JP7032839B1 - Polyolefin resin aqueous dispersion and its manufacturing method - Google Patents
Polyolefin resin aqueous dispersion and its manufacturing method Download PDFInfo
- Publication number
- JP7032839B1 JP7032839B1 JP2021125838A JP2021125838A JP7032839B1 JP 7032839 B1 JP7032839 B1 JP 7032839B1 JP 2021125838 A JP2021125838 A JP 2021125838A JP 2021125838 A JP2021125838 A JP 2021125838A JP 7032839 B1 JP7032839 B1 JP 7032839B1
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- JP
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- Prior art keywords
- polyolefin resin
- aqueous dispersion
- particle size
- less
- coating film
- 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.)
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- 239000006185 dispersion Substances 0.000 title claims abstract description 127
- 229920005672 polyolefin resin Polymers 0.000 title claims abstract description 103
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 239000002245 particle Substances 0.000 claims abstract description 82
- 239000011248 coating agent Substances 0.000 claims abstract description 66
- 238000000576 coating method Methods 0.000 claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 36
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000012736 aqueous medium Substances 0.000 claims abstract description 18
- 238000007561 laser diffraction method Methods 0.000 claims abstract description 16
- 238000002296 dynamic light scattering Methods 0.000 claims abstract description 15
- 238000009826 distribution Methods 0.000 claims abstract description 14
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract 2
- 238000001816 cooling Methods 0.000 claims description 45
- 238000003756 stirring Methods 0.000 claims description 24
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 28
- 230000004888 barrier function Effects 0.000 abstract description 21
- 230000002265 prevention Effects 0.000 abstract description 14
- 230000007547 defect Effects 0.000 abstract description 12
- 238000010586 diagram Methods 0.000 abstract 1
- -1 ethylene, propylene, isoprene Chemical class 0.000 description 34
- 229920001577 copolymer Polymers 0.000 description 32
- 239000003960 organic solvent Substances 0.000 description 28
- 229920005989 resin Polymers 0.000 description 24
- 239000011347 resin Substances 0.000 description 24
- 238000001035 drying Methods 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 16
- 239000000853 adhesive Substances 0.000 description 14
- 230000001070 adhesive effect Effects 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 14
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 13
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- 239000011976 maleic acid Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 7
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 7
- 150000007514 bases Chemical class 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 7
- 239000003995 emulsifying agent Substances 0.000 description 7
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 6
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000001993 wax Substances 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 239000010954 inorganic particle Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 description 3
- FYZUENZXIZCLAZ-UHFFFAOYSA-N 2-methylhept-2-enoic acid Chemical compound CCCCC=C(C)C(O)=O FYZUENZXIZCLAZ-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000012972 dimethylethanolamine Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 229920001567 vinyl ester resin Polymers 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- JJYWRQLLQAKNAD-UHFFFAOYSA-N 2-methylpent-2-enoic acid Chemical compound CCC=C(C)C(O)=O JJYWRQLLQAKNAD-UHFFFAOYSA-N 0.000 description 2
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 2
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- UIERETOOQGIECD-UHFFFAOYSA-N Angelic acid Natural products CC=C(C)C(O)=O UIERETOOQGIECD-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 229910001335 Galvanized steel Inorganic materials 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000008397 galvanized steel Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000012875 nonionic emulsifier Substances 0.000 description 2
- 229920006284 nylon film Polymers 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000003449 preventive effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UIERETOOQGIECD-ONEGZZNKSA-N tiglic acid Chemical compound C\C=C(/C)C(O)=O UIERETOOQGIECD-ONEGZZNKSA-N 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- QKWWDTYDYOFRJL-UHFFFAOYSA-N 2,2-dimethoxyethanamine Chemical compound COC(CN)OC QKWWDTYDYOFRJL-UHFFFAOYSA-N 0.000 description 1
- RXDAPJJFRLSRPX-UHFFFAOYSA-N 2,3-dimethoxypropan-1-ol Chemical compound COCC(CO)OC RXDAPJJFRLSRPX-UHFFFAOYSA-N 0.000 description 1
- GFTPTQVIOIDDRL-UHFFFAOYSA-N 2,3-dimethylbutane-1,2,3-triol Chemical compound CC(C)(O)C(C)(O)CO GFTPTQVIOIDDRL-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/05—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
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Abstract
【課題】外観欠点が抑制され、バリア性、防錆性に優れる塗膜を得ることができる、ポリオレフィン樹脂水性分散体を提供する。【解決手段】ポリオレフィン樹脂粒子および水性媒体を含有するポリオレフィン樹脂水性分散体である。ポリオレフィン樹脂が不飽和カルボン酸成分0.1~10質量%と(メタ)アクリル酸エステル成分1~20質量%とを含む。ポリオレフィン樹脂粒子の動的光散乱法で測定した体積平均粒子径が0.3μm以下であって、かつレーザー回折法で測定した体積粒度分布において、小粒径側から積算した体積粒子径積算分布の99.9%径が10μm以下である。【選択図】なしPROBLEM TO BE SOLVED: To provide an aqueous polyolefin resin dispersion capable of obtaining a coating film excellent in barrier property and rust prevention property while suppressing appearance defects. A polyolefin resin aqueous dispersion containing polyolefin resin particles and an aqueous medium. The polyolefin resin contains an unsaturated carboxylic acid component of 0.1 to 10% by mass and a (meth) acrylic acid ester component of 1 to 20% by mass. The volume average particle size measured by the dynamic light scattering method of the polyolefin resin particles is 0.3 μm or less, and the volume particle size distribution measured by the laser diffraction method shows the volume particle size integrated distribution integrated from the small particle size side. The 99.9% diameter is 10 μm or less. [Selection diagram] None
Description
本発明は、ポリオレフィン樹脂の水性分散体に関する。 The present invention relates to an aqueous dispersion of a polyolefin resin.
ポリオレフィン樹脂の水性分散体は、様々な基材に対して優れた密着性を有する塗膜が得られることから、幅広い用途へ展開されている。なかでも、(メタ)アクリル酸エステルを共重合成分として含む酸変性ポリオレフィン樹脂を用いた水性分散体は、使用できる基材の汎用性が高く、コーティング剤、接着剤等に広く用いられている(例えば、特許文献1)。 Aqueous dispersions of polyolefin resins have been developed into a wide range of applications because they can obtain coating films having excellent adhesion to various substrates. Among them, an aqueous dispersion using an acid-modified polyolefin resin containing (meth) acrylic acid ester as a copolymerization component has high versatility as a usable base material, and is widely used as a coating agent, an adhesive, etc. ( For example, Patent Document 1).
前記水性分散体から得られる塗膜の用途の中でも、特に、湿度のような周囲環境に影響を受け易い用途、または長期間安定して内容物を保管する用途(金属製品、電子機器、自動車部品、包装材料等)においては、バリア性や防錆性が求められる場合があり、性能向上が望まれている。 Among the applications of the coating film obtained from the aqueous dispersion, in particular, applications that are easily affected by the surrounding environment such as humidity, or applications that stably store the contents for a long period of time (metal products, electronic devices, automobile parts). , Packaging materials, etc.) may be required to have barrier properties and rust prevention properties, and improvement in performance is desired.
本発明者らは、上記課題を解決するために鋭意検討した結果、特定組成のポリオレフィン樹脂の水性分散体において、従来の一般的な樹脂粒子径の測定方法である動的光散乱法では確認できなかった粗大な樹脂粒子の存在が、塗膜とした場合の外観欠点(ブツ、クラック等)につながり、その結果、バリア性や防錆性の低下要因となることを突き止めた。
すなわち、本発明者は、レーザー回折法を用いて測定された樹脂粒子径が特定範囲であるポリオレフィン樹脂粒子を含有する水性分散体は、粗大な樹脂粒子を含まず均一に水性媒体に分散しているので、塗膜の外観欠点が抑制され、バリア性、防錆性に優れることを見出し、本発明に達した。すなわち本発明の要旨は下記の通りである。
(1)ポリオレフィン樹脂粒子および水性媒体を含有するポリオレフィン樹脂水性分散体であって、ポリオレフィン樹脂が不飽和カルボン酸成分0.1~10質量%と、(メタ)アクリル酸エステル成分1~20質量%とを含み、ポリオレフィン樹脂粒子の動的光散乱法で測定した体積平均粒子径が0.3μm以下であって、かつレーザー回折法で測定した体積粒度分布において、小粒子径側から積算した体積粒子径積算分布の99.9%径が10μm以下である、ポリオレフィン樹脂水性分散体。
(2)(1)のポリオレフィン樹脂水性分散体から得られた塗膜。
(3)(1)のポリオレフィン樹脂水性分散体を製造する方法であって、110℃以上の温度で、ポリオレフィン樹脂と水性媒体とを攪拌する攪拌工程後に、1℃/分以下の速度で冷却する冷却工程を含む、ポリオレフィン樹脂水性分散体の製造方法。
(4)冷却工程が、1℃/分以下の冷却速度で最高温度から100℃以下かつ40℃を超える温度に冷却する第一の冷却工程後に、3℃/分以下の冷却速度で40℃以下に冷却する第二の冷却工程を含む、(3)のポリオレフィン樹脂水性分散体の製造方法。
(5)攪拌工程が、110℃以上かつ、ポリオレフィン樹脂の融点よりも20℃以上高い温度で攪拌するものである、(3)または(4)のポリオレフィン樹脂水性分散体の製造方法。
As a result of diligent studies to solve the above problems, the present inventors have confirmed that an aqueous dispersion of a polyolefin resin having a specific composition can be confirmed by a dynamic light scattering method, which is a conventional general method for measuring a resin particle size. It was found that the presence of the coarse resin particles that did not exist leads to appearance defects (bumps, cracks, etc.) in the case of a coating film, and as a result, it becomes a factor of lowering the barrier property and the rust resistance.
That is, the present inventor has determined that the aqueous dispersion containing the polyolefin resin particles having a resin particle diameter in a specific range measured by the laser diffraction method is uniformly dispersed in the aqueous medium without containing coarse resin particles. Therefore, it has been found that the appearance defects of the coating film are suppressed and the barrier property and the rust prevention property are excellent, and the present invention has been achieved. That is, the gist of the present invention is as follows.
(1) A polyolefin resin aqueous dispersion containing polyolefin resin particles and an aqueous medium, wherein the polyolefin resin has an unsaturated carboxylic acid component of 0.1 to 10% by mass and a (meth) acrylic acid ester component of 1 to 20% by mass. The volume average particle size measured by the dynamic light scattering method of the polyolefin resin particles is 0.3 μm or less, and the volume particles integrated from the small particle size side in the volume particle size distribution measured by the laser diffraction method. A polyolefin resin aqueous dispersion having a 99.9% diameter of a diameter integrated distribution of 10 μm or less.
(2) A coating film obtained from the polyolefin resin aqueous dispersion of (1).
(3) The method for producing an aqueous dispersion of a polyolefin resin according to (1), which is cooled at a rate of 1 ° C./min or less after a stirring step of stirring the polyolefin resin and the aqueous medium at a temperature of 110 ° C. or higher. A method for producing an aqueous dispersion of a polyolefin resin, which comprises a cooling step.
(4) After the first cooling step in which the cooling step cools from the maximum temperature to a temperature of 100 ° C. or lower and more than 40 ° C. at a cooling rate of 1 ° C./min or less, the cooling rate is 40 ° C. or lower at a cooling rate of 3 ° C./min or less. The method for producing an aqueous dispersion of a polyolefin resin according to (3), which comprises a second cooling step of cooling.
(5) The method for producing an aqueous dispersion of a polyolefin resin according to (3) or (4), wherein the stirring step is stirring at a temperature of 110 ° C. or higher and 20 ° C. or higher higher than the melting point of the polyolefin resin.
本発明のポリオレフィン樹脂水性分散体は、ポリオレフィン樹脂粒子が小さい粒子径で安定的に、かつ粗大な粒子を含まず均一に水性媒体に分散しているので、得られた塗膜は、外観欠点が抑制され、バリア性、防錆性に優れる。 In the polyolefin resin aqueous dispersion of the present invention, the polyolefin resin particles are stably dispersed in the aqueous medium with a small particle size and do not contain coarse particles, so that the obtained coating film has a defect in appearance. It is suppressed and has excellent barrier properties and rust resistance.
本発明のポリオレフィン樹脂水性分散体(以下、単に「水性分散体」と称する場合がある)は、ポリオレフィン樹脂粒子および水性媒体を含む。
ポリオレフィン樹脂粒子は、2種類の方法(動的光散乱法、およびレーザー回折法)で測定される粒子径が、何れも特定範囲を満足するものである。
The polyolefin resin aqueous dispersion of the present invention (hereinafter, may be simply referred to as “aqueous dispersion”) includes polyolefin resin particles and an aqueous medium.
The particle size of the polyolefin resin particles measured by two types of methods (dynamic light scattering method and laser diffraction method) satisfies a specific range.
本発明の水性分散体に含有されるポリオレフィン樹脂粒子は、微細かつ安定に分散される観点から、動的光散乱法で測定した体積平均粒子径が0.3μm以下であり、0.25μm以下であることが好ましく、0.2μm以下であることがより好ましく、0.15μm以下であることがさらに好ましい。
体積平均粒子径は、例えば、後述の製造方法において、添加させる塩基性化合物や有機溶剤の種類の選択や、これらの添加量の調整により、制御することができる。
The polyolefin resin particles contained in the aqueous dispersion of the present invention have a volume average particle diameter of 0.3 μm or less and 0.25 μm or less as measured by a dynamic light scattering method from the viewpoint of fine and stable dispersion. It is preferably 0.2 μm or less, more preferably 0.15 μm or less, and further preferably 0.15 μm or less.
The volume average particle size can be controlled, for example, by selecting the types of basic compounds and organic solvents to be added and adjusting the amount of these additions in the production method described later.
さらに、本発明の水性分散体に含有されるポリオレフィン樹脂粒子は、レーザー回折法で測定した際に得られる体積粒度分布において、小粒径側から積算した体積粒子径積算分布の99.9%径(以下、単に「99.9%径」と称する場合がある)が10μm以下であり、7μm以下が好ましく、5μm以下がより好ましく、2μm以下がさらに好ましく、1μm以下が特に好ましい。 Further, the polyolefin resin particles contained in the aqueous dispersion of the present invention have a 99.9% diameter of the volume particle size integrated distribution integrated from the small particle size side in the volume particle size distribution obtained when measured by the laser diffraction method. (Hereinafter, it may be simply referred to as "99.9% diameter") is 10 μm or less, preferably 7 μm or less, more preferably 5 μm or less, further preferably 2 μm or less, and particularly preferably 1 μm or less.
水性分散体中に含有される樹脂粒子径の測定方法としては、動的光散乱法が一般的である。動的光散乱法の原理による粒子径測定可能範囲は1nm~数μm程度とされており、水性分散体の性能評価に必要な範囲をほぼ網羅するからである。これに対して、レーザー回折法の測定可能範囲は10nm~3000μm程度であり、動的光散乱法の測定可能上限をはるかに超える、大きな粒子径の測定が可能である。
本発明者は、ポリオレフィン樹脂水性分散体の動的光散乱法による粒子径測定結果およびレーザー回折法による粒子径測定結果に着目した結果、動的光散乱法において十分に平均粒子径が小さい場合であっても、動的光散乱法の測定可能範囲上限を超える粗大粒子がレーザー回折法で観測される場合があるとの知見を得た。そして、動的光散乱法で測定した体積平均粒子径が0.3μm以下で、かつ、レーザー回折法により概ね10μmを超える粒子が観測されないこと、言い換えれば、レーザー回折法の体積粒度分布における99.9%径が10μm以下であれば、こうした水性分散体から得られる塗膜の外観欠点が抑制され、バリア性、防錆性に優れることを見出したのである。
A dynamic light scattering method is generally used as a method for measuring the diameter of resin particles contained in an aqueous dispersion. This is because the particle size measurable range based on the principle of the dynamic light scattering method is about 1 nm to several μm, which almost covers the range necessary for the performance evaluation of the aqueous dispersion. On the other hand, the measurable range of the laser diffraction method is about 10 nm to 3000 μm, and it is possible to measure a large particle size far exceeding the measurable upper limit of the dynamic light scattering method.
As a result of paying attention to the particle size measurement result by the dynamic light scattering method and the particle size measurement result by the laser diffraction method of the polyolefin resin aqueous dispersion, the present inventor has a case where the average particle size is sufficiently small in the dynamic light scattering method. Even so, it was found that coarse particles exceeding the upper limit of the measurable range of the dynamic light scattering method may be observed by the laser diffraction method. The volume average particle diameter measured by the dynamic light scattering method is 0.3 μm or less, and no particles exceeding about 10 μm are observed by the laser diffraction method. In other words, 99. In the volume particle size distribution of the laser diffraction method. It has been found that when the 9% diameter is 10 μm or less, the appearance defects of the coating film obtained from such an aqueous dispersion are suppressed, and the barrier property and the rust resistance are excellent.
樹脂粒子径を上記のレーザー回折法による99.9%径を特定範囲とするための手法としては、後述する本発明の水性分散体の製造方法において、ポリオレフィン樹脂を分散させる際の平均冷却速度を特定の範囲とすることが好ましい。 As a method for setting the resin particle diameter to a specific range of 99.9% diameter by the above laser diffraction method, the average cooling rate when dispersing the polyolefin resin in the method for producing an aqueous dispersion of the present invention described later is used. It is preferably in a specific range.
ポリオレフィン樹脂の主成分であるオレフィン成分は、特に限定されないが、エチレン、プロピレン、イソブチレン、2-ブテン、1-ブテン、1-ペンテン、1-ヘキセン、1-オクテン、4-メチル-1-ペンテン、3-メチル-1-ペンテン、ノルボルネン類等のアルケン類、ブタジエンやイソプレン等のジエン類等が挙げられる。これらの混合物であってもよい。また、オレフィン成分の2種類以上が共重合されたものを用いてもよい。 The olefin component which is the main component of the polyolefin resin is not particularly limited, but ethylene, propylene, isoprene, 2-butene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, Examples thereof include alkenes such as 3-methyl-1-pentene and norbornene, and dienes such as butadiene and isoprene. It may be a mixture of these. Further, those obtained by copolymerizing two or more kinds of olefin components may be used.
ポリオレフィン樹脂は、不飽和カルボン酸成分を含有する。不飽和カルボン酸成分としては、例えば、アクリル酸、メタクリル酸、マレイン酸、無水マレイン酸、イタコン酸、無水イタコン酸、フマル酸、クロトン酸等のほか、不飽和ジカルボン酸のハーフエステル、ハーフアミド等が挙げられる。中でも、接着性にいっそう優れる観点から、アクリル酸、メタクリル酸、マレイン酸、無水マレイン酸が好ましく、特にアクリル酸、無水マレイン酸が好ましい。 The polyolefin resin contains an unsaturated carboxylic acid component. Examples of the unsaturated carboxylic acid component include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid and the like, as well as unsaturated dicarboxylic acid half esters and halfamides. Can be mentioned. Of these, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are preferable, and acrylic acid and maleic anhydride are particularly preferable, from the viewpoint of further excellent adhesiveness.
ポリオレフィン樹脂中の不飽和カルボン酸成分は、ランダム共重合、ブロック共重合、グラフト共重合(グラフト変性)等により含有される。 The unsaturated carboxylic acid component in the polyolefin resin is contained by random copolymerization, block copolymerization, graft copolymerization (graft modification) and the like.
ポリオレフィン樹脂における不飽和カルボン酸成分の含有量は0.1~10質量%であり、1~8質量%であることが好ましく、2~5質量%であることがより好ましい。含有量が0.1質量%未満であると、ポリオレフィン樹脂粒子の2種類の粒子径が特定範囲である水性分散体を得ることが困難となったり、樹脂の水性分散化が困難となることがある。また、10質量%を超えると、オレフィン樹脂の有する低吸水性や耐水性が失われるため、上記の2種類の粒子径が特定範囲であっても、塗膜とした際のバリア性や防錆性に劣る場合がある。 The content of the unsaturated carboxylic acid component in the polyolefin resin is 0.1 to 10% by mass, preferably 1 to 8% by mass, and more preferably 2 to 5% by mass. If the content is less than 0.1% by mass, it may be difficult to obtain an aqueous dispersion in which the particle diameters of the two types of polyolefin resin particles are in a specific range, or it may be difficult to disperse the resin in water. be. Further, if it exceeds 10% by mass, the low water absorption and water resistance of the olefin resin are lost. Therefore, even if the above two types of particle diameters are in a specific range, the barrier property and rust prevention when the coating film is formed. It may be inferior in sex.
ポリオレフィン樹脂における(メタ)アクリル酸エステル成分の含有量は1~20質量%であり、2~19質量%であることがより好ましく、4~18質量%であることがさらに好ましい。
(メタ)アクリル酸エステル成分の含有量が上記範囲を外れると、上記の2種類の粒子径が特定範囲であっても、塗膜とした際のバリア性や防錆性に劣るものとなる。
(メタ)アクリル酸エステル成分としては、例えば、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸ブチル等の(メタ)アクリル酸エステル成分、マレイン酸ジメチル、マレイン酸ジエチル、マレイン酸ジブチル等のマレイン酸ジエステル成分、メチルビニルエーテル、エチルビニルエーテル等のアルキルビニルエーテル成分、ギ酸ビニル、酢酸ビニル、プロピオン酸ビニル、ピバリン酸ビニル、バーサチック酸ビニル等のビニルエステル成分、ビニルエステル成分を塩基性化合物等でケン化して得られるビニルアルコール、(メタ)アクリル酸アミド成分等が挙げられ、これらの混和物であってもよい。中でも、(メタ)アクリル酸エステル成分、ビニルエステル成分が好ましく、(メタ)アクリル酸エステル成分がより好ましい。なお、「(メタ)アクリル酸~」とは、「アクリル酸~またはメタクリル酸~」を意味する。
The content of the (meth) acrylic acid ester component in the polyolefin resin is 1 to 20% by mass, more preferably 2 to 19% by mass, and further preferably 4 to 18% by mass.
When the content of the (meth) acrylic acid ester component is out of the above range, even if the above two types of particle diameters are in the specific range, the barrier property and the rust preventive property when formed into a coating film are inferior.
Examples of the (meth) acrylic acid ester component include (meth) acrylic acid ester components such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate, dimethyl maleate, diethyl maleate, and the like. Basic maleic acid diester components such as dibutyl maleate, alkyl vinyl ether components such as methyl vinyl ether and ethyl vinyl ether, vinyl ester components such as vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl versatic acid, and vinyl ester components. Examples thereof include vinyl alcohol obtained by saponification with a compound and the like, a (meth) acrylic acid amide component, and a mixture thereof may be used. Among them, the (meth) acrylic acid ester component and the vinyl ester component are preferable, and the (meth) acrylic acid ester component is more preferable. In addition, "(meth) acrylic acid-" means "acrylic acid-or methacrylic acid-".
ポリオレフィン樹脂の具体例としては、エチレン/アクリル酸メチル/無水マレイン酸共重合体、エチレン/メタアクリル酸メチル/無水マレイン酸共重合体、エチレン/アクリル酸エチル/無水マレイン酸共重合体、エチレン/メタアクリル酸エチル/無水マレイン酸共重合体、エチレン/アクリル酸ブチル/無水マレイン酸共重合体、エチレン/メタアクリル酸ブチル/無水マレイン酸共重合体、プロピレン/1-ブテン/アクリル酸メチル/無水マレイン酸共重合体、プロピレン/1-ブテン/メタアクリル酸メチル/無水マレイン酸共重合体、プロピレン/1-ブテン/アクリル酸エチル/無水マレイン酸共重合体、プロピレン/1-ブテン/メタアクリル酸エチル/無水マレイン酸共重合体、プロピレン/1-ブテン/アクリル酸ブチル/無水マレイン酸共重合体、プロピレン/1-ブテン/メタアクリル酸ブチル/無水マレイン酸共重合体、プロピレン/アクリル酸メチル/無水マレイン酸共重合体、プロピレン/メタアクリル酸メチル/無水マレイン酸共重合体、プロピレン/アクリル酸エチル/無水マレイン酸共重合体、プロピレン/メタアクリル酸エチル/無水マレイン酸共重合体、プロピレン/アクリル酸ブチル/無水マレイン酸共重合体、プロピレン/メタアクリル酸ブチル/無水マレイン酸共重合体、エチレン/プロピレン/アクリル酸メチル/無水マレイン酸共重合体、エチレン/プロピレン/メタアクリル酸メチル/無水マレイン酸共重合体、エチレン/プロピレン/アクリル酸エチル/無水マレイン酸共重合体、エチレン/プロピレン/メタアクリル酸エチル/無水マレイン酸共重合体、エチレン/プロピレン/アクリル酸ブチル/無水マレイン酸共重合体、エチレン/プロピレン/メタアクリル酸ブチル/無水マレイン酸共重合体、等が挙げられる。 Specific examples of the polyolefin resin include ethylene / methyl acrylate / maleic anhydride copolymer, ethylene / methyl methacrylate / maleic anhydride copolymer, ethylene / ethyl acrylate / maleic anhydride copolymer, and ethylene / Ethyl methacrylic acid / maleic anhydride copolymer, ethylene / butyl acrylate / maleic anhydride copolymer, ethylene / butyl methacrylic acid / maleic anhydride copolymer, propylene / 1-butene / methyl acrylate / anhydrous Maleic acid copolymer, propylene / 1-butene / methyl methacrylic acid / maleic anhydride copolymer, propylene / 1-butene / ethyl acrylate / maleic anhydride copolymer, propylene / 1-butene / methacrylic acid Ethyl / maleic anhydride copolymer, propylene / 1-butene / butyl acrylate / maleic anhydride copolymer, propylene / 1-butene / butyl methacrylic acid / maleic anhydride copolymer, propylene / methyl acrylate / Maleic anhydride copolymer, propylene / methyl methacrylic acid / maleic anhydride copolymer, propylene / ethyl acrylate / maleic anhydride copolymer, propylene / ethyl methacrylate / maleic anhydride copolymer, propylene / Butyl acrylate / maleic anhydride copolymer, propylene / butyl methacrylic acid / maleic anhydride copolymer, ethylene / propylene / methyl acrylate / maleic anhydride copolymer, ethylene / propylene / methyl methacrylate / anhydrous Maleic acid copolymer, ethylene / propylene / ethyl acrylate / maleic anhydride copolymer, ethylene / propylene / ethyl methacrylic acid / maleic anhydride copolymer, ethylene / propylene / butyl acrylate / maleic anhydride copolymer Examples thereof include coalescence, ethylene / propylene / butyl methacrylate / maleic anhydride copolymer, and the like.
ポリオレフィン樹脂は5~40質量%の範囲で塩素化されていてもよい。 The polyolefin resin may be chlorinated in the range of 5 to 40% by mass.
ポリオレフィン樹脂は、N,N-ジメチルアミノエチル基、N,N-ジメチルアミノプロピル基、N,N-ジメチルアミノブチル基、N,N-ジエチルアミノエチル基、N,N-ジエチルアミノプロピル基、N,N-ジエチルアミノブチル基等の、N-置換イミド単位を含有していてもよい。 The polyolefin resin includes N, N-dimethylaminoethyl group, N, N-dimethylaminopropyl group, N, N-dimethylaminobutyl group, N, N-diethylaminoethyl group, N, N-diethylaminopropyl group, N, N. -It may contain an N-substituted imide unit such as a diethylaminobutyl group.
本発明の水性分散体は、ポリオレフィン樹脂粒子が水性媒体中に分散されている。本発明において水性媒体とは水を主成分とする液体であり、後述する有機溶剤や塩基性化合物を含有していてもよい。 In the aqueous dispersion of the present invention, polyolefin resin particles are dispersed in an aqueous medium. In the present invention, the aqueous medium is a liquid containing water as a main component, and may contain an organic solvent or a basic compound described later.
本発明の水性分散体は、得られる塗膜のバリア性に優れるものである。バリア性は、水蒸気透過度を指標とするものであり、本発明においては、80℃で乾燥して得られた塗膜の水蒸気透過度が150ml/(m2・day・MPa)以下であることが好ましく、100ml/(m2・day・MPa)以下であることがより好ましい。水蒸気透過度の測定方法は、実施例において詳述する。 The aqueous dispersion of the present invention is excellent in the barrier property of the obtained coating film. The barrier property is based on the water vapor transmission rate, and in the present invention, the water vapor transmission rate of the coating film obtained by drying at 80 ° C. is 150 ml / (m 2 , day, MPa) or less. Is preferable, and it is more preferably 100 ml / (m 2 , day, MPa) or less. The method for measuring the water vapor transmission rate will be described in detail in Examples.
本発明の水性分散体は、得られる塗膜の防錆性に優れるものである。本発明においては、金属板上に80℃で乾燥して得られた塗膜に対して、NaCl水溶液の噴霧を行い、100時間後の発錆面積率50%未満であることが好ましい。発錆面積率の算出方法は、実施例において詳述する。 The aqueous dispersion of the present invention is excellent in rust prevention property of the obtained coating film. In the present invention, it is preferable that the coating film obtained by drying at 80 ° C. on a metal plate is sprayed with an aqueous solution of NaCl, and the rusted area ratio is less than 50% after 100 hours. The method of calculating the rusted area ratio will be described in detail in Examples.
上記のように、本発明の水性分散体においては、ポリオレフィン樹脂粒子が小さい粒子径で安定的に、かつ粗大な樹脂粒子を含まず均一に水性媒体に分散しているので、外観欠点を抑制することができ、バリア性、防錆性に優れた塗膜を得ることができる。 As described above, in the aqueous dispersion of the present invention, the polyolefin resin particles are stably dispersed in the aqueous medium with a small particle size and do not contain coarse resin particles, so that appearance defects are suppressed. It is possible to obtain a coating film having excellent barrier properties and rust resistance.
本発明の水性分散体は、不揮発性水性化助剤の使用を排除するものではないが、不揮発性水性化助剤を実質的に含有しないことが好ましい。本発明においては不揮発性水性化助剤を実質的に含有せずとも、ポリオレフィン樹脂粒子の分散安定性に優れ、かつ粗大な樹脂粒子が存在しない水性分散体を製造することが可能である。 The aqueous dispersion of the present invention does not preclude the use of the non-volatile aqueous aid, but preferably does not substantially contain the non-volatile aqueous aid. In the present invention, it is possible to produce an aqueous dispersion having excellent dispersion stability of the polyolefin resin particles and free of coarse resin particles without substantially containing a non-volatile aqueous auxiliary.
ここで、「水性化助剤」とは、水性分散体の製造において、水性分散化促進や水性分散体の安定化の目的で添加される薬剤や化合物のことであり、「不揮発性」とは、常圧での沸点を有さないか、もしくは常圧で高沸点(例えば300℃以上)であることを指す。 Here, the "aqueous auxiliary" is a drug or compound added for the purpose of promoting the aqueous dispersion and stabilizing the aqueous dispersion in the production of the aqueous dispersion, and the "nonvolatile" is used. It means that it does not have a boiling point at normal pressure or has a high boiling point at normal pressure (for example, 300 ° C. or higher).
「不揮発性水性化助剤を実質的に含有しない」とは、こうした助剤を製造時(ポリオレフィン樹脂の水性分散化時)に用いず、得られる水性分散体が結果的にこの助剤を含有しないことを意味する。不揮発性水性化助剤は、ポリオレフィン樹脂成分に対して5質量%以下であることが好ましく、より好ましくは2質量%以下、さらに好ましくは0.5質量%未満であり、0質量%であることが最も好ましい。 "Substantially free of non-volatile aqueous auxiliary" means that such an auxiliary is not used at the time of production (at the time of aqueous dispersion of the polyolefin resin), and the obtained aqueous dispersion eventually contains this auxiliary. Means not. The non-volatile aqueous aid is preferably 5% by mass or less, more preferably 2% by mass or less, still more preferably less than 0.5% by mass, and 0% by mass with respect to the polyolefin resin component. Is the most preferable.
本発明でいう不揮発性水性化助剤としては、例えば、乳化剤、保護コロイド作用を有する化合物、変性ワックス類、高酸価の酸変性化合物、水溶性高分子等が挙げられる。 Examples of the non-volatile aqueous aid in the present invention include emulsifiers, compounds having a protective colloidal action, modified waxes, acid-modified compounds having a high acid value, water-soluble polymers and the like.
乳化剤としては、カチオン性乳化剤、アニオン性乳化剤、ノニオン性乳化剤、両性乳化剤が挙げられ、一般に乳化重合に用いられるもののほか、界面活性剤類も含まれる。例えば、アニオン性乳化剤としては、高級アルコールの硫酸エステル塩、高級アルキルスルホン酸塩、高級カルボン酸塩、アルキルベンゼンスルホン酸塩、ポリオキシエチレンアルキルサルフェート塩、ポリオキシエチレンアルキルフェニルエーテルサルフェート塩、ビニルスルホサクシネート等が挙げられ、ノニオン性乳化剤としては、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリエチレングリコール脂肪酸エステル、エチレンオキサイドプロピレンオキサイドブロック共重合体、ポリオキシエチレン脂肪酸アミド、エチレンオキサイド-プロピレンオキサイド共重合体等のポリオキシエチレン構造を有する化合物やポリオキシエチレンソルビタン脂肪酸エステル等のソルビタン誘導体等が挙げられ、両性乳化剤としては、ラウリルベタイン、ラウリルジメチルアミンオキサイド等が挙げられる。 Examples of the emulsifier include a cationic emulsifier, an anionic emulsifier, a nonionic emulsifier, and an amphoteric emulsifier, and in addition to those generally used for emulsion polymerization, surfactants are also included. For example, examples of anionic emulsifiers include sulfate ester salts of higher alcohols, higher alkyl sulfonates, higher carboxylates, alkylbenzene sulfonates, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, and vinyl sulfosuccinates. Examples of the nonionic emulsifier include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol fatty acid ester, ethylene oxide propylene oxide block copolymer, polyoxyethylene fatty acid amide, and ethylene oxide-propylene oxide. Examples thereof include compounds having a polyoxyethylene structure such as copolymers and sorbitan derivatives such as polyoxyethylene sorbitan fatty acid ester, and examples of the amphoteric emulsifier include laurylbetaine and lauryldimethylamine oxide.
保護コロイド作用を有する化合物、変性ワックス類、高酸価の酸変性化合物、水溶性高分子としては、ポリビニルアルコール、カルボキシル基変性ポリビニルアルコール、カルボキシメチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、変性デンプン、ポリビニルピロリドン、ポリアクリル酸およびその塩、カルボキシル基含有ポリエチレンワックス、カルボキシル基含有ポリプロピレンワックス、カルボキシル基含有ポリエチレン-プロピレンワックス等の数平均分子量が通常5000以下の酸変性ポリオレフィンワックス類およびその塩、アクリル酸-無水マレイン酸共重合体およびその塩、スチレン-(メタ)アクリル酸共重合体、エチレン-(メタ)アクリル酸共重合体、イソブチレン-無水マレイン酸交互共重合体、(メタ)アクリル酸-(メタ)アクリル酸エステル共重合体等の不飽和カルボン酸含有量が10質量%以上のカルボキシル基含有ポリマーおよびその塩、ポリイタコン酸およびその塩、アミノ基を有する水溶性アクリル系共重合体、ゼラチン、アラビアゴム、カゼイン等、一般に微粒子の分散安定剤として用いられている化合物等が挙げられる。 Compounds with protective colloid action, modified waxes, acid-modified compounds with high acid value, and as water-soluble polymers, polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, modified starch, polyvinylpyrrolidone. , Polyacrylic acid and its salts, carboxyl group-containing polyethylene wax, carboxyl group-containing polypropylene wax, carboxyl group-containing polyethylene-propylene wax and other acid-modified polyolefin waxes having a number average molecular weight of usually 5000 or less and salts thereof, acrylic acid-anhydrous. Maleic acid copolymer and its salt, styrene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid copolymer, isobutylene-anhydrous maleic acid alternating copolymer, (meth) acrylic acid- (meth) A carboxyl group-containing polymer having an unsaturated carboxylic acid content of 10% by mass or more, such as an acrylic acid ester copolymer and a salt thereof, polyitaconic acid and a salt thereof, a water-soluble acrylic copolymer having an amino group, gelatin, and gum arabic. , Casein and the like, which are generally used as dispersion stabilizers for fine particles.
本発明の水性分散体は、目的に応じて性能をさらに向上させるために、他の重合体、粘着付与剤、無機粒子、架橋剤、顔料、染料等を含有してもよい。
他の重合体や粘着付与剤は、特に限定されない。例えば、ポリ酢酸ビニル、エチレン-酢酸ビニル共重合体、ポリ塩化ビニル、ポリ塩化ビリニデン、エチレン-(メタ)アクリル酸共重合体、エチレン-(メタ)アクリル酸エステル-無水マレイン酸共重合体、スチレン-マレイン酸樹脂、スチレン-ブタジエン樹脂、ブタジエン樹脂、アクリロニトリル-ブタジエン樹脂、ポリウレタン樹脂、ポリ(メタ)アクリロニトリル樹脂、(メタ)アクリルアミド樹脂、塩素化ポリエチレン樹脂、塩素化ポリプロピレン樹脂、ポリエステル樹脂、変性ナイロン樹脂、ロジン、フェノール樹脂、シリコーン樹脂、エポキシ樹脂等、またはこれらを含む粘着付与剤が挙げられ、必要に応じて複数のものを混合使用してもよい。
なお、これらの重合体は、固形状のままで使用に供してもよいが、水性分散体の安定性維持の点では、水性分散体に加工したものを用いることが好ましい。
The aqueous dispersion of the present invention may contain other polymers, tackifiers, inorganic particles, cross-linking agents, pigments, dyes and the like in order to further improve the performance depending on the intended purpose.
Other polymers and tackifiers are not particularly limited. For example, polyvinyl acetate, ethylene-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester-maleic anhydride copolymer, styrene. -Maleic acid resin, styrene-butadiene resin, butadiene resin, acrylonitrile-butadiene resin, polyurethane resin, poly (meth) acrylonitrile resin, (meth) acrylamide resin, chlorinated polyethylene resin, chlorinated polypropylene resin, polyester resin, modified nylon resin , Login, phenol resin, silicone resin, epoxy resin, etc., or a tackifier containing these, and a plurality of them may be mixed and used as needed.
Although these polymers may be used as they are in a solid state, it is preferable to use those processed into an aqueous dispersion from the viewpoint of maintaining the stability of the aqueous dispersion.
無機粒子としては、酸化マグネシウム、酸化亜鉛、酸化すず等の金属酸化物、炭酸カルシウム、シリカ等の無機粒子や、バーミキュライト、モンモリロナイト、ヘクトライト、ハイドロタルサイト、合成雲母等の層状無機化合物等が挙げられる。これらの無機粒子の平均粒子径は、塗膜の透明性等の観点から、0.005~10μmであることが好ましい。なお、無機粒子として複数のものを混合して使用してもよい。 Examples of the inorganic particles include metal oxides such as magnesium oxide, zinc oxide and tin oxide, inorganic particles such as calcium carbonate and silica, and layered inorganic compounds such as vermiculite, montmorillonite, hectorite, hydrotalcite and synthetic mica. Be done. The average particle size of these inorganic particles is preferably 0.005 to 10 μm from the viewpoint of transparency of the coating film and the like. A plurality of inorganic particles may be mixed and used.
架橋剤としては、自己架橋性を有する架橋剤、不飽和カルボン酸成分と反応する官能基を分子内に複数個有する化合物、多価の配位座を有する金属等を用いることができる。
具体的には、オキサゾリン基含有化合物、カルボジイミド基含有化合物、イソシアネート基含有化合物、エポキシ基含有化合物、メラミン化合物、尿素化合物、ジルコニウム塩化合物、シランカップリング剤等が挙げられ、必要に応じて複数のものを混合使用してもよい。中でも、取り扱い易さの観点から、オキサゾリン基含有化合物、カルボジイミド基含有化合物、イソシアネート基含有化合物、エポキシ基含有化合物が好ましい。
As the cross-linking agent, a cross-linking agent having a self-cross-linking property, a compound having a plurality of functional groups reacting with an unsaturated carboxylic acid component in the molecule, a metal having a polyvalent coordination position, or the like can be used.
Specific examples thereof include an oxazoline group-containing compound, a carbodiimide group-containing compound, an isocyanate group-containing compound, an epoxy group-containing compound, a melamine compound, a urea compound, a zirconium salt compound, a silane coupling agent, and the like. Those may be mixed and used. Of these, oxazoline group-containing compounds, carbodiimide group-containing compounds, isocyanate group-containing compounds, and epoxy group-containing compounds are preferable from the viewpoint of ease of handling.
顔料、染料としては、酸化チタン、亜鉛華、カーボンブラック等が挙げられ、分散染料、酸性染料、カチオン染料、反応染料等いずれのものも使用することが可能である。
本発明の水性分散体は、さらに必要に応じて、レベリング剤、消泡剤、ワキ防止剤、顔料分散剤、紫外線吸収剤、増粘剤、耐候剤、難燃剤等の各種薬剤を含有してもよい。
Examples of pigments and dyes include titanium oxide, zinc oxide, carbon black and the like, and any of disperse dyes, acid dyes, cationic dyes, reactive dyes and the like can be used.
The aqueous dispersion of the present invention further contains various agents such as a leveling agent, an antifoaming agent, an armpit inhibitor, a pigment dispersant, an ultraviolet absorber, a thickener, a weather resistant agent, and a flame retardant, if necessary. May be good.
本発明の水性分散体は、接着剤、コーティング剤、プライマー、塗料、インキ等として好適に使用できる。
本発明の水性分散体は、塗膜とした際のバリア性、防錆性にいっそう優れるので、金属製品用途、電子機器用途、包装材料用途、自動車部品用途等に特に好適に用いられる。
これら用途の具体例としては、PP押出ラミ用アンカーコート剤、二次電池セパレータ用コーティング剤、UV硬化型コート剤用プライマー、靴用プライマー、自動車バンパー用プライマー、クリアボックス用プライマー、PP基材用塗料、包装材料用接着剤、紙容器用接着剤、蓋材用接着剤、インモールド転写箔用接着剤、PP鋼板用接着剤、太陽電池モジュール用接着剤、植毛用接着剤、二次電池電極用バインダー用接着剤、二次電池外装用接着剤、自動車用ベルトモール用接着剤、自動車部材用接着剤、異種基材用接着剤、繊維収束剤等が挙げられる。
The aqueous dispersion of the present invention can be suitably used as an adhesive, a coating agent, a primer, a paint, an ink and the like.
Since the aqueous dispersion of the present invention is more excellent in barrier property and rust prevention property when formed into a coating film, it is particularly preferably used for metal product applications, electronic device applications, packaging material applications, automobile parts applications and the like.
Specific examples of these applications include anchor coating agents for PP extruded lami, coating agents for secondary battery separators, primers for UV curable coating agents, primer for shoes, primers for automobile bumpers, primers for clear boxes, and PP substrates. Adhesives for paints, packaging materials, adhesives for paper containers, adhesives for lids, adhesives for in-mold transfer foils, adhesives for PP steel plates, adhesives for solar cell modules, adhesives for flocking, secondary battery electrodes Examples thereof include adhesives for binders for secondary batteries, adhesives for exteriors of secondary batteries, adhesives for belt moldings for automobiles, adhesives for automobile parts, adhesives for dissimilar base materials, fiber converging agents and the like.
本発明の水性分散体は、塗膜形成能に優れる。本発明の水性分散体から塗膜を形成するためには、例えば、本発明の水性分散体を、各種基材表面に均一に塗布し、必要に応じて室温付近でセッティングした後、乾燥または乾燥と焼き付けのための加熱処理に供することが挙げられる。これにより、均一な塗膜を各種基材表面に接着させることができる。 The aqueous dispersion of the present invention is excellent in coating film forming ability. In order to form a coating film from the aqueous dispersion of the present invention, for example, the aqueous dispersion of the present invention is uniformly applied to the surface of various substrates, set at around room temperature as necessary, and then dried or dried. And to be used for heat treatment for baking. As a result, a uniform coating film can be adhered to the surface of various base materials.
基材への水性分散体の塗布には、公知の方法、例えばグラビアロールコーティング、リバースロールコーティング、ワイヤーバーコーティング、リップコーティング、エアナイフコーティング、カーテンフローコーティング、スプレーコーティング、浸漬コーティング、はけ塗り法等が採用できる。 Known methods for applying the aqueous dispersion to the substrate include, for example, gravure roll coating, reverse roll coating, wire bar coating, lip coating, air knife coating, curtain flow coating, spray coating, dip coating, brush coating, etc. Can be adopted.
基材への水性分散体の塗布量は特に限定されず、その用途によって適宜選択されるものであるが、乾燥後の塗布量として0.01~100g/m2であることが好ましく、0.1~50g/m2であることがより好ましく、0.2~30g/m2であることがさらに好ましい。 The amount of the aqueous dispersion applied to the substrate is not particularly limited and may be appropriately selected depending on the intended use, but the amount of the aqueous dispersion applied after drying is preferably 0.01 to 100 g / m 2 . It is more preferably 1 to 50 g / m 2 , and even more preferably 0.2 to 30 g / m 2 .
なお、塗布量を調節するためには、塗布に用いる装置やその使用条件を適宜選択することに加えて、目的とする塗膜の厚さに応じて濃度調整された水性分散体を使用することが好ましい。水性分散体の濃度は、調製時の仕込み組成により調整することが可能であり、また、一旦調製した水性分散体を、適宜希釈したり、あるいは濃縮したりして調整してもよい。 In order to adjust the coating amount, in addition to appropriately selecting the apparatus used for coating and the conditions of use thereof, an aqueous dispersion whose concentration is adjusted according to the thickness of the target coating film should be used. Is preferable. The concentration of the aqueous dispersion can be adjusted by the preparation composition at the time of preparation, and the aqueous dispersion once prepared may be appropriately diluted or concentrated to be adjusted.
塗布後の加熱処理のための加熱装置として、通常の熱風循環型のオーブンや赤外線ヒーター等を使用することができる。
加熱温度や加熱時間は、基材の特性または水性分散体中に任意に配合しうる各種成分の添加量により適宜選択されるが、エネルギーコストや基材へのダメージの観点からは加熱温度は低いほうが好ましく、生産性の観点からは加熱時間は短いほうが好ましい。加熱温度としては、20~130℃であることが好ましく、30~120℃であることがより好ましく、40~100℃であることがさらに好ましい。加熱時間は、1秒~20分であることが好ましく、5秒~15分であることがより好ましく、5秒~10分であることがさらに好ましい。
なお、本発明の水性分散体に架橋剤を含有させる場合は、ポリオレフィン樹脂中のカルボキシル基と架橋剤との反応を十分進行させるために、加熱温度および時間は架橋剤の種類によって適宜選定することが望ましい。
As a heating device for heat treatment after coating, a normal hot air circulation type oven, an infrared heater, or the like can be used.
The heating temperature and heating time are appropriately selected depending on the characteristics of the substrate or the amount of various components that can be arbitrarily blended in the aqueous dispersion, but the heating temperature is low from the viewpoint of energy cost and damage to the substrate. It is preferable, and from the viewpoint of productivity, it is preferable that the heating time is short. The heating temperature is preferably 20 to 130 ° C, more preferably 30 to 120 ° C, and even more preferably 40 to 100 ° C. The heating time is preferably 1 second to 20 minutes, more preferably 5 seconds to 15 minutes, and even more preferably 5 seconds to 10 minutes.
When the aqueous dispersion of the present invention contains a cross-linking agent, the heating temperature and time should be appropriately selected depending on the type of the cross-linking agent in order to sufficiently proceed the reaction between the carboxyl group in the polyolefin resin and the cross-linking agent. Is desirable.
本発明の水性分散体を得るための製造方法としては、特に限定されるものではないが、上記した各種成分、すなわち、ポリオレフィン樹脂、水性媒体、任意の各種添加剤、さらに必要に応じて有機溶剤、塩基性化合物等を、密閉可能な容器中で加熱、攪拌し、樹脂を分散させる方法を採用することができる。 The production method for obtaining the aqueous dispersion of the present invention is not particularly limited, but is not limited to the above-mentioned various components, that is, a polyolefin resin, an aqueous medium, any various additives, and if necessary, an organic solvent. , A method of heating and stirring a basic compound or the like in a sealable container to disperse the resin can be adopted.
容器としては、固/液撹拌装置や乳化機として使用されている装置を使用することができ、例えば、0.1MPa以上の加圧が可能な装置を使用することが好ましい。撹拌の方法、撹拌の回転速度は特に限定されないが、ポリオレフィン樹脂が水性媒体中で均一な状態となる程度の低速の撹拌でよい。したがって、高速撹拌(例えば1000rpm以上)は必須ではなく、簡便な装置でも水性分散体の製造が可能である。 As the container, an apparatus used as a solid / liquid agitator or an emulsifier can be used, and for example, an apparatus capable of pressurizing 0.1 MPa or more is preferably used. The stirring method and the rotation speed of the stirring are not particularly limited, but the stirring may be performed at a low speed so that the polyolefin resin becomes a uniform state in the aqueous medium. Therefore, high-speed stirring (for example, 1000 rpm or more) is not essential, and an aqueous dispersion can be produced even with a simple device.
中でも、水性分散体の製造方法としては、ポリオレフィン樹脂、水性媒体等の原料を混合し、攪拌した後に、1℃/分以下の平均冷却速度で攪拌温度から最低温度に冷却することが好ましい。 Above all, as a method for producing an aqueous dispersion, it is preferable to mix raw materials such as a polyolefin resin and an aqueous medium, stir, and then cool from the stirring temperature to the lowest temperature at an average cooling rate of 1 ° C./min or less.
詳細なメカニズムは分かっていないが、本発明者は様々に検討した結果、1℃/分以下の平均冷却速度で比較的遅く冷却することで、上記のレーザー回折法で測定したポリオレフィン樹脂粒子の99.9%径を、特定範囲とすることができることを見出した。
平均冷却速度は遅いことがより好ましく、0.9℃/分以下であることがさらに好ましく、0.7℃/分以下であることが特に好ましい。
Although the detailed mechanism is not known, as a result of various studies, the present inventor has obtained 99 of the polyolefin resin particles measured by the above laser diffraction method by cooling relatively slowly at an average cooling rate of 1 ° C./min or less. It has been found that a 9.9% diameter can be a specific range.
The average cooling rate is more preferably slow, more preferably 0.9 ° C./min or less, and particularly preferably 0.7 ° C./min or less.
攪拌温度は、装置の耐圧や加熱性能、エネルギーコスト等の観点から適宜設定することが可能であるが、樹脂の粒子径を上記範囲とする観点、分散安定性の観点からは高いことが好ましく、110℃以上であることが好ましく、120℃以上がより好ましく、140℃以上であることがさらに好ましい。 The stirring temperature can be appropriately set from the viewpoint of the pressure resistance of the device, the heating performance, the energy cost, etc., but it is preferably high from the viewpoint of setting the particle size of the resin within the above range and the dispersion stability. The temperature is preferably 110 ° C. or higher, more preferably 120 ° C. or higher, and even more preferably 140 ° C. or higher.
なお、冷却後の最低温度は特に限定されるものではないが、例えば100℃以下であり、40℃以下であることがより好ましい。 The minimum temperature after cooling is not particularly limited, but is, for example, 100 ° C. or lower, more preferably 40 ° C. or lower.
冷却は、1℃/分以下の平均冷却速度で1段階での冷却を行ってもよいし、平均冷却速度の異なる2段階以上の冷却を複数段階で行ってもよい。
例えば、1℃/分以下の平均冷却速度で攪拌温度から100℃以下かつ40℃を超える温度に冷却する冷却の後に、3℃/分以下の平均冷却速度で40℃以下に冷却させるような、2段階の冷却を採用してもよい。この場合、2段階目の平均冷却速度は3℃/分以下であることが好ましく、2℃/分以下であることがより好ましく、1℃/分以下であることがさらに好ましい。
The cooling may be performed in one step at an average cooling rate of 1 ° C./min or less, or may be cooled in two or more steps with different average cooling rates in a plurality of steps.
For example, after cooling from the stirring temperature to a temperature of 100 ° C. or lower and exceeding 40 ° C. at an average cooling rate of 1 ° C./min or less, cooling to 40 ° C. or lower at an average cooling rate of 3 ° C./min or less. Two stages of cooling may be adopted. In this case, the average cooling rate in the second stage is preferably 3 ° C./min or less, more preferably 2 ° C./min or less, and even more preferably 1 ° C./min or less.
上記の平均冷却温度を調整する方法は、特に限定されるものではなく、例えば電力を調整したり、ジャケットを備えた容器を使用する場合は、ジャケット内の蒸気、熱媒、水等の温度を調製したりする方法が挙げられる。 The method for adjusting the average cooling temperature described above is not particularly limited. For example, when adjusting the electric power or using a container equipped with a jacket, the temperature of steam, heat medium, water, etc. in the jacket is adjusted. There is a method of preparing.
塩基性化合物としては、アンモニア、トリエチルアミン、N,N-ジメチルエタノールアミン、イソプロピルアミン、アミノエタノール、ジメチルアミノエタノール、ジエチルアミノエタノール、エチルアミン、ジエチルアミン、イソブチルアミン、ジプロピルアミン、3-エトキシプロピルアミン、3-ジエチルアミノプロピルアミン、sec-ブチルアミン、プロピルアミン、n-ブチルアミン、2-メトキシエチルアミン、3-メトキシプロピルアミン、2,2-ジメトキシエチルアミン、モノエタノールアミン、モルホリン、N-メチルモルホリン、N-エチルモルホリン、ピロール、ピリジン等が挙げられる。
中でも、樹脂の分散促進の観点から、アンモニア、トリエチルアミン、N,N-ジメチルエタノールアミンが好ましい。
Basic compounds include ammonia, triethylamine, N, N-dimethylethanolamine, isopropylamine, aminoethanol, dimethylaminoethanol, diethylaminoethanol, ethylamine, diethylamine, isobutylamine, dipropylamine, 3-ethoxypropylamine, 3- Diethylaminopropylamine, sec-butylamine, propylamine, n-butylamine, 2-methoxyethylamine, 3-methoxypropylamine, 2,2-dimethoxyethylamine, monoethanolamine, morpholine, N-methylmorpholine, N-ethylmorpholine, pyrrole , Pyridine and the like.
Of these, ammonia, triethylamine, and N, N-dimethylethanolamine are preferable from the viewpoint of promoting the dispersion of the resin.
塩基性化合物の添加量は、ポリオレフィン樹脂中のカルボキシル基に対して0.5~10倍当量であることが好ましく、0.8~8倍当量であることがより好ましく、1.0~5倍当量であることが特に好ましい。0.5倍当量未満では分散が不十分となり、本発明で規定する樹脂粒子径の水性分散体を得ることが難しい場合がある。10倍当量を超えると塗膜形成時の乾燥時間が長くなったり、得られる水性分散体の安定性が低下したりする場合がある。 The amount of the basic compound added is preferably 0.5 to 10 times equivalent, more preferably 0.8 to 8 times equivalent, and 1.0 to 5 times the equivalent of the carboxyl group in the polyolefin resin. Equivalents are particularly preferred. If the equivalent is less than 0.5 times, the dispersion becomes insufficient, and it may be difficult to obtain an aqueous dispersion having the resin particle size specified in the present invention. If it exceeds 10 times equivalent, the drying time at the time of forming the coating film may be long, or the stability of the obtained aqueous dispersion may be lowered.
ポリオレフィン樹脂粒子の分散を促進し、分散粒子径を小さくし、本発明で規定する粒子径を満足するために、水性分散の際に親水性有機溶剤を添加することが好ましい。親水性有機溶剤の含有量としては、水性媒体全体に対し50質量%以下であることが好ましく、1~45質量%であることがより好ましく、10~40質量%であることがさらに好ましく、25~35質量%であることが特に好ましい。親水性有機溶剤の含有量が50質量%を超える場合には、実質的に水性媒体と見なせなくなり、本発明の目的のひとつ(環境保護)を逸脱するだけでなく、使用する親水性有機溶剤によっては水性分散体の安定性が低下することがある。 In order to promote the dispersion of the polyolefin resin particles, reduce the dispersed particle size, and satisfy the particle size specified in the present invention, it is preferable to add a hydrophilic organic solvent at the time of aqueous dispersion. The content of the hydrophilic organic solvent is preferably 50% by mass or less, more preferably 1 to 45% by mass, still more preferably 10 to 40% by mass, and 25 by mass with respect to the entire aqueous medium. It is particularly preferable that the content is ~ 35% by mass. When the content of the hydrophilic organic solvent exceeds 50% by mass, it cannot be regarded as an aqueous medium substantially, which not only deviates from one of the objects of the present invention (environmental protection) but also uses a hydrophilic organic solvent. In some cases, the stability of the aqueous dispersion may decrease.
親水性有機溶剤としては、分散安定性が良好な水性分散体を得るという点から、20℃の水に対する溶解性が10g/L以上のものが好ましく、20g/L以上のものがより好ましく、50g/L以上のものがさらに好ましい。 The hydrophilic organic solvent preferably has a solubility in water at 20 ° C. of 10 g / L or more, more preferably 20 g / L or more, and more preferably 50 g, from the viewpoint of obtaining an aqueous dispersion having good dispersion stability. More than / L is more preferable.
親水性有機溶剤としては、塗膜を形成する過程で、効率よく乾燥除去させる観点から、沸点が100℃以下のものが好ましい。沸点が100℃を超える親水性有機溶剤は、塗膜から乾燥により飛散させることが困難となる傾向にあり、特に低温乾燥時の塗膜の耐水性や基材との接着性等が低下することがある。 The hydrophilic organic solvent preferably has a boiling point of 100 ° C. or lower from the viewpoint of efficient drying and removal in the process of forming the coating film. Hydrophilic organic solvents having a boiling point of more than 100 ° C. tend to be difficult to disperse from the coating film by drying, and in particular, the water resistance of the coating film during low-temperature drying and the adhesiveness to the substrate are lowered. There is.
好ましい親水性有機溶剤としては、例えば、メタノール、エタノール、n-プロパノール、イソプロパノール、n-ブタノール、イソブタノール、sec-ブタノール、tert-ブタノール、n-アミルアルコール、イソアミルアルコール、sec-アミルアルコール、tert-アミルアルコール、1-エチル-1-プロパノール、2-メチル-1-ブタノール、n-ヘキサノール、シクロヘキサノール等のアルコール類、メチルエチルケトン、メチルイソブチルケトン、エチルブチルケトン、シクロヘキサノン等のケトン類、テトラヒドロフラン、ジオキサン等のエーテル類、酢酸エチル、酢酸-n-プロピル、酢酸イソプロピル、酢酸-n-ブチル、酢酸イソブチル、酢酸-sec-ブチル、酢酸-3-メトキシブチル、プロピオン酸メチル、プロピオン酸エチル、炭酸ジエチル、炭酸ジメチル等のエステル類、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールエチルエーテルアセテート等のグリコール誘導体、さらには、1-メトキシ-2-プロパノール、1-エトキシ-2-プロパノール、3-メトキシ-3-メチル-1-ブタノール、メトキシブタノール、アセトニトリル、ジメチルホルムアミド、ジメチルアセトアミド、ジアセトンアルコール、アセト酢酸エチル、1,2-ジメチルグリセリン、1,3-ジメチルグリセリン、トリメチルグリセリン等が挙げられる。 Preferred hydrophilic organic solvents include, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, tert-. Alcohols such as amyl alcohol, 1-ethyl-1-propanol, 2-methyl-1-butanol, n-hexanol, cyclohexanol, ketones such as methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, cyclohexanone, tetrahydrofuran, dioxane, etc. Ethers, ethyl acetate, -n-propyl acetate, isopropyl acetate, -n-butyl acetate, isobutyl acetate, -sec-butyl acetate, -3-methoxybutyl acetate, methyl propionate, ethyl propionate, diethyl carbonate, carbonic acid Esters such as dimethyl, glycol derivatives such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol ethyl ether acetate, and further, 1-methoxy-2-propanol, 1 -Ethoxy-2-propanol, 3-methoxy-3-methyl-1-butanol, methoxybutanol, acetonitrile, dimethylformamide, dimethylacetamide, diacetone alcohol, ethyl acetoacetate, 1,2-dimethylglycerin, 1,3-dimethyl Examples thereof include glycerin and trimethylglycerin.
中でも、エタノール、n-プロパノール、イソプロパノール、n-ブタノール、メチルエチルケトン、シクロヘキサノン、テトラヒドロフラン、ジオキサン、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテルを用いると、ポリオレフィン樹脂粒子の分散促進により効果的であり好ましく、イソプロパノールが特に好ましい。 Among them, ethanol, n-propanol, isopropanol, n-butanol, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, dioxane, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and diethylene glycol monomethyl ether are used to obtain polyolefin resin particles. It is more effective and preferable for promoting dispersion, and isopropanol is particularly preferable.
本発明では、これらの親水性有機溶剤を複数混合して使用してもよい。またポリオレフィン樹脂の水性分散化をより促進させるために、疎水性有機溶剤をさらに添加してもよい。 In the present invention, a plurality of these hydrophilic organic solvents may be mixed and used. Further, in order to further promote the aqueous dispersion of the polyolefin resin, a hydrophobic organic solvent may be further added.
疎水性有機溶剤としては、分散安定性が良好な水性分散体を得るという点から、20℃の水に対する溶解性が10g/L未満である有機溶剤が好ましい。また、塗膜を形成する過程で、効率よく乾燥除去させる観点から、沸点が150℃以下である有機溶剤が好ましい。このような疎水性有機溶剤としては、例えば、n-ペンタン、n-ヘキサン、n-ヘプタン、シクロヘプタン、シクロヘキサン、石油エーテル等のオレフィン系溶剤、ベンゼン、トルエン、キシレン等の芳香族系溶剤、四塩化炭素、1,2-ジクロロエタン、1,1-ジクロロエチレン、トリクロロエチレン、1,1,1-トリクロロエタン、クロロホルム等のハロゲン系溶媒等が挙げられる。これらの疎水性有機溶剤の含有量は、水性分散体に対して15質量%以下であることが好ましく、10質量%以下であることがより好ましく、5質量%以下であることがさらに好ましい。疎水性有機溶剤の含有量が15質量%を超えると、ゲル化等を引き起こすことがある。 As the hydrophobic organic solvent, an organic solvent having a solubility in water at 20 ° C. of less than 10 g / L is preferable from the viewpoint of obtaining an aqueous dispersion having good dispersion stability. Further, from the viewpoint of efficient drying and removal in the process of forming the coating film, an organic solvent having a boiling point of 150 ° C. or lower is preferable. Examples of such hydrophobic organic solvents include olefin solvents such as n-pentane, n-hexane, n-heptane, cycloheptane, cyclohexane and petroleum ether, aromatic solvents such as benzene, toluene and xylene, and four. Examples thereof include halogen-based solvents such as carbon chloride, 1,2-dichloroethane, 1,1-dichloroethylene, trichlorethylene, 1,1,1-trichloroethane, and chloroform. The content of these hydrophobic organic solvents is preferably 15% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less with respect to the aqueous dispersion. If the content of the hydrophobic organic solvent exceeds 15% by mass, gelation or the like may be caused.
水性分散体の製造時に上記の有機溶剤を用いた場合には、ポリオレフィン樹脂の水性分散化の後に、その一部を、一般に「ストリッピング」と呼ばれる脱溶剤処理によって系外へ留去させ、有機溶剤の含有量を低減させてもよい。ストリッピングにより、水性分散体中の有機溶剤含有量は、10質量%以下とすることができ、5質量%以下とすればより好ましく、1質量%以下とすることが、環境上より好ましい。ストリッピングの工程では、水性分散化に使用した有機溶剤を実質的に全て留去することもできるが、装置の減圧度を高めたり、操業時間を長くしたりする必要があるため、こうした生産性を考慮した場合、有機溶剤含有量の下限は0.01質量%程度が好ましい。 When the above-mentioned organic solvent is used in the production of the aqueous dispersion, after the aqueous dispersion of the polyolefin resin, a part thereof is distilled off from the system by a solvent removal treatment generally called "stripping" to make it organic. The solvent content may be reduced. By stripping, the organic solvent content in the aqueous dispersion can be 10% by mass or less, more preferably 5% by mass or less, and more preferably 1% by mass or less from the environment. In the stripping process, substantially all of the organic solvent used for the aqueous dispersion can be distilled off, but such productivity is required because the degree of decompression of the apparatus needs to be increased and the operating time must be lengthened. In consideration of the above, the lower limit of the organic solvent content is preferably about 0.01% by mass.
ストリッピングの方法としては、常圧または減圧下で水性分散体を攪拌しながら加熱し、有機溶剤を留去する方法が挙げられる。また、水性媒体が留去されることにより、固形分濃度が高くなるので、例えば、粘度が上昇して作業性が低下するような場合には、予め水性分散体に水を添加しておいてもよい。 Examples of the stripping method include a method in which the aqueous dispersion is heated with stirring under normal pressure or reduced pressure to distill off the organic solvent. Further, since the solid content concentration is increased by distilling off the aqueous medium, for example, when the viscosity increases and the workability decreases, water is added to the aqueous dispersion in advance. May be good.
水性分散体の固形分濃度は、特に限定されず用途等に応じて適宜に選択することができ、例えば、水性媒体を留去する方法や、水で希釈する方法により調整することができる。 The solid content concentration of the aqueous dispersion is not particularly limited and can be appropriately selected depending on the intended use and the like, and can be adjusted by, for example, a method of distilling off an aqueous medium or a method of diluting with water.
以下、実施例によって本発明を具体的に説明するが、本発明はこれらに限定されるものではない。
各種の構成や特性は、以下の方法により測定または評価した。
Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto.
Various configurations and characteristics were measured or evaluated by the following methods.
(1)ポリオレフィン樹脂の組成
1H-NMR分析装置(日本電子社製、ECA500、500MHz)より求めた。テトラクロロエタン(d2)を溶媒とし、120℃で測定した。
(1) Composition of polyolefin resin
1 Obtained from an H-NMR analyzer (manufactured by JEOL Ltd., ECA500, 500 MHz). The measurement was carried out at 120 ° C. using tetrachloroethane (d2) as a solvent.
(2)ポリオレフィン樹脂の融点
パーキンエルマー社製、DSC7を用いてDSC法にて測定した。試料をアルミパンに詰め、10℃/分で200℃まで昇温し、5分間保持した後、10℃/分で-10℃まで降温し、次いで10℃/分で200℃まで昇温した際の、吸熱および発熱に伴う曲線から求めた。
(2) Melting point of polyolefin resin The measurement was carried out by the DSC method using DSC7 manufactured by PerkinElmer. When the sample is packed in an aluminum pan, heated to 200 ° C at 10 ° C / min, held for 5 minutes, cooled to -10 ° C at 10 ° C / min, and then heated to 200 ° C at 10 ° C / min. It was obtained from the curves associated with endothermic and heat generation.
(3)ポリオレフィン樹脂のメルトフローレート(MFR)
JIS K7210:1999記載の方法に準じ、190℃、2160g荷重で測定した。
(3) Melt flow rate (MFR) of polyolefin resin
JIS K7210: Measured according to the method described in 1999 at 190 ° C. and a load of 2160 g.
(4)水性分散体の固形分濃度
水性分散体を適量秤量し、これを150℃で残存物(固形分)の質量が恒量に達するまで加熱し、固形分濃度を求めた。
(4) Solid Content Concentration of Aqueous Dispersion An appropriate amount of the aqueous dispersion was weighed and heated at 150 ° C. until the mass of the residue (solid content) reached a constant amount to determine the solid content concentration.
(5)ポリオレフィン樹脂粒子の数平均粒子径、体積平均粒子径(動的光散乱法)
日機装社製、Nanotrac Wave-UZ152粒度分布測定装置を用いて、数平均粒子径(mn)、体積平均粒子径(mw)を測定した。なお樹脂の屈折率は1.5とした。
(5) Number average particle size and volume average particle size of polyolefin resin particles (dynamic light scattering method)
The number average particle size (mn) and the volume average particle size (mw) were measured using a Nanotrac Wave-UZ152 particle size distribution measuring device manufactured by Nikkiso Co., Ltd. The refractive index of the resin was 1.5.
(6)ポリオレフィン樹脂粒子の99.9%径(レーザー回折法)
マルバーン社製、レーザー回折粒子径マスターサイザー3000を用いて、粒子径を測定し、体積粒度分布において小粒径側から積算した体積粒子径積算分布の99.9%径を確認した。
(6) 99.9% diameter of polyolefin resin particles (laser diffraction method)
The particle size was measured using a laser diffraction particle size master sizer 3000 manufactured by Malvern, and a 99.9% diameter of the volume particle size integrated distribution integrated from the small particle size side was confirmed in the volume particle size distribution.
(7)水性分散体の粘度
濾過後の水性分散体を、B型粘度計(トキメック社製、DVL-BII型デジタル粘度計)を用い、温度20℃における回転粘度(mPa・s)を測定した。
(7) Viscosity of Aqueous Dispersion The filtered aqueous dispersion was measured for rotational viscosity (mPa · s) at a temperature of 20 ° C. using a B-type viscometer (DVL-BII type digital viscometer manufactured by Tokimec). ..
(8)pH
HORIBA社製 ポータプル型pHメーター D-74を用い、20℃におけるpHを測定した。
(8) pH
The pH at 20 ° C. was measured using a portable pH meter D-74 manufactured by HORIBA.
(9)塗膜の外観欠点
グラビヤコーターを用いて、PETフィルム(東レ社製 ルミラー T60-#50 厚み50μm 幅1m)に、塗膜厚みが1μmになるように水性分散体を塗布し、100℃で15秒の乾燥を行い、1000mを巻き取った後、透過型欠点検出装置(ヒューテック社製)を設置したフィルムワインダーを通し(スキャン速度0.5m/秒、検出感度0.5mm以上に設定)、欠点(ブツ、クラック等)の検査を行った。検知回数から以下の基準で判断した。
〇:1000m2あたり10回未満
△:1000m2あたり10回以上100回未満
×:1000m2あたり100回以上
(9) Disadvantages of the appearance of the coating film Using a gravure coater, an aqueous dispersion was applied to a PET film (Toray Industries, Inc. Lumirror T60- # 50, thickness 50 μm, width 1 m) so that the coating film thickness was 1 μm, and the temperature was 100 ° C. After drying for 15 seconds and winding 1000 m, pass through a film winder equipped with a transmission type defect detection device (manufactured by Hutec) (scan speed 0.5 m / sec, detection sensitivity 0.5 mm or more). , Defects (bumps, cracks, etc.) were inspected. Judgment was made based on the following criteria from the number of detections.
〇: 1000m less than 10 times per 2 △: 1000m 10 times or more and less than 100 times per 2 ×: 1000m 100 times or more per 2
(10)塗膜の水蒸気透過度(バリア性)
(低温乾燥での製膜)
ナイロンフィルム(ユニチカ社製 ON-15)のコロナ処理面に、マイヤーバーを用いて、乾燥後の塗膜厚みが10μmになるように水性分散体を塗布し、80℃で乾燥を行って塗膜を形成した。得られたサンプルの水蒸気透過度を、透湿度測定器(モコン社製 PERMATRAN-W3/31MW)を用いて、40℃、100%RHの条件で測定した。
(10) Moisture vapor transmission rate (barrier property) of the coating film
(Film formation by low temperature drying)
Using a Meyer bar, apply an aqueous dispersion to the corona-treated surface of a nylon film (ON-15 manufactured by Unitika Ltd.) so that the coating film thickness after drying is 10 μm, and dry at 80 ° C. to apply the coating film. Formed. The water vapor transmission rate of the obtained sample was measured using a moisture permeability measuring device (PERMATRAN-W3 / 31MW manufactured by Mocon) at 40 ° C. and 100% RH.
(高温乾燥での製膜)
ナイロンフィルム(ユニチカ社製 ON-15)のコロナ処理面に、マイヤーバーを用いて、乾燥後の塗膜厚みが10μmになるように水性分散体を塗布し、150℃で乾燥を行って塗膜を形成した。得られたサンプルの水蒸気透過度を、透湿度測定器(モコン社製 PERMATRAN-W3/31MW)を用いて、40℃、100%RHの条件で測定した。
(Film formation by high temperature drying)
Using a Meyer bar, apply an aqueous dispersion to the corona-treated surface of a nylon film (ON-15 manufactured by Unitika Ltd.) so that the coating film thickness after drying is 10 μm, and dry at 150 ° C. to apply the coating film. Formed. The water vapor transmission rate of the obtained sample was measured using a moisture permeability measuring device (PERMATRAN-W3 / 31MW manufactured by Mocon) at 40 ° C. and 100% RH.
(11)防錆性
(低温乾燥での製膜)
脱脂した溶融亜鉛メッキ鋼板(日本テストパネル社製、サイズ70mm×150mm×0.8mmt)に、マイヤーバーを用いて、乾燥後の塗膜厚みが2μmになるように水性分散体を塗布し、80℃で乾燥を行って塗膜を形成した。得られたサンプルに対して、JIS Z-2371規格の塩水噴霧試験機を用いて、35℃で5質量%のNaCl水溶液の噴霧を行い、100時間後の塗膜表面の発錆面積状態を観察した。サンプルの全面積に対する発錆面積を算出し、以下のように評価した。
◎:発錆面積率5%未満
○:発錆面積率5%以上、10%未満
△:発錆面積率10%以上、50%未満
×:発錆面積率50%以上
(11) Rust prevention (film formation by low temperature drying)
A degreased hot-dip galvanized steel sheet (manufactured by Nippon Test Panel Co., Ltd., size 70 mm x 150 mm x 0.8 mmt) is coated with an aqueous dispersion using a Meyer bar so that the coating film thickness after drying is 2 μm. The coating film was formed by drying at ° C. The obtained sample was sprayed with a 5% by mass NaCl aqueous solution at 35 ° C. using a JIS Z-2371 standard salt spray tester, and the rusted area state of the coating film surface after 100 hours was observed. did. The rusted area for the total area of the sample was calculated and evaluated as follows.
⊚: Rust area ratio less than 5% ○: Rust area ratio 5% or more and less than 10% Δ: Rust area ratio 10% or more and less than 50% ×: Rust area ratio 50% or more
(高温乾燥での製膜)
脱脂した溶融亜鉛メッキ鋼板(日本テストパネル社製、サイズ70mm×150mm×0.8mmt)に、マイヤーバーを用いて、乾燥後の塗膜厚みが2μmになるように水性分散体を塗布し、200℃で乾燥を行って塗膜を形成した。得られたサンプルに対して、JIS Z-2371規格の塩水噴霧試験機を用いて、35℃で5質量%のNaCl水溶液の噴霧を行い、100時間後の塗膜表面の発錆状態を観察した。サンプルの全面積に対する発錆面積を算出し、以下のように評価した。
◎:発錆面積率5%未満
○:発錆面積率5%以上、10%未満
△:発錆面積率10%以上、50%未満
×:発錆面積率50%以上
(Film formation by high temperature drying)
A degreased hot-dip galvanized steel sheet (manufactured by Nippon Test Panel Co., Ltd., size 70 mm x 150 mm x 0.8 mmt) is coated with an aqueous dispersion using a Meyer bar so that the coating film thickness after drying is 2 μm, and 200 The coating film was formed by drying at ° C. The obtained sample was sprayed with a 5% by mass NaCl aqueous solution at 35 ° C. using a JIS Z-2371 standard salt spray tester, and the rusted state of the coating film surface after 100 hours was observed. .. The rusted area for the total area of the sample was calculated and evaluated as follows.
⊚: Rust area ratio less than 5% ○: Rust area ratio 5% or more and less than 10% Δ: Rust area ratio 10% or more and less than 50% ×: Rust area ratio 50% or more
実施例、比較例に用いたポリオレフィン樹脂(P-1)~(P-13)は、以下の通りで
ある。これらのポリオレフィン樹脂の組成、物性を表1に示す。
The polyolefin resins (P-1) to (P-13) used in Examples and Comparative Examples are as follows. Table 1 shows the composition and physical properties of these polyolefin resins.
ポリオレフィン樹脂(P-1)
エチレン-アクリル酸エチル-無水マレイン酸共重合体(ボンダインHX-8290 アルケマ社製)を用いた。
Polyolefin resin (P-1)
An ethylene-ethyl acrylate-maleic anhydride copolymer (manufactured by Bondine HX-8290 Arkema) was used.
ポリオレフィン樹脂(P-2)
エチレン-アクリル酸エチル-無水マレイン酸共重合体(ボンダインLX-4110 アルケマ社製)を用いた。
Polyolefin resin (P-2)
An ethylene-ethyl acrylate-maleic anhydride copolymer (manufactured by Bondine LX-4110 Arkema) was used.
ポリオレフィン樹脂(P-3)、(P-4)、(P-7)、(P-8)、(P-12)、(P-13)
特開昭61-60709号公報の実施例1に記載された方法をもとに、表1に示す組成となるように、エチレン-アクリル酸エチル-無水マレイン酸共重合体(P-3)を得た。
同様にして、表1に示す組成となるように、ポリオレフィン樹脂(P-4)、(P-7)、(P-8)、(P-12)、(P-13)を得た。
Polyolefin resin (P-3), (P-4), (P-7), (P-8), (P-12), (P-13)
Based on the method described in Example 1 of JP-A-61-60709, an ethylene-ethyl acrylate-maleic anhydride copolymer (P-3) was prepared so as to have the composition shown in Table 1. Obtained.
Similarly, polyolefin resins (P-4), (P-7), (P-8), (P-12), and (P-13) were obtained so as to have the compositions shown in Table 1.
ポリオレフィン樹脂(P-5)
プロピレン-ブテン共重合体(質量比:プロピレン/1-ブテン=65/35)280gを4つ口フラスコ中、窒素雰囲気下でキシレン470gに加熱溶解させた後、系内温度を140℃に保って攪拌しつつ、無水マレイン酸40.0g、アクリル酸エチル60.0gと、ジクミルパーオキサイド28.0gをそれぞれ2時間かけて加え、その後6時間反応させた。反応終了後、得られた反応物を多量のアセトン中に投入し、樹脂を析出させ、ポリオレフィン樹脂(P-5)を得た。
Polyolefin resin (P-5)
After 280 g of a propylene-butene copolymer (mass ratio: propylene / 1-butene = 65/35) was heat-dissolved in 470 g of xylene under a nitrogen atmosphere in a four-necked flask, the temperature inside the system was maintained at 140 ° C. While stirring, 40.0 g of maleic anhydride, 60.0 g of ethyl acrylate and 28.0 g of dicumyl peroxide were added over 2 hours, respectively, and then reacted for 6 hours. After completion of the reaction, the obtained reaction product was put into a large amount of acetone to precipitate a resin, and a polyolefin resin (P-5) was obtained.
ポリオレフィン樹脂(P-6)
アイソタクチック構造のホモポリプロピレン樹脂(MFR=0.1g/10分-170℃・2160g)を窒素ガス通気下、常圧において、360℃×80分の熱減成処理を施し、得られたポリプロピレン樹脂1000gをジャケット付き反応器に入れ、窒素置換した。次いで、180℃まで加熱昇温し溶融させた後、無水マレイン酸125g、アクリル酸エチル100gを加え、均一に混合した。そこに、ジクミルパーオキサイド6.3gを溶解させたキシレン125gを滴下し、180℃で30分撹拌し反応させた。反応終了後、得られた反応物を多量のアセトン中に投入し、樹脂を析出させ、ポリオレフィン樹脂(P-6)を得た。
Polyolefin resin (P-6)
Polypropylene obtained by subjecting an isotactic structure homopolypropylene resin (MFR = 0.1 g / 10 minutes-170 ° C., 2160 g) to heat reduction treatment at normal pressure for 360 ° C. x 80 minutes under nitrogen gas aeration. 1000 g of the resin was placed in a reactor with a jacket and replaced with nitrogen. Then, after heating to 180 ° C. and melting, 125 g of maleic anhydride and 100 g of ethyl acrylate were added and mixed uniformly. 125 g of xylene in which 6.3 g of dicumyl peroxide was dissolved was added dropwise thereto, and the mixture was stirred and reacted at 180 ° C. for 30 minutes. After completion of the reaction, the obtained reaction product was put into a large amount of acetone to precipitate a resin, and a polyolefin resin (P-6) was obtained.
ポリオレフィン樹脂(P-9)
ポリオレフィン樹脂(P-5)の製造において、アクリル酸エチルを加えなかった以外は同様の操作を行って、ポリオレフィン樹脂(P-9)を得た。
Polyolefin resin (P-9)
In the production of the polyolefin resin (P-5), the same operation was carried out except that ethyl acrylate was not added to obtain a polyolefin resin (P-9).
ポリオレフィン樹脂(P-10)
ポリオレフィン樹脂(P-6)の製造において、アクリル酸エチルを加えなかった以外は同様の操作を行って、ポリオレフィン樹脂(P-10)を得た。
Polyolefin resin (P-10)
In the production of the polyolefin resin (P-6), the same operation was carried out except that ethyl acrylate was not added to obtain a polyolefin resin (P-10).
ポリオレフィン樹脂(P-11)
エチレン-メタクリル酸共重合体(ニュクレルAN42115C 三井・デュポンケミカル社製)を用いた。
Polyolefin resin (P-11)
An ethylene-methacrylic acid copolymer (Nucrel AN42115C manufactured by Mitsui DuPont Chemical Co., Ltd.) was used.
実施例1
ヒーター付きの密閉できる耐圧1L容ガラス容器を備えた攪拌機を用いて、60.0gのポリオレフィン樹脂(P-1)、60.0gのイソプロパノール(以下、IPA)3.9g(樹脂中の無水マレイン酸のカルボキシル基に対して1.2倍当量)のN,N-ジメチルエタノールアミン(以下、DMEA)および176.1gの蒸留水をガラス容器内に仕込み、攪拌翼の回転速度を300rpmとして攪拌しながら、ヒーターの電源を入れ、140℃まで昇温した。140℃に保った状態で、60分間攪拌を行った。その後、攪拌速度を維持したまま加熱を止め、100℃まで60分間かけて冷却した後、水浴につけて、40℃まで30分間かけて冷却した。300メッシュのステンレス製フィルター(線径0.035mm、平織)で加圧濾過(空気圧0.2MPa)し、乳白色の均一な水性分散体を得た。
Example 1
Using a stirrer equipped with a sealed glass container with a pressure resistance of 1 L with a heater, 60.0 g of polyolefin resin (P-1) and 60.0 g of isopropanol (hereinafter, IPA) 3.9 g (maleic anhydride in the resin). N, N-dimethylethanolamine (hereinafter referred to as DMEA) and 176.1 g of distilled water (1.2 times the equivalent of the carboxyl group of the above) are charged in a glass container, and the stirring blade is stirred at a rotation speed of 300 rpm. The heater was turned on and the temperature was raised to 140 ° C. The mixture was stirred for 60 minutes while being kept at 140 ° C. Then, the heating was stopped while maintaining the stirring speed, and after cooling to 100 ° C. for 60 minutes, the mixture was immersed in a water bath and cooled to 40 ° C. for 30 minutes. A 300-mesh stainless steel filter (wire diameter 0.035 mm, plain weave) was used for pressure filtration (pneumatic pressure 0.2 MPa) to obtain a milky white uniform aqueous dispersion.
実施例2
実施例1において、表2に示したようにDMEAの量を変更した以外は同様の操作を行った。
Example 2
In Example 1, the same operation was performed except that the amount of DMEA was changed as shown in Table 2.
実施例3
実施例1において、表2に示したように攪拌温度(140℃)から100℃までの平均冷却速度を変更した以外は同様の操作を行った。
Example 3
In Example 1, the same operation was performed except that the average cooling rate from the stirring temperature (140 ° C.) to 100 ° C. was changed as shown in Table 2.
実施例4
実施例1において、表2に示したように100℃から40℃までの平均冷却速度を変更した以外は同様の操作を行った。
Example 4
In Example 1, the same operation was performed except that the average cooling rate from 100 ° C. to 40 ° C. was changed as shown in Table 2.
実施例5
実施例1において、攪拌時の温度を120℃に変更した以外は同様の操作を行った。
Example 5
In Example 1, the same operation was performed except that the temperature at the time of stirring was changed to 120 ° C.
実施例6、8~11
実施例1において、ポリオレフィン樹脂を、表2に示すように、それぞれP-2~P-6に変更した以外は同様の操作を行った。
Examples 6, 8-11
In Example 1, the same operation was performed except that the polyolefin resin was changed to P-2 to P-6, respectively, as shown in Table 2.
実施例7
実施例6において、攪拌時の温度を120℃に変更した以外は同様の操作を行った。
Example 7
In Example 6, the same operation was performed except that the temperature at the time of stirring was changed to 120 ° C.
実施例12
実施例1において、2段階で冷却せず、攪拌温度(140℃)から40℃まで100分かけて1段階で冷却した以外は同様の操作を行った。
Example 12
In Example 1, the same operation was performed except that the mixture was not cooled in two steps and was cooled in one step from the stirring temperature (140 ° C.) to 40 ° C. over 100 minutes.
実施例13
実施例1において、1段階目の冷却を攪拌温度から80℃まで90分かけて行い、2段階目の冷却を80℃から40℃まで20分かけて行った以外は、同様の操作を行った。
Example 13
In Example 1, the same operation was performed except that the first stage cooling was performed from the stirring temperature to 80 ° C. over 90 minutes, and the second stage cooling was performed from 80 ° C. to 40 ° C. over 20 minutes. ..
実施例14
実施例1において、有機溶剤をテトラヒドロフラン(THF)に変更した以外は、同様の操作を行った。
Example 14
In Example 1, the same operation was performed except that the organic solvent was changed to tetrahydrofuran (THF).
実施例15
実施例1において、表2に示すようにIPAの添加量を変更した以外は、同様の操作を行った。
Example 15
In Example 1, the same operation was performed except that the amount of IPA added was changed as shown in Table 2.
比較例1
実施例1において、表2に示すように140℃から100℃までの平均冷却速度を変更した以外は、同様の操作を行った。
Comparative Example 1
In Example 1, the same operation was performed except that the average cooling rate from 140 ° C. to 100 ° C. was changed as shown in Table 2.
比較例2~6
比較例1において、ポリオレフィン樹脂を、表2に示すように、それぞれP-2、P-4、P-5、P-6、P-7に変更した以外は、同様の操作を行った。
Comparative Examples 2 to 6
In Comparative Example 1, the same operation was performed except that the polyolefin resin was changed to P-2, P-4, P-5, P-6, and P-7, respectively, as shown in Table 2.
比較例7
実施例1において、表2に示すようにIPAの添加量、DMEAの添加量を変更した以外は、同様の操作を行った。
Comparative Example 7
In Example 1, the same operation was performed except that the amount of IPA added and the amount of DMEA added were changed as shown in Table 2.
比較例8~14
実施例1において、ポリオレフィン樹脂を、表2に示すように、それぞれP-7~P-13に変更した以外は同様の操作を行った。
Comparative Examples 8-14
In Example 1, the same operation was performed except that the polyolefin resin was changed to P-7 to P-13, respectively, as shown in Table 2.
実施例、比較例における水性分散体の製造条件を、表2にまとめて示す。
実施例1~15、比較例1~14で得られた水性分散体、およびそれらからなる塗膜の構成、評価結果を表3、表4にまとめて示す。 Tables 3 and 4 show the configurations and evaluation results of the aqueous dispersions obtained in Examples 1 to 15 and Comparative Examples 1 to 14, and the coating film composed of them.
実施例1~15のように、本発明の水性分散体は、塗膜とした場合の外観欠点が抑制され、バリア性、防錆性に優れる塗膜を得ることが可能であった。
また、実施例2のように水性分散時の塩基性化合物の添加量を少なくしたり、実施例15のように有機溶剤の添加量を少なくしたりしても、本発明の水性分散体を得ることができ、各性能に優れる塗膜を得ることが可能であった。
さらにまた、実施例3または4のように水性分散時の平均冷却速度を早くしたり、実施例5のように水性分散時の攪拌温度を低くしたり、実施例12のように2段階ではなく1段階で冷却したり、実施例13のように1段階目の冷却における温度を変更したりしても、本発明の水性分散体を得ることができ、各性能に優れる塗膜を得ることが可能であった。
さらにまた、実施例6~11のように用いるポリオレフィン樹脂の種類を変更したり、実施例14のように添加する有機溶剤の種類を変更したりしても、本発明の水性分散体を得ることができ、各性能に優れる塗膜を得ることが可能であった。
As in Examples 1 to 15, the aqueous dispersion of the present invention suppresses appearance defects when used as a coating film, and it is possible to obtain a coating film having excellent barrier properties and rust prevention properties.
Further, the aqueous dispersion of the present invention can be obtained even if the addition amount of the basic compound at the time of aqueous dispersion is reduced as in Example 2 or the addition amount of the organic solvent is reduced as in Example 15. It was possible to obtain a coating film having excellent performance.
Furthermore, the average cooling rate during aqueous dispersion is increased as in Example 3 or 4, the stirring temperature during aqueous dispersion is lowered as in Example 5, and the two steps are not used as in Example 12. The aqueous dispersion of the present invention can be obtained even by cooling in one step or changing the temperature in the first step cooling as in Example 13, and a coating film having excellent performance can be obtained. It was possible.
Furthermore, the aqueous dispersion of the present invention can be obtained by changing the type of the polyolefin resin used as in Examples 6 to 11 or changing the type of the organic solvent to be added as in Example 14. It was possible to obtain a coating film with excellent performance.
比較例1~5では、水性分散時における冷却時の平均冷却速度が速かったことから、得られた水性分散体においては、レーザー回折法で測定した体積粒度分布において99.9%径が10μmを超えた。この水性分散体から得られた塗膜は、外観欠点が多く、バリア性、防錆性に劣る結果となった。 In Comparative Examples 1 to 5, since the average cooling rate during cooling during aqueous dispersion was high, the obtained aqueous dispersion had a 99.9% diameter of 10 μm in the volume particle size distribution measured by the laser diffraction method. Beyond. The coating film obtained from this aqueous dispersion has many defects in appearance, resulting in inferior barrier properties and rust prevention properties.
比較例6は、(メタ)アクリル酸エステル成分の含有量が本発明の規定範囲を下回るポリオレフィン樹脂中を用いて、水性分散時における冷却時の平均冷却速度を速い条件としたものである。得られた水性分散体は、レーザー回折法で測定した体積粒度分布において99.9%径が10μmを超えており、また、この水性分散体から得られた塗膜は、外観欠点が多く、バリア性、防錆性に劣る結果となった。 In Comparative Example 6, the content of the (meth) acrylic acid ester component is less than the specified range of the present invention in the polyolefin resin, and the average cooling rate at the time of cooling at the time of aqueous dispersion is set to a high condition. The obtained aqueous dispersion has a 99.9% diameter of more than 10 μm in the volume particle size distribution measured by the laser diffraction method, and the coating film obtained from this aqueous dispersion has many defects in appearance and is a barrier. The result was inferior in properties and rust prevention.
比較例7では、水性分散時における有機溶剤、塩基性化合物の添加量が少なかったため、動的光散乱法で測定される体積平均粒子径が0.3μmを超える水性分散体が得られた。この水性分散体から得られた塗膜における外観欠点は少なかったものの、バリア性、防錆性に劣る結果となった。 In Comparative Example 7, since the amount of the organic solvent and the basic compound added at the time of aqueous dispersion was small, an aqueous dispersion having a volume average particle diameter of more than 0.3 μm measured by a dynamic light scattering method was obtained. Although there were few appearance defects in the coating film obtained from this aqueous dispersion, the result was that the barrier property and the rust preventive property were inferior.
比較例8の水性分散体は、(メタ)アクリル酸エステル成分の含有量が本発明の規定範囲を下回るポリオレフィン樹脂を用いたものである。この水性分散体の99.9%径、体積平均粒子径は本発明の範囲であったが、得られた塗膜は、バリア性、防錆性に劣る結果となった。 The aqueous dispersion of Comparative Example 8 uses a polyolefin resin in which the content of the (meth) acrylic acid ester component is less than the specified range of the present invention. The 99.9% diameter and volume average particle diameter of this aqueous dispersion were within the range of the present invention, but the obtained coating film was inferior in barrier property and rust prevention property.
比較例9の水性分散体は、(メタ)アクリル酸エステル成分の含有量が本発明の規定範囲を上回るポリオレフィン樹脂を用いたものである。この水性分散体の99.9%径、体積平均粒子径は本発明の範囲であったが、得られた塗膜は、バリア性、防錆性に劣る結果となった。 The aqueous dispersion of Comparative Example 9 uses a polyolefin resin in which the content of the (meth) acrylic acid ester component exceeds the specified range of the present invention. The 99.9% diameter and volume average particle diameter of this aqueous dispersion were within the range of the present invention, but the obtained coating film was inferior in barrier property and rust prevention property.
比較例10~12の水性分散体は、(メタ)アクリル酸エステル成分を含まないポリオレフィン樹脂を用いたものである。この水性分散体の99.9%径、体積平均粒子径は本発明の範囲であったが、得られた塗膜は、バリア性、防錆性に劣る結果となった。 The aqueous dispersions of Comparative Examples 10 to 12 used a polyolefin resin containing no (meth) acrylic acid ester component. The 99.9% diameter and volume average particle diameter of this aqueous dispersion were within the range of the present invention, but the obtained coating film was inferior in barrier property and rust prevention property.
比較例13は、不飽和カルボン酸成分の含有量が本発明の規定範囲を下回るポリオレフィン樹脂を用いたものである。ポリオレフィン樹脂が溶媒によって膨潤するのみで分散せず、水性分散体を得ることができなかった。 Comparative Example 13 uses a polyolefin resin in which the content of the unsaturated carboxylic acid component is below the specified range of the present invention. The polyolefin resin only swelled with the solvent and did not disperse, so that an aqueous dispersion could not be obtained.
比較例14の水性分散体は、不飽和カルボン酸成分の含有量が本発明の規定範囲を上回るポリオレフィン樹脂を用いたものである。この水性分散体は、99.9%径、体積平均粒子径は本発明の範囲であったが、得られた塗膜は、バリア性、防錆性に劣る結果となった。
The aqueous dispersion of Comparative Example 14 uses a polyolefin resin in which the content of the unsaturated carboxylic acid component exceeds the specified range of the present invention. This aqueous dispersion had a diameter of 99.9% and a volume average particle diameter within the range of the present invention, but the obtained coating film was inferior in barrier property and rust prevention property.
Claims (5)
The method for producing an aqueous dispersion of a polyolefin resin according to claim 3 or 4, wherein the stirring step is stirring at a temperature of 110 ° C. or higher and 20 ° C. or higher higher than the melting point of the polyolefin resin.
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