WO2022181204A1 - 水系樹脂分散体、前記水系樹脂分散体を原料とする組成物、前記組成物の乾燥物を含む積層体 - Google Patents
水系樹脂分散体、前記水系樹脂分散体を原料とする組成物、前記組成物の乾燥物を含む積層体 Download PDFInfo
- Publication number
- WO2022181204A1 WO2022181204A1 PCT/JP2022/003333 JP2022003333W WO2022181204A1 WO 2022181204 A1 WO2022181204 A1 WO 2022181204A1 JP 2022003333 W JP2022003333 W JP 2022003333W WO 2022181204 A1 WO2022181204 A1 WO 2022181204A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polymer
- composition
- water
- resin dispersion
- based resin
- Prior art date
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 138
- 239000011347 resin Substances 0.000 title claims abstract description 138
- 239000006185 dispersion Substances 0.000 title claims abstract description 123
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000000203 mixture Substances 0.000 title claims description 68
- 239000002994 raw material Substances 0.000 title description 4
- 229920000642 polymer Polymers 0.000 claims abstract description 165
- 239000000178 monomer Substances 0.000 claims abstract description 111
- 239000002245 particle Substances 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 21
- 229920000098 polyolefin Polymers 0.000 claims description 45
- 238000000576 coating method Methods 0.000 claims description 38
- 239000011248 coating agent Substances 0.000 claims description 34
- 239000000758 substrate Substances 0.000 claims description 28
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 22
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 22
- 239000011888 foil Substances 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 239000012462 polypropylene substrate Substances 0.000 claims description 15
- 239000000853 adhesive Substances 0.000 claims description 14
- 230000001070 adhesive effect Effects 0.000 claims description 14
- 229920005992 thermoplastic resin Polymers 0.000 claims description 13
- 230000009477 glass transition Effects 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 239000005003 food packaging material Substances 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 abstract description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 10
- -1 polypropylene Polymers 0.000 description 59
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 56
- 229920001577 copolymer Polymers 0.000 description 52
- 238000000034 method Methods 0.000 description 37
- 238000006116 polymerization reaction Methods 0.000 description 36
- 238000004519 manufacturing process Methods 0.000 description 34
- 239000004743 Polypropylene Substances 0.000 description 33
- 229920001155 polypropylene Polymers 0.000 description 33
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 26
- 229920002554 vinyl polymer Polymers 0.000 description 19
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 17
- 238000007789 sealing Methods 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 13
- 229910052782 aluminium Inorganic materials 0.000 description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 13
- 230000000379 polymerizing effect Effects 0.000 description 13
- 239000004711 α-olefin Substances 0.000 description 13
- 238000007740 vapor deposition Methods 0.000 description 12
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 229920000578 graft copolymer Polymers 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000004094 surface-active agent Substances 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical group CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- 239000005026 oriented polypropylene Substances 0.000 description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 229920001384 propylene homopolymer Polymers 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 230000009466 transformation Effects 0.000 description 6
- 239000000080 wetting agent Substances 0.000 description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 229920001519 homopolymer Polymers 0.000 description 5
- 229920001477 hydrophilic polymer Polymers 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000007870 radical polymerization initiator Substances 0.000 description 5
- 239000012945 sealing adhesive Substances 0.000 description 5
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 4
- 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 4
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 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 4
- 229920001778 nylon Polymers 0.000 description 4
- 150000001451 organic peroxides Chemical class 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 4
- 229920006122 polyamide resin Polymers 0.000 description 4
- 229920001225 polyester resin Polymers 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 125000002843 carboxylic acid group Chemical group 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000011790 ferrous sulphate Substances 0.000 description 3
- 235000003891 ferrous sulphate Nutrition 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 229920002050 silicone resin Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229920006132 styrene block copolymer Polymers 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 2
- 125000003504 2-oxazolinyl group Chemical class O1C(=NCC1)* 0.000 description 2
- 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 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- 239000004709 Chlorinated polyethylene Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 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
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004962 Polyamide-imide Substances 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 2
- 239000011354 acetal resin Substances 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 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 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 229920001893 acrylonitrile styrene Polymers 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical class C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 239000012461 cellulose resin Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000012718 coordination polymerization Methods 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 239000006063 cullet Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-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
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000002429 hydrazines Chemical class 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000012968 metallocene catalyst Substances 0.000 description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920002312 polyamide-imide Polymers 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 229920005678 polyethylene based resin Polymers 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 229920005673 polypropylene based resin Polymers 0.000 description 2
- 229920005606 polypropylene copolymer Polymers 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 2
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 2
- 229940080818 propionamide Drugs 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- NKESWEQTVZVSSF-DMWQRSMXSA-M sodium;(2r)-2-[(1r)-1,2-dihydroxyethyl]-4-hydroxy-5-oxo-2h-furan-3-olate;hydrate Chemical compound O.[Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] NKESWEQTVZVSSF-DMWQRSMXSA-M 0.000 description 2
- 125000004079 stearyl 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])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- 229920001059 synthetic polymer Polymers 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
- 239000008096 xylene Substances 0.000 description 2
- 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
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-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
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 1
- UVHXEHGUEKARKZ-UHFFFAOYSA-N 1-ethenylanthracene Chemical compound C1=CC=C2C=C3C(C=C)=CC=CC3=CC2=C1 UVHXEHGUEKARKZ-UHFFFAOYSA-N 0.000 description 1
- WPMHMYHJGDAHKX-UHFFFAOYSA-N 1-ethenylpyrene Chemical compound C1=C2C(C=C)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 WPMHMYHJGDAHKX-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- VBHXIMACZBQHPX-UHFFFAOYSA-N 2,2,2-trifluoroethyl prop-2-enoate Chemical compound FC(F)(F)COC(=O)C=C VBHXIMACZBQHPX-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 1
- COXCGWKSEPPDAA-UHFFFAOYSA-N 2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)C#N COXCGWKSEPPDAA-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- PFHOSZAOXCYAGJ-UHFFFAOYSA-N 2-[(2-cyano-4-methoxy-4-methylpentan-2-yl)diazenyl]-4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)(C)OC PFHOSZAOXCYAGJ-UHFFFAOYSA-N 0.000 description 1
- AEZBIUBWOJAYOA-UHFFFAOYSA-N 2-[2-[2-[2-[1-(2-hydroxyethyl)-4,5-dihydroimidazol-2-yl]propan-2-yldiazenyl]propan-2-yl]-4,5-dihydroimidazol-1-yl]ethanol Chemical compound N=1CCN(CCO)C=1C(C)(C)N=NC(C)(C)C1=NCCN1CCO AEZBIUBWOJAYOA-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 229940093475 2-ethoxyethanol Drugs 0.000 description 1
- DEDUBNVYPMOFDR-UHFFFAOYSA-N 2-ethoxypropan-1-ol Chemical compound CCOC(C)CO DEDUBNVYPMOFDR-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- YTTFFPATQICAQN-UHFFFAOYSA-N 2-methoxypropan-1-ol Chemical compound COC(C)CO YTTFFPATQICAQN-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CEXQWAAGPPNOQF-UHFFFAOYSA-N 2-phenoxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC1=CC=CC=C1 CEXQWAAGPPNOQF-UHFFFAOYSA-N 0.000 description 1
- BQARUDWASOOSRH-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-yl hydrogen carbonate Chemical compound CC(C)(C)OOC(C)(C)OC(O)=O BQARUDWASOOSRH-UHFFFAOYSA-N 0.000 description 1
- SLJFKNONPLNAPF-UHFFFAOYSA-N 3-Vinyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1C(C=C)CCC2OC21 SLJFKNONPLNAPF-UHFFFAOYSA-N 0.000 description 1
- MNULHGQAROOBFB-UHFFFAOYSA-N 3-[(1-amino-2-methylpropylidene)amino]propanoic acid Chemical compound CC(C)C(N)=NCCC(O)=O MNULHGQAROOBFB-UHFFFAOYSA-N 0.000 description 1
- YCIGYTFKOXGYTA-UHFFFAOYSA-N 4-(3-cyanopropyldiazenyl)butanenitrile Chemical compound N#CCCCN=NCCCC#N YCIGYTFKOXGYTA-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- OPPHXULEHGYZRW-UHFFFAOYSA-N 4-methoxy-2,4-dimethyl-2-phenyldiazenylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC1=CC=CC=C1 OPPHXULEHGYZRW-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000007754 air knife coating Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- BWHOZHOGCMHOBV-UHFFFAOYSA-N benzylideneacetone Chemical compound CC(=O)C=CC1=CC=CC=C1 BWHOZHOGCMHOBV-UHFFFAOYSA-N 0.000 description 1
- LWMFAFLIWMPZSX-UHFFFAOYSA-N bis[2-(4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene Chemical compound N=1CCNC=1C(C)(C)N=NC(C)(C)C1=NCCN1 LWMFAFLIWMPZSX-UHFFFAOYSA-N 0.000 description 1
- GYCUTPICSQQWKP-UHFFFAOYSA-N bis[2-(5-methyl-4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene Chemical compound N1C(C)CN=C1C(C)(C)N=NC(C)(C)C1=NCC(C)N1 GYCUTPICSQQWKP-UHFFFAOYSA-N 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011109 contamination Methods 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
- 229960002887 deanol Drugs 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
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 230000014759 maintenance of location Effects 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
- 238000000691 measurement method Methods 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 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
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000002794 monomerizing effect Effects 0.000 description 1
- BUGISVZCMXHOHO-UHFFFAOYSA-N n-[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]-2-[[1-[[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]amino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCC(CO)(CO)NC(=O)C(C)(C)N=NC(C)(C)C(=O)NC(CO)(CO)CO BUGISVZCMXHOHO-UHFFFAOYSA-N 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- SFBTTWXNCQVIEC-UHFFFAOYSA-N o-Vinylanisole Chemical compound COC1=CC=CC=C1C=C SFBTTWXNCQVIEC-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- FURYAADUZGZUGQ-UHFFFAOYSA-N phenoxybenzene;sulfuric acid Chemical compound OS(O)(=O)=O.C=1C=CC=CC=1OC1=CC=CC=C1 FURYAADUZGZUGQ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000013615 primer Substances 0.000 description 1
- 239000002987 primer (paints) Substances 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 238000007763 reverse roll coating Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- 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
-
- 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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/10—Homopolymers or copolymers of propene
Definitions
- the present invention relates to an aqueous resin dispersion, a composition using the aqueous resin dispersion as a raw material, and a laminate containing a dried product of the composition.
- Polyolefins such as propylene-based polymers and propylene- ⁇ -olefin copolymers are inexpensive and have excellent mechanical properties, heat resistance, chemical resistance, water resistance, etc., so they are used in a wide range of fields.
- the polyolefin does not have a polar group in the molecule, it generally has a low polarity and is difficult to be coated and adhered. Therefore, improvement of the paintability and adhesion has been desired.
- Various techniques have been tried. However, all of the above methods not only require special equipment, but are also not always effective in improving paintability and adhesiveness.
- chlorinated polypropylene, acid-modified propylene- ⁇ -olefin copolymer, and acid-modified chlorinated polyolefin, for example, propylene-based polymer can be given good paintability and adhesiveness by a relatively simple method.
- Modified polyolefins such as polypropylene have been proposed.
- the modified polyolefin is generally characterized in that it can be applied to the surface of a polyolefin molded article as a surface treatment agent, adhesive, paint, or the like.
- the modified polyolefin is usually used by applying it in the form of a solution in an organic solvent, a dispersion in water, or the like.
- Aqueous dispersions are generally preferred from the standpoint of safety and health and environmental pollution.
- Patent Document 1 a resin dispersion in which a polymer obtained by bonding a hydrophilic polymer to an acid-modified polyolefin is dispersed in an aqueous medium can be used as a polyolefin paint, primer, or adhesive, and a laminate as a coated product is described. It is The method described in Patent Document 1 does not refer to the control of the physical properties of the dry coating such as the elastic modulus of the coating, leaving a problem of low-temperature heat-sealability.
- Patent Document 2 describes the use of a resin dispersion of an olefin polymer and an acrylic polymer as a heat sealing agent.
- the method described in Patent Document 2 mentions that the heat sealing agent may be used on a polypropylene base material, but mentions the effect of adhesion to a non-polar polypropylene base material as a specific example.
- the adhesiveness to the polypropylene base material is unknown and a problem remains.
- Patent Document 3 describes that the use of a resin dispersion of an olefin polymer and an acrylic polymer improves the adhesion to a polypropylene substrate, but heat sealing is performed at a low temperature.
- there is no description of the specific effect of physical properties such as the elastic modulus of the dried coating film, and there remains the problem of low-temperature heat-sealing properties.
- An object of the present invention is to provide an adhesive that uses a water-based resin dispersion that exhibits excellent low-temperature heat-sealability to polyolefin substrates and that can be easily adhered to polyolefin substrates by heating at a low temperature for a short period of time.
- An object of the present invention is to provide a laminate containing a dried adhesive.
- the gist of the present invention is the following [1] to [39].
- the water-based resin dispersion C, wherein the elastic modulus of the coating film obtained by drying the water-based resin dispersion C at 80° C. for 30 minutes is greater than 0 MPa and 35 MPa or less.
- the polymer A is a polymer A1 having a structural unit derived from an olefinic monomer having no reactive group, and a modified polymer having a reactive group and a structural unit derived from an olefinic monomer.
- the aqueous resin dispersion C according to any one of [1] to [4], comprising at least one selected from the group consisting of A2.
- the polymer A contains the polymer A1, and the polymer A1 is at least one selected from the group consisting of homopolymers of ethylene or propylene, copolymers of ethylene and propylene, and ethylene and propylene.
- the aqueous resin dispersion C is particularly preferable, the aqueous resin dispersion C according to any one of [1] to [6].
- the molecular weight distribution (Mw/Mn) of the polymer A is preferably 0.5 to 5.0, more preferably 1.0 to 4.0, even more preferably 1.5 to 3.0. 1] to the aqueous resin dispersion C according to any one of [7].
- the glass transition temperature of the polymer B is preferably ⁇ 80° C. or higher and 20° C. or lower, more preferably ⁇ 80° C. or higher and 10° C. or lower, further preferably ⁇ 70° C. or higher and 5° C. or lower, and ⁇ 60° C.
- the aqueous resin dispersion C according to any one of [1] to [8], which is particularly preferably less than 3°C.
- the radically polymerizable monomer preferably contains a vinyl monomer; (meth)acrylic monomer, aromatic monomer, amide monomer, (meth)acrylonitrile, More preferably, it contains at least one selected from the group consisting of vinyl acetate, vinyl propionate, and vinyl versatate; consisting of (meth)acrylic acid, (meth)acrylic acid ester, styrene, and ⁇ -methylstyrene More preferably, at least one selected from the group; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylic acid-n-butyl, isobutyl (meth)acrylate, t-butyl (meth)acrylate,
- the radically polymerizable monomer contains a vinyl-based monomer, the vinyl-based monomer has at least one selected from the group consisting of a hydroxyl group and an epoxy group, and the vinyl-based monomer
- the mass ratio of structural units derived from the body is preferably 1.0% by mass or more and 30% by mass or less, more preferably 1.5% by mass or more and 20% by mass or less, relative to the total mass of the structural units constituting the polymer B.
- the aqueous resin dispersion according to any one of [1] to [10], which is preferably 2.0% by mass or more and 15% by mass or less, more preferably 5.0% by mass or more and 10.0% by mass or less. body C.
- the radically polymerizable monomer contains an aromatic monomer, and the mass ratio of the structural units derived from the aromatic monomer is the total mass of the structural units constituting the polymer B.
- the aqueous resin dispersion C according to any one of [1] to [11], which is particularly preferably not more than mass%.
- the mass ratio of the polymer A to the total mass of the polymer A and the polymer B is preferably 30% by mass or more and 90% by mass or less, more preferably 50% by mass or more and 80% by mass or less, and 60% by mass. % or more and 75 mass % is more preferable, and 65 mass % or more and 70 mass % or less is particularly preferable, the aqueous resin dispersion C according to any one of [1] to [12].
- the mass ratio of the polymer B to the total mass of the polymer A and the polymer B is preferably 10% by mass or more and 70% by mass or less, more preferably 30% by mass or more and 60% by mass or less, and 35% by mass.
- the aqueous resin dispersion C according to any one of [1] to [13].
- the mass ratio represented by [mass of polymer A]:[mass of polymer B] is preferably 30:70 to 90:10, more preferably 40:60 to 80:20, and 50 :
- the elastic modulus of the coating film formed by drying the aqueous resin dispersion C at 80 ° C. for 30 minutes is more than 0 MPa and 35 MPa or less, preferably 5 MPa or more and 35 MPa or less, more preferably 10 MPa or more and 25 MPa or less.
- the breaking elongation of the coating film formed by drying the aqueous resin dispersion C at 80 ° C. for 30 minutes is preferably 100% or more and 3000% or less, more preferably 800% or more and 3000% or less, and 1000% or more and 2500%.
- the average particle diameter of the particles is preferably more than 0 ⁇ m and 0.5 ⁇ m or less, more preferably 0.05 ⁇ m or more and 0.3 ⁇ m or less, further preferably 0.1 ⁇ m or more and 0.2 ⁇ m or less, [1] to [18] ] Water-based resin dispersion C according to any one of the above.
- the water-based resin dispersion C of [1] to [19] is obtained by polymerizing the radically polymerizable monomer in the dispersion of the polymer A to form the polymer B.
- a laminate containing a dried product of the composition D is formed from the composition D containing the water-based resin dispersion C, a test piece having a width of 15 mm is taken from the laminate, and a test piece having a width of 15 mm is measured using a tensile tester.
- the peel strength of the composition D when the interface was peeled from the edge of the test piece by peeling is 1.00 N / 15 mm or more.
- the aqueous resin dispersion C according to any one of [1] to [20], which is particularly preferably 4.00 N/15 mm or more and 6.00 N/15 mm or less.
- composition D containing the aqueous resin dispersion C according to any one of [1] to [21].
- composition D according to any one of [22] to [26], wherein the polymer B has a glass transition temperature of -80°C or higher and lower than -3°C.
- the mass ratio of the aqueous resin dispersion C to the total mass of the composition D is preferably 80% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less. 27].
- the laminate according to [29], wherein the dried product is a layer made of the composition D dried product.
- a polypropylene substrate layer 1, a layer 2 made of a dried product of the composition D, at least one layer 3 selected from the group consisting of a metal foil, an inorganic deposited film layer and a thermoplastic resin layer, are laminated in this order, the laminate according to [29] or [30].
- the thickness of the layer made of the dried composition D is preferably 10 ⁇ m or more and 60 ⁇ m or less, more preferably 20 ⁇ m or more and 50 ⁇ m or less.
- the laminate according to [31] or [32], wherein the thickness of the layer 1 is preferably 10 ⁇ m or more and 60 ⁇ m or less, more preferably 20 ⁇ m or more and 50 ⁇ m or less.
- the layer 3 is a thermoplastic resin layer
- the thermoplastic resin layer is a polyethylene-based resin, a polypropylene-based resin, a cyclic polyolefin-based resin, a fluorine-based resin, a polystyrene-based resin, an acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyvinyl chloride-based resin, fluorine-based resin, poly(meth)acrylic-based resin, polycarbonate-based resin, polyester-based resin such as polyethylene terephthalate and polyethylene naphthalate Resins, polyamide resins such as various nylons, polyimide resins, polyamideimide resins, polyarylphthalate resins, silicone resins, polysulfone resins, polyphenylene sulfide resins, polyethersulfone resins, It is preferably a film or sheet containing at
- the layer 3 is a metal foil or an inorganic vapor deposition film layer, and the metal foil or the inorganic vapor deposition film layer includes a soft metal foil such as an aluminum foil, an aluminum vapor deposition layer, a silica vapor deposition layer, an alumina vapor deposition layer, and preferably at least one selected from the group consisting of silica-alumina two-source vapor deposition inorganic vapor deposition layers; more preferably at least one selected from the group consisting of aluminum foil and aluminum vapor deposition films, [31] The laminate according to any one of [34].
- the radically polymerizable monomer is supplied in an amount of 80 to 100% by weight with respect to the total amount of the radically polymerizable monomer, and the radically polymerizable monomer is polymerized during the polymerization.
- the method for producing a water-based resin dispersion C according to [38] comprising supplying the remaining amount of the polymer and polymerizing it.
- an adhesive that uses a water-based resin dispersion that has excellent low-temperature heat-sealing properties to polyolefin substrates and that can be easily adhered to polyolefin substrates by heating at a low temperature for a short period of time; A laminate containing the dried adhesive can be provided.
- ⁇ means including the numbers before and after it.
- dispersion means a state in which dispersed particles are extremely small and dispersed as monomolecules, and a state in which it can be said to be substantially dissolved.
- (meth)acryl means a generic term for acryl and methacryl.
- the aqueous resin dispersion C of the present invention is an aqueous resin dispersion containing a polymer A having a structural unit derived from an olefinic monomer and a polymer B having a structural unit derived from a radically polymerizable monomer in the same particles. Body C. Each component is described below.
- a polymer having a structural unit derived from an olefinic monomer means a polymer using an olefin as a raw material monomer, and a structure derived from an olefinic monomer such as an olefin homopolymer or copolymer. It means a polymer A having a unit (hereinafter sometimes referred to as "polymer A") and the like.
- polymer A1 As the polymer A having a structural unit derived from an olefinic monomer, a polymer A1 having a structural unit derived from an olefinic monomer having no reactive group (hereinafter referred to as "polymer A1" ), a modified polymer A2 having a reactive group and a structural unit derived from an olefinic monomer (hereinafter sometimes referred to as "polymer A2”), and the like.
- polymer A1 a polymer A1 having a structural unit derived from an olefinic monomer having no reactive group
- polymer A2 a modified polymer A2 having a reactive group and a structural unit derived from an olefinic monomer
- Preferred embodiments of the polymer A include propylene-based polymers satisfying the following (1) and (2).
- the propylene content of the polymer A is preferably 50 mol % or more, more preferably 60 mol % or more, and even more preferably 70 mol % or more, from the viewpoint of good adhesion to the propylene substrate.
- the melting point [Tm] of the polymer A is preferably 120° C. or less, more preferably 100° C. or less, and further preferably 90° C. or less, in terms of good adhesion at low temperature heat sealing at 120° C. or less. preferable.
- the lower limit of Tm is preferably 60° C. or higher from the viewpoint of excellent blocking property.
- Polymer A1 having a structural unit derived from an olefinic monomer having no reactive group Known olefinic polymers and olefinic copolymers can be used as the polymer A1.
- the polymer A1 is not particularly limited, but at least one selected from the group consisting of homopolymers of ethylene or propylene; copolymers of ethylene and propylene; ethylene and propylene; For example, copolymers with ⁇ -olefin monomers having 2 or more carbon atoms such as 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, cyclopentene, cyclohexene, and norbornene, or the ⁇ - Copolymers of two or more kinds of olefin monomers; Copolymers of the above ⁇ -olefin monomers with monomers such as vinyl acetate, acrylic acid esters, and methacrylic acid esters; and a copolymer of
- an ⁇ -olefin monomer having 2 to 4 carbon atoms is preferred in that the polymer A1 having a structural unit derived from an olefinic monomer is soluble in a solvent and can be easily reacted.
- the various copolymers described above may be at least one selected from the group consisting of random copolymers and block copolymers. Chlorinated polyolefin obtained by chlorinating polyolefin can also be used as the various copolymers.
- the degree of chlorination of the chlorinated polyolefin is preferably 5% by weight or more, more preferably 10% by weight or more, relative to the total mass of the polyolefins, from the viewpoint of improving the solubility of the olefin polymer A1 in solvents. Moreover, 40 weight% or less is preferable and 30 weight% or less is more preferable.
- polystyrene block copolymer examples include polyethylene, polypropylene, ethylene-butene copolymer, ethylene-propylene copolymer, propylene-butene copolymer, propylene-hexene copolymer, chlorinated polyethylene, chlorinated polypropylene, Chlorinated ethylene-propylene copolymer, chlorinated propylene-butene copolymer, ethylene-vinyl acetate copolymer, hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene-styrene block copolymer Examples include hydrogenated polymers (SEPS) and the like.
- SEBS hydrogenated styrene-butadiene-styrene block copolymer
- SEBS hydrogenated styrene-isoprene-styrene block copolymer
- SEPS hydrogenated
- the polymer A1 is preferably a propylene homopolymer, a copolymer of propylene and another ⁇ -olefin, and a chlorinated polymer thereof, in terms of good adhesion to the propylene substrate.
- a propylene homopolymer, an ethylene-propylene copolymer, a propylene-butene copolymer, a chlorinated polypropylene, a chlorinated ethylene-propylene copolymer, or a chlorinated propylene-butene copolymer are more preferred, and do not contain chlorine. More preferred are propylene homopolymers, ethylene-propylene copolymers, propylene-butene copolymers, and ethylene-propylene-butene copolymers.
- the polymer A1 may be used singly or in combination of two or more.
- the polymer A1 is preferably a propylene-based polymer having a propylene-derived structural unit as its structural unit. That is, the olefinic monomer preferably contains propylene. When the olefin-based monomer contains propylene, there is a tendency for the adhesion to polypropylene substrates to increase.
- the ratio of the structural units derived from propylene to the total structural units of the propylene-based polymer is preferably 50 mol% or more, more preferably 60 mol% or more, and even more preferably 70 mol% or more. Within the above range, there is a tendency that the higher the ratio of the propylene-derived structural unit, the higher the adhesion to the polypropylene substrate.
- the weight average molecular weight Mw of the polymer A1 can be measured by GPC (Gel Permeation Chromatography) and converted with the calibration curve of each polyolefin to obtain the Mw.
- the weight average molecular weight Mw of the polymer A1 is preferably 5,000 or more, more preferably 10,000 or more, still more preferably 50,000 or more, and particularly preferably 100,000 or more. Moreover, 500,000 or less are preferable and 300,000 or less are more preferable.
- the higher the Mw the lower the degree of stickiness and the tendency to increase the adhesion to the substrate.
- the lower the Mw the lower the viscosity, which tends to facilitate the preparation of the water-based resin dispersion.
- the measurement of the weight average molecular weight Mw by GPC can be performed by a conventionally known method using a commercially available GPC device using ortho-dichlorobenzene or the like as a solvent.
- the melting point Tm of the polymer A1 is preferably 120°C or lower, more preferably 100°C or lower, and even more preferably 90°C or lower. Moreover, the melting point Tm of the polymer A1 is preferably 50° C. or higher. Within the above range, the higher the melting point, the better the blocking property tends to be. Also, the lower the melting point, the more the low-temperature heat-sealability tends to improve.
- the method for producing the polymer A1 is not particularly limited as long as it can produce a polymer that satisfies the requirements of the present invention, and any production method may be used.
- any production method may be used.
- radical polymerization, cationic polymerization, anionic polymerization, coordination polymerization, etc. may be mentioned, and living polymerization may be used.
- a method of polymerization using a Ziegler-Natta catalyst and a method of polymerization using a single-site catalyst can be used.
- the method of polymerizing with a single-site catalyst is preferable in that the molecular weight distribution and the stereoregularity distribution can be sharpened by designing the ligand.
- a metallocene catalyst or a Brookhart catalyst can be used as the single-site catalyst.
- an appropriate catalyst such as C1 symmetric type, C2 symmetric type, C2V symmetric type, CS symmetric type, etc. may be selected according to the stereoregularity of the polyolefin to be polymerized.
- any polymerization form such as solution polymerization, slurry polymerization, bulk polymerization, and gas phase polymerization can be carried out.
- Solvents for solution polymerization and slurry polymerization include aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane, heptane and octane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; Examples include hydrocarbons, esters, ketones, ethers and the like.
- aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons are preferable, and toluene, xylene, heptane, and cyclohexane are more preferable, in terms of easily dissolving the polymer A1.
- aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons are preferable, and toluene, xylene, heptane, and cyclohexane are more preferable, in terms of easily dissolving the polymer A1.
- These may be used individually by 1 type, and may be used in combination of 2 or more type.
- the molecular structure of the polymer A1 may be linear or branched.
- the polymer A2 includes a copolymer A2a obtained by copolymerizing an olefin and an unsaturated compound having a reactive group during modification polymerization, and a radically polymerizable unsaturated compound having a reactive group derived from an olefin monomer.
- a graft polymer A2b obtained by graft polymerization to a polymer having a unit may be mentioned.
- the copolymer A2a is obtained by copolymerizing an olefin and an unsaturated compound having a reactive group, and is a copolymer in which the unsaturated compound having a reactive group is introduced into the main chain.
- the copolymer A2a include copolymers of ⁇ -olefins such as ethylene, propylene and butene, and ⁇ , ⁇ -unsaturated carboxylic acids such as acrylic acid and maleic anhydride, or their anhydrides. .
- an ethylene-acrylic acid copolymer, an ethylene-acrylic acid ester-maleic anhydride copolymer, or the like can be used. These may be used individually by 1 type, and may be used in combination of 2 or more type.
- the method described for the polymer A1 can be used in the same manner.
- the graft polymer A2b can be obtained by graft-polymerizing a radically polymerizable unsaturated compound having a reactive group to a polymer having structural units derived from an olefinic monomer.
- the reactive group include a carboxyl group, an amino group, an epoxy group, an isocyanate group, a sulfonyl group, and a hydroxyl group.
- the carboxyl group and its anhydride are preferable as the reactive group because the reactive group is excellent in reactivity.
- graft polymer A2b for example, a polymer obtained by graft-polymerizing (meth)acrylic acid, fumaric acid, maleic acid, itaconic acid or their anhydrides, crotonic acid, etc. onto a polyolefin such as polyethylene or polypropylene. mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.
- the polymer A1 can be used as the polymer having a structural unit derived from an olefin monomer that can be used for the graft polymer A2b.
- the graft polymer A2b include maleic anhydride-modified polypropylene and its chlorinated products, maleic anhydride-modified ethylene-propylene copolymer and its chlorinated products, maleic anhydride-modified propylene-butene copolymer, acrylic acid-modified polypropylene and its Examples thereof include chlorinated products, acrylic acid-modified ethylene-propylene copolymers and their chlorinated products, acrylic acid-modified propylene-butene copolymers, and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.
- the radical polymerization initiator used in the production of the graft polymer A2b can be appropriately selected from ordinary radical polymerization initiators, and examples thereof include organic peroxides and azonitrile.
- organic peroxide include peroxyketals such as di(t-butylperoxy)cyclohexane; hydroperoxides such as cumene hydroperoxide; dialkyl peroxides such as di(t-butyl)peroxide; benzoyl diacyl peroxides such as peroxide; peroxyesters such as t-butyl peroxyisopropyl monocarbonate;
- the azonitrile include azobisbutyronitrile and azobisisopropylnitrile.
- benzoyl peroxide and t-butylperoxyisopropyl monocarbonate are preferred in terms of strong hydrogen abstraction and excellent graft reaction. These may be used individually by 1 type, and may be used in combination of 2 or more type.
- the reaction temperature is preferably 50°C or higher, more preferably 80 to 200°C. Within the above range, the graft reaction proceeds due to the hydrogen abstraction force of the radical polymerization initiator.
- the reaction time is usually about 2 to 20 hours.
- the method for producing the polymer A2b is not particularly limited, and any production method may be used.
- Examples of the method for producing the polymer A2b include a method of reacting by heating and stirring in a solution, a method of melting, heating and stirring in the absence of a solvent, and a method of heating and kneading with an extruder to react.
- the solvent for the production in the solution the same solvent as described for the polymer A1 can be used.
- the content of the reactive group in the polymer A2 is preferably 0.01 mmol/g or more, more preferably 0.05 mmol/g or more, and even more preferably 0.1 mmol/g or more per 1 g of the polymer A2. Also, it is preferably 1 mmol/g or less, more preferably 0.5 mmol/g or less, and even more preferably 0.3 mmol/g or less. Within the above range, the higher the hydrophilicity, the smaller the dispersed particle size, and the lower the particle size, the higher the adhesion to the polypropylene substrate.
- Examples of the method for producing a dispersion of the polymer A include a method of dispersing the polymer A by adding a surfactant to the polymer A, and a graft copolymer in which a hydrophilic polymer is graft-bonded to the polymer A.
- the reactive group of the polymer A2 is an acidic group such as a carboxyl group, an anhydride thereof, or a sulfonyl group
- the acidic group is made basic.
- Examples include a method of dispersing the polymer A2 by neutralizing with a compound.
- the hydrophilic polymer used in the polymer A dispersion means a polymer having an insoluble content of 1% by weight or less when dissolved in water at 25°C at a concentration of 10% by weight.
- the hydrophilic polymer can be used without any particular limitation as long as it does not significantly impair the effects of the present invention, and synthetic polymers, semi-synthetic polymers, natural polymers and the like can be used.
- the number-average molecular weight Mn of the hydrophilic polymer is preferably 300 or more from the viewpoint of excellent mechanical stability of the polyolefin dispersion.
- Examples of the basic compound used in the polymer A dispersion include inorganic bases such as sodium hydroxide and potassium hydroxide; ammonia, triethylamine, diethylamine, ethanolamine, dimethylethanolamine, 2-methyl-2-amino- Organic bases such as propanol, triethanolamine, morpholine, pyridine and the like are included.
- the neutralization rate with the basic compound is not particularly limited as long as dispersibility in water is obtained, but is preferably 1 to 100 mol %, more preferably 50 mol % or more, relative to the acidic groups. Within the above range, the higher the neutralization rate, the better the dispersibility in water.
- the term "dispersion" means a state in which dispersed particles are extremely small and dispersed as monomolecules, including a state in which it can be said to be substantially dissolved. Therefore, the lower limit of the average particle size of the dispersion may be 0 ⁇ m.
- the average particle size of the polymer A dispersion used in the present invention is preferably 0.5 ⁇ m or less, more preferably 0.3 ⁇ m or less, and even more preferably 0.2 ⁇ m or less. Further, the average particle size of the polymer A dispersion is preferably 0 ⁇ m or more. Within the above range, dispersion stability is improved and aggregation is less likely to occur. Incidentally, the dispersed particle size can be measured by a dynamic light scattering method, a laser Doppler method, or the like.
- the solid content of the dispersion of polymer A is preferably 5% by weight or more, more preferably 10% by weight or more, and even more preferably 20% by weight or more, relative to the total weight of the dispersion of polymer A. . Also, it is preferably 70% by weight or less, more preferably 60% by weight or less, and even more preferably 50% by weight or less. Within the above range, the lower the solids content, the lower the viscosity and the better the polymerizability with the radically polymerizable monomer. Also, the higher the solid content, the less energy is required for drying, and the drying property tends to be excellent.
- the ratio of the solvent other than water in the polymer A dispersion is preferably 50% by weight or less, more preferably 20% by weight or less, and 10% by weight or less, relative to the total weight of the polymer A dispersion. More preferred. Within the above range, the less the solvent, the more excellent the storage stability tends to be. From the viewpoint of good storage stability of the water-based resin dispersion C, the solvent is preferably a solvent that dissolves in water in an amount of 1% by weight or more, and more preferably a solvent that dissolves in water in an amount of 5% by weight or more.
- solvent other than water examples include methyl ethyl ketone, cyclohexanone, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, cyclohexanol, tetrahydrofuran, 2-methoxyethanol, 2-ethoxyethanol, and 2-butoxyethanol. , 2-methoxypropanol, and 2-ethoxypropanol. These may be used individually by 1 type, and may be used in combination of 2 or more type.
- Aurorene and Superchron manufactured by Nippon Paper Industries Co., Ltd., Hardren manufactured by Toyobo Co., Ltd., Aptlock manufactured by Mitsubishi Chemical Corporation, Arrow Base manufactured by Unitika Corporation, etc. can be used.
- Aurorene, Hardren, Aptoloc, and Arrowbase are preferred, and Aptolok is more preferred, because they do not contain chlorine.
- the glass transition temperature of the polymer B is preferably 20°C or lower, more preferably 10°C or lower, still more preferably 5°C or lower, and particularly preferably lower than -3°C. If the glass transition temperature of the polymer B is 20° C. or lower, the flexibility and film-forming properties of the coating film are improved, and the low-temperature heat-sealing property is improved. From the viewpoint of improving the blocking property of the coating film, the glass transition temperature of the acrylic polymer B is preferably ⁇ 80° C. or higher, more preferably ⁇ 70° C. or higher, and even more preferably ⁇ 60° C. or higher. That is, the glass transition temperature of the polymer B is preferably -80°C or higher and 20°C or lower, more preferably -80°C or higher and lower than -3°C.
- the glass transition temperature of the polymer B means a value obtained by the Fox calculation formula represented by the following formula (i).
- Wi indicates the mass fraction of the monomer i
- Tgi indicates the Tg (° C.) of the homopolymer of the monomer i.
- the homopolymer of each monomer As the glass transition temperature, the value described in Polymer Handbook Fourth Edition (POLYMER HANDBOOK Fourth Edition), John Wiley & Sons, Inc. (1999) can be used.)
- the radically polymerizable monomer is preferably a vinyl-based monomer because of its excellent polymerizability.
- Vinyl monomers include (meth) acrylic monomers such as (meth) acrylic acid and (meth) acrylic acid esters; aromatic monomers such as styrene and ⁇ -methylstyrene; (meth) acrylamide , dimethyl(meth)acrylamide; and the like; (meth)acrylonitrile, vinyl acetate, vinyl propionate, vinyl versatate and the like.
- Vinyl monomers can be used without any particular limitation as long as they do not significantly impair the effects of the present invention.
- (meth)acrylic acid esters are preferable in terms of the weather resistance and solvent resistance of the coating film.
- Specific examples of the (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylate- n-butyl, isobutyl (meth)acrylate, t-butyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, 2-(meth)acrylate Ethylhexyl, nonyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, (meth)acrylic acid esters having an aryl or aralkyl group having 6 to 12 carbon atoms, such as (meth)
- isobutyl (meth)acrylate, butyl (meth)acrylate, t-butyl (meth)acrylate, cyclohexyl (meth)acrylate, and (meth)acrylic Acid-2-ethylhexyl and styrene are preferred.
- the adhesion of the cured product layer 2 of the composition to the polypropylene base layer 1 and at least one layer 3 selected from the group consisting of a metal foil, an inorganic vapor deposition film layer and a thermoplastic resin is improved. It is preferable that the polymer B has 1.0% by mass or more and 30.0% by mass or less of structural units derived from aromatic monomers based on all structural units.
- styrene phenoxyethyl methacrylate, ⁇ -methylstyrene, vinylnaphthalene, vinylanthracene, vinylpyrene, vinylanisole, vinylbenzoate, and acetylstyrene.
- styrene is preferred from the viewpoint of polymerizability.
- the coating film performance is improved, so the radically polymerizable monomer is a vinyl monomer having a hydroxyl group. It preferably contains a monomer or a vinyl-based monomer having an epoxy group. Vinyl monomers having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.
- Vinyl-based monomers having an epoxy group include glycidyl (meth)acrylate, 1,2-epoxy-4-vinylcyclohexane, and 4-(2,3-epoxypropoxy)butyl (meth)acrylate.
- the amount of the vinyl-based monomer having a hydroxyl group or an epoxy group is preferably 30% by weight or less, more preferably 20% by weight or less, based on the total amount of the radically polymerizable monomers. Within the above range, the adhesion to the polypropylene substrate tends to be good.
- the radically polymerizable monomer preferably contains a vinyl-based monomer having a carboxylic acid group or a phosphoric acid group.
- Vinyl monomers having a carboxylic acid group include (meth)acrylic acid and the like.
- the amount of the vinyl monomer having a carboxylic acid group used is preferably 10% by weight or less, more preferably 5% by weight or less, relative to the total amount of the radically polymerizable monomers used. Within the above range, the adhesion to the metal substrate and the polypropylene substrate tends to be good.
- the mass ratio of the polymer B to the total mass of the polymer A and the polymer B is preferably 10% by mass or more, and more preferably 30% by mass or more. Moreover, 70 mass % or less is preferable and 50 mass % or less is more preferable. Within the above range, the adhesion to the polypropylene substrate is excellent.
- the mass ratio of the polymer A to the total mass of the polymer A and the polymer B is preferably 30% by mass or more, more preferably 50% by mass or more, and even more preferably 65% by mass or more. Within the above range, the adhesion to the polypropylene substrate is excellent.
- Method for producing polymer B As a method for producing the polymer B, a method of polymerizing in a state in which the radically polymerizable monomer is dissolved in a dispersion of the polymer A, and a method in which both the polymer A and the radically polymerizable monomer are dispersed. Examples thereof include a method of polymerizing in a state of dispersion, and a method of emulsion polymerization using the radically polymerizable monomer and a surfactant.
- the radically polymerizable monomer may be polymerized in the dispersion of the polymer A, and either batch polymerization or dropwise polymerization may be used as long as the effects of the present invention are not significantly impaired. can also be used.
- the collective polymerization is a method in which the total amount of radically polymerizable monomers is charged into a reaction vessel and polymerized at once.
- a water-soluble initiator or an organic peroxide and a redox initiator containing a reducing agent such as sodium thiosulfate for example, after mixing the total amount of the radically polymerizable monomer with the dispersion of the polymer A, a water-soluble initiator or an organic peroxide and a redox initiator containing a reducing agent such as sodium thiosulfate.
- the dropping polymerization is a method of polymerizing while dropping a monomer little by little into a reaction vessel.
- the method for producing the polymer B for example, polymerization can be performed while dropping the radically polymerizable monomer into the dispersion of the polymer A.
- a surfactant for emulsion polymerization examples include various anionic, cationic, or nonionic surfactants having an HLB of 8 or more. Reactive surfactants can also be used. Among these, it is preferable to use an anionic surfactant from the viewpoint of improving the storage stability of the resulting dispersion.
- anionic surfactant examples include, but are not limited to, reactive surfactants such as Adekal Soap SR manufactured by ADEKA Co., Ltd., and non-reactive surfactants such as Neocol SW-C and Newcol 707SF. can.
- the amount of the surfactant for emulsion polymerization used is preferably 5 parts by weight or less, more preferably 3 parts by weight or less, relative to 100 parts by weight of the radically polymerizable monomer. Within the above range, the water resistance tends to be excellent.
- initiators generally used for radical polymerization can be used.
- the initiator include persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate; (2,4-dimethylvaleronitrile), 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile and other oil-soluble azo Compounds; 2,2′-azobis ⁇ 2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide ⁇ , 2,2′-azobis ⁇ 2-methyl-N-[ 2-(1-hydroxyethyl)]propionamide ⁇ , 2,2′-azobis ⁇ 2-methyl-N-[2-(1-hydroxybutyl)]propionamide ⁇ , 2,2′-azobis[2-( 5-methyl-2-imidazolin-2-yl)propane] and its salts; 2,2
- a reducing agent such as sodium bisulfite, ferrous sulfate, isoascorbate, or Rongalite in combination with a water-soluble polymerization catalyst. preferable.
- the polymerization temperature is preferably 50°C or higher from the viewpoint of the polymerization rate of the polymer B to be obtained.
- the polymerization time is preferably 30 minutes or more. When the polymerization time is 30 minutes or longer, the radically polymerizable monomer is sufficiently polymerized, and the polymerization rate tends to improve. Moreover, the polymerization time is preferably 3 hours or less. When the polymerization time is 3 hours or less, cullet is less likely to occur during polymerization, and production efficiency tends to improve.
- chain transfer agents such as n-dodecylmercaptan, t-dodecylmercaptan, and ⁇ -methylstyrene dimer may be used as molecular weight modifiers.
- the filtration method a known method can be used, and nylon mesh, bag filter, filter paper, metal mesh, etc. can be used.
- the elastic modulus of the coating film obtained by drying the aqueous resin dispersion C at 80° C. for 30 minutes is greater than 0 MPa and 35 MPa or less, preferably 5 MPa or more and 35 MPa or less, and more preferably 10 MPa or more and 25 MPa or less. If the elastic modulus of the coating film is more than 35 MPa, the fluidity of the coating film is low, and the heat-sealing property tends to be poor. If the elastic modulus is 0 MPa or less, the coating film tends to have tackiness and the blocking property tends to be poor.
- the elongation at break of the coating film is preferably 100% or more and 3000% or less, more preferably 800% or more and 3000% or less, even more preferably 1000% or more, and particularly preferably 1500% or more. If the elongation at break of the coating film is less than 100%, the coating film tends to be brittle and the adhesion strength tends to be poor.
- a method for producing the water-based resin dispersion C a method of polymerizing the radically polymerizable monomer in the dispersion of the polymer A, or dissolving the olefinic polymer A and the radically polymerizable monomer, and polymerizing after dispersion. and so on. It is preferable to polymerize the radically polymerizable monomer in the dispersion of the polymer A from the viewpoint of adhesion to the polypropylene substrate.
- the method for polymerizing the radically polymerizable monomer in the method for producing the aqueous resin dispersion C can be performed by the same polymerization method as the method for producing the polymer B.
- composition D The composition D of the present invention preferably uses the aqueous resin dispersion C as a raw material.
- the aqueous resin dispersion C can be used as the composition D of the present invention as it is.
- other resins other than the water-based resin dispersion C may be contained as necessary. Examples of the other resins include additives and cross-linking agents.
- the additive examples include polyvinyl acetate, ethylene-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, styrene-butadiene resin, butadiene resin, poly(meth)acrylonitrile resin, (meth)acrylamide resin, polyester resin, Examples include nylon resin, urethane resin, phenol resin, silicone resin, and epoxy resin.
- the content of the other resins is preferably less than 50% by weight, more preferably less than 30% by weight, and even more preferably less than 20% by weight, relative to the total weight of the aqueous resin dispersion C.
- the cross-linking agent is not particularly limited, but includes compounds having a functional group of two or more.
- examples of the cross-linking agent include polyfunctional epoxy compounds, polyfunctional isocyanate compounds, polyfunctional amine compounds, polyfunctional oxazoline compounds, hydrazine compounds, and the like.
- polyfunctional epoxy compounds, polyfunctional oxazoline compounds, and hydrazine compounds are preferred from the viewpoint of reactivity with the carboxyl groups of the acid-modified polyolefin.
- the composition D of the present invention may or may not contain a film-forming aid, a wetting agent, or the like for the purpose of increasing the drying speed or obtaining a surface with a good finish.
- An organic solvent can be used as the film-forming aid and the wetting agent.
- the organic solvent include alcohols such as methanol, ethanol and isopropanol; ketones such as acetone; glycols such as ethylene glycol, propylene glycol, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether and propylene glycol monomethyl ether; and ethers thereof. etc.
- a siloxane-based wetting agent can also be used as the wetting agent.
- Composition D of the present invention is an aqueous resin dispersion containing polymer A having a structural unit derived from an olefinic monomer and polymer B having a structural unit derived from a radically polymerizable monomer in the same particles. It preferably contains C and, if necessary, the other resins described above.
- Examples of the method for producing the composition D include a method for mixing each of the above components with a commonly used stirrer.
- the composition D is preferably a heat-sealing adhesive for polyolefin substrates because it has excellent low-temperature heat-sealing adhesion to polyolefin substrates.
- a heat-sealing adhesive for polyolefin substrates By using the composition D in a heat-sealing adhesive for polyolefin substrates, the low-temperature heat-sealing property to polyolefin substrates is improved, and adhesion to polyolefin substrates is facilitated by heating at a low temperature for a short period of time. tend to be better.
- the laminate of the present invention is preferably a laminate containing the dried product of the resin composition D.
- the laminate of the present invention includes a polypropylene base layer 1, a layer 2 formed from the dried composition D (hereinafter also referred to as "cured layer 2 of composition D"), and a metal foil , and at least one layer 3 selected from the group consisting of an inorganic deposited film layer and a thermoplastic resin are preferably laminated in this order.
- FIG. 1 shows a polypropylene substrate layer 1, a cured product layer 2 of composition D, and at least one layer 3 selected from the group consisting of a metal foil, an inorganic deposition film layer and a thermoplastic resin, and this It shows a stack 10 stacked in sequence.
- polypropylene base layer 1 in the present invention examples include polypropylene resins, acid-modified polypropylene, polypropylene resins such as polypropylene- ⁇ -olefin copolymers, and the like. Among them, polypropylene resins, propylene-ethylene copolymer resins, and propylene-butene copolymer resins are preferred, and polypropylene resins are more preferred, from the viewpoint of protecting the contents as a packaging material.
- polypropylene substrate layer 1 examples include polypropylene-based substrates such as oriented polypropylene (OPP), non-oriented polypropylene (CPP), aluminum-deposited polypropylene, and co-extruded film polypropylene.
- OPP oriented polypropylene
- CPP non-oriented polypropylene
- aluminum-deposited polypropylene aluminum-deposited polypropylene
- co-extruded film polypropylene co-extruded film polypropylene.
- OPP oriented polypropylene
- OPP oriented polypropylene
- the cured product layer 2 of the composition may be formed from the dried product of the composition D, and the amount of the composition D used is preferably 0.01 to 20 g/m 2 with respect to the area of the bonding surface, and 0 .1 to 10 g/m 2 is more preferred, and 0.3 to 5 g/m 2 is even more preferred. If the amount used is less than 0.01 g/m 2 , sufficient adhesiveness cannot be obtained, and if it exceeds 20 g/m 2 , it takes a long time to dry, which is economically disadvantageous.
- the cured product layer 2 of the composition may be formed from a dried product of the composition D, and the composition D is added to at least one layer 3 selected from the group consisting of a metal foil, an inorganic vapor deposition film layer, and a thermoplastic resin.
- the drying temperature is preferably 60 to 150°C. If the temperature is 60° C. or higher, the composition D can be dried in a short time. If the temperature is 150° C. or lower, the composition D has excellent transparency.
- a known coating method can be used as the coating method.
- coating methods include gravure roll coating, reverse roll coating, wire bar coating, lip coating, air knife coating, curtain flow coating, spray coating, dip coating and brush coating.
- the composition D is uniformly coated on the substrate surface by the coating method, and the cured product layer 2 of the composition is adhered to the layer 3 such as a thermoplastic resin by subjecting it to a drying treatment or a heat treatment for drying.
- the metal foil and the inorganic deposition film layer include, as a barrier layer having light shielding properties and gas barrier properties, a soft metal foil such as an aluminum foil; A vapor deposition layer is mentioned.
- Aluminum foil or vapor-deposited aluminum film is preferable because it is inexpensive, has high barrier properties, and can impart light-shielding properties.
- the aluminum foil layer constituting the laminate may be subjected to a hydrothermal transformation treatment on the surface in contact with the cured product layer 2 of the composition to improve adhesion.
- the treated water used in the hydrothermal transformation treatment of the surface of the aluminum foil includes tap water, deionized water, distilled water, deionized distilled water, and the like. Among them, deionized distilled water is preferred.
- the hydrothermal transformation treatment on the surface of the aluminum foil the surface is coated with various hydrated oxide films depending on the treatment temperature to form a hydrothermal transformation treatment layer.
- a boehmite treatment hydroothermal transformation treatment carried out under conditions of about 80 to 100° C. under normal pressure is preferable.
- thermoplastic resin layer polyethylene-based resin, polypropylene-based resin, cyclic polyolefin-based resin, fluorine-based resin, polystyrene-based resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin ), polyvinyl chloride resins, fluorine resins, poly(meth)acrylic resins, polycarbonate resins, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyamide resins such as various nylons, polyimide resins , polyamideimide resin, polyarylphthalate resin, silicone resin, polysulfone resin, polyphenylene sulfide resin, polyethersulfone resin, polyurethane resin, acetal resin, cellulose resin Films or sheets of various resins such as resins and polyvinyl alcohol resins can be used. In the present invention, among these, it is preferable thermo
- various plastic compounding agents and additives can be added to the film or sheet, and the amount to be added may be arbitrarily determined according to the purpose.
- the additives include lubricants, cross-linking agents, antioxidants, ultraviolet absorbers, light stabilizers, fillers, antistatic agents, lubricants, anti-blocking agents, coloring agents such as dyes and pigments, and modifying resins. Can be used arbitrarily.
- composition D of the present invention can be suitably used in the fields of adhesives for polypropylene substrates, heat-sealing adhesives for packaging materials, paints, etc.
- the laminate of the present invention includes a heat-sealing adhesive.
- a food packaging material is preferred.
- the composition D is laminated on at least one layer 3 selected from the group consisting of a metal foil, an inorganic vapor deposition film layer and a thermoplastic resin, and the polypropylene base layer 1 is laminated.
- the cured product layer 2 of the composition may be adhered by heat sealing.
- the temperature condition for the heat sealing is preferably 140° C. or lower, more preferably 120° C. or lower, from the viewpoint of the appearance of the polypropylene substrate layer 1 . 100° C. or lower is more preferable.
- GPC measurement was performed using GPC HLC-8020 manufactured by Tosoh Corporation in which TSKgel GMHXL-L (30 cm ⁇ 2 columns) was equipped with a guard column TSKguard column HXL-H as a column. Measurement conditions were as follows: injection amount of sample solution: 50 ⁇ L; column temperature: 40° C.; solvent: tetrahydrofuran; flow rate: 1.0 mL/min.
- the molecular weight is obtained by measuring a commercially available monodisperse polystyrene standard sample as a standard sample, creating a calibration curve from the retention time and molecular weight of the standard sample, and obtaining the weight average molecular weight of polymer A having a structural unit derived from an olefinic monomer. [Mw] and molecular weight distribution [Mw/Mn] were calculated.
- the temperature was raised to 200° C. at a rate of 10° C./min, and the amount of heat was detected at intervals of 0.5 seconds.
- one exothermic peak was observed in the cooling process, and one endothermic peak was observed in the final heating process.
- the temperature at the peak top of the peak in the final temperature rising process was taken as the melting point [Tm] of the polymer A having the structural unit derived from the olefinic monomer.
- the obtained dried coating film was sheared to 30 mm ⁇ 5 mm, and a tensile test was performed using a small tabletop tester EZ manufactured by Shimadzu Corporation under the conditions of a measurement temperature of 23 ° C., a tensile speed of 50 mm / min, and a chuck distance of 10 mm. . From the obtained stress-strain curve, the elastic modulus and breaking elongation of the coating film after drying of the water-based resin dispersion were determined. The results are listed in Table 1.
- thermoplastic resin OPP A test piece having a thickness of 10 ⁇ m (10 g/m 2 ) was obtained from the untreated film layer 3 and the cured composition layer 2 . Furthermore, as the polypropylene base layer 1, the same type of film as the OPP film was used, and the untreated surface of the film was applied to the surface of the cured product layer 2 of the composition of the obtained test piece with a heat sealer. A laminate was obtained by heat-sealing at the indicated temperature for 10 seconds with a load of 1 kg.
- a test piece with a width of 15 mm was taken from the obtained laminate, and the interface between the polypropylene substrate layer 1 and the polypropylene substrate (1) was peeled from the end of the test piece by 90 degree peeling using a tensile tester.
- evaluation conditions 23 ° C., 65% RH atmosphere, tensile speed 50 mm / min
- evaluation of the adhesion test of composition D to polyolefin base layers 1 and 3 It was evaluated according to the following evaluation criteria. The evaluation results are shown in Table 2.
- B The peel strength is 1.00 N/15 mm or more and less than 2.00 N/15 mm, and the adhesion is good.
- C The peel strength is less than 1.00 N/15 mm and the adhesion is poor.
- Examples 1 to 6, Comparative Examples 1 to 3 A laminate was prepared as shown in Table 2, and an adhesion test to the polyolefin base layer 1 and layer 3 was performed. The evaluation results are shown in Table 2.
- the abbreviations in Table 1 are as follows.
- Aptlock BW-5683 Olefin emulsion, manufactured by Mitsubishi Chemical Corporation EHA: Ethylhexyl acrylate, manufactured by Mitsubishi Chemical Corporation iBMA: Isobutyl methacrylate, manufactured by Mitsubishi Chemical Corporation tBMA: t-butyl methacrylate, manufactured by Mitsubishi Chemical Corporation ST: Styrene, NS GMA manufactured by Styrene Monomer Co., Ltd.: Glycidyl methacrylate, manufactured by Mitsubishi Chemical Corporation
- OPP in Table 2 means a stretched polypropylene film.
- Examples 1 to 6 contain the polymer A and the polymer B in the same particles, and the elastic modulus of the coating film obtained by drying the aqueous resin dispersion C at 80 ° C. is within the range specified in the present application. was used, the adhesion to the polyolefin substrate layers 1 and 3 was good. Comparative Example 1 used a water-based resin dispersion in which the elastic modulus of the coating film obtained by drying the water-based resin dispersion at 80° C. was outside the range specified in the present application, so that the adhesion to the polyolefin base layers 1 and 3 was poor. .
- Comparative Example 2 the adhesion to the polyolefin base layer 1 and layer 3 was poor because the water-based resin dispersion, which is a blend in which the polymer A and the polymer B were not contained in the same particles, was used. Comparative Example 3 used an aqueous resin dispersion that did not contain the polymer B in the same particles, so the adhesion to the polyolefin substrate layers 1 and 3 at 100° C. was poor.
- an adhesive that uses a water-based resin dispersion that exhibits excellent low-temperature heat-sealing properties with respect to polyolefin substrates and that easily adheres to polyolefin substrates by heating at a low temperature for a short period of time, and the above-mentioned adhesive.
- the adhesive of the present invention can be suitably used in the fields of adhesives for polypropylene substrates, heat-sealing adhesives for packaging materials, paints, and the like, and is industrially extremely important.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Laminated Bodies (AREA)
Abstract
Description
本願は、2021年2月26日に、日本に出願された特願2021-029842号に基づき優先権を主張し、その内容をここに援用する。
[1]オレフィン系単量体由来の構成単位を有する重合体Aと、ラジカル重合性単量体由来の構成単位を有する重合体Bとを同一粒子内に含む水系樹脂分散体Cであって、前記水系樹脂分散体Cを80℃で30分間乾燥した塗膜の弾性率が0MPaよりも大きく35MPa以下である、水系樹脂分散体C。
[2]前記水系樹脂分散体Cを80℃で30分間乾燥した塗膜の破断伸度が100%以上3000%以下である、[1]に記載の水系樹脂分散体C。
[3]前記水系樹脂分散体Cを80℃で30分間乾燥した塗膜の破断伸度が800%以上3000%以下である、[1]又は[2]に記載の水系樹脂分散体C。
[4]前記重合体Bの全構成単位に対する芳香族系単量体由来の構成単位の質量割合が1.0質量%以上30.0質量%以下である、[1]~[3]のいずれか一項に記載の水系樹脂分散体C。
[5]前記重合体Aが、反応性基を有さないオレフィン系単量体由来の構成単位を有する重合体A1、及び反応性基及びオレフィン系単量体由来の構成単位を有する変性重合体A2からなる群から選択される少なくとも1種を含む、[1]~[4]のいずれか一項に記載の水系樹脂分散体C。
[6]前記重合体Aが前記重合体A1を含み、前記重合体A1が、エチレン又はプロピレンの単独重合体、エチレン及びプロピレンの共重合体、エチレン及びプロピレンからなる群から選択される少なくとも1種と、1-ブテン、1-ペンテン、1-ヘキセン、1-ヘプテン、1-オクテン、シクロペンテン、シクロヘキセン、及びノルボルネンからなる群(以下、「α-オレフィン単量体」ともいう。)から選択される少なくとも1種との共重合体、前記α-オレフィン単量体から選択される少なくとも1種と、酢酸ビニル、アクリル酸エステル、及びメタクリル酸エステルからなる群から選択される少なくとも1種との共重合体、前記α-オレフィン単量体から選択される少なくとも1種と、芳香族ビニル単量体との共重合体及びその水素添加体、共役ジエンブロック共重合体及びその水素添加物からなる群から選択される少なくとも1種を含むことが好ましく;ポリエチレン、ポリプロピレン、エチレン-ブテン共重合体、エチレン-プロピレン共重合体、プロピレン-ブテン共重合体、プロピレン-ヘキセン共重合体、塩素化ポリエチレン、塩素化ポリプロピレン、塩素化エチレン-プロピレン共重合体、塩素化プロピレン-ブテン共重合体、エチレン-酢酸ビニル共重合体、スチレン-ブタジエン-スチレンブロック共重合体の水素添加物(SEBS)、及びスチレン-イソプレン-スチレンブロック共重合体の水素添加物(SEPS)からなる群から選択される少なくとも1種を含むことがより好ましく;プロピレン単独重合体、プロピレンと他のα-オレフィンとの共重合体、及びこれらの塩素化された重合体からなる群から選択される少なくとも1種を含むことがさらに好ましく;プロピレン単独重合体、エチレン-プロピレン共重合体、プロピレン-ブテン共重合体、塩素化ポリプロピレン、塩素化エチレン-プロピレン共重合体、又は塩素化プロピレン-ブテン共重合体がより好ましく、塩素を含有しないプロピレン単独重合体、エチレン-プロピレン共重合体、プロピレン-ブテン共重合体、及びエチレン-プロピレン-ブテン共重合体からなる群から選択される少なくとも1種を含むことが特に好ましい、[5]に記載の水系樹脂分散体C。
[7]前記重合体Aの重量平均分子量(Mw)が、5,000以上500,000以下が好ましく、10,000以上500,000以下がより好ましく、50,000以上300,000以下がさらに好ましく、100,000以上300,000以下が特に好ましい、[1]~[6]のいずれか一項に記載の水系樹脂分散体C。
[8]前記重合体Aの分子量分布(Mw/Mn)が、0.5~5.0が好ましく、1.0~4.0がより好ましく、1.5~3.0がさらに好ましい、[1]~[7]のいずれか一項に記載の水系樹脂分散体C。
[9]前記重合体Bのガラス転移温度が、-80℃以上20℃以下が好ましく、-80℃以上10℃以下がより好ましく、-70℃以上5℃以下がさらに好ましく、-60℃以上-3℃未満が特に好ましい、[1]~[8]のいずれか一項に記載の水系樹脂分散体C。
[10]前記ラジカル重合性単量体が、ビニル系単量体を含むことが好ましく;(メタ)アクリル系単量体、芳香族系単量体、アミド系単量体、(メタ)アクリロニトリル、酢酸ビニル、プロピオン酸ビニル、及びバーサチック酸ビニルからなる群から選択される少なくとも1種を含むことがより好ましく;(メタ)アクリル酸、(メタ)アクリル酸エステル、スチレン、及びα-メチルスチレンからなる群から選択される少なくとも1種を含むことがさらに好ましく;(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸-n-プロピル、(メタ)アクリル酸イソプロピル、(メタ)アクリル酸-n-ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸-t-ブチル、(メタ)アクリル酸ヘキシル、(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸オクチル、(メタ)アクリル酸-2-エチルヘキシル、(メタ)アクリル酸ノニル、(メタ)アクリル酸ラウリル、(メタ)アクリル酸ステアリル、(メタ)アクリル酸ベンジル、(メタ)アクリル酸ジメチルアミノエチル、(メタ)アクリル酸ジエチルアミノエチル、(メタ)アクリル酸-2-アミノエチル、(メタ)アクリル酸グリシジル、(メタ)アクリル酸-2-メトキシエチル、(メタ)アクリル酸-3-メトキシプロピル、(メタ)アクリル酸とポリエチレンオキサイドの付加物、(メタ)アクリル酸トリフルオロメチルメチル、(メタ)アクリル酸2-トリフルオロメチルエチル、(メタ)アクリル酸-2-パ-フルオロエチルエチル、スチレン、及びα-メチルスチレンからなる群から選択される少なくとも1種を含むことが特に好ましく;(メタ)アクリル酸イソブチル、(メタ)アクリル酸ブチル、(メタ)アクリル酸-t-ブチル、(メタ)アククリル酸シクロヘキシル、(メタ)アクリル酸-2-エチルヘキシル、(メタ)アクリル酸グリシジル、及びスチレンからなる群から選択される少なくとも1種を含むことが最も好ましい、[1]~[9]のいずれか一項に記載の水系樹脂分散体C。
[11]前記ラジカル重合性単量体が、ビニル系単量体を含み、前記ビニル系単量体が水酸基及びエポキシ基からなる群から選択される少なくとも1種を有し、前記ビニル系単量体由来の構成単位の質量割合は、前記重合体Bを構成する構成単位の総質量に対して1.0質量%以上30質量%以下が好ましく、1.5質量%以上20質量%以下がより好ましく、2.0質量%以上15質量%以下がさらに好ましく、5.0質量%以上10.0質量%以下が特に好ましい、[1]~[10]のいずれか一項に記載の水系樹脂分散体C。
[12]前記ラジカル重合性単量体が、芳香族系単量体を含み、前記芳香族系単量体由来の構成単位の質量割合は、前記重合体Bを構成する構成単位の総質量に対して5.0質量%以上80質量%以下が好ましく、8.0質量%以上70質量%以下がより好ましく、10.0質量%以上65質量%以下がさらに好ましく、12.0質量%以上60質量%以下が特に好ましい、[1]~[11]のいずれか一項に記載の水系樹脂分散体C。
[13]前記重合体Aと前記重合体Bの合計質量に対する前記重合体Aの質量割合は、30質量%以上90質量%以下が好ましく、50質量%以上80質量%以下がより好ましく、60質量%以上75質量%がさらに好ましく、65質量%以上70質量%以下が特に好ましい、[1]~[12]のいずれか一項に記載の水系樹脂分散体C。
[14]前記重合体Aと前記重合体Bの合計質量に対する前記重合体Bの質量割合は、10質量%以上70質量%以下が好ましく、30質量%以上60質量%以下がより好ましく、35質量%以上55質量%以下がさらに好ましい、[1]~[13]のいずれか一項に記載の水系樹脂分散体C。
[15][前記重合体Aの質量]:[前記重合体Bの質量]で表される質量割合は、30:70~90:10が好ましく、40:60~80:20がより好ましく、50:50~70:30がさらに好ましい、[1]~[14]のいずれか一項に記載の水系樹脂分散体C。
[16]前記粒子が、実質的に前記重合体Aと、前記重合体Bとからなる、[1]~[15]のいずれか一項に記載の水系樹脂分散体C。
[17]前記水系樹脂分散体Cを80℃で30分間乾燥して形成した塗膜の弾性率が0MPa超35MPa以下であり、5MPa以上35MPa以下が好ましく、10MPa以上25MPa以下がより好ましい、[1]~[16]のいずれか一項に記載の水系樹脂分散体C。
[18]前記水系樹脂分散体Cを80℃で30分間乾燥して形成した塗膜の破断伸度が100%以上3000%以下が好ましく、800%以上3000%以下がより好ましく、1000%以上2500%以下がさら好ましく、1500%以上2000%以下が特に好ましい、[1]~[17]のいずれか一項に記載の水系樹脂分散体C。
[19]前記粒子の平均粒子径が、0μm超0.5μm以下が好ましく、0.05μm以上0.3μm以下がより好ましく、0.1μm以上0.2μm以下がさらに好ましい、[1]~[18]のいずれか一項に記載の水系樹脂分散体C。
[20]前記水系樹脂分散体Cが、前記重合体Aの分散体中で前記ラジカル重合性単量体を重合させて前記重合体Bを形成させて得られる、[1]~[19]のいずれか一項に記載の水系樹脂分散体C。
[21]前記水系樹脂分散体Cを含む組成物Dから前記組成物Dの乾燥物を含む積層体を形成し、前記積層体から幅15mmの試験片を採取し、引張り試験機を用い、90度剥離により試験片の端部から界面を剥離した際の前記組成物Dの剥離強度(測定条件:23℃、65%RHの雰囲気中、引張速度50mm/分)が、1.00N/15mm以上10.00N/15mm以下であることが好ましく、2.00N/15mm以上8.00N/15mm以下であることがより好ましく、3.00N/15mm以上7.00N/15mm以下であることがさらに好ましく、4.00N/15mm以上6.00N/15mm以下であることが特に好ましい、[1]~[20]のいずれか一項に記載の水系樹脂分散体C。
[23]前記組成物Dがポリオレフィン基材用のヒートシール接着剤である、[22]に記載の組成物D。
[24]前記重合体Aと前記重合体Bとの合計質量に対する前記重合体Aの質量割合が30質量%以上である、[22]又は[23]に記載の組成物D。
[25]前記オレフィン系単量体がプロピレンを含む、[22]~[24]のいずれか一項に記載の組成物D。
[26]前記重合体Bのガラス転移温度が-80℃以上20℃以下である、[22]~[25]のいずれか一項に記載の組成物D。
[27]前記重合体Bのガラス転移温度が-80℃以上-3℃未満である、[22]~[26]のいずれか一項に記載の組成物D。
[28]前記組成物Dの総質量に対する前記水系樹脂分散体Cの質量割合が、80質量%以上100質量%以下が好ましく、90質量%以上100質量%以下がより好ましい、[22]~[27]のいずれか一項に記載の組成物D。
[30]前記乾燥物が、前記組成物Dの乾燥物からなる層である、[29]に記載の積層体。
[31]ポリプロピレン基材層1と、前記組成物Dの乾燥物からなる層2と、金属箔、無機蒸着膜層及び熱可塑性樹脂層からなる群から選択される少なくとも1種の層3と、がこの順序で積層している、[29]又は[30]に記載の積層体。
[32]前記組成物Dの乾燥物からなる層の厚みが、10μm以上60μm以下が好ましく、20μm以上50μm以下がより好ましい、[30]又は[31]に記載の積層体。
[33]前記層1の厚みが、10μm以上60μm以下が好ましく、20μm以上50μm以下がより好ましい、[31]又は[32]に記載の積層体。
[34]前記層3の厚みが、10μm以上60μm以下が好ましく、20μm以上50μm以下がより好ましい、[31]~[33]のいずれか一項に記載の積層体。
[35]前記層3が、熱可塑性樹脂層であり、前記熱可塑性樹脂層がポリエチレン系樹脂、ポリプロピレン系樹脂、環状ポリオレフィン系樹脂、フッ素系樹脂、ポリスチレン系樹脂、アクリロニトリル-スチレン共重合体(AS樹脂)、アクリロニトリル-ブタジエン-スチレン共重合体(ABS樹脂)、ポリ塩化ビニル系樹脂、フッ素系樹脂、ポリ(メタ)アクリル系樹脂、ポリカーボネート系樹脂、ポリエチレンテレフタレート、ポリエチレンナフタレ-ト等のポリエステル系樹脂、各種のナイロン等のポリアミド系樹脂、ポリイミド系樹脂、ポリアミドイミド系樹脂、ポリアリールフタレ-ト系樹脂、シリコ-ン系樹脂、ポリスルホン系樹脂、ポリフェニレンスルフィド系樹脂、ポリエ-テルスルホン系樹脂、ポリウレタン系樹脂、アセタ-ル系樹脂、セルロ-ス系樹脂、及びポリビニルアルコール樹脂からなる群から選択される少なくとも1種の樹脂を含むフィルム又はシ-トであることが好ましく;ポリプロピレン系樹脂、ポリエステル系樹脂、及びポリアミド系樹脂からなる群から選択される少なくとも1種の樹脂を含むフィルム又はシ-トであることがより好ましい、[31]~[34]のいずれか一項に記載の積層体。
[36]前記層3が、金属箔又は無機蒸着膜層であり、前記金属箔又は前記無機蒸着膜層としては、アルミニウム箔等の軟質金属箔、アルミニウム蒸着層、シリカ蒸着層、アルミナ蒸着層、及びシリカアルミナ2元蒸着の無機蒸着層からなる群から選択される少なくとも1種であることが好ましく;アルミニウム箔、及びアルミニウム蒸着膜からなる群から選択される少なくとも1種であることがより好ましい、[31]~[34]のいずれか一項に記載の積層体。
[37][23]に記載の組成物Dを含む、食品包装材。
[38]前記重合体Aの分散体中でラジカル重合性単量体を重合する工程を有する、[1]~[21]のいずれか一項に記載の水系樹脂分散体Cの製造方法。
[39]前記重合する工程において、前記ラジカル重合性単量体の全量に対して80~100重量%の量のラジカル重合性単量体を供給して重合し、重合途中で前記ラジカル重合性単量体の残量を供給して重合することを含む、[38]に記載の水系樹脂分散体Cの製造方法。
以下に各成分について記載する。
オレフィン系単量体由来の構成単位を有する重合体とは、オレフィンを原料の単量体とする重合体を意味し、オレフィンの単独重合体や共重合体等のオレフィン系単量体由来の構成単位を有する重合体A(以下、「重合体A」と記載することがある。)等を意味する。
(1)プロピレン基材への密着性が良好となる点で、前記重合体Aのプロピレン含有率は、50モル%以上が好ましく、60モル%以上がより好ましく、70モル%以上がさらに好ましい。
(2)120℃以下の低温ヒートシール時の密着性が良好となる点で、前記重合体Aの融点[Tm]は、120℃以下が好ましく、100℃以下がより好ましく、90℃以下がさらに好ましい。また、Tmの下限は、ブロッキング性に優れる点から60℃以上が好ましい。
前記重合体A1としては、公知のオレフィン系重合体及びオレフィン系共重合体を用いることができる。前記重合体A1としては、特に限定されないが、エチレン又はプロピレンの単独重合体;エチレン及びプロピレンの共重合体;エチレン及びプロピレンからなる群から選択される少なくとも1種と、その他の単量体として、例えば、1-ブテン、1-ペンテン、1-ヘキセン、1-ヘプテン、1-オクテン、シクロペンテン、シクロヘキセン、及びノルボルネン等の炭素数2以上のα-オレフィン単量体との共重合体、もしくは前記α-オレフィン単量体の2種類以上の共重合体;前記α-オレフィン単量体と、酢酸ビニル、アクリル酸エステル、メタクリル酸エステル等の単量体との共重合体;前記α-オレフィン単量体と、芳香族ビニル単量体等の単量体との共重合体又はその水素添加体;共役ジエンブロック共重合体又はその水素添加物等が挙げられる。
なお、前記の各種共重合体はランダム共重合体及びブロック共重合体からなる群から選択される少なくとも1種であってもよい。前記の各種共重合体としては、ポリオレフィンを塩素化した塩素化ポリオレフィンを使用することもできる。オレフィン系重合体A1の溶剤への溶解性が向上する点で、前記塩素化ポリオレフィンの塩素化度は、ポリオレフィンの合計質量に対して、5重量%以上が好ましく、10重量%以上がより好ましい。また40重量%以下が好ましく、30重量%以下がより好ましい。
前記重合体A2としては、変性重合時にオレフィンと反応性基を有する不飽和化合物とを共重合した共重合体A2a、反応性基を有するラジカル重合性不飽和化合物をオレフィン系単量体由来の構成単位を有する重合体にグラフト重合したグラフト重合体A2b等が挙げられる。
前記重合体Aの分散体の製造方法としては、前記重合体Aに界面活性剤を含有させて前記重合体Aを分散させる方法、前記重合体Aに親水系高分子をグラフト結合させたグラフト共重合体を用いてグラフト共重合体を分散させる方法、前記重合体A2の前記反応性基が、カルボキシル基又はその無水物、スルホニル基の等の酸性基である場合に、前記酸性基を塩基性化合物で中和することにより、前記重合体A2を分散させる方法等が挙げられる。
重合体Bのガラス転移温度は、20℃以下が好ましく、10℃以下がより好ましく、5℃以下がさらに好ましく、-3℃未満が特に好ましい。重合体Bのガラス転移温度が20℃以下であれば、塗膜の柔軟性及び成膜性が向上し、低温ヒートシール性が向上する。また、塗膜のブロッキング性が向上する観点から、アクリル重合体Bのガラス転移温度は、-80℃以上が好ましく、-70℃以上がより好ましく、-60℃以上がさらに好ましい。即ち、前記重合体Bのガラス転移温度は-80℃以上20℃以下が好ましく、-80℃以上-3℃未満がより好ましい。
(式(i)中、Wiは単量体iの質量分率を示し、Tgiは単量体iの単独重合体のTg(℃)を示す。ここで、各単量体の単独重合体のガラス転移温度は、ポリマーハンドブック第4版(POLYMER HANDBOOK Fourth Edition),John Wiley & Sons, Inc.(1999)に記載されている値を使用することができる。)
前記重合体Bの製造方法としては、前記重合体Aの分散体中で前記ラジカル重合性単量体が溶解した状態で重合する方法、前記重合体Aとラジカル重合性単量の両方が分散した状態の分散体中で重合する方法、前記ラジカル重合性単量体と界面活性剤を用いて乳化重合する方法等が挙げられる。
前記一括重合とは、一度にラジカル重合性単量体の全量を反応容器に仕込んで重合する方法である。前記重合体Bの製造方法に一括重合を採用する場合は、例えば、前記重合体Aの分散体に、ラジカル重合性単量体の全量を混合した後に、水溶性の開始剤や有機過酸化物とチオ硫酸ナトリウム等の還元剤を含むレドックス系開始剤等を添加して重合を行うことができる。また、前記滴下重合とは、単量体を少量ずつ反応容器に滴下しながら重合する方法である。前記重合体Bの製造方法に滴下重合を採用する場合は、例えば、前記重合体Aの分散体に、ラジカル重合性単量体を滴下しながら重合を行うことができる。
重合安定性及びプロピレン基材に対する接着性の点から、前記重合体Bの製造方法に前記一括重合を採用することが好ましく、前記一括重合は、ラジカル重合性単量体の全量に対して80~100重量%の量のラジカル重合性単量体を供給して重合し、重合途中でラジカル重合性単量体の残量を供給して重合することがより好ましい。
前記乳化重合用界面活性剤としては、各種のアニオン性、カチオン性、又はHLBが8以上のノニオン性の界面活性剤等が挙げられ、界面活性剤成分中にエチレン性不飽和結合を有する、いわゆる反応性界面活性剤も使用することができる。これらの中でも、得られる分散体の貯蔵安定性の向上の点から、アニオン性の界面活性剤を用いることが好ましい。アニオン性界面活性剤としては、特に限定されないが、反応性界面活性剤である株式会社ADEKA製アデカリアソープSR、非反応性界面活性剤であるネオコールSW-C、ニューコール707SF等を用いることができる。
水系樹脂分散体Cの前記重合体A及びラジカル重合性単量体由来の構成単位を有する前記重合体Bの質量割合は、A:B=30:70~90:10が好ましい。前記範囲内であれば、前記重合体Aの分散体中で前記ラジカル重合性単量体が溶解した状態で重合する方法、前記重合体Aとラジカル重合性単量の両方が分散した状態の分散体中で重合する方法等を用いることができ、本発明の効果を著しく損なわない範囲で、通常知られる製造方法によって前記水系樹脂分散体Cを製造することができる。
前記塗膜の破断伸度は100%以上3000%以下が好ましく、800%以上3000%以下がより好ましく、1000%以上がさら好ましく、1500%以上が特に好ましい。
前記塗膜の破断伸度は100%より小さいと塗膜が脆く、密着強度が劣る傾向となる。
前記水系樹脂分散体Cの製造方法におけるラジカル重合性単量体の重合方法は、前記重合体Bの製造方法と同様の重合方法によって行うことができる。
本発明の組成物Dは水系樹脂分散体Cを原料とすることが好ましい。
前記水系樹脂分散体Cはそのまま本発明の組成物Dとして用いることができる。前記組成物Dの接着強度、耐水系、耐熱性、耐薬品性、濡れ性等の性能を向上させるために、必要に応じて水系樹脂分散体C以外のその他の樹脂を含有させてもよい。前記その他の樹脂としては、添加剤や架橋剤等を挙げることができる。
また、湿潤剤としては、シロキサン系湿潤剤を用いることもできる。
本発明の積層体は、前記樹脂組成物Dの乾燥物を含む積層体であることが好ましい。前記樹脂組成物Dの乾燥物を含むことで、ポリオレフィン基材に対する低温ヒートシール性、密着性が良好となる。
また、本発明の積層体は、ポリプロピレン基材層1と、組成物のDの乾燥物から形成される層2(以下、「組成物Dの硬化物層2」ともいう。)と、金属箔、無機蒸着膜層及び熱可塑性樹脂からなる群から選択される少なくとも1種の層3と、がこの順序で積層していることが好ましい。D図1は、ポリプロピレン基材層1と、組成物Dの硬化物層2と、金属箔、無機蒸着膜層及び熱可塑性樹脂からなる群から選択される少なくとも1種の層3と、がこの順序で積層している積層体10を表している。
組成物の硬化物層2は組成物Dの乾燥物から形成されていればよく、組成物Dの使用量は、接着面の面積に対して、0.01~20g/m2が好ましく、0.1~10g/m2がより好ましく、0.3~5g/m2がさらに好ましい。前記使用量が、0.01g/m2未満では十分な接着性が得られず、20g/m2を超えると、乾燥に時間がかかり、経済的にも不利になる。
前記添加剤としては、滑剤、架橋剤、酸化防止剤、紫外線吸収剤、光安定剤、充填剤、帯電防止剤、滑剤、アンチブロッキング剤、染料、顔料等の着色剤、改質用樹脂等を任意に使用することができる。
なお、実施例及び比較例における「部」及び「%」は、各々、「質量部」及び「質量%」を意味する。また、表中における各成分に係る数値は、それぞれ質量部を意味する。
(1)オレフィン系重合体Aの重量平均分子量[Mw]及び分子量分布[Mw/Mn]の測定方法
オレフィン系重合体Aの試料5mgを10mLのバイアル瓶に採取し、安定剤としてジブチルヒドロキシトルエン 250ppmを含有するテトラヒドロフランを5g添加し、50℃で完全に溶解させたる。室温に冷却後、孔径0.45μmのフィルターでろ過し、ポリマー濃度0.1質重量%の試料溶液を調製した。次に、カラムとしてTSKgel GMHXL-L(30cm×2本)にガードカラムTSKguardcolumnHXL-Hを装着した東ソー(株)社製GPC HLC-8020を使用してGPC測定を行った。測定条件としては、試料溶液のインジェクション量:50μL、カラム温度:40℃、溶媒:テトラヒドロフラン、流量1.0mL/minで測定した。分子量は、標準試料として市販の単分散のポリスチレン標準試料を測定し、標準試料の保持時間と分子量から検量線を作成してオレフィン系単量体由来の構成単位を有する重合体Aの重量平均分子量[Mw]及び分子量分布[Mw/Mn]を算出した。
セイコーインスツル(株)社製 示差走査熱量計 DSC 220Cを使用して測定した。オレフィン系単量体由来の構成単位を有する重合体Aの試料5±1mgをアルミニウム製のパンに入れアルミニウム製の蓋をし、空のアルミニウム製のパンをリファレンスとして検出器にのせた。200℃まで100℃/分の速度で昇温した。同温度で5分間保持した後、10℃/分の速度で冷却し、-10℃まで0.5秒間隔で熱量を検出した。同温度で1分保持した後10℃/分の速度で200℃まで昇温させ、0.5秒間隔で熱量を検出した。
各試料とも冷却過程において発熱ピークが1つ、最後の昇温過程において吸熱ピークが1つ観測された。最後の昇温過程におけるピークのピークトップ時の温度をオレフィン系単量体由来の構成単位を有する重合体Aの融点[Tm]とした。
水系樹脂分散体を濃厚系粒径アナライザー FPAR-1000(商品名、大塚電子社製)を用いて、平均粒径を求めた。結果を表1に記載した。
水系樹脂分散体をイソプロパノールで表面を脱脂したガラス基材に膜厚300μmになるようにアプリケーターで塗装を行った。その後、80℃に設定したセーフベンドライヤーで30分間乾燥を行い、膜厚100μmの水系樹脂分散体の乾燥後の塗膜を得た。得られた乾燥後の塗膜を30mm×5mmにせん断し、島津社製小型卓上試験機 EZを用いて測定温度23℃で引張速度50mm/min、チャック間距離10mmの条件で引張試験を行った。得られた応力歪み曲線より、水系樹脂分散体の乾燥後の塗膜の弾性率と破断伸度を求めた。結果を表1に記載した。
層3として熱可塑性樹脂製のOPPフィルム(東洋紡社製パイレン(登録商標)、フィルム-OT P2108(商品名))の未処理面(コロナ処理をしていない面)へ水系樹脂分散体C100部と濡れ剤としてシロキサン系基材湿潤剤(エボニック社製TEGO(登録商標)、Wet KL 245(商品名)7部を混合し、組成物Dを得た。得られた組成物Dをバーコーターで前記層3の未処理面に塗装後、100℃で3分の乾燥を行うことで、熱可塑性樹脂製のOPP未処理フィルムである層3と組成物の硬化物層2の厚さ10μm(10g/m2)の試験片を得た。
さらに、ポリプロピレン基材層1として、前記OPPフィルムと同じ種類のフィルムを用い、前記フィルムの未処理面を、得られた試験片の組成物の硬化物層2の表面にヒートシーラーで表2に記載の温度で10秒、1kg荷重でヒートシールを行うことで、積層体を得た。
得られた積層体から幅15mmの試験片を採取し、引張り試験機を用い、90度剥離により試験片の端部からポリプロピレン基材層1とポリプロピレン基材(1)の界面を剥離して組成物Dの剥離強度(測定条件:23℃、65%RHの雰囲気中、引張速度50mm/分)を測定することで、組成物Dのポリオレフィン基材層1及び層3に対する密着性試験の評価を以下評価基準で評価した。評価結果を表2に記載した。
(評価基準)
A:剥離強度が2.00N/15mm以上で密着性が優れている。
B:剥離強度が1.00N/15mm以上2.00N/15mm未満で密着性が良好である。
C:剥離強度が1.00N/15mm未満で密着性が悪い。
攪拌機、還流冷却管及び温度制御装置を備えたフラスコに、オレフィン系単量体由来の構成単位を有する重合体Aの分散体としてアプトロック(登録商標)BW-5683(三菱ケミカル社製:固形分30.0%、重量平均分子量210000、分子量分布2.2 融点70℃)を333.3部(固形分で100部)、脱イオン水を115.4部仕込み、50℃に昇温した。 次いで、ラジカル重合性単量体としてアクリル酸-2-エチルヘキシル(2EHA)41.5部、スチレン(ST)6部、メタクリル酸グリシジル(GMA)2.5部とを入れ、1時間保持した。さらに、開始剤としてパーブチル(登録商標)H69(商品名、日油社製、固形分69%)0.05部、還元剤として硫酸第一鉄0.0001部、エチレンジアミン四酢酸(EDTA)0.00014部、イソアスコルビン酸ナトリウム一水和物0.04部、及び脱イオン水0.5部を添加し、重合を開始した。
重合の発熱ピークを検出した後、パーブチル(登録商標)H69を0.05部と、脱イオン水10部を30分間かけて滴下した。滴下終了後、60℃で30分間熟成し、50%平均粒子径110nmの水系樹脂分散体(1)を得た。結果を表1に記載した。
ラジカル重合性単量体由来の構成単位を表1に記載の通りに変更した以外は製造例1と同様の操作を行うことで水系樹脂分散体(2)~(5)、(8)、及び(9)を得た。結果を表1に記載した。
ラジカル重合性単量体としてアクリル酸-2-エチルヘキシル(2EHA)41.5部、スチレン(ST)6部、メタクリル酸グリシジル(GMA)2.5部と脱イオン水20部と界面活性剤としてニューコール707SF5部(日本乳化剤株式会社社製、固形分30%、ポリオキシエチレン多環フェニルエーテル硫酸塩)をホモミクサー(プライミクス株式会社製、ホモミクサーMART II)で乳化し、プレエマルションを得た。攪拌機、還流冷却管及び温度制御装置を備えたフラスコに、脱イオン水80.4部と得られたプレエマルション75部を入れ、50℃に昇温した。1時間保持後に、開始剤としてパーブチル(登録商標)H69(商品名、日油社製、固形分69%)0.05部、還元剤として硫酸第一鉄0.0001部、エチレンジアミン四酢酸(EDTA)0.00014部、イソアスコルビン酸ナトリウム一水和物0.04部、及び脱イオン水0.5部を添加し、重合を開始した。
重合の発熱ピークを検出した後、パーブチル(登録商標)H69を0.05部と、脱イオン水10部を30分間かけて滴下した。滴下終了後、60℃で30分間熟成した。冷却後にアプトロック(登録商標)BW-5683を333.3部入れ、50%平均粒子径110nmの重合体Aと重合体Bの配合物である水系樹脂分散体(6)を得た。結果を表1に記載した。
オレフィン系単量体由来の構成単位を有する重合体Aの分散体としてアプトロック(登録商標)BW-5683(三菱ケミカル社製:固形分30.0%、重量平均分子量210000、分子量分布2.2 融点70℃)333.3部(固形分で100部)を水系樹脂分散体(7)として使用した。結果を表1に記載した。
表2に記載の通りに積層体を作成し、前記ポリオレフィン基材層1及び層3に対する密着性試験を行った。評価結果を表2に記載した。
なお、表1中の略号は以下の通りである。
アプトロックBW-5683:オレフィンエマルション、三菱ケミカル社製
EHA:アクリル酸エチルヘキシル、三菱ケミカル社製
iBMA:メタクリル酸イソブチル、三菱ケミカル社製
tBMA:メタクリル酸t-ブチル、三菱ケミカル社製
ST:スチレン、NSスチレン単量体社製
GMA:メタクリル酸グリシジル、三菱ケミカル社製
Claims (13)
- オレフィン系単量体由来の構成単位を有する重合体Aと、ラジカル重合性単量体由来の構成単位を有する重合体Bとを同一粒子内に含む水系樹脂分散体Cであって、前記水系樹脂分散体Cを80℃で30分間乾燥した塗膜の弾性率が0MPaよりも大きく35MPa以下である、水系樹脂分散体C。
- 前記水系樹脂分散体Cを80℃で30分間乾燥した塗膜の破断伸度が100%以上3000%以下である、請求項1に記載の水系樹脂分散体C。
- 前記水系樹脂分散体Cを80℃で30分間乾燥した塗膜の破断伸度が800%以上3000%以下である、請求項1又は請求項2に記載の水系樹脂分散体C。
- 前記重合体Bの全構成単位に対する芳香族系単量体由来の構成単位の質量割合が1.0質量%以上30.0質量%以下である、請求項1~3のいずれか一項に記載の水系樹脂分散体C。
- 請求項1~4のいずれか一項に記載の水系樹脂分散体Cを含む組成物D。
- 前記組成物Dがポリオレフィン基材用のヒートシール接着剤である、請求項5に記載の組成物D。
- 前記重合体Aと前記重合体Bの合計質量に対する前記重合体Aの質量割合が30質量%以上である、請求項5又は請求項6に記載の組成物D。
- 前記オレフィン系単量体がプロピレンを含む、請求項5~7のいずれか一項に記載の組成物D。
- 前記重合体Bのガラス転移温度が-80℃以上20℃以下である、請求項5~8のいずれか一項に記載の組成物D。
- 前記重合体Bのガラス転移温度が-80℃以上-3℃未満である、請求項5~9のいずれか一項に記載の組成物D。
- 請求項5~10のいずれか一項に記載の組成物Dの乾燥物を含む積層体。
- ポリプロピレン基材層1と、前記組成物Dの乾燥物からなる層2と、金属箔、無機蒸着膜層及び熱可塑性樹脂層からなる群から選択される少なくとも1種の層3と、がこの順序で積層している、請求項11に記載の積層体。
- 請求項6に記載の組成物Dを含む、食品包装材。
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2023502212A JPWO2022181204A1 (ja) | 2021-02-26 | 2022-01-28 | |
CN202280007854.5A CN116529083A (zh) | 2021-02-26 | 2022-01-28 | 水系树脂分散体、以所述水系树脂分散体为原料的组合物、包含所述组合物干燥物的层叠体 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2021-029842 | 2021-02-26 | ||
JP2021029842 | 2021-02-26 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2022181204A1 true WO2022181204A1 (ja) | 2022-09-01 |
Family
ID=83049212
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2022/003333 WO2022181204A1 (ja) | 2021-02-26 | 2022-01-28 | 水系樹脂分散体、前記水系樹脂分散体を原料とする組成物、前記組成物の乾燥物を含む積層体 |
Country Status (3)
Country | Link |
---|---|
JP (1) | JPWO2022181204A1 (ja) |
CN (1) | CN116529083A (ja) |
WO (1) | WO2022181204A1 (ja) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0867726A (ja) * | 1994-06-23 | 1996-03-12 | Nippon Paper Ind Co Ltd | 水性樹脂組成物、その製造方法及び用途 |
JP2000264934A (ja) * | 1999-03-18 | 2000-09-26 | Mitsui Chemicals Inc | エマルション組成物及びその製造方法 |
JP2002105418A (ja) * | 2000-09-27 | 2002-04-10 | Mitsui Chemicals Inc | 接着剤組成物およびそれを用いた熱シール接着用材料 |
JP2003165872A (ja) * | 2001-11-29 | 2003-06-10 | Toagosei Co Ltd | ポリオレフィン系樹脂組成物 |
JP2018104620A (ja) * | 2016-12-28 | 2018-07-05 | 三菱ケミカル株式会社 | 水性樹脂分散体 |
WO2019112039A1 (ja) * | 2017-12-07 | 2019-06-13 | 三菱ケミカル株式会社 | 水性樹脂分散体、水性樹脂分散体の製造方法、水性塗料、接着剤 |
-
2022
- 2022-01-28 CN CN202280007854.5A patent/CN116529083A/zh active Pending
- 2022-01-28 JP JP2023502212A patent/JPWO2022181204A1/ja active Pending
- 2022-01-28 WO PCT/JP2022/003333 patent/WO2022181204A1/ja active Application Filing
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0867726A (ja) * | 1994-06-23 | 1996-03-12 | Nippon Paper Ind Co Ltd | 水性樹脂組成物、その製造方法及び用途 |
JP2000264934A (ja) * | 1999-03-18 | 2000-09-26 | Mitsui Chemicals Inc | エマルション組成物及びその製造方法 |
JP2002105418A (ja) * | 2000-09-27 | 2002-04-10 | Mitsui Chemicals Inc | 接着剤組成物およびそれを用いた熱シール接着用材料 |
JP2003165872A (ja) * | 2001-11-29 | 2003-06-10 | Toagosei Co Ltd | ポリオレフィン系樹脂組成物 |
JP2018104620A (ja) * | 2016-12-28 | 2018-07-05 | 三菱ケミカル株式会社 | 水性樹脂分散体 |
WO2019112039A1 (ja) * | 2017-12-07 | 2019-06-13 | 三菱ケミカル株式会社 | 水性樹脂分散体、水性樹脂分散体の製造方法、水性塗料、接着剤 |
Also Published As
Publication number | Publication date |
---|---|
CN116529083A (zh) | 2023-08-01 |
JPWO2022181204A1 (ja) | 2022-09-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JPWO2005082963A1 (ja) | 変性ポリオレフィン樹脂 | |
JP6970095B2 (ja) | 変性ポリオレフィン系樹脂 | |
JP5491099B2 (ja) | ポリオレフィン系複合樹脂水性分散体及びその製造方法 | |
WO2006011402A1 (ja) | 水性樹脂組成物、その製造方法、塗料、インキ、接着剤、シール剤およびプライマー | |
EP1240223A1 (en) | Aqueous, polymodal, multistage polymer emulsions | |
TWI639620B (zh) | Modified polyolefin resin | |
JP2007204671A (ja) | 水性分散体および積層体 | |
JP7322207B2 (ja) | 塩素化ポリオレフィン系樹脂組成物 | |
JP2018104620A (ja) | 水性樹脂分散体 | |
US11421101B2 (en) | Aqueous resin dispersion, method for producing aqueous resin dispersion, aqueous coating material, and adhesive | |
JP2018044056A (ja) | 易接着層形成用樹脂組成物及び易接着性材料 | |
WO2022181204A1 (ja) | 水系樹脂分散体、前記水系樹脂分散体を原料とする組成物、前記組成物の乾燥物を含む積層体 | |
JP2005126483A (ja) | (メタ)アクリル変性ポリオレフィン系樹脂、その製法及び組成物 | |
JP2008069254A (ja) | 水性接着剤およびそれを用いた積層体 | |
JP7482597B2 (ja) | 水性樹脂分散体 | |
JP7124316B2 (ja) | 水性樹脂分散体の製造方法 | |
JP2023128772A (ja) | 重合体組成物、接着剤及び積層体 | |
JP7297736B2 (ja) | 変性ポリオレフィン樹脂及びその用途 | |
JP4270791B2 (ja) | 合成紙用水性接着剤及び積層体 | |
JP2002080687A (ja) | 水性分散液 | |
WO2023182275A1 (ja) | 非水ディスパージョン組成物、接着剤組成物、ヒートシールラッカー、及びコーティング組成物 | |
JP2006291138A (ja) | ラミネート用水性接着剤 | |
JP5987184B1 (ja) | 水性のヒートシール性樹脂組成物 | |
JP3867566B2 (ja) | 塗料用樹脂組成物 | |
WO2022196121A1 (ja) | アクリルオレフィン複合樹脂組成物、非水系樹脂組成物、非水系樹脂組成物の製造方法、アクリルオレフィン複合樹脂組成物の製造方法、コーティング組成物、インキ組成物、接着剤組成物、フィルム及び成形材 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 22759245 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2023502212 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 202280007854.5 Country of ref document: CN |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 22759245 Country of ref document: EP Kind code of ref document: A1 |