JP2007092010A - 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
- JP2007092010A JP2007092010A JP2005319883A JP2005319883A JP2007092010A JP 2007092010 A JP2007092010 A JP 2007092010A JP 2005319883 A JP2005319883 A JP 2005319883A JP 2005319883 A JP2005319883 A JP 2005319883A JP 2007092010 A JP2007092010 A JP 2007092010A
- Authority
- JP
- Japan
- Prior art keywords
- emulsion
- emulsifier
- emulsion polymerization
- polymerization
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003995 emulsifying agent Substances 0.000 title claims abstract description 75
- 238000007720 emulsion polymerization reaction Methods 0.000 title claims abstract description 69
- 229920000642 polymer Polymers 0.000 title claims abstract description 46
- 239000000839 emulsion Substances 0.000 title claims description 59
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 3
- 239000000178 monomer Substances 0.000 claims description 31
- 238000006116 polymerization reaction Methods 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 12
- 239000002736 nonionic surfactant Substances 0.000 claims description 6
- 239000003945 anionic surfactant Substances 0.000 claims description 5
- 239000003093 cationic surfactant Substances 0.000 claims description 5
- 239000012736 aqueous medium Substances 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 23
- 229920006254 polymer film Polymers 0.000 abstract description 11
- 150000002430 hydrocarbons Chemical group 0.000 abstract description 8
- 239000004215 Carbon black (E152) Chemical group 0.000 abstract 1
- 229930195733 hydrocarbon Chemical group 0.000 abstract 1
- -1 2-ethylhexyl Chemical group 0.000 description 50
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 9
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 8
- 150000001298 alcohols Chemical class 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 239000004744 fabric Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000012855 volatile organic compound Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 150000001299 aldehydes Chemical class 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000005215 alkyl ethers Chemical class 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XUJLWPFSUCHPQL-UHFFFAOYSA-N 11-methyldodecan-1-ol Chemical compound CC(C)CCCCCCCCCCO XUJLWPFSUCHPQL-UHFFFAOYSA-N 0.000 description 3
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 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
- 125000000217 alkyl group Chemical group 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 239000012874 anionic emulsifier Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 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
- 238000004040 coloring Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 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
- 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 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 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
- 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
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- 239000003957 anion exchange resin Substances 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000006172 buffering agent Substances 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 239000003795 chemical substances by application 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
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 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
- 238000011033 desalting Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 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
- 229920001971 elastomer Polymers 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
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000005394 methallyl group Chemical group 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000006386 neutralization reaction Methods 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
- 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
- 239000000123 paper Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 239000002244 precipitate 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
- 239000012744 reinforcing agent Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 239000007787 solid 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
- 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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 1
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- 0 *C1OCC(COC(CO*)COCC(*)=C)OC1* Chemical compound *C1OCC(COC(CO*)COCC(*)=C)OC1* 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- 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
- BYLSIPUARIZAHZ-UHFFFAOYSA-N 2,4,6-tris(1-phenylethyl)phenol Chemical compound C=1C(C(C)C=2C=CC=CC=2)=C(O)C(C(C)C=2C=CC=CC=2)=CC=1C(C)C1=CC=CC=C1 BYLSIPUARIZAHZ-UHFFFAOYSA-N 0.000 description 1
- LQZDDWKUQKQXGC-UHFFFAOYSA-N 2-(2-methylprop-2-enoxymethyl)oxirane Chemical compound CC(=C)COCC1CO1 LQZDDWKUQKQXGC-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
- NPKKFQUHBHQTSH-UHFFFAOYSA-N 2-(decoxymethyl)oxirane Chemical compound CCCCCCCCCCOCC1CO1 NPKKFQUHBHQTSH-UHFFFAOYSA-N 0.000 description 1
- VMSIYTPWZLSMOH-UHFFFAOYSA-N 2-(dodecoxymethyl)oxirane Chemical compound CCCCCCCCCCCCOCC1CO1 VMSIYTPWZLSMOH-UHFFFAOYSA-N 0.000 description 1
- WOFPPJOZXUTRAU-UHFFFAOYSA-N 2-Ethyl-1-hexanol Natural products CCCCC(O)CCC WOFPPJOZXUTRAU-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
- QNJAZNNWHWYOEO-UHFFFAOYSA-N 2-ethylheptan-1-ol Chemical compound CCCCCC(CC)CO QNJAZNNWHWYOEO-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 description 1
- GTJOHISYCKPIMT-UHFFFAOYSA-N 2-methylundecane Chemical compound CCCCCCCCCC(C)C GTJOHISYCKPIMT-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- FFTPMKGZLYSQAS-UHFFFAOYSA-N 2-propyloctan-1-ol Chemical compound CCCCCCC(CO)CCC FFTPMKGZLYSQAS-UHFFFAOYSA-N 0.000 description 1
- UQRONKZLYKUEMO-UHFFFAOYSA-N 4-methyl-1-(2,4,6-trimethylphenyl)pent-4-en-2-one Chemical group CC(=C)CC(=O)Cc1c(C)cc(C)cc1C UQRONKZLYKUEMO-UHFFFAOYSA-N 0.000 description 1
- VZXWJVFQXZUFQS-UHFFFAOYSA-N 4-methyl-2-propylhexan-1-ol Chemical compound CCCC(CO)CC(C)CC VZXWJVFQXZUFQS-UHFFFAOYSA-N 0.000 description 1
- QEVWDMOIPOLQBL-UHFFFAOYSA-N 5-methyl-2-propylhexan-1-ol Chemical compound CCCC(CO)CCC(C)C QEVWDMOIPOLQBL-UHFFFAOYSA-N 0.000 description 1
- QDTDKYHPHANITQ-UHFFFAOYSA-N 7-methyloctan-1-ol Chemical compound CC(C)CCCCCCO QDTDKYHPHANITQ-UHFFFAOYSA-N 0.000 description 1
- PLLBRTOLHQQAQQ-UHFFFAOYSA-N 8-methylnonan-1-ol Chemical compound CC(C)CCCCCCCO PLLBRTOLHQQAQQ-UHFFFAOYSA-N 0.000 description 1
- JTKHUJNVHQWSAY-UHFFFAOYSA-N 9-methyldecan-1-ol Chemical compound CC(C)CCCCCCCCO JTKHUJNVHQWSAY-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
- FDQGNLOWMMVRQL-UHFFFAOYSA-N Allobarbital Chemical class C=CCC1(CC=C)C(=O)NC(=O)NC1=O FDQGNLOWMMVRQL-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 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
- 229920002799 BoPET Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
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- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
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- PDSVZUAJOIQXRK-UHFFFAOYSA-N trimethyl(octadecyl)azanium Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)C PDSVZUAJOIQXRK-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyethers (AREA)
- Polymerisation Methods In General (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
Description
本発明は乳化重合する際に用いられる乳化重合用乳化剤、その乳化重合用乳化剤を使用したポリマーエマルションの製造方法、及びその製造方法により得られうるポリマーエマルションに関する。 The present invention relates to an emulsifier for emulsion polymerization used in emulsion polymerization, a method for producing a polymer emulsion using the emulsifier for emulsion polymerization, and a polymer emulsion obtainable by the method.
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単独あるいは併用で使用されているが、ポリマーエマルションの安定性、また該エマルションから得られたポリマーフィルムの性質等は、必ずしも充分に満足し得るものではなく、多くの解決すべき問題点が残されている。 Conventionally, as nonionic emulsifiers for emulsion polymerization, polyoxyalkylene alkyl phenyl ethers obtained by adding alkylene oxide to nonylphenol or octylphenol and polyoxyalkylene alkyl ethers obtained by adding alkylene oxide to higher alcohols are used alone or in combination. However, the stability of the polymer emulsion and the properties of the polymer film obtained from the emulsion are not always satisfactory, and many problems to be solved remain.
例えば、エマルションの重合安定性、得られたエマルションの機械安定性、化学安定性、凍結融解安定性、顔料混和性、貯蔵安定性等の問題が挙げられる。特に、機械的安定性については、改善すべき問題点が残されている。 Examples thereof include problems such as polymerization stability of the emulsion, mechanical stability of the obtained emulsion, chemical stability, freeze-thaw stability, pigment miscibility, and storage stability. In particular, the mechanical stability remains a problem to be improved.
さらに、エマルシ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中に残留するため、フィルムの耐水性、接着性が劣る等の問題を生じている。また、エマルションを塩析または酸析等の手段によって破壊し、ポリマーを取り出す際、排水中に多くの乳化剤が含有され、河川汚濁などの環境汚染の原因となるため、乳化剤の除去処理に多大の労力が必要となっている。 Furthermore, when a polymer film is prepared from the emulsion, the used emulsifier remains in the polymer film in a free state, causing problems such as poor water resistance and adhesion of the film. In addition, when the emulsion is broken down by means such as salting out or aciding out and the polymer is taken out, a large amount of emulsifier is contained in the waste water, which causes environmental pollution such as river pollution. Labor is needed.
このような観点から従来の乳化重合用乳化剤の問題点を改善するため、反応基として共重合性の不飽和基を有し、親水基としてポリオキシアルキレン鎖を持った反応性乳化剤が数多く提案され、各種モノマーについて乳化重合が試みられている。これらの反応性乳化剤を乳化剤として使用したエマルションは重合時の安定性が良く、また、該エマルションから得られたポリマーフィルムは耐水性、接着性、耐熱性、耐候性において優れた性能を示すものである（例えば、特許文献１〜４）。 From this point of view, in order to improve the problems of conventional emulsifiers for emulsion polymerization, many reactive emulsifiers having a copolymerizable unsaturated group as a reactive group and a polyoxyalkylene chain as a hydrophilic group have been proposed. Emulsion polymerization has been attempted for various monomers. Emulsions using these reactive emulsifiers as emulsifiers have good stability during polymerization, and polymer films obtained from the emulsions exhibit excellent performance in water resistance, adhesiveness, heat resistance, and weather resistance. Yes (for example, Patent Documents 1 to 4).
しかしながら、このようなアルキレンオキサイドから誘導される反応性乳化剤の問題点として、未反応のアルキ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、合成時の有害なジオキサンの生成や、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重合用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。
本発明は、上記実情に鑑みてなされたものであって、その目的は親水基としてポリオキシアルキレン鎖を持たず、乳化重合時の安定性を良好なものとし、しかも、ポリマー及びポリマーフィルムの耐水性、接着性、耐熱性、耐候性などの諸特性が著しく改善された反応性乳化重合用乳化剤を提供することにある。 The present invention has been made in view of the above circumstances, and its purpose is to have no polyoxyalkylene chain as a hydrophilic group, to improve stability during emulsion polymerization, and to provide water resistance of the polymer and polymer film. It is to provide an emulsifier for reactive emulsion polymerization in which various properties such as property, adhesiveness, heat resistance, and weather resistance are remarkably improved.
本発明者らは、上記課題を解決するため鋭意研究を重ねた結果、共重合性を有する不飽和基としてアリル基或いはメタリル基を有し、親水基部分がポリグリセリンである乳化重合用乳化剤が適していることを見出し、本発明に到達したものである。 As a result of intensive studies to solve the above problems, the present inventors have found that an emulsifier for emulsion polymerization having an allyl group or a methallyl group as a copolymerizable unsaturated group and a hydrophilic group portion being polyglycerin. It has been found that it is suitable, and the present invention has been achieved.
すなわち、本発明は、下記一般式（１）で表される化合物を含有することを特徴とする乳化重合用乳化剤である。
（式中、Ｒ１は炭化水素基、Ｒ２は水素原子またはメチル基であり、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 1 is a hydrocarbon group, R 2 is a hydrogen atom or a methyl group, n is 1 to 200, and X 1 and X 2 are a hydrogen atom or a hydrocarbon group.)
本発明の乳化重合用乳化剤は、前記一般式（１）で表される化合物と、該化合物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良い。 The emulsifier for emulsion polymerization of the present invention is at least one selected from the group consisting of the compound represented by the general formula (1) and other nonionic surfactants, anionic surfactants and cationic surfactants other than the compounds. It may be a mixture with various types of surfactants.
また、本発明のポリマーエマルションの製造方法は、モノマーに対して前記の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のポリマーに添加することにある。 Also, the method for producing a polymer emulsion of the present invention uses the above-mentioned emulsifier for emulsion polymerization in an amount of 0.1 to 20% by weight based on the monomer, and polymerizes the monomer in an aqueous medium, or the monomer polymerization. It is to be added to the later polymer.
そして、本発明のポリマーエマルションは、前記のポリマーエマルションの製造方法により得られうるものである。 And the polymer emulsion of this invention can be obtained by the manufacturing method of the said polymer emulsion.
本発明の乳化重合用乳化剤によれば、乳化重合時のモノマーの重合性、共重合性に優れ、ポリマー組成に組み込まれやすく、該乳化重合用乳化剤を用いて重合されたポリマーエマルションから得られるフィルムの耐水性、接着性、耐熱性、耐候性などの諸特性の向上に極めて優れた効果を発揮する。かつポリマーエマルションの泡立ち、機械安定性等が著しく改善される。さらに、ジオキサンやアルデヒド類などの有害物質を大幅に低減したポリマーエマルションを得ることができる。 According to the emulsifier for emulsion polymerization of the present invention, a film obtained from a polymer emulsion excellent in polymerizability and copolymerizability of monomers during emulsion polymerization, easily incorporated into a polymer composition, and polymerized using the emulsifier for emulsion polymerization. It is extremely effective in improving various properties such as water resistance, adhesiveness, heat resistance, and weather resistance. In addition, foaming and mechanical stability of the polymer emulsion are remarkably improved. Furthermore, a polymer emulsion in which harmful substances such as dioxane and aldehydes are greatly reduced can be obtained.
本発明の乳化重合用乳化剤は、下記一般式（１）で表される化合物を含有することにある。
上記一般式（１）の化合物において、式中Ｒ１は炭化水素基を表わす。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。 In the compound of the general formula (1), R 1 represents a hydrocarbon group. Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, a cycloalkenyl group, and the like.
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、Ｒ１は上記に記載の炭化水素基を２種類以上含んでいても良い。 R 1 may contain two or more types of the hydrocarbon groups described above.
さらに、一般式（１）において、Ｒ１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好ましい。 Furthermore, in the general formula (1), R 1 is preferably an alkyl group or alkenyl group having 6 to 20 carbon atoms.
通常、Ｒ１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である。 Usually, R 1 is a residue obtained by removing a hydroxyl group from alcohol. These alcohols are naturally derived alcohols or industrially produced alcohols.
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ある。 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、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（Ｎｅｏｄｏｌ）シリーズ、三菱化学社製のダイヤドール（Ｄｉａｄｏｌ）シリーズ、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 are listed, and the Exxal series manufactured by Exxon Mobil is available as a commercial product. In addition, as a mixture of linear and branched alcohols produced by an oxo process via olefins derived from n-paraffins and ethylene oligomers, Shell's Neodol series, Mitsubishi Chemical's diamonds There are a doll (Diadol) series, a Safol (Safol) series made by Sasol, and a real (Lial) series.
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−エチル−1−ヘキサノール、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。 In addition, Gerve alcohol obtained by dimerization of alcohol by Gerve reaction includes 2-ethyl-1-hexanol, 2-butyl-1-hexanol, 2-ethyl-1-heptanol, 2-propyl-1-octanol, 2- Propyl-1-heptanol, 4-methyl-2-propyl-1-hexanol, 2-propyl-5-methyl-1-hexanol, etc., or manufactured by air oxidation of paraffin, hydroxyl group other than carbon chain end There are secondary alcohols that are randomly bound to each other.
これらのアルコールは、２種類以上を配合して使用することも可能である。 These alcohols can be used in combination of two or more.
一般式（１）において、Ｒ２は水素原子またはメチル基であり、Ｘ１、Ｘ２は水素原子または上記に記載の炭化水素基である。また、ｎは１〜２００で、好ましくは２〜５０である。 In the general formula (1), R 2 is a hydrogen atom or a methyl group, and X 1 and X 2 are a hydrogen atom or the hydrocarbon group described above. N is 1 to 200, preferably 2 to 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良く、図１に示すように樹状に繋がっているものでも良い。 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.
本発明の乳化重合用乳化剤は、炭化水素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 of the present invention, it is advantageous that the molar ratio of the hydrocarbon group portion to the polyglycerin portion is 1: 1 to 5: 1.
［乳化重合用乳化剤の合成方法］
本発明の乳化重合用乳化剤を得るための反応条件は特に限定されるものではなく、例えば、高級アルコールとアリルグリシジルエーテル、または、高級アルコールとエピクロルヒドリンから誘導されるアルキルグリシジルエーテルとアリルアルコールを触媒存在下反応させた後、得られた反応組成物にポリグリセリン部分を導入して、本発明の乳化重合用乳化剤を得ることができる。
[Synthesis Method of Emulsifier for Emulsion Polymerization]
The reaction conditions for obtaining the emulsifier for emulsion polymerization of the present invention are not particularly limited. For example, a catalyst containing a higher alcohol and allyl glycidyl ether or an alkyl glycidyl ether derived from a higher alcohol and epichlorohydrin and allyl alcohol is present. After the lower reaction, a polyglycerin moiety is introduced into the obtained reaction composition to obtain the emulsifier for emulsion polymerization of the present invention.
反応性基を持った疎水基部分へのポリグリセリンの導入は、ポリグリセリンアルキルエーテルの公知の製造方法を適用することにより可能である。ポリグリセリンアルキルエーテルの製造方法は、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。 Polyglycerin can be introduced into the hydrophobic group having a reactive group by applying a known production method of polyglycerin alkyl ether. The production method of polyglycerin alkyl ether is, for example, according to the method disclosed in JP 2001-114720 A, JP 2000-38365 A, JP 9-188755 A, JP 6-293688 A. Can do.
［乳化重合用モノマー］
本発明の乳化重合用乳化剤を用いた乳化重合に適用されうるモノマーとしては各種のものを挙げることができ、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、メタクリル酸メチル、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ステル等のアクリル系モノマー、例えば、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系ジオレフィン系モノマー等の他、エチレン、無水マレイン酸、マレイン酸メチル等がある。本発明の乳化重合用乳化剤は、上記モノマーの１種または２種以上の乳化重合または懸濁重合に利用できる。
[Emulsion polymerization monomer]
Examples of the monomer that can be applied to the emulsion polymerization using the emulsifier for emulsion polymerization of the present invention include various monomers such as acrylic acid, methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and methyl methacrylate. Acrylic monomers such as acrylonitrile, acrylamide, and acrylic acid hydroxy ester, aromatic monomers such as styrene and divinylbenzene, vinyl ester monomers such as vinyl acetate, halogenated olefin monomers such as vinyl chloride and vinylidene chloride, butadiene, In addition to conjugated diolefin monomers such as isoprene and chloroprene, there are ethylene, maleic anhydride, methyl maleate and the like. The emulsifier for emulsion polymerization of the present invention can be used for emulsion polymerization or suspension polymerization of one or more of the above monomers.
［重合条件］
本発明の乳化重合用乳化剤を使用した乳化重合反応において使用される重合開始剤は従来から公知のものでよく、例えば、過酸化水素、過硫酸カリウム、アゾビスイソブチロニトリル、ベンゾイルパーオキサイド等が利用できる。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使用できる。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。
[Polymerization conditions]
The polymerization initiator used in the emulsion polymerization reaction using the emulsifier for emulsion polymerization of the present invention may be a conventionally known one, such as hydrogen peroxide, potassium persulfate, azobisisobutyronitrile, benzoyl peroxide, etc. Is available. As the polymerization accelerator, sodium bisulfite, ferrous ammonium sulfate, and the like can be used. 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.
本発明の乳化重合用乳化剤の使用量は、通常、全モノマーに対して０．１〜２０．０重量％が適当である。なお、より好ましくは、０．２〜１０．０重量％が適当である。 The amount of the emulsifier for emulsion polymerization of the present invention is usually 0.1 to 20.0% by weight based on the total monomers. In addition, More preferably, 0.2-10.0 weight% is suitable.
本発明の乳化重合用乳化剤は、それ単独でも乳化重合を良好に完結しうるが、さらに他のノニオン界面活性剤、アニオン界面活性剤及びカチオン界面活性剤を併用してもよく、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。 The emulsifier for emulsion polymerization of the present invention alone can satisfactorily complete the emulsion polymerization, but other nonionic surfactants, anionic surfactants and cationic surfactants may be used in combination, thereby emulsion polymerization. The polymerization stability at the time can be improved, and the processing characteristics in the subsequent process can be improved.
かかる他のノニオン界面活性剤、アニオン界面活性剤及び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、アルキルグルコシド、ポリグリセリンアルキルエーテル、ポリグリセリン脂肪酸エステル、ポリオキシアルキレン脂肪酸エステル、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。その使用量としては、本発明の乳化重合用乳化剤１００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, alkyl glucoside, Examples include glycerin alkyl ethers, polyglycerin fatty acid esters, polyoxyalkylene fatty acid esters, sorbitan fatty acid esters, and the like. Examples of anionic surfactants include fatty acid soaps, rosin acid soaps, alkyl sulfonates, alkyl aryl sulfonates, alkyl sulfosuccinates. Acid salts, polyoxyethylene alkyl sulfates, polyoxyethylene aryl sulfates, etc., and cationic surfactants include stearyl trimethyl ammonium, cetyl Methyl ammonium, lauryl trimethyl ammonium. The amount 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 emulsifier for emulsion polymerization of the present invention. 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。 Moreover, a well-known protective colloid agent can be used together in order to improve the polymerization stability at the time of 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.
本発明の乳化重合用乳化剤の他の使用方法としては、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に添加し使用することができる。 As another method of using the emulsifier for emulsion polymerization of the present invention, it can be added to the polymer after completion of polymerization in order to improve the stability of the polymer emulsion.
［作用、その他］
本発明の乳化重合用乳化剤は、その分子中の疎水基部分に共重合性の二重結合であるアリル基或いはメタリル基を有し、重合性モノマー、殊にビニル系モノマー等との共重合性に優れ、ポリマー組成に組み込まれやすい。そのため、共重合性の反応性乳化剤として、ポリマーエマルションから得られたポリマーフィルム中に遊離した状態で存在する乳化剤量が著しく減少し、フィルムの耐水性、接着性、耐熱性、耐候性向上に極めて優れた効果を発揮する。かつポリマーエマルションの泡立ち、機械安定性等が著しく改善される。
[Action, other]
The emulsifier for emulsion polymerization of the present invention has an allyl group or methallyl group which is a copolymerizable double bond in the hydrophobic group portion of the molecule, and is copolymerizable with a polymerizable monomer, particularly a vinyl monomer. And is easily incorporated into a polymer composition. Therefore, as a copolymerizable reactive emulsifier, the amount of the emulsifier present in the polymer film obtained from the polymer emulsion is remarkably reduced, and the water resistance, adhesiveness, heat resistance and weather resistance of the film are greatly improved. Exhibits excellent effects. In addition, foaming and mechanical stability of the polymer emulsion are remarkably improved.
さらに、ジオキサンやアルデヒド類などの有害物質を大幅に低減したポリマーエマルションを得ることができる。 Furthermore, a polymer emulsion in which harmful substances such as dioxane and aldehydes are greatly reduced can be obtained.
本発明の乳化重合用乳化剤を添加して得られるポリマーエマルションは、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などに適用することができる。また、エマルションあるいはラテックスから取り出したポリマーは樹脂、ゴム、ポリマーの改質剤等に使用することができる。 The polymer emulsion obtained by adding the emulsifier for emulsion polymerization of the present invention can be applied to wood, metal, paper, cloth, other concrete, etc. as, for example, an adhesive, a coating agent, and an impregnation reinforcing agent. The polymer taken out from the emulsion or latex can be used as a resin, rubber, polymer modifier or the like.
以下、実施例および比較例により本発明の実施様態につき述べるが、これにより本発明は何ら限定されるものではない。なお、文中「部」は特に記載がない限り質量基準である。 Hereinafter, although an embodiment of the present invention is described by an example and a comparative example, the present invention is not limited at all by this. In the text, “part” is based on mass unless otherwise specified.
〈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部と触媒として水酸化ナトリウムを仕込み、１０５℃で３０分間減圧脱水を行った。９０℃に冷却した後、アリルグリシジルエーテル１１４部を滴下し、９０℃で５時間熟成した。次に、得られた生成物を１２０℃まで昇温させグリシドール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た後、減圧脱水して本発明品の乳化重合用乳化剤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 sodium hydroxide as a catalyst were charged, and dehydration was performed at 105 ° C. for 30 minutes. After cooling to 90 ° C., 114 parts of allyl glycidyl ether were added dropwise and aged at 90 ° C. for 5 hours. Next, the obtained product was heated to 120 ° C., 370 parts of glycidol was added dropwise over 1 hour, and the mixture was further stirred for 2 hours. Water was added to the product to pass through a cation exchange resin and an anion exchange resin for desalting, followed by dehydration under reduced pressure to obtain an emulsifier A for emulsion polymerization of the present invention.
〈製造例２〉
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部と触媒として三フッ化ホウ素エーテル錯体を仕込み、１０５℃で３０分間減圧脱水を行った。９０℃に冷却した後、メタリルグリシジルエーテル１２８部を滴下し、９０℃で５時間熟成した。得られた生成物に水酸化カリウムを触媒として加え、１２０℃まで昇温させグリシドール１１１０部を１時間かけて滴下し、さらに２時間撹拌した。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た後、減圧脱水して本発明品の乳化重合用乳化剤Ｂを得た。
<Production Example 2>
A reactor equipped with a stirrer, a nitrogen introduction tube, and a thermometer was charged with 200 parts of isotridecyl alcohol and a boron trifluoride ether complex as a catalyst, and dehydrated under reduced pressure at 105 ° C. for 30 minutes. After cooling to 90 ° C., 128 parts of methallyl glycidyl ether was added dropwise and aged at 90 ° C. for 5 hours. To the obtained product, potassium hydroxide was added as a catalyst, the temperature was raised to 120 ° C., and 1110 parts of glycidol was added dropwise over 1 hour, followed by further stirring for 2 hours. Water was added to the product to pass through a cation exchange resin and an anion exchange resin for desalting, followed by dehydration under reduced pressure to obtain an emulsifier B for emulsion polymerization 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部と触媒として水酸化ナトリウムを仕込み、１０５℃で３０分間減圧脱水を行った。９０℃に冷却した後、アリルグリシジルエーテル１１４部を滴下し、９０℃で５時間熟成した。次に、得られた生成物を１２０℃まで昇温させグリシドール２９６部を１時間かけて滴下し、さらに２時間撹拌した。生成物に硫酸を加え中和後、脱水し、析出物を濾別して本発明品の乳化重合用乳化剤Ｃを得た。
<Production Example 3>
Into a reactor equipped with a stirrer, a nitrogen introducing tube, and a thermometer, 186 parts of lauryl alcohol and sodium hydroxide as a catalyst were charged and dehydrated under reduced pressure at 105 ° C. for 30 minutes. After cooling to 90 ° C., 114 parts of allyl glycidyl ether were added dropwise and aged at 90 ° C. for 5 hours. Next, the obtained product was heated to 120 ° C., and 296 parts of glycidol was added dropwise over 1 hour, followed by further stirring for 2 hours. Sulfuric acid was added to the product for neutralization, followed by dehydration, and the precipitate was filtered off to obtain an emulsifier C for emulsion polymerization of the present invention.
〈製造例４〉
製造例１の方法に準じて、ネオドール２３を１９２部、またグリシドールを７４０部とした以外は同様の条件で反応、精製して本発明品の乳化重合用乳化剤Ｄを得た。
<Production Example 4>
According to the method of Production Example 1, reaction and purification were performed under the same conditions except that 192 parts of neodol 23 and 740 parts of glycidol were used to obtain an emulsifier D for emulsion polymerization according to the present invention.
〈製造例５〉
撹拌機、窒素導入管、及び温度計を備えた反応器にアリルアルコール８７部、触媒として水酸化カリウムを仕込み、ラウリルグリシジルエーテル２４２部を滴下し、８０℃にて５時間撹拌反応を行った。次に、１２０℃に昇温し、減圧により過剰のアリルアルコールを除去した。次に、得られた生成物を１２０℃まで昇温させグリシドール２９６０部を１時間かけて滴下し、さらに２時間撹拌した。生成物に硫酸を加え中和後、脱水し、析出物を濾別して本発明品の乳化重合用乳化剤Ｅを得た。
<Production Example 5>
A reactor equipped with a stirrer, a nitrogen introduction tube, and a thermometer was charged with 87 parts of allyl alcohol and potassium hydroxide as a catalyst, 242 parts of lauryl glycidyl ether was added dropwise, and the reaction was stirred at 80 ° C. for 5 hours. Next, the temperature was raised to 120 ° C., and excess allyl alcohol was removed by decompression. Next, the obtained product was heated to 120 ° C., 2960 parts of glycidol was added dropwise over 1 hour, and the mixture was further stirred for 2 hours. Sulfuric acid was added to the product for neutralization, followed by dehydration, and the precipitate was filtered off to obtain an emulsifier E for emulsion polymerization of the present invention.
〈製造例６〉
製造例２の方法に準じて、Ｅｘｘａｌ ｌｌを１７２部、またグリシドールを５９２０部とした以外は同様の条件で反応して本発明品の乳化重合用乳化剤Ｆを得た。
<Production Example 6>
According to the method of Production Example 2, an emulsifier F for emulsion polymerization of the present invention was obtained by reacting under the same conditions except that Exxal ll was 172 parts and glycidol was 5920 parts.
〈製造例７〉
製造例３の方法に準じて、２−プロピル−１−ヘプタノールを１５８部、またグリシドール２２２部とした以外は同様の条件で反応、中和して本発明品の乳化重合用乳化剤Ｇを得た。
<Production Example 7>
According to the method of Production Example 3, an emulsifier G for emulsion polymerization of the present invention was obtained by reacting and neutralizing under the same conditions except that 158 parts of 2-propyl-1-heptanol and 222 parts of glycidol were used. .
〈製造例８〉
製造例５の方法に準じて、メタリルアルコールを１０８部、デシルグリシジルエーテルを２１４部、またグリシドールを７４０部とした以外は同様の条件で反応して本発明品の乳化重合用乳化剤Ｈを得た。
<Production Example 8>
According to the method of Production Example 5, an emulsifier H for emulsion polymerization of the present invention was obtained by reacting under the same conditions except that 108 parts of methallyl alcohol, 214 parts of decyl glycidyl ether and 740 parts of glycidol were used. It was.
〈製造例９〉
製造例１の方法に準じて、スチレン化フェノール（モノ体、ジ体、トリ体混合物）３０５部、またグリシドール３７０部とした以外は同様の条件で反応、精製して本発明品の乳化重合用乳化剤Ｉを得た。
<Production Example 9>
For the emulsion polymerization of the product of the present invention by reacting and purifying under the same conditions except for using 305 parts of styrenated phenol (mono, di, and tri mixture) and 370 parts of glycidol according to the method of Production Example 1. Emulsifier I was obtained.
〈実施例及び比較例〉
実施例及び比較例に用いた乳化重合用乳化剤は表１の通りである。比較品Ａ〜Ｆは表１に示す化学構造を有するエチレンオキサイドを付加した従来の乳化重合用乳化剤である。
<Examples and Comparative Examples>
Table 1 shows emulsifiers for emulsion polymerization used in Examples and Comparative Examples. Comparative products A to F are conventional emulsifiers for emulsion polymerization to which ethylene oxide having the chemical structure shown in Table 1 is added.
〈使用例１〉
アクリル酸ブチル１００部、スチレン１００部、イオン交換水２９０部および乳化重合用乳化剤１０部を混合して混合モノマー乳濁液を調製し、窒素ガスにて溶存酸素を除去した。次に攪拌機、還流冷却器、温度計および滴下漏斗を備えた反応器に、上記混合モノマー乳濁液を１００部仕込み、８０℃に昇温し、過硫酸カリウム０．５部を加えて先行重合させた。次いで、重合開始１０分後より３時間かけて、残りの混合モノマー乳濁液４００部を滴下して重合させた。さらに、続けて重合温度にて２時間熟成した後、冷却してポリマーエマルションを得た。
<Usage example 1>
A mixed monomer emulsion was prepared by mixing 100 parts of butyl acrylate, 100 parts of styrene, 290 parts of ion-exchanged water and 10 parts of an emulsifier for emulsion polymerization, and dissolved oxygen was removed with nitrogen gas. Next, a reactor equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel was charged with 100 parts of the above mixed monomer emulsion, heated to 80 ° C., and 0.5 parts of potassium persulfate was added for prepolymerization. I let you. Next, over 10 hours after 10 minutes from the start of polymerization, 400 parts of the remaining mixed monomer emulsion was added dropwise for polymerization. Further, after aging for 2 hours at the polymerization temperature, the mixture was cooled to obtain a polymer emulsion.
使用した乳化重合用乳化剤は表２に示す通りである。また、乳化重合用乳化剤の内１０重量％を併用アニオン性乳化剤としてラウリル硫酸エステルナトリウム塩を用いた。 The emulsifiers for emulsion polymerization used are as shown in Table 2. Further, 10% by weight of the emulsifier for emulsion polymerization was used as a combined anionic emulsifier, and lauryl sulfate sodium salt was used.
使用した乳化重合用乳化剤のジオキサン及びホルム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、機械安定性、粒子径、起泡性、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 formaldehyde as the emulsifier for emulsion polymerization used, and the obtained polymer emulsion were evaluated for polymerization stability, mechanical stability, particle diameter, foamability, and gloss of the film. The evaluation method is as follows. The results are shown in Table 2.
［ジオキサン及びホルムアルデヒドの含有量］
乳化重合用乳化剤に含まれるジオキサンを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。結果、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：×、として示した。
[Contents of dioxane and formaldehyde]
The dioxane contained in the emulsifier for emulsion polymerization was determined by spectrophotometry using GC and formaldehyde using the acetylacetone method. As a result, the dioxane amount was shown as less than 1 ppm: ○, 1-10 ppm: Δ, 10 ppm or more: ×, and the formaldehyde amount was 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濾過し、濾布上の残渣を水洗後、乾燥し、その重量をエマルションの固形分に対し％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, and the weight was expressed as a percentage of the solid content of the emulsion.
［機械安定性］
ポリマーエマルション５０ｇをマーロン型試験器にて荷重１０Ｋｇ、回転数１０００ｒｐｍで５分間撹拌し、生成した凝集物を８０メッシュの金網で濾過し、残渣を水洗後、乾燥し、その重量をエマルションの固形分に対し％で表示した。
[Machine stability]
50 g of the polymer emulsion was stirred for 5 minutes at a load of 10 kg at a rotation speed of 1000 rpm with a Marlon type tester, the resulting agglomerate was filtered through an 80-mesh wire mesh, the residue was washed with water and dried, and its weight was determined as the solid content of the emulsion In%.
［粒子径］
動的光散乱式粒度分布測定装置（日機装製 ＭＩＣＲＯＴＲＡＣ ＵＰＡ ９３４０）にて測定しμｍで表示した。
[Particle size]
It measured with the dynamic light-scattering type particle size distribution analyzer (MICROTRAC UPA 9340 made by Nikkiso) and displayed in μm.
［起泡性］
エマルションを水で２倍希釈し、１００ｍｌネスラー管に３０ｃｃ入れ、３０回倒立させてから静置５分後における泡の量を測定し、ｍｌで表示した。
[Foaming]
The emulsion was diluted 2 times with water, put in 30 cc into a 100 ml Nessler tube, inverted 30 times, and then measured for the amount of foam 5 minutes after standing, and expressed in ml.
［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).
〈使用例２〉
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、イオン交換水１３５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、イオン交換水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。
<Usage example 2>
A reactor equipped with a stirrer, reflux condenser, thermometer and dropping funnel was charged with 135 parts of ion-exchanged water and 0.5 part of sodium bicarbonate as a buffering agent, heated to 80 ° C. Dissolved 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 ion-exchanged 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３に示す通りである。また、乳化重合用乳化剤の内１０重量％を併用アニオン性乳化剤として直鎖アルキルベンゼンスルホン酸ナトリウム塩を用いた。 The emulsifiers for emulsion polymerization used are as shown in Table 3. Further, 10% by weight of the emulsifier for emulsion polymerization was used as a combined anionic emulsifier, and linear alkylbenzene sulfonic acid sodium salt was used.
得られたポリマーエマルションについて、重合安定性、粒子径、ＶＯＣ量、未反応乳化剤量、耐水性をそれぞれ評価した。重合安定性、粒子径の評価方法は上記と同様である。ＶＯＣ量、未反応乳化剤量、耐水性評価方法は以下の通りである。結果は表３に示す。 The obtained polymer emulsion was evaluated for polymerization stability, particle diameter, VOC amount, unreacted emulsifier amount, and water resistance. The evaluation methods for polymerization stability and particle diameter are the same as described above. The amount of VOC, the amount of unreacted emulsifier, and the water resistance evaluation method are 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。その結果、１０ｐｐｍ未満：○、１０〜５０ｐｐｍ：△、５０ｐｐｍ以上：×、として示した。
[VOC amount]
The amount of VOC contained in the polymer emulsion was measured by headspace GC. As a result, it showed as less than 10 ppm: (circle), 10-50 ppm: (triangle | delta), 50 ppm or more: x.
［未反応乳化剤量］
ポリマーエマルションにメタノールを加えて、ポリマーを凝固し、遠心分離処理後、その上澄みを用い、ＨＰＬＣ−ＭＳ法にて未反応乳化剤量を測定し、％で表示した。
[Unreacted emulsifier amount]
Methanol was added to the polymer emulsion to solidify the polymer, and after centrifugation, the amount of unreacted emulsifier was measured by HPLC-MS using the supernatant, and expressed in%.
［耐水性試験］
ガラス板上に０．５ｍｍ厚のポリマーフィルムを作製し、これを水に浸漬し、前記ポリマーフィルムを透して４．５ポイント文字が読めなくなるまでの時間を測定した。結果、３００時間以上：○、３００〜２００時間：△、２００時間未満：×、として示した。
[Water resistance test]
A polymer film having a thickness of 0.5 mm was prepared on a glass plate, immersed in water, and the time until 4.5 point characters could not be read through the polymer film was measured. The results are shown as 300 hours or more: ○, 300 to 200 hours: Δ, less than 200 hours: x.
〈使用例３〉
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、イオン交換水２５０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。次にアクリル酸ブチル１２５部とアクリル酸２−エチルヘキシル１２５部に乳化重合用乳化剤５部を溶解させた混合モノマー液のうち５０部を反応器に仕込み、次いで過硫酸アンモニウム０．５部を加えて先行重合させ、重合開始１０分後より３時間かけて残りの混合モノマー液２０５部を滴下して重合させた。続けて重合温度にてさらに２時間熟成した後、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。
<Usage example 3>
A reactor equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel was charged with 250 parts of ion-exchanged water, heated to 80 ° C., and dissolved oxygen in water was removed with nitrogen gas. Next, 50 parts of a mixed monomer solution prepared by dissolving 5 parts of an emulsifier for emulsion polymerization in 125 parts of butyl acrylate and 125 parts of 2-ethylhexyl acrylate was charged into the reactor, and then 0.5 part of ammonium persulfate was added to the reactor. Polymerization was performed, and the remaining 205 parts of the mixed monomer solution was added dropwise over 3 hours from 10 minutes after the start of the polymerization. Subsequently, the mixture was further aged for 2 hours at the polymerization temperature, 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４に示す通りである。また、乳化重合用乳化剤の内１０重量％を併用アニオン性乳化剤としてポリオキシエチレンスチレン化フェニルエーテルリン酸エステル（ＥＯ８モル付加体）を用いた。 The emulsifiers for emulsion polymerization used are as shown in Table 4. Further, 10% by weight of the emulsifier for emulsion polymerization was used as a combined anionic emulsifier, and polyoxyethylene styrenated phenyl ether phosphate ester (EO 8 mol adduct) was used.
得られたポリマーエマルションについて、重合安定性、機械安定性、未反応乳化剤量、耐熱着色性、接着性をそれぞれ評価した。重合安定性、機械安定性、未反応乳化剤量の評価方法は上記と同様である。耐熱着色性、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。 About the obtained polymer emulsion, polymerization stability, mechanical stability, the amount of unreacted emulsifier, heat-resistant coloring property, and adhesiveness were evaluated, respectively. The evaluation methods for polymerization stability, mechanical stability, and amount of unreacted emulsifier are the same as described above. The evaluation methods for heat resistant colorability and adhesiveness are as follows. The results are shown in Table 4.
［耐熱着色性］
ガラス板上に０．５ｍｍ厚のポリマーフィルムを作製し、２００℃に調整した熱風乾燥器内で３０分間熱処理して、ポリマーフィルムの着色を目視で観察した。結果、全く着色が認められない：○、淡い黄色に着色している：△、濃い褐色に着色している：×、として示した。
[Heat resistant coloring]
A polymer film having a thickness of 0.5 mm was prepared on a glass plate, heat-treated for 30 minutes in a hot air drier adjusted to 200 ° C., and coloring of the polymer film was visually observed. As a result, no coloration was observed: ○, pale yellow coloration: Δ, dark brown coloration: 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（秒）を測定した。
[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 adhesive surface was 5 cm × 5 cm, and a time (second) until the film was peeled off by hanging a weight of 200 g on the edge of the film was measured.
〈使用例４〉
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、イオン交換水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、イオン交換水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。使用した乳化重合用乳化剤は表５に示す通りである。
<Usage example 4>
A reactor equipped with a stirrer, reflux condenser, thermometer and dropping funnel was charged with 131 parts of ion-exchanged water and 0.5 part of sodium bicarbonate as a buffering agent, heated to 70 ° C. Dissolved oxygen was removed. Separately, 250 parts of vinyl acetate, 8 parts of an emulsifier for emulsion polymerization, and 110 parts of ion-exchanged 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. The emulsifiers for emulsion polymerization used are as shown in Table 5.
得られたポリマーエマルションについて、重合安定性、粒子径、接着性をそれぞれ評価した。重合安定性、粒子径の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５に示す。 The obtained polymer emulsion was evaluated for polymerization stability, particle diameter, and adhesiveness. The evaluation method of polymerization stability and particle diameter is the same as the above evaluation method. The evaluation method of adhesiveness is as follows. The results are shown in Table 5.
［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、剥がした布の端に１Ｋｇの重りを吊り下げて剥がれるまでの時間（秒）を測定した。
[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 adhesion surface became 5 cm × 5 cm, and a time (second) until the piece was peeled off by hanging a 1 kg weight on the edge of the peeled cloth was measured.
表２〜表５の結果から、本発明にかか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、機械安定性が良好で、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、未反応の乳化剤量が少なく、得られたポリマーエマルションのフィルム光沢性、接着性、耐水性などの諸特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ることが明らかである。 From the results of Tables 2 to 5, the emulsifier for emulsion polymerization according to the present invention has a very small amount of aldehyde and dioxane contained in the emulsifier, good polymerization stability and mechanical stability of the emulsion, and harmful such as VOC. Generation of by-products can be reduced. In addition, the amount of unreacted emulsifier is small, and the resulting polymer emulsion has superior properties such as film gloss, adhesiveness, water resistance, and the like using a comparative emulsifier made of a conventional nonionic surfactant. it is obvious.
本発明により得られたポリマーエマルションは、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などに好適である。また、エマルションあるいはラテックスから取り出したポリマーは樹脂、ゴム、ポリマーの改質剤等に使用することができる。 The polymer emulsion obtained by the present invention is suitable for wood, metal, paper, cloth, other concrete, etc. as an adhesive, a coating agent, an impregnation reinforcing agent, and the like. The polymer taken out from the emulsion or latex can be used as a resin, rubber, polymer modifier or the like.
Claims (4)
A polymer emulsion obtained by the method for producing a polymer emulsion according to claim 3.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005319883A JP4157125B2 (en) | 2005-08-29 | 2005-11-02 | Emulsifier for emulsion polymerization, method for producing polymer emulsion, and polymer emulsion |
| TW095130102A TW200718715A (en) | 2005-08-29 | 2006-08-16 | Emulsifier for emulsion polymerization, production method of polymer emulsion and polymer emulsion |
| US11/509,722 US20070049687A1 (en) | 2005-08-29 | 2006-08-24 | Emulsifier for emulsion polymerization, production method of polymer emulsion and polymer emulsion |
| DE602006013238T DE602006013238D1 (en) | 2005-08-29 | 2006-08-28 | Emulsifier for emulsion polymerization, production method for polymer emulsions and polymer emulsions |
| KR1020060081643A KR100788106B1 (en) | 2005-08-29 | 2006-08-28 | Emulsifier for emulsion polymerization, process for preparing polymer emulsion, and polymer emulsion |
| EP06017910A EP1760095B1 (en) | 2005-08-29 | 2006-08-28 | Emulsifier for emulsion polymerization, production method of polymer emulsion and polymer emulsion |
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| JP2005248460 | 2005-08-29 | ||
| JP2005319883A JP4157125B2 (en) | 2005-08-29 | 2005-11-02 | Emulsifier for emulsion polymerization, method for producing polymer emulsion, and polymer emulsion |
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| JP4157125B2 JP4157125B2 (en) | 2008-09-24 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013184894A (en) * | 2012-03-06 | 2013-09-19 | Daicel Corp | Emulsifier for forming liquid crystal, and liquid crystal-forming emulsion composition containing the emulsifier |
| JP2013184911A (en) * | 2012-03-07 | 2013-09-19 | Daicel Corp | Foamable aerosol composition |
| JP2013203662A (en) * | 2012-03-27 | 2013-10-07 | Daicel Corp | Composition for lamella liquid crystal-type cosmetic |
| JP2015030709A (en) * | 2013-08-06 | 2015-02-16 | 株式会社ダイセル | Moisturizing cosmetic composition |
-
2005
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013184894A (en) * | 2012-03-06 | 2013-09-19 | Daicel Corp | Emulsifier for forming liquid crystal, and liquid crystal-forming emulsion composition containing the emulsifier |
| JP2013184911A (en) * | 2012-03-07 | 2013-09-19 | Daicel Corp | Foamable aerosol composition |
| JP2013203662A (en) * | 2012-03-27 | 2013-10-07 | Daicel Corp | Composition for lamella liquid crystal-type cosmetic |
| JP2015030709A (en) * | 2013-08-06 | 2015-02-16 | 株式会社ダイセル | Moisturizing cosmetic composition |
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