JPS62221431A - Emulsifier for aqueous resin dispersion - Google Patents
Emulsifier for aqueous resin dispersionInfo
- Publication number
- JPS62221431A JPS62221431A JP61066935A JP6693586A JPS62221431A JP S62221431 A JPS62221431 A JP S62221431A JP 61066935 A JP61066935 A JP 61066935A JP 6693586 A JP6693586 A JP 6693586A JP S62221431 A JPS62221431 A JP S62221431A
- Authority
- JP
- Japan
- Prior art keywords
- emulsifier
- group
- aqueous resin
- resin dispersion
- emulsion
- 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 39
- 239000006185 dispersion Substances 0.000 title claims abstract description 8
- 229920005989 resin Polymers 0.000 title claims abstract description 8
- 239000011347 resin Substances 0.000 title claims abstract description 8
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims 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 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 125000005156 substituted alkylene group Chemical group 0.000 claims description 3
- 150000001340 alkali metals Chemical group 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- -1 Alkyl phenol Chemical compound 0.000 abstract description 17
- 239000000178 monomer Substances 0.000 abstract description 15
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 11
- 239000000203 mixture Substances 0.000 abstract description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 5
- 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
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 3
- 239000005977 Ethylene Substances 0.000 abstract description 3
- 230000001180 sulfating effect Effects 0.000 abstract description 3
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000019635 sulfation Effects 0.000 abstract description 2
- 238000005670 sulfation reaction Methods 0.000 abstract description 2
- QIRNGVVZBINFMX-UHFFFAOYSA-N 2-allylphenol Chemical compound OC1=CC=CC=C1CC=C QIRNGVVZBINFMX-UHFFFAOYSA-N 0.000 abstract 1
- 238000000034 method Methods 0.000 abstract 1
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 abstract 1
- 229940124530 sulfonamide Drugs 0.000 abstract 1
- 239000000839 emulsion Substances 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 8
- 229920006254 polymer film Polymers 0.000 description 7
- 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
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000000704 physical effect Effects 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
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-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
- 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
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 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
- 125000004435 hydrogen atom Chemical group [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
- 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
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 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
- 230000002087 whitening effect Effects 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
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 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
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-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
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 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
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 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
- 239000002563 ionic surfactant Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000012545 processing Methods 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
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 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
- 239000002023 wood Substances 0.000 description 1
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
性不飽和単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 monomers.
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７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肪酸
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, emulsifiers for emulsion polymerization include 7-ionic surfactants such as alkyl sulfate salts, alkylbenzene sulfonate salts, dialkyl sulfosuccinate salts, polyoxyalkylene alkyl (aryl) ether sulfate salts, polyoxyalkylene alkyl ( aryl)
Nonionic surfactants such as ethers, polyoxyethylene polyoxypropylene block copolymers, and polyoxyethylene sorbitan fatty acid esters have been used alone or in combination; The properties of the film 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１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, 1. Mechanical stability should be improved. Problems remain.
さらに、エマルジョンからポリマーフィルムを作成した
際、使用した乳化剤が遊離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 free 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、持分１１ｆ
１４Ｂ−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５
６−２８２０８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
分に発揮しきれない等の問題点を有している。For example, as an anionic reactive emulsifier, equity 11f
No. 14B-12472, JP-A-54-144317,
Japanese Patent Publication No. 46-34894, Japanese Patent Publication No. 56-29657, Japanese Patent Publication No. 30285-1985, Japanese Patent Publication No. 49-46291
As a nonionic reactive emulsifier,
No. 6-28208, JP-A No. 50-98484, etc., and attempts have been made as emulsifiers for emulsion polymerization of various types of hexamers, but when these reactive emulsifiers are used alone as emulsifiers, they are The stability of these products is often insufficient, and when used in combination with conventional emulsifiers, polymerization does not proceed smoothly, leading to problems such as not being able to fully demonstrate its original performance. .
以上のように１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。Although various attempts have been made as described above, 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、
［但し、Ｒ１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、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６
換アルキレン基、ｎは２〜２００の整数であり、Ｍはア
ルカリ全屈原子、ＮＨ４、アルカノールアミン残基であ
る。］で表される化合物の少なくとも一つを含有するこ
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。The present inventor has arrived at the present invention as a result of intensive research to solve these problems. That is, the present invention has the following formula: [wherein R1 is an alkyl group, alkenyl group, or aralkyl group having 4 to 18 carbon atoms, R2 is hydrogen or an alkyl group, alkenyl group, or aralkyl group having 4 to 18 carbon atoms, A is a fullkylene group having 2 to 4 carbon atoms, or 6
The substituted alkylene group, n is an integer from 2 to 200, and M is an alkali fully bent atom, NH4, or an alkanolamine residue. The present invention provides an emulsifier for an aqueous resin dispersion characterized by containing at least one of the compounds 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、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 above 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
れる。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 alkenyl group include butenyl, imbutenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, and the like. Examples of the aralkyl group include styryl, benzyl, cumyl, etc., and mixtures thereof may be used.
Ｒ２は水素または炭素数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、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、へブタデシル、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。R2 is hydrogen or 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,
Examples include heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, hebutadecyl, octadecyl, and mixtures thereof.
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、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 the alkenyl group include butenyl, imbutenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, and 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のア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、イソブチレン等であり、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 an alkylene group or a substituted alkylene group having 2 to 4 carbon atoms, such as ethylene, propylene, butylene, isobutylene, etc., and may be a single group or a block or random mixture thereof.
ｎは２〜２００の整数であり、より好ましくは２〜１０
０の範囲である。n is an integer of 2 to 200, more preferably 2 to 10
The range is 0.
また１Ｍはナトリウム、カリウム等のアルカリ金属原子
、アンモニウムまたはモノエタノールアミン、トリエタ
ノールアミン等のフルカノールアミン残基があり、これ
らの混合物であっても良い。Further, 1M includes alkali metal atoms such as sodium and potassium, ammonium or flukanolamine residues such as monoethanolamine and triethanolamine, and may be a mixture thereof.
さらに１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次に硫酸、スルファミン酸等の硫酸化
剤にて硫酸化を行ない、要すればアルカリ物質で中和す
ることにより１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 sulfated with an alkylene oxide in a conventional manner using a sulfating agent such as sulfuric acid or sulfamic acid, and if necessary is neutralized with an alkaline substance. By combining the two, an emulsifier of the present invention can be obtained.
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糸
上ツマ−、スチレン、ジビニルベンゼン等の芳香族七ツ
マー１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上ツマ−、ブタ
ジェン、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、その他エチレン、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 thread monomers such as acrylonitrile, acrylamide, acrylic acid hydroxyethyl ester, aromatic monomers such as styrene and divinylbenzene, vinyl ester monomers such as vinyl acetate, and halogen-containing monomers such as vinyl chloride and vinylidene chloride. , butadiene, isoprene, chloroprene, and other conjugated diolefin monomers, as well as ethylene, maleic anhydride, methyl maleate, and the like.
本発明の乳化剤はこれらのモノマーの１種または２Ｍ１
以上の乳化重合に使用できる。The emulsifier of the present invention is one of these monomers or 2M1
It can be used for the above emulsion polymerization.
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、過硫酸カリウム、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,
Examples include hydrogen peroxide, potassium persulfate, azobisisobutylnitrile, and benzyl peroxide.
また１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。Further, examples of monopolymerization accelerators 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重量％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、
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
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.
［５１部とあるはｆｆｉ量基準を示す、］製造例１
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［１，０モル］、触媒として炭酸カリウ
ム５ｇを仕込み、つぎにアクリルクロライド８４ｇ［１
，１モル］を滴下し４０℃にて２時間攪拌した。[51 parts indicates the amount of ffi] Production Example 1 220 g [1.0 mol] of nonylphenol and 5 g of potassium carbonate as a catalyst were charged into a reaction vessel equipped with a stirrer, a thermometer, and a reflux tube, and then acrylic chloride was added. 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時間攪拌しり後、
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 after stirring 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
モル付加体を得た。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.
A molar adduct was obtained.
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モル付加体３５０ｇ（０
，５モル）スルファミン酸５８．２ｇ（０，６モル）を
仕込み、１２０℃に昇温し。Next, in a reaction vessel equipped with a stirrer and a thermometer, 350 g of allylnonylphenol ethylene oxide 10 mole adduct (0.0
, 5 moles) was charged with 58.2 g (0.6 moles) of sulfamic acid, and the temperature was raised to 120°C.
３時間攪拌反応し、硫酸化を行なった。未反応スルファ
ミン酸を日別除去して、得られた組成物を本発明の乳化
剤［Ａ］ とした。The reaction was stirred for 3 hours to perform sulfation. Unreacted sulfamic acid was removed daily, and the resulting composition was used as the emulsifier [A] of the present invention.
製造例２
１造Ｎ１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。Production Example 2 7lyl octylphenol was obtained by the same synthesis method using octylphenol in place of the nonylphenol of 1-manufacturing N1.
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、
スルファミン酸を用いて硫酸化することにより得られた
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,
Compositions obtained by sulfating with sulfamic acid were used as emulsifiers [B] to [E] of the present invention, and 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ポリマーフィルム
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 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２９５ｇ、乳化剤 ５部を溶解し、７０℃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、重合温度にて１時間熟晟した後、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, add 20 parts of 7mer and 0.0 parts of ammonium persulfate.
5 parts were added to carry out preliminary polymerization, and 180 parts were added dropwise over a period of 3 hours starting 10 minutes after the start of polymerization to carry out polymerization. Thereafter, the emulsion was allowed to mature for 1 hour at the polymerization temperature, and then cooled, and the emulsion was taken out and 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時間乾繰、ならびにその乾燥塗膜を１００℃、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 100° 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、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、その後１時
間８０”０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 for preliminary polymerization, 10 minutes after the start of polymerization, 180 parts of the above mixed monomer was added dropwise over a period of about 3 hours, and then aged at 80"0 for 1 hour. After that, it was cooled and the emulsion was taken out and used 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時間乾爆、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 coated on a glass plate and dry-bombed 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。The emulsion obtained as described above.
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、比較品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 polymer film obtained from the emulsion are shown in Table 3. In addition, examples of conventional emulsifiers are also shown in Table 3 as comparative products.
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、得られたエマルシコンおよび、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 emulsicon and a polymer film obtained from the emulsion were tested. The results are shown in Table 5.
直ちに白化 ・ Ｘ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
ス網でルムの白化状況を評価した。Immediate whitening - After processing the emulsion for X minutes, the whitening status of the coagulum was evaluated using an 80-mesh stainless steel screen.
Claims (1)
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２〜２００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
基である。］で表される化合物の少なくとも一つを含有
することを特徴とする水性樹脂分散体用乳化剤。[Claims] General formula▲ Numerical formula, chemical formula, table, etc.▼ [However, R_1 is an alkyl group, alkenyl group, or aralkyl group having 4 to 18 carbon atoms, and R_2 is hydrogen or an alkyl group having 4 to 18 carbon atoms. group, alkenyl group, or aralkyl group, A is an alkylene group having 2 to 4 carbon atoms, or a substituted alkylene group, n is an integer of 2 to 200, M
is an alkali metal atom, NH_4, and an alkanolamine residue. ] An emulsifier for an aqueous resin dispersion, characterized by containing at least one compound represented by the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61066935A JPS62221431A (en) | 1986-03-24 | 1986-03-24 | Emulsifier for aqueous resin dispersion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61066935A JPS62221431A (en) | 1986-03-24 | 1986-03-24 | Emulsifier for aqueous resin dispersion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62221431A true JPS62221431A (en) | 1987-09-29 |
| JPH0223561B2 JPH0223561B2 (en) | 1990-05-24 |
Family
ID=13330349
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61066935A Granted JPS62221431A (en) | 1986-03-24 | 1986-03-24 | Emulsifier for aqueous resin dispersion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62221431A (en) |
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| WO2001096483A1 (en) | 2000-06-07 | 2001-12-20 | Seiko Epson Corporation | Ink-jet recording ink, ink-jet recording ink set, recording method, print, and ink-jet recording apparatus |
| EP1721952A2 (en) | 2005-04-20 | 2006-11-15 | Seiko Epson Corporation | Microencapsulated particulate metal material, method for producing the same, and aqueous dispersion and ink jet ink using the same |
| WO2009063996A1 (en) | 2007-11-15 | 2009-05-22 | Seiko Epson Corporation | Ink composition |
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-
1986
- 1986-03-24 JP JP61066935A patent/JPS62221431A/en active Granted
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|---|---|
| JPH0223561B2 (en) | 1990-05-24 |
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