JPS63147530A - Emulsifier for water-based resin dispersion - Google Patents
Emulsifier for water-based resin dispersionInfo
- Publication number
- JPS63147530A JPS63147530A JP61297229A JP29722986A JPS63147530A JP S63147530 A JPS63147530 A JP S63147530A JP 61297229 A JP61297229 A JP 61297229A JP 29722986 A JP29722986 A JP 29722986A JP S63147530 A JPS63147530 A JP S63147530A
- Authority
- JP
- Japan
- Prior art keywords
- emulsifier
- group
- emulsion
- emulsion polymerization
- emulsifiers
- 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 43
- 239000006185 dispersion Substances 0.000 title claims description 7
- 229920005989 resin Polymers 0.000 title claims description 7
- 239000011347 resin Substances 0.000 title claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 150000001875 compounds Chemical group 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000005156 substituted alkylene group Chemical group 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 15
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 14
- 125000001165 hydrophobic group Chemical group 0.000 abstract description 4
- 125000005394 methallyl group Chemical group 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 1
- -1 alkyl sulfate salts Chemical class 0.000 description 16
- 239000000839 emulsion Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 229920006254 polymer film Polymers 0.000 description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 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
- 125000000129 anionic group Chemical group 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
- 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
- 238000013007 heat curing Methods 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
- 239000002736 nonionic surfactant Substances 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
- 229920000642 polymer Polymers 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
- 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
- OHXAOPZTJOUYKM-UHFFFAOYSA-N 3-Chloro-2-methylpropene Chemical compound CC(=C)CCl OHXAOPZTJOUYKM-UHFFFAOYSA-N 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-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
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-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
- 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
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910052799 carbon Inorganic materials 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
- 230000002542 deteriorative effect Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 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
- 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
- 238000000034 method Methods 0.000 description 1
- 150000002978 peroxides Chemical class 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
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 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
- 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
- 239000002356 single layer Substances 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 238000012546 transfer 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
Landscapes
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (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，ＰＦ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 more particularly to a novel and useful emulsifier for use in aqueous emulsion polymerization of ethylenically unsaturated monomers in PF.
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 polyoxypropylene block copolymer, and polyoxyethylene sorbitan fatty acid ester may be used alone or in combination.
In addition, the properties of the film produced from the emulsion are as follows:
The results are not always 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。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 emulsion obtained.
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。In particular, problems remain that need to be improved regarding mechanical stability.
さらに、エマルジョンからポリマーフィルムを製造した
際、使用した乳化剤がＴｔ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
を生じてしくる。Furthermore, when a polymer film is produced from an emulsion, the emulsifier used remains in the polymer film in a Tt-like 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だめ、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 requires a great deal of effort 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、４．￥公開
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
−２８２０８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、アニオン性の反応性乳化剤の場合、用途的
に制約を受ける場合が多く、また重合体エマルシコンの
安定性においても、不充分な点が多い。For example, as an anionic reactive emulsifier, 4. ¥ Publication No. 46-12472, Japanese Patent Publication No. 54-144317, Special Publication No. 46-34894, Special Publication No. 56-29657,
JP-A-51-30285, JP-B-49-46291, etc., and as a nonionic reactive emulsifier, JP-A-56
-28208, JP-A-50-98484, etc.
It has been tried as an emulsifier for emulsion polymerization of various monomers, but in the case of anionic reactive emulsifiers, there are many restrictions in terms of use, and there are many shortcomings in terms of stability of polymer emulsicone. .
非イオン性の反応性乳化剤は、あまり用途的な制約は受
けず、広範囲にわたって、使用できるが、エマルジョン
重合時の安定性が不充分であり、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の
問題点を有している。Non-ionic reactive emulsifiers are not subject to many application restrictions and can be used in a wide range of applications, but their stability during emulsion polymerization is insufficient, and when used in combination with conventional emulsifiers, polymerization may occur. There are problems such as the fact that the process does not proceed smoothly.
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、 ＣＨ３
［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、アルケニル基ふ、もしくはアラ
ルキル基、Ａは炭素数２〜４のアルキレン哉、もしくは
置換アルキレン基、ｎは２〜２００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
４．′Ｆ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: CH3 [wherein R1 is an alkyl group, alkenyl group, or aralkyl group having 4 to 18 carbon atoms, and R2 is hydrogen or an alkyl group, alkenyl group, or aralkyl group having 4 to 18 carbon atoms] The group A is an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group, and n is an integer of 2 to 200. ] Containing at least one of the compounds represented by 4. The present invention provides an emulsifier for an aqueous resin dispersion which exhibits an F characteristic.
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, etc.
アルケニル基としては１例えば、ブテニル、・ｒツブテ
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 alkenyl groups include butenyl, .rbutenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl,
Examples include tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, and the like. Aralkyl groups include styryl, benzyl,
Examples include cumyl, and mixtures thereof may also be used.
Ｒ２は水素または炭素ｆ１．４〜１８のアルキル基。R2 is hydrogen or an alkyl group having carbon f1.4 to f18.
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。An alkenyl group or an aralkyl group (where the alkyl group includes, for example, butyl, isobutyl, pentyl,
hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, hebutadecyl, octadecyl,
etc., and a mixture thereof may also be used.
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、外ブテニル、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, exobutenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, and mixtures thereof. Also 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
ックあるいはう゛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.
ｎは２〜２００の整数であり、より好ましくは５〜１０
０の範囲である０本発明の乳化剤は、疎水基として乳化
重合用乳化剤で最も汎用性があり。n is an integer of 2 to 200, more preferably 5 to 10
The emulsifier of the present invention has a hydrophobic group in the range of 0, and is the most versatile emulsifier for emulsion polymerization.
乳化剤として性能の優れたアルキルフェノール、アルケ
ニルフェノール、アラルキルフェノールを用い、更にそ
の疎水基にメタリル基を結合させることにより、従来の
非イオン活性剤の特徴を低下させることなく、前述の問
題点を解消できる。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。By using alkylphenols, alkenylphenols, and aralkylphenols that have excellent performance as emulsifiers, and further bonding methallyl groups to their hydrophobic groups, the above-mentioned problems can be solved without deteriorating the characteristics of conventional nonionic surfactants. . 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、メタ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。That is, an alkylphenol such as nonylphenol is used as a raw material, methallyl chloride is heated and reacted in the presence of a catalyst, and then distilled under reduced pressure.
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、本発明の乳化剤を
得ることができる。The emulsifier of the present invention can be obtained by further adding alkylene oxide to the reaction composition thus obtained in a conventional manner.
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、アクリル酎ブチル、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イ含有モノマー、
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 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,
Conjugated diolefin monomers such as butadiene, isoprene, chloroprene, and others include ethylene, maleic anhydride, methyl maleate, and the like.
本発明の乳化剤はこれらのモノで−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 in the emulsion polymerization of one or more of these compounds.
重合開始剤としては、従来公知のものでよく１例えば、
過酸化水素、過硫酸カリウ１１、アゾビスイソブチルニ
トリル、ペンゾイルパーオギ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 11, azobisisobutylnitrile, penzoyl 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、全モノヤーに対してＯ３１〜２
０重量％、さらに好ましくは、０．５〜１０重量％であ
る。The emulsifier of the present invention is usually O31-2 based on the total monolayer.
0% by weight, more preferably 0.5 to 10% by weight.
また、本発明の乳化剤はｔｌｉ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、４ｊ、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, 4J, other concrete, etc.
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、つぎにメタリルクロライド１１７ｇ［
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 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 methallyl was added. Chloride 117g [
1.1 mol] was added dropwise and stirred at 40°C for 2 hours.
その後、温度を２２０°Ｃに昇温し、３時間ＩＷけした
後、減圧にて分溜し、メタリルノニルフェ／−ル２２０
ｇを（ＩＩた。 この収率は約８０％であった０次に、
分溜して得られたメタリルノニルフェノールをオートク
レーブに移し、１．Ｙ性カリウムを触媒として、圧力１
．５ｋｇ／ａｍ２、温度１３０℃の条件にてエチレンオ
キサイドをメクリルノニルフェノールに対して、３０モ
ル付加し、得られた組成物を本発明の乳化剤［Ａ］とし
た。Thereafter, the temperature was raised to 220°C, and after IWing for 3 hours, fractional distillation was carried out under reduced pressure.
g (II). This yield was approximately 80%.
Transfer the methallylnonylphenol obtained by fractional distillation to an autoclave, 1. Using Y potassium as a catalyst, pressure 1
．． 30 moles of ethylene oxide was added to mecrylnonylphenol under conditions of 5 kg/am2 and a temperature of 130°C, and the resulting composition was used as the emulsifier [A] of the present invention.
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。Production Example 2 7lyloctylphenol was obtained by the same synthesis method as in Production Example 1, except that octylphenol was used instead of nonylphenol.
このメタリルオクチルフェア′−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、本発明の乳化剤［Ｂ］〜［Ｅ］とした。Various types of fulkylene oxides as shown in Table 1 were added to this methallyl octyl faire by a conventional method to obtain emulsifiers [B] to [E] 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２表に示した。°The results are shown in Table 2.
［乳化重合処方］
水２９０ｇ、乳化剤１０部を溶解し、７０’ｃまでＡ、
温する。つぎに、モノマー２０部と過硫酸アンモニウム
０．１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峙間熟成した後
、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 290 g of water and 10 parts of emulsifier, and add A to 70'c.
Warm up. Next, 20 parts of monomer and 0.1 part of ammonium persulfate were added for preliminary polymerization, and 180 parts were added dropwise over a period of 3 hours starting 10 minutes after the start of polymerization to perform polymerization. Thereafter, the emulsion was aged for one 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１１草を１１０℃、
３分間熱キユアーしポリマーフィルムを製造した。Next, this test sample was applied to a glass plate and dried at room temperature for 24 hours, and the dried coating was heated at 110°C.
A polymer film was produced by heat curing for 3 minutes.
実施例２
水２７０部、乳化剤として第３表に示す各種併用乳化剤
１０部を溶解し、８０°Ｃ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２０ｉ’ｉ’３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？Ｂ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 2 270 parts of water and 10 parts of various combined emulsifiers shown in Table 3 as emulsifiers were dissolved, heated to 80°C, and mixed monomers of n-butyl acrylate/styrene = 7/3 were mixed as monomers 20 i'i '3 and 0.3 parts of ammonium persulfate were prepolymerized, and 10 minutes after the start of polymerization, approximately 3 parts of ammonium persulfate was added.
The above mixed monomer 180? After adding B dropwise, the mixture was aged at 80° C. for 1 hour, cooled, and the emulsion was taken out to be 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製造した。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 produced 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 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 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.
０．５〜２％のと彦： ○
直ちに白化 ×フィルムの
白化状況を評価した。0.5-2% Tomohiko: ○ Immediate whitening × The whitening status of the film was evaluated.
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] 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, and n is an integer of 2 to 200. ] An emulsifier for an aqueous resin dispersion, characterized by containing at least one compound represented by the following.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61297229A JPS63147530A (en) | 1986-12-12 | 1986-12-12 | Emulsifier for water-based resin dispersion |
| US07/119,460 US4918211A (en) | 1986-12-12 | 1987-11-10 | Surface active compounds having a polymerizable moiety |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61297229A JPS63147530A (en) | 1986-12-12 | 1986-12-12 | Emulsifier for water-based resin dispersion |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63147530A true JPS63147530A (en) | 1988-06-20 |
Family
ID=17843836
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61297229A Pending JPS63147530A (en) | 1986-12-12 | 1986-12-12 | Emulsifier for water-based resin dispersion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63147530A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017202480A (en) * | 2016-05-10 | 2017-11-16 | 中日合成化學股▲分▼有限公司 | Manufacturing method of surfactant, surfactant and water-based paint resin |
-
1986
- 1986-12-12 JP JP61297229A patent/JPS63147530A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017202480A (en) * | 2016-05-10 | 2017-11-16 | 中日合成化學股▲分▼有限公司 | Manufacturing method of surfactant, surfactant and water-based paint resin |
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