JP5085151B2 - Aqueous dispersion and method for producing the same - Google Patents
Aqueous dispersion and method for producing the same Download PDFInfo
- Publication number
- JP5085151B2 JP5085151B2 JP2007032621A JP2007032621A JP5085151B2 JP 5085151 B2 JP5085151 B2 JP 5085151B2 JP 2007032621 A JP2007032621 A JP 2007032621A JP 2007032621 A JP2007032621 A JP 2007032621A JP 5085151 B2 JP5085151 B2 JP 5085151B2
- Authority
- JP
- Japan
- Prior art keywords
- butene
- propylene
- acid
- aqueous dispersion
- mass
- 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.)
- Active
Links
- 239000006185 dispersion Substances 0.000 title claims description 117
- 238000004519 manufacturing process Methods 0.000 title claims description 43
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 220
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 120
- 239000005977 Ethylene Substances 0.000 claims description 120
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 117
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 111
- 229920001897 terpolymer Polymers 0.000 claims description 105
- 229920000098 polyolefin Polymers 0.000 claims description 90
- 239000002253 acid Substances 0.000 claims description 21
- 239000003945 anionic surfactant Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-DYCDLGHISA-N deuterium hydrogen oxide Chemical compound [2H]O XLYOFNOQVPJJNP-DYCDLGHISA-N 0.000 claims description 14
- 238000004898 kneading Methods 0.000 claims description 13
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 6
- 150000008064 anhydrides Chemical class 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 99
- 230000000052 comparative effect Effects 0.000 description 57
- 239000002245 particle Substances 0.000 description 39
- -1 polypropylene Polymers 0.000 description 38
- 239000004743 Polypropylene Substances 0.000 description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 229920001155 polypropylene Polymers 0.000 description 19
- 238000000034 method Methods 0.000 description 18
- 238000000576 coating method Methods 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 13
- 229940096992 potassium oleate Drugs 0.000 description 12
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 12
- 239000000178 monomer Substances 0.000 description 10
- 235000014113 dietary fatty acids Nutrition 0.000 description 9
- 239000000194 fatty acid Substances 0.000 description 9
- 229930195729 fatty acid Natural products 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 150000003871 sulfonates Chemical class 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 238000007792 addition Methods 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000012968 metallocene catalyst Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- MEZLKOACVSPNER-GFCCVEGCSA-N selegiline Chemical compound C#CCN(C)[C@H](C)CC1=CC=CC=C1 MEZLKOACVSPNER-GFCCVEGCSA-N 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 1
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- LEAQUNCACNBDEV-KHPPLWFESA-N (Z)-undec-1-en-1-ol Chemical compound CCCCCCCCC\C=C/O LEAQUNCACNBDEV-KHPPLWFESA-N 0.000 description 1
- GCORITRBZMICMI-CMDGGOBGSA-N (e)-dodec-4-enoic acid Chemical compound CCCCCCC\C=C\CCC(O)=O GCORITRBZMICMI-CMDGGOBGSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 1
- WTQBISBWKRKLIJ-UHFFFAOYSA-N 5-methylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C)CC1C=C2 WTQBISBWKRKLIJ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- GCORITRBZMICMI-UHFFFAOYSA-N Linderic acid Natural products CCCCCCCC=CCCC(O)=O GCORITRBZMICMI-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229940114079 arachidonic acid Drugs 0.000 description 1
- 235000021342 arachidonic acid Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229960002969 oleic acid Drugs 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- 229960002703 undecylenic acid Drugs 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、結晶化度が低いオレフィン共重合体を主成分とする水性分散体およびその製造方法に関する。 The present invention relates to an aqueous dispersion mainly composed of an olefin copolymer having a low crystallinity and a method for producing the same.
ポリオレフィン樹脂の成形体に対して塗装や接着を行う場合には、従来は、溶剤中に塩素化ポリオレフィンを含有するものが多く用いられてきた。しかしながら、近年の環境問題への配慮から、溶剤も塩素も含有しない塗料や接着剤、あるいは、プライマーの成分として使用できる水性の分散体が求められている。
そこで、特許文献１では、酸変性ポリオレフィンと変性澱粉と乳化剤とを含み、ｐＨが６以上の水性分散体が提案されている。
Therefore, Patent Document 1 proposes an aqueous dispersion having an acid-modified polyolefin, a modified starch, and an emulsifier, and having a pH of 6 or more.
しかしながら、特許文献１に記載の水性分散体は、溶剤型の塗料や接着剤程の付着性を発揮しなかった。特に、基材がポリプロピレン成形体である場合には、付着性が低かった。また、特許文献１に記載の水性分散体は、得られる被膜の耐水性も不充分であった。
本発明は、前記事情を鑑みてなされたものであり、有機溶剤および塩素原子含有ポリマーを含まないにもかかわらず、充分な付着性、とりわけポリプロピレン成形体に対する付着性が高く、得られる被膜の耐水性に優れる水性分散体およびその製造方法を提供することを目的とする。
However, the aqueous dispersion described in Patent Document 1 did not exhibit as much adhesion as a solvent-type paint or adhesive. In particular, when the substrate was a polypropylene molded body, the adhesion was low. In addition, the aqueous dispersion described in Patent Document 1 has insufficient water resistance of the resulting film.
The present invention has been made in view of the above circumstances, and although it does not contain an organic solvent and a chlorine atom-containing polymer, it has sufficient adhesion, particularly high adhesion to a polypropylene molded article, and the water resistance of the resulting coating is high. An object is to provide an aqueous dispersion having excellent properties and a method for producing the same.
本発明は、以下の態様を包含する。
［１］ プロピレン／１−ブテン／エチレン三元共重合体（Ａ）と、プロピレン／１−ブテン／エチレン三元共重合体（Ａ）１００質量部に対して、５〜２０質量部の酸変性ポリオレフィン（Ｂ）と、１〜１０質量部のアニオン型界面活性剤（Ｃ）と、０．５〜２０質量部の水（Ｄ）とを含有する水性分散体であって、
プロピレン／１−ブテン／エチレン三元共重合体（Ａ）は、プロピレン単位を４０〜７０質量％、１−ブテン単位を２０〜４０質量％、エチレン単位を５〜２５質量％含有し、かつ、重量平均分子量が１２０，０００〜４００，０００、結晶化度が０．１〜１６％であり、
酸変性ポリオレフィン（Ｂ）は、エチレン性不飽和カルボン酸またはその無水物で変性されたオレフィン系重合体であり、重量平均分子量が１，８００〜３５，０００、酸価が３〜８０ｍｇ／ｇであることを特徴とする水性分散体。
The present invention includes the following aspects.
[1] 5 to 20 parts by mass of acid modification with respect to 100 parts by mass of propylene / 1-butene / ethylene terpolymer (A) and propylene / 1-butene / ethylene terpolymer (A) An aqueous dispersion containing a polyolefin (B), 1 to 10 parts by weight of an anionic surfactant (C), and 0.5 to 20 parts by weight of water (D),
The propylene / 1-butene / ethylene terpolymer (A) contains 40 to 70% by mass of propylene units, 20 to 40% by mass of 1-butene units, 5 to 25% by mass of ethylene units, and The weight average molecular weight is 120,000 to 400,000, the crystallinity is 0.1 to 16%,
The acid-modified polyolefin (B) is an olefin polymer modified with an ethylenically unsaturated carboxylic acid or an anhydride thereof, and has a weight average molecular weight of 1,800 to 35,000 and an acid value of 3 to 80 mg / g. An aqueous dispersion characterized by being.
［２］ プロピレン／１−ブテン／エチレン三元共重合体（Ａ）と、プロピレン／１−ブテン／エチレン三元共重合体（Ａ）１００質量部に対して５〜２０質量部の酸変性ポリオレフィン（Ｂ）と、プロピレン／１−ブテン／エチレン三元共重合体（Ａ）１００質量部に対して１〜１０質量部のアニオン型界面活性剤（Ｃ）とを溶融混練して混練物を得る工程と、
該混練物に、水（Ｄ）を、プロピレン／１−ブテン／エチレン三元共重合体（Ａ）１００質量部に対して０．５〜２０質量部添加した後、さらに溶融混練する工程とを有する水性分散体の製造方法であって、
プロピレン／１−ブテン／エチレン三元共重合体（Ａ）として、プロピレン単位を４０〜７０質量％、１−ブテン単位を２０〜４０質量％、エチレン単位を５〜２５質量％含有し、かつ、重量平均分子量が１２０，０００〜４００，０００、結晶化度が０．１〜１６％のものを用い、
酸変性ポリオレフィン（Ｂ）として、エチレン性不飽和カルボン酸またはその無水物で変性されたオレフィン系重合体であり、重量平均分子量が１，８００〜３５，０００、酸価が３〜８０ｍｇ／ｇのものを用いることを特徴とする水性分散体の製造方法。
[2] 5 to 20 parts by mass of acid-modified polyolefin with respect to 100 parts by mass of propylene / 1-butene / ethylene terpolymer (A) and propylene / 1-butene / ethylene terpolymer (A) (B) and 1-10 parts by mass of an anionic surfactant (C) are melt-kneaded with 100 parts by mass of propylene / 1-butene / ethylene terpolymer (A) to obtain a kneaded product. Process,
Adding 0.5 to 20 parts by mass of water (D) to 100 parts by mass of propylene / 1-butene / ethylene terpolymer (A), and further melt-kneading the kneaded product. A method for producing an aqueous dispersion having
As propylene / 1-butene / ethylene terpolymer (A), it contains 40 to 70% by mass of propylene units, 20 to 40% by mass of 1-butene units, 5 to 25% by mass of ethylene units, and Using a weight average molecular weight of 120,000 to 400,000 and a crystallinity of 0.1 to 16%,
The acid-modified polyolefin (B) is an olefin polymer modified with an ethylenically unsaturated carboxylic acid or an anhydride thereof, having a weight average molecular weight of 1,800 to 35,000 and an acid value of 3 to 80 mg / g. What is claimed is: 1. A method for producing an aqueous dispersion, comprising:
本発明の水性分散体は、有機溶剤および塩素原子含有ポリマーを含まないにもかかわらず、充分な付着性、とりわけポリオレフィン成形体に対する付着性が高く、得られる被膜の耐水性に優れる。
本発明の水性分散体の製造方法によれば、有機溶剤および塩素原子含有ポリマーを含まないにもかかわらず、充分な付着性、とりわけポリオレフィン成形体に対する付着性が高く、得られる被膜の耐水性に優れる水性分散体を製造できる。
Although the aqueous dispersion of the present invention does not contain an organic solvent and a chlorine atom-containing polymer, the aqueous dispersion has sufficient adhesion, particularly high adhesion to a polyolefin molded article, and is excellent in water resistance of the resulting coating.
According to the method for producing an aqueous dispersion of the present invention, although it does not contain an organic solvent and a chlorine atom-containing polymer, sufficient adhesion, particularly adhesion to a polyolefin molded body is high, and the resulting coating has water resistance. An excellent aqueous dispersion can be produced.
「水性分散体」
本発明の水性分散体は、プロピレン／１−ブテン／エチレン三元共重合体（Ａ）と酸変性ポリオレフィン（Ｂ）とアニオン型界面活性剤（Ｃ）と水（Ｄ）とを含有するものである。
"Aqueous dispersion"
The aqueous dispersion of the present invention contains a propylene / 1-butene / ethylene terpolymer (A), an acid-modified polyolefin (B), an anionic surfactant (C), and water (D). is there.
（プロピレン／１−ブテン／エチレン三元共重合体（Ａ））
プロピレン／１−ブテン／エチレン三元共重合体（Ａ）は、プロピレン単位を４０〜７０質量％を有する。プロピレン／１−ブテン／エチレン三元共重合体（Ａ）におけるプロピレン単位含有量が４０質量％未満であっても、７０質量％を超えても、得られた水性分散体を、ポリプロピレンの成形体に塗布した場合の付着性が低くなり、また、得られる被膜の耐水性が低下する。
また、プロピレン／１−ブテン／エチレン三元共重合体（Ａ）は、１−ブテン単位を２０〜４０質量％を含有する。プロピレン／１−ブテン／エチレン三元共重合体（Ａ）における１−ブテン単位含有量が２０質量％未満であっても、４０質量％を超えても、付着性、特にポリプロピレンの成形体に対する付着性が低くなり、また、得られる被膜の耐水性が低下する。
また、プロピレン／１−ブテン／エチレン三元共重合体（Ａ）は、エチレン単位を５〜２５質量％含有する。プロピレン／１−ブテン／エチレン三元共重合体（Ａ）におけるエチレン単位含有量が５質量％未満であっても、２５質量％を超えても、付着性、特にポリプロピレンの成形体に対する付着性が低くなり、また、得られる被膜の耐水性が低下する。
(Propylene / 1-butene / ethylene terpolymer (A))
The propylene / 1-butene / ethylene terpolymer (A) has 40 to 70% by mass of propylene units. When the propylene unit content in the propylene / 1-butene / ethylene terpolymer (A) is less than 40% by mass or more than 70% by mass, the obtained aqueous dispersion is converted into a polypropylene molded product. Adhesiveness when applied to the coating is lowered, and the water resistance of the resulting coating is lowered.
Moreover, a propylene / 1-butene / ethylene terpolymer (A) contains 20-40 mass% of 1-butene units. Even if the 1-butene unit content in the propylene / 1-butene / ethylene terpolymer (A) is less than 20% by mass or more than 40% by mass, adhesion, particularly adhesion to a molded product of polypropylene. And the water resistance of the resulting coating is reduced.
The propylene / 1-butene / ethylene terpolymer (A) contains 5 to 25% by mass of ethylene units. Even if the ethylene unit content in the propylene / 1-butene / ethylene terpolymer (A) is less than 5% by mass or more than 25% by mass, the adhesiveness, in particular, the adhesiveness to the molded product of polypropylene can be obtained. In addition, the water resistance of the resulting coating is lowered.
プロピレン／１−ブテン／エチレンの三元共重合体（Ａ）は、上記構成単位以外に、本発明の効果を阻害しない範囲内で他の単量体単位を含有してもよい。
他の単量体としては、例えば、ブタジエン、イソプレン等の共役ジエン；１，４−ヘキサジエン、１，７−オクタジエン、ジシクロペンタジエン、５−エチリデン−２−ノルボルネン、５−ビニル−２−ノルボルネン、５−メチレン−２−ノルボルネン、２，５−ノルボナジエン等の非共役ジエン；（メタ）アクリル酸、（メタ）アクリル酸塩、（メタ）アクリル酸エステル、酢酸ビニル、ビニルアルコール、１−ウンデシレン酸、１−ウンデセノール、無水マレイン酸成分単位などの極性ビニル単量体；スチレン、ビニルトルエン、α−メチルスチレン、インデンなどの芳香族性ビニル単量体などが挙げられる。他の単量体は１種が単独で含有されていてもよいし、２種以上が含有されていてもよい。
The propylene / 1-butene / ethylene terpolymer (A) may contain other monomer units in addition to the above structural units within a range not inhibiting the effects of the present invention.
Examples of other monomers include conjugated dienes such as butadiene and isoprene; 1,4-hexadiene, 1,7-octadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, Non-conjugated dienes such as 5-methylene-2-norbornene and 2,5-norbornadiene; (meth) acrylic acid, (meth) acrylate, (meth) acrylate ester, vinyl acetate, vinyl alcohol, 1-undecylenic acid, Examples include polar vinyl monomers such as 1-undecenol and maleic anhydride component units; aromatic vinyl monomers such as styrene, vinyltoluene, α-methylstyrene, and indene. As for another monomer, 1 type may be contained independently and 2 or more types may contain.
プロピレン／１−ブテン／エチレン三元共重合体（Ａ）の結晶化度は０．１〜１６％であり、好ましくは０．１〜８％である。プロピレン／１−ブテン／エチレン三元共重合体（Ａ）の結晶化度が１６％を超えると、得られる水性分散体のポリオレフィン成形体、特にポリプロピレン成形体に対する付着性が低くなり、耐水性も低くなる。一方、プロピレン／１−ブテン／エチレン三元共重合体（Ａ）の結晶化度が０．１％未満であっても、得られる水性分散体の付着性および耐水性が低くなる。 The degree of crystallinity of the propylene / 1-butene / ethylene terpolymer (A) is 0.1 to 16%, preferably 0.1 to 8%. When the crystallinity of the propylene / 1-butene / ethylene terpolymer (A) exceeds 16%, the adhesion of the resulting aqueous dispersion to a polyolefin molded product, particularly a polypropylene molded product is lowered, and water resistance is also improved. Lower. On the other hand, even if the crystallinity of the propylene / 1-butene / ethylene terpolymer (A) is less than 0.1%, the adhesion and water resistance of the resulting aqueous dispersion are lowered.
プロピレン／１−ブテン／エチレン三元共重合体（Ａ）の重量平均分子量は、１２０，０００〜４００，０００である。プロピレン／１−ブテン／エチレン三元共重合体（Ａ）の重量平均分子量が１２０，０００未満であっても、４００，０００を超えても、付着性、特にポリプロピレンの成形体に対する付着性が低くなる。 The weight average molecular weight of the propylene / 1-butene / ethylene terpolymer (A) is 120,000 to 400,000. Even if the weight average molecular weight of the propylene / 1-butene / ethylene terpolymer (A) is less than 120,000 or more than 400,000, the adhesiveness, particularly the adhesiveness to polypropylene molded articles is low. Become.
プロピレン／１−ブテン／エチレンの三元共重合体（Ａ）の製造方法は、特に制限されず、例えば、バナジウム系触媒、マグネシウム、チタン、ハロゲン等を成分とするチタン系触媒などを用いて、プロピレンと１−ブテンとエチレンと必要に応じて他の単量体とを共重合させる方法などが挙げられる。
結晶化度を制御したプロピレン／１−ブテン／エチレン三元共重合体（Ａ）を製造する方法としては、メタロセン系触媒を用いることが好ましい。メタロセン系触媒としては、シクロペンタジエニル骨格を少なくとも１個有する周期律表第４族〜第６族の遷移金属錯体を挙げることができる。例えば特開平９−１５１２０５号公報に記載されたメタロセン触媒を用いることができる。
プロピレン／１−ブテン／エチレン三元共重合体（Ａ）の組成は、プロピレン／１−ブテン／エチレン三元共重合体（Ａ）重合時のプロピレンと１−ブテンとエチレンとの供給組成を適宜変更することにより、調節できる。
プロピレン／１−ブテン／エチレン三元共重合体（Ａ）の重量平均分子量は、重合時に水素ガスを供給し、その供給量を適宜変更することにより、調節できる。
The production method of the propylene / 1-butene / ethylene terpolymer (A) is not particularly limited. For example, using a vanadium catalyst, a titanium catalyst containing magnesium, titanium, halogen, or the like as a component, Examples thereof include a method of copolymerizing propylene, 1-butene, ethylene and other monomers as required.
As a method for producing the propylene / 1-butene / ethylene terpolymer (A) with controlled crystallinity, it is preferable to use a metallocene catalyst. Examples of the metallocene catalyst include transition metal complexes of Groups 4 to 6 of the periodic table having at least one cyclopentadienyl skeleton. For example, a metallocene catalyst described in JP-A-9-151205 can be used.
The composition of the propylene / 1-butene / ethylene terpolymer (A) is appropriately determined according to the propylene / 1-butene / ethylene terpolymer (A) supply composition of propylene, 1-butene and ethylene during polymerization. It can be adjusted by changing.
The weight average molecular weight of the propylene / 1-butene / ethylene terpolymer (A) can be adjusted by supplying hydrogen gas during polymerization and appropriately changing the supply amount.
（酸変性ポリオレフィン（Ｂ））
酸変性ポリオレフィン（Ｂ）は、エチレン性不飽和カルボン酸またはその無水物で変性されたオレフィン系重合体である。エチレン性不飽和カルボン酸としては、例えば、（メタ）アクリル酸等が挙げられ、エチレン性不飽和カルボン酸の無水物としては、例えば、無水マレイン酸等が挙げられる。
酸変性ポリオレフィン（Ｂ）としては、例えば、酸価が３〜８０ｍｇ／ｇの酸変性ポリエチレン、酸変性エチレン−プロピレン共重合体、酸変性ポリプロピレン、エチレン−（メタ）アクリル酸共重合体などが挙げられる。
酸変性ポリオレフィン（Ｂ）は１種を単独で使用してもよいし、２種以上を併用してもよい。
(Acid-modified polyolefin (B))
The acid-modified polyolefin (B) is an olefin polymer modified with an ethylenically unsaturated carboxylic acid or an anhydride thereof. Examples of the ethylenically unsaturated carboxylic acid include (meth) acrylic acid, and examples of the ethylenically unsaturated carboxylic acid anhydride include maleic anhydride.
Examples of the acid-modified polyolefin (B) include acid-modified polyethylene having an acid value of 3 to 80 mg / g, acid-modified ethylene-propylene copolymer, acid-modified polypropylene, and ethylene- (meth) acrylic acid copolymer. It is done.
Acid-modified polyolefin (B) may be used individually by 1 type, and may use 2 or more types together.
酸変性ポリオレフィン（Ｂ）の重量平均分子量は１，８００〜３５，０００であり、好ましくは１，８００〜２０，０００である。酸変性ポリオレフィン（Ｂ）の重量平均分子量が１，８００未満であると、プロピレン／１−ブテン／エチレン三元共重合体（Ａ）を分散させることができないため、水性分散体が得られず、３５，０００を超えると、付着性および耐水性が低下する。 The weight average molecular weight of the acid-modified polyolefin (B) is 1,800 to 35,000, preferably 1,800 to 20,000. When the weight average molecular weight of the acid-modified polyolefin (B) is less than 1,800, since the propylene / 1-butene / ethylene terpolymer (A) cannot be dispersed, an aqueous dispersion cannot be obtained, When it exceeds 35,000, adhesion and water resistance are lowered.
酸変性ポリオレフィン（Ｂ）の酸価は３〜８０ｍｇ／ｇであり、好ましくは１０〜７０ｍｇ／ｇである。ここでいう酸価は、変性ポリオレフィン１ｇを中和するのに必要な水酸化カリウムのｍｇ数である。酸変性ポリオレフィン（Ｂ）の酸価が３ｍｇ／ｇ未満であると、プロピレン／１−ブテン／エチレン三元共重合体（Ａ）を分散させることができないため、水性分散体が得られず、８０ｍｇ／ｇを超えると、付着性および耐水性が低くなる。 The acid value of the acid-modified polyolefin (B) is 3 to 80 mg / g, preferably 10 to 70 mg / g. The acid value here is the number of mg of potassium hydroxide required to neutralize 1 g of the modified polyolefin. When the acid value of the acid-modified polyolefin (B) is less than 3 mg / g, the aqueous dispersion cannot be obtained because the propylene / 1-butene / ethylene terpolymer (A) cannot be dispersed. When it exceeds / g, adhesion and water resistance are lowered.
酸変性ポリオレフィン（Ｂ）の量は、プロピレン／１−ブテン／エチレン三元共重合体（Ａ）１００質量部に対して５〜２０質量部であり、好ましくは５〜１０質量部である。酸変性ポリオレフィン（Ｂ）の量が５質量部未満であると、プロピレン／１−ブテン／エチレン三元共重合体（Ａ）を分散させることができないため、水性分散体が得られず、２０質量部を超えると、得られる水性分散体は粒子径の大きなものとなり、付着性および耐水性が低下する。 The amount of the acid-modified polyolefin (B) is 5 to 20 parts by mass, preferably 5 to 10 parts by mass with respect to 100 parts by mass of the propylene / 1-butene / ethylene terpolymer (A). When the amount of the acid-modified polyolefin (B) is less than 5 parts by mass, since the propylene / 1-butene / ethylene terpolymer (A) cannot be dispersed, an aqueous dispersion cannot be obtained and 20 masses. When the amount exceeds 50 parts, the resulting aqueous dispersion has a large particle size, and adhesion and water resistance decrease.
（アニオン型界面活性剤（Ｃ））
アニオン型界面活性剤（Ｃ）としては、例えば、第１級高級脂肪酸塩、第２級高級脂肪酸塩、第１級高級アルコール硫酸エステル塩、第２級高級アルコール硫酸エステル塩、第１級高級アルキルスルホン酸塩、第２級高級アルキルスルホン酸塩、高級アルキルジスルホン酸塩、スルホン化高級脂肪酸塩、高級脂肪酸硫酸エステル塩、高級脂肪酸エステルスルホン酸塩、高級アルコールエーテルの硫酸エステル塩、高級アルコールエーテルのスルホン酸塩、高級脂肪酸アミドのアルキロール化硫酸エステル塩、アルキルベンゼンスルホン酸塩、アルキルフェノールスルホン酸塩、アルキルナフタリンスルホン酸塩、アルキルベンゾイルイミダゾールスルホン酸塩などが挙げられる。
上記のアニオン型界面活性剤を構成する高級脂肪酸としては、カプリン酸、ウンデカン酸、ラウリン酸、ミリスチン酸、パルミチン酸、マーガリン酸、ステアリン酸、アラキン酸等の飽和脂肪酸、リンデル酸、ツズ酸、ペトロセリン酸、オレイン酸、リノール酸、リノレン酸、アラキドン酸等の不飽和脂肪酸と、これらの混合物が挙げられる。
高級脂肪酸と塩を形成するための元素としては、ナトリウム、カリウム等のアルカリ金属が挙げられる。
アニオン型界面活性剤は１種を単独で使用してもよいし、２種以上を組合せて使用してもよい。これらのアニオン型界面活性剤の中でも牛脂脂肪酸カリウムや、オレイン酸カリウムが、耐水性の面からより好ましい。
(Anionic surfactant (C))
Examples of the anionic surfactant (C) include primary higher fatty acid salts, secondary higher fatty acid salts, primary higher alcohol sulfates, secondary higher alcohol sulfates, and primary higher alkyls. Sulfonates, secondary higher alkyl sulfonates, higher alkyl disulfonates, sulfonated higher fatty acid salts, higher fatty acid sulfate esters, higher fatty acid ester sulfonates, higher alcohol ether sulfates, higher alcohol ethers Examples thereof include sulfonates, alkylol sulfates of higher fatty acid amides, alkylbenzene sulfonates, alkylphenol sulfonates, alkylnaphthalene sulfonates, and alkylbenzoylimidazole sulfonates.
Higher fatty acids constituting the above anionic surfactants include capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachidic acid and other saturated fatty acids, Linderic acid, Tuzic acid, Examples include unsaturated fatty acids such as petroceric acid, oleic acid, linoleic acid, linolenic acid, and arachidonic acid, and mixtures thereof.
Examples of elements for forming salts with higher fatty acids include alkali metals such as sodium and potassium.
An anionic surfactant may be used individually by 1 type, and may be used in combination of 2 or more type. Among these anionic surfactants, potassium tallow fatty acid and potassium oleate are more preferable from the viewpoint of water resistance.
アニオン型界面活性剤（Ｃ）の量は、プロピレン／１−ブテン／エチレン三元共重合体（Ａ）１００質量部に対して１〜１０質量部であり、好ましくは２〜５質量部である。アニオン型界面活性剤（Ｃ）の量が１質量部未満であると、水性分散体の分散安定性が低くなり、１０質量部を超えると、付着性および耐水性が低くなる。 The amount of the anionic surfactant (C) is 1 to 10 parts by mass, preferably 2 to 5 parts by mass with respect to 100 parts by mass of the propylene / 1-butene / ethylene terpolymer (A). . When the amount of the anionic surfactant (C) is less than 1 part by mass, the dispersion stability of the aqueous dispersion is lowered, and when it exceeds 10 parts by mass, adhesion and water resistance are lowered.
（水（Ｄ））
水性分散体中の水（Ｄ）は転相時に必要な水であり、プロピレン／１−ブテン／エチレン三元共重合体（Ａ）１００質量部に対して、０．５〜２０質量部である。
なお、水（Ｄ）の量が前記範囲である水性分散体の固形分濃度は８４質量％以上であり、実質的に固体である。そのため、この水性分散体を既存の塗工方法を適用するため、あるいは、他の薬剤を混合しやすくするためには、粘度を適切な範囲にする目的で、水性分散体に５０質量部以上の希釈水を添加し、希釈して、固形分濃度が１０〜６０質量％の水性分散液とすることが好ましい。
(Water (D))
Water (D) in the aqueous dispersion is water necessary for phase inversion, and is 0.5 to 20 parts by mass with respect to 100 parts by mass of propylene / 1-butene / ethylene terpolymer (A). .
In addition, solid content concentration of the aqueous dispersion whose quantity of water (D) is the said range is 84 mass% or more, and is substantially solid. Therefore, in order to apply the existing coating method to this aqueous dispersion, or to make it easy to mix other chemicals, 50 parts by mass or more is added to the aqueous dispersion for the purpose of adjusting the viscosity to an appropriate range. It is preferable to add dilution water and dilute to obtain an aqueous dispersion having a solid content concentration of 10 to 60% by mass.
（副資材）
水性分散体には、必要に応じて、各種副資材が含まれてもよい。副資材としては、例えば、カチオン型界面活性剤、ノニオン型界面活性剤等の分散剤、乳化剤、安定化剤、湿潤剤、増粘剤、起泡剤、消泡剤、ゲル化剤、老化防止剤、軟化剤、可塑剤、充填剤、着色剤、付香剤、粘着防止剤、離型剤、造膜助剤、レベリング剤等が挙げられる。
(Auxiliary materials)
The aqueous dispersion may contain various auxiliary materials as necessary. Secondary materials include, for example, dispersants such as cationic surfactants and nonionic surfactants, emulsifiers, stabilizers, wetting agents, thickeners, foaming agents, antifoaming agents, gelling agents, and anti-aging agents. Agents, softeners, plasticizers, fillers, colorants, flavoring agents, anti-tacking agents, mold release agents, film-forming aids, leveling agents and the like.
以上説明した水性分散体では、酸変性ポリオレフィン（Ｂ）を含有しており、これが転相前の段階で界面活性剤を均一分散させる効果があるものと推定される。界面活性剤が均一分散した結果、アニオン型界面活性剤（Ｃ）の含有量が１〜１０質量部と比較的に少ない量でも、１μ未満の平均粒子径で、エチレン／１−ブテン／エチレン三元共重合体（Ａ）を水に分散させることができる。その結果、基材に対する水性分散体の付着性を向上させることができ、また、得られる被膜の耐水性を向上させることができる。
また、水性分散体は、分散媒として水を使用しているので、環境上の問題が少なく、取り扱い性に優れる。
The aqueous dispersion described above contains the acid-modified polyolefin (B), which is presumed to have an effect of uniformly dispersing the surfactant in the stage before phase inversion. As a result of the uniform dispersion of the surfactant, even if the content of the anionic surfactant (C) is as relatively small as 1 to 10 parts by mass, the average particle diameter of less than 1 μm, ethylene / 1-butene / ethylene The original copolymer (A) can be dispersed in water. As a result, the adhesion of the aqueous dispersion to the substrate can be improved, and the water resistance of the resulting coating can be improved.
In addition, since the aqueous dispersion uses water as a dispersion medium, there are few environmental problems and excellent handleability.
（使用方法）
水性分散体は各種基材に塗布されて使用される。基材としては、例えば、紙、繊維織物、プラスチック成形品、木材、金属などが挙げられる。これらの中でも、プラスチック成形品、とりわけポリエチレン成形品やポリプロピレン成形品に対しては、水性分散体の高い付着性が顕著に発揮される。該ポリエチレン成形品やポリプロピレン成形品に、他のポリオレフィン（例えば、エチレン・プロピレン共重合体ゴム等）、無機フィラー（例えば、タルク、ガラス繊維、炭酸カルシウム等）、安定剤、着色剤などの各種添加剤が含まれている場合も、発揮される効果は同等である。
水性分散体の塗布方法としては、例えば、各種塗工機を用いる方法、スプレーを用いる方法、刷毛塗りなどを採ることができる。
(how to use)
The aqueous dispersion is used by being applied to various substrates. Examples of the substrate include paper, fiber fabric, plastic molded product, wood, metal, and the like. Among these, high adhesiveness of the aqueous dispersion is remarkably exhibited for plastic molded products, particularly polyethylene molded products and polypropylene molded products. Various additions such as other polyolefins (for example, ethylene / propylene copolymer rubber), inorganic fillers (for example, talc, glass fiber, calcium carbonate, etc.), stabilizers, colorants, etc. to the polyethylene molded products and polypropylene molded products Even when an agent is included, the effect exerted is the same.
As a coating method of the aqueous dispersion, for example, a method using various coating machines, a method using a spray, a brush coating, or the like can be employed.
「水性分散体の製造方法」
本発明の水性分散体の製造方法は、プロピレン／１−ブテン／エチレン三元共重合体（Ａ）と酸変性ポリオレフィン（Ｂ）とアニオン型界面活性剤（Ｃ）とを含む混合物を溶融混練して混練物を得る工程（以下、第１の工程という。）と、該混練物に水（Ｄ）を添加した後、さらに溶融混練する工程（以下、第２の工程という。）とを有する。
"Method for producing aqueous dispersion"
In the method for producing an aqueous dispersion of the present invention, a mixture containing a propylene / 1-butene / ethylene terpolymer (A), an acid-modified polyolefin (B) and an anionic surfactant (C) is melt-kneaded. To obtain a kneaded product (hereinafter referred to as the first step), and further, after adding water (D) to the kneaded product, further melt-kneaded (hereinafter referred to as the second step).
（第１の工程）
第１の工程における酸変性ポリオレフィン（Ｂ）の配合量は、水性分散体における酸変性ポリオレフィン（Ｂ）の含有量と同様に、プロピレン／１−ブテン／エチレン三元共重合体（Ａ）１００質量部に対して５〜２０質量部であり、好ましくは５〜１０質量部である。
アニオン型界面活性剤（Ｃ）の配合量は、水性分散体におけるアニオン型界面活性剤（Ｃ）の含有量と同様に、プロピレン／１−ブテン／エチレン三元共重合体（Ａ）１００質量部に対して１〜１０質量部であり、好ましくは２〜５質量部である。
(First step)
The blending amount of the acid-modified polyolefin (B) in the first step is 100 masses of propylene / 1-butene / ethylene terpolymer (A), similar to the content of the acid-modified polyolefin (B) in the aqueous dispersion. It is 5-20 mass parts with respect to a part, Preferably it is 5-10 mass parts.
The blending amount of the anionic surfactant (C) is 100 parts by mass of the propylene / 1-butene / ethylene terpolymer (A) as in the content of the anionic surfactant (C) in the aqueous dispersion. 1 to 10 parts by mass, preferably 2 to 5 parts by mass.
プロピレン／１−ブテン／エチレン三元共重合体（Ａ）と酸変性ポリオレフィン（Ｂ）とアニオン型界面活性剤（Ｃ）とを溶融混練する際には、例えば、ニーダー、バンバリーミキサー、多軸スクリュー押出機を適用することができる。
溶融混練条件は、プロピレン／１−ブテン／エチレン三元共重合体（Ａ）の物性により適宜選択されるが、溶融混練温度は１６０℃〜２５０℃とすることが好ましい。溶融混練温度が１６０℃以上であれば、溶融粘度が充分に低くなるため容易に混練でき、２５０℃以下であれば、必要以上に加熱しないから、三元共重合体（Ａ）の劣化や熱分解を抑制し、且つ、エネルギー使用量を削減できる。
When melt-kneading the propylene / 1-butene / ethylene terpolymer (A), the acid-modified polyolefin (B) and the anionic surfactant (C), for example, a kneader, a Banbury mixer, a multiaxial screw An extruder can be applied.
The melt-kneading conditions are appropriately selected depending on the physical properties of the propylene / 1-butene / ethylene terpolymer (A), but the melt-kneading temperature is preferably 160 ° C to 250 ° C. If the melt-kneading temperature is 160 ° C. or higher, the melt viscosity is sufficiently low so that it can be easily kneaded. Decomposition can be suppressed and energy consumption can be reduced.
（第２の工程）
第１の工程に引続く第２の工程では、第１の工程で得た混練物に水（Ｄ）を注入して、プロピレン／１−ブテン／エチレン三元共重合体（Ａ）および酸変性ポリオレフィン（Ｂ）を含む樹脂固形分に水を含有させる。その水（Ｄ）の添加では、水のみを添加してもよいし、他の添加成分を溶解した水溶液の形態で添加してもよい。他の添加成分としては、酸変性ポリオレフィン（Ｂ）由来の酸を中和して、水性分散体をより容易に製造できることから、水酸化カリウム、水酸化ナトリウムや有機アミン等のアルカリ成分が好ましい。
水（Ｄ）の添加量は、プロピレン／１−ブテン／エチレン三元共重合体（Ａ）１００質量部に対して０．５〜２０質量部であることが好ましく、２〜１０質量部であることがより好ましい。水（Ｄ）の添加量が０．５質量部未満であると、水性分散体は得られず、２０質量部を超えると、水性分散体の樹脂固形分の平均粒子径が大きくなって、付着性および耐水性が低くなる。
(Second step)
In the second step following the first step, water (D) is injected into the kneaded product obtained in the first step, and propylene / 1-butene / ethylene terpolymer (A) and acid-modified Water is contained in the resin solids containing the polyolefin (B). In the addition of water (D), only water may be added, or it may be added in the form of an aqueous solution in which other additive components are dissolved. As other additive components, alkaline components such as potassium hydroxide, sodium hydroxide and organic amines are preferable because the acid-modified polyolefin (B) -derived acid can be neutralized to produce an aqueous dispersion more easily.
The amount of water (D) added is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of propylene / 1-butene / ethylene terpolymer (A), and 2 to 10 parts by mass. It is more preferable. If the amount of water (D) added is less than 0.5 parts by mass, an aqueous dispersion cannot be obtained, and if it exceeds 20 parts by mass, the average particle size of the resin solid content of the aqueous dispersion becomes large and adheres. And water resistance are lowered.
第２の工程における溶融混練では、樹脂固形分に水が含まれる状態から、水に樹脂固形分が分散する状態に転相させる。
第２の工程における溶融混練においても、第１の工程と同様に、ニーダー、バンバリーミキサー、多軸スクリュー押出機を適用することができる。
第２の工程における溶融混練温度は、第１の工程と同様に１６０〜２５０℃とすることが好ましい。溶融混練温度が１６０℃以上であれば、容易に転相させることができ、２５０℃以下であれば、必要以上に加熱しないから、樹脂の劣化や熱分解を抑制し、且つ、エネルギー使用量を削減できる。
In the melt-kneading in the second step, the phase is changed from a state in which the resin solid content contains water to a state in which the resin solid content is dispersed in water.
Also in the melt-kneading in the second step, a kneader, a Banbury mixer, and a multi-screw extruder can be applied as in the first step.
The melt kneading temperature in the second step is preferably 160 to 250 ° C. as in the first step. If the melt kneading temperature is 160 ° C. or higher, phase inversion can be easily performed, and if it is 250 ° C. or lower, the resin is not heated more than necessary, so that the deterioration and thermal decomposition of the resin are suppressed, and the energy consumption is reduced. Can be reduced.
第２の工程終了後、得られた水性分散体にさらに水を添加し、希釈した水性分散液とすることが好ましい。水をさらに添加すれば、水性分散体の粘度が下がり、流動性が高くなる。さらに添加する水の量は水性分散体の使用目的および使用方法により適宜選択されるが、水性分散体の固形分濃度が１０〜６０質量％の範囲になる量が好ましい。 After completion of the second step, it is preferable to add water to the obtained aqueous dispersion to obtain a diluted aqueous dispersion. If water is further added, the viscosity of the aqueous dispersion decreases and the fluidity increases. Further, the amount of water to be added is appropriately selected depending on the purpose and method of use of the aqueous dispersion, but is preferably such that the solid content concentration of the aqueous dispersion is in the range of 10 to 60% by mass.
本発明以外の他の製造方法では、界面活性剤量を１〜１０質量部という少ない量とすると、０．１〜１μｍ程度の小さな平均粒子径の水性分散体を得ることは困難である。しかし、上記水性分散体の製造方法によれば、１〜１０質量部という少ない界面活性剤量であっても０．１〜１μｍ程度の小さな平均粒子径の水性分散体を得ることができる。これは、本製造方法で使用する酸変性ポリオレフィン（Ｂ）が、転相前のプロピレン／１−ブテン／エチレン三元共重合体（Ａ）が連続相である段階で、界面活性剤をミクロ分散させる効果を発揮するためであると推定される。したがって、酸変性ポリオレフィン（Ｂ）は本製造方法における必須の成分である。これに対し、他の分散方法では僅かな粘度の低減効果しか見られず、必須ではない。
また、上記製造方法により得られた水性分散体から形成される塗膜は、付着性、耐水性が優れたものとなる。
In other production methods other than the present invention, it is difficult to obtain an aqueous dispersion having a small average particle diameter of about 0.1 to 1 μm when the amount of the surfactant is as small as 1 to 10 parts by mass. However, according to the method for producing an aqueous dispersion, an aqueous dispersion having a small average particle diameter of about 0.1 to 1 μm can be obtained even with a small amount of surfactant of 1 to 10 parts by mass. This is because the acid-modified polyolefin (B) used in this production method is a stage in which the propylene / 1-butene / ethylene terpolymer (A) before phase inversion is a continuous phase, and the surfactant is microdispersed. It is presumed that this is to exert the effect of Accordingly, the acid-modified polyolefin (B) is an essential component in the production method. On the other hand, other dispersion methods show only a slight viscosity reduction effect and are not essential.
Moreover, the coating film formed from the aqueous dispersion obtained by the said manufacturing method becomes what was excellent in adhesiveness and water resistance.
以下、本発明を実施例により具体的に説明するが、本発明は以下の実施例に限定されるものではない。なお、以下の例において「％」は「質量％」、「部」は「質量部」のことを意味する。
また、以下の例におけるプロピレン／１−ブテン／エチレン三元共重合体および酸変性ポリオレフィンの特性は、下記のようにして測定した。
・ポリオレフィン単位の定量：日本電子（株）製、高分解能フーリエ変換核磁気共鳴装置ＪＮＭ−ＡＬ４００型によりモル比を測定して求めた。
・ポリオレフィンおよび酸変性ポリオレフィンの重量平均分子量：ウォーターズ社製、アライアンスＧＰＣ Ｖ２０００型により測定した。
・ポリオレフィンの結晶化度：理学電機（株）製、広角Ｘ線回折装置ＲＡＤ−ＲＸ型により求めた。
・平均粒子径：マウンテック（Ｍｏｕｎｔｅｃｈ）社製のマイクロトラックＵＰＡにて測定した。
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to a following example. In the following examples, “%” means “mass%” and “part” means “part by mass”.
The properties of propylene / 1-butene / ethylene terpolymer and acid-modified polyolefin in the following examples were measured as follows.
-Quantification of polyolefin unit: It was determined by measuring the molar ratio with a high resolution Fourier transform nuclear magnetic resonance apparatus JNM-AL400 manufactured by JEOL Ltd.
-Weight average molecular weight of polyolefin and acid-modified polyolefin: Measured by Alliance GPC V2000, manufactured by Waters.
Polyolefin crystallinity: Determined by a wide-angle X-ray diffractometer RAD-RX manufactured by Rigaku Corporation.
Average particle size: Measured with a Microtrac UPA manufactured by Mounttech.
以下の実施例、比較例において、（Ａ）成分として、下記の（Ａ−１）〜（Ａ−１７）を用いた。
プロピレン／１−ブテン／エチレン三元共重合体（Ａ−１）
攪拌機を備えた１００Ｌのステンレス製重合槽を減圧乾燥し、分子量調節用として水素を供給し、以下の方法で連続的に重合させてプロピレン／１−ブテン／エチレン三元共重合体（Ａ−１）を得た。
重合槽の下部から、重合溶媒としてのヘキサンを１００Ｌ／時間の供給速度で、プロピレンを１０．５ｋｇ／時間の供給速度で, １−ブテンを９．５ｋｇ／時間の供給速度で、エチレンを５ｋｇ／時間の供給速度で、水素ガスを９０g／時間の供給速度で、それぞれ連続的に供給した。
また、重合槽の上部から、重合槽中の反応混合物の容積が１００Ｌを保持するように反応混合物を連続的に抜き出した。
それと同時に、重合槽の下部から、重合用触媒の成分として、ジメチルシリル（シクロペンタジエニル）（３−ｔｅｒｔ−ブチル−５−メチル−２−フェノキシ）チタニウムジクロライドを０．００５ｇ／時間の供給速度で、トリフェニルメチルテトラキス（ペンタフルオロフェニル）ボレートを０．３０ｇ／時間の供給速度で、トリイソブチルアルミニウムを２．３ｇ／１０時間の供給速度で、それぞれ連続的に供給した。
それと同時に、重合槽の上部から、重合槽中の反応混合物の容積が１００Ｌを保持するように反応混合物を連続的に抜き出した。
重合反応は、重合槽の外部に有するジャケットに冷却水を循環させることによって、４５℃で行った。
重合槽の上部から連続的に抜き出された反応混合物に少量のエタノールを添加して重合反応を停止させた後、脱モノマーおよび水洗浄した。次いで、大量の水中でスチームによって溶媒を除去し、８０℃で１昼夜減圧乾燥することによって、プロピレン／１−ブテン／エチレン三元共重合体（Ａ−１）を得た。
プロピレン／１−ブテン／エチレン三元共重合体（Ａ−１）の各単量体単位の組成、結晶化度、重量平均分子量を以下のようにして測定した。その結果を表１に示す。
In the following examples and comparative examples, the following (A-1) to (A-17) were used as the component (A).
Propylene / 1-butene / ethylene terpolymer (A-1)
A 100 L stainless steel polymerization tank equipped with a stirrer is dried under reduced pressure, hydrogen is supplied for molecular weight adjustment, and polymerized continuously by the following method to produce a propylene / 1-butene / ethylene terpolymer (A-1 )
From the bottom of the polymerization tank, hexane as a polymerization solvent is supplied at a rate of 100 L / hour, propylene is supplied at a supply rate of 10.5 kg / hour, 1-butene is supplied at a supply rate of 9.5 kg / hour, and ethylene is supplied at 5 kg / hour. Hydrogen gas was continuously supplied at a supply rate of 90 g / hour at a supply rate of time.
Moreover, the reaction mixture was continuously extracted from the upper part of the polymerization tank so that the volume of the reaction mixture in the polymerization tank was maintained at 100 L.
At the same time, a supply rate of 0.005 g / hour of dimethylsilyl (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride as a component of the polymerization catalyst from the lower part of the polymerization tank. Then, triphenylmethyltetrakis (pentafluorophenyl) borate was continuously supplied at a supply rate of 0.30 g / hour and triisobutylaluminum was continuously supplied at a supply rate of 2.3 g / 10 hours.
At the same time, the reaction mixture was continuously extracted from the upper part of the polymerization tank so that the volume of the reaction mixture in the polymerization tank was maintained at 100 L.
The polymerization reaction was performed at 45 ° C. by circulating cooling water through a jacket provided outside the polymerization tank.
A small amount of ethanol was added to the reaction mixture continuously extracted from the upper part of the polymerization tank to stop the polymerization reaction, and then the monomer was removed and washed with water. Next, the solvent was removed with steam in a large amount of water and dried under reduced pressure at 80 ° C. for one day to obtain a propylene / 1-butene / ethylene terpolymer (A-1).
The composition, crystallinity, and weight average molecular weight of each monomer unit of propylene / 1-butene / ethylene terpolymer (A-1) were measured as follows. The results are shown in Table 1.
また、単量体単位の組成が表１または表２のようになるように、プロピレン、１−ブテン、エチレンの供給速度を変更したこと以外は、上述したプロピレン／１−ブテン／エチレン三元共重合体（Ａ−１）の製造方法と同様にして、プロピレン／１−ブテン／エチレン三元共重合体（Ａ−２）〜（Ａ−１７）を得た。
プロピレン／１−ブテン／エチレン三元共重合体（Ａ−２）〜（Ａ−１７）における各単量体単位の組成、結晶化度、重量平均分子量を表１または表２に示す。
In addition, the propylene / 1-butene / ethylene ternary copolymer described above was used except that the supply rate of propylene, 1-butene and ethylene was changed so that the composition of the monomer units was as shown in Table 1 or Table 2. Propylene / 1-butene / ethylene terpolymers (A-2) to (A-17) were obtained in the same manner as in the method for producing the polymer (A-1).
Table 1 or Table 2 shows the composition, crystallinity, and weight average molecular weight of each monomer unit in the propylene / 1-butene / ethylene terpolymers (A-2) to (A-17).
（Ｂ）成分としては、下記（Ｂ−１）〜（Ｂ−８）を用いた。
酸変性ポリオレフィン（Ｂ−１）：酸価４０ｍｇ／ｇ、重量平均分子量３，０００の酸変性ポリプロピレンワックスであるクラリアント社製の「ＴＰ Ｌｉｃｏｃｅｎｅ ＰＰＭＡ ６２５２」。
酸変性ポリオレフィン（Ｂ−２）：酸価３．５ｍｇ／ｇ、重量平均分子量１０，０００の酸変性ポリプロピレンである三洋化成工業製「ユーメックス１００ＴＳ」。
酸変性ポリオレフィン（Ｂ−３）：酸価３０ｍｇ／ｇ、重量平均分子量２，０００の酸変性ポリエチレンワックスである三井化学製「ハイワックス ２２０３Ａ」。
酸変性ポリオレフィン（Ｂ−４）：酸価５２ｍｇ／ｇ、重量平均分子量３０，０００の酸変性ポリプロピレンである三洋化成工業製「ユーメックス１０１０」。
酸変性ポリオレフィン（Ｂ−５）：酸価２６ｍｇ／ｇ、重量平均分子量４０，０００の酸変性ポリプロピレンである三洋化成工業製「ユーメックス１００１」。
酸変性ポリオレフィン（Ｂ−６）：酸価６０ｍｇ／ｇ、重量平均分子量１，１００の酸変性ポリエチレンである三井化学製「ハイワックス１１０５Ａ」。
ポリプロピレンワックス（Ｂ−７）：酸変性されておらず、重量平均分子量７，０００のポリプロピレンワックスである三井化学製「ハイワックスＮＰ０５５」。
酸変性ポリオレフィン（Ｂ−８）：酸価１１０ｍｇ／ｇ、重量平均分子量１０，０００のα−オレフィン／無水マレイン酸共重合物である三菱化学製「ダイヤカルナ３０」。
As the component (B), the following (B-1) to (B-8) were used.
Acid-modified polyolefin (B-1): “TP Licocene PPMA 6252” manufactured by Clariant, which is an acid-modified polypropylene wax having an acid value of 40 mg / g and a weight average molecular weight of 3,000.
Acid-modified polyolefin (B-2): “Yumex 100TS” manufactured by Sanyo Chemical Industries, which is an acid-modified polypropylene having an acid value of 3.5 mg / g and a weight average molecular weight of 10,000.
Acid-modified polyolefin (B-3): “High Wax 2203A” manufactured by Mitsui Chemicals, which is an acid-modified polyethylene wax having an acid value of 30 mg / g and a weight average molecular weight of 2,000.
Acid-modified polyolefin (B-4): “Yumex 1010” manufactured by Sanyo Chemical Industries, which is an acid-modified polypropylene having an acid value of 52 mg / g and a weight average molecular weight of 30,000.
Acid-modified polyolefin (B-5): “Yumex 1001” manufactured by Sanyo Chemical Industries, which is an acid-modified polypropylene having an acid value of 26 mg / g and a weight average molecular weight of 40,000.
Acid-modified polyolefin (B-6): “High Wax 1105A” manufactured by Mitsui Chemicals, which is acid-modified polyethylene having an acid value of 60 mg / g and a weight average molecular weight of 1,100.
Polypropylene wax (B-7): “High Wax NP055” manufactured by Mitsui Chemicals, which is a polypropylene wax that is not acid-modified and has a weight average molecular weight of 7,000.
Acid-modified polyolefin (B-8): “Diacarna 30” manufactured by Mitsubishi Chemical, which is an α-olefin / maleic anhydride copolymer having an acid value of 110 mg / g and a weight average molecular weight of 10,000.
（実施例１）
プロピレン／１−ブテン／エチレン三元共重合体（Ａ−１）と、プロピレン／１−ブテン／エチレン三元共重合体１００部に対して１２部の酸変性ポリオレフィン（Ｂ−１）と、プロピレン／１−ブテン／エチレン三元共重合体１００部に対して３部のオレイン酸カリウムを、二軸押出機（スクリュー径；３０ｍｍ、Ｌ／Ｄ；４０、バレル温度；２００℃）にその投入口から供給して溶融混練した。なお、上記３つの原料の合計の供給速度を３，４５０ｇ／時間とした。
また、該二軸押出機のベント部に設けた供給口より１４％の水酸化カリウム水溶液を、ポリオレフィン１００部に対する水の量が４部になるように、１.８ＭＰａで圧入した。
そして、二軸押出機先端より押し出された固形状の乳化物を、温水中で分散させて、平均粒子径０．２１μｍの水性分散体を得た。
Example 1
Propylene / 1-butene / ethylene terpolymer (A-1), 12 parts of acid-modified polyolefin (B-1) with respect to 100 parts of propylene / 1-butene / ethylene terpolymer, propylene 3 parts of potassium oleate with respect to 100 parts of -1-butene / ethylene terpolymer are charged into a twin screw extruder (screw diameter; 30 mm, L / D; 40, barrel temperature; 200 ° C.). And melt-kneaded. The total supply rate of the three raw materials was 3,450 g / hour.
Further, a 14% potassium hydroxide aqueous solution was press-fitted at 1.8 MPa so that the amount of water relative to 100 parts of polyolefin was 4 parts from a supply port provided in the vent part of the twin-screw extruder.
The solid emulsion extruded from the tip of the twin screw extruder was dispersed in warm water to obtain an aqueous dispersion having an average particle size of 0.21 μm.
得られた水性分散体の付着性および水性分散体より得た被膜の耐水性を、以下のように評価した。その結果を表３に示す。なお、他の実施例、比較例についてもこの評価方法を適用した。
［試験片の作製］
ホモＰＰであるプライムポリマー社製の「Ｊ１０６Ｇ」と、ブロックＰＰの「Ｊ７１５Ｍ」について、それぞれ、１００×１００ｍｍ、厚さ２ｍｍの平板を射出成形により得た。
この平板の表面を脱脂処理した後、Ｎｏ．１３のコーティングバーを使用して、厚さ１０μｍになるように水性分散体を塗布した。そして、７０℃で２０分間乾燥し、室温で２４時間静置して被膜を形成し、被膜を形成した平板を試験片として用いた。
［付着性試験］
カッターにより被膜にＰＰ製平板に達する切れ目を、１ｍｍ間隔で１００個のマス目が形成されるように形成した。それらのマス目にセロハンテープ（登録商標、ニチバン社製）を密着させた後、引き剥がし、残存したマス目の数を記録した。残存したマス目の数が多い程、付着性に優れる。
［耐水性試験］
金属製のカゴの中に入れた試験片を、４０℃の温水中に完全に浸漬させ、１０日間放置した。その後、温水中から取出し、外観に異常が認められなければ、引き続き、上記付着性試験と同様の試験を行った。残存したマス目の数が多い程、耐水性に優れる。
The adhesion of the obtained aqueous dispersion and the water resistance of the coating obtained from the aqueous dispersion were evaluated as follows. The results are shown in Table 3. This evaluation method was applied to other examples and comparative examples.
[Preparation of test piece]
A plate of 100 × 100 mm and a thickness of 2 mm was obtained by injection molding for “J106G” manufactured by Prime Polymer Co., which is a homo PP, and “J715M” of a block PP, respectively.
After degreasing the surface of this flat plate, No. The aqueous dispersion was applied to a thickness of 10 μm using 13 coating bars. And it dried at 70 degreeC for 20 minute (s), and left still at room temperature for 24 hours, the film was formed, and the flat plate in which the film was formed was used as a test piece.
[Adhesion test]
The cuts reaching the PP flat plate were formed on the film by a cutter so that 100 squares were formed at 1 mm intervals. Cellophane tape (registered trademark, manufactured by Nichiban Co., Ltd.) was adhered to the cells, and then peeled off, and the number of cells remaining was recorded. The greater the number of remaining cells, the better the adhesion.
[Water resistance test]
The test piece placed in a metal cage was completely immersed in warm water at 40 ° C. and left for 10 days. Then, it took out from warm water, and if the abnormality was not recognized in the external appearance, the same test as the said adhesion test was performed continuously. The greater the number of remaining cells, the better the water resistance.
（実施例２）
酸変性ポリプロピレンワックス（Ｂ−１）を、ポリオレフィン１００部に対して６部添加した以外は実施例１と同様にして、平均粒子径０．２５μｍの水性分散体を得た。そして、実施例１と同様にして付着性および耐水性を評価した。その結果を表３に示す。
(Example 2)
An aqueous dispersion having an average particle size of 0.25 μm was obtained in the same manner as in Example 1 except that 6 parts of acid-modified polypropylene wax (B-1) was added to 100 parts of polyolefin. Then, adhesion and water resistance were evaluated in the same manner as in Example 1. The results are shown in Table 3.
（実施例３）
酸変性ポリプロピレンワックス（Ｂ−１）を、ポリオレフィン１００部に対して１８部添加した以外は実施例１と同様にして、平均粒子径０．２７μｍの水性分散体を得た。その付着性および耐水性の結果を表３に示す。
(Example 3)
An aqueous dispersion having an average particle diameter of 0.27 μm was obtained in the same manner as in Example 1 except that 18 parts of acid-modified polypropylene wax (B-1) was added to 100 parts of polyolefin. The adhesion and water resistance results are shown in Table 3.
（実施例４）
プロピレン／１−ブテン／エチレン三元共重合体（Ａ−１）の代わりにプロピレン／１−ブテン／エチレン三元共重合体（Ａ−２）を使用した以外は実施例１と同様にして、平均粒子径０．２２μｍの水性分散体を得た。その付着性および耐水性の結果を表３に示す。
Example 4
Except for using propylene / 1-butene / ethylene terpolymer (A-2) instead of propylene / 1-butene / ethylene terpolymer (A-1), the same procedure as in Example 1 was carried out. An aqueous dispersion having an average particle size of 0.22 μm was obtained. The adhesion and water resistance results are shown in Table 3.
（実施例５）
プロピレン／１−ブテン／エチレン三元共重合体（Ａ−１）の代わりにプロピレン／１−ブテン／エチレン三元共重合体（Ａ−３）を使用した以外は実施例１と同様にして、平均粒子径０．２０μｍの水性分散体を得た。その付着性および耐水性の結果を表３に示す。
(Example 5)
Except for using propylene / 1-butene / ethylene terpolymer (A-3) instead of propylene / 1-butene / ethylene terpolymer (A-1), the same procedure as in Example 1 was carried out. An aqueous dispersion having an average particle size of 0.20 μm was obtained. The adhesion and water resistance results are shown in Table 3.
（実施例６）
プロピレン／１−ブテン／エチレン三元共重合体（Ａ−１）の代わりにプロピレン／１−ブテン／エチレン三元共重合体（Ａ−４）を使用した以外は実施例１と同様にして、平均粒子径０．３０μｍの水性分散体を得た。その付着性および耐水性の結果を表３に示す。
(Example 6)
Except for using propylene / 1-butene / ethylene terpolymer (A-4) instead of propylene / 1-butene / ethylene terpolymer (A-1), the same procedure as in Example 1 was carried out. An aqueous dispersion having an average particle size of 0.30 μm was obtained. The adhesion and water resistance results are shown in Table 3.
（実施例７）
プロピレン／１−ブテン／エチレン三元共重合体（Ａ−１）の代わりにプロピレン／１−ブテン／エチレン三元共重合体（Ａ−５）を使用した以外は実施例１と同様にして、平均粒子径０．２３μｍの水性分散体を得た。その付着性および耐水性の結果を表３に示す。
(Example 7)
Except for using propylene / 1-butene / ethylene terpolymer (A-5) instead of propylene / 1-butene / ethylene terpolymer (A-1), the same procedure as in Example 1 was carried out. An aqueous dispersion having an average particle size of 0.23 μm was obtained. The adhesion and water resistance results are shown in Table 3.
（実施例８）
プロピレン／１−ブテン／エチレン三元共重合体（Ａ−１）の代わりにプロピレン／１−ブテン／エチレン三元共重合体（Ａ−６）を使用した以外は実施例７と同様にして、平均粒子径０．２１μｍの水性分散体を得た。その付着性および耐水性の結果を表３に示す。
(Example 8)
Except for using propylene / 1-butene / ethylene terpolymer (A-6) instead of propylene / 1-butene / ethylene terpolymer (A-1), the same as in Example 7, An aqueous dispersion having an average particle size of 0.21 μm was obtained. The adhesion and water resistance results are shown in Table 3.
（実施例９）
プロピレン／１−ブテン／エチレン三元共重合体（Ａ−１）の代わりにプロピレン／１−ブテン／エチレン三元共重合体（Ａ−７）を使用した以外は実施例７と同様にして、平均粒子径０．３２μｍの水性分散体を得た。その付着性および耐水性の結果を表３に示す。
Example 9
Except for using propylene / 1-butene / ethylene terpolymer (A-7) instead of propylene / 1-butene / ethylene terpolymer (A-1), the same as in Example 7, An aqueous dispersion having an average particle size of 0.32 μm was obtained. The adhesion and water resistance results are shown in Table 3.
（実施例１０）
酸変性ポリオレフィン（Ｂ−１）の代わりに酸変性ポリオレフィン（Ｂ−２）を使用した以外は実施例５と同様にして、平均粒子径０．２２μｍの水性分散体を得た。その付着性および耐水性の結果を表４に示す。
(Example 10)
An aqueous dispersion having an average particle size of 0.22 μm was obtained in the same manner as in Example 5 except that the acid-modified polyolefin (B-2) was used instead of the acid-modified polyolefin (B-1). The adhesion and water resistance results are shown in Table 4.
（実施例１１）
酸変性ポリオレフィン（Ｂ−１）の代わりに酸変性ポリオレフィン（Ｂ−３）を使用した以外は実施例５と同様にして、平均粒子径０．２６μｍの水性分散体を得た。その付着性および耐水性の結果を表４に示す。
(Example 11)
An aqueous dispersion having an average particle size of 0.26 μm was obtained in the same manner as in Example 5 except that the acid-modified polyolefin (B-3) was used instead of the acid-modified polyolefin (B-1). The adhesion and water resistance results are shown in Table 4.
（実施例１２）
酸変性ポリオレフィン（Ｂ−１）の代わりに酸変性ポリオレフィン（Ｂ−４）を使用した以外は実施例５と同様にして、平均粒子径０．２３μｍの水性分散体を得た。その付着性および耐水性の結果を表４に示す。
(Example 12)
An aqueous dispersion having an average particle size of 0.23 μm was obtained in the same manner as in Example 5 except that the acid-modified polyolefin (B-4) was used instead of the acid-modified polyolefin (B-1). The adhesion and water resistance results are shown in Table 4.
（実施例１３）
アニオン型界面活性剤としてオレイン酸カリウムの代わりにドデシルベンゼンスルフォン酸（表中では、ＤＢＳと表記する。）を使用した以外は実施例５と同様にして、平均粒子径０．２５μｍの水性分散体を得た。その付着性および耐水性の結果を表４に示す。
(Example 13)
An aqueous dispersion having an average particle size of 0.25 μm in the same manner as in Example 5 except that dodecylbenzenesulfonic acid (in the table, DBS is used) is used as an anionic surfactant instead of potassium oleate. Got. The adhesion and water resistance results are shown in Table 4.
（実施例１４）
水酸化カリウム水溶液を、ポリオレフィン１００部に対する水の量が１．０部になるように添加した以外は実施例５と同様にして、平均粒子径０．３８μｍの水性分散体を得た。その付着性および耐水性の結果を表４に示す。
(Example 14)
An aqueous dispersion having an average particle size of 0.38 μm was obtained in the same manner as in Example 5 except that an aqueous potassium hydroxide solution was added so that the amount of water relative to 100 parts of polyolefin was 1.0 part. The adhesion and water resistance results are shown in Table 4.
（実施例１５）
水酸化カリウム水溶液を、ポリオレフィン１００部に対する水の量が１５部になるように添加した以外は実施例５と同様にして、平均粒子径０．３３μｍの水性分散体を得た。その付着性および耐水性の結果を表４に示す。
(Example 15)
An aqueous dispersion having an average particle size of 0.33 μm was obtained in the same manner as in Example 5 except that an aqueous potassium hydroxide solution was added so that the amount of water relative to 100 parts of polyolefin was 15 parts. The adhesion and water resistance results are shown in Table 4.
（比較例１）
攪拌機を備えた内容積２リットルのオートクレーブ内に、プロピレン／１−ブテン／エチレン三元共重合体（Ａ−１）１００部とトルエン５００部を仕込み、１２５℃で１時間攪拌して溶解した後、９０℃に冷却した。
また、これとは別に、攪拌機を備えた内容積２リットルのオートクレーブ内で、オレイン酸カリウム３部と水６００部を含む水溶液を９０℃に加熱し、その中に、前記ポリオレフィンのトルエン溶液を攪拌継続下で添加した。２時間攪拌して分散した後、エスエムテー社製（ＨＧ−９２型）高速ホモジナイザーで、１０，０００ｒｐｍで１０分間、分散した。
次いで、攪拌翼による攪拌を継続したまま、凝縮水を還流させながら、２時間水蒸気蒸留してトルエンを留去したが、トルエンを留去するにつれて凝集物が発生し、トルエンの全量を留去する前に凝集物が９９部に達し、水性分散体を得ることができなかった。
(Comparative Example 1)
In an autoclave with an internal volume of 2 liters equipped with a stirrer, 100 parts of propylene / 1-butene / ethylene terpolymer (A-1) and 500 parts of toluene were charged and dissolved by stirring at 125 ° C. for 1 hour. And cooled to 90 ° C.
Separately, an aqueous solution containing 3 parts of potassium oleate and 600 parts of water is heated to 90 ° C. in an autoclave having an internal volume of 2 liters equipped with a stirrer, and the toluene solution of the polyolefin is stirred therein. Added under continuation. After stirring for 2 hours to disperse, the mixture was dispersed with a high speed homogenizer manufactured by SMT (HG-92) at 10,000 rpm for 10 minutes.
Next, while continuing the stirring by the stirring blade, while condensing water is refluxed, the steam is distilled for 2 hours to distill off the toluene, but as the toluene is distilled off, agglomerates are generated and the entire amount of toluene is distilled off. The aggregate reached 99 parts before and an aqueous dispersion could not be obtained.
（比較例２）
オレイン酸カリウムの量を１０部に変更した以外は比較例１と同様にして水性分散体を得ようとしたが、水性分散体を得ることができなかった。
(Comparative Example 2)
An aqueous dispersion was obtained in the same manner as in Comparative Example 1 except that the amount of potassium oleate was changed to 10 parts. However, an aqueous dispersion could not be obtained.
（比較例３）
オレイン酸カリウムの量を２０部に変更した以外は比較例１と同様にしたところ、１２部の凝集物を副生したが、濃度１４％で平均粒子径７．８μｍの水性分散体を得た。その付着性および耐水性の結果を表５に示す。
(Comparative Example 3)
Except that the amount of potassium oleate was changed to 20 parts, the same procedure as in Comparative Example 1 was carried out. As a result, 12 parts of aggregates were by-produced. . The adhesion and water resistance results are shown in Table 5.
（比較例４）
比較例３の水性分散体の調製方法において、酸変性ポリオレフィン（Ｂ−１）１２部をプロピレン／１−ブテン／エチレン三元共重合体（Ａ−１）と同様にトルエンに溶解し、オレイン酸カリウム２０部を添加した以外は比較例１と同様にしたところ、凝集物が１８部副生したが、濃度１６％で平均粒子径８．１μｍの水性分散体を得た。その付着性および耐水性の結果を表５に示す。
(Comparative Example 4)
In the method for preparing the aqueous dispersion of Comparative Example 3, 12 parts of acid-modified polyolefin (B-1) was dissolved in toluene in the same manner as propylene / 1-butene / ethylene terpolymer (A-1), and oleic acid was dissolved. Except for adding 20 parts of potassium, the same procedure as in Comparative Example 1 was performed. As a result, 18 parts of aggregates were by-produced, but an aqueous dispersion having a concentration of 16% and an average particle size of 8.1 μm was obtained. The adhesion and water resistance results are shown in Table 5.
（比較例５）
プロピレン／１−ブテン／エチレン三元共重合体（Ａ−１）の全量に替えて、酸変性ポリオレフィン（Ｂ−１）１００部をトルエンに溶解した以外は比較例１と同様にしたところ、凝集物が１部副生したが、平均粒子径０．３μｍの水性分散体を得た。その付着性および耐水性の結果を表５に示す。
(Comparative Example 5)
In place of the total amount of propylene / 1-butene / ethylene terpolymer (A-1), except that 100 parts of acid-modified polyolefin (B-1) was dissolved in toluene, the same procedure as in Comparative Example 1 was conducted. Although 1 part of the product was by-produced, an aqueous dispersion having an average particle size of 0.3 μm was obtained. The adhesion and water resistance results are shown in Table 5.
（比較例６）
プロピレン／１−ブテン／エチレン三元共重合体（Ａ−１）の代わりにプロピレン／１−ブテン／エチレン三元共重合体（Ａ−８）を使用した以外は実施例１と同様にして、平均粒子径０．２２μｍの水性分散体を得た。その付着性および耐水性の結果を表６に示す。
(Comparative Example 6)
Except for using propylene / 1-butene / ethylene terpolymer (A-8) instead of propylene / 1-butene / ethylene terpolymer (A-1), the same as in Example 1, An aqueous dispersion having an average particle size of 0.22 μm was obtained. The adhesion and water resistance results are shown in Table 6.
（比較例７）
プロピレン／１−ブテン／エチレン三元共重合体（Ａ−１）の代わりにプロピレン／１−ブテン／エチレン三元共重合体（Ａ−９）を使用した以外は実施例１と同様にして、平均粒子径０．２２μｍの水性分散体を得た。その付着性および耐水性の結果を表６に示す。
(Comparative Example 7)
Except having used propylene / 1-butene / ethylene terpolymer (A-9) instead of propylene / 1-butene / ethylene terpolymer (A-1), it was carried out similarly to Example 1, An aqueous dispersion having an average particle size of 0.22 μm was obtained. The adhesion and water resistance results are shown in Table 6.
（比較例８）
プロピレン／１−ブテン／エチレン三元共重合体（Ａ−１）の代わりにプロピレン／１−ブテン／エチレン三元共重合体（Ａ−１０）を使用した以外は実施例１と同様にして、平均粒子径０．２３μｍの水性分散体を得た。その付着性および耐水性の結果を表６に示す。
(Comparative Example 8)
Except for using propylene / 1-butene / ethylene terpolymer (A-10) instead of propylene / 1-butene / ethylene terpolymer (A-1), the same as in Example 1, An aqueous dispersion having an average particle size of 0.23 μm was obtained. The adhesion and water resistance results are shown in Table 6.
（比較例９）
プロピレン／１−ブテン／エチレン三元共重合体（Ａ−１）の代わりにプロピレン／１−ブテン／エチレン三元共重合体（Ａ−１１）を使用した以外は実施例１と同様にして、平均粒子径０．２１μｍの水性分散体を得た。その付着性および耐水性の結果を表６に示す。
(Comparative Example 9)
Except for using propylene / 1-butene / ethylene terpolymer (A-11) instead of propylene / 1-butene / ethylene terpolymer (A-1), the same as in Example 1, An aqueous dispersion having an average particle size of 0.21 μm was obtained. The adhesion and water resistance results are shown in Table 6.
（比較例１０）
プロピレン／１−ブテン／エチレン三元共重合体（Ａ−１）の代わりにプロピレン／１−ブテン／エチレン三元共重合体（Ａ−１２）を使用した以外は実施例１と同様にして、平均粒子径０．２５μｍの水性分散体を得た。その付着性および耐水性の結果を表６に示す。
(Comparative Example 10)
Except for using propylene / 1-butene / ethylene terpolymer (A-12) instead of propylene / 1-butene / ethylene terpolymer (A-1), the same as in Example 1, An aqueous dispersion having an average particle size of 0.25 μm was obtained. The adhesion and water resistance results are shown in Table 6.
（比較例１１）
プロピレン／１−ブテン／エチレン三元共重合体（Ａ−１）の代わりにプロピレン／１−ブテン／エチレン三元共重合体（Ａ−１３）を使用した以外は実施例１と同様にして、平均粒子径０．２６μｍの水性分散体を得た。その付着性および耐水性の結果を表６に示す。
(Comparative Example 11)
Except for using propylene / 1-butene / ethylene terpolymer (A-13) instead of propylene / 1-butene / ethylene terpolymer (A-1), the same procedure as in Example 1 was carried out. An aqueous dispersion having an average particle size of 0.26 μm was obtained. The adhesion and water resistance results are shown in Table 6.
（比較例１２）
プロピレン／１−ブテン／エチレン三元共重合体（Ａ−１）の代わりにプロピレン／１−ブテン／エチレン三元共重合体（Ａ−１４）を使用した以外は実施例１と同様にして、平均粒子径０．２１μｍの水性分散体を得た。その付着性および耐水性の結果を表６に示す。
(Comparative Example 12)
Except for using propylene / 1-butene / ethylene terpolymer (A-14) instead of propylene / 1-butene / ethylene terpolymer (A-1), the same procedure as in Example 1 was carried out. An aqueous dispersion having an average particle size of 0.21 μm was obtained. The adhesion and water resistance results are shown in Table 6.
（比較例１３）
プロピレン／１−ブテン／エチレン三元共重合体（Ａ−１）の代わりにプロピレン／１−ブテン／エチレン三元共重合体（Ａ−１５）を使用した以外は実施例１と同様にして、平均粒子径０．２２μｍの水性分散体を得た。その付着性および耐水性の結果を表６に示す。
(Comparative Example 13)
Except for using propylene / 1-butene / ethylene terpolymer (A-15) instead of propylene / 1-butene / ethylene terpolymer (A-1), the same procedure as in Example 1 was carried out. An aqueous dispersion having an average particle size of 0.22 μm was obtained. The adhesion and water resistance results are shown in Table 6.
（比較例１４）
プロピレン／１−ブテン／エチレン三元共重合体（Ａ−１）の代わりにプロピレン／１−ブテン／エチレン三元共重合体（Ａ−１６）を使用した以外は実施例１と同様にして、平均粒子径０．２１μｍの水性分散体を得た。その付着性および耐水性の結果を表６に示す。
(Comparative Example 14)
Except for using propylene / 1-butene / ethylene terpolymer (A-16) instead of propylene / 1-butene / ethylene terpolymer (A-1), the same as in Example 1, An aqueous dispersion having an average particle size of 0.21 μm was obtained. The adhesion and water resistance results are shown in Table 6.
（比較例１５）
プロピレン／１−ブテン／エチレン三元共重合体（Ａ−１）の代わりにプロピレン／１−ブテン／エチレン三元共重合体（Ａ−１７）を使用した以外は実施例１と同様にして、平均粒子径０．２８μｍの水性分散体を得た。その付着性および耐水性の結果を表６に示す。
(Comparative Example 15)
Except for using propylene / 1-butene / ethylene terpolymer (A-17) instead of propylene / 1-butene / ethylene terpolymer (A-1), the same as in Example 1, An aqueous dispersion having an average particle size of 0.28 μm was obtained. The adhesion and water resistance results are shown in Table 6.
（比較例１６）
酸変性ポリオレフィン（Ｂ−１）の代わりに酸変性ポリオレフィン（Ｂ−５）を使用した以外は実施例５と同様にして、平均粒子径０．２４μｍの水性分散体を得た。その付着性および耐水性の結果を表７に示す。
(Comparative Example 16)
An aqueous dispersion having an average particle size of 0.24 μm was obtained in the same manner as in Example 5 except that the acid-modified polyolefin (B-5) was used instead of the acid-modified polyolefin (B-1). The adhesion and water resistance results are shown in Table 7.
（比較例１７）
酸変性ポリオレフィン（Ｂ−１）の代わりに酸変性ポリオレフィン（Ｂ−６）を使用した以外は実施例５と同様にして水性分散体を得ようとしたが、温水に希釈されず、凝集物ばかり生成して、水性分散体は得られなかった。
(Comparative Example 17)
An aqueous dispersion was obtained in the same manner as in Example 5 except that the acid-modified polyolefin (B-6) was used in place of the acid-modified polyolefin (B-1). As a result, an aqueous dispersion was not obtained.
（比較例１８）
酸変性ポリオレフィン（Ｂ−１）の代わりに酸変性ポリオレフィン（Ｂ−７）を使用した以外は実施例５と同様にして水性分散体を得ようとしたが、温水に希釈されず、凝集物ばかり生成して、水性分散体は得られなかった。
(Comparative Example 18)
An aqueous dispersion was obtained in the same manner as in Example 5 except that the acid-modified polyolefin (B-7) was used instead of the acid-modified polyolefin (B-1). As a result, an aqueous dispersion was not obtained.
（比較例１９）
酸変性ポリオレフィン（Ｂ−１）の代わりに酸変性ポリオレフィン（Ｂ−８）を使用した以外は実施例５と同様にして、平均粒子径０．３０μｍの水性分散体を得た。その付着性および耐水性の結果を表７に示す。
(Comparative Example 19)
An aqueous dispersion having an average particle size of 0.30 μm was obtained in the same manner as in Example 5 except that the acid-modified polyolefin (B-8) was used instead of the acid-modified polyolefin (B-1). The adhesion and water resistance results are shown in Table 7.
（比較例２０）
酸変性ポリオレフィン（Ｂ−１）の量を４部に変更した以外は実施例５と同様にして水性分散体を得ようとしたが、温水に希釈されず、凝集物ばかり生成して、水性分散体は得られなかった。
(Comparative Example 20)
An aqueous dispersion was obtained in the same manner as in Example 5 except that the amount of the acid-modified polyolefin (B-1) was changed to 4 parts. However, the aqueous dispersion was not diluted with warm water, but only aggregates were formed. No body was obtained.
（比較例２１）
酸変性ポリオレフィン（Ｂ−１）の量を２５部に変更した以外は実施例５と同様にして、平均粒子径０．２９μｍの水性分散体を得た。その付着性および耐水性の結果を表７に示す。
(Comparative Example 21)
An aqueous dispersion having an average particle size of 0.29 μm was obtained in the same manner as in Example 5 except that the amount of the acid-modified polyolefin (B-1) was changed to 25 parts. The adhesion and water resistance results are shown in Table 7.
（比較例２２）
オレイン酸カリウムの量を０．４部に変更した以外は実施例５と同様にして水性分散体を得ようとしたが、温水に希釈されず、凝集物ばかり生成して、水性分散体は得られなかった。
(Comparative Example 22)
An aqueous dispersion was tried to be obtained in the same manner as in Example 5 except that the amount of potassium oleate was changed to 0.4 part. However, the aqueous dispersion was not diluted with warm water but only aggregates were formed. I couldn't.
（比較例２３）
オレイン酸カリウムの量を１２部に変更した以外は実施例５と同様にして、平均粒子径０．３１μｍの水性分散体を得た。その付着性および耐水性の結果を表７に示す。
(Comparative Example 23)
An aqueous dispersion having an average particle size of 0.31 μm was obtained in the same manner as in Example 5 except that the amount of potassium oleate was changed to 12 parts. The adhesion and water resistance results are shown in Table 7.
（比較例２４）
水酸化カリウム水溶液を、ポリオレフィン１００部に対する水の量が０．３部になるように添加した以外は実施例５と同様にして水性分散体を得ようとしたが、温水に希釈されず、凝集物ばかり生成して、水性分散体は得られなかった。
(Comparative Example 24)
An aqueous dispersion was obtained in the same manner as in Example 5 except that an aqueous potassium hydroxide solution was added so that the amount of water relative to 100 parts of polyolefin was 0.3 parts. No matter how much was formed, no aqueous dispersion was obtained.
（比較例２５）
水酸化カリウム水溶液を、ポリオレフィン１００部に対する水の量が２２部になるように添加した以外は実施例５と同様にして、平均粒子径０．３８μｍの水性分散体を得た。その付着性および耐水性の結果を表７に示す。
(Comparative Example 25)
An aqueous dispersion having an average particle size of 0.38 μm was obtained in the same manner as in Example 5 except that an aqueous potassium hydroxide solution was added so that the amount of water relative to 100 parts of polyolefin was 22 parts. The adhesion and water resistance results are shown in Table 7.
特定のプロピレン／１−ブテン／エチレン三元共重合体（Ａ）と酸変性ポリオレフィン（Ｂ）とアニオン型界面活性剤（Ｃ）とを溶融混練して混練物を得る工程と、該混練物に水（Ｄ）を注入した後、さらに溶融混練する工程とを有する実施例１〜１５の製造方法で得た水性分散体は、ポリプロピレンに対する付着性に優れていた。また、水性分散体より得られる被膜の耐水性に優れていた。
これに対し、溶剤の存在下、オレイン酸カリウム量が１０質量部以下の条件で高速攪拌によりポリオレフィン（Ａ）を分散させた比較例１，２の製造方法では、水性分散体が得られなかった。
オレイン酸カリウムの添加量を増量した比較例３の製造方法では、水性分散体は得られたが、付着性および耐水性が低かった。
また、比較例３の製造方法に酸変性ポリオレフィン（Ｂ）を加えた比較例４でも、付着性、耐水性は低かった。
酸変性ポリオレフィン（Ｂ）を含むが、ポリオレフィン（Ａ）を含まない比較例５の製造方法では、平均粒子径０．４μｍのものが得られたが、付着性、耐水性は発現しなかった。
プロピレン単位が４０％未満のプロピレン／１−ブテン／エチレン三元共重合体（Ａ）を用いた比較例６の製造方法では、付着性および耐水性が低かった。
プロピレン単位が７０％を超えるプロピレン／１−ブテン／エチレン三元共重合体（Ａ）を用いた比較例７の製造方法では、付着性および耐水性が低かった。
１−ブテン単位が２０％未満のプロピレン／１−ブテン／エチレン三元共重合体（Ａ）を用いた比較例８の製造方法では、付着性および耐水性が低かった。
１−ブテン単位が４０％を超えるプロピレン／１−ブテン／エチレン三元共重合体（Ａ）を用いた比較例９の製造方法では、付着性および耐水性が低かった。
エチレン単位が５％未満のプロピレン／１−ブテン／エチレン三元共重合体（Ａ）を用いた比較例１０の製造方法では、付着性および耐水性が低かった。
エチレン単位が２５％を超えるプロピレン／１−ブテン／エチレン三元共重合体（Ａ）を用いた比較例１１の製造方法では、付着性および耐水性が低かった。
結晶化度が０．１％未満のプロピレン／１−ブテン／エチレン三元共重合体（Ａ）を用いた比較例１２の製造方法では、付着性および耐水性が低かった。
結晶化度が１６％を超えるプロピレン／１−ブテン／エチレン三元共重合体（Ａ）を用いた比較例１３の製造方法では、付着性および耐水性が低かった。
重量平均分子量が１２０，０００未満のプロピレン／１−ブテン／エチレン三元共重合体（Ａ）を用いた比較例１４の製造方法では、付着性および耐水性が低かった。
重量平均分子量が４００，０００を超えるプロピレン／１−ブテン／エチレン三元共重合体（Ａ）を用いた比較例１５の製造方法では、付着性および耐水性が低かった。
重量平均分子量が３５，０００を超える酸変性ポリオレフィン（Ｂ）を用いた比較例１６の製造方法では、付着性および耐水性が低かった。
重量平均分子量が１，８００未満の酸変性ポリオレフィン（Ｂ）を用いた比較例１７の製造方法では、水性分散体が得られなかった。
酸価が３ｍｇ／ｇ未満の酸変性ポリオレフィン（Ｂ）を用いた比較例１８の製造方法では、水性分散体が得られなかった。
酸価が８０ｍｇ／ｇを超える酸変性ポリオレフィン（Ｂ）を用いた比較例１９の製造方法では、付着性および耐水性が低かった。
酸変性ポリオレフィン（Ｂ）の添加量を５部未満とした比較例２０の製造方法では、水性分散体が得られなかった。
酸変性ポリオレフィン（Ｂ）の添加量を２０部より多くした比較例２１の製造方法では、付着性および耐水性が低かった。
オレイン酸カリウムの添加量が１部未満であった比較例２２の製造方法では、水性分散体が得られなかった。
オレイン酸カリウムの添加量が１０部を超えていた比較例２３の製造方法では、付着性および耐水性が低かった。
水の添加量が０．５部未満であった比較例２４の製造方法では、水性分散体が得られなかった。
水の添加量が２０部を超えていた比較例２５の製造方法では、付着性および耐水性が低かった。
A step of melt-kneading a specific propylene / 1-butene / ethylene terpolymer (A), acid-modified polyolefin (B) and an anionic surfactant (C) to obtain a kneaded product; After injecting water (D), the aqueous dispersion obtained by the production method of Examples 1 to 15 having a step of further melt-kneading was excellent in adhesion to polypropylene. Moreover, the water resistance of the film obtained from the aqueous dispersion was excellent.
In contrast, in the production methods of Comparative Examples 1 and 2 in which the polyolefin (A) was dispersed by high-speed stirring under the condition that the amount of potassium oleate was 10 parts by mass or less in the presence of a solvent, an aqueous dispersion could not be obtained. .
In the production method of Comparative Example 3 in which the amount of potassium oleate added was increased, an aqueous dispersion was obtained, but adhesion and water resistance were low.
Also in Comparative Example 4 in which acid-modified polyolefin (B) was added to the production method of Comparative Example 3, the adhesion and water resistance were low.
In the production method of Comparative Example 5 containing acid-modified polyolefin (B) but not containing polyolefin (A), an average particle size of 0.4 μm was obtained, but adhesion and water resistance were not expressed.
In the production method of Comparative Example 6 using the propylene / 1-butene / ethylene terpolymer (A) having a propylene unit of less than 40%, adhesion and water resistance were low.
In the production method of Comparative Example 7 using propylene / 1-butene / ethylene terpolymer (A) having a propylene unit exceeding 70%, adhesion and water resistance were low.
In the production method of Comparative Example 8 using the propylene / 1-butene / ethylene terpolymer (A) having a 1-butene unit of less than 20%, adhesion and water resistance were low.
In the production method of Comparative Example 9 using the propylene / 1-butene / ethylene terpolymer (A) having a 1-butene unit exceeding 40%, adhesion and water resistance were low.
In the production method of Comparative Example 10 using the propylene / 1-butene / ethylene terpolymer (A) having an ethylene unit of less than 5%, adhesion and water resistance were low.
In the production method of Comparative Example 11 using the propylene / 1-butene / ethylene terpolymer (A) having an ethylene unit exceeding 25%, adhesion and water resistance were low.
In the production method of Comparative Example 12 using the propylene / 1-butene / ethylene terpolymer (A) having a crystallinity of less than 0.1%, adhesion and water resistance were low.
In the production method of Comparative Example 13 using the propylene / 1-butene / ethylene terpolymer (A) having a crystallinity exceeding 16%, the adhesion and water resistance were low.
In the production method of Comparative Example 14 using the propylene / 1-butene / ethylene terpolymer (A) having a weight average molecular weight of less than 120,000, adhesion and water resistance were low.
In the production method of Comparative Example 15 using the propylene / 1-butene / ethylene terpolymer (A) having a weight average molecular weight exceeding 400,000, adhesion and water resistance were low.
In the production method of Comparative Example 16 using the acid-modified polyolefin (B) having a weight average molecular weight exceeding 35,000, adhesion and water resistance were low.
In the production method of Comparative Example 17 using the acid-modified polyolefin (B) having a weight average molecular weight of less than 1,800, an aqueous dispersion was not obtained.
In the production method of Comparative Example 18 using the acid-modified polyolefin (B) having an acid value of less than 3 mg / g, an aqueous dispersion was not obtained.
In the production method of Comparative Example 19 using the acid-modified polyolefin (B) having an acid value exceeding 80 mg / g, adhesion and water resistance were low.
In the production method of Comparative Example 20 in which the addition amount of the acid-modified polyolefin (B) was less than 5 parts, an aqueous dispersion could not be obtained.
In the production method of Comparative Example 21 in which the addition amount of the acid-modified polyolefin (B) was more than 20 parts, adhesion and water resistance were low.
In the production method of Comparative Example 22 in which the amount of potassium oleate added was less than 1 part, an aqueous dispersion could not be obtained.
In the production method of Comparative Example 23 in which the amount of potassium oleate added exceeded 10 parts, adhesion and water resistance were low.
In the production method of Comparative Example 24 in which the amount of water added was less than 0.5 part, an aqueous dispersion could not be obtained.
In the production method of Comparative Example 25 in which the amount of water added exceeded 20 parts, adhesion and water resistance were low.
Claims (2)
プロピレン／１−ブテン／エチレン三元共重合体（Ａ）は、プロピレン単位を４０〜７０質量％、１−ブテン単位を２０〜４０質量％、エチレン単位を５〜２５質量％含有し、かつ、重量平均分子量が１２０，０００〜４００，０００、結晶化度が０．１〜１６％であり、
酸変性ポリオレフィン（Ｂ）は、エチレン性不飽和カルボン酸またはその無水物で変性されたオレフィン系重合体であり、重量平均分子量が１，８００〜３５，０００、酸価が３〜８０ｍｇ／ｇであることを特徴とする水性分散体。 5 to 20 parts by mass of acid-modified polyolefin (B) with respect to 100 parts by mass of propylene / 1-butene / ethylene terpolymer (A) and propylene / 1-butene / ethylene terpolymer (A). ), 1 to 10 parts by weight of an anionic surfactant (C), and 0.5 to 20 parts by weight of water (D),
The propylene / 1-butene / ethylene terpolymer (A) contains 40 to 70% by mass of propylene units, 20 to 40% by mass of 1-butene units, 5 to 25% by mass of ethylene units, and The weight average molecular weight is 120,000 to 400,000, the crystallinity is 0.1 to 16%,
The acid-modified polyolefin (B) is an olefin polymer modified with an ethylenically unsaturated carboxylic acid or an anhydride thereof, and has a weight average molecular weight of 1,800 to 35,000 and an acid value of 3 to 80 mg / g. An aqueous dispersion characterized by being.
該混練物に、水（Ｄ）を、プロピレン／１−ブテン／エチレン三元共重合体（Ａ）１００質量部に対して０．５〜２０質量部添加した後、さらに溶融混練する工程とを有する水性分散体の製造方法であって、
プロピレン／１−ブテン／エチレン三元共重合体（Ａ）として、プロピレン単位を４０〜７０質量％、１−ブテン単位を２０〜４０質量％、エチレン単位を５〜２５質量％含有し、かつ、重量平均分子量が１２０，０００〜４００，０００、結晶化度が０．１〜１６％のものを用い、
酸変性ポリオレフィン（Ｂ）として、エチレン性不飽和カルボン酸またはその無水物で変性されたオレフィン系重合体であり、重量平均分子量が１，８００〜３５，０００、酸価が３〜８０ｍｇ／ｇのものを用いることを特徴とする水性分散体の製造方法。 5-20 parts by mass of acid-modified polyolefin (B) with respect to 100 parts by mass of propylene / 1-butene / ethylene terpolymer (A) and propylene / 1-butene / ethylene terpolymer (A) And a step of melt-kneading 1 to 10 parts by mass of an anionic surfactant (C) with respect to 100 parts by mass of propylene / 1-butene / ethylene terpolymer (A) to obtain a kneaded product,
Adding 0.5 to 20 parts by mass of water (D) to 100 parts by mass of propylene / 1-butene / ethylene terpolymer (A), and further melt-kneading the kneaded product. A method for producing an aqueous dispersion having
As propylene / 1-butene / ethylene terpolymer (A), it contains 40 to 70% by mass of propylene units, 20 to 40% by mass of 1-butene units, 5 to 25% by mass of ethylene units, and Using a weight average molecular weight of 120,000 to 400,000 and a crystallinity of 0.1 to 16%,
The acid-modified polyolefin (B) is an olefin polymer modified with an ethylenically unsaturated carboxylic acid or an anhydride thereof, having a weight average molecular weight of 1,800 to 35,000 and an acid value of 3 to 80 mg / g. What is claimed is: 1. A method for producing an aqueous dispersion, comprising:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007032621A JP5085151B2 (en) | 2007-02-13 | 2007-02-13 | Aqueous dispersion and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007032621A JP5085151B2 (en) | 2007-02-13 | 2007-02-13 | Aqueous dispersion and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2008195833A JP2008195833A (en) | 2008-08-28 |
| JP5085151B2 true JP5085151B2 (en) | 2012-11-28 |
Family
ID=39755079
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007032621A Active JP5085151B2 (en) | 2007-02-13 | 2007-02-13 | Aqueous dispersion and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5085151B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009173756A (en) * | 2008-01-23 | 2009-08-06 | Umg Abs Ltd | Aqueous dispersion, method for producing it, coating composition, and coated body |
| JP5049944B2 (en) * | 2008-10-31 | 2012-10-17 | ユーエムジー・エービーエス株式会社 | Aqueous dispersion, coating composition and painted body |
| CN102257209B (en) * | 2008-12-25 | 2013-04-10 | 三井化学株式会社 | Aqueous dispersion for treatment of fibers |
| JP5586509B2 (en) * | 2011-03-18 | 2014-09-10 | ユーエムジー・エービーエス株式会社 | Method for producing acid-modified olefin-based aqueous dispersion |
| CN109689738A (en) * | 2016-09-27 | 2019-04-26 | 陶氏环球技术有限责任公司 | Composite polymer particle and the method for preparing particle |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004010651A (en) * | 2002-06-04 | 2004-01-15 | Mitsui Chemicals Inc | Olefin resin aqueous dispersion |
| JP5063953B2 (en) * | 2006-08-08 | 2012-10-31 | ユーエムジー・エービーエス株式会社 | Aqueous dispersion and method for producing the same |
-
2007
- 2007-02-13 JP JP2007032621A patent/JP5085151B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2008195833A (en) | 2008-08-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5323321B2 (en) | Aqueous dispersion and method for producing the same | |
| KR100756744B1 (en) | Aqueous dispersion | |
| JP5374488B2 (en) | Aqueous dispersion composition imparting chipping resistance | |
| JP5114116B2 (en) | Aqueous dispersion and method for producing the same, and aqueous dispersion mixture | |
| JP2006199961A (en) | Water-based flock adhesives for thermoplastic substrate | |
| JP5085151B2 (en) | Aqueous dispersion and method for producing the same | |
| JP2009091426A (en) | Aqueous dispersion, its manufacturing method and layered product | |
| JP4892410B2 (en) | Aqueous dispersion and method for producing the same | |
| JP2011046777A (en) | Aqueous dispersion of polyolefin-based conjugated resin and method for producing the same | |
| JP5049944B2 (en) | Aqueous dispersion, coating composition and painted body | |
| JP2008056746A (en) | Aqueous emulsified dispersion of polyolefin resin and its production method | |
| JPH11193340A (en) | Aqueous dispersion and its production | |
| WO2019225731A1 (en) | Resin material, aqueous solution, and adhesive | |
| JP5063953B2 (en) | Aqueous dispersion and method for producing the same | |
| JP2009173756A (en) | Aqueous dispersion, method for producing it, coating composition, and coated body | |
| JP2002012812A (en) | Water-based coating material | |
| JP5037012B2 (en) | Method for producing aqueous polyolefin resin dispersion | |
| JP3470331B2 (en) | Aqueous dispersion | |
| JP5586509B2 (en) | Method for producing acid-modified olefin-based aqueous dispersion | |
| JP2011016991A (en) | Aqueous emulsion | |
| JP2013127069A (en) | Water-base resin-dispersed composition | |
| JP2019123791A (en) | Aqueous dispersion and method for producing the same, and coating material | |
| JP2012149199A (en) | Aqueous coating material composition and method for producing the same | |
| US20210395505A1 (en) | A thermoplastic vulcanate-like material | |
| TW202104414A (en) | Aqueous dispersion composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20091224 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20110922 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110927 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20111125 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20120828 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20120905 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5085151 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150914 Year of fee payment: 3 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |