如き不飽和二
塩基酸のノエステル類：マレイン酸、フマル酸もしくは
イタコン酸の如き不飽和二塩基またはこれらの半エステ
ル類や塩類；（メタ）アクリル酸、ビニルスルホン酸も
シくはビニルトルエンスルホ／酸の如き一塩基酸または
これらの塩類；（メタ）アクリルアミドもしくはマレイ
ン酸アミドの如きα、β−エチレン性不飽和カルボン酸
のアミド類；Ｎ−メチロールアミドもしくはジアセトン
アクリルアミドの如き不飽和カルボン酸の置換アミド類
；酢酸ビニル、プロピオ／酸ビニルもしくは第三級カル
ボン酸ビニルの如キビニルエステル類；スチレンもしく
は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；塩化ビニリデン
もしくはぶつ化ビニリデンの如きハロダン化ビニリデン
類；エチレｙもしくはプロピレンの如きα−オレフィン
類：ブタジェンの如きジエン類；ジアリルフタレート、
ジビニルベンゼン、アリルアクリレートモジくハトリメ
チロールプロパントリメタクリレートの如き。Here, to mention only particularly representative α,β-ethylenically unsaturated monomers, methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylic flll-n- (Meth)acrylic acid esters such as butyl, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate or lauryl (meth)acrylate; unsaturated such as diethyl maleate, diethyl fumarate or dibutyl itaconate Noesters of dibasic acids: unsaturated dibasic acids such as maleic acid, fumaric acid or itaconic acid, or half esters and salts thereof; such as (meth)acrylic acid, vinylsulfonic acid or vinyltoluenesulfonate/acid. Monobasic acids or their salts; Amides of α,β-ethylenically unsaturated carboxylic acids such as (meth)acrylamide or maleic acid amide; Substituted amides of unsaturated carboxylic acids such as N-methylolamide or diacetone acrylamide ; vinyl esters such as vinyl acetate, propio/vinyl acids or vinyl tertiary carboxylates; aromatic vinyl compounds such as styrene or vinyltoluene; heterocyclic vinyl compounds such as vinylpyrrolidone; vinylidene halides such as; α-olefins such as ethylene or propylene; dienes such as butadiene; diallylphthalate,
Such as divinylbenzene, allyl acrylate, and trimethylolpropane trimethacrylate.
−分子中に２個以上の不飽和結合を有する単量体；ある
いは塩化ビニル、アクリロニトリル、ビニルエーテル、
ビニルケトンまだはビニルアミドなどであり、これらは
単独使用でも２種以上の併用でもよいことは勿論である
。- Monomers having two or more unsaturated bonds in the molecule; or vinyl chloride, acrylonitrile, vinyl ether,
Vinyl ketones include vinylamide and the like, and it goes without saying that these may be used alone or in combination of two or more.
上掲された如き各種単量体の組み合わせのうちでも特に
望ましいものとしては、アクリル系、アクリル−スチレ
ン系、スチレン−ブタジェン系。Among the various combinations of monomers listed above, particularly preferred are acrylic, acrylic-styrene, and styrene-butadiene.
ビニルエステル系、サラン系（塩化ヒニ・リチン系）；
塩化ビニル系またはエチレン−酢酸ビニル系などが挙げ
られる。Vinyl ester type, Saran type (hinic chloride/lithine type);
Examples include vinyl chloride type and ethylene-vinyl acetate type.
上掲のα、β−エチレン性不飽和単量体から？リマー水
性分散体を得るには、公知慣用の乳化重合法が適用でき
る。From the α, β-ethylenically unsaturated monomer listed above? A known and commonly used emulsion polymerization method can be applied to obtain the remer aqueous dispersion.
このさい、使用される乳化剤としては、−船釣に乳化重
合に用いられているものであれば、いずれでもよく、そ
のうちでも代表的なものとしては。In this case, any emulsifier used may be used as long as it is used for emulsion polymerization in boat fishing, and among these, representative ones include:
ポリオキシエチレンアルキルニーテルモＬ＜ハ４リオキ
シエチレンアルキルフェノールエーテルの如き非イオン
系乳化剤；高級アルコール硫酸エステル類もしくはアル
キルベンゼンスルホン酸塩類の如きアニオン系乳化剤；
または高級アルコール第四級アンモニウム塩もしくはア
ルキルアミンの如きカチオン系乳化剤などが挙げられる
。Nonionic emulsifiers such as polyoxyethylene alkyl phenol ether; anionic emulsifiers such as higher alcohol sulfates or alkylbenzene sulfonates;
Alternatively, cationic emulsifiers such as higher alcohol quaternary ammonium salts or alkyl amines may be mentioned.
また、保護コロイドとしては、ポリビニルアルコールマ
タハヒドロキシエチルセルロースの如キ非イオ／性水溶
性高分子化合物などが代表的なものである。Typical protective colloids include non-ionic/water-soluble polymer compounds such as polyvinyl alcohol hydroxyethyl cellulose.
これらの乳化剤や保護コロイドはそれぞれ、１種もしく
は２種以上の混合物として用いられるが。Each of these emulsifiers and protective colloids may be used alone or as a mixture of two or more.
それぞれの使用量としては、粉末組成物を得るという本
発明の目的からすれば、できるだけ少量であることが望
ましく、通常、単量体総量の０．１〜８重量％程度に止
めおくべきである。From the purpose of the present invention, which is to obtain a powder composition, it is desirable that the amount of each used be as small as possible, and usually it should be kept at about 0.1 to 8% by weight of the total amount of monomers. .
さらに、重合開始剤としては特に制限がなくていずれで
もよいが１通常は、過硫酸塩類や過酸化水素などの水溶
性ラジカル触媒とか、アゾ系化合物などの有機過酸化物
が用いられ、その使用蓋としては、単量体総量の０．１
〜２重量−程度が好適である。さらに必要に応じて、亜
硫酸ナトリウムやロンガリット塩などの還元剤を併用し
てもよいことは勿論である。Furthermore, there are no particular restrictions on the polymerization initiator, and any polymerization initiator may be used; usually, water-soluble radical catalysts such as persulfates and hydrogen peroxide, and organic peroxides such as azo compounds are used. For the lid, 0.1 of the total amount of monomers is used.
~2 weight is preferred. Furthermore, it goes without saying that a reducing agent such as sodium sulfite or Rongalite salt may be used in combination, if necessary.
そして、乳化重合の温度および圧力は、使用する単量体
の種類により、種々選択できるが４好ましくは０〜１０
０℃なる範囲内の温度、そして１００に９／ｃｙｎ 以
下の圧力である。The temperature and pressure for emulsion polymerization can be variously selected depending on the type of monomer used, but preferably 0 to 10
The temperature is in the range of 0° C. and the pressure is less than 9 in 100/cyn.
かくして得られる４リマ一水性分散体は、荷電に応じて
非イオン性、アニオン性またはカチオン性に大別される
が、前記スルホン化メラミン樹脂（Ｂ）との混和性を考
慮するならば、カチオン性のものの使用は推奨できない
。The 4Lima monoaqueous dispersion thus obtained is roughly classified into nonionic, anionic, or cationic depending on the charge, but if miscibility with the sulfonated melamine resin (B) is considered, it is cationic. The use of sexual substances is not recommended.
当該水性分散体囚の乳化重合体たるポリマーのガラス転
移温度としては３０℃以下であることが望ましい。それ
は５本発明方法により得られる粉末状樹脂組成物の主な
用途の一つが水硬性セメントの添加剤であり、セメント
に十分な基材付着性や柔軟性などを付与させるといった
使用目的のためにも望ましいことである。The glass transition temperature of the emulsion polymer of the aqueous dispersion is preferably 30°C or lower. 5 One of the main uses of the powdered resin composition obtained by the method of the present invention is as an additive for hydraulic cement. is also desirable.
次に、前記したスルホン化メラミン樹脂（Ｂ）としては
、たとえば、メラミンを主成分とするアミン基含有物質
とホルムアルデヒドおよび亜硫酸塩とを水性媒体中で、
ｐ）１を１０以上として、６０〜８０℃なる範囲内の
温度で、０．５〜６時間反応させ（以上を前段反応と略
記する。）１次いで１反応混合物の−を３，５〜６．５
に調節し、２０〜７０℃なる温度で１〜１５時間反応さ
せ（これを後段反応という。）、シかるのち１反応混合
物の〆（を７〜１３に調節するというような方法によっ
て得られるものが挙げられる。Next, as the above-mentioned sulfonated melamine resin (B), for example, an amine group-containing substance containing melamine as a main component, formaldehyde and a sulfite are mixed in an aqueous medium,
p) 1 is set to 10 or more, and the reaction is carried out at a temperature within the range of 60 to 80°C for 0.5 to 6 hours (the above is abbreviated as the first stage reaction). .5
and react at a temperature of 20 to 70°C for 1 to 15 hours (this is called the second stage reaction), and then adjust the temperature of the reaction mixture to 7 to 13. can be mentioned.
かかるスルホン化メラミン樹脂、つまりメラミンスルホ
ン酸塩のホルマリン縮合物といっり、コの種の基本構造
を有するもののうち、重量平均分子量が５，０００〜５
０．０００なる範囲内のスルホン化メラミン樹脂として
は、特公昭５２−１３９９号公報や特開昭５７−１００
９５９号公報などに開示されているようなセメント分散
剤たる、いわゆる減水剤組成物が知られているだけであ
る。Among such sulfonated melamine resins, that is, formalin condensates of melamine sulfonate, which have the basic structure of the following types, those having a weight average molecular weight of 5,000 to 5
As the sulfonated melamine resin within the range of 0.000, Japanese Patent Publication No. 52-1399 and Japanese Patent Application Laid-Open No. 57-100
Only so-called water reducing agent compositions, which are cement dispersants, as disclosed in Japanese Patent No. 959, etc., are known.
しかるに１本発明において用いられる当該スルホン化メ
ラミン樹脂（Ｂ）それ自体は１０万以上という著しく高
分子量物である処から、当該樹脂（Ｂ）それ自体には、
セメントや５責などに対する分散能力が殆んど認められ
ない。However, since the sulfonated melamine resin (B) used in the present invention itself has an extremely high molecular weight of 100,000 or more, the resin (B) itself has
It has almost no dispersion ability against cement or 5-oxide particles.
前述した如きスルホン化メラミン樹脂（Ｂ）の調製時に
おける前段反応のさいに用いられる５メラミンを主成分
とするアミン基含有物質としては、メラミン単独、また
はメラミンとこのメラミンに対して２０重ｉ％以下の尿
素、グアナミン類、ノシアンソアミドもしくはチオ尿素
などとの混合物などが代表的なものであり、また、ホル
ムアルデヒドとしてはホルマリンまたはノぞラホルムア
ルデヒドなどが代表的なものであり、さらに亜硫酸塩と
しては亜硫酸水素ナトリウム、亜硫酸ナトリウムまたは
重亜硫酸ナトリウムなどが代表的なものである。The amine group-containing substance containing 5-melamine as a main component used in the first stage reaction during the preparation of the sulfonated melamine resin (B) as described above may be melamine alone or melamine and 20% by weight based on the melamine. Typical examples include mixtures with urea, guanamines, nocyanthamide, or thiourea, etc.; typical formaldehydes include formalin and nozora formaldehyde; and sulfites include sulfite. Representative examples include sodium hydrogen, sodium sulfite, and sodium bisulfite.
前段反応と後段反応との間で、−調整に用いられる酸性
物質としては、硫酸、硝酸、燐酸、蟻酸またはアミドス
ルホン酸類などが代表的なものである。Typical acidic substances used for adjustment between the first and second reactions include sulfuric acid, nitric acid, phosphoric acid, formic acid, and amidosulfonic acids.
ところで９本発明方法において用いられる１垂蓋平均分
子蚤が１０万以上なるスルホン化メラミン樹脂（Ｂ）を
得るためには、単に、縮合反応である後段反応の反応時
間を延長せしめるという方法のほかに、前段反応中に生
成した。あるいは別途に調製された。メラミン分子中の
アミン基に存在する６個の水素原子のうちの３個以上を
メチロール基で置換した形のメチロールメラミンを架橋
点となすことによって架橋高分子化せしめるという方法
もある。By the way, in order to obtain the sulfonated melamine resin (B) having an average molecular weight of 100,000 or more used in the method of the present invention, there are two methods, in addition to simply extending the reaction time of the subsequent reaction, which is the condensation reaction. was formed during the first stage reaction. Or prepared separately. There is also a method of crosslinking polymerization by using methylolmelamine, in which three or more of the six hydrogen atoms present in the amine groups in the melamine molecule are substituted with methylol groups, as a crosslinking point.
以上のようにして得られたポリマー水性分散体（Ａ）と
スルホン化メラミン樹脂（Ｂ）とを、必須の成分として
、これらを配合せしめるには、使用直前にブレンドする
のが、配合物の安定性の上でも望プしいけれども、決し
て１本発明は斯かる方法のみに限定されるものではない
。In order to blend the aqueous polymer dispersion (A) obtained as above and the sulfonated melamine resin (B) as essential components, it is best to blend them immediately before use to stabilize the blend. Although desirable in terms of performance, the present invention is by no means limited to only such a method.
そして、これら両必須成分の配合割合としては。And what is the blending ratio of both these essential ingredients?
固形分重量比で、（Ａ）成分＝（Ｂ）成分が７５：２５
〜９９：１なる範囲内が好適である。Solid weight ratio: (A) component = (B) component: 75:25
A range of 99:1 to 99:1 is preferred.
（Ｂ）成分の比率が２５を超えて多く用いてみても。(B) Even if the ratio of the components exceeds 25 and is used in large quantities.
（Ｂ）成分それ自体の効果が、それ以上には期待できな
いし、−万、この比率が１未満であると、どうしても、
乾燥工程中、あるいは粉末化されたのちの保存中におけ
る融着防止効果が十分に発現され得なくなるので、いず
れも好ましくない。(B) The effect of the component itself cannot be expected to be any greater, and if this ratio is less than 1, then
Both are unfavorable since the effect of preventing fusion during the drying process or during storage after being powdered cannot be sufficiently expressed.
不発明方法に従って目的とする。再分散可能な粉末組成
物を得るには１種々の乾燥方法があるが。Aim according to the non-inventive method. There are various drying methods to obtain redispersible powder compositions.
噴霧乾燥法や凍結乾燥法などが、特に代表的なものであ
る。そのうちでも、特に平行流式の噴霧乾燥法が推奨さ
れる。Particularly typical methods include spray drying and freeze drying. Among these, the parallel flow spray drying method is particularly recommended.
また、必要に応じて、目的粉末組成物の放置安定性およ
び再分散性などを一層向上させるために。Also, if necessary, to further improve the storage stability and redispersibility of the target powder composition.
粘土、メルク、シリカ、珪藻土または炭酸カルシウムな
どの無機質充填剤やポリビニルアルコールなどを、本発
明の効果を損わない範囲内で添加して噴霧乾燥せしめる
こともできる。Inorganic fillers such as clay, Merck, silica, diatomaceous earth, or calcium carbonate, polyvinyl alcohol, and the like may be added to the spray-drying method within a range that does not impair the effects of the present invention.
かくして１本発明の方法により得られる粉末組成物は、
水やアルカリ性物質が添加された弱アルカリ性水溶液中
に５安定な水分散液として、容易に再分散せしめること
ができる。Thus, one powder composition obtained by the method of the present invention is
It can be easily redispersed as a stable aqueous dispersion in a weakly alkaline aqueous solution containing water or an alkaline substance.
得られた水分散型樹脂粉末組成物の再分散液には、必要
に応じて、さらに他の水溶性ないしは水分散性の合成ま
たは天然樹脂、メルクもしくはシリカの如き無機質充填
剤、酸化チタンもしくはクレーの如き顔料をはじめ、他
の分散剤、保護コロイド、湿潤剤、消泡剤、可塑剤、凍
結安定剤または防腐剤、あるいは溶剤などの１株または
２種以上を選択して用いることができるのは勿論である
。The resulting redispersion of the water-dispersible resin powder composition may optionally contain other water-soluble or water-dispersible synthetic or natural resins, inorganic fillers such as Merck or silica, titanium oxide or clay. In addition to pigments such as, other dispersants, protective colloids, wetting agents, antifoaming agents, plasticizers, freeze stabilizers or preservatives, or solvents, etc., or one or more of them can be selected and used. Of course.
本発明の方法に従って得られる水分散型樹脂粉末組成物
は、それぞれ１部定された範囲の特別のポリマー水性分
散体（Ａ）とスルホン化メラミン樹脂（Ｂ）とを必須の
成分として含んでいるものである処から、従来公知の利
用分野のすべてに適用できるのは勿論であり、とりわけ
、水硬性セメントなどに使用された場合、には、すぐれ
た物理的強度ならびに基材付着性などを発現するもので
あり、当該粉末組成物の利用性は一層、確かなものとな
ろう。The water-dispersed resin powder composition obtained according to the method of the present invention each contains as essential components a special aqueous polymer dispersion (A) and a sulfonated melamine resin (B), each in a defined range. Since it is a material, it can of course be applied to all conventionally known fields of use, and in particular, when used in hydraulic cement, etc., it exhibits excellent physical strength and adhesion to substrates. Therefore, the usability of the powder composition will be even more certain.
次に、本発明を参考例、実施例および比較例により一層
、具体的に説明するが、以下において部およびうは特記
のない限り、すべて重量基準であるものとする
参考例１〔ポリマー水性分散体（Ａ）の調製例〕電磁回
転撹拌機、温度計および還流冷却器を備えた耐圧反応容
器中に１次の組成からなる溶液を入れて撹拌を開始する
。Next, the present invention will be explained in more detail with Reference Examples, Examples, and Comparative Examples. In the following, unless otherwise specified, all parts and cells are based on weight. Reference Example 1 [Polymer Aqueous Dispersion] Preparation Example of Product (A)] A solution having the following composition is placed in a pressure-resistant reaction vessel equipped with an electromagnetic rotary stirrer, a thermometer, and a reflux condenser, and stirring is started.
イオン交換水 ６００部「ゴーセ
ノール ＧＨ−２０Ｊ １０部〔
日本合成化学工業（株）製の部分けん化ホリビニルアル
コール〕
ＮａＨＣｏ、 ３部ハ
イドロサルファイドナトリウム
３部この溶液に５０部の酢酸ビニルを加えてから。Ion exchange water 600 parts "Gohsenol GH-20J 10 parts [
Partially saponified polyvinyl alcohol manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd.] NaHCo, 3-part sodium hydrosulfide
Add 3 parts of vinyl acetate to this solution and then add 50 parts of vinyl acetate.
エチレンを圧入して４０℃に昇温し、５部の過硫酸カリ
ウムを添加したのち４５０部の酢酸ビニルを４時間に亘
って滴下した。Ethylene was introduced under pressure, the temperature was raised to 40°C, 5 parts of potassium persulfate was added, and 450 parts of vinyl acetate was added dropwise over 4 hours.
滴下終了後も、さらに同温度に１時間保持して重合を完
結させた。After the dropwise addition was completed, the same temperature was further maintained for 1 hour to complete the polymerization.
上記重合中、エチレン圧を３０に９／σとなるように常
時、調節する。During the above polymerization, the ethylene pressure is constantly adjusted to 30:9/σ.
反応完結後のポリマーのエチレン含有率は１５チであっ
た・
次いで、固形分濃度を５０％にして、これを水性分散体
（Ａ−１）と略記する。The ethylene content of the polymer after the reaction was completed was 15%.Next, the solid content concentration was increased to 50%, and this was abbreviated as aqueous dispersion (A-1).
参考例２（同上）
回転撹拌機、温度計および還流冷却器を備えた反応容器
中に１次の組成の溶液を仕込んで１反応系の温度を８０
℃とした。Reference Example 2 (same as above) A solution having the following composition was charged into a reaction vessel equipped with a rotary stirrer, a thermometer, and a reflux condenser, and the temperature of the reaction system was brought to 80°C.
℃.
イオン交換水 １００部「エマー
ル １０」 １部〔花
王（株）製のアニオン性乳化剤〕
［エマルグン ９４０ｊ
４部〔同上社製の非イオン性乳化剤〕
次いで、ここへ０５部の過（Ａ酸カリウムを加え。Ion-exchanged water 100 parts "Emarl 10" 1 part [Anionic emulsifier manufactured by Kao Corporation] [Emulgun 940j
4 parts [Nonionic emulsifier made by the same company] Next, 05 parts of potassium peroxide (A acid) was added thereto.
さらにアクリル酸−２−エチルヘキシルの５０部。Additionally 50 parts of 2-ethylhexyl acrylate.
メタクリル酸メチルの４８部およびメタクリル酸の２部
よりなる単量体混合物を３時間かけて滴下した。A monomer mixture consisting of 48 parts of methyl methacrylate and 2 parts of methacrylic acid was added dropwise over 3 hours.
滴下終了後、さらに過硫酸カリウムの０．１部を加えて
８０℃に２時間保持してから室温まで冷却し、１４％ア
ンモニア水とイオン交換水とで−を８．７に、固形分を
４５％に調整した。以下、これを水性分散体（Ａ−２）
と略記する。After the addition, 0.1 part of potassium persulfate was added and the temperature was kept at 80°C for 2 hours, then cooled to room temperature, and the solid content was reduced to 8.7 with 14% ammonia water and ion-exchanged water. It was adjusted to 45%. Hereinafter, this will be referred to as an aqueous dispersion (A-2).
It is abbreviated as
参考例３（同上）
単量体組成を、アクリル酸−ｎ−エチルの４３部、スチ
レンの５５部およびアクリル酸の２部に変更した以外は
、参考例１と同様にして、固形分が４５チで、かつ−が
８．８なる水性分散体（Ａ−３）を得た。Reference Example 3 (same as above) The solid content was 45 parts in the same manner as in Reference Example 1, except that the monomer composition was changed to 43 parts of n-ethyl acrylate, 55 parts of styrene, and 2 parts of acrylic acid. An aqueous dispersion (A-3) was obtained in which H was 8.8 and - was 8.8.
参考例４（対照用ポリマー水性分散体の調製例）単量体
組成を、アクリル酸−ｎ−ブチルの７０部。Reference Example 4 (Example of Preparation of Aqueous Polymer Dispersion for Control) The monomer composition was 70 parts of n-butyl acrylate.
メタクリル酸メチルの２８部およびメタクリル酸の２部
に変更した以外は、参考例２と同様にして。The same procedure as Reference Example 2 was carried out except that 28 parts of methyl methacrylate and 2 parts of methacrylic acid were used.
固形分が４５％で、かつｐｉ（が９．０なる対照用分散
体を得た。以下、これを水性分散体（ｐ、’−１）と略
記する。A control dispersion with a solids content of 45% and pi (9.0) was obtained. Hereinafter, this will be abbreviated as an aqueous dispersion (p,'-1).
参考例５〔スルホン化メラミン樹脂（Ｂ）の調製例〕参
考例１と同様の反応容器に、撹拌しつつ、次の組成物を
仕込んで１反応系の−を１３．０としてから７５℃に昇
温し、同温度に２．５時間保持しもイオン交換水
４９部メラミン ４２
部
３７％ホルマリン ８１部亜硫酸水素ナト
リウム ２６部水酸化ナトリウム
４．４部次いで１反応系内の温度を５５℃とし、７
．１部の濃硫酸を１００部の水で希釈したものを１時間
かけて滴下し、−を４．４とした。Reference Example 5 [Example of Preparation of Sulfonated Melamine Resin (B)] Into the same reaction vessel as in Reference Example 1, the following composition was charged with stirring to bring the - of one reaction system to 13.0, and then heated to 75°C. Raise the temperature and keep it at the same temperature for 2.5 hours.
49 parts melamine 42
Part 37% Formalin 81 parts Sodium bisulfite 26 parts Sodium hydroxide
4.4 parts Then, the temperature in one reaction system was set to 55°C, and 7
．． A solution prepared by diluting 1 part of concentrated sulfuric acid with 100 parts of water was added dropwise over 1 hour, and - was set to 4.4.
さらに、同温度に１時間保持した処で１反応混合物が粘
稠となり、つまり２５℃におけるブルックフィールド粘
度（以下同様）は１５，０００ ｃｐｓを示した。この
時点で、１５０部の水を添加して更に同温度に３時間保
持した。Furthermore, one reaction mixture became viscous after being maintained at the same temperature for 1 hour, that is, the Brookfield viscosity (hereinafter the same) at 25° C. was 15,000 cps. At this point, 150 parts of water was added and the temperature was maintained for an additional 3 hours.
しかるのち、水酸化ナトリウムの５部と水の７０部とを
添加して室温まで冷却した。Thereafter, 5 parts of sodium hydroxide and 70 parts of water were added and the mixture was cooled to room temperature.
得られた樹脂は無色半透明の液状物で、固形分が２０％
で、粘度が１８０ ｃｐｓで、ｐＨが１１．２で。The resulting resin is a colorless, translucent liquid with a solids content of 20%.
The viscosity is 180 cps and the pH is 11.2.
かつ重量平均分子量が３０万なるものであった。And the weight average molecular weight was 300,000.
以下、樹脂（Ｂ−２）と略記する。Hereinafter, it will be abbreviated as resin (B-2).
参考例６（同上）
参考例３と同様の装置を用い、次のような組成物を仕込
んで反応系内の−を１２として７５℃に１時間保持した
。Reference Example 6 (same as above) Using the same apparatus as in Reference Example 3, the following composition was charged, the - in the reaction system was set to 12, and the temperature was maintained at 75°C for 1 hour.
イオン交換水 ５８ 部メラミン
４２部
３７チホルマリン ８１ 部属硫酸水素ナ
トリウム ３４，７部水酸化ナトリウム
２．２部次いで、系内の温度を５５℃とし、
＃硫酸の７．５部とイオン交換水の１００部とを加えて
−を３．９とした。さらに、同温度に１２時間保持して
、水酸化ナトリウムの５部と水とで固形分を２０％とし
、Ｐ［−１を１２に調整して冷却した。Ion exchange water 58 parts melamine
42 parts 37 formalin 81 parts Sodium hydrogen sulfate 34.7 parts Sodium hydroxide
2.2 parts Then, the temperature in the system was set to 55°C,
#7.5 parts of sulfuric acid and 100 parts of ion-exchanged water were added to make -3.9. Further, the temperature was maintained at the same temperature for 12 hours, the solid content was adjusted to 20% with 5 parts of sodium hydroxide and water, P[-1 was adjusted to 12, and the mixture was cooled.
得られた樹脂は無色透明な液状物で１重量平均分子量が
１２万なるものであった。以下、これを樹脂（Ｂ−２）
と略記する。The resulting resin was a colorless and transparent liquid with a weight average molecular weight of 120,000. Hereinafter, this will be referred to as resin (B-2).
It is abbreviated as
／
どつ
実施例１〜５および比較例１〜８
ポリマー水性分散体とスルホン化メラミン樹脂とを、さ
らにはポリビニルアルコールをも、第３表に示されてい
るような固形分重量比で、配合させてから、それぞれの
配合物の固形分＃匣を水で３０％に調整した。/ Dotsu Examples 1 to 5 and Comparative Examples 1 to 8 Aqueous polymer dispersion, sulfonated melamine resin, and even polyvinyl alcohol were blended at solid content weight ratios as shown in Table 3. Then, the solids content of each formulation was adjusted to 30% with water.
調整済みの各配合物を、まず、研究用平行流式噴霧乾燥
器を用いて噴霧乾燥せしめ、そのさいの該乾燥装置の壁
面への固着状態や、樹脂粉末のブロック生成状態などを
総合的に観察して、「粉末化の状態」を評価判定した。Each of the prepared formulations was first spray-dried using a research parallel flow spray dryer, and the adhesion to the wall of the dryer and the state of block formation of the resin powder were comprehensively checked. The "state of powderization" was evaluated and determined by observation.
なお、かかる噴霧乾燥中の熱風入口温度は１２０℃とし
、出口温度は５０℃とした。The hot air inlet temperature during the spray drying was 120°C, and the outlet temperature was 50°C.
次いで、かくして得られたそれぞれの粉末組成物を２０
℃、６０％Ｒ，Ｈ，なる室内に３力月保存したのち、水
に対して固形分濃度が４０チとなる量の粉末組成物を溶
解せしめることにより、そのさいの「再分散性」を評価
判定した。Then, each of the powder compositions thus obtained was
After storing it in a room at 60% R and H for 3 months, the powder composition was dissolved in water in an amount to give a solid concentration of 40%, thereby improving its "redispersibility". The evaluation was determined.
かくて、それぞれの配合物についての「粉末化の状態」
と、各配合物を乾燥し粉末化せしめて得られたそれぞれ
の粉末組成物についての「再分散性」との結果を、同表
にまとめて示す。Thus, the “state of powdering” for each formulation
The results of "redispersibility" for each powder composition obtained by drying and powdering each formulation are summarized in the same table.
さらに、実施例１〜５の粉末組成物（ＰＣ−１）〜（ｐ
ｃ−５）と、比較例４〜７で得られた対照用の粉末組成
物（ｐ ｃ −１’ ）〜（ＰＣ−４’）を用い、下記
の配合に従って各別にポリマーセメントモルタルを調製
して、それぞれのモルタル配合物についてのポットライ
フ、曲げ強度、圧縮強度ならびに付着強度を観察し測定
した。Furthermore, powder compositions (PC-1) to (p
Using c-5) and the control powder compositions (pc-1') to (PC-4') obtained in Comparative Examples 4 to 7, polymer cement mortars were prepared separately according to the following formulations. The pot life, bending strength, compressive strength, and adhesive strength of each mortar composition were observed and measured.
普通ポルトランドセメント １００部豊浦標準砂
２００部粉末組成物
１０部昔フロー値が１７０±１０となるように
調節すべき量なお、養生の条件としては、湿空２日後、
２０℃で６０ Ｓ Ｒ，Ｈ，なる気乾養生という条件を
用いた。Ordinary Portland cement 100 parts Toyoura standard sand
200 parts powder composition
The amount that should be adjusted so that the flow value becomes 170 ± 10.The curing conditions are as follows: 2 days in a humid air,
Air-dry curing conditions of 60 SR,H at 20°C were used.
また、それぞれの試験法は１次のような要領に行なった
ものである。In addition, each test method was conducted in the following manner.
「ポットライフ」・・・モルタル配合時からの鏝作業可
能な時間を測定したものであるが、このさい
２０℃で６０ Ｓ Ｒ，Ｈ，なる条件下で行なったもの
であり、鏝作業可能な状態としては、フロー値が１５０
以上なる条件を設定した。"Pot life": Measures the time that can be worked with a trowel after mixing the mortar, and this was done under conditions of 60 S R, H at 20°C, which means that it is possible to work with a trowel. As for the state, the flow value is 150
The above conditions were set.
該ポットライフの評価判定基準は次の通りとした。The criteria for evaluating the pot life were as follows.
○・・・１．５時間以上
Δ・・・０．５時間以上１．５時間未満×・・・０．５
時間未満
「曲げ強度」・・・両強度とも、 ＪＩＳ Ｒ−５２０
１に準拠してモおよび ルタル試片を炸裂して、
材令７日と２８「圧縮強度」 日とについて行なったも
のである。○...1.5 hours or more Δ...0.5 hours or more and less than 1.5 hours ×...0.5
"Bending strength" for less than hours...Both strengths are JIS R-520
Explosive Mo and Rutal specimens in accordance with 1.
This was carried out on the 7th day of the material age and the 28th day of "compressive strength".
「付着強度」・・・下記する如き両基材に、モルタルを
３龍厚に鏝で塗布して、材令２８日で、建研式接着力試
験機にて測定したものである。"Adhesion strength": Mortar was applied to both substrates as described below with a trowel to a thickness of 30 cm, and measured using a Kenken type adhesive strength tester at 28 days old.
すなわち、コンクリート基材としては
３０ Ｘ ３０ｃｍなる大きさのコンクリート歩道板を
用いたし、磁器タイルとしては。That is, a concrete sidewalk board with a size of 30 x 30 cm was used as the concrete base material, and as the porcelain tile.
ＪＩＳ Ａ−５２０９に準拠したものの表面を付着面と
して用いた。A surface conforming to JIS A-5209 was used as the attachment surface.
以上の各物性試験の結果は、まとめて第４表に示す。但
し、比較例８はブランク・テスト例である。The results of each of the above physical property tests are summarized in Table 4. However, Comparative Example 8 is a blank test example.
／
〔発明の効果〕
第３表および第４表の結果からも明らかなように、不発
明の方法に従って得られる水分散型樹脂粉末組成物は、
水に対する再分散性にもすぐれるし、取り扱いも容易で
あるし、応用配合物の物性も改善されていることが知れ
る。/ [Effect of the invention] As is clear from the results in Tables 3 and 4, the water-dispersed resin powder composition obtained according to the method of the invention has the following effects:
It is known that it has excellent redispersibility in water, is easy to handle, and has improved physical properties of applied formulations.
このことは、スルホン化メラミン樹脂が単なる水性分散
体の癒着防止という働きだけでなく１分子量が非常に高
いものである処から、塩＃染を惹起し難く、加えて、水
性分散体に吸着して保護コロイドや官能基的な働きをも
有しているためであると推測される。This is because the sulfonated melamine resin not only has the function of preventing adhesion of the aqueous dispersion, but also has a very high molecular weight, so it is difficult to cause salt staining, and in addition, it does not adsorb to the aqueous dispersion. This is presumed to be because it also functions as a protective colloid or a functional group.
代理人 弁理士 高 橋 勝 利Agent Patent Attorney Katsutoshi Takahashi
Claims (1)
によって得られる、ガラス転移温度が ３０℃以下なるポリマーの水性分散体と、 （Ｂ）重量平均分子量が１０万以上なる、メラミンスル
ホン酸塩のホルマリン縮合物 とを必須の成分として、上記水性分散体（Ａ）：ホルマ
リン縮合物（Ｂ）なる固形分重量比が７５：２５〜９９
：１となるように含んで成る樹脂組成物を乾燥粉末化せ
しめることを特徴とする、水分散型樹脂粉末組成物の製
造方法。[Scope of Claims] 1. (A) an aqueous dispersion of a polymer having a glass transition temperature of 30° C. or less obtained by emulsion polymerization of an α,β-ethylenically unsaturated monomer; (B) a weight average molecular weight 100,000 or more and a formalin condensate of melamine sulfonate as an essential component, the solid content weight ratio of the aqueous dispersion (A):formalin condensate (B) is 75:25 to 99.
A method for producing a water-dispersed resin powder composition, which comprises drying and powdering a resin composition comprising: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63231686A JP2666406B2 (en) | 1988-09-16 | 1988-09-16 | Method for producing water-dispersed resin powder composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63231686A JP2666406B2 (en) | 1988-09-16 | 1988-09-16 | Method for producing water-dispersed resin powder composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0280452A true JPH0280452A (en) | 1990-03-20 |
| JP2666406B2 JP2666406B2 (en) | 1997-10-22 |
Family
ID=16927403
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63231686A Expired - Fee Related JP2666406B2 (en) | 1988-09-16 | 1988-09-16 | Method for producing water-dispersed resin powder composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2666406B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997034952A1 (en) * | 1996-03-21 | 1997-09-25 | Daiso Co., Ltd. | Novel melamine resin composition and use thereof |
| KR100543545B1 (en) * | 2000-12-28 | 2006-01-20 | 니폰 쇼쿠바이 컴파니 리미티드 | Process for producing amino resin particles |
| JP2008143918A (en) * | 2005-11-24 | 2008-06-26 | Nichigo-Mowinyl Co Ltd | Re-emulsifiable resin powder, aqueous emulsion and adhesive composition using same |
-
1988
- 1988-09-16 JP JP63231686A patent/JP2666406B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997034952A1 (en) * | 1996-03-21 | 1997-09-25 | Daiso Co., Ltd. | Novel melamine resin composition and use thereof |
| AU715580B2 (en) * | 1996-03-21 | 2000-02-03 | Daiso Co. Ltd. | Novel melamine resin composition and use thereof |
| KR100543545B1 (en) * | 2000-12-28 | 2006-01-20 | 니폰 쇼쿠바이 컴파니 리미티드 | Process for producing amino resin particles |
| JP2008143918A (en) * | 2005-11-24 | 2008-06-26 | Nichigo-Mowinyl Co Ltd | Re-emulsifiable resin powder, aqueous emulsion and adhesive composition using same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2666406B2 (en) | 1997-10-22 |
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