JPS6377530A - Emulsifier for aqueous resin dispersion - Google Patents
Emulsifier for aqueous resin dispersionInfo
- Publication number
- JPS6377530A JPS6377530A JP61220022A JP22002286A JPS6377530A JP S6377530 A JPS6377530 A JP S6377530A JP 61220022 A JP61220022 A JP 61220022A JP 22002286 A JP22002286 A JP 22002286A JP S6377530 A JPS6377530 A JP S6377530A
- Authority
- JP
- Japan
- Prior art keywords
- emulsifier
- group
- emulsion
- added
- integer
- 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.)
- Pending
Links
- 239000003995 emulsifying agent Substances 0.000 title claims abstract description 47
- 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
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 8
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 5
- 125000002877 alkyl aryl group Chemical group 0.000 claims abstract description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000005156 substituted alkylene group Chemical group 0.000 claims description 3
- 150000001875 compounds Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000000178 monomer Substances 0.000 abstract description 16
- 239000003054 catalyst Substances 0.000 abstract description 12
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 12
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-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
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 abstract description 4
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 22
- 239000000839 emulsion Substances 0.000 description 15
- -1 alkyl sulfate salts Chemical class 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 9
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 8
- 229920006254 polymer film Polymers 0.000 description 7
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 239000003518 caustics Substances 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- 229910015900 BF3 Inorganic materials 0.000 description 4
- 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
- 238000010992 reflux Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-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
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-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
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- JKTAIYGNOFSMCE-UHFFFAOYSA-N 2,3-di(nonyl)phenol Chemical compound CCCCCCCCCC1=CC=CC(O)=C1CCCCCCCCC JKTAIYGNOFSMCE-UHFFFAOYSA-N 0.000 description 1
- NSENZNPLAVRFMJ-UHFFFAOYSA-N 2,3-dibutylphenol Chemical compound CCCCC1=CC=CC(O)=C1CCCC NSENZNPLAVRFMJ-UHFFFAOYSA-N 0.000 description 1
- 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
- CDMGNVWZXRKJNS-UHFFFAOYSA-N 2-benzylphenol Chemical class OC1=CC=CC=C1CC1=CC=CC=C1 CDMGNVWZXRKJNS-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
- KZPMXWBRKHQGQJ-UHFFFAOYSA-N 2-methyl-4-(oxiran-2-yl)but-2-enoic acid oxiran-2-ylmethyl 2-methylprop-2-enoate Chemical compound O1C(CC=C(C(=O)O)C)C1.C(C(=C)C)(=O)OCC1CO1 KZPMXWBRKHQGQJ-UHFFFAOYSA-N 0.000 description 1
- WJORGWQDTVMZDR-UHFFFAOYSA-N 2-methyloxirane;phenol Chemical class CC1CO1.OC1=CC=CC=C1 WJORGWQDTVMZDR-UHFFFAOYSA-N 0.000 description 1
- CYYZDBDROVLTJU-UHFFFAOYSA-N 4-n-Butylphenol Chemical compound CCCCC1=CC=C(O)C=C1 CYYZDBDROVLTJU-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- CXBBTDFFSDZASM-UHFFFAOYSA-N C1C(C)O1.C(CCC)C1=C(C=CC=C1)O Chemical compound C1C(C)O1.C(CCC)C1=C(C=CC=C1)O CXBBTDFFSDZASM-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 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
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 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
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000001204 arachidyl 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])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 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
- 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 1
- 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 1
- 150000001993 dienes Chemical class 0.000 description 1
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 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
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 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
- 238000009472 formulation Methods 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 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 1
- 125000001196 nonadecyl 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])C([H])([H])[H] 0.000 description 1
- 125000005187 nonenyl group Chemical group C(=CCCCCCCC)* 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 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 1
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 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 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000000123 paper Substances 0.000 description 1
- 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 1
- 150000002989 phenols Chemical class 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
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 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
- 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 1
- 125000005063 tetradecenyl group Chemical group C(=CCCCCCCCCCCCC)* 0.000 description 1
- 125000005040 tridecenyl group Chemical group C(=CCCCCCCCCCCC)* 0.000 description 1
- 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 1
- 125000005065 undecenyl group Chemical group C(=CCCCCCCCCC)* 0.000 description 1
- 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 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ブロビレンブ
ロック共亜合体、ポリオキシエチレンソルビタン脂肪敢
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 ether, polyoxyethylene polyoxybrobylene block copolymer, and polyoxyethylene sorbitan aliphatic ester are used alone or in combination, but the stability of the emulsion and the production from the emulsion are affected. The properties of the obtained films are not necessarily completely 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Ｕｆｆｌ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 and the polymer is taken out, a large amount of emulsifier is contained in the wastewater, resulting in river pollution, and 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
モノマー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., have been tried as emulsifiers for emulsion polymerization of various monomers, but when these reactive emulsifiers are used alone as emulsifiers, they lack stability during emulsion polymerization. In many cases, it is sufficient, but when used, there are problems in that the original performance cannot be fully exhibited, such as polymerization not proceeding smoothly unless used in combination with conventional emulsifiers.
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、 ＯＲ２ｌｌ
Ｒｔ Ｏ（ＡＯ）ｎＣＨ２ＣＨＣＨ２ＱＣ−Ｃ＝ＣＨ２
寵
０（ＡＯ）ｍＨ
［但し、上記式中Ｒ１は炭素数８〜３０のアルキル基、
アルケニル基、もしぐはアルキルアリール基、アラルキ
ルアリール基、Ｒ２は水素原子もしくはメチル基、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０−１００の整数であり、ｍは１〜２００の整
数である。］で表わ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 general formula: OR2ll Rt O(AO)nCH2CHCH2QC-C=CH2
AO (AO)mH [However, in the above formula, R1 is an alkyl group having 8 to 30 carbon atoms,
Alkenyl group, alkylaryl group, aralkylaryl group, R2 is a hydrogen atom or methyl group, A is an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group, n is an integer from 0 to 100, m is It is an integer from 1 to 200. The present invention provides an emulsifier for an aqueous resin dispersion characterized by containing at least one compound represented by the following.
前記一般式中、Ｒ１は炭素数８〜３０のアルキル基、ア
ルケニル基、アルキルアリール基、もしくはアラルキル
アリール基であり、アルキル基としては、例えば、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、ノナデシル、エイコシル等
が挙げられる。In the general formula, R1 is an alkyl group, alkenyl group, alkylaryl group, or aralkylaryl group having 8 to 30 carbon atoms, and examples of the alkyl group include octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, and tetradecyl. , pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, and the like.
アルケニル基としては、例えば、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。Examples of the alkenyl group include octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl,
Examples include heptadecenyl and octadecenyl.
アルキルアリール基としては、モノブチルフェノール、
ジブチルフェノール、Ｓｅｃ、ブチルフェノール、ジｓ
ｅｃ、ブチルフェノール、ｔｅｒｔ、ブチルフェノール
、オクチルフェノール、ノニルフェノール、ジノニルフ
ェノール等が挙げられる。As the alkylaryl group, monobutylphenol,
dibutylphenol, Sec, butylphenol, di-s
Examples include ec, butylphenol, tert, butylphenol, octylphenol, nonylphenol, dinonylphenol, and the like.
アラルキルフェノールとしては、スチリル化フェノール
、ベンジルフェノール、クミルフェノール等のモノ、ジ
、トリの単独あるいは、これらの混合物等が挙げられ、
これらのアルキル基等の混合物であってもよい。Examples of aralkylphenols include mono-, di-, and tri-styrylated phenols, benzylphenols, cumylphenols, etc., or mixtures thereof.
A mixture of these alkyl groups and the like 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
ー２り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 mixture thereof or a blown or random mixture thereof.
ｎはＯ〜１００の整数、ｍは１〜２００の整数であり、
より好ましくはｎは０または１〜５０、ｍは２〜ｌＯＯ
の範囲である。n is an integer of 0 to 100, m is an integer of 1 to 200,
More preferably n is 0 or 1-50, m is 2-1OO
is within the range of
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１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、ノニルフェノールまたはラウリルアルコールを原
料とし、要すればアルキレンオキサイドを付加し、グリ
シジルメタクリレートを触媒存在下のもとで加熱反応し
、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、付加させて本発明の乳化剤を得ることがで
きる。That is, nonylphenol or lauryl alcohol is used as a raw material, alkylene oxide is added if necessary, glycidyl methacrylate is heated and reacted in the presence of a catalyst, and alkylene oxide is further added to the obtained reaction composition by a conventional method. , can be added to obtain the emulsifier of the present invention.
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、アクリごニトリル、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／
マー、酢醜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モノマー、ブ
タジェン、イソプレン、クロロブ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。 本発明の乳化剤はこれらのモ
ノマーの１種または２種以上の乳化重合に使用できる。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, acrylonitrile, acrylamide, acrylic acid hydroxyethyl ester, aromatic monomers such as styrene, divinylbenzene, etc.
Examples include vinyl ester monomers such as vinyl chloride and vinyl chloride, halogen-containing monomers such as vinyl chloride and vinylidene chloride, conjugated diolefin monomers such as butadiene, isoprene, and chlorobrene, and ethylene, maleic anhydride, methyl maleate, and the like. The emulsifier of the present invention can be used for emulsion polymerization of one or more of these monomers.
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、ベンゾイ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 benzoyl peroxide.
また、重合促進剤としては亜硫酸水素ナトリウム、硫醜
第１鉄アンモニウム等が挙げられる。Further, examples of the polymerization accelerator include sodium hydrogen sulfite, ferrous ammonium sulfate, and the like.
本発明の乳化剤は通常、全モノマーに対して０゜１〜２
０ｉｉ％、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° relative to the total monomers.
0ii%, 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.
［％、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、触媒としてトリエチルアミン１．５ｇ
を仕込み、つぎにグリシジルメタクリレ−）１４２ｇを
滴下し８０℃にて５時間攪拌反応した。[%, parts and parts are based on weight] Production Example In a reaction vessel equipped with a stirrer, thermometer and reflux tube, 220 g of nonylphenol and 1.5 g of triethylamine as a catalyst were added.
Next, 142 g of glycidyl methacrylate (glycidyl methacrylate) was added dropwise, and the mixture was stirred and reacted at 80° C. for 5 hours.
次に、得られた反応組成物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反応組成物
に対して１０モル、および３０モル付加した。Next, the obtained reaction composition was transferred to an autoclave, and 10 moles and 30 moles of ethylene oxide were added to the reaction composition at a pressure of 1.5 kg/Cm2 and a temperature of 130°C using caustic potassium as a catalyst. did.
得られた反応組成物をエチレンオキサイド１０モル付加
体を本発明乳化剤［Ａ］ とし、エチレンオキサイド３
０モル付加体を本発明乳化剤［Ｂ］とした。In the obtained reaction composition, 10 moles of ethylene oxide was used as the emulsifier [A] of the present invention, and ethylene oxide 3
The 0 mol adduct was designated as the emulsifier [B] of the present invention.
製造例２
攪拌機、温度計、還流管を備えた反応容器にラウリルア
ルコール１８６ｇ、触媒として三フフ化ホウ素エーテル
錯体０．５ｇを仕込み、つぎにグリシジルメタクリレー
ト１４２ｇを滴下し８０℃にて５時間攪拌反応した。Production Example 2 A reaction vessel equipped with a stirrer, a thermometer, and a reflux tube was charged with 186 g of lauryl alcohol and 0.5 g of boron trifluoride ether complex as a catalyst, and then 142 g of glycidyl methacrylate was added dropwise and the reaction was stirred at 80°C for 5 hours. did.
次に、得られた反応組成物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／ ｃ ｍ
２、温度１３０℃の条件にてエチレンオキサイドを反応
組成物に対して２０モル付加して得られた反応組成物を
本発明乳化剤［Ｃ］とした。Next, the obtained reaction composition was transferred to an autoclave and heated at a pressure of 1.5 kg/cm using caustic potassium as a catalyst.
2. The reaction composition obtained by adding 20 moles of ethylene oxide to the reaction composition at a temperature of 130°C was used as the emulsifier [C] of the present invention.
製造例３
攪拌機、温度計、還流管を備えた反応容器にジスチレン
化フェノールプロピレンオキサイド２モル、エチレンオ
キサイド５モルブロック付加体６３６ｇ、触媒として三
フッ化ホウ素エーテル錯体２ｇを仕込み、つぎにグリシ
ジルメタクリレート１４２ｇを滴下し８０℃にて５時間
攪拌反応した。Production Example 3 Into a reaction vessel equipped with a stirrer, a thermometer, and a reflux tube, 2 moles of distyrenated phenol propylene oxide, 636 g of a 5 mole block adduct of ethylene oxide, and 2 g of boron trifluoride ether complex as a catalyst were charged, followed by 142 g of glycidyl methacrylate. was added dropwise, and the mixture was stirred and reacted at 80°C for 5 hours.
次に、得られた反応組成物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反応組成物
に対して５０モル、および１００モル付加した。得られ
た反応組成物を本発明乳化剤［Ｄ］ とし、得られたエ
チレンオキサイド１００モル付加体を本発明乳化剤［Ｅ
］とした。Next, the obtained reaction composition was transferred to an autoclave, and caustic potassium was used as a catalyst at a pressure of 1.5 kg/cm2. Ethylene oxide was added at 50 moles and 100 moles to the reaction composition at a temperature of 130°C. The obtained reaction composition was used as the emulsifier of the present invention [D], and the obtained 100 mol ethylene oxide adduct was used as the emulsifier of the present invention [E].
].
製造例４
攪拌機、温度計、還流管を備えた反応容器にオレイルア
ルコールエチレンオキサイド５０モル付加体２４６８ｇ
、触媒として三フッ化ホウ素エーテル錯体５ｇを仕込み
、つぎにグリシジルメタクリレ−）１４２ｇを滴下し８
０℃にて５時間攪拌反応した。Production Example 4 2468 g of oleyl alcohol ethylene oxide 50 mole adduct was placed in a reaction vessel equipped with a stirrer, thermometer, and reflux tube.
, 5 g of boron trifluoride ether complex was charged as a catalyst, and then 142 g of glycidyl methacrylate was added dropwise.
The reaction was stirred at 0°C for 5 hours.
次に、得られた反応組成物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４０モル、プ
ロピレンオキサイド４０モルを反応組成物に対してラン
ダムに付加し、得られた反応組成物を本発明乳化剤［Ｆ
］とした。Next, the obtained reaction composition was transferred to an autoclave, and caustic potassium was used as a catalyst at a pressure of 1.5 kg/cm2. 40 moles of ethylene oxide and 40 moles of propylene oxide were randomly added to the reaction composition at a temperature of 130°C, and the resulting reaction composition was added to the emulsifier [F] of the present invention.
].
製造例５
攪拌機、温度計、還流管を備えた反応容器にジＳｅｃ、
ブチルフェノールプロピレンオキサイド１０モル付加体
７８６ｇ、触媒として三フフ化ホウ素エーテル錯体４ｇ
を仕込み、つぎにグリシジルアクリレ−）１２８ｇを滴
下し８０℃にて５時間攪拌反応した。Production Example 5 DiSec,
786 g of 10 mole adduct of butylphenol propylene oxide, 4 g of boron trifluoride ether complex as catalyst
Next, 128 g of glycidyl acrylate was added dropwise, and the reaction was stirred at 80° C. for 5 hours.
次に、得られた反応組成物をオートクレーブに多し、苛
性カリウムを触媒として、圧力１．５ｋｇ／ｃｍ２．ｍ
度１３０℃の条件にてエチレンオキサイドを反応組成物
に対して２０モル付加し、得られた反応生成物を本発明
乳化剤［Ｇ］とした。Next, the obtained reaction composition was placed in an autoclave, and caustic potassium was used as a catalyst at a pressure of 1.5 kg/cm2. m
20 mol of ethylene oxide was added to the reaction composition at 130°C, and the resulting reaction product was used as the emulsifier [G] of the present invention.
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１表に示した。The results are shown in Table 1.
［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、モノマー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 monomer and 0.0 parts of ammonium persulfate were added.
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 aged for 1 hour at the 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
て上記の混合上ツマー１８０部を滴下して、その後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 for preliminary polymerization, and 180 parts of the above-mentioned mixture was added dropwise over a period of about 3 hours starting 10 minutes after the polymerization started, and then aged at 80°C 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、比較品として従来の乳化剤の例も併
せて第２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 2 as comparative products.
実施例３
本発明乳化剤［Ａ］、 ［Ｆ］、 ［Ｇ］を５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。Example 3 Emulsifiers [A], [F], and [G] of the present invention were prepared as follows: Example 1
Emulsion polymerization was carried out using the following emulsion polymerization formulation, and the physical properties of the resulting emulsion and the polymer film obtained from the emulsion were tested.
その結果を第３表に示した。The results are shown in Table 3.
Claims (1)
、アルケニル基、もしくはアルキルアリール基、アラル
キルアリール基、Ｒ＿２は水素原子もしくはメチル基、
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０〜１００の整数でり、ｍは１〜２００の
整数である。］で表わ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] There are general formulas, ▲mathematical formulas, chemical formulas, tables, etc.▼ [However, in the above formula, R_1 is an alkyl group having 8 to 30 carbon atoms, an alkenyl group, or an alkylaryl group, and R_2 is an aralkylaryl group. hydrogen atom or methyl group,
A is an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group, n is an integer of 0 to 100, and m is an integer of 1 to 200. ] 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 |
|---|---|---|---|
| JP61220022A JPS6377530A (en) | 1986-09-17 | 1986-09-17 | Emulsifier for aqueous resin dispersion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61220022A JPS6377530A (en) | 1986-09-17 | 1986-09-17 | Emulsifier for aqueous resin dispersion |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6377530A true JPS6377530A (en) | 1988-04-07 |
Family
ID=16744705
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61220022A Pending JPS6377530A (en) | 1986-09-17 | 1986-09-17 | Emulsifier for aqueous resin dispersion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6377530A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01170607A (en) * | 1987-12-25 | 1989-07-05 | Sanyo Chem Ind Ltd | Modifying agent and modification |
| JP2012057030A (en) * | 2010-09-08 | 2012-03-22 | Kao Corp | Method for producing polyalkylene glycol monomer |
| CN106608815A (en) * | 2015-10-23 | 2017-05-03 | 中日合成化学股份有限公司 | Process for producing hypoalkoxy derivative and use thereof |
-
1986
- 1986-09-17 JP JP61220022A patent/JPS6377530A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01170607A (en) * | 1987-12-25 | 1989-07-05 | Sanyo Chem Ind Ltd | Modifying agent and modification |
| JP2012057030A (en) * | 2010-09-08 | 2012-03-22 | Kao Corp | Method for producing polyalkylene glycol monomer |
| CN106608815A (en) * | 2015-10-23 | 2017-05-03 | 中日合成化学股份有限公司 | Process for producing hypoalkoxy derivative and use thereof |
| JP2017081893A (en) * | 2015-10-23 | 2017-05-18 | 中日合成化學股▲分▼有限公司 | Production process for alkylene derivative, and application thereof |
| CN106608815B (en) * | 2015-10-23 | 2019-10-15 | 中日合成化学股份有限公司 | Process for producing hypoalkoxy derivative and use thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2611772B2 (en) | Emulsifier for emulsion polymerization | |
| JPH0223561B2 (en) | ||
| JPS62100502A (en) | Emulsifier for aqueous resin dispersion | |
| JP2596441B2 (en) | Emulsifier for aqueous resin dispersion | |
| JPS6384625A (en) | Emulsifier for aqueous resin dispersion | |
| JPS6377530A (en) | Emulsifier for aqueous resin dispersion | |
| US3541138A (en) | Crosslinking polymerizable surfactants | |
| JPS6354930A (en) | Emulsifier for water-based resin dispersion | |
| JPH07228613A (en) | Emulsifying dispersion agent for polymerization | |
| JPS6377531A (en) | Emulsifier for aqueous resin dispersion | |
| JPS62221432A (en) | Emulsifier for aqueous resin dispersion | |
| JP2887551B2 (en) | Emulsifier for emulsion polymerization | |
| JPS6312334A (en) | Emulsifying agent for aqueous resin dispersion | |
| JP2007063338A (en) | Emulsifier for emulsion polymerization, method for producing polymer emulsion and polymer emulsion | |
| JPS6384624A (en) | Emulsifier for aqueous resin dispersion | |
| JPS62286528A (en) | Aqueous resin dispersion emulsifier | |
| JPS6377532A (en) | Emulsifier for aqueous resin dispersion | |
| US4198520A (en) | Nonionic monomeric emulsion stabilizers | |
| JPS5912681B2 (en) | Emulsifier for aqueous polymerization | |
| JPH0199639A (en) | Emulsifier for aqueous resin dispersion | |
| JP2611776B2 (en) | Emulsifier for emulsion polymerization | |
| JP2001163938A (en) | Surfactant composition and emulsifier composition for aqueous resin dispersion | |
| JPS62225237A (en) | Emulsifier for water-based resin dispersion | |
| JPS62240304A (en) | Emulsifying agent for aqueous resin dispersion | |
| JPS63147530A (en) | Emulsifier for water-based resin dispersion |