CN117715972A - Aqueous polyolefin resin dispersion and process for producing the same - Google Patents
Aqueous polyolefin resin dispersion and process for producing the same Download PDFInfo
- Publication number
- CN117715972A CN117715972A CN202280052222.0A CN202280052222A CN117715972A CN 117715972 A CN117715972 A CN 117715972A CN 202280052222 A CN202280052222 A CN 202280052222A CN 117715972 A CN117715972 A CN 117715972A
- Authority
- CN
- China
- Prior art keywords
- polyolefin resin
- aqueous dispersion
- aqueous
- particle diameter
- cooling
- Prior art date
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- Pending
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- 239000006185 dispersion Substances 0.000 title claims abstract description 135
- 229920005672 polyolefin resin Polymers 0.000 title claims abstract description 110
- 238000000034 method Methods 0.000 title claims abstract description 55
- 230000008569 process Effects 0.000 title claims description 5
- 239000002245 particle Substances 0.000 claims abstract description 86
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000012736 aqueous medium Substances 0.000 claims abstract description 25
- 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
- 230000001186 cumulative effect Effects 0.000 claims abstract description 7
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract 2
- 239000011248 coating agent Substances 0.000 claims description 74
- 238000000576 coating method Methods 0.000 claims description 70
- 238000001816 cooling Methods 0.000 claims description 49
- 238000003756 stirring Methods 0.000 claims description 28
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 4
- 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 description 35
- 239000003960 organic solvent Substances 0.000 description 34
- 229920005989 resin Polymers 0.000 description 28
- 239000011347 resin Substances 0.000 description 28
- 230000004888 barrier function Effects 0.000 description 22
- -1 ethylene, propylene, isobutylene Chemical group 0.000 description 22
- 229920001577 copolymer Polymers 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 19
- 150000001875 compounds Chemical class 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 16
- 238000001035 drying Methods 0.000 description 15
- 239000000853 adhesive Substances 0.000 description 14
- 230000001070 adhesive effect Effects 0.000 description 14
- 230000007547 defect Effects 0.000 description 14
- 239000000758 substrate Substances 0.000 description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 150000007514 bases Chemical class 0.000 description 9
- 230000002401 inhibitory effect Effects 0.000 description 9
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000003995 emulsifying agent Substances 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000004743 Polypropylene Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 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
- 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 6
- 230000002209 hydrophobic effect Effects 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000010954 inorganic particle Substances 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 4
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920001155 polypropylene 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
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-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
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 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
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-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
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000007334 copolymerization reaction 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
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 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
- 239000011780 sodium chloride Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 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
- 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
- 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
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-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
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-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
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 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
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- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 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
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
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- 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
- 239000000084 colloidal system Substances 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
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- 125000003700 epoxy group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 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
- 239000008397 galvanized steel Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
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- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
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- 239000007788 liquid Substances 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
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- 230000000704 physical effect Effects 0.000 description 2
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- 239000000047 product Substances 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 235000014692 zinc oxide Nutrition 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
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- 238000005160 1H NMR spectroscopy Methods 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
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- ASUDFOJKTJLAIK-UHFFFAOYSA-N 2-methoxyethanamine Chemical compound COCCN ASUDFOJKTJLAIK-UHFFFAOYSA-N 0.000 description 1
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 1
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 1
- SOYBEXQHNURCGE-UHFFFAOYSA-N 3-ethoxypropan-1-amine Chemical compound CCOCCCN SOYBEXQHNURCGE-UHFFFAOYSA-N 0.000 description 1
- JSGVZVOGOQILFM-UHFFFAOYSA-N 3-methoxy-1-butanol Chemical compound COC(C)CCO JSGVZVOGOQILFM-UHFFFAOYSA-N 0.000 description 1
- MFKRHJVUCZRDTF-UHFFFAOYSA-N 3-methoxy-3-methylbutan-1-ol Chemical compound COC(C)(C)CCO MFKRHJVUCZRDTF-UHFFFAOYSA-N 0.000 description 1
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- 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
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Abstract
An aqueous polyolefin resin dispersion contains polyolefin resin particles and an aqueous medium. The polyolefin resin contains 0.1 to 10 mass% of an unsaturated carboxylic acid component and 1 to 20 mass% of a (meth) acrylic acid ester component. The polyolefin resin particles have a volume average particle diameter of 0.3 [ mu ] m or less as measured by a dynamic light scattering method, and 99.9% of a volume particle diameter cumulative distribution accumulated from the small particle diameter side among volume particle diameter distributions as measured by a laser diffraction method has a diameter of 10 [ mu ] m or less.
Description
Technical Field
The present invention relates to an aqueous dispersion of a polyolefin resin.
Background
Since an aqueous dispersion of a polyolefin resin can provide a coating film having excellent adhesion to various substrates, a wide range of applications have been developed. Among them, an aqueous dispersion using an acid-modified polyolefin resin containing a (meth) acrylic acid ester as a copolymerization component has high versatility as a substrate, and is widely used for a coating agent, an adhesive, and the like (for example, patent document 1).
Prior art literature
Patent literature
Patent document 1: japanese patent No. 3699935
Disclosure of Invention
In particular, in applications where the aqueous dispersion is susceptible to the surrounding environment such as humidity or applications where the content is stored stably for a long period of time (metal products, electronic devices, automobile parts, packaging materials, etc.), barrier properties and rust resistance are sometimes required, and improvement of performance is desired. That is, the technical problem of the present invention is to provide an aqueous dispersion capable of forming a coating film having few appearance defects and excellent barrier properties and rust resistance.
As a result of intensive studies to solve the above problems, the present inventors have found that coarse resin particles which cannot be confirmed by a dynamic light scattering method, which is a conventional method for measuring a resin particle diameter, exist in the aqueous dispersion, and that the presence of the coarse resin particles causes appearance defects (fine protrusions on the surface of the coating film, cracks in the coating film, and the like) of the coating film, and as a result, barrier properties and rust preventing properties are found to be reduced in the coating film.
That is, the present inventors have found that if the resin particle diameter of an aqueous dispersion containing polyolefin resin particles is within a specific range as measured by a laser diffraction method, the coating film obtained from the aqueous dispersion is suppressed in appearance defects and is excellent in barrier properties and rust inhibitive performance because coarse resin particles are not contained and are uniformly dispersed in an aqueous medium, and completed the present invention. Namely, the gist of the present invention is as follows.
The aqueous polyolefin resin dispersion containing polyolefin resin particles and an aqueous medium is characterized in that the polyolefin resin contains 0.1-10 mass% of an unsaturated carboxylic acid component and 1-20 mass% of a (meth) acrylic acid ester component, the polyolefin resin particles have a volume average particle diameter of 0.3 [ mu ] m or less as measured by a dynamic light scattering method, and 99.9% of a volume particle diameter cumulative distribution accumulated from the small particle diameter side among the volume particle diameter distributions as measured by a laser diffraction method has a diameter of 10 [ mu ] m or less.
The coating film of the present invention is obtained from the above-mentioned aqueous polyolefin resin dispersion.
The method for producing an aqueous polyolefin resin dispersion of the present invention is a method for producing the above-mentioned aqueous polyolefin resin dispersion, and is characterized by comprising: and a cooling step of cooling the polyolefin resin and the aqueous medium at a speed of 1 ℃ per minute or less after the stirring step of stirring the polyolefin resin and the aqueous medium at a temperature of 110 ℃ or more.
According to the method for producing an aqueous polyolefin resin dispersion of the present invention, the cooling step preferably comprises: a first cooling step of cooling from the highest temperature to a temperature of 100 ℃ or lower and exceeding 40 ℃ at a cooling rate of 1 ℃ per minute or lower, and a second cooling step of cooling to 40 ℃ or lower at a cooling rate of 3 ℃ per minute or lower.
According to the method for producing an aqueous polyolefin resin dispersion of the present invention, the stirring step is preferably carried out at a temperature of 110℃or higher and 20℃or higher than the melting point of the polyolefin resin.
The aqueous polyolefin resin dispersion of the present invention has polyolefin resin particles stably and uniformly dispersed in an aqueous medium with a small particle diameter and without containing coarse particles, and thus the appearance defect of the obtained coating film is suppressed, and the barrier property and the rust inhibitive performance are excellent.
Detailed Description
The aqueous polyolefin resin dispersion of the present invention (hereinafter, sometimes simply referred to as "aqueous dispersion") contains polyolefin resin particles and an aqueous medium.
(polyolefin resin)
The olefin component as the main component of the polyolefin resin is not particularly limited, and examples thereof include olefins such as ethylene, propylene, isobutylene, 2-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-pentene, norbornene and the like, dienes such as butadiene and isoprene and the like. Or a mixture thereof. In addition, a copolymer obtained by copolymerizing 2 or more kinds of olefin components may be used.
The polyolefin resin contains an unsaturated carboxylic acid component. Examples of the unsaturated carboxylic acid component include half esters and half amides of unsaturated dicarboxylic acids, in addition to acrylic acid, methacrylic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, and crotonic acid. Among them, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are preferable, and acrylic acid and maleic anhydride are particularly preferable, from the viewpoint of obtaining a coating film having more excellent adhesion to a substrate.
The unsaturated carboxylic acid component in the polyolefin resin is contained by random copolymerization, block copolymerization, graft copolymerization (graft modification), or the like.
The content of the unsaturated carboxylic acid component in the polyolefin resin is desirably 0.1 to 10% by mass, preferably 1 to 8% by mass, and more preferably 2 to 5% by mass. If the content of the unsaturated carboxylic acid component in the polyolefin resin is less than 0.1 mass%, it may be difficult to obtain 2 kinds of resin particles having a particle diameter in a specific range, or it may be difficult to disperse the resin in an aqueous state. In addition, if the content of the unsaturated carboxylic acid component in the polyolefin resin exceeds 10 mass%, the polyolefin resin may lose its low water absorption and water resistance, and therefore, even if the above 2 kinds of particle diameters are within a specific range, the obtained coating film may be poor in barrier property and rust resistance.
The content of the (meth) acrylate component in the polyolefin resin is desirably 1 to 20 mass%, preferably 2 to 19 mass%, more preferably 4 to 18 mass%.
If the content of the (meth) acrylic acid ester component of the polyolefin resin deviates from the above range, the barrier property and rust inhibitive performance of the obtained coating film are poor even if the above 2 particle diameters are within the specific range.
Examples of the (meth) acrylic acid ester component include a (meth) acrylic acid ester component such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, a maleic acid diester component such as dimethyl maleate, diethyl maleate, dibutyl maleate, an alkyl vinyl ether component such as methyl vinyl ether and ethyl vinyl ether, a vinyl ester component such as vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl versatate, a vinyl alcohol obtained by saponifying a vinyl ester component with a basic compound or the like, a (meth) acrylamide component, and the like, and mixtures thereof. Among them, the (meth) acrylate component and the vinyl ester component are preferable, and the (meth) acrylate component is more preferable. The term "(meth) acrylic acid" means "acrylic acid to methacrylic acid".
Specific examples of the polyolefin resin include ethylene/(meth) acrylic acid methyl ester/maleic anhydride copolymer, ethylene/(meth) acrylic acid ethyl ester/maleic anhydride copolymer, ethylene/(meth) acrylic acid butyl ester/maleic anhydride copolymer, propylene/1-butene/(meth) acrylic acid methyl ester/maleic anhydride copolymer, propylene/1-butene/(meth) acrylic acid ethyl ester/maleic anhydride copolymer, propylene/1-butene/(meth) acrylic acid butyl ester/maleic anhydride copolymer, propylene/(meth) acrylic acid methyl ester/maleic anhydride copolymer, propylene/(meth) acrylic acid ethyl ester/maleic anhydride copolymer, propylene/(meth) acrylic acid butyl ester/maleic anhydride copolymer, ethylene/propylene/(meth) acrylic acid methyl ester/maleic anhydride copolymer, ethylene/propylene/(meth) acrylic acid ethyl ester/maleic anhydride copolymer, and ethylene/propylene/(meth) acrylic acid butyl ester/maleic anhydride copolymer.
The polyolefin resin may be chlorinated in a range of 5 to 40 mass%.
The maleic anhydride component constituting the polyolefin resin may be imidized, and the N-position thereof may be substituted with N, N-dimethylaminoethyl, N-dimethylaminopropyl, N-dimethylaminobutyl, N-diethylaminoethyl, N-diethylaminopropyl, N-diethylaminobutyl or the like.
(polyolefin resin particles)
In the aqueous dispersion of the present invention, the particle diameters of the polyolefin resin particles measured by 2 methods (dynamic light scattering method and laser diffraction method) all satisfy a specific range.
The volume average particle diameter of the polyolefin resin particles in the aqueous dispersion of the present invention is required to be 0.3 μm or less, preferably 0.25 μm or less, more preferably 0.2 μm or less, and even more preferably 0.15 μm or less, as measured by a dynamic light scattering method, from the viewpoint of fine and stable dispersion.
The volume average particle diameter of the polyolefin resin particles can be controlled by, for example, selecting the type of the basic compound and the organic solvent to be added to the aqueous medium and adjusting the amount of the basic compound and the organic solvent to be added in the method for producing an aqueous polyolefin resin dispersion described later.
In addition, the polyolefin resin particles contained in the aqueous dispersion of the present invention need to have a diameter of 99.9% of the cumulative volume particle diameter distribution (hereinafter, sometimes simply referred to as "99.9% diameter") that is cumulative from the small particle diameter side, of the cumulative volume particle diameter distribution obtained when measured by the laser diffraction method, of 10 μm or less, preferably 7 μm or less, more preferably 5 μm or less, still more preferably 2 μm or less, and particularly preferably 1 μm or less.
As a method for measuring the particle size of the resin contained in the aqueous dispersion, a dynamic light scattering method is generally used. This is because the particle diameter measurable range based on the principle of the dynamic light scattering method is considered to be about 1nm to several μm, and almost covers the range required for evaluating the performance of the aqueous dispersion. In contrast, the measurable range of the laser diffraction method is about 10nm to 3000 μm, and a large particle diameter can be measured which is far beyond the measurable upper limit of the dynamic light scattering method.
The present inventors focused on the results of particle diameter measurement by a dynamic light scattering method and the results of particle diameter measurement by a laser diffraction method of an aqueous polyolefin resin dispersion, and found the following findings: even when the average particle diameter is sufficiently small in the dynamic light scattering method, coarse particles exceeding the upper limit of the measurable range of the dynamic light scattering method may be observed by the laser diffraction method. Moreover, the present inventors found that: when the volume average particle diameter measured by the dynamic light scattering method is 0.3 μm or less and no particles exceeding approximately 10 μm are observed by the laser diffraction method, in other words, when 99.9% of the volume particle size distribution by the laser diffraction method is 10 μm or less in diameter, appearance defects of a coating film obtained from such an aqueous dispersion are suppressed, and barrier properties and rust inhibitive performance are excellent.
As a method for setting the 99.9% diameter of the resin particle diameter to a specific range by the laser diffraction method, it is preferable to set the cooling rate at the time of dispersing the polyolefin resin to a specific range in the method for producing an aqueous dispersion of the present invention described later.
(aqueous Medium)
The polyolefin resin particles of the aqueous dispersion of the present invention are dispersed in an aqueous medium. The aqueous medium of the present invention is a liquid containing water as a main component, and may contain an organic solvent or an alkaline compound, which will be described later.
(hydrophilic organic solvent)
In order to promote the dispersion of the polyolefin resin particles and reduce the dispersion particle diameter, the particle diameter specified in the present invention is satisfied, and the aqueous medium preferably contains a hydrophilic organic solvent. 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 particularly preferably 25 to 35% by mass, relative to the total aqueous medium. An aqueous medium having a content of the hydrophilic organic solvent exceeding 50 mass% cannot be considered as an aqueous medium substantially, and not only does not depart from one of the objects of the present invention (environmental protection), but also the stability of the aqueous dispersion may be lowered due to the hydrophilic organic solvent used.
In view of obtaining an aqueous dispersion having good dispersion stability, the solubility of the hydrophilic organic solvent in water at 20℃is preferably 10g/L or more, more preferably 20g/L or more, and still more preferably 50g/L or more.
The boiling point of the hydrophilic organic solvent is preferably 100 ℃ or less from the viewpoint of efficient drying and removal in the process of forming a coating film. Hydrophilic organic solvents having a boiling point exceeding 100 ℃ tend to be difficult to scatter from the coating film by drying, and particularly, the coating film dried at low temperature may have reduced water resistance, adhesion to a substrate, and the like.
Examples of the preferable hydrophilic organic solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, sec-pentanol, tert-pentanol, 1-ethyl-1-propanol, 2-methyl-1-butanol, n-hexanol, cyclohexanol, ketones such as methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, and cyclohexanone, tetrahydrofuran, and di-n-butanolEthers such as alkyl, ethers such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, 3-methoxybutyl acetate, methyl propionate, ethyl propionate, diethyl carbonate, esters such as dimethyl carbonate, glycol monomethyl ether, glycol monoethyl ether, glycol monopropyl ether, glycol monobutyl ether, glycol ethyl ether acetate and glycol derivatives such as 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 3-methoxy-3-methyl-1-butanol, methoxybutanol, acetonitrile, dimethylformamide, dimethylacetamide, diacetone alcohol, ethyl acetoacetate, 1, 2-dimethylglycerol, 1, 3-dimethylglycerol, and trimethylglycerol.
Wherein ethanol, n-propanol, isopropanol, n-butanol, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, and di-butanol are usedIn the case of an alkane, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, or diethylene glycol monomethyl ether, the dispersion of the polyolefin resin particles is more effectively promoted, and isopropyl alcohol is particularly preferable.
(hydrophobic organic solvent)
In the present invention, the aqueous dispersion may contain a plurality of these hydrophilic organic solvents in combination. In order to further promote the aqueous dispersion of the polyolefin resin, a hydrophobic organic solvent may be further contained.
As the hydrophobic organic solvent, an organic solvent having a solubility in water of less than 10g/L at 20 ℃ is preferable from the viewpoint of obtaining an aqueous dispersion having good dispersion stability. In addition, from the viewpoint of efficient drying and removal in the process of forming a coating film, an organic solvent having a boiling point of 150 ℃ or less 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 halogen solvents such as carbon tetrachloride, 1, 2-dichloroethane, 1-dichloroethylene, trichloroethylene, 1-trichloroethane, and chloroform. The content of the hydrophobic organic solvent is preferably 15% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less relative to the aqueous dispersion. If the content of the hydrophobic organic solvent exceeds 15 mass%, gelation or the like may occur.
When the organic solvent is used in the production of the aqueous dispersion, a part of the polyolefin resin may be distilled out of the system by a solvent removal treatment commonly called "stripping" after the aqueous dispersion of the polyolefin resin has been completed, thereby reducing the content of the organic solvent. The organic solvent content in the aqueous dispersion can be made 10 mass% or less by stripping, and if it is 5 mass% or less, it is more preferable that it is 1 mass% or less from the viewpoint of environment. In the stripping step, the organic solvent used for the aqueous dispersion can be distilled off substantially entirely, but the reduction in pressure of the apparatus is required to be increased or the working time is required to be prolonged, so that the lower limit of the organic solvent content is preferably about 0.01 mass% in consideration of the productivity thus produced.
The stripping method may be a method of distilling off the organic solvent by heating the aqueous dispersion under normal pressure or reduced pressure with stirring. Further, since the concentration of the solid content increases by distilling off the aqueous medium, for example, when the viscosity increases and the workability decreases, water may be added to the aqueous dispersion in advance.
The solid content concentration of the aqueous dispersion is not particularly limited and may be appropriately selected depending on the application, and for example, the aqueous dispersion may be adjusted by a method of distilling off the aqueous medium or a method of diluting with water.
(alkaline Compound)
Examples of the basic compound contained in the aqueous medium include ammonia, triethylamine, N-dimethylethanolamine, isopropylamine, aminoethanol, dimethylaminoethanol, diethylaminoethanol, ethylamine, diethylamine, isobutylamine, dipropylamine, 3-ethoxypropylamine, 3-diethylaminopropylamine, sec-butylamine, propylamine, N-butylamine, 2-methoxyethylamine, 3-methoxypropylamine, 2-dimethoxyethylamine, monoethanolamine, morpholine, N-methylmorpholine, N-ethylmorpholine, pyrrole, pyridine, and the like. Among them, ammonia, triethylamine, and N, N-dimethylethanolamine are preferable from the viewpoint of promoting dispersion of the resin.
The amount of the basic compound to be added is preferably 0.5 to 10 times equivalent, more preferably 0.8 to 8 times equivalent, particularly preferably 1.0 to 5 times equivalent, to the carboxyl group in the polyolefin resin. When the amount is less than 0.5 times the equivalent weight, 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 the amount exceeds 10 times the equivalent amount, the drying time at the time of forming a coating film may be long, or the stability of the resulting aqueous dispersion may be lowered.
(production of aqueous Dispersion)
The method for producing the aqueous dispersion of the present invention is not particularly limited, and the following method can be used: the above-mentioned various components, namely, the polyolefin resin, the aqueous medium, any of various additives, and if necessary, the organic solvent, the basic compound, and the like are heated and stirred in a sealable container to disperse the resin.
As the vessel, a solid/liquid stirring device or a device used as an emulsifying machine can be used, and for example, a device capable of pressurizing at least 0.1MPa is preferably used. The method of stirring and the rotation speed of stirring are not particularly limited, and the stirring may be performed at a low speed to such an extent that the polyolefin resin is in a uniform state in the aqueous medium. Therefore, the aqueous dispersion can be produced even in a simple apparatus without stirring at a high speed (for example, 1000rpm or more).
Among them, as a method for producing the aqueous dispersion, it is preferable to mix and stir the raw materials such as the polyolefin resin and the aqueous medium and then cool the mixture from the stirring temperature to the minimum temperature at a cooling rate of 1 ℃/min or less.
The detailed mechanism is not clear, and the inventors have conducted various studies and as a result found that: by cooling at a cooling rate of 1 ℃/min or less, 99.9% of the diameter of the polyolefin resin particles measured by the laser diffraction method can be set to a specific range.
The cooling rate is more preferably low, still more preferably 0.9 ℃/min or less, particularly preferably 0.7 ℃/min or less.
The stirring temperature may be appropriately set from the viewpoints of pressure resistance, heating performance, energy cost, and the like of the apparatus, and is preferably high, preferably 110 ℃ or higher, more preferably 120 ℃ or higher, and even more preferably 140 ℃ or higher, from the viewpoints of setting the particle diameter of the resin to the above range and dispersion stability.
The minimum temperature after cooling is not particularly limited, but is, for example, preferably 100 ℃ or lower, and more preferably 40 ℃ or lower.
The cooling may be performed in 1 stage at a cooling rate of 1 ℃/min or less, or may be performed in a plurality of stages of 2 or more stages having different cooling rates.
For example, it is possible to use 2-stage cooling in which the stirring temperature is cooled to 100 ℃ or lower and a temperature exceeding 40 ℃ at a cooling rate of 1 ℃ or lower and then cooled to 40 ℃ or lower at a cooling rate of 3 ℃ or lower. In this case, the cooling rate in the 2 nd stage is preferably 3 ℃/min or less, more preferably 2 ℃/min or less, and still more preferably 1 ℃/min or less.
The method for adjusting the cooling temperature is not particularly limited, and examples thereof include the following methods: the temperature of the heater of the vessel is adjusted, or the temperature of vapor, heat medium, water, etc. in the jacket is adjusted when using the vessel having the jacket.
(non-volatile Water-based auxiliary agent)
The aqueous dispersion of the invention does not exclude the inclusion of non-volatile, but preferably does not substantially contain non-volatile, aqueous adjuvants. The present invention can produce an aqueous dispersion having excellent dispersion stability of polyolefin resin particles and no coarse resin particles, even if the aqueous dispersion does not substantially contain a nonvolatile aqueous auxiliary agent.
The "aqueous auxiliary" refers to a reagent or a compound added to promote the aqueous dispersion and stabilize the aqueous dispersion in the production of the aqueous dispersion, and the "nonvolatile" refers to a compound having no boiling point at normal pressure or a high boiling point (for example, 300 ℃ or higher) at normal pressure.
By "substantially free of nonvolatile aqueous auxiliary" is meant that such auxiliary is not used in the production (in the case of aqueous dispersion of polyolefin resin), and the resulting aqueous dispersion does not contain such auxiliary. The nonvolatile water-based auxiliary agent is preferably 5 mass% or less, more preferably 2 mass% or less, further preferably less than 0.5 mass%, and most preferably 0 mass% relative to the polyolefin resin component.
Examples of the nonvolatile water-based auxiliary agent in the present invention include an emulsifier, a compound having a protective colloid function, a modified wax, an acid-modified compound having a high acid value, and a water-soluble polymer.
Examples of the emulsifier include cationic emulsifiers, anionic emulsifiers, nonionic emulsifiers, and amphoteric emulsifiers, and surfactants are included in addition to emulsifiers generally used in emulsion polymerization. Examples of the anionic emulsifier include higher alcohol sulfate, higher alkyl sulfonate, higher carboxylate, alkylbenzenesulfonate, polyoxyethylene alkyl sulfate, polyoxyethylene alkylphenyl ether sulfate, and vinyl sulfosuccinate. Examples of the nonionic emulsifier include polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyethylene glycol fatty acid ester, ethylene oxide-propylene oxide block copolymer, polyoxyethylene fatty acid amide, and a compound having a polyoxyethylene structure such as an ethylene oxide-propylene oxide copolymer, and sorbitan derivative such as polyoxyethylene sorbitan fatty acid ester. Examples of the amphoteric emulsifier include lauryl betaine and lauryl dimethylamine oxide.
Examples of the compound having a protective colloid function, modified wax, acid-modified compound having a high acid value, and water-soluble polymer include polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, modified starch, polyvinylpyrrolidone, polyacrylic acid and salts thereof, carboxyl-containing polyethylene wax, carboxyl-containing polypropylene wax, acid-modified polyolefin wax having a number average molecular weight of usually 5000 or less and salts thereof, acrylic acid-maleic anhydride copolymer and salts thereof, styrene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid copolymer, isobutylene-maleic anhydride alternating copolymer, carboxyl-containing polymer having an unsaturated carboxylic acid content of 10% by mass or more such as (meth) acrylic acid- (meth) acrylic acid ester copolymer and salts thereof, polyitaconic acid and salts thereof, amino-containing water-soluble acrylic acid copolymer, gelatin, acacia, casein, and the like, which are generally used as dispersion stabilizers for fine particles.
(additive)
The aqueous dispersion of the present invention may contain other polymers, adhesion imparting agents, inorganic particles, crosslinking agents, pigments, dyes, etc. in order to further improve the properties according to the purpose.
The other polymer and the adhesion imparting agent are not particularly limited. For example, polyvinyl acetate, an ethylene-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, an ethylene- (meth) acrylic acid copolymer, an ethylene- (meth) acrylic acid ester-maleic anhydride copolymer, a styrene-maleic acid resin, a styrene-butadiene resin, a butadiene resin, an acrylonitrile-butadiene resin, a polyurethane resin, a poly (meth) acrylonitrile resin, (meth) acrylamide resin, a chlorinated polyethylene resin, a chlorinated polypropylene resin, a polyester resin, a modified nylon resin, rosin, a phenol resin, a silicone resin, an epoxy resin, or the like, or an adhesion imparting agent containing them may be used in combination as required.
These polymers may be used in a solid state, but in terms of maintaining the stability of the aqueous dispersion, a substance processed into an aqueous dispersion is preferably used.
Examples of the inorganic particles include metal oxides such as magnesium oxide, zinc oxide, and tin oxide, inorganic compounds such as calcium carbonate, and silica, and layered inorganic compounds such as vermiculite, montmorillonite, hectorite, hydrotalcite, and synthetic mica. The average particle diameter of these inorganic particles is preferably 0.005 to 10 μm from the viewpoint of transparency of the coating film, etc. As the inorganic particles, a plurality of inorganic particles may be used in combination.
As the crosslinking agent, a crosslinking agent having self-crosslinking property, a compound having a plurality of functional groups reactive with an unsaturated carboxylic acid component in the molecule, a metal having polyvalent coordination teeth, or the like can be used.
Specifically, the composition containsThe oxazoline group-containing compound, carbodiimide group-containing compound, isocyanate group-containing compound, epoxy group-containing compound, melamine compound, urea compound, zirconium salt compound, silane coupling agent, etc., may be used in combination as required. Among them, from the viewpoint of easy handling, it is preferable to contain +.>An oxazoline group-containing compound, a carbodiimide group-containing compound, an isocyanate group-containing compound, and an epoxy group-containing compound.
Examples of the pigment and dye include titanium oxide, zinc white, and carbon black, and any of disperse dyes, acid dyes, cationic dyes, and reactive dyes can be used.
The aqueous dispersion of the present invention may further contain various agents such as leveling agents, defoaming agents, air bubble and pore preventing agents, pigment dispersing agents, ultraviolet absorbers, thickeners, weather-proofing agents, flame retardants, and the like, as necessary.
(film coating)
The coating film of the present invention is obtained from the aqueous dispersion and is excellent in barrier properties. The barrier property is measured by the water vapor transmission rate, and in the present invention, the water vapor transmission rate of the coating film obtained by drying at 80℃is preferably 150 ml/(m) 2 Day MPa) or less, more preferably 100 ml/(m) 2 Day MPa) or less. The method for measuring the water vapor permeability is described in detail in examples.
The coating film obtained from the aqueous dispersion of the present invention is excellent in rust inhibitive performance. In the present invention, the coating film obtained by drying at 80 ℃ on the metal plate is sprayed with an aqueous NaCl solution, and the rust area ratio after 100 hours is preferably less than 50%. The method of calculating the rust area ratio is described in detail in examples.
As described above, in the aqueous dispersion of the present invention, since the polyolefin resin particles have a small and stable particle diameter and are uniformly dispersed in the aqueous medium without containing coarse resin particles, defects in appearance can be suppressed, and a coating film excellent in barrier properties and rust resistance can be obtained.
(formation of coating film)
The aqueous dispersion of the present invention is excellent in film forming ability. As a method for forming a coating film from the aqueous dispersion of the present invention, for example, the following methods are mentioned: the aqueous dispersion of the present invention is uniformly applied to the surfaces of various substrates, and if necessary, is set around room temperature, and then subjected to a heat treatment for drying or drying and sintering. This allows the uniform coating film to be adhered to the surfaces of various substrates.
The aqueous dispersion may be applied to the substrate by a known method such as gravure roll coating, reverse roll coating, bar coating, lip coating, air knife coating, curtain coating, spray coating, dip coating, brush coating, etc.
The coating amount of the aqueous dispersion to the substrate is not particularly limited, and is appropriately selected according to the application, and the coating amount after drying is preferably 0.01 to 100g/m 2 More preferably 0.1 to 50g/m 2 More preferably 0.2 to 30g/m 2 。
In order to adjust the coating amount, it is preferable to appropriately select a device used for coating or a use condition thereof and use the aqueous dispersion having the concentration adjusted according to the target coating film thickness. The concentration of the aqueous dispersion may be adjusted according to the composition of the charge at the time of preparation, and the aqueous dispersion once prepared may be appropriately diluted or concentrated.
As a heating device for the heat treatment after the coating, a general hot air circulation type oven, an infrared heater, or the like can be used.
The heating temperature and the heating time are appropriately selected according to the characteristics of the substrate or the addition amount of each component which can be optionally blended in the aqueous dispersion, and the lower the heating temperature, the better the heating time from the viewpoint of energy cost and damage to the substrate, and the shorter the heating time from the viewpoint of productivity. The heating temperature is preferably 20 to 130 ℃, more preferably 30 to 120 ℃, and even more preferably 40 to 100 ℃. The heating time is preferably 1 second to 20 minutes, more preferably 5 seconds to 15 minutes, and still more preferably 5 seconds to 10 minutes.
When the aqueous dispersion of the present invention contains a crosslinking agent, the heating temperature and the heating time are preferably appropriately selected depending on the type of the crosslinking agent so that the reaction between the carboxyl groups in the polyolefin resin and the crosslinking agent proceeds sufficiently.
(use)
The aqueous dispersion of the present invention can be suitably used as an adhesive, a coating agent, a primer, a paint, an ink, or the like
The aqueous dispersion of the present invention is particularly suitable for use in metal product applications, electronic equipment applications, packaging material applications, automobile parts applications, and the like, because it is more excellent in barrier properties and rust resistance when it is formed into a coating film.
Specific examples of such applications include anchor coating agents for PP extruded laminates, coating agents for secondary battery separators, primers for UV curable coating agents, primers for shoes, primers for automobile bumpers, primers for transparent cases, coatings for PP substrates, adhesives for packaging materials, adhesives for paper containers, adhesives for cover sheets, adhesives for in-mold transfer foils, adhesives for PP steel sheets, adhesives for solar cell modules, adhesives for hair-planting, adhesives for secondary battery electrodes, adhesives for secondary battery exterior, adhesives for automobile tape molding, adhesives for automobile parts, adhesives for different types of substrates, and fiber bundles.
Examples
Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
The constitution, physical properties, coating film characteristics, and the like of the aqueous polyolefin resin dispersion were measured or evaluated by the following methods.
(1) Composition of polyolefin resin
By means of 1 The measurement was performed by an H-NMR analyzer (ECA 500, 500MHz, manufactured by Japanese electronics Co., ltd.). The measurement was carried out at 120℃using tetrachloroethane (d 2) as a solvent.
(2) Melting Point of polyolefin resin
The measurement was performed by DSC method using DSC7 manufactured by Perkinelmer corporation. The sample was filled into an aluminum pan and was obtained from a curve accompanied by heat absorption and heat release when the temperature was raised to 200℃at 10℃per minute, and then lowered to-10℃at 10℃per minute, and then raised to 200℃at 10℃per minute after holding at 200℃for 5 minutes.
(3) Melt Flow Rate (MFR) of polyolefin resin
According to JIS K7210:1999, measured at 190℃under a load of 2160 g.
(4) Concentration of solid content of aqueous Dispersion
An appropriate amount of the aqueous dispersion was weighed and heated at 150℃until the mass of the residue (solid content) became constant, and the solid content concentration was determined.
(5) Number average particle diameter and volume average particle diameter of polyolefin resin particles (dynamic light scattering method)
The number average particle diameter (mn) and the volume average particle diameter (mv) were measured using a Nanotrac Wave-UZ152 particle size distribution measuring apparatus manufactured by daily necessities. The refractive index of the resin was 1.5.
(6) 99.9% diameter of polyolefin resin particles (laser diffraction method)
The particle diameter was measured by using a laser diffraction particle diameter Mastersizer 3000 manufactured by Malvern corporation, and 99.9% diameter of the cumulative distribution of volume particle diameters accumulated from the small particle diameter side in the volumetric particle size distribution was confirmed.
(7) Viscosity of aqueous dispersion
The filtered aqueous dispersion was subjected to measurement of rotational viscosity (mPas) at 20℃using a type B viscometer (DVL-BII type digital viscometer manufactured by Tokimec Co.).
(8)pH
The pH at 20℃was measured using a hand-held pH meter D-74 manufactured by HORIBA Co.
(9) Appearance defects of the coating film
The aqueous dispersion was applied to a PET film (Lumilar T60- #50, manufactured by Toray Co., ltd., thickness 50 μm width 1 m) using a gravure coater so that the thickness of the coating film was 1 μm, dried at 100℃for 15 seconds, and wound for 1000m, and then inspected for defects (fine protrusions on the surface of the coating film, cracks in the coating film, etc.) by a film winding machine (set to a scanning speed of 0.5 m/sec, and a detection sensitivity of 0.5mm or more) equipped with a transmission type defect inspection and measurement device (manufactured by FUTEC Co., ltd.). The judgment is made according to the following criteria based on the number of times of detection.
And (2) the following steps: every 1000m 2 Less than 10 times
Delta: every 1000m 2 More than 10 times and less than 100 times
X: every 1000m 2 Is more than 100 times
(10) Water vapor transmission rate (barrier property) of the coating film
(film formation under Low temperature drying)
The aqueous dispersion was applied to a corona-treated surface of a nylon film (You Niji, available from Corp. ON-15) using a Meyer rod so that the thickness of the dried coating film was 10. Mu.m, and dried at 80℃to form a coating film. The water vapor permeability of the obtained sample was measured using a moisture permeability meter (MOCON Co., ltd. PERMATRAN-W3/31 MW) at 40℃and 100% RH.
(film formation under high temperature drying)
The aqueous dispersion was applied to a corona-treated surface of a nylon film (You Niji, available from Corp. ON-15) using a Meyer rod so that the thickness of the dried coating film was 10. Mu.m, and dried at 150℃to form a coating film. The water vapor permeability of the obtained sample was measured using a moisture permeability meter (MOCON Co., ltd. PERMATRAN-W3/31 MW) at 40℃and 100% RH.
(11) Rust resistance
(film formation under Low temperature drying)
The aqueous dispersion was applied to a hot dip galvanized steel sheet (manufactured by Nippon Testpanel, inc., size 70 mm. Times.150 mm. Times.0.8 mmt) after degreasing using a Meyer bar so that the thickness of the coating film after drying was 2. Mu.m, and dried at 80℃to form a coating film. The obtained sample was sprayed with a 5 mass% aqueous NaCl solution at 35℃using a salt spray tester according to JIS Z-2371, and the rust area state of the coating film surface after 100 hours was observed. The rust area relative to the total area of the sample was calculated and evaluated as follows.
And (3) the following materials: the rust area rate is less than 5 percent
O: the rust area ratio is more than 5% and less than 10%
Delta: the rust area rate is more than 10% and less than 50%
X: the rust area rate is more than 50 percent
(film formation under high temperature drying)
The aqueous dispersion was applied to a hot dip galvanized steel sheet (manufactured by Nippon Testpanel, inc., size 70 mm. Times.150 mm. Times.0.8 mmt) after degreasing using a Meyer bar so that the thickness of the coating film after drying was 2. Mu.m, and dried at 200℃to form a coating film. The obtained sample was sprayed with a 5 mass% aqueous NaCl solution at 35℃using a salt spray tester according to JIS Z-2371, and the rust state of the coating film surface after 100 hours was observed. The rust area relative to the total area of the sample was calculated and evaluated as follows.
And (3) the following materials: the rust area rate is less than 5 percent
O: the rust area ratio is more than 5% and less than 10%
Delta: the rust area rate is more than 10% and less than 50%
X: the rust area rate is more than 50 percent
The polyolefin resins (P-1) to (P-13) used in the examples and comparative examples are as follows. The compositions and physical properties of these polyolefin resins are shown in Table 1.
TABLE 1
Polyolefin resin (P-1)
Ethylene-ethyl acrylate-maleic anhydride copolymer (BONDINE HX-8290, manufactured by Arkema Co.) was used.
Polyolefin resin (P-2)
An ethylene-ethyl acrylate-maleic anhydride copolymer (BONDINE LX-4110, manufactured by Arkema Co.) was used.
Polyolefin resins (P-3), (P-4), (P-7), (P-8), (P-12) and (P-13)
According to the method described in example 1 of Japanese patent application laid-open No. 61-60709, an ethylene-ethyl acrylate-maleic anhydride copolymer (P-3) was obtained so as to have the composition shown in Table 1.
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.
Polyolefin resin (P-5)
280g of a propylene-butene copolymer (mass ratio: propylene/1-butene=65/35) was dissolved in 470g of xylene under nitrogen atmosphere in a four-necked flask, and after maintaining the temperature in the system at 140℃and stirring, 40.0g of maleic anhydride, 60.0g of ethyl acrylate and 28.0g of dicumyl peroxide were added thereto over 2 hours, respectively, and then the reaction was carried out for 6 hours. After the completion of the reaction, the obtained reaction product was poured into a large amount of acetone to precipitate a resin, thereby obtaining a polyolefin resin (P-5).
Polyolefin resin (P-6)
A heat decomposition treatment was performed under nitrogen aeration at a normal pressure for 360℃X 80 minutes on a isotactic polypropylene resin (MFR=0.1 g/10 min-170℃2160 g), and 1000g of the obtained polypropylene resin was placed in a jacketed reactor to be subjected to nitrogen substitution. Then, after heating to 180℃and melting, 125g of maleic anhydride and 100g of ethyl acrylate were added and mixed uniformly. To this was added dropwise 125g of xylene in which 6.3g of dicumyl peroxide was dissolved, and the mixture was stirred at 180℃for 30 minutes to effect a reaction. After the completion of the reaction, the obtained reaction product was poured into a large amount of acetone to precipitate a resin, thereby obtaining a polyolefin resin (P-6).
Polyolefin resin (P-9)
The same procedure was conducted except that ethyl acrylate was not added in the production of the polyolefin resin (P-5), to obtain a polyolefin resin (P-9).
Polyolefin resin (P-10)
The same procedure was conducted except that ethyl acrylate was not added in the production of the polyolefin resin (P-6), to obtain a polyolefin resin (P-10).
Polyolefin resin (P-11)
Ethylene-methacrylic acid copolymer (NUCREL AN42115C, manufactured by mitsubishi dupont chemical company) was used.
Example 1
60.0g of a polyolefin resin (P-1), 60.0g of isopropyl alcohol (IPA), 3.9g (1.2 times equivalent of carboxyl groups of maleic anhydride in the resin) of N, N-Dimethylethanolamine (DMEA) and 176.1g of distilled water were placed in a glass vessel using a stirrer having a pressure-resistant 1L-capacity glass vessel capable of being sealed with a heater, and the temperature was raised to 140℃by turning on the power supply of the heater while stirring the resin at a rotation speed of 300 rpm. Stirring was carried out for 60 minutes while maintaining the temperature at 140 ℃. Then, heating was stopped while maintaining the stirring speed, cooled to 100℃over 60 minutes, and then placed in a water bath, and cooled to 40℃over 30 minutes. The resulting aqueous dispersion was subjected to pressure filtration (air pressure: 0.2 MPa) using a 300-mesh stainless steel filter (wire diameter: 0.035mm, plain weave) to obtain a milky uniform aqueous dispersion.
Example 2
The same procedure was carried out except that the amount of DMEA was changed as shown in table 2 in example 1.
Example 3
The same procedure as in example 1 was carried out except that the cooling rate from the stirring temperature (140 ℃) to 100℃was changed as shown in Table 2.
Example 4
The same procedure as in example 1 was conducted except that the cooling rate was changed from 100℃to 40℃as shown in Table 2.
Example 5
The same procedure as in example 1 was conducted except that the temperature during stirring was changed to 120 ℃.
Examples 6 to 8 to 11
The same procedure as in example 1 was conducted except that the polyolefin resins were changed to P-2 to P-6 as shown in tables 2 and 3, respectively.
Example 7
The same procedure as defined in example 6 was conducted except that the temperature during stirring was changed to 120 ℃.
Example 12
The same procedure was carried out except that in example 1, the cooling was not carried out in 2 stages and the stirring temperature (140 ℃) was cooled to 40℃for 100 minutes in 1 stage.
Example 13
The same procedure as in example 1 was repeated except that the cooling in the 1 st stage was performed at a temperature of from 80℃to stirring temperature for 90 minutes and the cooling in the 2 nd stage was performed at a temperature of from 80℃to 40℃for 20 minutes.
Example 14
The same procedure as defined in example 1 was repeated except that the organic solvent was changed to Tetrahydrofuran (THF).
Example 15
The same procedure as in example 1 was carried out except that the amount of IPA added was changed as shown in Table 3.
Comparative example 1
The same procedure as in example 1 was carried out except that the cooling rate was changed from 140℃to 100℃as shown in Table 4.
Comparative examples 2 to 6
The same procedure was conducted except that the polyolefin resins in comparative example 1 were changed to P-2, P-4, P-5, P-6 and P-7 as shown in Table 4.
Comparative example 7
The same procedure as in example 1 was carried out except that the amount of IPA added and the amount of DMEA added were changed as shown in table 4.
Comparative examples 8 to 14
The same procedure as in example 1 was conducted except that the polyolefin resins were changed to P-7 to P-13 as shown in Table 5.
The conditions for producing the aqueous dispersions of examples and comparative examples, and the compositions of the aqueous dispersions obtained and the coating films formed from the aqueous dispersions, and the evaluation results are shown in tables 2 to 5.
TABLE 2
TABLE 3
1: cooling time and speed at 90 minutes from stirring temperature to 80 DEG C
2: cooling time and speed of cooling from 80 ℃ to 40 ℃ in 20 minutes.
TABLE 4
TABLE 5
In both examples and comparative examples, an aqueous dispersion was obtained by using an organic solvent and a basic compound, and performing a stirring step at a high temperature and filtration using a filter. However, when the cooling rate was high as in comparative examples 1 to 7, even though an organic solvent and an alkaline compound were used and stirred and filtered, only an aqueous dispersion having a diameter of 99.9% of the polyolefin resin particles of more than 10 μm was obtained, and when compared with examples, appearance defects were large when coating films were produced, and barrier properties and rust resistance were poor.
That is, as in examples 1 to 15, the aqueous dispersion of the present invention can suppress appearance defects in the production of a coating film, and can provide a coating film excellent in barrier properties and rust resistance.
In addition, even if the amount of the basic compound added during the aqueous dispersion is reduced as in example 2 or the amount of the organic solvent added is reduced as in example 15, the aqueous dispersion of the present invention can be obtained, and a coating film excellent in each property can be obtained.
Further, even if the cooling rate at the time of aqueous dispersion is increased as in example 3 or 4, or the stirring temperature at the time of aqueous dispersion is decreased as in example 5, or the cooling is performed in 1 stage instead of 2 stages as in example 12, or the temperature at the time of cooling in 1 st stage is changed as in example 13, the aqueous dispersion of the present invention can be obtained, and a coating film excellent in each property can be obtained.
Further, even if the type of the polyolefin resin used is changed as in examples 6 to 11 or the type of the organic solvent added is changed as in example 14, the aqueous dispersion of the present invention can be obtained, and a coating film excellent in each property can be obtained.
In comparative examples 1 to 5, since the cooling rate at the time of cooling at the time of aqueous dispersion was high, 99.9% of the volume particle size distribution in the obtained aqueous dispersion was more than 10 μm in diameter as measured by the laser diffraction method. As a result, the coating film obtained from the aqueous dispersion has many appearance defects and is poor in barrier property and rust resistance.
Comparative example 6 was conducted under conditions that the cooling rate at the time of cooling in the aqueous dispersion was made faster by using a polyolefin resin having a content of the (meth) acrylic acid ester component lower than the predetermined range of the present invention. The aqueous dispersion obtained had a volume particle size distribution of 99.9% of a diameter exceeding 10. Mu.m, as measured by a laser diffraction method, and a coating film obtained from the aqueous dispersion had a large number of appearance defects and was poor in barrier property and rust resistance.
In comparative example 7, since the addition amount of the organic solvent and the basic compound at the time of aqueous dispersion was small, an aqueous dispersion having a volume average particle diameter exceeding 0.3 μm as measured by the dynamic light scattering method was obtained. As a result, the coating film obtained from the aqueous dispersion has many appearance defects and is poor in barrier property and rust resistance.
The aqueous dispersion of comparative example 8 used a polyolefin resin having a content of the (meth) acrylic acid ester component below the prescribed range of the present invention. Although the 99.9% diameter and volume average particle diameter of the aqueous dispersion were within the range of the present invention, the resulting coating film was inferior in barrier property and rust inhibitive performance.
The aqueous dispersion of comparative example 9 used a polyolefin resin having a content of the (meth) acrylic acid ester component higher than the prescribed range of the present invention. Although the 99.9% diameter and volume average particle diameter of the aqueous dispersion were within the range of the present invention, the resulting coating film was inferior in barrier property and rust inhibitive performance.
The aqueous dispersions of comparative examples 10 to 12 used polyolefin resins containing no (meth) acrylate component. The aqueous dispersion has a 99.9% diameter and a volume average particle diameter within the range of the present invention, but the resulting coating film has poor barrier properties and rust inhibitive performance.
In comparative example 13, a polyolefin resin having an unsaturated carboxylic acid component content lower than the predetermined range of the present invention was used. The polyolefin resin is swollen only by the solvent without being dispersed, and an aqueous dispersion cannot be obtained.
The aqueous dispersion of comparative example 14 used a polyolefin resin having an unsaturated carboxylic acid component content higher than the predetermined range of the present invention. The aqueous dispersion has a 99.9% diameter and a volume average particle diameter within the range of the present invention, but the resulting coating film has poor barrier properties and rust inhibitive performance.
Claims (5)
1. An aqueous polyolefin resin dispersion comprising polyolefin resin particles and an aqueous medium, wherein the polyolefin resin comprises 0.1 to 10 mass% of an unsaturated carboxylic acid component and 1 to 20 mass% of a (meth) acrylic acid ester component, the polyolefin resin particles have a volume average particle diameter of 0.3 [ mu ] m or less as measured by a dynamic light scattering method, and 99.9% of a volume particle diameter cumulative distribution accumulated from the small particle diameter side among the volume particle diameter distributions as measured by a laser diffraction method has a diameter of 10 [ mu ] m or less.
2. A coating film obtained from the aqueous polyolefin resin dispersion according to claim 1.
3. A process for producing the aqueous polyolefin resin dispersion according to claim 1, which comprises: and a cooling step of cooling the polyolefin resin and the aqueous medium to 100 ℃ or lower at a rate of 1 ℃/min or lower after the stirring step of stirring the polyolefin resin and the aqueous medium at a temperature of 110 ℃ or higher.
4. The method for producing an aqueous polyolefin resin dispersion according to claim 3, wherein the cooling step comprises: a second cooling step of cooling the material from the highest temperature to a temperature of 100 ℃ or lower and exceeding 40 ℃ at a cooling rate of 3 ℃ or lower after the first cooling step of cooling the material at a cooling rate of 1 ℃ or lower per minute to a temperature of 40 ℃ or lower.
5. The method for producing an aqueous polyolefin resin dispersion according to claim 3 or 4, wherein the stirring step is carried out at a temperature of 110℃or higher and 20℃or higher than the melting point of the polyolefin resin.
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| JP2021-125838 | 2021-07-30 | ||
| JP2021125838A JP7032839B1 (en) | 2021-07-30 | 2021-07-30 | Polyolefin resin aqueous dispersion and its manufacturing method |
| PCT/JP2022/027882 WO2023008235A1 (en) | 2021-07-30 | 2022-07-15 | Polyolefin resin dispersion and method for manufacturing same |
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| JP2003171512A (en) * | 2001-12-05 | 2003-06-20 | Unitika Ltd | Polyolefin resin aqueous dispersion, and its production method |
| EP1632530B1 (en) * | 2003-05-22 | 2010-08-18 | Unitika Ltd. | Aqueous polyolefin resin dispersion, process for producing the same, and water-based coating material comprising the same |
| JP4606806B2 (en) * | 2004-08-03 | 2011-01-05 | 住友精化株式会社 | Method for producing polyolefin resin particles |
| JP5477632B2 (en) * | 2010-01-12 | 2014-04-23 | Ｄｉｃ株式会社 | Method for producing polypropylene wax dispersion |
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