WO2022202172A1 - Water-based resin composition, water-based coating material, and article coated with said water-based coating material - Google Patents
Water-based resin composition, water-based coating material, and article coated with said water-based coating material Download PDFInfo
- Publication number
- WO2022202172A1 WO2022202172A1 PCT/JP2022/009015 JP2022009015W WO2022202172A1 WO 2022202172 A1 WO2022202172 A1 WO 2022202172A1 JP 2022009015 W JP2022009015 W JP 2022009015W WO 2022202172 A1 WO2022202172 A1 WO 2022202172A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- water
- polypropylene
- resin composition
- meth
- acrylate
- Prior art date
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000011342 resin composition Substances 0.000 title claims abstract description 52
- 238000000576 coating method Methods 0.000 title abstract description 23
- 239000011248 coating agent Substances 0.000 title abstract description 22
- 239000000463 material Substances 0.000 title abstract description 6
- -1 polypropylene Polymers 0.000 claims abstract description 62
- 239000004743 Polypropylene Substances 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 229920001155 polypropylene Polymers 0.000 claims abstract description 33
- 239000000178 monomer Substances 0.000 claims abstract description 31
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Polymers C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 6
- 229920001519 homopolymer Polymers 0.000 claims abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 5
- 239000003973 paint Substances 0.000 claims description 24
- 239000012736 aqueous medium Substances 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 239000000758 substrate Substances 0.000 abstract description 17
- 238000003860 storage Methods 0.000 abstract description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 51
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 39
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 26
- 239000006185 dispersion Substances 0.000 description 22
- 239000000243 solution Substances 0.000 description 21
- 239000004793 Polystyrene Substances 0.000 description 17
- 229920002223 polystyrene Polymers 0.000 description 17
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 13
- 239000002245 particle Substances 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- 239000004698 Polyethylene Substances 0.000 description 11
- 239000012298 atmosphere Substances 0.000 description 11
- 239000011261 inert gas Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 8
- IAXXETNIOYFMLW-GYSYKLTISA-N [(1r,3r,4r)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@@]2(C)[C@H](OC(=O)C(=C)C)C[C@@H]1C2(C)C IAXXETNIOYFMLW-GYSYKLTISA-N 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 241000209094 Oryza Species 0.000 description 5
- 235000007164 Oryza sativa Nutrition 0.000 description 5
- 150000007514 bases Chemical class 0.000 description 5
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000001294 propane Substances 0.000 description 5
- 235000009566 rice Nutrition 0.000 description 5
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 3
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 102100026735 Coagulation factor VIII Human genes 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 3
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 229920005629 polypropylene homopolymer Polymers 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- BRQMAAFGEXNUOL-UHFFFAOYSA-N 2-ethylhexyl (2-methylpropan-2-yl)oxy carbonate Chemical compound CCCCC(CC)COC(=O)OOC(C)(C)C BRQMAAFGEXNUOL-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- PVCVRLMCLUQGBT-UHFFFAOYSA-N (1-tert-butylcyclohexyl) (1-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CCCCC1(C(C)(C)C)OC(=O)OOC(=O)OC1(C(C)(C)C)CCCCC1 PVCVRLMCLUQGBT-UHFFFAOYSA-N 0.000 description 1
- BOOBDAVNHSOIDB-UHFFFAOYSA-N (2,3-dichlorobenzoyl) 2,3-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC=CC(C(=O)OOC(=O)C=2C(=C(Cl)C=CC=2)Cl)=C1Cl BOOBDAVNHSOIDB-UHFFFAOYSA-N 0.000 description 1
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- RIPYNJLMMFGZSX-UHFFFAOYSA-N (5-benzoylperoxy-2,5-dimethylhexan-2-yl) benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C1=CC=CC=C1 RIPYNJLMMFGZSX-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- KQIXMZWXFFHRAQ-UHFFFAOYSA-N 1-(2-hydroxybutylamino)butan-2-ol Chemical compound CCC(O)CNCC(O)CC KQIXMZWXFFHRAQ-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- OSNILPMOSNGHLC-UHFFFAOYSA-N 1-[4-methoxy-3-(piperidin-1-ylmethyl)phenyl]ethanone Chemical compound COC1=CC=C(C(C)=O)C=C1CN1CCCCC1 OSNILPMOSNGHLC-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- YKTNISGZEGZHIS-UHFFFAOYSA-N 2-$l^{1}-oxidanyloxy-2-methylpropane Chemical group CC(C)(C)O[O] YKTNISGZEGZHIS-UHFFFAOYSA-N 0.000 description 1
- AOFFRVQVWKIQEV-UHFFFAOYSA-N 2-(2-hydroxy-4-prop-2-enoyloxybutoxy)carbonylbenzoic acid Chemical compound C=CC(=O)OCCC(O)COC(=O)C1=CC=CC=C1C(O)=O AOFFRVQVWKIQEV-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- 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 1
- HRWADRITRNUCIY-UHFFFAOYSA-N 2-(2-propan-2-yloxyethoxy)ethanol Chemical compound CC(C)OCCOCCO HRWADRITRNUCIY-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
- KRDXTHSSNCTAGY-UHFFFAOYSA-N 2-cyclohexylpyrrolidine Chemical compound C1CCNC1C1CCCCC1 KRDXTHSSNCTAGY-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- IFXDUNDBQDXPQZ-UHFFFAOYSA-N 2-methylbutan-2-yl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)CC IFXDUNDBQDXPQZ-UHFFFAOYSA-N 0.000 description 1
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 description 1
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-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
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 description 1
- LDMRLRNXHLPZJN-UHFFFAOYSA-N 3-propoxypropan-1-ol Chemical compound CCCOCCCO LDMRLRNXHLPZJN-UHFFFAOYSA-N 0.000 description 1
- UZDMJPAQQFSMMV-UHFFFAOYSA-N 4-oxo-4-(2-prop-2-enoyloxyethoxy)butanoic acid Chemical compound OC(=O)CCC(=O)OCCOC(=O)C=C UZDMJPAQQFSMMV-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical class C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 1
- XFSBVAOIAHNAPC-WSORPINJSA-N acetylbenzoylaconine Chemical compound O([C@H]1[C@]2(O)C[C@H]3C45[C@@H]6[C@@H]([C@@]([C@H]31)(OC(C)=O)[C@@H](O)[C@@H]2OC)[C@H](OC)C4[C@]([C@@H](C[C@H]5OC)O)(COC)CN6CC)C(=O)C1=CC=CC=C1 XFSBVAOIAHNAPC-WSORPINJSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- BXIQXYOPGBXIEM-UHFFFAOYSA-N butyl 4,4-bis(tert-butylperoxy)pentanoate Chemical compound CCCCOC(=O)CCC(C)(OOC(C)(C)C)OOC(C)(C)C BXIQXYOPGBXIEM-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- ZLFVRXUOSPRRKQ-UHFFFAOYSA-N chembl2138372 Chemical compound [O-][N+](=O)C1=CC(C)=CC=C1N=NC1=C(O)C=CC2=CC=CC=C12 ZLFVRXUOSPRRKQ-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- XJOBOFWTZOKMOH-UHFFFAOYSA-N decanoyl decaneperoxoate Chemical compound CCCCCCCCCC(=O)OOC(=O)CCCCCCCCC XJOBOFWTZOKMOH-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- POSWICCRDBKBMH-UHFFFAOYSA-N dihydroisophorone Natural products CC1CC(=O)CC(C)(C)C1 POSWICCRDBKBMH-UHFFFAOYSA-N 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- 229940043276 diisopropanolamine Drugs 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 238000007591 painting process Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000004978 peroxycarbonates Chemical class 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000012462 polypropylene substrate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- KEROTHRUZYBWCY-UHFFFAOYSA-N tridecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C(C)=C KEROTHRUZYBWCY-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
Definitions
- the present invention relates to a water-based resin composition, a water-based paint, and an article coated with the water-based paint.
- acrylic resins have been widely used for paints, inks, adhesives, synthetic leathers, and the like, due to their excellent weather resistance, flexibility, strength, adhesiveness, and the like.
- base resin for paint applications, in the fields of automobiles, home appliances, building materials, etc., it is used as a base resin for paints that coat various base materials (e.g., metals, wood, paper, plastics). resin has been developed.
- plastic molded products for example, products made from olefin resins such as polyethylene and polypropylene are widely used due to their light weight and ease of molding.
- olefin resins such as polyethylene and polypropylene
- polyethylene and polypropylene have very low polarity, there is a problem that acrylic resin cannot exhibit sufficient adhesion.
- the problem to be solved by the present invention is to provide a water-based resin composition, a paint, and an article coated with the paint, which is excellent in storage stability and capable of obtaining a coating film with excellent adhesion to various substrates. is.
- aqueous resin composition containing a specific polypropylene, a polypropylene-modified acrylic resin which is a reaction product of an unsaturated monomer mixture, and an aqueous medium.
- the inventors found that a coating film having excellent storage stability and excellent adhesion to various substrates can be obtained, and completed the invention.
- the present invention provides an aqueous resin composition containing a polypropylene-modified acrylic resin that is a reaction product of polypropylene (A) and an unsaturated monomer mixture (B), and an aqueous medium, wherein the polypropylene is a homopolymer and the polypropylene-modified acrylic resin has an acid value of 20 to 80 mgKOH/g.
- the aqueous resin composition of the present invention has excellent storage stability and can obtain a coating film having excellent adhesion to various substrates. It can be suitably used as a paint for coating various articles such as housings for equipment; housings for home electric appliances such as televisions, refrigerators, washing machines, and air conditioners; automobile bumpers, and interior materials for various vehicles such as automobiles and railway vehicles. .
- the aqueous resin composition of the present invention is an aqueous resin composition containing a polypropylene-modified acrylic resin that is a reaction product of polypropylene (A) and an unsaturated monomer mixture (B), and an aqueous medium, wherein the polypropylene is a homopolymer, and the acid value of the polypropylene-modified acrylic resin is 20 to 80 mgKOH/g.
- polypropylene (A) will be explained. It is important that this polypropylene (A) is a homopolymer, so that a coating film with excellent adhesion to various substrates can be obtained. In addition, polypropylene (A) can be used alone or in combination of two or more.
- the weight average molecular weight of the polypropylene (A) is preferably from 15,000 to 200,000, more preferably from 20,000 to 80,000, because the adhesion to the substrate is further improved.
- the melting point of the propylene (A) is preferably 40 to 120°C, more preferably 40 to 90°C, because the adhesion to the substrate is further improved.
- This unsaturated monomer mixture (B) contains the unsaturated monomer (b1) having a carboxyl group as an essential component.
- Examples of the unsaturated monomer (b1) having a carboxyl group include (meth)acrylic acid, crotonic acid, ⁇ -carboxyethyl (meth)acrylate, ⁇ -carboxy-polycaprolactone mono(meth)acrylate, 2- Unsaturated monocarboxylic acids such as (meth)acryloyloxyethyl succinate and 2-(meth)acryloyloxyethylhexahydrophthalic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; A half ester etc. are mentioned. Among these, (meth)acrylic acid is preferred because of its superior dispersibility in water. These unsaturated monomers (b1) can be used alone or in combination of two or more.
- (meth)acrylic acid refers to one or both of methacrylic acid and acrylic acid
- (meth)acrylate refers to one or both of methacrylate and acrylate
- (meth) ) “acryloyl group” refers to one or both of a methacryloyl group and an acryloyl group.
- the unsaturated monomer mixture (B) contains the unsaturated monomer (b1) as an essential component, and other unsaturated monomers (b2) include, for example, methyl (meta) Acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth) Acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate Acrylate, tridecyl (meth)acrylate, cetyl (meth)
- the unsaturated monomer (b1) in the unsaturated monomer mixture (B) is preferably 2 to 40% by mass, and 5 to 20% by mass, because it further improves water dispersibility and storage stability. more preferred.
- the unsaturated monomer (b2) in the unsaturated monomer mixture (B) is the balance of 100% by mass minus the usage ratio of the unsaturated monomer (b1), but the amount of the unsaturated monomer (b2) is the remainder of 100% by mass.
- n-octyl (meth) acrylate 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, cetyl ( Alkyl (meth)acrylates having an alkyl group having 6 to 12 carbon atoms such as meth)acrylate, cyclohexyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate; styrene, ⁇ - It is more preferable to contain at least one monomer selected from the group consisting of styrene compounds such as methylstyrene, p-methylstyrene and p-methoxystyrene in an amount of 5% by mass or more.
- the polypropylene-modified acrylic resin is preferably a reaction product obtained by polymerizing the unsaturated monomer mixture (B) in the presence of the polypropylene (A).
- a method for obtaining the polypropylene-modified acrylic resin a method of radically polymerizing the unsaturated monomer mixture (B) in the presence of the polypropylene (A) and a solvent is preferable because it is simple.
- the above radical polymerization method is a method of dissolving each raw material monomer in a solvent and performing a polymerization reaction in the presence of a polymerization initiator.
- solvents that can be used at this time include aromatic hydrocarbon compounds such as toluene and xylene; alicyclic hydrocarbon compounds such as cyclohexane, methylcyclohexane, and ethylcyclohexane; acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
- Ester compounds such as ethyl acetate, n-butyl acetate, isobutyl acetate and propylene glycol monomethyl ether acetate; Alcohol compounds such as n-butanol, isopropyl alcohol and cyclohexanol; Ethylene glycol monobutyl ether, propylene glycol monomethyl ether, Glycol compounds such as diethylene glycol dimethyl ether; aliphatic hydrocarbon compounds such as heptane, hexane, octane, and mineral terpene; Among these, it is preferable to use a water-miscible organic solvent because it can be used as it is as an aqueous medium contained in the aqueous resin composition of the present invention. These solvents can be used alone or in combination of two or more.
- polymerization initiator examples include ketone peroxide compounds such as cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide and methylcyclohexanone peroxide; 1,1-bis(tert-butylperoxy)-3, 3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, n-butyl-4,4-bis(tert-butylperoxy)valerate, 2,2-bis(4,4-di tert-butylperoxycyclohexyl)propane, 2,2-bis(4,4-ditert-amylperoxycyclohexyl)propane, 2,2-bis(4,4-ditert-hexylperoxycyclohexyl)propane, 2 , 2-bis(4,4-di-tert-octylperoxycyclohexyl)propane, 2,2-bis(4,4-dic
- the mass ratio (A/B) of the polypropylene (A) and the unsaturated monomer mixture (B) is 10/90 to 70, since the substrate adhesion of the resulting coating film is further improved. /40 is preferred, and 20/80 to 50/50 is more preferred.
- the acid value of the polypropylene-modified acrylic resin is preferably in the range of 20 to 80 mgKOH/g, 25 to 65 mgKOH/ A range of g is more preferred.
- the acid value of the resin of the present invention is a calculated value obtained from the raw material composition.
- the weight average molecular weight of the polypropylene-modified acrylic resin is preferably from 7,000 to 150,000, more preferably from 10,000 to 60,000, because the adhesion to the substrate of the obtained coating film is further improved.
- the molecular weight dispersity (weight average molecular weight/number average molecular weight) of the polypropylene-modified acrylic resin is preferably 5 to 20, since the obtained coating film has better adhesion to the substrate.
- the average molecular weight of the present invention is a value converted to polystyrene based on gel permeation chromatography (hereinafter abbreviated as "GPC") measurement.
- aqueous medium examples include water, hydrophilic organic solvents, and mixtures thereof.
- hydrophilic organic solvent a water-miscible organic solvent that is miscible with water without separating is preferable, and among them, an organic solvent having a solubility in water (number of grams of organic solvent dissolved in 100 g of water) of 3 g or more at 25° C. is preferable. .
- water-miscible organic solvents include alcohol solvents such as methanol, ethanol, propanol, butanol, 3-methoxybutanol, and 3-methyl-3-methoxybutanol; ketone solvents such as acetone and methyl ethyl ketone; ethylene glycol monomethyl; Ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono Isopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, prop
- the aqueous resin composition of the present invention contains a polypropylene-modified acrylic resin and an aqueous medium, it is preferable that the polypropylene-modified acrylic resin obtained by the above method is dissolved or dispersed in an aqueous medium. is more preferred.
- Examples of the basic compound include monoalkanolamines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, butylamine, dibutylamine, tributylamine, N,N-dimethylethanolamine and 2-aminoethanol, and diethanolamine. , diisopropanolamine, dibutanolamine and other organic amines; ammonia, sodium hydroxide, potassium hydroxide and other inorganic basic compounds; tetramethylammonium hydroxide, tetra-n-butylammonium hydroxide, trimethylbenzylammonium hydroxide, etc. and quaternary ammonium hydroxide. Among these, it is preferable to use organic amines and ammonia (aqueous ammonia may be used). These basic compounds can be used alone or in combination of two or more.
- the neutralization rate of the carboxyl groups possessed by the polypropylene-modified acrylic resin is in the range of 50 to 100%. Amount is preferred.
- the paint of the present invention contains the aqueous resin composition of the present invention, and other ingredients such as an antifoaming agent, a viscosity modifier, a light stabilizer, a weather stabilizer, a heat stabilizer, and an ultraviolet absorber. , antioxidants, leveling agents, pigment dispersants, and other additives may be used. Pigments such as titanium oxide, calcium carbonate, aluminum powder, copper powder, mica powder, iron oxide, carbon black, phthalocyanine blue, toluidine red, perylene, quinacridone, and benzidine yellow can also be used.
- Examples of the coating method of the paint of the present invention include spray, applicator, bar coater, gravure coater, roll coater, comma coater, knife coater, air knife coater, curtain coater, kiss coater, shower coater, wheeler coater, spin coater, dipping, A method such as screen printing can be used.
- a method of forming a coating film after coating a method of drying in the range of normal temperature to 120° C. can be mentioned.
- the paint of the present invention has high adhesion to plastic substrates, it can be suitably used as a paint for coating various plastic molded articles.
- the housing of electronic equipment such as mobile phones, smartphones, tablet terminals, personal computers, digital cameras, and game consoles; the housing of home appliances such as televisions, refrigerators, washing machines, and air conditioners; Examples include interior materials for various vehicles.
- Measuring device high-speed GPC device ("HLC-8220GPC” manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were connected in series and used. "TSKgel G5000" (7.8mm I.D. x 30cm) x 1 "TSKgel G4000” (7.8mm I.D. x 30cm) x 1 "TSKgel G3000” (7.8mm I.D. x 30cm) x 1 Book “TSKgel G2000" (7.8 mm I.D.
- Example 1 Production of aqueous resin composition (1)
- polypropylene homopolymer manufactured by Idemitsu Kosan "L-MODU S600", melting point 80 ° C., weight average molecular weight 75,000; hereinafter abbreviated as "polypropylene (A-1)”
- polypropylene (A-1) was added, and the temperature was raised to 100°C in an inert gas atmosphere.
- a mixed liquid consisting of 29.5 g of MMA, 50 g of St, 40.5 g of BA, 4.6 g of CHMA, 15.4 g of AA, and 5.2 g of PO was added dropwise over 4 hours, and further 3 hours. Stirred.
- a water dispersion step the above reaction solution is cooled to 75° C., and 100 g of methylcyclohexane, 400 g of isopropyl alcohol, 19.1 g of N,N-dimethylethanolamine, and 440 g of water are added successively to obtain a water-dispersed particle solution.
- Example 2 Production of aqueous resin composition (2)
- 150 g of toluene and 90 g of polypropylene (A-1) were added to a 2 L four-necked flask, and the temperature was raised to 100° C. under an inert gas atmosphere.
- a mixed liquid consisting of 10 g of MMA, 40 g of St, 24 g of CHMA, 20 g of SLMA, 15.4 g of AA, and 5.2 g of PO was added dropwise over 4 hours, followed by stirring for 3 hours.
- a water dispersion step the above reaction solution is cooled to 75° C., and 100 g of methylcyclohexane, 400 g of isopropyl alcohol, 19.1 g of N,N-dimethylethanolamine, and 440 g of water are added successively to obtain a water-dispersed particle solution.
- Example 3 Production of aqueous resin composition (3)
- 80 g of toluene, polypropylene homopolymer manufactured by Idemitsu Kosan "L-MODU S400", melting point 80 ° C., weight average molecular weight 45,000; hereinafter abbreviated as "polypropylene (A-2)”
- polypropylene (A-2) was added, and the temperature was raised to 100°C in an inert gas atmosphere.
- A-2 polypropylene
- a mixture of 25 g of St, 24 g of CHMA, 20 g of SLMA, 12 g of maleic anhydride, and 5.2 g of ABN-E was added dropwise over 4 hours, followed by stirring for 3 hours.
- the above reaction liquid was cooled to 75° C., and 200 g of methylcyclohexane, 400 g of isopropyl alcohol, 28 g of triethylamine and 440 g of water were successively added to obtain a water-dispersed particle solution.
- Toluene, methylcyclohexane, and isopropyl alcohol were removed from the obtained water-dispersed particle solution under reduced pressure using an evaporator to obtain an aqueous resin composition (3) as an aqueous dispersion having a solid content concentration of 25% by mass.
- Example 4 Production of aqueous resin composition (4)
- 225 g of butyl acetate and 60 g of polypropylene (A-2) were added to a 2 L four-necked flask, and the temperature was raised to 120° C. under an inert gas atmosphere.
- A-2 polypropylene
- a mixture of 50 g of MMA, 10 g of St, 68 g of EA, 11.2 g of AA and 8.5 g of PO was added dropwise over 4 hours, and the mixture was further stirred for 3 hours.
- the above reaction solution is cooled to 75° C., and 180 g of methylcyclohexane, 510 g of isopropyl alcohol, 13.9 g of N,N-dimethylethanolamine, and 510 g of water are successively added to obtain a water-dispersed particle solution.
- Butyl acetate, methylcyclohexane, and isopropyl alcohol were removed from the obtained water-dispersed particle solution under reduced pressure using an evaporator to obtain an aqueous resin composition (4) as an aqueous dispersion having a solid content concentration of 27% by mass.
- Example 5 Production of aqueous resin composition (5)
- 270 g of butyl acetate and 90 g of polypropylene (A-2) were added to a 2 L four-necked flask, and the temperature was raised to 120° C. under an inert gas atmosphere.
- A-2 polypropylene
- a mixture of 5.4 g of MMA, 42.5 g of EA, 48.6 g of IBXMA, 11.5 g of AA and 4 g of PE was added dropwise over 4 hours, followed by stirring for 3 hours.
- the above reaction solution was cooled to 75° C., and 190 g of methylcyclohexane, 400 g of isopropyl alcohol, 14.2 g of N,N-dimethylethanolamine, and 540 g of water were successively added to obtain a water-dispersed particle solution.
- Butyl acetate, methylcyclohexane, and isopropyl alcohol were removed from the obtained water-dispersed particle solution under reduced pressure using an evaporator to obtain an aqueous resin composition (5) as an aqueous dispersion having a solid content concentration of 26% by mass.
- Example 6 Production of aqueous resin composition (6)
- polypropylene homopolymer manufactured by Idemitsu Kosan "L-MODU S901", melting point 80 ° C., weight average molecular weight 130,000; hereinafter abbreviated as "polypropylene (A-3)”
- A-3 weight average molecular weight 130,000
- a mixed liquid consisting of 15 g of St, 40 g of IBXMA, 20 g of 2EHMA, 30 g of SLMA, 60 g of AM-130G, 3 g of AA, and 4.5 g of PE was added dropwise over 4 hours, followed by stirring for 3 hours.
- the above reaction liquid is cooled to 75 ° C., N,N-dimethylethanolamine 3.7 g and water 380 g are sequentially added to form a water dispersion with a solid content concentration of 30% by mass.
- a composition (6) was obtained.
- Example 7 Production of aqueous resin composition (7)
- 70 g of diethylene glycol dimethyl ether and 60 g of polypropylene (A-2) were added to a 2 L four-necked flask, and the temperature was raised to 120° C. under an inert gas atmosphere.
- a mixed liquid consisting of 35 g of St, 40 g of IBXMA, 20 g of 2EHMA, 30 g of SLMA, 15 g of HEMA, 8 g of AA, and 4.5 g of PE was added dropwise over 4 hours, followed by stirring for 3 hours.
- Example 8 Production of aqueous resin composition (8)
- 250 g of toluene and 18 g of polypropylene (A-2) were added to a 2 L four-necked flask, and the temperature was raised to 100° C. under an inert gas atmosphere.
- A-2 polypropylene
- a mixture of 29.5 g of MMA, 47 g of St, 25.5 g of BA, 64.6 g of CHMA, 11 g of AA and 4.5 g of PE was added dropwise over 4 hours, and the mixture was further stirred for 3 hours.
- the reaction solution was cooled to 75° C., and 100 g of methylcyclohexane, 400 g of isopropyl alcohol, 13.6 g of N,N-dimethylethanolamine, and 440 g of water were successively added to obtain a water-dispersed particle solution.
- aqueous resin composition (R1) 70 g of butyrocellosolve and 30 g of a polypropylene copolymer (manufactured by Evonik "Bestplast 750", propylene/ethylene/1-butene copolymer, melting point 107° C.) were added to a four-necked flask with a capacity of 2 L, and an inert gas atmosphere was added. The temperature was raised to 140° C. below.
- a mixed liquid consisting of 15.0 g of St, 40 g of IBXMA, 20 g of 2EHMA, 30 g of SLMA, 60 g of AM-130G, 3 g of AA, and 4.5 g of PE was added dropwise over 4 hours, followed by stirring for 3 hours. did.
- a water dispersion step the above reaction solution is cooled to 75 ° C., and 3.7 g of N,N-dimethylethanolamine and 380 g of water are successively added to form a water dispersion having a solid content of 30% by mass.
- a composition (R1) was obtained.
- Tables 1 and 2 show the compositions and evaluation results of the aqueous resin compositions (1) to (8) obtained above.
- Table 3 shows the compositions and evaluation results of the comparative aqueous resin compositions (R1) to (R3) obtained above.
- Example 9 Preparation and evaluation of water-based paint (1)
- aqueous resin composition (1) obtained above 0.2 g of BYK-348 (manufactured by BYK Chemie) as a leveling agent and 0.1 g of SN Deformer 777 (manufactured by San Nopco Co., Ltd.) as an antifoaming agent are added, and the mixture is stirred for 15 minutes. Stirred. Next, the mixture was diluted with deionized water until the paint viscosity reached 12 seconds using a viscosity cup NK-2 (manufactured by Anest Iwata Co., Ltd.) to obtain water-based paint (1).
- BYK-348 manufactured by BYK Chemie
- SN Deformer 777 manufactured by San Nopco Co., Ltd.
- Example 10 to 16 Preparation and evaluation of water-based paints (2) to (8)
- Water-based paints (2) to (8) were prepared in the same manner as in Example 9, except that the water-based resin composition (1) was changed to the water-based resin compositions (2) to (8), and substrate adhesion was evaluated.
- the aqueous resin composition of the present invention has excellent storage stability, and that the resulting coating film has excellent adhesion to various substrates.
- Comparative Example 1 is an example in which the homopolymer of polypropylene, which is an essential component of the present invention, was not used. Adhesion to was insufficient.
- Comparative Example 2 is an example in which the acid value of the polypropylene-modified acrylic resin is greater than the upper limit of the present invention of 80 mgKOH/g, but the resulting coating film is based on a polypropylene base and an acrylonitrile-butadiene-styrene copolymer base. , the adhesion to the nylon substrate was insufficient.
- Comparative Example 3 is an example in which the acid value of the polypropylene-modified acrylic resin is less than 20 mgKOH/g, which is the lower limit of the present invention. Adhesion was insufficient.
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Abstract
Provided is a water-based resin composition which comprises a polypropylene-modified acrylic resin that is a reaction product of polypropylene (A) and an unsaturated monomer mixture (B) and a water-based medium, the water-based resin composition being characterized in that the polypropylene (A) is a homopolymer, the unsaturated monomer mixture (B) contains an unsaturated monomer (b1) having a carboxyl group, and the acid value of the polypropylene-modified acrylic resin is 20 to 80 mgKOH/g. The water-based resin composition has excellent storage stability, and can provide a coating film having excellent adhesion to various types of substrates, and therefore the water-based resin composition can be used suitably for various types of coating materials.
Description
本発明は、水性樹脂組成物、水性塗料及び該水性塗料で塗装された物品に関する。
The present invention relates to a water-based resin composition, a water-based paint, and an article coated with the water-based paint.
従来、アクリル樹脂は、耐候性、柔軟性、強度、接着性等に優れていることから、塗料、インキ、接着剤、合成皮革等の用途に広く使用されている。特に、塗料用途においては、自動車、家庭電化製品、建材等の分野で、各種基材（例えば、金属、木材、紙、プラスチック）を塗装する塗料のベース樹脂として、それぞれの要求性能に併せたアクリル樹脂が開発されている。
BACKGROUND ART Conventionally, acrylic resins have been widely used for paints, inks, adhesives, synthetic leathers, and the like, due to their excellent weather resistance, flexibility, strength, adhesiveness, and the like. In particular, for paint applications, in the fields of automobiles, home appliances, building materials, etc., it is used as a base resin for paints that coat various base materials (e.g., metals, wood, paper, plastics). resin has been developed.
一方、プラスチック成形品としては、例えば、ポリエチレンやポリプロピレン等のオレフィン樹脂を素材としたものが、軽量であることと成形のしやすさから、多用されている。しかしながら、ポリエチレンやポリプロピレンは、極性が非常に小さいため、アクリル樹脂では十分な密着性を発現できないという問題があった。
On the other hand, as plastic molded products, for example, products made from olefin resins such as polyethylene and polypropylene are widely used due to their light weight and ease of molding. However, since polyethylene and polypropylene have very low polarity, there is a problem that acrylic resin cannot exhibit sufficient adhesion.
更に、近年は環境規制の厳格化に伴い、塗装工程で排出される揮発性有機化合物、所謂「ＶＯＣ」の削減が強く求められている。この結果、従来用いられてきた有機溶剤を溶媒とする溶剤系塗料は使用が難しくなってきており、低ＶＯＣである水性塗料への代替の動きが全世界で顕著である。
Furthermore, in recent years, with the tightening of environmental regulations, there is a strong demand for the reduction of volatile organic compounds, so-called "VOCs", emitted during the painting process. As a result, it has become difficult to use conventional solvent-based paints that use organic solvents as solvents, and there has been a marked worldwide trend to switch to low-VOC water-based paints.
上述したポリエチレンやポリプロピレン基材への密着を目的として、プロピレン―エチレン及びまたはブテン共重合物したポリオレフィンに、さらにアクリル変性した樹脂組成物が提案されている（例えば、特許文献１参照。）。この樹脂組成物を用いた塗膜は、オレフィン基材との密着性は向上するものの、電子機器などに使用されるポリカーボネートなどの他のプラスチックやアルミへの密着性が低いという問題があった。
For the purpose of adhering to the above-mentioned polyethylene or polypropylene substrate, a resin composition in which propylene-ethylene and/or butene copolymerized polyolefin is further acrylic-modified has been proposed (see, for example, Patent Document 1). Coating films using this resin composition have improved adhesion to olefin substrates, but have the problem of low adhesion to aluminum and other plastics such as polycarbonate used in electronic devices and the like.
本発明が解決しようとする課題は、貯蔵安定性に優れ、各種基材との付着性に優れる塗膜を得ることができる水性樹脂組成物、塗料及び該塗料で塗装された物品を提供することである。
The problem to be solved by the present invention is to provide a water-based resin composition, a paint, and an article coated with the paint, which is excellent in storage stability and capable of obtaining a coating film with excellent adhesion to various substrates. is.
本発明者等は、上記の課題を解決するため鋭意研究した結果、特定のポリプロピレンと、不飽和単量体混合物との反応物であるポリプロピレン変性アクリル樹脂と水性媒体とを含有する水性樹脂組成物が、貯蔵安定性に優れ、各種基材との付着性に優れる塗膜を得られることを見出し、発明を完成させた。
As a result of intensive research to solve the above problems, the present inventors have found an aqueous resin composition containing a specific polypropylene, a polypropylene-modified acrylic resin which is a reaction product of an unsaturated monomer mixture, and an aqueous medium. However, the inventors found that a coating film having excellent storage stability and excellent adhesion to various substrates can be obtained, and completed the invention.
すなわち、本発明は、ポリプロピレン（Ａ）及び不飽和単量体混合物（Ｂ）の反応物であるポリプロピレン変性アクリル樹脂と、水性媒体とを含有する水性樹脂組成物であって、前記ポリプロピレンがホモポリマーであり、前記ポリプロピレン変性アクリル樹脂の酸価が２０～８０ｍｇＫＯＨ／ｇであることを特徴とする水性樹脂組成物に関する。
That is, the present invention provides an aqueous resin composition containing a polypropylene-modified acrylic resin that is a reaction product of polypropylene (A) and an unsaturated monomer mixture (B), and an aqueous medium, wherein the polypropylene is a homopolymer and the polypropylene-modified acrylic resin has an acid value of 20 to 80 mgKOH/g.
本発明の水性樹脂組成物は、貯蔵安定性に優れ、各種基材との付着性に優れる塗膜を得られることから、携帯電話、スマートフォン、タブレット端末、パソコン、デジタルカメラ、ゲーム機等の電子機器の筐体；テレビ、冷蔵庫、洗濯機、エアコン等の家電製品の筐体；自動車バンパー、自動車や鉄道車輌等の各種車輌の内装材などの各種物品を塗装する塗料に好適に用いることができる。
The aqueous resin composition of the present invention has excellent storage stability and can obtain a coating film having excellent adhesion to various substrates. It can be suitably used as a paint for coating various articles such as housings for equipment; housings for home electric appliances such as televisions, refrigerators, washing machines, and air conditioners; automobile bumpers, and interior materials for various vehicles such as automobiles and railway vehicles. .
本発明の水性樹脂組成物は、ポリプロピレン（Ａ）及び不飽和単量体混合物（Ｂ）の反応物であるポリプロピレン変性アクリル樹脂と、水性媒体とを含有する水性樹脂組成物であって、前記ポリプロピレンがホモポリマーであり、前記ポリプロピレン変性アクリル樹脂の酸価が２０～８０ｍｇＫＯＨ／ｇであるものである。
The aqueous resin composition of the present invention is an aqueous resin composition containing a polypropylene-modified acrylic resin that is a reaction product of polypropylene (A) and an unsaturated monomer mixture (B), and an aqueous medium, wherein the polypropylene is a homopolymer, and the acid value of the polypropylene-modified acrylic resin is 20 to 80 mgKOH/g.
まず、ポリプロピレン（Ａ）について説明する。このポリプロピレン（Ａ）は、ホモポリマーであることが重要であり、これにより、各種基材との付着性に優れる塗膜が得られる。なお、ポリプロピレン（Ａ）は、単独で用いることも２種以上併用することもできる
First, the polypropylene (A) will be explained. It is important that this polypropylene (A) is a homopolymer, so that a coating film with excellent adhesion to various substrates can be obtained. In addition, polypropylene (A) can be used alone or in combination of two or more.
前記ポリプロピレン（Ａ）の重量平均分子量は、基材付着性がより向上することから、１５，０００～２００, ０００が好ましく、２０，０００～８０，０００の範囲がより好ましい。
The weight average molecular weight of the polypropylene (A) is preferably from 15,000 to 200,000, more preferably from 20,000 to 80,000, because the adhesion to the substrate is further improved.
また、前記プロピレン（Ａ）の融点は、基材付着性がより向上することから、４０～１２０℃が好ましく、４０～９０℃がより好ましい。
Further, the melting point of the propylene (A) is preferably 40 to 120°C, more preferably 40 to 90°C, because the adhesion to the substrate is further improved.
次に、前記不飽和単量体混合物（Ｂ）について説明する。この不飽和単量体混合物（Ｂ）は、カルボキシル基を有する不飽和単量体（ｂ１）を必須成分として含有するものである。
Next, the unsaturated monomer mixture (B) will be described. This unsaturated monomer mixture (B) contains the unsaturated monomer (b1) having a carboxyl group as an essential component.
前記カルボキシル基を有する不飽和単量体（ｂ１）としては、例えば、（メタ）アクリル酸、クロトン酸、β－カルボキシエチル（メタ）アクリレート、ω－カルボキシ－ポリカプロラクトンモノ（メタ）アクリレート、２－（メタ）アクリロイルオキシエチルサクシネート、２－（メタ）アクリロイルオキシエチルヘキサヒドロフタル酸等の不飽和モノカルボン酸；マレイン酸、フマル酸、イタコン酸等の不飽和ジカルボン酸又はこれら不飽和ジカルボン酸のハーフエステルなどが挙げられる。これらの中でも、水への分散性がより優れることから、（メタ）アクリル酸が好ましい。なお、これらの不飽和単量体（ｂ１）は、単独で用いることも２種以上併用することもできる。
Examples of the unsaturated monomer (b1) having a carboxyl group include (meth)acrylic acid, crotonic acid, β-carboxyethyl (meth)acrylate, ω-carboxy-polycaprolactone mono(meth)acrylate, 2- Unsaturated monocarboxylic acids such as (meth)acryloyloxyethyl succinate and 2-(meth)acryloyloxyethylhexahydrophthalic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; A half ester etc. are mentioned. Among these, (meth)acrylic acid is preferred because of its superior dispersibility in water. These unsaturated monomers (b1) can be used alone or in combination of two or more.
なお、本発明において、「（メタ）アクリル酸」とは、メタクリル酸とアクリル酸の一方又は両方をいい、「（メタ）アクリレート」とは、メタクリレートとアクリレートの一方又は両方をいい、「（メタ）アクリロイル基」とは、メタクリロイル基とアクリロイル基の一方又は両方をいう。
In the present invention, "(meth)acrylic acid" refers to one or both of methacrylic acid and acrylic acid, "(meth)acrylate" refers to one or both of methacrylate and acrylate, and "(meth) ) “acryloyl group” refers to one or both of a methacryloyl group and an acryloyl group.
前記不飽和単量体混合物（Ｂ）は、前記不飽和単量体（ｂ１）を必須成分とするものであるが、その他の不飽和単量体（ｂ２）としては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、ｎ－ペンチル（メタ）アクリレート、ｎ－ヘキシル（メタ）アクリレート、ｎ－ヘプチル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ノニル（メタ）アクリレート、デシル（メタ）アクリレート、ドデシル（メタ）アクリレート、トリデシル（メタ）アクリレート、セチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、４－ｔｅｒｔ－ブチルシクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシ－ｎ－ブチル（メタ）アクリレート、２－ヒドロキシ－ｎ－ブチル（メタ）アクリレート、３－ヒドロキシ－ｎ－ブチル（メタ）アクリレート、１，４－シクロヘキサンジメタノールモノ（メタ）アクリレート、グリセリンモノ（メタ）アクリレート、ポリオキシエチレンモノ（メタ）アクリレート、ポリオキシプロピレンモノ（メタ）アクリレート、ポリオキシブチレンモノ（メタ）アクリレート、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート、２－（メタ）アクリロイルオキシエチル－２－ヒドロキシエチルフタレート、ポリカプロラクトン変性ヒドロキシエチルモノ（メタ）アクリレート、アクリルアミド、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、（メタ）アクリロニトリル、３－（メタ）アクリロイルオキシプロピルトリメトキシシラン、Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリレート、２－（メタ）アクリロイルオキシエチルアシッドホスフェート、グリシジル（メタ）アクリレート、酢酸ビニル、スチレン、α－メチルスチレン、ｐ－メチルスチレン、ｐ－メトキシスチレン、エチレングリコールジアクリレート等が挙げられる。また、これらの不飽和単量体（ｂ２）は、単独で用いることも２種以上併用することもできる。
The unsaturated monomer mixture (B) contains the unsaturated monomer (b1) as an essential component, and other unsaturated monomers (b2) include, for example, methyl (meta) Acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth) Acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate Acrylate, tridecyl (meth)acrylate, cetyl (meth)acrylate, cyclohexyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxy-n-butyl (meth) acrylate, 2-hydroxy-n-butyl (meth) acrylate, 3-hydroxy-n-butyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, glycerin mono (meth) acrylate, polyoxyethylene mono (meth) acrylate, polyoxypropylene mono (meth) acrylate, polyoxybutylene mono (meth) acrylate, 2-hydroxy -3-phenoxypropyl (meth) acrylate, 2-(meth) acryloyloxyethyl-2-hydroxyethyl phthalate, polycaprolactone-modified hydroxyethyl mono (meth) acrylate, acrylamide, N,N-dimethyl (meth) acrylamide, (meth) ) Acrylonitrile, 3-(meth)acryloyloxypropyltrimethoxysilane, N,N-dimethylaminoethyl (meth)acrylate, 2-(meth)acryloyloxyethyl acid phosphate, glycidyl (meth)acrylate, vinyl acetate, styrene, α -methylstyrene, p-methylstyrene, p-methoxystyrene, ethylene glycol diacrylate and the like. Also, these unsaturated monomers (b2) can be used alone or in combination of two or more.
前記不飽和単量体混合物（Ｂ）中の不飽和単量体（ｂ１）は、水分散性及び保存安定性がより向上することから、２～４０質量％が好ましく、５～２０質量％がより好ましい。
The unsaturated monomer (b1) in the unsaturated monomer mixture (B) is preferably 2 to 40% by mass, and 5 to 20% by mass, because it further improves water dispersibility and storage stability. more preferred.
前記不飽和単量体混合物（Ｂ）中の不飽和単量体（ｂ２）は、１００質量％から上記の不飽和単量体（ｂ１）の使用比率を除いた残部となるが、基材付着性がより向上することから、ｎ－オクチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ノニル（メタ）アクリレート、デシル（メタ）アクリレート、ドデシル（メタ）アクリレート、トリデシル（メタ）アクリレート、セチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、４－ｔｅｒｔ－ブチルシクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート等の炭素原子数が６～１２のアルキル基を有するアルキル（メタ）アクリレート；スチレン、α－メチルスチレン、ｐ－メチルスチレン、ｐ－メトキシスチレン等のスチレン化合物からなる群より選ばれる少なくとも１以上の単量体を５質量％以上含有することがより好ましい。
The unsaturated monomer (b2) in the unsaturated monomer mixture (B) is the balance of 100% by mass minus the usage ratio of the unsaturated monomer (b1), but the amount of the unsaturated monomer (b2) is the remainder of 100% by mass. n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, cetyl ( Alkyl (meth)acrylates having an alkyl group having 6 to 12 carbon atoms such as meth)acrylate, cyclohexyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate; styrene, α- It is more preferable to contain at least one monomer selected from the group consisting of styrene compounds such as methylstyrene, p-methylstyrene and p-methoxystyrene in an amount of 5% by mass or more.
前記ポリプロピレン変性アクリル樹脂は、前記ポリプロピレン（Ａ）の存在下、前記不飽和単量体混合物（Ｂ）を重合した反応物であることが好ましい。
The polypropylene-modified acrylic resin is preferably a reaction product obtained by polymerizing the unsaturated monomer mixture (B) in the presence of the polypropylene (A).
前記ポリプロピレン変性アクリル樹脂を得る方法としては、前記ポリプロピレン（Ａ）及び溶剤の存在下、前記不飽和単量体混合物（Ｂ）をラジカル重合する方法が簡便であることから好ましい。
As a method for obtaining the polypropylene-modified acrylic resin, a method of radically polymerizing the unsaturated monomer mixture (B) in the presence of the polypropylene (A) and a solvent is preferable because it is simple.
上記のラジカル重合法は、原料である各単量体を溶剤に溶解し、重合開始剤存在下で重合反応を行う方法である。この際に用いることができる溶剤としては、例えば、トルエン、キシレン等の芳香族系炭化水素化合物；シクロヘキサン、メチルシクロヘキサン、エチルシクロヘキサン等の脂環式炭化水素化合物；アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン化合物；酢酸エチル、酢酸ｎ－ブチル、酢酸イソブチル、プロピレングリコールモノメチルエーテルアセテート等のエステル化合物；ｎ－ブタノール、イソプロピルアルコール、シクロヘキサノール等のアルコール化合物；エチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、ジエチレングリコールジメチルエーテル等のグリコール化合物；ヘプタン、ヘキサン、オクタン、ミネラルターペン等の脂肪族炭化水素化合物などが挙げられる。これらの中でも、本発明の水性樹脂組成物中に含有する水性媒体としてそのまま利用できることから、水混和性有機溶剤を使用することが好ましい。なお、これらの溶剤は、単独で用いることも２種以上併用することもできる。
The above radical polymerization method is a method of dissolving each raw material monomer in a solvent and performing a polymerization reaction in the presence of a polymerization initiator. Examples of solvents that can be used at this time include aromatic hydrocarbon compounds such as toluene and xylene; alicyclic hydrocarbon compounds such as cyclohexane, methylcyclohexane, and ethylcyclohexane; acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Ester compounds such as ethyl acetate, n-butyl acetate, isobutyl acetate and propylene glycol monomethyl ether acetate; Alcohol compounds such as n-butanol, isopropyl alcohol and cyclohexanol; Ethylene glycol monobutyl ether, propylene glycol monomethyl ether, Glycol compounds such as diethylene glycol dimethyl ether; aliphatic hydrocarbon compounds such as heptane, hexane, octane, and mineral terpene; Among these, it is preferable to use a water-miscible organic solvent because it can be used as it is as an aqueous medium contained in the aqueous resin composition of the present invention. These solvents can be used alone or in combination of two or more.
前記重合開始剤としては、例えば、シクロヘキサノンパーオキサイド、３，３，５－トリメチルシクロヘキサノンパーオキサイド、メチルシクロヘキサノンパーオキサイド等のケトンパーオキサイド化合物；１，１－ビス（ｔｅｒｔ－ブチルパーオキシ）－３，３，５－トリメチルシクロヘキサン、１，１－ビス（ｔｅｒｔ－ブチルパーオキシ）シクロヘキサン、ｎ－ブチル－４，４－ビス（ｔｅｒｔ－ブチルパーオキシ）バレレート、２，２－ビス（４，４－ジｔｅｒｔ－ブチルパーオキシシクロヘキシル）プロパン、２，２－ビス（４，４－ジｔｅｒｔ－アミルパーオキシシクロヘキシル）プロパン、２，２－ビス（４，４－ジｔｅｒｔ－ヘキシルパーオキシシクロヘキシル）プロパン、２，２－ビス（４，４－ジｔｅｒｔ－オクチルパーオキシシクロヘキシル）プロパン、２，２－ビス（４，４－ジクミルパーオキシシクロヘキシル）プロパン等のパーオキシケタール化合物；クメンハイドロパーオキサイド、２，５－ジメチルヘキサン－２，５－ジハイドロパーオキサイド等のハイドロパーオキサイド化合物；１，３－ビス（ｔｅｒｔ－ブチルパーオキシ－ｍ－イソプロピル）ベンゼン、２，５－ジメチル－２，５－ジ（ｔｅｒｔ－ブチルパーオキシ）ヘキサン、ジイソプロピルベンゼンパーオキサイド、ｔｅｒｔ－ブチルクミルパーオキサイド、ジｔｅｒｔ－ブチルパーオキサイド等のジアルキルパーオキサイド化合物；デカノイルパーオキサイド、ラウロイルパーオキサイド、ベンゾイルパーオキサイド、２，４－ジクロロベンゾイルパーオキサイド等のジアシルパーオキサイド化合物；ビス（ｔｅｒｔ－ブチルシクロヘキシル）パーオキシジカーボネート、ｔｅｒｔ－ブチルパーオキシ－２－エチルヘキシルモノカーボネート等のパーオキシカーボネート化合物；ｔｅｒｔ－ブチルパーオキシ－２－エチルヘキサノエート、ｔｅｒｔ－アミルパーオキシ－２－エチルヘキサノエート、ｔｅｒｔ－ブチルパーオキシベンゾエート、２，５－ジメチル－２，５－ジ（ベンゾイルパーオキシ）ヘキサン等のパーオキシエステル化合物などの有機過酸化物と、２，２’－アゾビスイソブチロニトリル、２，２’－アゾビス（２－メチル）ブチロニトリル、１，１’－アゾビス（シクロヘキサン－１－カルボニトリル）等のアゾ化合物とが挙げられる。
Examples of the polymerization initiator include ketone peroxide compounds such as cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide and methylcyclohexanone peroxide; 1,1-bis(tert-butylperoxy)-3, 3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, n-butyl-4,4-bis(tert-butylperoxy)valerate, 2,2-bis(4,4-di tert-butylperoxycyclohexyl)propane, 2,2-bis(4,4-ditert-amylperoxycyclohexyl)propane, 2,2-bis(4,4-ditert-hexylperoxycyclohexyl)propane, 2 , 2-bis(4,4-di-tert-octylperoxycyclohexyl)propane, 2,2-bis(4,4-dicumylperoxycyclohexyl)propane and other peroxyketal compounds; cumene hydroperoxide, 2, Hydroperoxide compounds such as 5-dimethylhexane-2,5-dihydroperoxide; 1,3-bis(tert-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di( dialkyl peroxide compounds such as tert-butylperoxy)hexane, diisopropylbenzene peroxide, tert-butylcumyl peroxide, ditert-butyl peroxide; decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, 2,4- diacyl peroxide compounds such as dichlorobenzoyl peroxide; peroxycarbonate compounds such as bis(tert-butylcyclohexyl)peroxydicarbonate and tert-butylperoxy-2-ethylhexyl monocarbonate; tert-butylperoxy-2-ethyl Peroxyester compounds such as hexanoate, tert-amylperoxy-2-ethylhexanoate, tert-butylperoxybenzoate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, etc. A peroxide and an azo compound such as 2,2′-azobisisobutyronitrile, 2,2′-azobis(2-methyl)butyronitrile, 1,1′-azobis(cyclohexane-1-carbonitrile) mentioned.
また、前記ポリプロピレン（Ａ）と前記不飽和単量体混合物（Ｂ）との質量比（Ａ／Ｂ）は、得られる塗膜の基材付着性がより向上することから、１０／９０～７０／４０が好ましく、２０／８０～５０／５０がより好ましい。
Further, the mass ratio (A/B) of the polypropylene (A) and the unsaturated monomer mixture (B) is 10/90 to 70, since the substrate adhesion of the resulting coating film is further improved. /40 is preferred, and 20/80 to 50/50 is more preferred.
前記ポリプロピレン変性アクリル樹脂の酸価は、水性樹脂組成物の貯蔵安定性、及び得られる塗膜の基材付着性がより向上することから、２０～８０ｍｇＫＯＨ／ｇの範囲が好ましく、２５～６５ｍｇＫＯＨ／ｇの範囲がより好ましい。
The acid value of the polypropylene-modified acrylic resin is preferably in the range of 20 to 80 mgKOH/g, 25 to 65 mgKOH/ A range of g is more preferred.
なお、本発明の樹脂の酸価は、原料組成から得られる計算値である。
The acid value of the resin of the present invention is a calculated value obtained from the raw material composition.
前記ポリプロピレン変性アクリル樹脂の重量平均分子量は、得られる塗膜の基材付着性がより向上することから、７，０００～１５０，０００が好ましく、１０，０００～６０，０００の範囲がより好ましい。
The weight average molecular weight of the polypropylene-modified acrylic resin is preferably from 7,000 to 150,000, more preferably from 10,000 to 60,000, because the adhesion to the substrate of the obtained coating film is further improved.
前記ポリプロピレン変性アクリル樹脂の分子量分散度（重量平均分子量／数平均分子量）は、得られる塗膜の基材付着性がより向上することから、５～２０が好ましい。
The molecular weight dispersity (weight average molecular weight/number average molecular weight) of the polypropylene-modified acrylic resin is preferably 5 to 20, since the obtained coating film has better adhesion to the substrate.
本発明の平均分子量はゲル浸透クロマトグラフィー（以下、「ＧＰＣ」と略記する。）測定に基づきポリスチレン換算した値である。
The average molecular weight of the present invention is a value converted to polystyrene based on gel permeation chromatography (hereinafter abbreviated as "GPC") measurement.
前記水性媒体としては、例えば、水、親水性有機溶剤、及びこれらの混合物が挙げられる。前記親水性有機溶剤としては水と分離することなく混和する水混和性有機溶剤が好ましく、中でも水に対する溶解度（水１００ｇに溶解する有機溶剤のグラム数）が２５℃において３ｇ以上の有機溶剤が好ましい。これら水混和性有機溶剤としては、例えば、メタノール、エタノール、プロパノール、ブタノール、３－メトキシブタノール、３－メチル－３－メトキシブタノール等のアルコール系溶剤；アセトン、メチルエチルケトン等のケトン系溶剤；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ジメチルエーテル、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ジエチルエーテル、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イソプロピルエーテル、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、ジエチレングリコールジメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールモノイソプロピルエーテル、ジエチレングリコールモノブチルエーテル、トリエチレングリコールモノメチルエーテル、トリエチレングリコールジメチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールジメチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールジメチルエーテル等のグリコールエーテル系溶剤などが挙げられる。これら水混和性有機溶剤は、それぞれ単独で用いても良いし、２種以上を併用しても良い。
Examples of the aqueous medium include water, hydrophilic organic solvents, and mixtures thereof. As the hydrophilic organic solvent, a water-miscible organic solvent that is miscible with water without separating is preferable, and among them, an organic solvent having a solubility in water (number of grams of organic solvent dissolved in 100 g of water) of 3 g or more at 25° C. is preferable. . Examples of these water-miscible organic solvents include alcohol solvents such as methanol, ethanol, propanol, butanol, 3-methoxybutanol, and 3-methyl-3-methoxybutanol; ketone solvents such as acetone and methyl ethyl ketone; ethylene glycol monomethyl; Ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono Isopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, etc. Glycol ether solvents and the like are included. These water-miscible organic solvents may be used alone or in combination of two or more.
本発明の水性樹脂組成物は、ポリプロピレン変性アクリル樹脂、及び水性媒体を含有するものであるが、上記した方法で得られたポリプロピレン変性アクリル樹脂が水性媒体に溶解または分散したものが好ましく、分散体がより好ましい。
Although the aqueous resin composition of the present invention contains a polypropylene-modified acrylic resin and an aqueous medium, it is preferable that the polypropylene-modified acrylic resin obtained by the above method is dissolved or dispersed in an aqueous medium. is more preferred.
前記ポリプロピレン変性アクリル樹脂を前記水性媒体に溶解または分散する方法としては、前記ポリプロピレン変性アクリル樹脂の有する酸基を塩基性化合物で中和したものと、前記水性媒体とを混合する方法が好ましい。
As a method for dissolving or dispersing the polypropylene-modified acrylic resin in the aqueous medium, it is preferable to mix the acid groups of the polypropylene-modified acrylic resin with a basic compound and the aqueous medium.
前記塩基性化合物としては、例えば、メチルアミン、ジメチルアミン、トリメチルアミン、エチルアミン、ジエチルアミン、トリエチルアミン、ブチルアミン、ジブチルアミン、トリブチルアミン、Ｎ，Ｎ－ジメチルエタノールアミン、２－アミノエタノール等のモノアルカノールアミン、ジエタノールアミン、ジイソプロパノールアミン、ジブタノールアミン等の有機アミン；アンモニア、水酸化ナトリウム、水酸化カリウム等の無機塩基性化合物；テトラメチルアンモニウムハイドロオキサイド、テトラ－ｎ－ブチルアンモニウムハイドロオキサイド、トリメチルベンジルアンモニウムハイドロオキサイド等の四級アンモニウムハイドロオキサイドなどが挙げられる。これらの中でも有機アミンおよびアンモニア（アンモニア水でもよい。）を使用することが好ましい。なお、これらの塩基性化合物は、単独で用いることも２種以上併用することもできる。
Examples of the basic compound include monoalkanolamines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, butylamine, dibutylamine, tributylamine, N,N-dimethylethanolamine and 2-aminoethanol, and diethanolamine. , diisopropanolamine, dibutanolamine and other organic amines; ammonia, sodium hydroxide, potassium hydroxide and other inorganic basic compounds; tetramethylammonium hydroxide, tetra-n-butylammonium hydroxide, trimethylbenzylammonium hydroxide, etc. and quaternary ammonium hydroxide. Among these, it is preferable to use organic amines and ammonia (aqueous ammonia may be used). These basic compounds can be used alone or in combination of two or more.
また、前記塩基性化合物の使用量としては、水性樹脂組成物の貯蔵安定性がより向上することから、前記ポリプロピレン変性アクリル樹脂の有するカルボキシル基の中和率が、５０～１００％の範囲となる量であることが好ましい。
In addition, since the storage stability of the aqueous resin composition is further improved as the amount of the basic compound used, the neutralization rate of the carboxyl groups possessed by the polypropylene-modified acrylic resin is in the range of 50 to 100%. Amount is preferred.
本発明の塗料は、本発明の水性樹脂組成物を含有するものであるが、その他の配合物として、消泡剤、粘度調整剤、耐光安定剤、耐候安定剤、耐熱安定剤、紫外線吸収剤、酸化防止剤、レベリング剤、顔料分散剤等の添加剤を使用することができる。また、酸化チタン、炭酸カルシウム、アルミニウム粉末、銅粉末、雲母粉末、酸化鉄、カーボンブラック、フタロシアニンブルー、トルイジンレッド、ペリレン、キナクリドン、ベンジジンイエロー等の顔料を使用することもできる。
The paint of the present invention contains the aqueous resin composition of the present invention, and other ingredients such as an antifoaming agent, a viscosity modifier, a light stabilizer, a weather stabilizer, a heat stabilizer, and an ultraviolet absorber. , antioxidants, leveling agents, pigment dispersants, and other additives may be used. Pigments such as titanium oxide, calcium carbonate, aluminum powder, copper powder, mica powder, iron oxide, carbon black, phthalocyanine blue, toluidine red, perylene, quinacridone, and benzidine yellow can also be used.
本発明の塗料の塗装方法としては、例えば、スプレー、アプリケーター、バーコーター、グラビアコーター、ロールコーター、コンマコーター、ナイフコーター、エアナイフコーター、カーテンコーター、キスコーター、シャワーコーター、ホイーラーコーター、スピンコーター、ディッピング、スクリーン印刷等の方法が挙げられる。また、塗装後、塗膜とする方法としては、常温～１２０℃の範囲で乾燥させる方法が挙げられる。
Examples of the coating method of the paint of the present invention include spray, applicator, bar coater, gravure coater, roll coater, comma coater, knife coater, air knife coater, curtain coater, kiss coater, shower coater, wheeler coater, spin coater, dipping, A method such as screen printing can be used. In addition, as a method of forming a coating film after coating, a method of drying in the range of normal temperature to 120° C. can be mentioned.
本発明の塗料は、プラスチック基材との高い付着性を有することから、各種プラスチック成形品を塗装する塗料として好適に用いることができるが、本発明の塗料を塗装することのできるプラスチック成形品としては、携帯電話、スマートフォン、タブレット端末、パソコン、デジタルカメラ、ゲーム機等の電子機器の筐体；テレビ、冷蔵庫、洗濯機、エアコン等の家電製品の筐体；自動車バンパー、自動車や鉄道車輌等の各種車輌の内装材などが挙げられる。
Since the paint of the present invention has high adhesion to plastic substrates, it can be suitably used as a paint for coating various plastic molded articles. is the housing of electronic equipment such as mobile phones, smartphones, tablet terminals, personal computers, digital cameras, and game consoles; the housing of home appliances such as televisions, refrigerators, washing machines, and air conditioners; Examples include interior materials for various vehicles.
以下に本発明を具体的な実施例を挙げてより詳細に説明する。
The present invention will be described in more detail below with specific examples.
［ＧＰＣ測定条件］
測定装置：高速ＧＰＣ装置（東ソー株式会社製「ＨＬＣ－８２２０ＧＰＣ」）
カラム：東ソー株式会社製の下記のカラムを直列に接続して使用した。
「ＴＳＫｇｅｌ Ｇ５０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
「ＴＳＫｇｅｌ Ｇ４０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
「ＴＳＫｇｅｌ Ｇ３０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
「ＴＳＫｇｅｌ Ｇ２０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
検出器：ＲＩ（示差屈折計）
カラム温度：４０℃
溶離液：テトラヒドロフラン（ＴＨＦ）
流速：１．０ｍＬ／分
注入量：１００μＬ（試料濃度４ｍｇ／ｍＬのテトラヒドロフラン溶液）
標準試料：下記の単分散ポリスチレンを用いて検量線を作成した。 [GPC measurement conditions]
Measuring device: high-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were connected in series and used.
"TSKgel G5000" (7.8mm I.D. x 30cm) x 1 "TSKgel G4000" (7.8mm I.D. x 30cm) x 1 "TSKgel G3000" (7.8mm I.D. x 30cm) x 1 Book "TSKgel G2000" (7.8 mm I.D. x 30 cm) x 1 Detector: RI (differential refractometer)
Column temperature: 40°C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL/min Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 4 mg/mL)
Standard sample: A calibration curve was created using the following monodisperse polystyrene.
測定装置：高速ＧＰＣ装置（東ソー株式会社製「ＨＬＣ－８２２０ＧＰＣ」）
カラム：東ソー株式会社製の下記のカラムを直列に接続して使用した。
「ＴＳＫｇｅｌ Ｇ５０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
「ＴＳＫｇｅｌ Ｇ４０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
「ＴＳＫｇｅｌ Ｇ３０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
「ＴＳＫｇｅｌ Ｇ２０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
検出器：ＲＩ（示差屈折計）
カラム温度：４０℃
溶離液：テトラヒドロフラン（ＴＨＦ）
流速：１．０ｍＬ／分
注入量：１００μＬ（試料濃度４ｍｇ／ｍＬのテトラヒドロフラン溶液）
標準試料：下記の単分散ポリスチレンを用いて検量線を作成した。 [GPC measurement conditions]
Measuring device: high-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were connected in series and used.
"TSKgel G5000" (7.8mm I.D. x 30cm) x 1 "TSKgel G4000" (7.8mm I.D. x 30cm) x 1 "TSKgel G3000" (7.8mm I.D. x 30cm) x 1 Book "TSKgel G2000" (7.8 mm I.D. x 30 cm) x 1 Detector: RI (differential refractometer)
Column temperature: 40°C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL/min Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 4 mg/mL)
Standard sample: A calibration curve was created using the following monodisperse polystyrene.
（単分散ポリスチレン）
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ－５００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ－１０００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ－２５００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ－５０００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－１」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－２」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－４」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－１０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－２０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－４０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－８０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－１２８」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－２８８」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－５５０」 (monodispersed polystyrene)
"TSKgel standard polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-2500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-5000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-1" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-10" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-288" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-550" manufactured by Tosoh Corporation
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ－５００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ－１０００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ－２５００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ－５０００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－１」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－２」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－４」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－１０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－２０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－４０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－８０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－１２８」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－２８８」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－５５０」 (monodispersed polystyrene)
"TSKgel standard polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-2500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-5000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-1" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-10" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-288" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-550" manufactured by Tosoh Corporation
以下で使用する不飽和単量体及び重合開始剤の略号は、それぞれ下記のものである。
ＭＭＡ：メチルメタクリレート
Ｓｔ：スチレン
ＢＡ：ブチルアクリレート
ＣＨＭＡ：シクロヘキシルメタクリレート
ＡＡ：アクリル酸
ＳＬＭＡ：ドデシルメタクリレートとトリデシルメタクリレートの混合物（三菱ケミカル株式会社製「アクリエステルＳＬ」）
ＥＡ：エチルアクリレート
ＩＢＸＭＡ：イソボルニルメタクリレート
２ＥＨＭＡ：２－エチルヘキシルメタクリレート
ＡＭ－１３０Ｇ：メトキシポリエチレングリコールアクリレート（新中村化学工業株式会社製「ＮＫエステルＡＭ－１３０Ｇ」）
ＨＥＭＡ：２－ヒドロキシエチルメタクリレート
Ｐ－Ｏ：ｔ－ブチルペルオキシ－２－エチルヘキサノエート
ＡＢＮ－Ｅ：２，２’－アゾビス（２－メチル）ブチロニトリル
Ｐ－Ｅ：ｔｅｒｔ－ブチルパーオキシ－２－エチルヘキシルモノカーボネート Abbreviations of unsaturated monomers and polymerization initiators used below are as follows.
MMA: Methyl methacrylate St: Styrene BA: Butyl acrylate CHMA: Cyclohexyl methacrylate AA: Acrylic acid SLMA: A mixture of dodecyl methacrylate and tridecyl methacrylate (manufactured by Mitsubishi Chemical Corporation "Acryester SL")
EA: Ethyl acrylate IBXMA: Isobornyl methacrylate 2EHMA: 2-Ethylhexyl methacrylate AM-130G: Methoxypolyethylene glycol acrylate (“NK Ester AM-130G” manufactured by Shin-Nakamura Chemical Co., Ltd.)
HEMA: 2-hydroxyethyl methacrylate PO: t-butylperoxy-2-ethylhexanoate ABN-E: 2,2'-azobis(2-methyl)butyronitrile PE: tert-butylperoxy-2- ethylhexyl monocarbonate
ＭＭＡ：メチルメタクリレート
Ｓｔ：スチレン
ＢＡ：ブチルアクリレート
ＣＨＭＡ：シクロヘキシルメタクリレート
ＡＡ：アクリル酸
ＳＬＭＡ：ドデシルメタクリレートとトリデシルメタクリレートの混合物（三菱ケミカル株式会社製「アクリエステルＳＬ」）
ＥＡ：エチルアクリレート
ＩＢＸＭＡ：イソボルニルメタクリレート
２ＥＨＭＡ：２－エチルヘキシルメタクリレート
ＡＭ－１３０Ｇ：メトキシポリエチレングリコールアクリレート（新中村化学工業株式会社製「ＮＫエステルＡＭ－１３０Ｇ」）
ＨＥＭＡ：２－ヒドロキシエチルメタクリレート
Ｐ－Ｏ：ｔ－ブチルペルオキシ－２－エチルヘキサノエート
ＡＢＮ－Ｅ：２，２’－アゾビス（２－メチル）ブチロニトリル
Ｐ－Ｅ：ｔｅｒｔ－ブチルパーオキシ－２－エチルヘキシルモノカーボネート Abbreviations of unsaturated monomers and polymerization initiators used below are as follows.
MMA: Methyl methacrylate St: Styrene BA: Butyl acrylate CHMA: Cyclohexyl methacrylate AA: Acrylic acid SLMA: A mixture of dodecyl methacrylate and tridecyl methacrylate (manufactured by Mitsubishi Chemical Corporation "Acryester SL")
EA: Ethyl acrylate IBXMA: Isobornyl methacrylate 2EHMA: 2-Ethylhexyl methacrylate AM-130G: Methoxypolyethylene glycol acrylate (“NK Ester AM-130G” manufactured by Shin-Nakamura Chemical Co., Ltd.)
HEMA: 2-hydroxyethyl methacrylate PO: t-butylperoxy-2-ethylhexanoate ABN-E: 2,2'-azobis(2-methyl)butyronitrile PE: tert-butylperoxy-2- ethylhexyl monocarbonate
（実施例１：水性樹脂組成物（１）の製造）
容量２Ｌの４つ口フラスコに、トルエン２５０ｇ、ポリプロピレンホモポリマー（出光興産製「Ｌ－ＭＯＤＵ Ｓ６００」、融点８０℃、重量平均分子量７５，０００；以下、「ポリプロピレン（Ａ－１）」と略記する。）６０ｇを加え、不活性ガス雰囲気下で１００℃に昇温した。
次に重合工程として、ＭＭＡ ２９．５ｇ、Ｓｔ ５０ｇ、ＢＡ ４０．５ｇ、ＣＨＭＡ ４．６ｇ、ＡＡ １５．４ｇ、Ｐ－Ｏ ５．２ｇからなる混合液を４時間かけて滴下し、更に３時間攪拌した。
次に水分散工程として、上述の反応液を７５℃に冷却し、メチルシクロヘキサン１００ｇ、イソプロピルアルコール４００ｇ、Ｎ，Ｎ－ジメチルエタノールアミン１９．１ｇ、水４４０ｇを逐次投入して水分散粒子溶液を得た。
得られた水分散粒子溶液からエバポレーターでトルエンとメチルシクロヘキサンとイソプロピルアルコールを減圧除去し、固形分濃度３０質量％の水分散体として、水性樹脂組成物（１）を得た。 (Example 1: Production of aqueous resin composition (1))
250 g of toluene, polypropylene homopolymer (manufactured by Idemitsu Kosan "L-MODU S600", melting point 80 ° C., weight average molecular weight 75,000; hereinafter abbreviated as "polypropylene (A-1)" ) was added, and the temperature was raised to 100°C in an inert gas atmosphere.
Next, as a polymerization step, a mixed liquid consisting of 29.5 g of MMA, 50 g of St, 40.5 g of BA, 4.6 g of CHMA, 15.4 g of AA, and 5.2 g of PO was added dropwise over 4 hours, and further 3 hours. Stirred.
Next, as a water dispersion step, the above reaction solution is cooled to 75° C., and 100 g of methylcyclohexane, 400 g of isopropyl alcohol, 19.1 g of N,N-dimethylethanolamine, and 440 g of water are added successively to obtain a water-dispersed particle solution. rice field.
Toluene, methylcyclohexane, and isopropyl alcohol were removed from the obtained water-dispersed particle solution under reduced pressure using an evaporator to obtain an aqueous resin composition (1) as an aqueous dispersion having a solid content concentration of 30% by mass.
容量２Ｌの４つ口フラスコに、トルエン２５０ｇ、ポリプロピレンホモポリマー（出光興産製「Ｌ－ＭＯＤＵ Ｓ６００」、融点８０℃、重量平均分子量７５，０００；以下、「ポリプロピレン（Ａ－１）」と略記する。）６０ｇを加え、不活性ガス雰囲気下で１００℃に昇温した。
次に重合工程として、ＭＭＡ ２９．５ｇ、Ｓｔ ５０ｇ、ＢＡ ４０．５ｇ、ＣＨＭＡ ４．６ｇ、ＡＡ １５．４ｇ、Ｐ－Ｏ ５．２ｇからなる混合液を４時間かけて滴下し、更に３時間攪拌した。
次に水分散工程として、上述の反応液を７５℃に冷却し、メチルシクロヘキサン１００ｇ、イソプロピルアルコール４００ｇ、Ｎ，Ｎ－ジメチルエタノールアミン１９．１ｇ、水４４０ｇを逐次投入して水分散粒子溶液を得た。
得られた水分散粒子溶液からエバポレーターでトルエンとメチルシクロヘキサンとイソプロピルアルコールを減圧除去し、固形分濃度３０質量％の水分散体として、水性樹脂組成物（１）を得た。 (Example 1: Production of aqueous resin composition (1))
250 g of toluene, polypropylene homopolymer (manufactured by Idemitsu Kosan "L-MODU S600", melting point 80 ° C., weight average molecular weight 75,000; hereinafter abbreviated as "polypropylene (A-1)" ) was added, and the temperature was raised to 100°C in an inert gas atmosphere.
Next, as a polymerization step, a mixed liquid consisting of 29.5 g of MMA, 50 g of St, 40.5 g of BA, 4.6 g of CHMA, 15.4 g of AA, and 5.2 g of PO was added dropwise over 4 hours, and further 3 hours. Stirred.
Next, as a water dispersion step, the above reaction solution is cooled to 75° C., and 100 g of methylcyclohexane, 400 g of isopropyl alcohol, 19.1 g of N,N-dimethylethanolamine, and 440 g of water are added successively to obtain a water-dispersed particle solution. rice field.
Toluene, methylcyclohexane, and isopropyl alcohol were removed from the obtained water-dispersed particle solution under reduced pressure using an evaporator to obtain an aqueous resin composition (1) as an aqueous dispersion having a solid content concentration of 30% by mass.
（実施例２：水性樹脂組成物（２）の製造）
容量２Ｌの４つ口フラスコに、トルエン１５０ｇ、ポリプロピレン（Ａ－１）９０ｇを加え、不活性ガス雰囲気下で１００℃に昇温した。
次に重合工程として、ＭＭＡ １０ｇ、Ｓｔ ４０ｇ、ＣＨＭＡ ２４ｇ、ＳＬＭＡ ２０ｇ、ＡＡ １５．４ｇ、Ｐ－Ｏ ５．２ｇからなる混合液を４時間かけて滴下し、更に３時間攪拌した。
次に水分散工程として、上述の反応液を７５℃に冷却し、メチルシクロヘキサン１００ｇ、イソプロピルアルコール４００ｇ、Ｎ，Ｎ－ジメチルエタノールアミン１９．１ｇ、水４４０ｇを逐次投入して水分散粒子溶液を得た。
得られた水分散粒子溶液からエバポレーターでトルエンとメチルシクロヘキサンとイソプロピルアルコールを減圧除去し、固形分濃度３０質量％の水分散体として、水性樹脂組成物（２）を得た。 (Example 2: Production of aqueous resin composition (2))
150 g of toluene and 90 g of polypropylene (A-1) were added to a 2 L four-necked flask, and the temperature was raised to 100° C. under an inert gas atmosphere.
Next, as a polymerization step, a mixed liquid consisting of 10 g of MMA, 40 g of St, 24 g of CHMA, 20 g of SLMA, 15.4 g of AA, and 5.2 g of PO was added dropwise over 4 hours, followed by stirring for 3 hours.
Next, as a water dispersion step, the above reaction solution is cooled to 75° C., and 100 g of methylcyclohexane, 400 g of isopropyl alcohol, 19.1 g of N,N-dimethylethanolamine, and 440 g of water are added successively to obtain a water-dispersed particle solution. rice field.
Toluene, methylcyclohexane, and isopropyl alcohol were removed from the obtained water-dispersed particle solution under reduced pressure using an evaporator to obtain an aqueous resin composition (2) as an aqueous dispersion having a solid content concentration of 30% by mass.
容量２Ｌの４つ口フラスコに、トルエン１５０ｇ、ポリプロピレン（Ａ－１）９０ｇを加え、不活性ガス雰囲気下で１００℃に昇温した。
次に重合工程として、ＭＭＡ １０ｇ、Ｓｔ ４０ｇ、ＣＨＭＡ ２４ｇ、ＳＬＭＡ ２０ｇ、ＡＡ １５．４ｇ、Ｐ－Ｏ ５．２ｇからなる混合液を４時間かけて滴下し、更に３時間攪拌した。
次に水分散工程として、上述の反応液を７５℃に冷却し、メチルシクロヘキサン１００ｇ、イソプロピルアルコール４００ｇ、Ｎ，Ｎ－ジメチルエタノールアミン１９．１ｇ、水４４０ｇを逐次投入して水分散粒子溶液を得た。
得られた水分散粒子溶液からエバポレーターでトルエンとメチルシクロヘキサンとイソプロピルアルコールを減圧除去し、固形分濃度３０質量％の水分散体として、水性樹脂組成物（２）を得た。 (Example 2: Production of aqueous resin composition (2))
150 g of toluene and 90 g of polypropylene (A-1) were added to a 2 L four-necked flask, and the temperature was raised to 100° C. under an inert gas atmosphere.
Next, as a polymerization step, a mixed liquid consisting of 10 g of MMA, 40 g of St, 24 g of CHMA, 20 g of SLMA, 15.4 g of AA, and 5.2 g of PO was added dropwise over 4 hours, followed by stirring for 3 hours.
Next, as a water dispersion step, the above reaction solution is cooled to 75° C., and 100 g of methylcyclohexane, 400 g of isopropyl alcohol, 19.1 g of N,N-dimethylethanolamine, and 440 g of water are added successively to obtain a water-dispersed particle solution. rice field.
Toluene, methylcyclohexane, and isopropyl alcohol were removed from the obtained water-dispersed particle solution under reduced pressure using an evaporator to obtain an aqueous resin composition (2) as an aqueous dispersion having a solid content concentration of 30% by mass.
（実施例３：水性樹脂組成物（３）の製造）
容量２Ｌの４つ口フラスコに、トルエン８０ｇ、ポリプロピレンホモポリマー（出光興産製「Ｌ－ＭＯＤＵ Ｓ４００」、融点８０℃、重量平均分子量４５，０００；以下、「ポリプロピレン（Ａ－２）」と略記する。）１２０ｇを加え、不活性ガス雰囲気下で１００℃に昇温した。
次に重合工程として、Ｓｔ２５ｇ、ＣＨＭＡ ２４ｇ、ＳＬＭＡ ２０ｇ、無水マレイン酸１２ｇ、ＡＢＮ－Ｅ ５．２ｇからなる混合液を４時間かけて滴下し、更に３時間攪拌した。
次に水分散工程として、上述の反応液を７５℃に冷却し、メチルシクロヘキサン２００ｇ、イソプロピルアルコール４００ｇ、トリエチルアミン２８ｇ、水４４０ｇを逐次投入して水分散粒子溶液を得た。
得られた水分散粒子溶液からエバポレーターでトルエンとメチルシクロヘキサンとイソプロピルアルコールを減圧除去し、固形分濃度２５質量％の水分散体として、水性樹脂組成物（３）を得た。 (Example 3: Production of aqueous resin composition (3))
80 g of toluene, polypropylene homopolymer (manufactured by Idemitsu Kosan "L-MODU S400", melting point 80 ° C., weight average molecular weight 45,000; hereinafter abbreviated as "polypropylene (A-2)" ) was added, and the temperature was raised to 100°C in an inert gas atmosphere.
Next, as a polymerization step, a mixture of 25 g of St, 24 g of CHMA, 20 g of SLMA, 12 g of maleic anhydride, and 5.2 g of ABN-E was added dropwise over 4 hours, followed by stirring for 3 hours.
Next, as a water dispersion step, the above reaction liquid was cooled to 75° C., and 200 g of methylcyclohexane, 400 g of isopropyl alcohol, 28 g of triethylamine and 440 g of water were successively added to obtain a water-dispersed particle solution.
Toluene, methylcyclohexane, and isopropyl alcohol were removed from the obtained water-dispersed particle solution under reduced pressure using an evaporator to obtain an aqueous resin composition (3) as an aqueous dispersion having a solid content concentration of 25% by mass.
容量２Ｌの４つ口フラスコに、トルエン８０ｇ、ポリプロピレンホモポリマー（出光興産製「Ｌ－ＭＯＤＵ Ｓ４００」、融点８０℃、重量平均分子量４５，０００；以下、「ポリプロピレン（Ａ－２）」と略記する。）１２０ｇを加え、不活性ガス雰囲気下で１００℃に昇温した。
次に重合工程として、Ｓｔ２５ｇ、ＣＨＭＡ ２４ｇ、ＳＬＭＡ ２０ｇ、無水マレイン酸１２ｇ、ＡＢＮ－Ｅ ５．２ｇからなる混合液を４時間かけて滴下し、更に３時間攪拌した。
次に水分散工程として、上述の反応液を７５℃に冷却し、メチルシクロヘキサン２００ｇ、イソプロピルアルコール４００ｇ、トリエチルアミン２８ｇ、水４４０ｇを逐次投入して水分散粒子溶液を得た。
得られた水分散粒子溶液からエバポレーターでトルエンとメチルシクロヘキサンとイソプロピルアルコールを減圧除去し、固形分濃度２５質量％の水分散体として、水性樹脂組成物（３）を得た。 (Example 3: Production of aqueous resin composition (3))
80 g of toluene, polypropylene homopolymer (manufactured by Idemitsu Kosan "L-MODU S400", melting point 80 ° C., weight average molecular weight 45,000; hereinafter abbreviated as "polypropylene (A-2)" ) was added, and the temperature was raised to 100°C in an inert gas atmosphere.
Next, as a polymerization step, a mixture of 25 g of St, 24 g of CHMA, 20 g of SLMA, 12 g of maleic anhydride, and 5.2 g of ABN-E was added dropwise over 4 hours, followed by stirring for 3 hours.
Next, as a water dispersion step, the above reaction liquid was cooled to 75° C., and 200 g of methylcyclohexane, 400 g of isopropyl alcohol, 28 g of triethylamine and 440 g of water were successively added to obtain a water-dispersed particle solution.
Toluene, methylcyclohexane, and isopropyl alcohol were removed from the obtained water-dispersed particle solution under reduced pressure using an evaporator to obtain an aqueous resin composition (3) as an aqueous dispersion having a solid content concentration of 25% by mass.
（実施例４：水性樹脂組成物（４）の製造）
容量２Ｌの４つ口フラスコに、酢酸ブチル２２５ｇ、ポリプロピレン（Ａ－２）６０ｇを加え、不活性ガス雰囲気下で１２０℃に昇温した。
次に重合工程として、ＭＭＡ ５０ｇ、Ｓｔ１０ｇ、ＥＡ ６８ｇ、ＡＡ １１．２ｇ、Ｐ－Ｏ８．５ｇからなる混合液を４時間かけて滴下し、更に３時間攪拌した。
次に水分散工程として、上述の反応液を７５℃に冷却し、メチルシクロヘキサン１８０ｇ、イソプロピルアルコール５１０ｇ、Ｎ，Ｎ－ジメチルエタノールアミン１３．９ｇ、水５１０ｇを逐次投入して水分散粒子溶液を得た。
得られた水分散粒子溶液からエバポレーターで酢酸ブチルとメチルシクロヘキサンとイソプロピルアルコールを減圧除去し、固形分濃度２７質量％の水分散体として、水性樹脂組成物（４）を得た。 (Example 4: Production of aqueous resin composition (4))
225 g of butyl acetate and 60 g of polypropylene (A-2) were added to a 2 L four-necked flask, and the temperature was raised to 120° C. under an inert gas atmosphere.
Next, as a polymerization step, a mixture of 50 g of MMA, 10 g of St, 68 g of EA, 11.2 g of AA and 8.5 g of PO was added dropwise over 4 hours, and the mixture was further stirred for 3 hours.
Next, in the water dispersion step, the above reaction solution is cooled to 75° C., and 180 g of methylcyclohexane, 510 g of isopropyl alcohol, 13.9 g of N,N-dimethylethanolamine, and 510 g of water are successively added to obtain a water-dispersed particle solution. rice field.
Butyl acetate, methylcyclohexane, and isopropyl alcohol were removed from the obtained water-dispersed particle solution under reduced pressure using an evaporator to obtain an aqueous resin composition (4) as an aqueous dispersion having a solid content concentration of 27% by mass.
容量２Ｌの４つ口フラスコに、酢酸ブチル２２５ｇ、ポリプロピレン（Ａ－２）６０ｇを加え、不活性ガス雰囲気下で１２０℃に昇温した。
次に重合工程として、ＭＭＡ ５０ｇ、Ｓｔ１０ｇ、ＥＡ ６８ｇ、ＡＡ １１．２ｇ、Ｐ－Ｏ８．５ｇからなる混合液を４時間かけて滴下し、更に３時間攪拌した。
次に水分散工程として、上述の反応液を７５℃に冷却し、メチルシクロヘキサン１８０ｇ、イソプロピルアルコール５１０ｇ、Ｎ，Ｎ－ジメチルエタノールアミン１３．９ｇ、水５１０ｇを逐次投入して水分散粒子溶液を得た。
得られた水分散粒子溶液からエバポレーターで酢酸ブチルとメチルシクロヘキサンとイソプロピルアルコールを減圧除去し、固形分濃度２７質量％の水分散体として、水性樹脂組成物（４）を得た。 (Example 4: Production of aqueous resin composition (4))
225 g of butyl acetate and 60 g of polypropylene (A-2) were added to a 2 L four-necked flask, and the temperature was raised to 120° C. under an inert gas atmosphere.
Next, as a polymerization step, a mixture of 50 g of MMA, 10 g of St, 68 g of EA, 11.2 g of AA and 8.5 g of PO was added dropwise over 4 hours, and the mixture was further stirred for 3 hours.
Next, in the water dispersion step, the above reaction solution is cooled to 75° C., and 180 g of methylcyclohexane, 510 g of isopropyl alcohol, 13.9 g of N,N-dimethylethanolamine, and 510 g of water are successively added to obtain a water-dispersed particle solution. rice field.
Butyl acetate, methylcyclohexane, and isopropyl alcohol were removed from the obtained water-dispersed particle solution under reduced pressure using an evaporator to obtain an aqueous resin composition (4) as an aqueous dispersion having a solid content concentration of 27% by mass.
（実施例５：水性樹脂組成物（５）の製造）
容量２Ｌの４つ口フラスコに、酢酸ブチル２７０ｇ、ポリプロピレン（Ａ－２）９０ｇを加え、不活性ガス雰囲気下で１２０℃に昇温した。
次に重合工程として、ＭＭＡ ５．４ｇ、ＥＡ ４２．５ｇ、ＩＢＸＭＡ ４８．６ｇ、ＡＡ １１．５ｇ、Ｐ－Ｅ ４ｇからなる混合液を４時間かけて滴下し、更に３時間攪拌した。
次に水分散工程として、上述の反応液を７５℃に冷却し、メチルシクロヘキサン１９０ｇ、イソプロピルアルコール４００ｇ、Ｎ，Ｎ－ジメチルエタノールアミン１４．２ｇ、水５４０ｇを逐次投入して水分散粒子溶液を得た。
得られた水分散粒子溶液からエバポレーターで酢酸ブチルとメチルシクロヘキサンとイソプロピルアルコールを減圧除去し、固形分濃度２６質量％の水分散体として、水性樹脂組成物（５）を得た。 (Example 5: Production of aqueous resin composition (5))
270 g of butyl acetate and 90 g of polypropylene (A-2) were added to a 2 L four-necked flask, and the temperature was raised to 120° C. under an inert gas atmosphere.
Next, as a polymerization step, a mixture of 5.4 g of MMA, 42.5 g of EA, 48.6 g of IBXMA, 11.5 g of AA and 4 g of PE was added dropwise over 4 hours, followed by stirring for 3 hours.
Next, in the water dispersion step, the above reaction solution was cooled to 75° C., and 190 g of methylcyclohexane, 400 g of isopropyl alcohol, 14.2 g of N,N-dimethylethanolamine, and 540 g of water were successively added to obtain a water-dispersed particle solution. rice field.
Butyl acetate, methylcyclohexane, and isopropyl alcohol were removed from the obtained water-dispersed particle solution under reduced pressure using an evaporator to obtain an aqueous resin composition (5) as an aqueous dispersion having a solid content concentration of 26% by mass.
容量２Ｌの４つ口フラスコに、酢酸ブチル２７０ｇ、ポリプロピレン（Ａ－２）９０ｇを加え、不活性ガス雰囲気下で１２０℃に昇温した。
次に重合工程として、ＭＭＡ ５．４ｇ、ＥＡ ４２．５ｇ、ＩＢＸＭＡ ４８．６ｇ、ＡＡ １１．５ｇ、Ｐ－Ｅ ４ｇからなる混合液を４時間かけて滴下し、更に３時間攪拌した。
次に水分散工程として、上述の反応液を７５℃に冷却し、メチルシクロヘキサン１９０ｇ、イソプロピルアルコール４００ｇ、Ｎ，Ｎ－ジメチルエタノールアミン１４．２ｇ、水５４０ｇを逐次投入して水分散粒子溶液を得た。
得られた水分散粒子溶液からエバポレーターで酢酸ブチルとメチルシクロヘキサンとイソプロピルアルコールを減圧除去し、固形分濃度２６質量％の水分散体として、水性樹脂組成物（５）を得た。 (Example 5: Production of aqueous resin composition (5))
270 g of butyl acetate and 90 g of polypropylene (A-2) were added to a 2 L four-necked flask, and the temperature was raised to 120° C. under an inert gas atmosphere.
Next, as a polymerization step, a mixture of 5.4 g of MMA, 42.5 g of EA, 48.6 g of IBXMA, 11.5 g of AA and 4 g of PE was added dropwise over 4 hours, followed by stirring for 3 hours.
Next, in the water dispersion step, the above reaction solution was cooled to 75° C., and 190 g of methylcyclohexane, 400 g of isopropyl alcohol, 14.2 g of N,N-dimethylethanolamine, and 540 g of water were successively added to obtain a water-dispersed particle solution. rice field.
Butyl acetate, methylcyclohexane, and isopropyl alcohol were removed from the obtained water-dispersed particle solution under reduced pressure using an evaporator to obtain an aqueous resin composition (5) as an aqueous dispersion having a solid content concentration of 26% by mass.
（実施例６：水性樹脂組成物（６）の製造）
容量２Ｌの４つ口フラスコに、ブチルセロソルブ７０ｇ、ポリプロピレンホモポリマー（出光興産製「Ｌ－ＭＯＤＵ Ｓ９０１」、融点８０℃、重量平均分子量１３０，０００；以下、「ポリプロピレン（Ａ－３）」と略記する。）３０ｇを加え、不活性ガス雰囲気下で１４０℃に昇温した。
次に重合工程として、Ｓｔ １５ｇ、ＩＢＸＭＡ ４０ｇ、２ＥＨＭＡ ２０ｇ、ＳＬＭＡ ３０ｇ、ＡＭ－１３０Ｇ ６０ｇ、ＡＡ ３ｇ、Ｐ－Ｅ ４．５ｇからなる混合液を４時間かけて滴下し、更に３時間攪拌した。
次に水分散工程として、上述の反応液を７５℃に冷却し、Ｎ，Ｎ－ジメチルエタノールアミン３．７ｇ、水３８０ｇを逐次投入し、固形分濃度３０質量％の水分散体として、水性樹脂組成物（６）を得た。
(Example 6: Production of aqueous resin composition (6))
In a four-necked flask with a capacity of 2 L, 70 g of butyl cellosolve, polypropylene homopolymer (manufactured by Idemitsu Kosan "L-MODU S901", melting point 80 ° C., weight average molecular weight 130,000; hereinafter abbreviated as "polypropylene (A-3)" ) was added, and the temperature was raised to 140°C in an inert gas atmosphere.
Next, as a polymerization step, a mixed liquid consisting of 15 g of St, 40 g of IBXMA, 20 g of 2EHMA, 30 g of SLMA, 60 g of AM-130G, 3 g of AA, and 4.5 g of PE was added dropwise over 4 hours, followed by stirring for 3 hours.
Next, as a water dispersion step, the above reaction liquid is cooled to 75 ° C., N,N-dimethylethanolamine 3.7 g and water 380 g are sequentially added to form a water dispersion with a solid content concentration of 30% by mass. A composition (6) was obtained.
容量２Ｌの４つ口フラスコに、ブチルセロソルブ７０ｇ、ポリプロピレンホモポリマー（出光興産製「Ｌ－ＭＯＤＵ Ｓ９０１」、融点８０℃、重量平均分子量１３０，０００；以下、「ポリプロピレン（Ａ－３）」と略記する。）３０ｇを加え、不活性ガス雰囲気下で１４０℃に昇温した。
次に重合工程として、Ｓｔ １５ｇ、ＩＢＸＭＡ ４０ｇ、２ＥＨＭＡ ２０ｇ、ＳＬＭＡ ３０ｇ、ＡＭ－１３０Ｇ ６０ｇ、ＡＡ ３ｇ、Ｐ－Ｅ ４．５ｇからなる混合液を４時間かけて滴下し、更に３時間攪拌した。
次に水分散工程として、上述の反応液を７５℃に冷却し、Ｎ，Ｎ－ジメチルエタノールアミン３．７ｇ、水３８０ｇを逐次投入し、固形分濃度３０質量％の水分散体として、水性樹脂組成物（６）を得た。
(Example 6: Production of aqueous resin composition (6))
In a four-necked flask with a capacity of 2 L, 70 g of butyl cellosolve, polypropylene homopolymer (manufactured by Idemitsu Kosan "L-MODU S901", melting point 80 ° C., weight average molecular weight 130,000; hereinafter abbreviated as "polypropylene (A-3)" ) was added, and the temperature was raised to 140°C in an inert gas atmosphere.
Next, as a polymerization step, a mixed liquid consisting of 15 g of St, 40 g of IBXMA, 20 g of 2EHMA, 30 g of SLMA, 60 g of AM-130G, 3 g of AA, and 4.5 g of PE was added dropwise over 4 hours, followed by stirring for 3 hours.
Next, as a water dispersion step, the above reaction liquid is cooled to 75 ° C., N,N-dimethylethanolamine 3.7 g and water 380 g are sequentially added to form a water dispersion with a solid content concentration of 30% by mass. A composition (6) was obtained.
（実施例７：水性樹脂組成物（７）の製造）
容量２Ｌの４つ口フラスコに、ジエチレングリコールジメチルエーテル７０ｇ、ポリプロピレン（Ａ－２）６０ｇを加え、不活性ガス雰囲気下で１２０℃に昇温した。
次に重合工程として、Ｓｔ３５ｇ、ＩＢＸＭＡ ４０ｇ、２ＥＨＭＡ ２０ｇ、ＳＬＭＡ ３０ｇ、ＨＥＭＡ １５ｇ、ＡＡ ８ｇ、Ｐ－Ｅ ４．５ｇからなる混合液を４時間かけて滴下し、更に３時間攪拌した。
次に水分散工程として、上述の反応液を７５℃に冷却し、２５％アンモニア水４２ｇ、水３８０ｇを逐次投入し、固形分濃度３０質量％の水分散体として、水性樹脂組成物（７）を得た。 (Example 7: Production of aqueous resin composition (7))
70 g of diethylene glycol dimethyl ether and 60 g of polypropylene (A-2) were added to a 2 L four-necked flask, and the temperature was raised to 120° C. under an inert gas atmosphere.
Next, as a polymerization step, a mixed liquid consisting of 35 g of St, 40 g of IBXMA, 20 g of 2EHMA, 30 g of SLMA, 15 g of HEMA, 8 g of AA, and 4.5 g of PE was added dropwise over 4 hours, followed by stirring for 3 hours.
Next, as a water dispersion step, the above reaction liquid is cooled to 75 ° C., 42 g of 25% aqueous ammonia and 380 g of water are successively added to obtain an aqueous resin composition (7) as an aqueous dispersion having a solid content concentration of 30% by mass. got
容量２Ｌの４つ口フラスコに、ジエチレングリコールジメチルエーテル７０ｇ、ポリプロピレン（Ａ－２）６０ｇを加え、不活性ガス雰囲気下で１２０℃に昇温した。
次に重合工程として、Ｓｔ３５ｇ、ＩＢＸＭＡ ４０ｇ、２ＥＨＭＡ ２０ｇ、ＳＬＭＡ ３０ｇ、ＨＥＭＡ １５ｇ、ＡＡ ８ｇ、Ｐ－Ｅ ４．５ｇからなる混合液を４時間かけて滴下し、更に３時間攪拌した。
次に水分散工程として、上述の反応液を７５℃に冷却し、２５％アンモニア水４２ｇ、水３８０ｇを逐次投入し、固形分濃度３０質量％の水分散体として、水性樹脂組成物（７）を得た。 (Example 7: Production of aqueous resin composition (7))
70 g of diethylene glycol dimethyl ether and 60 g of polypropylene (A-2) were added to a 2 L four-necked flask, and the temperature was raised to 120° C. under an inert gas atmosphere.
Next, as a polymerization step, a mixed liquid consisting of 35 g of St, 40 g of IBXMA, 20 g of 2EHMA, 30 g of SLMA, 15 g of HEMA, 8 g of AA, and 4.5 g of PE was added dropwise over 4 hours, followed by stirring for 3 hours.
Next, as a water dispersion step, the above reaction liquid is cooled to 75 ° C., 42 g of 25% aqueous ammonia and 380 g of water are successively added to obtain an aqueous resin composition (7) as an aqueous dispersion having a solid content concentration of 30% by mass. got
（実施例８：水性樹脂組成物（８）の製造）
容量２Ｌの４つ口フラスコに、トルエン２５０ｇ、ポリプロピレン（Ａ－２）１８ｇを加え、不活性ガス雰囲気下で１００℃に昇温した。
次に重合工程として、ＭＭＡ ２９．５ｇ、Ｓｔ４７ｇ、ＢＡ ２５．５ｇ、ＣＨＭＡ ６４．６ｇ、ＡＡ １１ｇ、Ｐ－Ｅ ４．５ｇからなる混合液を４時間かけて滴下し、更に３時間攪拌した。
次に水分散工程として、上述の反応液を７５℃に冷却し、メチルシクロヘキサン１００ｇ、イソプロピルアルコール４００ｇ、Ｎ，Ｎ－ジメチルエタノールアミン１３．６ｇ、水４４０ｇを逐次投入して水分散粒子溶液を得た。
得られた水分散粒子溶液からエバポレーターでトルエンとメチルシクロヘキサンとイソプロピルアルコールを減圧除去し、固形分濃度３０質量％の水分散体として、水性樹脂組成物（８）を得た。 (Example 8: Production of aqueous resin composition (8))
250 g of toluene and 18 g of polypropylene (A-2) were added to a 2 L four-necked flask, and the temperature was raised to 100° C. under an inert gas atmosphere.
Next, as a polymerization step, a mixture of 29.5 g of MMA, 47 g of St, 25.5 g of BA, 64.6 g of CHMA, 11 g of AA and 4.5 g of PE was added dropwise over 4 hours, and the mixture was further stirred for 3 hours.
Next, as a water dispersion step, the reaction solution was cooled to 75° C., and 100 g of methylcyclohexane, 400 g of isopropyl alcohol, 13.6 g of N,N-dimethylethanolamine, and 440 g of water were successively added to obtain a water-dispersed particle solution. rice field.
Toluene, methylcyclohexane, and isopropyl alcohol were removed from the obtained water-dispersed particle solution under reduced pressure using an evaporator to obtain an aqueous resin composition (8) as an aqueous dispersion having a solid content concentration of 30% by mass.
容量２Ｌの４つ口フラスコに、トルエン２５０ｇ、ポリプロピレン（Ａ－２）１８ｇを加え、不活性ガス雰囲気下で１００℃に昇温した。
次に重合工程として、ＭＭＡ ２９．５ｇ、Ｓｔ４７ｇ、ＢＡ ２５．５ｇ、ＣＨＭＡ ６４．６ｇ、ＡＡ １１ｇ、Ｐ－Ｅ ４．５ｇからなる混合液を４時間かけて滴下し、更に３時間攪拌した。
次に水分散工程として、上述の反応液を７５℃に冷却し、メチルシクロヘキサン１００ｇ、イソプロピルアルコール４００ｇ、Ｎ，Ｎ－ジメチルエタノールアミン１３．６ｇ、水４４０ｇを逐次投入して水分散粒子溶液を得た。
得られた水分散粒子溶液からエバポレーターでトルエンとメチルシクロヘキサンとイソプロピルアルコールを減圧除去し、固形分濃度３０質量％の水分散体として、水性樹脂組成物（８）を得た。 (Example 8: Production of aqueous resin composition (8))
250 g of toluene and 18 g of polypropylene (A-2) were added to a 2 L four-necked flask, and the temperature was raised to 100° C. under an inert gas atmosphere.
Next, as a polymerization step, a mixture of 29.5 g of MMA, 47 g of St, 25.5 g of BA, 64.6 g of CHMA, 11 g of AA and 4.5 g of PE was added dropwise over 4 hours, and the mixture was further stirred for 3 hours.
Next, as a water dispersion step, the reaction solution was cooled to 75° C., and 100 g of methylcyclohexane, 400 g of isopropyl alcohol, 13.6 g of N,N-dimethylethanolamine, and 440 g of water were successively added to obtain a water-dispersed particle solution. rice field.
Toluene, methylcyclohexane, and isopropyl alcohol were removed from the obtained water-dispersed particle solution under reduced pressure using an evaporator to obtain an aqueous resin composition (8) as an aqueous dispersion having a solid content concentration of 30% by mass.
（比較例１：水性樹脂組成物（Ｒ１）の製造）
容量２Ｌの４つ口フラスコに、ブチロセロソルブ７０ｇ、ポリプロピレン共重合体（エボニック社製「ベストプラスト７５０」、プロピレン／エチレン／１－ブテン共重合物、融点１０７℃）３０ｇ加え、不活性ガス雰囲気下で１４０℃に昇温した。
次に重合工程として、Ｓｔ １５．０ｇ、ＩＢＸＭＡ ４０ｇ、２ＥＨＭＡ ２０ｇ、ＳＬＭＡ ３０ｇ、ＡＭ－１３０Ｇ ６０ｇ、ＡＡ ３ｇ、Ｐ－Ｅ ４．５ｇからなる混合液を４時間かけて滴下し、更に３時間攪拌した。
次に水分散工程として、上述の反応液を７５℃に冷却し、Ｎ，Ｎ－ジメチルエタノールアミン ３．７ｇ、水３８０ｇを逐次投入して固形分濃度３０質量％の水分散体として、水性樹脂組成物（Ｒ１）を得た。 (Comparative Example 1: Production of aqueous resin composition (R1))
70 g of butyrocellosolve and 30 g of a polypropylene copolymer (manufactured by Evonik "Bestplast 750", propylene/ethylene/1-butene copolymer, melting point 107° C.) were added to a four-necked flask with a capacity of 2 L, and an inert gas atmosphere was added. The temperature was raised to 140° C. below.
Next, as a polymerization step, a mixed liquid consisting of 15.0 g of St, 40 g of IBXMA, 20 g of 2EHMA, 30 g of SLMA, 60 g of AM-130G, 3 g of AA, and 4.5 g of PE was added dropwise over 4 hours, followed by stirring for 3 hours. did.
Next, as a water dispersion step, the above reaction solution is cooled to 75 ° C., and 3.7 g of N,N-dimethylethanolamine and 380 g of water are successively added to form a water dispersion having a solid content of 30% by mass. A composition (R1) was obtained.
容量２Ｌの４つ口フラスコに、ブチロセロソルブ７０ｇ、ポリプロピレン共重合体（エボニック社製「ベストプラスト７５０」、プロピレン／エチレン／１－ブテン共重合物、融点１０７℃）３０ｇ加え、不活性ガス雰囲気下で１４０℃に昇温した。
次に重合工程として、Ｓｔ １５．０ｇ、ＩＢＸＭＡ ４０ｇ、２ＥＨＭＡ ２０ｇ、ＳＬＭＡ ３０ｇ、ＡＭ－１３０Ｇ ６０ｇ、ＡＡ ３ｇ、Ｐ－Ｅ ４．５ｇからなる混合液を４時間かけて滴下し、更に３時間攪拌した。
次に水分散工程として、上述の反応液を７５℃に冷却し、Ｎ，Ｎ－ジメチルエタノールアミン ３．７ｇ、水３８０ｇを逐次投入して固形分濃度３０質量％の水分散体として、水性樹脂組成物（Ｒ１）を得た。 (Comparative Example 1: Production of aqueous resin composition (R1))
70 g of butyrocellosolve and 30 g of a polypropylene copolymer (manufactured by Evonik "Bestplast 750", propylene/ethylene/1-butene copolymer, melting point 107° C.) were added to a four-necked flask with a capacity of 2 L, and an inert gas atmosphere was added. The temperature was raised to 140° C. below.
Next, as a polymerization step, a mixed liquid consisting of 15.0 g of St, 40 g of IBXMA, 20 g of 2EHMA, 30 g of SLMA, 60 g of AM-130G, 3 g of AA, and 4.5 g of PE was added dropwise over 4 hours, followed by stirring for 3 hours. did.
Next, as a water dispersion step, the above reaction solution is cooled to 75 ° C., and 3.7 g of N,N-dimethylethanolamine and 380 g of water are successively added to form a water dispersion having a solid content of 30% by mass. A composition (R1) was obtained.
（比較例２：水性樹脂組成物（Ｒ２）の製造）
容量２Ｌの４つ口フラスコに、ジエチレングリコールジメチルエーテル７０ｇ、ポリプロピレン（Ａ－２）６０ｇ加え、不活性ガス雰囲気下で１２０℃に昇温した。
次に重合工程として、Ｓｔ ３５ｇ、ＩＢＸＭＡ ２３ｇ、２ＥＨＭＡ ２０ｇ、ＳＬＭＡ ３０ｇ、ＨＥＭＡ １５ｇ、ＡＡ ２５ｇ、Ｐ－Ｅ ４．５ｇからなる混合液を４時間かけて滴下し、更に３時間攪拌した。
次に水分散工程として、上述の反応液を７５℃に冷却し、２５％アンモニア水１２４ｇ、水３８０ｇを逐次投入して固形分濃度３０質量％の水分散体として、水性樹脂組成物（Ｒ２）を得た。 (Comparative Example 2: Production of aqueous resin composition (R2))
70 g of diethylene glycol dimethyl ether and 60 g of polypropylene (A-2) were added to a 2 L four-necked flask, and the temperature was raised to 120° C. under an inert gas atmosphere.
Next, as a polymerization step, a mixed liquid consisting of 35 g of St, 23 g of IBXMA, 20 g of 2EHMA, 30 g of SLMA, 15 g of HEMA, 25 g of AA, and 4.5 g of PE was added dropwise over 4 hours, followed by stirring for 3 hours.
Next, as a water dispersion step, the above reaction liquid is cooled to 75 ° C., 124 g of 25% aqueous ammonia and 380 g of water are successively added to obtain an aqueous resin composition (R2) as a water dispersion having a solid content concentration of 30% by mass. got
容量２Ｌの４つ口フラスコに、ジエチレングリコールジメチルエーテル７０ｇ、ポリプロピレン（Ａ－２）６０ｇ加え、不活性ガス雰囲気下で１２０℃に昇温した。
次に重合工程として、Ｓｔ ３５ｇ、ＩＢＸＭＡ ２３ｇ、２ＥＨＭＡ ２０ｇ、ＳＬＭＡ ３０ｇ、ＨＥＭＡ １５ｇ、ＡＡ ２５ｇ、Ｐ－Ｅ ４．５ｇからなる混合液を４時間かけて滴下し、更に３時間攪拌した。
次に水分散工程として、上述の反応液を７５℃に冷却し、２５％アンモニア水１２４ｇ、水３８０ｇを逐次投入して固形分濃度３０質量％の水分散体として、水性樹脂組成物（Ｒ２）を得た。 (Comparative Example 2: Production of aqueous resin composition (R2))
70 g of diethylene glycol dimethyl ether and 60 g of polypropylene (A-2) were added to a 2 L four-necked flask, and the temperature was raised to 120° C. under an inert gas atmosphere.
Next, as a polymerization step, a mixed liquid consisting of 35 g of St, 23 g of IBXMA, 20 g of 2EHMA, 30 g of SLMA, 15 g of HEMA, 25 g of AA, and 4.5 g of PE was added dropwise over 4 hours, followed by stirring for 3 hours.
Next, as a water dispersion step, the above reaction liquid is cooled to 75 ° C., 124 g of 25% aqueous ammonia and 380 g of water are successively added to obtain an aqueous resin composition (R2) as a water dispersion having a solid content concentration of 30% by mass. got
（比較例３：水性樹脂組成物（Ｒ３）の製造）
容量２Ｌの４つ口フラスコに、ブチルセロソルブ７０ｇ、ポリプロピレン（Ａ－２）６０ｇを加え、不活性ガス雰囲気下で１２０℃に昇温した。
次に重合工程として、ＭＭＡ ３０ｇ、Ｓｔ ５０ｇ、ＢＡ ４０ｇ、ＣＨＭＡ ２０ｇ、ＡＡ ２．６ｇ、Ｐ－Ｅ ４．５ｇからなる混合液を４時間かけて滴下し、更に３時間攪拌した。
次に水分散工程として、上述の反応液を７５℃に冷却し、Ｎ，Ｎ－ジメチルエタノールアミン ３．２ｇ、水３８０ｇを逐次投入して固形分濃度３０質量％の水分散体として、水性樹脂組成物（Ｒ３）を得た。 (Comparative Example 3: Production of aqueous resin composition (R3))
70 g of butyl cellosolve and 60 g of polypropylene (A-2) were added to a 2 L four-necked flask, and the temperature was raised to 120° C. under an inert gas atmosphere.
Next, as a polymerization step, a mixed liquid consisting of 30 g of MMA, 50 g of St, 40 g of BA, 20 g of CHMA, 2.6 g of AA and 4.5 g of PE was added dropwise over 4 hours, and the mixture was further stirred for 3 hours.
Next, as a water dispersion step, the above reaction solution is cooled to 75 ° C., and 3.2 g of N,N-dimethylethanolamine and 380 g of water are successively added to form a water dispersion having a solid content of 30% by mass. A composition (R3) was obtained.
容量２Ｌの４つ口フラスコに、ブチルセロソルブ７０ｇ、ポリプロピレン（Ａ－２）６０ｇを加え、不活性ガス雰囲気下で１２０℃に昇温した。
次に重合工程として、ＭＭＡ ３０ｇ、Ｓｔ ５０ｇ、ＢＡ ４０ｇ、ＣＨＭＡ ２０ｇ、ＡＡ ２．６ｇ、Ｐ－Ｅ ４．５ｇからなる混合液を４時間かけて滴下し、更に３時間攪拌した。
次に水分散工程として、上述の反応液を７５℃に冷却し、Ｎ，Ｎ－ジメチルエタノールアミン ３．２ｇ、水３８０ｇを逐次投入して固形分濃度３０質量％の水分散体として、水性樹脂組成物（Ｒ３）を得た。 (Comparative Example 3: Production of aqueous resin composition (R3))
70 g of butyl cellosolve and 60 g of polypropylene (A-2) were added to a 2 L four-necked flask, and the temperature was raised to 120° C. under an inert gas atmosphere.
Next, as a polymerization step, a mixed liquid consisting of 30 g of MMA, 50 g of St, 40 g of BA, 20 g of CHMA, 2.6 g of AA and 4.5 g of PE was added dropwise over 4 hours, and the mixture was further stirred for 3 hours.
Next, as a water dispersion step, the above reaction solution is cooled to 75 ° C., and 3.2 g of N,N-dimethylethanolamine and 380 g of water are successively added to form a water dispersion having a solid content of 30% by mass. A composition (R3) was obtained.
［貯蔵安定性の評価］
上記で得た水性樹脂組成物を、４０℃で３か月間静置保存し、その外観を目視で観察して、下記の基準により貯蔵安定性を評価した。◎、○であれば、実用上差支えない性能であると見做す。
◎：外観に有意差なし
○：溶液最表面に僅かな溶媒分離が認められるが、軽く混合すると均一になる。
×：樹脂分が沈降分離しており、激しく混合しても再び分離する。 [Evaluation of storage stability]
The aqueous resin composition obtained above was stored at rest at 40° C. for 3 months, its appearance was visually observed, and storage stability was evaluated according to the following criteria. If it is ⊚ or ◯, it is considered that the performance is acceptable for practical use.
⊚: No significant difference in appearance ◯: Slight solvent separation is observed on the outermost surface of the solution, but becomes uniform when lightly mixed.
x: The resin component sediments and separates, and separates again even if vigorously mixed.
上記で得た水性樹脂組成物を、４０℃で３か月間静置保存し、その外観を目視で観察して、下記の基準により貯蔵安定性を評価した。◎、○であれば、実用上差支えない性能であると見做す。
◎：外観に有意差なし
○：溶液最表面に僅かな溶媒分離が認められるが、軽く混合すると均一になる。
×：樹脂分が沈降分離しており、激しく混合しても再び分離する。 [Evaluation of storage stability]
The aqueous resin composition obtained above was stored at rest at 40° C. for 3 months, its appearance was visually observed, and storage stability was evaluated according to the following criteria. If it is ⊚ or ◯, it is considered that the performance is acceptable for practical use.
⊚: No significant difference in appearance ◯: Slight solvent separation is observed on the outermost surface of the solution, but becomes uniform when lightly mixed.
x: The resin component sediments and separates, and separates again even if vigorously mixed.
上記で得た水性樹脂組成物（１）～（８）の組成及び評価結果を表１及び２に示す。
Tables 1 and 2 show the compositions and evaluation results of the aqueous resin compositions (1) to (8) obtained above.
上記で得た比較用水性樹脂組成物（Ｒ１）～（Ｒ３）の組成及び評価結果を表３に示す。
Table 3 shows the compositions and evaluation results of the comparative aqueous resin compositions (R1) to (R3) obtained above.
（実施例９：水性塗料（１）の調製及び評価）
上記で得た水性樹脂組成物（１） １００ｇに、レベリング剤としてＢＹＫ－３４８（ＢＹＫ Ｃｈｅｍｉｅ製）０．２ｇ、消泡剤としてＳＮデフォーマー７７７（サンノプコ株式会社製）０．１ｇを加え、１５分間攪拌した。次に、塗料粘度が粘度カップＮＫ－２（アネスト岩田株式会社製）で１２秒になるまでイオン交換水を用いて希釈し、水性塗料（１）を得た。 (Example 9: Preparation and evaluation of water-based paint (1))
To 100 g of the aqueous resin composition (1) obtained above, 0.2 g of BYK-348 (manufactured by BYK Chemie) as a leveling agent and 0.1 g of SN Deformer 777 (manufactured by San Nopco Co., Ltd.) as an antifoaming agent are added, and the mixture is stirred for 15 minutes. Stirred. Next, the mixture was diluted with deionized water until the paint viscosity reached 12 seconds using a viscosity cup NK-2 (manufactured by Anest Iwata Co., Ltd.) to obtain water-based paint (1).
上記で得た水性樹脂組成物（１） １００ｇに、レベリング剤としてＢＹＫ－３４８（ＢＹＫ Ｃｈｅｍｉｅ製）０．２ｇ、消泡剤としてＳＮデフォーマー７７７（サンノプコ株式会社製）０．１ｇを加え、１５分間攪拌した。次に、塗料粘度が粘度カップＮＫ－２（アネスト岩田株式会社製）で１２秒になるまでイオン交換水を用いて希釈し、水性塗料（１）を得た。 (Example 9: Preparation and evaluation of water-based paint (1))
To 100 g of the aqueous resin composition (1) obtained above, 0.2 g of BYK-348 (manufactured by BYK Chemie) as a leveling agent and 0.1 g of SN Deformer 777 (manufactured by San Nopco Co., Ltd.) as an antifoaming agent are added, and the mixture is stirred for 15 minutes. Stirred. Next, the mixture was diluted with deionized water until the paint viscosity reached 12 seconds using a viscosity cup NK-2 (manufactured by Anest Iwata Co., Ltd.) to obtain water-based paint (1).
［評価用硬化塗膜の作製］
上記で得た水性塗料を、ＰＣ（ポリカーボネート）板、ＰＰ（ポリプロピレン、ＴＳＯＰ６）板、Ａｌ５０５２Ｐ板、ＡＢＳ（アクリロニトリル－ブタジエン－スチレン共重合体）板、ナイロン（６ナイロン）板にスプレーガンを用いて、乾燥膜厚が２０μｍとなるように塗装した。その後乾燥機にて９５℃、２０分間加熱乾燥処理を施し、評価用塗膜を作製した。 [Preparation of cured coating film for evaluation]
The water-based paint obtained above is applied to a PC (polycarbonate) plate, a PP (polypropylene, TSOP6) plate, an Al5052P plate, an ABS (acrylonitrile-butadiene-styrene copolymer) plate, and a nylon (6 nylon) plate using a spray gun. , and the dry film thickness was 20 μm. After that, heat drying treatment was performed at 95° C. for 20 minutes in a dryer to prepare a coating film for evaluation.
上記で得た水性塗料を、ＰＣ（ポリカーボネート）板、ＰＰ（ポリプロピレン、ＴＳＯＰ６）板、Ａｌ５０５２Ｐ板、ＡＢＳ（アクリロニトリル－ブタジエン－スチレン共重合体）板、ナイロン（６ナイロン）板にスプレーガンを用いて、乾燥膜厚が２０μｍとなるように塗装した。その後乾燥機にて９５℃、２０分間加熱乾燥処理を施し、評価用塗膜を作製した。 [Preparation of cured coating film for evaluation]
The water-based paint obtained above is applied to a PC (polycarbonate) plate, a PP (polypropylene, TSOP6) plate, an Al5052P plate, an ABS (acrylonitrile-butadiene-styrene copolymer) plate, and a nylon (6 nylon) plate using a spray gun. , and the dry film thickness was 20 μm. After that, heat drying treatment was performed at 95° C. for 20 minutes in a dryer to prepare a coating film for evaluation.
［基材付着性の評価］
スプレー塗装で得られた乾燥塗膜をＪＩＳ Ｋ－５６００の碁盤目試験法に基づいて評価した。前記塗膜の上にカッターで２ｍｍ幅の切込みを入れ碁盤目の数を２５個とし、全ての碁盤目を覆うようにセロハンテープを貼り付け、素早く引き剥がした。ＪＩＳ規格の試験結果２以下の付着が認められれば実用上差支えない性能である。 [Evaluation of adhesion to substrate]
A dry coating film obtained by spray coating was evaluated based on the cross-cut test method of JIS K-5600. A cut of 2 mm width was made on the coating film with a cutter so that the number of grids was 25, and cellophane tape was attached so as to cover all the grids and quickly peeled off. If adhesion of JIS standard test result 2 or less is recognized, the performance is practically acceptable.
スプレー塗装で得られた乾燥塗膜をＪＩＳ Ｋ－５６００の碁盤目試験法に基づいて評価した。前記塗膜の上にカッターで２ｍｍ幅の切込みを入れ碁盤目の数を２５個とし、全ての碁盤目を覆うようにセロハンテープを貼り付け、素早く引き剥がした。ＪＩＳ規格の試験結果２以下の付着が認められれば実用上差支えない性能である。 [Evaluation of adhesion to substrate]
A dry coating film obtained by spray coating was evaluated based on the cross-cut test method of JIS K-5600. A cut of 2 mm width was made on the coating film with a cutter so that the number of grids was 25, and cellophane tape was attached so as to cover all the grids and quickly peeled off. If adhesion of JIS standard test result 2 or less is recognized, the performance is practically acceptable.
（実施例１０～１６：水性塗料（２）～（８）の調製及び評価）
水性樹脂組成物（１）を水性樹脂組成物（２）～（８）に変更した以外は、実施例９と同様にして、水性塗料（２）～（８）を調製し、基材付着性の評価を行った。 (Examples 10 to 16: Preparation and evaluation of water-based paints (2) to (8))
Water-based paints (2) to (8) were prepared in the same manner as in Example 9, except that the water-based resin composition (1) was changed to the water-based resin compositions (2) to (8), and substrate adhesion was evaluated.
水性樹脂組成物（１）を水性樹脂組成物（２）～（８）に変更した以外は、実施例９と同様にして、水性塗料（２）～（８）を調製し、基材付着性の評価を行った。 (Examples 10 to 16: Preparation and evaluation of water-based paints (2) to (8))
Water-based paints (2) to (8) were prepared in the same manner as in Example 9, except that the water-based resin composition (1) was changed to the water-based resin compositions (2) to (8), and substrate adhesion was evaluated.
（比較例４～６：水性塗料（Ｒ１）～（Ｒ３）の調製及び評価）
水性樹脂組成物（１）を水性樹脂組成物（Ｒ１）～（Ｒ３）に変更した以外は、実施例１４と同様にして、水性塗料（Ｒ１）～（Ｒ３）を調製し、基材付着性の評価を行った。 (Comparative Examples 4 to 6: Preparation and evaluation of water-based paints (R1) to (R3))
Water-based paints (R1)-(R3) were prepared in the same manner as in Example 14, except that the water-based resin composition (1) was changed to the water-based resin compositions (R1)-(R3), and substrate adhesion was evaluated.
水性樹脂組成物（１）を水性樹脂組成物（Ｒ１）～（Ｒ３）に変更した以外は、実施例１４と同様にして、水性塗料（Ｒ１）～（Ｒ３）を調製し、基材付着性の評価を行った。 (Comparative Examples 4 to 6: Preparation and evaluation of water-based paints (R1) to (R3))
Water-based paints (R1)-(R3) were prepared in the same manner as in Example 14, except that the water-based resin composition (1) was changed to the water-based resin compositions (R1)-(R3), and substrate adhesion was evaluated.
上記の実施例９～１６及び比較例４～６の評価結果を表４～６に示す。
The evaluation results of Examples 9-16 and Comparative Examples 4-6 are shown in Tables 4-6.
本発明の水性樹脂組成物は貯蔵安定性に優れ、得られる塗膜は、各種基材の付着性に優れることが確認された。
It was confirmed that the aqueous resin composition of the present invention has excellent storage stability, and that the resulting coating film has excellent adhesion to various substrates.
一方、比較例１は、本発明の必須成分であるポリプロピレンのホモポリマーを使用しなかった例であるが、貯蔵安定性が不十分であり、得られる塗膜は、アルミ基材やナイロン基材への付着性が不十分であった。
On the other hand, Comparative Example 1 is an example in which the homopolymer of polypropylene, which is an essential component of the present invention, was not used. Adhesion to was insufficient.
比較例２は、ポリプロピレン変性アクリル樹脂の酸価が、本発明の上限である８０ｍｇＫＯＨ／ｇより大きい例であるが、得られる塗膜は、ポリプロピレン基材、アクリロニトリル－ブタジエン－スチレン共重合体基材、ナイロン基材への付着性が不十分であった。
Comparative Example 2 is an example in which the acid value of the polypropylene-modified acrylic resin is greater than the upper limit of the present invention of 80 mgKOH/g, but the resulting coating film is based on a polypropylene base and an acrylonitrile-butadiene-styrene copolymer base. , the adhesion to the nylon substrate was insufficient.
比較例３は、ポリプロピレン変性アクリル樹脂の酸価が、本発明の下限である２０ｍｇＫＯＨ／ｇより小さい例であるが、貯蔵安定性が不十分であり、得られる塗膜は、ナイロン基材への付着性が不十分であった。
Comparative Example 3 is an example in which the acid value of the polypropylene-modified acrylic resin is less than 20 mgKOH/g, which is the lower limit of the present invention. Adhesion was insufficient.
Claims (6)
- ポリプロピレン（Ａ）及び不飽和単量体混合物（Ｂ）の反応物であるポリプロピレン変性アクリル樹脂と、水性媒体とを含有する水性樹脂組成物であって、前記ポリプロピレン（Ａ）がホモポリマーであり、前記不飽和単量体混合物（Ｂ）がカルボキシル基を有する不飽和単量体（ｂ１）を含むものであり、前記ポリプロピレン変性アクリル樹脂の酸価が２０～８０ｍｇＫＯＨ／ｇであることを特徴とする水性樹脂組成物。 An aqueous resin composition containing a polypropylene-modified acrylic resin that is a reaction product of polypropylene (A) and an unsaturated monomer mixture (B), and an aqueous medium, wherein the polypropylene (A) is a homopolymer, The unsaturated monomer mixture (B) contains an unsaturated monomer (b1) having a carboxyl group, and the polypropylene-modified acrylic resin has an acid value of 20 to 80 mgKOH/g. Aqueous resin composition.
- 前記ポリプロピレン変性アクリル樹脂の分子量分散度（重量平均分子量／数平均分子量）が５～２０である請求項１記載の水性樹脂組成物。 The aqueous resin composition according to claim 1, wherein the polypropylene-modified acrylic resin has a molecular weight distribution (weight average molecular weight/number average molecular weight) of 5 to 20.
- 前記ポリプロピレン（Ａ）の融点が４０～１２０℃である請求項１又は２記載の水性樹脂組成物。 The aqueous resin composition according to claim 1 or 2, wherein the polypropylene (A) has a melting point of 40 to 120°C.
- 前記ポリプロピレン（Ａ）と前記不飽和単量体混合物（Ｂ）との質量比（Ａ／Ｂ）が１０／９０～６０／４０である請求項１～３いずれか１記載の水性樹脂組成物。 The aqueous resin composition according to any one of claims 1 to 3, wherein the mass ratio (A/B) between the polypropylene (A) and the unsaturated monomer mixture (B) is 10/90 to 60/40.
- 請求項１～４のいずれか１項記載の水性樹脂組成物を含有することを特徴とする水性塗料。 A water-based paint characterized by containing the water-based resin composition according to any one of claims 1 to 4.
- 請求項５記載の水性塗料で塗装されたことを特徴とする物品。 An article characterized by being painted with the water-based paint according to claim 5.
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|---|---|---|---|
| CN202280011576.0A CN116724085A (en) | 2021-03-23 | 2022-03-03 | Aqueous resin composition, aqueous paint and article coated with the aqueous paint |
| JP2023508875A JP7364115B2 (en) | 2021-03-23 | 2022-03-03 | Water-based resin compositions, water-based paints, and articles coated with the water-based paints |
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| JP (1) | JP7364115B2 (en) |
| CN (1) | CN116724085A (en) |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11269206A (en) * | 1998-03-23 | 1999-10-05 | Toyo Kasei Kogyo Co Ltd | Preparation of modified polyolefin-based aqueous resin composition |
| JP2005036076A (en) * | 2003-07-18 | 2005-02-10 | Toyo Kasei Kogyo Co Ltd | High molecular weight polyolefin aqueous emulsion composition |
| US20060235160A1 (en) * | 2005-04-19 | 2006-10-19 | Dpi Co., Ltd. | Water-borne resin composition for polyolefin and method of preparing the same |
| JP2014185399A (en) * | 2013-03-22 | 2014-10-02 | Sanyo Chem Ind Ltd | Dyeability improver for polyolefin resin |
-
2022
- 2022-02-08 TW TW111104613A patent/TW202300585A/en unknown
- 2022-03-03 WO PCT/JP2022/009015 patent/WO2022202172A1/en active Application Filing
- 2022-03-03 CN CN202280011576.0A patent/CN116724085A/en active Pending
- 2022-03-03 JP JP2023508875A patent/JP7364115B2/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11269206A (en) * | 1998-03-23 | 1999-10-05 | Toyo Kasei Kogyo Co Ltd | Preparation of modified polyolefin-based aqueous resin composition |
| JP2005036076A (en) * | 2003-07-18 | 2005-02-10 | Toyo Kasei Kogyo Co Ltd | High molecular weight polyolefin aqueous emulsion composition |
| US20060235160A1 (en) * | 2005-04-19 | 2006-10-19 | Dpi Co., Ltd. | Water-borne resin composition for polyolefin and method of preparing the same |
| JP2014185399A (en) * | 2013-03-22 | 2014-10-02 | Sanyo Chem Ind Ltd | Dyeability improver for polyolefin resin |
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| CN116724085A (en) | 2023-09-08 |
| JPWO2022202172A1 (en) | 2022-09-29 |
| JP7364115B2 (en) | 2023-10-18 |
| TW202300585A (en) | 2023-01-01 |
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