JP2007056081A - Emulsifier for emulsion polymerization, method for producing polymer emulsion, and polymer emulsion - Google Patents
Emulsifier for emulsion polymerization, method for producing polymer emulsion, and polymer emulsion Download PDFInfo
- Publication number
- JP2007056081A JP2007056081A JP2005240498A JP2005240498A JP2007056081A JP 2007056081 A JP2007056081 A JP 2007056081A JP 2005240498 A JP2005240498 A JP 2005240498A JP 2005240498 A JP2005240498 A JP 2005240498A JP 2007056081 A JP2007056081 A JP 2007056081A
- Authority
- JP
- Japan
- Prior art keywords
- emulsion
- emulsifier
- polymerization
- emulsion polymerization
- parts
- 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
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- 239000000839 emulsion Substances 0.000 title claims abstract description 55
- 239000003995 emulsifying agent Substances 0.000 title claims abstract description 46
- 238000007720 emulsion polymerization reaction Methods 0.000 title claims abstract description 45
- 229920000642 polymer Polymers 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims description 32
- 150000005215 alkyl ethers Chemical class 0.000 claims abstract description 31
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 4
- 239000000178 monomer Substances 0.000 claims description 27
- 238000006116 polymerization reaction Methods 0.000 claims description 21
- 239000002736 nonionic surfactant Substances 0.000 claims description 10
- 239000003945 anionic surfactant Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 239000003093 cationic surfactant Substances 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 239000012736 aqueous medium Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 12
- 229920000223 polyglycerol Polymers 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 2
- -1 alkylphenyl ethers Chemical class 0.000 description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 239000000047 product Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 150000001298 alcohols Chemical class 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 9
- 125000002947 alkylene group Chemical group 0.000 description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 239000004744 fabric Substances 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000012855 volatile organic compound Substances 0.000 description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 150000002430 hydrocarbons Chemical group 0.000 description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 150000001299 aldehydes Chemical class 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- XUJLWPFSUCHPQL-UHFFFAOYSA-N 11-methyldodecan-1-ol Chemical compound CC(C)CCCCCCCCCCO XUJLWPFSUCHPQL-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000000872 buffer Substances 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 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
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical class CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 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
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 125000000392 cycloalkenyl group Chemical group 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000004817 gas chromatography 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
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 125000002496 methyl group Chemical group [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
- 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
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 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
- 239000003973 paint Substances 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
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- YLQLIQIAXYRMDL-UHFFFAOYSA-N propylheptyl alcohol Chemical compound CCCCCC(CO)CCC YLQLIQIAXYRMDL-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 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
- 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
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- 0 *C(*)(C(*)(*)ONNC(*)(*)O*)ONC=C Chemical compound *C(*)(C(*)(*)ONNC(*)(*)O*)ONC=C 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
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- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 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
- LAPPDPWPIZBBJY-UHFFFAOYSA-N 2-butylhexan-1-ol Chemical compound CCCCC(CO)CCCC LAPPDPWPIZBBJY-UHFFFAOYSA-N 0.000 description 1
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- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
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- QDTDKYHPHANITQ-UHFFFAOYSA-N 7-methyloctan-1-ol Chemical compound CC(C)CCCCCCO QDTDKYHPHANITQ-UHFFFAOYSA-N 0.000 description 1
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- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
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- 241000978776 Senegalia senegal Species 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
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Images
Abstract
Description
本発明は乳化重合用乳化剤、ポリマーエマルションの製造方法、及びポリマーエマルションに関し、詳しくはポリグリセリンアルキルエーテルを含む乳化重合用乳化剤、該乳化重合用乳化剤を用いたポリマーエマルションの製造方法、及びその方法により得られたポリマーエマルションに関する。 The present invention relates to an emulsifier for emulsion polymerization, a method for producing a polymer emulsion, and a polymer emulsion, and more specifically, an emulsifier for emulsion polymerization containing polyglycerin alkyl ether, a method for producing a polymer emulsion using the emulsifier for emulsion polymerization, and a method thereof. It relates to the resulting polymer emulsion.
従来、ノニオン性の乳化重合用乳化剤としては、ノニルフェノールやオクチルフェノールにアルキレンオキサイドを付加したポリオキシアルキレンアルキルフェニルエーテルや高級アルコールにアルキレンオキサイドを付加したポリオキシアルキレンアルキルエーテルが広く用いられてきた。これらの乳化剤は、アルキル基の種類、またはアルキル基に付加するアルキレンオキサイドの付加モル数を変えることによりその性能を操作することができる。 Conventionally, as nonionic emulsifiers for emulsion polymerization, polyoxyalkylene alkylphenyl ethers obtained by adding alkylene oxide to nonylphenol or octylphenol and polyoxyalkylene alkyl ethers obtained by adding alkylene oxide to higher alcohols have been widely used. These emulsifiers can manipulate their performance by changing the type of alkyl group or the number of moles of alkylene oxide added to the alkyl group.
しかし、ポリオキシアルキレンアルキルフェニルエーテルは、その生分解生成物の生態毒性が問題視されており、自然環境に排出された場合、生態系に悪影響を及ぼすことが問題となっている。よって、ポリオキシアルキレンアルキルエーテルといったアルキルフェノールを疎水基に含まない乳化剤への代替が進められてきている。 However, polyoxyalkylene alkylphenyl ethers have a problem of ecotoxicity of biodegradation products, and have a problem of adversely affecting the ecosystem when discharged into the natural environment. Therefore, the substitution to the emulsifier which does not contain alkylphenols, such as polyoxyalkylene alkyl ether, in a hydrophobic group has been advanced.
また、ポリオキシアルキレンアルキルエーテルは、乳化重合用乳化剤として性能不足である場合や、水生生物毒性、皮膚刺激性などのため使用できる範囲が限られることがある。 In addition, polyoxyalkylene alkyl ethers may have limited performance as emulsifiers for emulsion polymerization, or due to aquatic toxicity and skin irritation.
さらに、ポリオキシアルキレンアルキルエーテルの問題点として、未反応のエチレンオキサイドやプロピレンオキサイドが製品中に残存すること、副生成物として発がん性や刺激性の高い物質が発生することが挙げられる。例えば、合成時には有害なジオキサンが生成することや、アルキレンオキサイド鎖の酸化分解により有害性のアルデヒド類を生成することが知られており、シックハウス症候群やＶＯＣ（揮発性有機化合物）問題が騒がれる近年、アルデヒド等を含む乳化剤をエマルションの製造に用いるのは好ましくない。 Furthermore, problems with polyoxyalkylene alkyl ethers include unreacted ethylene oxide and propylene oxide remaining in the product, and generation of highly carcinogenic and irritating substances as by-products. For example, it is known that harmful dioxane is generated at the time of synthesis, and harmful aldehydes are generated by oxidative decomposition of the alkylene oxide chain. In recent years, sick house syndrome and VOC (volatile organic compound) problems have been heard. It is not preferable to use an emulsifier containing aldehyde or the like for the production of an emulsion.
これに対し、アルキレンオキサイドから誘導されないノニオン界面活性剤として、ポリグリセリン脂肪酸エステルを乳化重合用乳化剤として用いたエマルションの製造方法が特表２００４−５２６８５１号公報に開示されている。 In contrast, as a nonionic surfactant not derived from alkylene oxide, a method for producing an emulsion using a polyglycerin fatty acid ester as an emulsifier for emulsion polymerization is disclosed in JP-T-2004-526851.
ポリグリセリン脂肪酸エステルは、ポリオキシアルキレンアルキルエーテルのように有害なジオキサンやホルムアルデヒドが発生せず、またアルキレンオキサイドを出発原料としていないため高い安全性を持った乳化剤である。 Polyglycerin fatty acid ester is an emulsifier having high safety because it does not generate harmful dioxane or formaldehyde like polyoxyalkylene alkyl ether and does not use alkylene oxide as a starting material.
また、ポリグリセリン脂肪酸エステルはその性能を変化させる場合、脂肪酸の種類、グリセリンの重合度を変えることにより操作できる。またモノエステル体だけでなく、脂肪酸とポリグリセリンのモル比を任意に変えることによりポリエステル体を作ることが可能であるため、ポリオキシアルキレンアルキルエーテルに比べ幅広い性質を持たすことができる利点がある。
しかしながら、上記のポリグリセリン脂肪酸エステルはアルカリ溶液中では加水分解を起こしやすいため、乳化重合用乳化剤として用いた場合、エマルションの安定性保持といった点で不安を残している。 However, since the polyglycerin fatty acid ester is easily hydrolyzed in an alkaline solution, when used as an emulsifier for emulsion polymerization, there remains anxiety in terms of maintaining the stability of the emulsion.
そこで本発明は、ポリマーエマルションの乳化重合において、重合時の乳化安定性、得られたポリマーエマルションの化学安定性が優れると共に、実際に使用した際のフィルム光沢性や接着性が優れたポリマーエマルションが得られ、さらに重合時の有害な副生成物の発生など従来のアルキレンオキサイドに起因する問題点を解消することができるアルキレンオキサイドから誘導されないノニオン性の乳化重合用乳化剤、その乳化重合用乳化剤を用いたポリマーエマルションの製造方法、及びその方法により得られるポリマーエマルションを提供することを目的とするものである。 Accordingly, the present invention provides a polymer emulsion having excellent film glossiness and adhesiveness when actually used in emulsion polymerization of a polymer emulsion, as well as excellent emulsion stability during polymerization and chemical stability of the obtained polymer emulsion. Further, nonionic emulsion polymerization emulsifiers that are not derived from alkylene oxides, which can eliminate the problems caused by conventional alkylene oxides such as generation of harmful by-products during polymerization, and the emulsion polymerization emulsifiers are used. It is an object of the present invention to provide a method for producing a polymer emulsion, and a polymer emulsion obtained by the method.
本発明者らは、ポリマーエマルションの製造に際して、ポリグリセリンアルキルエーテルを含む乳化重合用乳化剤を用いることにより上記の課題が解決されることを見出し本発明を完成するに至った。 The present inventors have found that the above-mentioned problems can be solved by using an emulsifier for emulsion polymerization containing a polyglycerin alkyl ether when producing a polymer emulsion, and have completed the present invention.
すなわち、本発明の乳化重合用乳化剤は、ポリグリセリンアルキルエーテルを含むことを特徴とするものである。 That is, the emulsifier for emulsion polymerization of the present invention is characterized by containing polyglycerin alkyl ether.
前記ポリグリセリンアルキルエーテルは、下記の一般式（１）で表される化合物を用いることができる。
（式中、Ｒは炭化水素基であり、ｎは１〜２００である。また、Ｘ１及びＸ２は水素原子または炭化水素基である。） (In the formula, R is a hydrocarbon group, n is 1 to 200, and X 1 and X 2 are a hydrogen atom or a hydrocarbon group.)
また、本発明の乳化重合用乳化剤は、前記ポリグリセリンアルキルエーテルと、該ポリグリセリンアルキルエーテル以外の他のノニオン界面活性剤及びアニオン界面活性剤及びカチオン界面活性剤の群から選ばれた少なくとも１種類の界面活性剤との混合物であってもよい。 Moreover, the emulsifier for emulsion polymerization of the present invention is at least one selected from the group of the polyglycerin alkyl ethers and other nonionic surfactants, anionic surfactants and cationic surfactants other than the polyglycerin alkyl ethers. It may be a mixture with a surfactant.
本発明のポリマーエマルションの製造方法は、オレフィン性モノマーに対して前記乳化重合用乳化剤を０．１〜２０重量％の量で使用し、水性媒体中で前記モノマーを重合させる、または前記モノマー重合後にポリマーに添加することにある。 In the method for producing a polymer emulsion of the present invention, the emulsifier for emulsion polymerization is used in an amount of 0.1 to 20% by weight based on the olefinic monomer, and the monomer is polymerized in an aqueous medium, or after the monomer polymerization. To be added to the polymer.
そして、本発明のポリマーエマルションは、上記の製造方法により得られたポリマーエマルションである。 And the polymer emulsion of this invention is a polymer emulsion obtained by said manufacturing method.
本発明のポリグリセリンアルキルエーテルを含む乳化重合用乳化剤によれば、重合時のエマルションの安定性が良く、化学安定性が良好なポリマーエマルションが得られ、有害な副生成物の発生を低減することができる。また、得られたポリマーエマルションのフィルム光沢性や接着性が良好である。 According to the emulsifier for emulsion polymerization containing the polyglycerin alkyl ether of the present invention, it is possible to obtain a polymer emulsion with good emulsion stability and good chemical stability during polymerization, and to reduce generation of harmful by-products. Can do. Moreover, the film glossiness and adhesiveness of the obtained polymer emulsion are good.
以下、本発明の実施の形態について説明する。 Embodiments of the present invention will be described below.
本発明のポリマーエマルションの製造方法は、少なくとも１種類のオレフィン性モノマーから構成されるポリマーエマルションを乳化重合により製造する際に、ポリグリセリンアルキルエーテルを乳化重合用乳化剤として用いることにある。 The manufacturing method of the polymer emulsion of this invention exists in using polyglycerin alkyl ether as an emulsifier for emulsion polymerization, when manufacturing the polymer emulsion comprised from an at least 1 type of olefin monomer by emulsion polymerization.
本発明に係る乳化重合用乳化剤として用いられるポリグリセリンアルキルエーテルは、下記の一般式（１）で表されるポリグリセリンアルキルエーテルを好適に使用することができる。
（式中、Ｒは炭化水素基であり、ｎは１〜２００である。また、Ｘ１及びＸ２は水素原子または炭化水素基である。） (In the formula, R is a hydrocarbon group, n is 1 to 200, and X 1 and X 2 are a hydrogen atom or a hydrocarbon group.)
上記式中Ｒの炭化水素基としては、例えば、アルキル基、アルケニル基、アリール基、シクロアルキル基、シクロアルケニル基等が挙げられる。 Examples of the hydrocarbon group represented by R in the above formula include an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, and a cycloalkenyl group.
アルキル基としては、例えば、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、２級ブチル、ターシャリブチル、ペンチル、イソペンチル、２級ペンチル、ネオペンチル、ターシャリペンチル、ヘキシル、２級ヘキシル、ヘプチル、２級ヘプチル、オクチル、２−エチルヘキシル、２級オクチル、ノニル、２級ノニル、デシル、２級デシル、ウンデシル、２級ウンデシル、ドデシル、２級ドデシル、トリデシル、イソトリデシル、２級トリデシル、テトラデシル、２級テトラデシル、ヘキサデシル、２級ヘキサデシル、ステアリル、イコシル、ドコシル、テトラコシル、トリアコンチル、２−ブチルオクチル、２−ブチルデシル、２−ヘキシルオクチル、２−ヘキシルデシル、２−オクチルデシル、２−ヘキシルドデシル、２−オクチルドデシル、２−デシルテトラデシル、２−ドデシルヘキサデシル、２−ヘキサデシルオクタデシル、２−テトラデシルオクタデシル、モノメチル分枝−イソステアリル基等が挙げられる。 Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, isopentyl, secondary pentyl, neopentyl, tertiary pentyl, hexyl, secondary hexyl, heptyl, 2 Secondary heptyl, octyl, 2-ethylhexyl, secondary octyl, nonyl, secondary nonyl, decyl, secondary decyl, undecyl, secondary undecyl, dodecyl, secondary dodecyl, tridecyl, isotridecyl, secondary tridecyl, tetradecyl, secondary tetradecyl , Hexadecyl, secondary hexadecyl, stearyl, icosyl, docosyl, tetracosyl, triacontyl, 2-butyloctyl, 2-butyldecyl, 2-hexyloctyl, 2-hexyldecyl, 2-octyldecyl, 2-hexyldecyl, - octyldodecyl, 2-decyltetradecyl, 2-dodecyl-hexadecyl, 2-hexadecyl octadecyl, 2-tetradecyl-octadecyl, monomethyl branched - and the like isostearyl group.
アルケニル基としては、例えば、ビニル、アリル、プロペニル、ブテニル、イソブテニル、ペンテニル、イソペンテニル、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、テトラデセニル、オレイル等が挙げられる。 Examples of the alkenyl group include vinyl, allyl, propenyl, butenyl, isobutenyl, pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, oleyl and the like.
アリール基としては、例えば、フェニル、トルイル、キシリル、クメニル、メシチル、ベンジル、フェネチル、スチリル、シンナミル、ベンズヒドリル、トリチル、エチルフェニル、プロピルフェニル、ブチルフェニル、ペンチルフェニル、ヘキシルフェニル、ヘプチルフェニル、オクチルフェニル、ノニルフェニル、デシルフェニル、ウンデシルフェニル、ドデシルフェニル、フェニルフェニル、ベンジルフェニル、スチレン化フェニル、ｐ−クミルフェニル、α−ナフチル、β−ナフチル基等が挙げられる。 As an aryl group, for example, phenyl, toluyl, xylyl, cumenyl, mesityl, benzyl, phenethyl, styryl, cinnamyl, benzhydryl, trityl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, Nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl, phenylphenyl, benzylphenyl, styrenated phenyl, p-cumylphenyl, α-naphthyl, β-naphthyl group and the like can be mentioned.
シクロアルキル基、シクロアルケニル基としては、例えば、シクロペンチル、シクロヘキシル、シクロヘプチル、メチルシクロペンチル、メチルシクロヘキシル、メチルシクロヘプチル、シクロペンテニル、シクロヘキセニル、シクロヘプテニル、メチルシクロペンテニル、メチルシクロヘキセニル、メチルシクロヘプテニル基等が挙げられる。 Examples of the cycloalkyl group and cycloalkenyl group include a cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl, methylcyclohexyl, methylcycloheptyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, methylcyclopentenyl, methylcyclohexenyl, methylcycloheptenyl group. Etc.
また、Ｒとしては上記の炭化水素基の中の２種類以上含んでいてもよい。 R may contain two or more of the above hydrocarbon groups.
一般式（１）において、Ｒは炭素数６から２０のアルキル基またはアルケニル基であることがより好ましい。 In the general formula (1), R is more preferably an alkyl group or alkenyl group having 6 to 20 carbon atoms.
通常、上記Ｒはアルコールから水酸基を除いた残基である。これらのアルコールは、天然由来のアルコール、または工業的に製造されるアルコールが使用できる。 Usually, R is a residue obtained by removing a hydroxyl group from alcohol. As these alcohols, naturally occurring alcohols or industrially produced alcohols can be used.
天然由来のアルコールとしては、オクチルアルコール、デシルアルコール、ラウリルアルコール、ミリスチルアルコール、セチルアルコール、ステアリルアルコール、オレイルアルコールなどが挙げられる。 Naturally occurring alcohols include octyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol and the like.
工業的に製造されるアルコールとしては、プロピレン或いはブテンまたはその混合物から誘導される高級オレフィンを経て、オキソ法により製造される分岐型飽和一級アルコールで、例えばイソノナノール、イソデカノール、イソウンデカノール、イソドデカノール、イソトリデカノールなどが挙げられる。これらアルコールの市販品としては、エクソン・モービル社製のＥｘｘａｌシリーズがある。また、ｎ−パラフィンやエチレンオリゴマーから誘導されるオレフィンを経て、オキソ法により製造される直鎖型と分岐型のアルコールの混合物として、Ｓｈｅｌｌ社製のネオドールシリーズ、三菱化学社製のダイヤドールシリーズやＳａｓｏｌ社製のサフォール（Ｓａｆｏｌ）シリーズやリアル（Ｌｉａｌ）シリーズがある。 Industrially produced alcohols are branched saturated primary alcohols produced by the oxo process via higher olefins derived from propylene or butene or mixtures thereof, such as isononanol, isodecanol, isoundecanol, isododecane. Nord, isotridecanol and the like. Commercial products of these alcohols include the Exxal series manufactured by Exxon Mobil. In addition, as a mixture of linear and branched alcohols produced by the oxo process via olefins derived from n-paraffins and ethylene oligomers, Shell's Neodol series, Mitsubishi Chemical's Diadol series And Sasol series and Real series manufactured by Sasol.
また、ゲルベ反応によるアルコールの２量化によって得られるゲルベアルコールには２−ブチル−１−ヘキサノール、２−エチル−１−ヘプタノール、２−プロピル−１−オクタノール、２−プロピル−１−ヘプタノール、４−メチル−２−プロピル−１−ヘキサノール、２−プロピル−５−メチル−１−ヘキサノールなどがあり、またはパラフィンを空気酸化して製造され、水酸基が炭素鎖の末端以外へランダムに結合しているセカンダリーアルコールなどがある。また、これらのアルコールを２種類以上配合して使用することも可能である。 In addition, Gerve alcohol obtained by dimerization of alcohol by Gerve reaction includes 2-butyl-1-hexanol, 2-ethyl-1-heptanol, 2-propyl-1-octanol, 2-propyl-1-heptanol, 4- Secondary that has methyl-2-propyl-1-hexanol, 2-propyl-5-methyl-1-hexanol, etc., or is produced by air oxidation of paraffin, and the hydroxyl group is randomly bonded to other than the end of the carbon chain There is alcohol. Moreover, it is also possible to mix and use two or more of these alcohols.
一般式（１）において、Ｘ１、Ｘ２は水素原子、または上記に記載の炭化水素基である。 In the general formula (1), X 1 and X 2 are a hydrogen atom or the hydrocarbon group described above.
また、一般式（１）において、ｎは１〜２００であり、好ましくは２〜５０である。 Moreover, in General formula (1), n is 1-200, Preferably it is 2-50.
また、一般式（１）のポリグリセリン部分は直鎖状に繋がっていてもよく、図１に示すように樹状に繋がっているものでもよい。 Moreover, the polyglycerin part of General formula (1) may be connected in linear form, and may be connected in dendritic form as shown in FIG.
本発明に用いられる乳化重合用乳化剤は、上記ポリグリセリンアルキルエーテルのアルキル基部分とポリグリセリン部分のモル比が、１：１〜５：１で含まれているのが有利である。 In the emulsifier for emulsion polymerization used in the present invention, it is advantageous that the molar ratio of the alkyl group part to the polyglycerin part of the polyglycerin alkyl ether is 1: 1 to 5: 1.
これらのポリグリセリンアルキルエーテルは、乳化重合用乳化剤として１種類を単独で用いてもよく、２種類以上を混合して用いてもよい。 These polyglycerin alkyl ethers may be used alone as an emulsifier for emulsion polymerization, or may be used in combination of two or more.
ポリグリセリンアルキルエーテルの製造方法は、特に限定されることはなく、従来からの公知技術により製造することができる。例えば、特開２００１−１１４７２０号公報、特開２０００−３８３６５号公報、特開平９−１８８７５５号公報、特開平６−２９３６８８号公報において開示されている方法によることができる。 The manufacturing method of polyglycerol alkyl ether is not specifically limited, It can manufacture by the conventionally well-known technique. For example, the methods disclosed in Japanese Patent Application Laid-Open Nos. 2001-114720, 2000-38365, 9-188755, and 6-293688 can be used.
本発明に係る乳化重合用乳化剤は、各種モノマーに適用することができ、モノマーの種類は特に限定されないが、例としては、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、アクリル酸２−エチルヘキシル、メタクリル酸メチル、メタクリル酸ブチル、メタクリル酸グリシジル、アクリロニトリル、メタクリロニトリル、α−クロルアクリロニトリル、アクリルアミド、メタクリルアミド、アクリル酸ヒドロキシエチルエステル、ヒドロキシプロピルアクリレート、ヒドロキシプロピルメタクリレート、アクリル酸、メタクリル酸等のアクリル系モノマー、スチレン、α−メチルスチレン、ジビニルベンゼン等の芳香族系モノマー、酢酸ビニル等のビニルエステル系モノマー、塩化ビニル、塩化ビニリデン等のハロゲン化オレフィンモノマー、ブタジエン、イソプレン、クロロプレン等の共役ジオレフィン系モノマー、その他、エチレン、イタコン酸、フマル酸、マレイン酸、マレイン酸メチル等が上げられる。これらのモノマーは１種類または２種類以上を用いることができる。 The emulsifier for emulsion polymerization according to the present invention can be applied to various monomers, and the type of the monomer is not particularly limited, but examples include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, Acrylic such as methyl methacrylate, butyl methacrylate, glycidyl methacrylate, acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, acrylamide, methacrylamide, hydroxyethyl ester acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, acrylic acid, methacrylic acid, etc. Monomers, aromatic monomers such as styrene, α-methylstyrene and divinylbenzene, vinyl ester monomers such as vinyl acetate, halogenated organic solvents such as vinyl chloride and vinylidene chloride And conjugated diolefin monomers such as ethylene monomer, butadiene, isoprene, and chloroprene, as well as ethylene, itaconic acid, fumaric acid, maleic acid, and methyl maleate. These monomers can be used alone or in combination of two or more.
上記乳化重合用乳化剤を用いる乳化重合には、従来公知の水溶性または油溶性の重合開始剤が特に制限なく使用できる。代表的な開始剤の例としては、過酸化水素、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム、過硫酸ベンゾイル、２、２’−アゾビスイソブチロニトリル、２、２’−アゾビス（２−アミジノプロパン）二塩酸塩等が挙げられる。 For emulsion polymerization using the above-mentioned emulsifier for emulsion polymerization, conventionally known water-soluble or oil-soluble polymerization initiators can be used without particular limitation. Examples of typical initiators include hydrogen peroxide, potassium persulfate, sodium persulfate, ammonium persulfate, benzoyl persulfate, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2- Amidinopropane) dihydrochloride and the like.
また、重合促進剤として、亜硫酸水素ナトリウム、第一硫酸鉄アンモニウム等を用い、レドックス重合を行うこともできる。 Moreover, redox polymerization can also be performed using sodium bisulfite, ammonium ferrous sulfate, or the like as a polymerization accelerator.
また、連鎖移動剤として、α−メチルスチレンダイマー、ｎ−ブチルメルカプタン、ｔ−ドデシルメルカプタンなどのメルカプタン類、四塩化炭素、四臭化炭素などのハロゲン化炭化水素などを用いてもよい。 Further, as a chain transfer agent, mercaptans such as α-methylstyrene dimer, n-butyl mercaptan, t-dodecyl mercaptan, halogenated hydrocarbons such as carbon tetrachloride and carbon tetrabromide may be used.
本発明では、乳化重合用乳化剤はモノマー総量に対して、０．１〜２０重量％、好ましくは０．２〜１０重量％で使用する。 In the present invention, the emulsifier for emulsion polymerization is used in an amount of 0.1 to 20% by weight, preferably 0.2 to 10% by weight, based on the total amount of monomers.
本発明においては、上記ポリグリセリンアルキルエーテルの１種類、または２種類以上の混合物を乳化重合用乳化剤として用い乳化重合を良好に完結することができるが、さらに他のノニオン界面活性剤及びアニオン界面活性剤、カチオン界面活性剤の１種類以上とを併用してもよく、これにより乳化重合時の重合安定性が向上し、また後工程における処理特性を向上させることができる。 In the present invention, one or a mixture of two or more of the polyglycerin alkyl ethers can be used as an emulsifier for emulsion polymerization, and emulsion polymerization can be completed satisfactorily. However, other nonionic surfactants and anionic surfactants can be used. One or more of an agent and a cationic surfactant may be used in combination, whereby the polymerization stability at the time of emulsion polymerization can be improved, and the processing characteristics in the subsequent step can be improved.
かかる他のノニオン界面活性剤、及びアニオン界面活性剤、カチオン界面活性剤としては特に限定されないが、例えば、ノニオン界面活性剤としては、ポリオキシアルキレンアルキルフェニルエーテル、ポリオキシアルキレンアルキルエーテル、脂肪酸ポリエチレングリコールエーテル、ソルビタン脂肪酸エステルなどが挙げられ、アニオン界面活性剤としては、脂肪酸セッケン、ロジン酸セッケン、アルキルスルホン酸塩、アルキルアリールスルホン酸塩、アルキルスルホコハク酸塩、ポリオキシエチレンアルキル硫酸塩、ポリオキシエチレンアリール硫酸塩などが挙げられ、カチオン界面活性剤としてはステアリルトリメチルアンモニウム、セチルトリメチルアンモニウム、ラウリルトリメチルアンモニウムなどが挙げられる。これらの他の界面活性剤の使用量としては、ポリグリセリンアルキルエーテル１００重量部に対して、０．５〜１００重量部含まれることが好ましく、より好ましくは５〜６０重量部である。さらに好ましくは１０〜３０重量部である。 Such other nonionic surfactants, anionic surfactants, and cationic surfactants are not particularly limited. For example, nonionic surfactants include polyoxyalkylene alkyl phenyl ether, polyoxyalkylene alkyl ether, fatty acid polyethylene glycol. Examples of the anionic surfactant include fatty acid soap, rosin acid soap, alkyl sulfonate, alkylaryl sulfonate, alkyl sulfosuccinate, polyoxyethylene alkyl sulfate, and polyoxyethylene. Examples of the cationic surfactant include stearyltrimethylammonium, cetyltrimethylammonium, and lauryltrimethylammonium. The amount of these other surfactants to be used is preferably 0.5 to 100 parts by weight, more preferably 5 to 60 parts by weight with respect to 100 parts by weight of the polyglycerin alkyl ether. More preferably, it is 10-30 weight part.
また、乳化重合時の重合安定性を向上させる目的で、公知の保護コロイド剤を併用することができる。併用できる保護コロイド剤としては、完全けん化ポリビニルアルコール（ＰＶＡ）、部分けん化ＰＶＡ、ヒドロキシエチルセルロース、カルボキシメチルセルロース、メチルセルロース、ポリアクリル酸、アラビアゴムなどがある。 In addition, a known protective colloid agent can be used in combination for the purpose of improving the polymerization stability during emulsion polymerization. Examples of protective colloid agents that can be used in combination include fully saponified polyvinyl alcohol (PVA), partially saponified PVA, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, polyacrylic acid, and gum arabic.
また、本発明においては、乳化重合用乳化剤の他の使用方法として、ポリマーエマルションの安定性を改善するために、重合終了後のポリマーエマルションに乳化重合用乳化剤を添加することができる。 Moreover, in this invention, in order to improve the stability of a polymer emulsion as another usage method of the emulsifier for emulsion polymerization, the emulsifier for emulsion polymerization can be added to the polymer emulsion after superposition | polymerization.
本発明の製造方法により得られるポリマーエマルションは、例えば、印刷インキ、塗料等のバインダー、インクジェット用メディアのバインダー、接着剤、粘着剤、被覆剤、含浸補強剤等として、木材、金属、紙、布、プラスチック、セラミック、その他のコンクリート等に適用することができる。 The polymer emulsion obtained by the production method of the present invention can be used, for example, as a binder for printing inks and paints, a binder for inkjet media, an adhesive, a pressure-sensitive adhesive, a coating agent, an impregnation reinforcing agent, etc. It can be applied to plastic, ceramic and other concrete.
以下、本発明を実施例により具体的に説明するが、本発明の範囲はこれに限定されるものではない。なお、「部」は特に記載がない限り重量基準である。 Hereinafter, the present invention will be specifically described by way of examples, but the scope of the present invention is not limited thereto. “Parts” are based on weight unless otherwise specified.
〈製造例〉
撹拌機、窒素導入管、及び温度計を備えた反応器に原料アルコールと、水酸化ナトリウムを仕込み、昇温させ減圧脱水する。次に一定温度を保持したままグリシドールを１時間かけて滴下し、さらに２時間撹拌することによりポリグリセリンアルキルエーテルからなる本発明にかかるノニオン界面活性剤を得ることができる。また、必要に応じ精製を行ってもよい。表１に下記製造例により得られたポリグリセリンアルキルエーテル（本発明品）ａ〜ｈ、および比較品ｊ〜ｎを示す。
<Production example>
Raw material alcohol and sodium hydroxide are charged into a reactor equipped with a stirrer, a nitrogen introduction tube, and a thermometer, and the temperature is raised and dehydrated under reduced pressure. Next, glycidol is dripped over 1 hour, maintaining a fixed temperature, and also it stirs for 2 hours, The nonionic surfactant concerning this invention which consists of polyglycerin alkyl ether can be obtained. Moreover, you may refine | purify as needed. Table 1 shows polyglycerin alkyl ethers (product of the present invention) a to h and comparative products j to n obtained by the following production examples.
〈製造例１〉
撹拌機、窒素導入管、及び温度計を備えた反応器にイソトリデシルアルコール２００部と、水酸化ナトリウム９部を仕込み、１２０℃まで昇温させ減圧脱水した。次に１２０℃を保持したままグリシドール１１１０部を１時間かけて滴下し、さらに２時間撹拌した。最後に硫酸で中和後、脱水し、析出物を濾別して本発明品ａを得た。
<Production Example 1>
In a reactor equipped with a stirrer, a nitrogen introduction tube, and a thermometer, 200 parts of isotridecyl alcohol and 9 parts of sodium hydroxide were charged, heated to 120 ° C. and dehydrated under reduced pressure. Next, 1110 parts of glycidol was dropped over 1 hour while maintaining 120 ° C., and the mixture was further stirred for 2 hours. Finally, it was neutralized with sulfuric acid, dehydrated, and the precipitate was filtered to obtain the product a of the present invention.
〈製造例２〉
イソトリデシルアルコール２００部とグリシドール１８５０部及び水酸化ナトリウム９部を製造例１と同様に反応し本発明品ｂを得た。
<Production Example 2>
200 parts of isotridecyl alcohol, 1850 parts of glycidol and 9 parts of sodium hydroxide were reacted in the same manner as in Production Example 1 to obtain a product b of the present invention.
〈製造例３〉
撹拌機、窒素導入管、及び温度計を備えた反応器にラウリルアルコール１８６部と、水酸化ナトリウム９部を仕込み、１２０℃まで昇温させ減圧脱水した。次に１２０℃を保持したままグリシドール３７０部を１時間かけて滴下し、さらに２時間撹拌した。生成物に水を加え陽イオン交換樹脂および陰イオン交換樹脂を通過させ脱塩し、減圧脱水して本発明品ｃを得た。
<Production Example 3>
A reactor equipped with a stirrer, a nitrogen introduction tube, and a thermometer was charged with 186 parts of lauryl alcohol and 9 parts of sodium hydroxide, heated to 120 ° C. and dehydrated under reduced pressure. Next, 370 parts of glycidol was dripped over 1 hour, maintaining 120 degreeC, and also it stirred for 2 hours. Water was added to the product to pass through a cation exchange resin and an anion exchange resin for desalting and dehydration under reduced pressure to obtain product c of the present invention.
〈製造例４〉
ネオドール２３ １９２部とグリシドール７４０部及び水酸化ナトリウム９部を製造例３と同様に反応、精製し本発明品ｄを得た。
<Production Example 4>
192 parts of Neodol 23, 740 parts of glycidol and 9 parts of sodium hydroxide were reacted and purified in the same manner as in Production Example 3 to obtain product d of the present invention.
〈製造例５〉
ラウリルアルコール１８６部とグリシドール１８５０部及び水酸化ナトリウム９部を製造例１と同様に反応し本発明品ｅを得た。
<Production Example 5>
186 parts of lauryl alcohol, 1850 parts of glycidol and 9 parts of sodium hydroxide were reacted in the same manner as in Production Example 1 to obtain a product e of the present invention.
〈製造例６〉
Ｅｘｘａｌ１１ １７２部とグリシドール７４００部及び水酸化ナトリウム９部を製造例１と同様に反応し本発明品ｆを得た。
<Production Example 6>
Exfal11 (172 parts), glycidol (7400 parts) and sodium hydroxide (9 parts) were reacted in the same manner as in Production Example 1 to obtain a product f of the present invention.
〈製造例７〉
デシルアルコール１５８部とグリシドール１１１０部及び水酸化ナトリウム９部を製造例３と同様に反応、精製し本発明品ｇを得た。
<Production Example 7>
158 parts of decyl alcohol, 1110 parts of glycidol and 9 parts of sodium hydroxide were reacted and purified in the same manner as in Production Example 3 to obtain product g of the present invention.
〈製造例８〉
２−プロピル−１−ヘプタノール１５８部とグリシドール１４８０部及び水酸化ナトリウム９部を製造例３と同様に反応、精製し本発明品ｈを得た。
<Production Example 8>
158 parts of 2-propyl-1-heptanol, 1480 parts of glycidol and 9 parts of sodium hydroxide were reacted and purified in the same manner as in Production Example 3 to obtain the product h of the present invention.
〈比較品Ｊ〜ｎの製造例〉
表１記載の原料アルコールを用いて、エチレンオキサイド（ＥＯ）の導入量を変更してＥＯを付加さし、ＥＯ付加モル数を調整した比較品ｊ〜ｎのノニオン界面活性剤を得た。
<Production example of comparative products J to n>
Using the raw material alcohols shown in Table 1, the amount of ethylene oxide (EO) introduced was changed and EO was added to obtain comparative nonionic surfactants j to n having an adjusted EO addition mole number.
〈実施例１〜８及び比較例１〜５〉
攪拌機、還流冷却器、温度計および滴下漏斗を備えた反応器に、蒸留水１３１部、緩衝剤として炭酸水素ナトリウム０．５部を仕込み、８０℃まで昇温させ、窒素ガスにて水中の溶存酸素を除去した。これとは別にメタクリル酸メチル７５部、アクリル酸エチル１７１部、アクリル酸４部、乳化重合用乳化剤８部、蒸留水１１０部とを混合して、モノマーエマルションを調製した。次に、上記で調製したモノマーエマルション４０部を一括して上記反応容器に添加し、１０分間撹拌後、重合開始剤である過硫酸アンモニウム０．５部を加え、１０分間撹拌した。次に残りのモノマーエマルションを３時間かけて滴下して重合反応を行い、４０℃まで冷却後、アンモニア水でｐＨ８〜９に調整してポリマーエマルションを得た。
<Examples 1-8 and Comparative Examples 1-5>
A reactor equipped with a stirrer, reflux condenser, thermometer and dropping funnel was charged with 131 parts of distilled water and 0.5 part of sodium hydrogen carbonate as a buffer, heated to 80 ° C., and dissolved in water with nitrogen gas Oxygen was removed. Separately, 75 parts of methyl methacrylate, 171 parts of ethyl acrylate, 4 parts of acrylic acid, 8 parts of an emulsifier for emulsion polymerization, and 110 parts of distilled water were mixed to prepare a monomer emulsion. Next, 40 parts of the monomer emulsion prepared above were added all at once to the reaction vessel, and after stirring for 10 minutes, 0.5 part of ammonium persulfate as a polymerization initiator was added and stirred for 10 minutes. Next, the remaining monomer emulsion was added dropwise over 3 hours to conduct a polymerization reaction, cooled to 40 ° C., and adjusted to pH 8-9 with aqueous ammonia to obtain a polymer emulsion.
使用した乳化重合用乳化剤は表１、表２に示す通りであり、また表２に示すアニオン界面活性剤Ａ〜Ｃを本発明品のノニオン界面活性剤に対して１０％で併用した。 The emulsifiers for emulsion polymerization used are as shown in Tables 1 and 2, and the anionic surfactants A to C shown in Table 2 were used in combination with the nonionic surfactant of the present invention at 10%.
使用した乳化剤のジオキサン及びアルデヒド類の含有量及び、得られたポリマーエマルションについて、重合安定性、化学安定性、粒子径、フィルムの光沢性をそれぞれ評価した。評価方法は以下の通りである。結果は表２に示す。 The contents of dioxane and aldehydes used in the emulsifier and the obtained polymer emulsion were evaluated for polymerization stability, chemical stability, particle diameter, and gloss of the film. The evaluation method is as follows. The results are shown in Table 2.
［ジオキサン及びアルデヒド類の含有量］
乳化重合用乳化剤に含まれるジオキサンをガスクロマトグラフィー（ＧＣ）、ホルムアルデヒドをアセチルアセトン法を用い吸光光度法で定量を行った。その結果を、ジオキサン量が、１ｐｐｍ未満：○、１〜１０ｐｐｍ：△、１０ｐｐｍ以上：×、ホルムアルデヒド量が１ｐｐｍ未満：○、１〜１０ｐｐｍ：△、１０ｐｐｍ以上：×、として表示した。
[Contents of dioxane and aldehydes]
The dioxane contained in the emulsifier for emulsion polymerization was quantified by absorptiometry using gas chromatography (GC) and formaldehyde using the acetylacetone method. The results were expressed as dioxane amount less than 1 ppm: ○, 1-10 ppm: Δ, 10 ppm or more: x, formaldehyde amount less than 1 ppm: ○, 1-10 ppm: Δ, 10 ppm or more: ×.
［重合安定性］
重合後のポリマーエマルションを８０メッシュの濾布を用いてろ過し、濾布上の残渣を水洗後、１０５℃×３時間乾燥した。乾燥後の残渣の重量を測定し、仕込みモノマー重量に対する重量比率（％）で表示した。
[Polymerization stability]
The polymer emulsion after polymerization was filtered using an 80 mesh filter cloth, and the residue on the filter cloth was washed with water and dried at 105 ° C. for 3 hours. The weight of the residue after drying was measured and displayed as a weight ratio (%) to the charged monomer weight.
［化学安定性］
ポリマーエマルション１０ｇに６モル／Ｌの水酸化カルシウム水溶液１０ｍｌを撹拌しつつ加え、５分間撹拌後に８０メッシュの濾布を用いてろ過し、濾布を通過しない凝集ポリマーの乾燥重量を測定して、仕込みモノマー重量に対する重量比率（％）で表示した。
[Chemical stability]
Add 10 ml of a 6 mol / L calcium hydroxide aqueous solution to 10 g of the polymer emulsion while stirring, and filter using an 80 mesh filter cloth after stirring for 5 minutes, and measure the dry weight of the aggregated polymer not passing through the filter cloth. It was expressed as a weight ratio (%) to the charged monomer weight.
［粒子径］
動的光散乱式粒度分布測定装置（日機装製 ＭＩＣＲＯＴＲＡＣ ＵＰＡ ９３４０）にて粒子径を測定し、μｍで表示した。
[Particle size]
The particle size was measured with a dynamic light scattering particle size distribution analyzer (MICROTRAC UPA 9340 manufactured by Nikkiso) and displayed in μm.
［フィルムの光沢性］
ガラスプレート上に０．５ｍｍ（ｗｅｔ）のエマルション膜を作り、室温で２４時間放置してフィルムを作成した。このフィルムの光沢性を目視にて、○（優）、△（可）、×（不可）の３段階で評価した。
[Glossiness of film]
A 0.5 mm (wet) emulsion film was formed on a glass plate and allowed to stand at room temperature for 24 hours to prepare a film. The glossiness of this film was visually evaluated in three stages: ○ (excellent), Δ (possible), and × (impossible).
〈実施例９〜１４及び比較例６〜１０〉
攪拌機、還流冷却器、温度計および滴下漏斗を備えた反応器に、蒸留水１３１部、緩衝剤として炭酸水素ナトリウム０．５部を仕込み、８０℃まで昇温させ、窒素ガスにて水中の溶存酸素を除去した。これとは別にアクリル酸２−エチルヘキシル１２３部、アクリル酸ブチル１２３部、アクリル酸４部、乳化重合用乳化剤８部、蒸留水１１０部とを混合して、モノマーエマルションを調製した。次に、上記で調製したモノマーエマルション４０部を一括して上記反応容器に添加し、１０分間撹拌後、重合開始剤である過硫酸アンモニウム０．５部を加え、１０分間撹拌した。次に残りのモノマーエマルションを３時間かけて滴下して重合反応を行い、４０℃まで冷却後、アンモニア水でｐＨ８〜９に調整してポリマーエマルションを得た。
<Examples 9 to 14 and Comparative Examples 6 to 10>
A reactor equipped with a stirrer, reflux condenser, thermometer and dropping funnel was charged with 131 parts of distilled water and 0.5 part of sodium hydrogen carbonate as a buffer, heated to 80 ° C., and dissolved in water with nitrogen gas Oxygen was removed. Separately from this, a monomer emulsion was prepared by mixing 123 parts of 2-ethylhexyl acrylate, 123 parts of butyl acrylate, 4 parts of acrylic acid, 8 parts of an emulsifier for emulsion polymerization, and 110 parts of distilled water. Next, 40 parts of the monomer emulsion prepared above were added all at once to the reaction vessel, and after stirring for 10 minutes, 0.5 part of ammonium persulfate as a polymerization initiator was added and stirred for 10 minutes. Next, the remaining monomer emulsion was added dropwise over 3 hours to conduct a polymerization reaction, cooled to 40 ° C., and adjusted to pH 8-9 with aqueous ammonia to obtain a polymer emulsion.
乳化重合用乳化剤は上記表１に示すものを用い、併用アニオン界面活性剤として全てポリオキシエチレンラウリル硫酸エステルナトリウム塩（５ＥＯ）を１０重量％用いた。 As the emulsifier for emulsion polymerization, those shown in Table 1 above were used, and 10% by weight of polyoxyethylene lauryl sulfate sodium salt (5EO) was used as the combined anionic surfactant.
得られたポリマーエマルションについて、重合安定性、化学安定性、ＶＯＣ量、粒子径、接着性をそれぞれ評価した。重合安定性、化学安定性、粒子径評価方法は上記の評価方法と同様である。ＶＯＣ量と接着性の評価方法は以下の通りである。結果を表３に示す。 The obtained polymer emulsion was evaluated for polymerization stability, chemical stability, VOC amount, particle size, and adhesiveness. The polymerization stability, chemical stability, and particle size evaluation method are the same as those described above. The evaluation method of the amount of VOC and adhesiveness is as follows. The results are shown in Table 3.
［ＶＯＣ量］
ポリマーエマルションに含まれるＶＯＣ量をヘッドスペースＧＣにより測定を行った。ＶＯＣ量が、１０ｐｐｍ未満：○、１０~５０ｐｐｍ：△、５０ｐｐｍ以上：×、として表示した。
[VOC amount]
The amount of VOC contained in the polymer emulsion was measured by headspace GC. The VOC amount was expressed as less than 10 ppm: ◯, 10-50 ppm: Δ, 50 ppm or more: x.
［接着性］
５ｃｍ幅に切ったＰＥＴフィルム上にエマルションを２５μｍ（ｄｒｙ）の厚さに塗工し、熱処理した後ＳＵＳ板に貼り付け、ローラ圧着する。接着面が５ｃｍ×５ｃｍとなるようにフィルムを剥がし、フィルムの端に２００ｇの重りを吊り下げて剥がれるまでの時間を測定し、秒（ｓ）で表示した。
[Adhesiveness]
The emulsion is applied to a thickness of 25 μm (dry) on a PET film cut to a width of 5 cm, heat-treated, then attached to a SUS plate, and roller-pressed. The film was peeled off so that the adhesion surface became 5 cm × 5 cm, and a time until it was peeled off by hanging a weight of 200 g on the edge of the film was measured and displayed in seconds (s).
〈実施例１５〜２０及び比較例１１〜１４〉
攪拌機、還流冷却器、温度計および滴下漏斗を備えた反応器に、蒸留水１３１部、緩衝剤として炭酸水素ナトリウム０．５部を仕込み、７０℃まで昇温させ、窒素ガスにて水中の溶存酸素を除去した。これとは別に酢酸ビニル２５０部、乳化重合用乳化剤８部、蒸留水１１０部とを混合して、モノマーエマルションを調製した。次に、上記で調製したモノマーエマルション４０部を一括して上記反応容器に添加し、１０分間撹拌後、重合開始剤である過硫酸アンモニウム０．５部を加え、１０分間撹拌した。次に残りのモノマーエマルションを３時間かけて滴下して重合反応を行い、４０℃まで冷却後、アンモニア水でｐＨ８〜９に調整してポリマーエマルションを得た。
<Examples 15 to 20 and Comparative Examples 11 to 14>
A reactor equipped with a stirrer, reflux condenser, thermometer and dropping funnel was charged with 131 parts of distilled water and 0.5 part of sodium hydrogen carbonate as a buffer, heated to 70 ° C., dissolved in water with nitrogen gas Oxygen was removed. Separately, 250 parts of vinyl acetate, 8 parts of an emulsifier for emulsion polymerization, and 110 parts of distilled water were mixed to prepare a monomer emulsion. Next, 40 parts of the monomer emulsion prepared above were added all at once to the reaction vessel, and after stirring for 10 minutes, 0.5 part of ammonium persulfate as a polymerization initiator was added and stirred for 10 minutes. Next, the remaining monomer emulsion was added dropwise over 3 hours to conduct a polymerization reaction, cooled to 40 ° C., and adjusted to pH 8-9 with aqueous ammonia to obtain a polymer emulsion.
乳化重合用乳化剤は上記表１に示すものを用い、得られたポリマーエマルションについて、重合安定性、化学安定性、粒子径、接着性をそれぞれ評価した。重合安定性、化学安定性、粒子径評価方法は上記の評価方法と同様である。接着性の評価方法は以下の通りである。結果を表４に示す。 As the emulsifier for emulsion polymerization, those shown in Table 1 above were used, and the obtained polymer emulsion was evaluated for polymerization stability, chemical stability, particle diameter, and adhesiveness. The polymerization stability, chemical stability, and particle size evaluation method are the same as those described above. The evaluation method of adhesiveness is as follows. The results are shown in Table 4.
［接着性］
５ｃｍ幅に切った合板上にエマルションを２５μｍ（ｄｒｙ）の厚さに塗工し、熱処理した後５ｃｍ幅の綿製の布を貼り付け、ローラ圧着する。接着面が５ｃｍ×５ｃｍとなるように布を剥がし、はがした布の端に１Ｋｇの重りを吊り下げて剥がれるまでの時間を測定し、秒（ｓ）で表示した。
[Adhesiveness]
The emulsion is coated on a plywood cut to a width of 5 cm to a thickness of 25 μm (dry), heat-treated, and then a 5 cm wide cotton cloth is affixed and roller-pressed. The cloth was peeled off so that the adhesive surface would be 5 cm × 5 cm, and a 1 kg weight was suspended from the edge of the peeled cloth, and the time until peeling was measured and displayed in seconds (s).
表２〜４の結果から知られるように、本発明に係る乳化重合用乳化剤は、乳化剤に含まれるアルデヒドやジオキサン量が極めて少量であり、エマルションの重合安定性、化学安定性が良好で、ＶＯＣなど有害な副生成物の発生を低減することができる。また、得られたポリマーエマルションのフィルム光沢性や接着性が従来のノニオン界面活性剤からなる比較品の乳化剤を用いたものより優れている。 As is known from the results in Tables 2 to 4, the emulsifier for emulsion polymerization according to the present invention has a very small amount of aldehyde and dioxane contained in the emulsifier, and has good polymerization stability and chemical stability of the emulsion, and VOC. The generation of harmful by-products can be reduced. Further, the film gloss and adhesion of the obtained polymer emulsion are superior to those using a comparative emulsifier made of a conventional nonionic surfactant.
本発明によるポリマーエマルションは、例えば、印刷インキ、塗料等のバインダー、インクジェット用メディアのバインダー、接着剤、粘着剤、被覆剤、含浸補強剤等として好適であり、木材、金属、紙、布、プラスチック、セラミック、その他のコンクリート等に適用することができる。 The polymer emulsion according to the present invention is suitable, for example, as a binder for printing inks and paints, a binder for inkjet media, an adhesive, a pressure-sensitive adhesive, a coating agent, an impregnation reinforcing agent, and the like, such as wood, metal, paper, cloth, and plastic. It can be applied to ceramics and other concrete.
Claims (5)
A polymer emulsion obtained by the production method according to claim 4.
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| JP2007091823A (en) * | 2005-09-27 | 2007-04-12 | Mitsubishi Chemicals Corp | Method for purifying polyglycerol, purified polyglycerol obtained by the method, and manufacturing method of fatty acid polyglyceride using the purified polyglycerol |
| JP2009227583A (en) * | 2008-03-19 | 2009-10-08 | Daicel Chem Ind Ltd | Polyglycerol alkyl ether type nonionic surfactant |
| JP2010275496A (en) * | 2009-06-01 | 2010-12-09 | Kao Corp | Method for producing polymer emulsion |
| US20140296432A1 (en) * | 2011-11-04 | 2014-10-02 | Coatex | Associative acrylic thickening agent containing polyglycerols and its use to increase the open time of thin or thick films |
| JP2017078033A (en) * | 2015-10-19 | 2017-04-27 | 株式会社ダイセル | Polyglycerol monoether and detergent composition |
| JP2017226781A (en) * | 2016-06-23 | 2017-12-28 | 株式会社クラレ | Vinyl alcohol-based polymer aqueous solution |
| WO2018079785A1 (en) * | 2016-10-31 | 2018-05-03 | 日本ゼオン株式会社 | Method for producing acrylic rubber |
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2005
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| JP2007091823A (en) * | 2005-09-27 | 2007-04-12 | Mitsubishi Chemicals Corp | Method for purifying polyglycerol, purified polyglycerol obtained by the method, and manufacturing method of fatty acid polyglyceride using the purified polyglycerol |
| JP2009227583A (en) * | 2008-03-19 | 2009-10-08 | Daicel Chem Ind Ltd | Polyglycerol alkyl ether type nonionic surfactant |
| EP2103674A3 (en) * | 2008-03-19 | 2012-04-04 | Daicel Chemical Industries, Ltd. | Polyglycerol alkyl ether type nonionic surfactant |
| JP2010275496A (en) * | 2009-06-01 | 2010-12-09 | Kao Corp | Method for producing polymer emulsion |
| US20140296432A1 (en) * | 2011-11-04 | 2014-10-02 | Coatex | Associative acrylic thickening agent containing polyglycerols and its use to increase the open time of thin or thick films |
| US9884968B2 (en) * | 2011-11-04 | 2018-02-06 | Coatex | Associative acrylic thickening agent containing polyglycerols and its use to increase the open time of thin or thick films |
| JP2017078033A (en) * | 2015-10-19 | 2017-04-27 | 株式会社ダイセル | Polyglycerol monoether and detergent composition |
| JP2017226781A (en) * | 2016-06-23 | 2017-12-28 | 株式会社クラレ | Vinyl alcohol-based polymer aqueous solution |
| WO2018079785A1 (en) * | 2016-10-31 | 2018-05-03 | 日本ゼオン株式会社 | Method for producing acrylic rubber |
| JPWO2018079785A1 (en) * | 2016-10-31 | 2018-10-25 | 日本ゼオン株式会社 | Acrylic rubber manufacturing method |
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| JP4279813B2 (en) | 2009-06-17 |
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