JPS62221432A - Emulsifier for aqueous resin dispersion - Google Patents
Emulsifier for aqueous resin dispersionInfo
- Publication number
- JPS62221432A JPS62221432A JP61066936A JP6693686A JPS62221432A JP S62221432 A JPS62221432 A JP S62221432A JP 61066936 A JP61066936 A JP 61066936A JP 6693686 A JP6693686 A JP 6693686A JP S62221432 A JPS62221432 A JP S62221432A
- Authority
- JP
- Japan
- Prior art keywords
- emulsifier
- group
- emulsion
- prepared
- aqueous 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
- 239000003995 emulsifying agent Substances 0.000 title claims abstract description 40
- 239000006185 dispersion Substances 0.000 title claims abstract description 9
- 229920005989 resin Polymers 0.000 title claims abstract description 8
- 239000011347 resin Substances 0.000 title claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical group 0.000 claims description 2
- 125000005156 substituted alkylene group Chemical group 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- -1 ester compound Chemical class 0.000 abstract description 18
- 239000000178 monomer Substances 0.000 abstract description 12
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 11
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 4
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 abstract description 4
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 abstract description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 2
- 239000005977 Ethylene Substances 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- QIRNGVVZBINFMX-UHFFFAOYSA-N 2-allylphenol Chemical compound OC1=CC=CC=C1CC=C QIRNGVVZBINFMX-UHFFFAOYSA-N 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- 150000008065 acid anhydrides Chemical class 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract 1
- 239000000839 emulsion Substances 0.000 description 16
- 238000006116 polymerization reaction Methods 0.000 description 8
- 229920006254 polymer film Polymers 0.000 description 7
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 125000003493 decenyl group Chemical group [H]C([*])=C([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])[H] 0.000 description 2
- 125000002704 decyl 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])* 0.000 description 2
- 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 2
- 238000004508 fractional distillation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000006038 hexenyl group Chemical group 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000002960 margaryl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([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])C([H])([H])[H] 0.000 description 2
- 125000005187 nonenyl group Chemical group C(=CCCCCCCC)* 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([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])[H] 0.000 description 2
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 2
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002958 pentadecyl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 238000006366 phosphorylation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000005504 styryl group Chemical group 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 125000005063 tetradecenyl group Chemical group C(=CCCCCCCCCCCCC)* 0.000 description 2
- 125000005040 tridecenyl group Chemical group C(=CCCCCCCCCCCC)* 0.000 description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([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])[H] 0.000 description 2
- 125000005065 undecenyl group Chemical group C(=CCCCCCCCCC)* 0.000 description 2
- 125000002948 undecyl group Chemical group [H]C([*])([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])[H] 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
- 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
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical class [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- KQNZLOUWXSAZGD-UHFFFAOYSA-N benzylperoxymethylbenzene Chemical compound C=1C=CC=CC=1COOCC1=CC=CC=C1 KQNZLOUWXSAZGD-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 230000026731 phosphorylation Effects 0.000 description 1
- 230000000865 phosphorylative effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Detergent Compositions (AREA)
- Polyethers (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は水性樹脂分散体用乳化剤に関し、特にエチレン
性不飽和tli量体の水系乳化重合に用いる新規、かつ
有用な乳化剤に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an emulsifier for aqueous resin dispersions, and particularly to a novel and useful emulsifier for use in aqueous emulsion polymerization of ethylenically unsaturated tli-mers.
従来、乳化゛重合用乳化剤としては、アルキル硫酸エス
テル塩、アルキルベンゼンスルホン酸塩、ジアルキルス
ルホコハク酸エステル塩、ポリオキシアルキレンアルキ
ル(アリール)エーテル硫酸エステル塩等のアニオン性
界面活性剤、ポリオキシアルキレンアルキル(アリール
)エーテル、ポリオキシエチレンポリオキシプロピレン
ブロック共重合体、ポリオキシエチレンソルビタン脂防
酸エステル等の非イオン性界面活性剤が、単独あるいは
併用で使用されているが、エマルジョンの安定性、また
エマルジョンから製造されたフィルムの性質等は、かな
らずしも充分に満足し得るものでなく、多くの解決すべ
き問題点が残されている。Conventionally, as emulsifiers for emulsion polymerization, anionic surfactants such as alkyl sulfate salts, alkylbenzene sulfonate salts, dialkyl sulfosuccinate salts, polyoxyalkylene alkyl (aryl) ether sulfate salts, polyoxyalkylene alkyl ( Nonionic surfactants such as polyoxyethylene aryl) ether, polyoxyethylene polyoxypropylene block copolymer, and polyoxyethylene sorbitan fatty acid ester are used alone or in combination, but they affect the stability of the emulsion and the emulsion. The properties of films produced from these materials are not always fully satisfactory, and many problems remain to be solved.
即ち、エマルジョンの重合安定性、得られたエマルジョ
ンの機械安定性、化学安定性、凍結融解安定性、顔料混
和性、貯蔵安定性等に問題があり、特に、機械安定性に
ついては、改善すべき問題点が残されている。That is, there are problems with the polymerization stability of the emulsion, the mechanical stability, chemical stability, freeze-thaw stability, pigment miscibility, storage stability, etc. of the obtained emulsion, and in particular, the mechanical stability should be improved. Problems remain.
サラに、エマルジョンからポリマーフィルムを作成した
際、使用した乳化剤がM敲の状態でポリマーフィルムに
残るため、フィルムの耐水性、接着性が劣る等の問題を
生じている。Furthermore, when a polymer film is made from an emulsion, the emulsifier used remains in the polymer film in a M-shaped state, resulting in problems such as poor water resistance and adhesive properties of the film.
また、エマルジョンを塩析等の手段によって破壊しポリ
マーを取り出すとき、排水中に多くの乳化剤が含有され
、河川汚濁の原因となるため、乳化剤の除去処理に多大
の労力が必要となる。Furthermore, when the emulsion is destroyed by means such as salting out to extract the polymer, a large amount of emulsifier is contained in the wastewater, which causes river pollution, and therefore a great deal of effort is required to remove the emulsifier.
このような観点から、従来の乳化剤の問題点を解決する
ため数多くの一般に反応性乳化剤といわれる新規乳化剤
に関する特許が提案されている。From this point of view, a number of patents relating to new emulsifiers, generally referred to as reactive emulsifiers, have been proposed in order to solve the problems of conventional emulsifiers.
例えば、アニオン性の反応性乳化剤として、特公昭46
−12472号、特開昭54−144317号、特公昭
46−34894号、特公昭56−29657号、特開
昭51−30285号、特公昭49−46291号等が
あり、非イオン性反応性乳化剤として、特開昭56−2
8208号、特開昭50−98484号等があり、各種
七ツマ−についての乳化重合用乳化剤として試みられて
いるが、これらの反応性乳化剤は乳化剤として単独使用
したときには、エマルジョン重合時の安定性が不充分な
場合が多く、使用に際しては、従来の乳化剤と併用しな
ければ重合が円滑に進行しない等、本来の性能を充分に
発揮できないところの問題点を有している。For example, as an anionic reactive emulsifier,
-12472, JP-A-54-144317, JP-A-46-34894, JP-A-56-29657, JP-A-51-30285, JP-A-49-46291, etc. Nonionic reactive emulsifiers As, JP-A-56-2
No. 8208, JP-A No. 50-98484, etc., and attempts have been made as emulsifiers for emulsion polymerization of various types of 7-mers, but these reactive emulsifiers have poor stability during emulsion polymerization when used alone as emulsifiers. In many cases, the emulsifying agent is insufficient, and when used, polymerization does not proceed smoothly unless it is used in combination with a conventional emulsifying agent, resulting in problems in that the original performance cannot be fully exhibited.
以上のように、種々の試みはなされているが、未だ前述
の問題点を充分に解決するまでには至っていないのが現
状である。As mentioned above, although various attempts have been made, the current situation is that the above-mentioned problems have not yet been satisfactorily solved.
本発明者は、これら問題点を解消すべく鋭意研究の結果
本発明に到達したものである。即ち、本発明は、
一般式。The present inventor has arrived at the present invention as a result of intensive research to solve these problems. That is, the present invention is based on the general formula.
CH2CH= CH20
M
・・・ (1)および、
一般式、
[但し、上記式中R1は炭素数4〜18のフルキル基、
アルケニル基、もしくはアラルキル基、R2は水素また
は炭素数4〜18のアルキル基、アルケニル基、もしく
はアラルキル基、Aは炭素数2〜4のフルキレン基、も
しくはご換アルキレン基、nは1〜200の整数であり
、Mはアルカリ金属原子、NH4、アルカノールアミン
残基または水素原子である。]
で表される一般式(1)、(2)の混合物からなること
を特徴とする水性樹脂分散体用乳化剤 を提供するもの
である。CH2CH=CH20M... (1) and the general formula, [However, in the above formula, R1 is a furkyl group having 4 to 18 carbon atoms,
alkenyl group or aralkyl group, R2 is hydrogen or an alkyl group having 4 to 18 carbon atoms, alkenyl group, or aralkyl group, A is a fullkylene group having 2 to 4 carbon atoms, or a modified alkylene group, n is 1 to 200 is an integer, and M is an alkali metal atom, NH4, an alkanolamine residue, or a hydrogen atom. ] An emulsifier for an aqueous resin dispersion characterized by comprising a mixture of general formulas (1) and (2) represented by the following.
前記一般式中、R1は炭素数4〜18のアルキル基、ア
ルケニル基、またはアラルキル基であり、アルキル基と
しては1例えばブチル、イソブチル、ペンチル、ヘキシ
ル、ヘプチル、オクチル、ノニル、デシル、ウンデシル
、ドデシル、トリデシル、テトラデシル、ペンタデシル
、ヘキサデシル、ヘプタデシル、オクタデシル等が挙げ
られる。In the general formula, R1 is an alkyl group, alkenyl group, or aralkyl group having 4 to 18 carbon atoms, and examples of the alkyl group include butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl. , tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and the like.
アルケニル基としては、例えば、ブテニル、インブテニ
ル、ペンテニル、ヘキセニル、ヘプテニル、オクテニル
、ノネニル、デセニル、ウンデセニル、トチセニル、ト
リデセニル、テトラデセニル、ペンタデセニル、ヘキサ
デセニル、ヘプタデセニル、オクタデセニル等が挙げら
れる。アラルキノ1人(とじては、スチリル、ベンジル
、クミル等が挙げられ、これらの混合物であっても良い
。Examples of the alkenyl group include butenyl, imbutenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, tothycenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, and the like. Examples of aralkines include styryl, benzyl, cumyl, etc., and mixtures thereof may also be used.
R2は水素または炭素数4〜18のアルキル基。R2 is hydrogen or an alkyl group having 4 to 18 carbon atoms.
アルケニル基、またはアラルキル基であり、アルキル基
としては、例えばブチル、イソブチル、ペンチル、ヘキ
シル、ヘプチル、オクチル、ノニル、デシル、ウンデシ
ル、ドデシル、トリデシル、テトラデシル、ペンタデシ
ル、ヘキサデシル、ヘプタデシル、オクタデシル、等が
挙げられ、これらの混合物であっても良い。It is an alkenyl group or an aralkyl group, and examples of the alkyl group include butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, etc. or a mixture thereof.
アルケニル基としては1例えば、ブテニル、インブテニ
ル、ペンテニル、ヘキセニル、ヘプテニル、オクテニル
、ノネニル、デセニル、ウンデセニル、ドデセニル、ト
リデセニル、テトラデセニル、ペンタデセニル、ヘキサ
デセニル、ヘプタデセニル、オクタデセニル等が挙げら
れ、これらの混合物であっても良い。Examples of alkenyl groups include butenyl, imbutenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, etc., and even mixtures thereof. good.
アラルキル基としては、スチリル、ベンジル、クミル等
が挙げられ、これらの混合物であっても良い。Examples of the aralkyl group include styryl, benzyl, cumyl, etc., and mixtures thereof may be used.
また、Aは炭素数2〜4のフルキレン基または置換アル
キレン基であり、例えば、エチレン、プロピレン、ブチ
レン、インブチレン等であり、それらの単独またはブロ
ックあるいはランダムの混合物であっても良い。Further, A is a fullkylene group or a substituted alkylene group having 2 to 4 carbon atoms, such as ethylene, propylene, butylene, imbutylene, etc., and may be a single group or a block or random mixture thereof.
ラム、カリウム等のアルカリ金d冥アンモニウム況合物
であっても良い。Alkali gold-metal ammonium compounds such as rum and potassium may also be used.
また、前記一般式(1)と一般式(2)の配合割合は、
任意の範囲において配合しても良い。In addition, the blending ratio of the general formula (1) and general formula (2) is:
They may be blended within any range.
さらに、本発明の乳化剤は工業的に容易に製造できるも
のであり、例えば次のようにして製造することができる
。Furthermore, the emulsifier of the present invention can be easily produced industrially, and can be produced, for example, as follows.
即ち、ノニルフェノール等のアルキルフェノールを原料
とし、アリルクロライドを触媒存在下のもとで加熱反応
し、その後、減圧にて蒸留する。このようにして得られ
た反応組成物に、更に、アルキレンオキサイドを常法に
て、付加させる0次に無水リン酸、オキシ塩化リン等の
リン酸化剤を用いてリン酸エステル化し、要すればアル
カリ物質で中和して本発明の乳化剤を得ることができる
。That is, using an alkylphenol such as nonylphenol as a raw material, allyl chloride is heated and reacted in the presence of a catalyst, and then distilled under reduced pressure. The reaction composition thus obtained is further phosphoric acid esterified using a phosphorylating agent such as zero-order phosphoric anhydride or phosphorous oxychloride to which an alkylene oxide is added in a conventional manner, and if necessary, The emulsifier of the present invention can be obtained by neutralizing with an alkaline substance.
本発明の乳化剤を適用する水性樹脂分散体用のモノマー
としては、各種のものを挙げることができる0例えば、
アクリル酸、アクリル酸メチル、アクリル酸ブチル、ア
クリル酸2−エチルヘキシル、メタアクリル酸メチル、
アクリロニトリル、アクリロニトリル、アクリルアミド
、アクリル酸ヒドロキシエチルエステル等のアクリル系
モノマー、スチレン、ジビニルベンゼン等の芳香族モノ
マー、酢酸ビニル等のビニルエステルモノマー、塩化ビ
ニル、塩化ビニリデン等のハロゲン含有子ツマ−、フタ
ジエン、イソプレン、クロロプレン等の共役ジオレフィ
ンモノマー、そノ他エチレン、無水マレイン酸、マレイ
ン酸メチル等がある。Various monomers can be mentioned as monomers for the aqueous resin dispersion to which the emulsifier of the present invention is applied.For example,
Acrylic acid, methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate,
Acrylic monomers such as acrylonitrile, acrylamide, acrylic acid hydroxyethyl ester, aromatic monomers such as styrene and divinylbenzene, vinyl ester monomers such as vinyl acetate, halogen-containing monomers such as vinyl chloride and vinylidene chloride, phtadiene, Conjugated diolefin monomers such as isoprene and chloroprene, as well as ethylene, maleic anhydride, methyl maleate, etc.
本発明の乳化剤はこれらの七ツマ−の1種または2種以
上の乳化重合に使用できる。The emulsifier of the present invention can be used for emulsion polymerization of one or more of these seven polymers.
重合開始剤としては、従来公知のものでよく、例えば、
過酸化水素、iI!S硫酸カリウム、アゾビスイソブチ
ルニトリル、ベンジルパーオキサイド等が挙げられる。As the polymerization initiator, conventionally known ones may be used, for example,
Hydrogen peroxide, iI! Examples include potassium S sulfate, azobisisobutylnitrile, benzyl peroxide, and the like.
また、重合促進剤としては亜硫酸水素ナトリウム、硫酸
第1鉄アンモニウム等が挙げられる。Examples of the polymerization accelerator include sodium hydrogen sulfite and ferrous ammonium sulfate.
本発明の乳化剤は通常、全七ツマ−に対して0゜1〜2
0重量%、さらに好ましくは、0.2〜5.0量%であ
る。The emulsifier of the present invention usually has a concentration of 0°1 to 2
0% by weight, more preferably 0.2 to 5.0% by weight.
また、本発明の乳化剤は単独でも良好な水性樹脂分散体
が得られるが、必要により、他の乳化剤あるいは保護コ
ロイド剤を併用してもよい。Although a good aqueous resin dispersion can be obtained using the emulsifier of the present invention alone, other emulsifiers or protective colloids may be used in combination, if necessary.
本発明の乳化剤を適用して得られる水性樹脂分散体は1
例えば、接着剤、被覆剤、含浸補強剤等として、木材、
金属、紙、布、その他コンクリート等に適用することが
できる。The aqueous resin dispersion obtained by applying the emulsifier of the present invention is 1
For example, wood,
It can be applied to metal, paper, cloth, and other materials such as concrete.
以下本発明を実施例により、具体的に説明する。The present invention will be specifically explained below using examples.
[%、部とあるは重量基準を示す、]
製製造例
攪拌機、温度計、還流管を備えた反応容器にノニルフェ
ノール220g[1,Oモル]、触媒として炭酸カリウ
ム5gを仕込み、つぎに7リルクロライド84g[1,
1モル]を滴下し40℃にて2時間攪拌した。[%, parts and parts are based on weight] Production Example: Into a reaction vessel equipped with a stirrer, a thermometer, and a reflux tube, 220 g of nonylphenol [1.0 mol] and 5 g of potassium carbonate as a catalyst were charged, and then 7 liters of potassium carbonate were charged. Chloride 84g [1,
1 mol] was added dropwise and stirred at 40°C for 2 hours.
その後、温度を220℃に昇温し、3時間攪拌した後、
減圧にて分溜し、アリルノニルフェノール209gを得
た。この収率は約80%であった。After that, the temperature was raised to 220°C and stirred for 3 hours,
Fractional distillation was carried out under reduced pressure to obtain 209 g of allylnonylphenol. The yield was about 80%.
次に、分溜して得られたアリルノニルフェノールをオー
トクレーブに移し、苛性カリウムを触媒として、圧力1
.5kg/Cm2.温度130℃の条件にてエチレンオ
キサイドをアリルノニルフェノールに対して、10モル
付加し、アリルノニルフェノールエチレンオキシド10
モル付加俸t−’4−%た。Next, the allylnonylphenol obtained by fractional distillation was transferred to an autoclave, and the pressure was 1°C using caustic potassium as a catalyst.
.. 5kg/cm2. At a temperature of 130°C, 10 moles of ethylene oxide was added to allylnonylphenol to obtain 10 moles of allylnonylphenol ethylene oxide.
The molar additional salary was t-'4-%.
次に攪拌機、温度計、を備えた反応容器にアリルノニル
フェノールエチレンオキシド10モル付加俸350[0
,5モル]無水リン酸22.7g [0,16モル]を
仕込み、攪拌しながら80℃にに昇温し、5時間リン酸
化反応を行ない、得られた組成物を本発明の乳化剤[A
]とした。Next, 350 [0
, 5 moles] was charged with 22.7 g [0.16 moles] of phosphoric anhydride, the temperature was raised to 80° C. with stirring, the phosphorylation reaction was carried out for 5 hours, and the resulting composition was mixed with the emulsifier [A
].
なお、本発明の乳化剤[A]はモノエステル、ジエステ
ルの割合がモル比で50150であった。In addition, in the emulsifier [A] of the present invention, the molar ratio of monoester to diester was 50,150.
[以下割合はモル比で示す。]
製造例2
製造例1のノニルフェノールの代りにオクチルフェノー
ルを用いて、同様の合成法にて7リルオクチルフエノー
ルを得た。[The following proportions are shown in molar ratios. ] Production Example 2 7lyl octylphenol was obtained by the same synthesis method as in Production Example 1, except that octylphenol was used instead of nonylphenol.
このアリルオクチルフェノールに対して第1表に示すよ
うに各種のフルキレンオキサイドを常法により付加し、
無水リン酸を用いてリン酸化することにより1、得られ
た組成物を本発明の乳化剤[B]〜[E] とした、そ
れらを第1表に示した。Various fullkylene oxides are added to this allyl octylphenol by a conventional method as shown in Table 1,
The compositions obtained by phosphorylation using phosphoric anhydride were used as emulsifiers [B] to [E] of the present invention, which are shown in Table 1.
実施例1
下記の乳化重合処方により、本発明乳化剤[A]〜[E
]を用いて乳化重合を行ない、得られたエマルジョンお
よび、そのエマルジョンから得られたホIJマーフィル
ムの物性を試験した。なお、比較として、従来の乳化剤
の例も併せて試験した。Example 1 Emulsifiers [A] to [E] of the present invention were prepared according to the following emulsion polymerization recipe.
] to conduct emulsion polymerization, and the physical properties of the resulting emulsion and the IJ polymer film obtained from the emulsion were tested. For comparison, examples of conventional emulsifiers were also tested.
その結果を第2表に示した。The results are shown in Table 2.
[乳化重合処方]
水295 g、乳化剤 5部を溶解し、70°Cまで昇
温する。つぎに、七ツマー20部と過硫酸アンモニウム
0.5部を加え、先行重合させ、さらに重合が開始して
から10分後より3時間を要して180部を滴下して重
合を行なった。その後1重合温度にて1時間熟成した後
、冷却し、エマルジョンを取り出し、供試サンプルとし
た。[Emulsion polymerization recipe] Dissolve 295 g of water and 5 parts of emulsifier, and raise the temperature to 70°C. Next, 20 parts of 7mer and 0.5 parts of ammonium persulfate were added to carry out preliminary polymerization, and 180 parts were added dropwise over 3 hours starting 10 minutes after the start of polymerization to carry out polymerization. Thereafter, the emulsion was aged for 1 hour at a polymerization temperature, cooled, and the emulsion was taken out to be used as a test sample.
つぎに、この供試サンプルをガラス板に塗布して常温で
24時間乾燥、ならびにその乾燥塗膜を110℃、3分
間熱キユアーしポリマーフィルムを作成した。Next, this test sample was applied to a glass plate and dried at room temperature for 24 hours, and the dried coating film was heat cured at 110° C. for 3 minutes to prepare a polymer film.
実施例2
水295部、乳化剤として第3表に示す各種併用乳化剤
5部を溶解し、80℃まで昇温し、モノマーとしてア
クリル酸n−ブチル/スチレン=7/3の混合モノマー
20部と、過硫酸アンモニウム0.3部を加え、先行重
合し1重合が開始してから10分後から約3時間を要し
て上記の混合モノマー180部を滴下して、その?&!
1時間80℃にて熟成を行った後、冷却し、エマルジョ
ンを取り出し供試サンプルとした。Example 2 295 parts of water and 5 parts of various combined emulsifiers shown in Table 3 as emulsifiers were dissolved, the temperature was raised to 80°C, and 20 parts of a mixed monomer of n-butyl acrylate/styrene = 7/3 was added as a monomer, 0.3 parts of ammonium persulfate was added, and 180 parts of the above mixed monomers were added dropwise over a period of about 3 hours starting 10 minutes after the first polymerization had started. &!
After aging at 80° C. for 1 hour, the emulsion was cooled and taken out as a test sample.
さらに、この供試サンプルをガラス板に塗布して、常温
で24時間乾燥、ならびに、その乾燥塗膜を110℃、
3分間熱キユアーして、ポリマーフィルムを作成した。Furthermore, this test sample was applied to a glass plate and dried at room temperature for 24 hours, and the dried coating film was heated at 110°C.
A polymer film was created by heat curing for 3 minutes.
以上のようにして得られたエマルジョンおよび、そのエ
マルジョンから得られたポリマーフィルムの物性を第3
表に示した。なお、比較量として従来の乳化剤の例も併
せて第3表に示した。The physical properties of the emulsion obtained as described above and the polymer film obtained from the emulsion were evaluated in the third experiment.
Shown in the table. In addition, examples of conventional emulsifiers are also shown in Table 3 as comparative amounts.
実施例3
製造例1の合成法に準じて第4表に示した乳化剤[F]
〜[H] を合成し、実施例1の乳化重合処方にて、乳
化重合を実施して、得られたエマルジョンおよび、その
エマルジョンから得られたポリマーフィルムの物性を試
験した。その結果を第5表に示した。Example 3 Emulsifier [F] shown in Table 4 according to the synthesis method of Production Example 1
- [H] was synthesized, emulsion polymerization was carried out using the emulsion polymerization recipe of Example 1, and the physical properties of the obtained emulsion and the polymer film obtained from the emulsion were tested. The results are shown in Table 5.
として評価した。It was evaluated as
pmの条件で5分間エマルジョンを処理したのち、凝析
物を80メツシユのステンレス網で蘭二侵漬し、フィル
ムの白化状況を評価した。After treating the emulsion for 5 minutes under pm conditions, the coagulated material was immersed in an 80-mesh stainless steel screen for a period of time to evaluate the whitening state of the film.
Claims (1)
、 一般式、 ▲数式、化学式、表等があります▼・・・(2) [但し、上記式中R_1は炭素数4〜18のアルキル基
、アルケニル基、もしくはアラルキル基、R_2は水素
または炭素数4〜18のアルキル基、アルケニル基、も
しくはアラルキル基、Aは炭素数2〜4のアルキレン基
、もしくは置換アルキレン基、nは1〜200の整数で
あり、Mはアルカリ金属原子、NH_4、アルカノール
アミン残基または水素原子である。] で表される一般式(1)、(2)の混合物からなること
を特徴とする水性樹脂分散体用乳化剤。[Claims] General formula, ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(1) and General formula, ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(2) [However, the above In the formula, R_1 is an alkyl group, alkenyl group, or aralkyl group having 4 to 18 carbon atoms, R_2 is hydrogen or an alkyl group, alkenyl group, or aralkyl group having 4 to 18 carbon atoms, and A is an alkylene group having 2 to 4 carbon atoms. , or a substituted alkylene group, n is an integer of 1 to 200, and M is an alkali metal atom, NH_4, an alkanolamine residue, or a hydrogen atom. ] An emulsifier for an aqueous resin dispersion, characterized by comprising a mixture of general formulas (1) and (2) represented by the following.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61066936A JPS62221432A (en) | 1986-03-24 | 1986-03-24 | Emulsifier for aqueous resin dispersion |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61066936A JPS62221432A (en) | 1986-03-24 | 1986-03-24 | Emulsifier for aqueous resin dispersion |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS62221432A true JPS62221432A (en) | 1987-09-29 |
JPH0223562B2 JPH0223562B2 (en) | 1990-05-24 |
Family
ID=13330379
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP61066936A Granted JPS62221432A (en) | 1986-03-24 | 1986-03-24 | Emulsifier for aqueous resin dispersion |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS62221432A (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03503168A (en) * | 1988-06-20 | 1991-07-18 | ピーピージー・インダストリーズ・インコーポレイテッド | Polymerizable surfactant |
WO2013108588A1 (en) * | 2012-01-16 | 2013-07-25 | 第一工業製薬株式会社 | Emulsifying agent for emulsion polymerization |
JP2021188000A (en) * | 2020-06-02 | 2021-12-13 | 第一工業製薬株式会社 | Water dispersion, coating agent for metal and coating film |
JP2021187997A (en) * | 2020-06-02 | 2021-12-13 | 第一工業製薬株式会社 | Aqueous dispersion, coating agent for metal, and coating |
JP2021187995A (en) * | 2020-06-02 | 2021-12-13 | 第一工業製薬株式会社 | Aqueous dispersion, coating agent for metal, and coating |
JP2021187996A (en) * | 2020-06-02 | 2021-12-13 | 第一工業製薬株式会社 | Aqueous dispersion, coating agent for metal, and coating |
-
1986
- 1986-03-24 JP JP61066936A patent/JPS62221432A/en active Granted
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03503168A (en) * | 1988-06-20 | 1991-07-18 | ピーピージー・インダストリーズ・インコーポレイテッド | Polymerizable surfactant |
WO2013108588A1 (en) * | 2012-01-16 | 2013-07-25 | 第一工業製薬株式会社 | Emulsifying agent for emulsion polymerization |
JP5367928B1 (en) * | 2012-01-16 | 2013-12-11 | 第一工業製薬株式会社 | Emulsifier for emulsion polymerization |
US9199902B2 (en) | 2012-01-16 | 2015-12-01 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Emulsifier for emulsion polymerization |
JP2021188000A (en) * | 2020-06-02 | 2021-12-13 | 第一工業製薬株式会社 | Water dispersion, coating agent for metal and coating film |
JP2021187997A (en) * | 2020-06-02 | 2021-12-13 | 第一工業製薬株式会社 | Aqueous dispersion, coating agent for metal, and coating |
JP2021187995A (en) * | 2020-06-02 | 2021-12-13 | 第一工業製薬株式会社 | Aqueous dispersion, coating agent for metal, and coating |
JP2021187996A (en) * | 2020-06-02 | 2021-12-13 | 第一工業製薬株式会社 | Aqueous dispersion, coating agent for metal, and coating |
Also Published As
Publication number | Publication date |
---|---|
JPH0223562B2 (en) | 1990-05-24 |
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