TWI838510B - 水性樹脂組成物 - Google Patents
水性樹脂組成物 Download PDFInfo
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- TWI838510B TWI838510B TW109111573A TW109111573A TWI838510B TW I838510 B TWI838510 B TW I838510B TW 109111573 A TW109111573 A TW 109111573A TW 109111573 A TW109111573 A TW 109111573A TW I838510 B TWI838510 B TW I838510B
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- Taiwan
- Prior art keywords
- meth
- acrylate
- resin composition
- water
- acid
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 59
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 83
- 229920001577 copolymer Polymers 0.000 claims abstract description 57
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 49
- 229920000098 polyolefin Polymers 0.000 claims abstract description 47
- 238000000576 coating method Methods 0.000 claims abstract description 38
- 239000000758 substrate Substances 0.000 claims abstract description 31
- 150000002148 esters Chemical class 0.000 claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 11
- 239000000853 adhesive Substances 0.000 claims abstract description 10
- 230000001070 adhesive effect Effects 0.000 claims abstract description 9
- 239000000565 sealant Substances 0.000 claims abstract description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 4
- 239000011248 coating agent Substances 0.000 claims description 27
- 239000000178 monomer Substances 0.000 claims description 25
- 238000002844 melting Methods 0.000 claims description 17
- 230000008018 melting Effects 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 230000009477 glass transition Effects 0.000 claims description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 3
- 238000007639 printing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 26
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- 239000000976 ink Substances 0.000 abstract description 5
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- 229920005989 resin Polymers 0.000 description 44
- 239000011347 resin Substances 0.000 description 44
- 239000002245 particle Substances 0.000 description 26
- 239000007787 solid Substances 0.000 description 21
- 238000004519 manufacturing process Methods 0.000 description 20
- 238000000034 method Methods 0.000 description 20
- 239000004711 α-olefin Substances 0.000 description 18
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000004945 emulsification Methods 0.000 description 12
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 10
- 229920001451 polypropylene glycol Polymers 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 9
- 239000000839 emulsion Substances 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 7
- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 229930195729 fatty acid Natural products 0.000 description 7
- 239000002736 nonionic surfactant Substances 0.000 description 7
- 230000007704 transition Effects 0.000 description 7
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 6
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 6
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 6
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 6
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 6
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 6
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 239000003945 anionic surfactant Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 5
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 4
- 239000004166 Lanolin Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 229940039717 lanolin Drugs 0.000 description 4
- 235000019388 lanolin Nutrition 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 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
- 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
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 229940069096 dodecene Drugs 0.000 description 3
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
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- 238000006467 substitution reaction Methods 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 2
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
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- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-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
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002958 pentadecyl 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])[H] 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
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- 230000001681 protective effect Effects 0.000 description 2
- 150000003254 radicals Chemical class 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
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
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- 239000000080 wetting agent Substances 0.000 description 2
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- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- GNWBLLYJQXKPIP-ZOGIJGBBSA-N (1s,3as,3bs,5ar,9ar,9bs,11as)-n,n-diethyl-6,9a,11a-trimethyl-7-oxo-2,3,3a,3b,4,5,5a,8,9,9b,10,11-dodecahydro-1h-indeno[5,4-f]quinoline-1-carboxamide Chemical compound CN([C@@H]1CC2)C(=O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H](C(=O)N(CC)CC)[C@@]2(C)CC1 GNWBLLYJQXKPIP-ZOGIJGBBSA-N 0.000 description 1
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- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- XXMBEHIWODXDTR-UHFFFAOYSA-N 1,2-diaminoethanol Chemical compound NCC(N)O XXMBEHIWODXDTR-UHFFFAOYSA-N 0.000 description 1
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical compound CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-UHFFFAOYSA-N 0.000 description 1
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 description 1
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- YOIZTLBZAMFVPK-UHFFFAOYSA-N 2-(3-ethoxy-4-hydroxyphenyl)-2-hydroxyacetic acid Chemical compound CCOC1=CC(C(O)C(O)=O)=CC=C1O YOIZTLBZAMFVPK-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
- XRIBIDPMFSLGFS-UHFFFAOYSA-N 2-(dimethylamino)-2-methylpropan-1-ol Chemical compound CN(C)C(C)(C)CO XRIBIDPMFSLGFS-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 description 1
- IUKSYUOJRHDWRR-UHFFFAOYSA-N 2-diazonio-4,6-dinitrophenolate Chemical compound [O-]C1=C([N+]#N)C=C([N+]([O-])=O)C=C1[N+]([O-])=O IUKSYUOJRHDWRR-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/08—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having four or more carbon atoms
- C08F255/10—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having four or more carbon atoms on to butene polymers
-
- 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
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
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Abstract
本發明之課題在於提供即使在80℃煅燒下仍對於聚烯烴基材表現高的剝離強度,且即使含有丙烯酸聚合物成分也不損及密接力之用於塗料、印墨、黏接劑、密封劑或底漆之聚烯烴與丙烯酸聚合物混合型的水性樹脂組成物。
一種水性樹脂組成物,含有酸改性聚烯烴樹脂(A)及(甲基)丙烯酸酯共聚物(B),其特徵為:酸改性聚烯烴樹脂(A)中以0.5~10質量%的範圍含有不飽和羧酸或其酸酐,(甲基)丙烯酸酯共聚物(B)就共聚合成分而言,含有酯部分係碳數12以上之(甲基)丙烯酸酯(B1)以及酯部分係碳數11以下之(甲基)丙烯酸酯(B2)。
Description
本發明有關對於聚烯烴基材具有高密接力的水性樹脂組成物。
一般來說,聚丙烯、聚乙烯、乙烯丙烯共聚物、乙烯丙烯二烯共聚物、聚4-甲基-1-戊烯等聚烯烴系樹脂,係較低廉且具有例如耐藥品性、耐水性、耐熱性等優異的性能,作為汽車零件、電力零件、建築資材、包裝用薄膜等材料而使用在廣泛的領域中。然而,聚烯烴系樹脂因為其結晶性及非極性,所以施行塗佈、黏接係有困難。
以往係使用對於聚烯烴系樹脂具有強附著力的氯化聚烯烴作為黏結劑樹脂來用於這種難黏接性的聚烯烴系樹脂的塗佈、黏接(參照專利文獻1、專利文獻2)。又,為了彌補氯化聚烯烴對基材的黏接性差或黏接對象受限定的缺點,將氯化聚烯烴與丙烯酸聚合物、胺甲酸脂、或聚酯樹脂進行混合,或將這些樹脂接枝聚合於氯化聚烯烴,作為黏結劑組成物來施行塗佈、黏接(參照專利文獻3、專利文獻4)。
然而,因為這些黏結劑組成物幾乎都是以溶解在甲苯、二甲苯等有機溶劑中的形式而使用,所以在塗佈時會釋放大量的有機溶劑於大氣中,在環境面、衛生面等並不理想。
因此,有人提出不包含有機溶劑之含聚烯烴樹脂的水性樹脂組成物(參照專利文獻5、專利文獻6)。然而,這些組成物中,聚烯烴系樹脂本身係極性低者,在與丙烯酸聚合物、胺甲酸脂、環氧、或聚酯樹脂混合使用時,會因為難以相溶而有無法展現期待之物性的問題。
針對此種課題,有人提出將聚烯烴溶解於丙烯酸系單體中進行轉相乳化後再將單體予以聚合的乳劑製造法(參照專利文獻7、專利文獻8)。這些製造法可藉由縮減脫溶劑步驟來壓抑成本,獲得因為含有丙烯酸聚合物而與其他樹脂間的相容性優異的水性樹脂組成物。
[專利文獻1]日本特開昭59-75958號公報
[專利文獻2]日本特開昭60-99138號公報
[專利文獻3]日本特開平6-16746號公報
[專利文獻4]日本特開平8-12913號公報
[專利文獻5]日本特開平6-256592號公報
[專利文獻6]日本特開2004-107539號公報
[專利文獻7]日本特開平6-80738號公報
[專利文獻8]日本特開2010-001334號公報
另一方面,因為這些組成物的樹脂成分的一半的量成為了丙烯酸聚合物,所以有與聚烯烴基材間的剝離強度降低的課題。
本發明之課題係欲解決上述課題,提供即使在80℃煅燒下仍對於聚烯烴基材表現高的剝離強度,且即使含有丙烯酸聚合物成分也不損及密接力之用於塗料、印墨、黏接劑、密封劑或底漆之聚烯烴與丙烯酸聚合物混合型的水性樹脂組成物。
本案發明人發現藉由含有酸改性聚烯烴樹脂(A)與(甲基)丙烯酸酯共聚物(B)的水性樹脂組成物能解決上述課題,上述(甲基)丙烯酸酯共聚物(B)含有酯部分係碳數12以上之烴基之(甲基)丙烯酸酯(B1)以及酯部分係碳數11以下之烴基之(甲基)丙烯酸酯(B2)。
本發明係如下所示。
一種水性樹脂組成物,含有酸改性聚烯烴樹脂(A)及(甲基)丙烯酸酯共聚物(B),其特徵為:酸改性聚烯烴樹脂(A)中以0.5~10質量%的範圍含有不飽和羧酸或其酸酐,(甲基)丙烯酸酯共聚物(B),含有酯部分係碳數12以上之(甲基)丙烯酸酯(B1)以及酯部分係碳數11以下之(甲基)丙烯酸酯(B2)。
(甲基)丙烯酸酯共聚物(B)宜更含有選自於由含有極性基之(甲基)丙烯酸酯、(甲基)丙烯酸及(甲基)丙烯醯胺構成之群組中之1種以上的含極性基之單體(B3)。
除了酸改性聚烯烴樹脂(A)與(甲基)丙烯酸酯共聚物(B)以外,宜含有界面活性劑及鹼性化合物中之任一者或兩者,且相對於酸改性聚烯烴樹脂(A)100質量份,(甲基)丙烯酸酯共聚物(B)的含量落在40~250質量份的範圍內較為理想。
(甲基)丙烯酸酯共聚物(B)含有之酯部分係碳數12以上的烴基的(甲基)丙烯酸酯(B1)與酯部分係碳數11以下的烴基的(甲基)丙烯酸酯(B2)之質量比係落在70/30~20/80的範圍內較為理想。
(甲基)丙烯酸酯共聚物(B)之玻璃轉移溫度(Tg)落在-40℃~80℃的範圍內較為理想,而酸改性聚烯烴樹脂(A)利用示差掃描型熱量計(DSC)測得之熔點為90℃以下較為理想。
上述任一者記載之水性樹脂組成物可利用於聚烯烴薄膜、片材或成形體用塗料、印墨、黏接劑、密封劑、或底漆。
本發明之水性樹脂組成物,即使在80℃煅燒下仍對於聚烯烴基材表現優異的密接性及耐水性,雖然含有丙烯酸系樹脂卻仍然發揮與改性聚烯烴樹脂單獨時同等的高剝離強度。又與各種極性樹脂間的相容性良好,且藉由不包含有機溶劑來獲得脫溶劑步驟經縮減之製造步驟,可提供用於塗料、印墨、黏接劑、密封劑或底漆的水性樹脂組成物。
以下,詳細地說明本發明。
本發明為一種水性樹脂組成物,含有酸改性聚烯烴樹脂(A)及(甲基)丙烯酸酯共聚物(B),其特徵為:酸改性聚烯烴樹脂(A)中以0.5~10質量%的範圍含有不飽和羧酸或其酸酐,(甲基)丙烯酸酯共聚物(B),含有酯部分係碳數12以上之(甲基)丙烯酸酯(B1)以及酯部分係碳數11以下之(甲基)丙烯酸酯(B2)。
<酸改性聚烯烴樹脂(A)>
本發明中所用之酸改性聚烯烴樹脂(A)係將選自於α,β-不飽和羧酸及其酸酐中之至少1種予以接枝共聚合於例如選自於聚丙烯、丙烯-α-烯烴共聚物、聚乙烯、乙烯-α-烯烴共聚物、聚1-丁烯及1-丁烯-α-烯烴共聚物中之至少1種的聚烯烴而得。
在此,所謂丙烯-α-烯烴共聚物,係指將丙烯作為主體並與α-烯烴進行共聚合所成者。就α-烯烴而言,可列舉如乙烯、1-丁烯、1-戊烯、1-己烯、1-庚烯、1-辛烯、1-癸烯、1-十二烯、1-十六烯、4-甲基-1-戊烯等碳原子數為2或4~20的α-烯烴。丙烯-α-烯烴共聚物中,丙烯成分的含量為50莫耳%以上較為理想,70莫耳%以上更為理想。若丙烯成分的含量為50莫耳%以上,則對於聚丙烯基材的密接性會變好。
所謂乙烯-α-烯烴共聚物,係指將乙烯作為主體並與α-烯烴進行共聚合所成者。就α-烯烴而言,可列舉如丙烯、1-丁烯、1-戊烯、1-己烯、1-庚烯、1-辛烯、1-癸烯、1-十二烯、1-十六烯、4-甲基-1-戊烯等碳原子數為3~20的α-烯烴。乙烯-α-烯烴共聚物中,乙烯成分的含量為75莫耳%以上較為理想。若乙烯成分的含量為75莫耳%以上,則對於聚乙烯基材的密接性會變好。
所謂1-丁烯-α-烯烴共聚物,係指將1-丁烯作為主體並與α-烯烴進行共聚合所成者。就α-烯烴而言,可列舉如乙烯、丙烯、1-戊烯、1-己烯、1-庚烯、1-辛烯、1-癸烯、1-十二烯、1-十六烯、4-甲基-1-戊烯等碳原子數為2~3或5~20的α-烯烴。1-丁烯-α-烯烴共聚物中,1-丁烯成分的含量為65莫耳%以上較為理想。若1-丁烯成分的含量為65莫耳%以上,則對於聚丙烯基材、聚1-丁烯基材的密接性會變好。
就接枝共聚合於聚烯烴的α,β-不飽和羧酸或其酸酐而言,可列舉如馬來酸、馬來酸酐、富馬酸、檸康酸、檸康酸酐、中康酸、衣康酸、衣康酸酐、烏頭酸、烏頭酸酐、納迪克酸酐等。這些當中尤以馬來酸酐、衣康酸酐較為理想。
酸改性聚烯烴樹脂(A)中,α,β-不飽和羧酸成分或其酸酐成分的含量為0.5~10質量%。0.7質量%以上較為理想,1質量%以上更為理想。又,5質量%以下更為理想,3質量%以下更甚理想。若α,β-不飽和羧酸成分或其酸酐成分的含量落在此範圍內,則轉相乳化會變容易,又從水性樹脂組成物所得之塗膜的耐水性會變好。
就將選自於α,β-不飽和羧酸及其酸酐中之至少1種予以接枝共聚合於聚烯烴的方法而言,可列舉如在自由基引發劑的存在下將該聚烯烴於熔點以上進行加熱熔融而使其反應的方法(熔融法),將該聚烯烴溶解於有機溶劑後在自由基引發劑的存在下進行加熱攪拌使其反應的方法(溶液法)等公知的方法。
本發明中所用之酸改性聚烯烴樹脂(A)利用高溫GPC(凝膠滲透層析儀)測得的重量平均分子量為3000~200000較為理想。10000以上更為理想,30000以上更甚理想,45000以上特別理想。又,150000以下更為理想,120000以下更甚理想。若落在上述範圍內,則酸改性聚烯烴對(甲基)丙烯酸酯(B1)及(甲基)丙烯酸酯(B2)的溶解會變好,轉相乳化會變容易。又,樹脂的凝聚力變充分,黏接力變好。
又,利用高溫GPC之重量平均分子量的測定,係可將鄰二氯苯作為溶劑,將聚苯乙烯作為標準物質,並使用市售的裝置以公知的方法來進行。具體而言,使用鄰二氯苯作為溶劑,在140℃下使用沃特斯(Waters)公司製之GPC150-C plus
型進行測定。管柱係使用東曹公司製之GMH6-HT、GMH6-HTL。重量平均分子量係將已知分子量的聚苯乙烯作為標準物質而算出。
亦可進一步使酸改性聚烯烴樹脂(A)進行氯化改性。就氯化聚烯烴而言,藉由將上述酸改性聚烯烴樹脂進行氯化所得之酸改性氯化聚烯烴較為理想。使酸改性聚烯烴樹脂(A)氯化時,考量溶液穩定性及聚烯烴基材與樹脂基材或金屬基材間之黏接性的觀點,氯含有率的下限為5質量%以上較為理想,8質量%以上更為理想,10質量%以上更甚理想,12質量%以上特別理想,14質量%以上最為理想。若為5質量%以上,則溶液穩定性會變好,變得易於乳化。上限為40質量%以下較為理想,38質量%以下更為理想,35質量%以下更甚理想,32質量%以下特別理想,30質量%以下最為理想。若在40質量%以下,則酸改性氯化聚烯烴的結晶性易變高,黏接強度易變強。
酸改性氯化聚烯烴之氯含有率可藉由依循JIS K-7229-1995之滴定進行測定。
本發明之酸改性聚烯烴樹脂(A)利用示差掃描型熱量計(以下DSC)測得之熔點為90℃以下較為理想。85℃以下更為理想,80℃以下特別理想。藉由落在上述範圍內,80℃煅燒時的成膜性會變理想,對於聚烯烴基材的密接性、耐水性、剝離強度會變好。
本發明中利用DSC之熔點的測定可依循JIS K7121-2012來測定,例如可藉由以下條件進行。使用DSC測定裝置(精工電子工業製),將約5mg的試樣在150℃下
保持10分鐘的加熱熔解狀態後,以10℃/分的速度予以降溫並以-50℃穩定保持後,再以10℃/分昇溫至150℃並測定熔解時的熔解峰值溫度,將該溫度作為熔點進行評價。此外,下述實施例中的熔點係以上述條件測定者。
<(甲基)丙烯酸酯共聚物(B)>
本發明中使用之(甲基)丙烯酸酯共聚物(B),就共聚合成分而言,係含有酯部分係碳數12以上之烴基之(甲基)丙烯酸酯(B1)以及酯部分係碳數11以下之烴基之(甲基)丙烯酸酯(B2)者。以下,簡單稱為(B1)、(B2)。
藉由含有(B1)及(B2),可充分地溶解酸改性聚烯烴樹脂(A)使轉相乳化變容易,此外即使含有丙烯酸聚合物成分,對於聚烯烴基材的密接性仍然變好。又藉由與聚烯烴以外的樹脂間的親和性變高,使與塗膜中其他樹脂間的相容性變好。
相對於酸改性聚烯烴樹脂(A)100質量份,(甲基)丙烯酸酯共聚物(B)的含量落在40~250質量份的範圍內較為理想。80~200的範圍更為理想,100~150的範圍更甚理想。若(B)的含量落在40~250的範圍內,則酸改性聚烯烴樹脂(A)的轉相乳化變容易,又對聚烯烴樹脂基材的密接性變好。
<(甲基)丙烯酸酯(B1)>
就本發明中使用之酯部分係碳數12以上之烴基之(甲基)丙烯酸酯(B1)而言,可列舉如(甲基)丙烯酸十二酯{(甲基)丙烯酸月桂酯}、(甲基)丙烯酸十三
酯、(甲基)丙烯酸十四酯、(甲基)丙烯酸十五酯、(甲基)丙烯酸十六酯、(甲基)丙烯酸十七酯、(甲基)丙烯酸十八酯、(甲基)丙烯酸異十八酯、(甲基)丙烯酸十九酯、(甲基)丙烯酸二十酯、(甲基)丙烯酸二十一酯、(甲基)丙烯酸二十二酯、(甲基)丙烯酸二十三酯、(甲基)丙烯酸二十四酯、(甲基)丙烯酸二十五酯、(甲基)丙烯酸二十六酯、(甲基)丙烯酸二十七酯、(甲基)丙烯酸二十八酯、(甲基)丙烯酸二十九酯、(甲基)丙烯酸三十酯、(甲基)丙烯酸三十一酯、(甲基)丙烯酸三十二酯、(甲基)丙烯酸三十四酯、(甲基)丙烯酸三十五酯等丙烯酸系單體。烴基可為直鏈亦可為分支,又含有環狀結構亦可。這些單體可單獨使用1種或混合使用2種以上。
(甲基)丙烯酸酯(B1)之酯部分的碳數為12以上,35以下較為理想,18以下更為理想。若為12以上35以下,則酸改性聚烯烴樹脂(A)的溶解性及乳化聚合時的聚合性會變理想。
<(甲基)丙烯酸酯(B2)>
就本發明中使用之酯部分係碳數11以下之烴基之(甲基)丙烯酸酯(B2)而言,可列舉如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸叔丁基環己酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸二環戊酯。這些單體可單獨使用1種或混合使用2種以上。
(甲基)丙烯酸酯(B2)之酯部分的碳數為1以上10以下較為理想,8以下更為理想。若為1以上10以下則酸改性聚烯烴的溶解性會變理想,轉相乳化及乳化聚合會變容易。
本發明中使用之(甲基)丙烯酸酯共聚物(B)含有之酯部分係碳數12以上的烴基的(甲基)丙烯酸酯(B1)與酯部分係碳數11以下的烴基的(甲基)丙烯酸酯(B2)之質量比落在70/30~20/80的範圍內較為理想。60/40~40/60更為理想。若落在上述範圍,則酸改性聚烯烴樹脂(A)的溶解性上升,轉相乳化會變容易。又,(甲基)丙烯酸酯共聚物與聚烯烴基材間的親和性更好,對於聚烯烴基材的密接性會變好。
<含極性基之單體(B3)>
本發明中使用之(甲基)丙烯酸酯共聚物(B)亦可再與含極性基之單體(B3)共聚合。(以下簡單稱為(B3)。)(B3)係為與(B1)及(B2)相異者,就(B3)而言,可列舉如在酯部中含有極性基之(甲基)丙烯酸酯、(甲基)丙烯酸及(甲基)丙烯醯胺,亦可使用選自於這些當中之1種以上。就在酯部中含有極性基之丙烯酸酯的極性基而言,可列舉如羥基、羧基、磷酸基、胺基、醯胺基、醚基、環氧基等。其中尤以使用醯胺基、羥基較為理想,使用羥基更為理想。就在酯部中含有極性基之丙烯酸酯而言,可列舉如(甲基)丙烯酸-2-羥乙酯、(甲基)丙烯酸-2-羥丙酯、(甲基)丙烯酸-2-羥丁酯、(甲基)丙烯酸-4-羥丁酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸環氧丙酯、(甲基)丙烯酸甲基環氧丙酯、甲基丙烯酸-3,4-環氧環己基甲酯、(甲基)丙烯酸四氫糠酯、單(甲基)丙烯酸聚乙二醇酯、二(甲基)丙烯酸聚乙
二醇酯、單(甲基)丙烯酸聚丙二醇酯、二(甲基)丙烯酸聚丙二醇酯、單(甲基)丙烯酸聚丁二醇酯、二(甲基)丙烯酸聚丁二醇酯、(甲基)丙烯酸二甲胺基乙酯、(甲基)丙烯酸二乙胺基乙酯等。就丙烯醯胺類而言,可列舉如(甲基)丙烯醯胺、二甲基(甲基)丙烯醯胺、二乙基(甲基)丙烯醯胺、二甲胺丙基(甲基)丙烯醯胺等。使用這些的1種以上較為理想,使用具有相同極性基的2種以上更為理想。藉由將這些(B3)與(B1)及(B2)組合使用,會使與極性基材、頂部塗覆塗料間的密接性比只有(B1)及(B2)的情況還要更好。又,單獨使用(B3)的話,酸改性聚烯烴樹脂(A)的溶解性會不好,但若與(B1)及(B2)組合使用的話,與酸改性聚烯烴樹脂(A)間的相容性會變好。
本發明中使用之(B3),相對於(甲基)丙烯酸酯共聚物(B)係使用1~40質量%較為理想。2質量%以上更為理想,4質量%以上更甚理想,6質量%以上特別理想。又,30質量%以下更為理想,25質量%以下更甚理想,20質量%以下最為理想。若落在上述範圍內,則酸改性聚烯烴(A)的溶解性上升,轉相乳化變容易。又,藉由使(甲基)丙烯酸酯共聚物(B)中之極性基含量落在理想範圍,則目標組成物之對於聚烯烴基材、極性基材、頂部塗覆塗料的密接性會變好。
本申請案中,「(甲基)丙烯酸酯」係指「丙烯酸酯或甲基丙烯酸酯」,「(甲基)丙烯酸」係指「丙烯酸或甲基丙烯酸」,「(甲基)丙烯醯基」係指「丙烯醯基或甲基丙烯醯基」。「(甲基)丙烯醯胺」係指「丙烯醯胺或甲基丙烯醯胺」。
此外,本發明之(甲基)丙烯酸酯共聚物(B)亦可含有(B1)、(B2)、(B3)以外的聚合性單體。就(B1)、(B2)、(B3)以外的聚合性單體而言,可列舉如苯乙烯、α-甲基苯乙烯、對甲基苯乙烯、二乙烯苯等苯乙烯系單體。然後,就除了上述以外之可併用的單體類而言,可列舉如乙酸乙烯酯等。這些單體可單獨使用1種或混合使用2種以上。
又(甲基)丙烯酸酯共聚物(B)之玻璃轉移溫度(Tg)落在-40℃~80℃的範圍內較為理想。-30℃以上更為理想,-20℃以上更甚理想。又,60℃以下更為理想,50℃以下更甚理想。若落在上述範圍內,則塗膜的柔軟性變理想,可抑制其他成分的滲出,且耐水性、塗膜外觀變好。又,80℃煅燒時之塗膜的成膜性亦變理想,對於聚烯烴基材的密接性、耐水性、剝離強度變好。
為了設計出具有所期望之Tg的(甲基)丙烯酸酯共聚物(B),係考量將(甲基)丙烯酸酯單體及含極性基之單體分別進行單獨聚合時所得之均聚物的玻璃轉移溫度(以下稱為「均聚物的Tg」)而決定出(甲基)丙烯酸酯單體及含極性基之單體的混合比。
具體而言(甲基)丙烯酸酯共聚物(B)的Tg,可藉由使用(甲基)丙烯酸酯共聚物之理論Tg的算式(FOX式)進行計算來求得。
1/Tg=C1/Tg1+C2/Tg2+…+Cn/Tgn:(FOX式)
[算式(FOX式)中,Tg為(甲基)丙烯酸酯共聚物之理論Tg,Cn為單體n在(甲基)丙烯酸酯共聚物(B)之單體混合物中含有的重量比例,Tgn為單體n之均聚物的Tg,n為構成(甲基)丙烯酸酯共聚物(B)之單體的數量,為正整數。]
例如,使用甲基丙烯酸月桂酯(Tg208.15K、46質量%)作為(B1),使用甲基丙烯酸環己酯(Tg339.15K、46質量%)作為(B2),並使用甲基丙烯酸-2-羥乙酯(Tg328.15K、4質量%)及丙烯酸-4-羥丁酯(Tg233.15K、4質量%)作為(B3)時的算式如下。算出之共聚物的理論Tg為259.1(K),經換算為-14.1℃。
1/Tg=0.46/208.15+0.46/339.15+0.04/328.15+0.04/233.15
又,本發明之Tg係定義為由上述算式求得之理論Tg(℃)。
(甲基)丙烯酸酯單體及含極性基之單體的均聚物的Tg,可使用記載於文獻中的數值。就這種文獻而言,可參照例如以下文獻:共榮社化學社的(甲基)丙烯酸酯目錄、三菱化學社的丙烯酸酯目錄;及高分子刊行會於1997年發行,由北岡協三著之「新高分子文庫7,塗料用合成樹脂入門」第168~169頁。
<界面活性劑>
本發明之水性樹脂組成物,在不損及本發明性能的範圍內可含有界面活性劑。就界面活性劑而言,可列舉如非離子性界面活性劑、陰離子性界面活性劑、陽離子性界面活性劑及兩性界面活性劑。這些當中,考量分散粒子之粒徑、及從目標組成物所得之塗膜的耐水的觀點,使用非離子性界面活性劑、陰離子性界面活性劑較為理想,使用非離子性界面活性劑更為理想。
就非離子性界面活性劑而言,可列舉如聚氧乙烯烷基醚、聚氧丙烯烷基醚、聚氧乙烯烷基苯醚、聚氧丙烯烷基苯醚、聚氧乙烯苯乙烯化苯醚、聚氧丙烯苯乙烯化苯醚、聚氧乙烯脂肪酸酯、聚氧丙烯脂肪酸酯、聚氧乙烯山梨醇酐脂肪酸酯、聚氧丙烯山梨醇酐脂肪酸酯、聚氧乙烯烷基胺醚、聚氧丙烯烷基胺醚、聚氧乙烯羊毛脂醇醚、聚氧丙烯羊毛脂醇醚、聚氧乙烯羊毛脂脂肪酸酯、聚氧丙烯羊毛脂脂肪酸酯、(聚氧乙烯氧丙烯)嵌段共聚物等。就其中一例而言,可列舉如Emarumin系列(三洋化成工業(股)公司製)Noigen系列(第一工業製藥(股)公司製)、Buraunon系列(青木油脂工業(股)公司製)等。
又,就這些非離子性界面活性劑而言,亦可使用在分子中具有聚合性雙鍵的反應性界面活性劑。就其中一例而言,可列舉如ADEKA Reasoap ER-10、ER-20、ER-30、ER-40(以上係ADEKA(股)公司製)等。
就陰離子性界面活性劑而言,可列舉如高級烷基硫酸酯類、烷基芳基聚氧乙烯硫酸酯鹽類、高級脂肪酸鹽類、烷基芳基磺酸鹽類、烷基磷酸酯鹽類等。就其中一例而言,可列舉如Neocol系列、Hitenol系列(第一工業製藥(股)公司製)等。
又,就這些陰離子性界面活性劑而言,亦可使用在分子中具有聚合性雙鍵的反應性界面活性劑。就其中一例而言,可列舉如ADEKA Reasoap NE-10、NE-20、NE-30、NE-40、SE-10N(以上係ADEKA(股)公司製)、Aqu.alon RN-20、
RN-30、RN-50、HS-10、HS-20(以上係第一工業製藥(股)公司製)、Eleminol JS-2、Eleminol RS-30(以上係三洋化成工業(股)公司製)等。
上述界面活性劑可使用單獨1種或混合使用2種以上。
本發明中,考量轉相乳化的容易性、塗膜的耐水性之觀點,界面活性劑的使用量相對於酸改性聚烯烴樹脂(A)100質量份為5~60質量份較為理想。40質量份以下更為理想,30質量份以下更甚理想。又,20質量份以下又更甚理想。
<鹼性化合物>
本發明亦可更含有鹼性化合物。又,可在本發明之水性樹脂組成物的製造中使用鹼性化合物,例如在將酸改性聚烯烴樹脂(A)進行轉相乳化時可使鹼性化合物共存。藉由使其存在於系統內,能使酸改性聚烯烴樹脂(A)的分散性更好。就鹼性化合物而言,可列舉如氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸鉀、碳酸銨等無機鹼性化合物類、三乙基胺、N,N-二甲基乙醇胺、胺基乙醇胺、N-甲基-N,N-二乙醇胺、異丙胺、亞胺基雙丙基胺、乙胺、二乙胺、3-乙氧基丙胺、3-二乙基胺基丙胺、仲丁胺、丙胺、甲基胺基丙胺、甲基亞胺基雙丙胺、3-甲氧基丙胺、單乙醇胺、二乙醇胺、三乙醇胺、啉、N-甲基啉、N-乙基啉、2-胺基-2-甲基-1-丙醇、2-二甲基胺基-2-甲基-1-丙醇等胺類、氨等。
鹼性化合物的添加量相對於酸改性聚烯烴樹脂(A)的羧基宜為0.3~4.0倍化學當量較為理想,0.7~2.5倍化學當量更為理想。若未達0.3倍化學當量,則會有
無法展現鹼性化合物的存在效果之虞。另一方面,若超過4.0倍化學當量,則會有在目標組成物之乾燥物中的殘存量變得過多之虞。
可不使用有機溶劑,將酸改性聚烯烴樹脂(A)溶解於(B1)及(B2)的混合液中並經由轉相乳化、聚合反應來獲得本發明之水性樹脂組成物。所謂不使用有機溶劑,係指水性分散體中之有機溶劑為0.5質量%以下,0.1質量%以下更為理想,0.01質量%以下更甚理想,0.001質量%以下又更甚理想,0質量%特別理想。因為不使用有機溶劑,所以沒有必要進行濃縮脫氣而可將製造步驟簡化,可縮小製造成本及時間。具體而言,可藉由使酸改性聚烯烴樹脂(A)之(甲基)丙烯酸酯溶液轉相乳化之後,再將(甲基)丙烯酸酯聚合而獲得。為了良好地提高聚合反應的效率,使用聚合開始劑較為理想。就聚合起始劑而言,以慣用量來使用經常用於一般的乳化聚合中之聚合開始劑較為理想。就此種聚合開始劑的例子而言,可列舉如過硫酸鉀、過硫酸銨、過氧化氫;4,4’-偶氮二(4-氰基戊酸)、2,2’-偶氮二[N-(2-羧基乙基)-2-甲基丙醯胺]、2,2’-偶氮二[2-甲基-N-[2-(1-羥基丁基)]丙醯胺]、2,2’-偶氮二[2-甲基-N-(2-羥乙基)丙醯胺]等偶氮系開始劑;過氧化苯甲醯、過氧化-2-乙基己酸叔丁酯、1,1-雙(叔丁基過氧化)-3,3,5-三甲基環己烷、過氧化苯甲酸叔丁酯、二-叔丁基過氧化物、叔丁基氫過氧化物、異丙苯氫過氧化物、對薄荷烷氫過氧化物、二異丙基苯氫過氧化物等過氧化物系起始劑等。這些可單獨使用1種或混合使用2種以上。又,亦可使用氧化還原系起始劑,就其例子而言,可列舉如由上述聚合開始劑與還原劑(例如亞硫酸鹽、亞硫酸氫鹽、鈷、鐵、銅等低離子價的鹽)組合所成者。
聚合條件,宜根據使用之聚合性單體、聚合開始劑的種類來進行適當地設定,聚合溫度通常為20~100℃,50~90℃較為理想。又,聚合時間一般為1~8小時。為了使聚合迅速地進行,以如氮氣等鈍性氣體來置換聚合系統內的氣體環境較為理想。
以如上述方式獲得之水性樹脂組成物中樹脂粒子的Z平均粒徑為10nm以上且500nm以下較為理想,200nm以下更為理想。若平均粒徑超過500nm的話,因為會有在塗佈後的塗膜中發生缺損的可能性,而會對各物性造成不好的影響,尤其在頂部塗覆塗料的使用會變困難所以並不理想。
本發明之水性樹脂組成物可直接以原狀態來作為透明清漆使用,但若以進一步的塗膜性能例如造膜性、塗膜硬度、耐候性、柔軟性等的改質為目的,在不損害對於聚烯烴基材之附著性的程度下可將各種塗料用添加劑、其他的樹脂乳劑予以摻混使用。例如可使用丙二醇單丙醚、二丙二醇單甲醚、丁基丙二醇等成膜助劑、消泡劑、防滴劑、潤濕劑、紫外線吸收劑等。尤其,藉由將丙烯酸系乳劑、胺甲酸脂系乳化液予以摻混使用,可提高耐候性、耐水性、塗膜強度、柔軟性等塗膜性能。
然後,可於本發明之水性樹脂組成物中視需要而適當地添加黏著賦予劑,例如松香、丹瑪樹脂、聚合松香、氫化松香、酯化松香、松香改性馬來酸樹脂、聚萜烯系樹脂、石油系樹脂、環戊二烯系樹脂、酚醛系樹脂、二甲苯系樹脂、苯並呋喃-茚系樹脂等的水系分散液,藉此可改善塗膜乾燥性、對於聚烯烴基材
的附著性。就添加量而言,相對於樹脂組成物的固體成分100質量份為固體成分5~100質量份較為理想,10~50質量份更為理想。添加量未達5質量份時,會有無法展現添加效果之虞。另一方面,若超過100質量份,則添加量過多而反倒會有發生附著性降低之虞。
本發明之水性樹脂組成物可理想地使用於以聚丙烯為首之各種聚烯烴基材用之塗料、印墨、黏接劑、密封劑、底漆等,惟不應限定於這些基材,例如亦可塗佈在其他塑膠、木材、金屬等。就聚烯烴基材而言可列舉如薄膜、片材、成形體等。塗佈方法並無特別限制。又,塗佈後之塗膜的乾燥即使在常溫下進行亦可,但在30~120℃下進行乾燥較為理想,在60~100℃下進行乾燥更甚理想。
[實施例]
接著,藉由實施例對本發明進行具體地說明,但本發明不應限定於這些實施例。
(1)利用高溫GPC進行之重量平均分子量的測定
使用鄰二氯苯作為溶劑,在140℃下使用沃特斯(Waters)公司製之GPC150-CPLUS型來進行。(管柱:東曹公司製之GMH6-HT+GMH6-HTL)重量平均分子量係將分子量已知的聚苯乙烯作為標準物質而算出。
(2)利用示差掃描型熱量計(DSC)進行之熔點的測定
依循JIS K7121-2012並使用DSC測定裝置(精工電子工業製),將約5mg之試樣在150℃下加熱10分鐘並加熱熔解狀態之後,以10℃/分的速度予以降溫並穩定保持在-50℃之後,再以10℃/分昇溫直至150℃並測定熔解時的熔解峰值溫度,將該溫度作為熔點進行評價。
(3)Z平均粒徑的測定(以下簡單稱作平均粒徑。)
使用Malvern公司製之“Zetasizer Nano-ZS Model ZEN3600”以動態光散射法根據強度分布來測定平均粒徑(Z平均粒徑)。將水性分散體組成物的固體成分調整為0.05g/L的濃度而成之試樣在25℃下測定3次,並取其平均值。
製造例1
將丙烯-丁烯共聚物(丙烯成分含量=70莫耳%、丁烯成分含量=30莫耳%)280g、馬來酸酐20g、過氧化二異丙基苯7g及甲苯420g加入設有攪拌機之高壓釜中,進行約5分鐘的氮氣置換後,一邊進行加熱攪拌一邊在140℃下進行5小時反應。反應結束後,將反應液投入大量的甲基乙基酮中使樹脂析出。將此樹脂進一步以甲基乙基酮洗淨數次,將未反應的馬來酸酐除去。藉由將所得之樹脂進行減壓乾燥而獲得酸改性聚烯烴樹脂的固體(PO-1)。由紅外吸收光譜的測定結果,馬來酸酐成分與馬來酸成分之合計含量為1.3質量%。又,利用高溫GPC測定之重量平均分子量為80000,利用DSC測定之熔點為70℃。
製造例2
將丙烯-乙烯共聚物(丙烯成分含量=94.1莫耳%、乙烯成分含量=5.9莫耳%)280g、馬來酸酐14g、過氧化二異丙基苯5.6g及甲苯420g置入設有攪拌機之高壓釜中,進行約5分鐘的氮氣置換後,一邊進行反應結束後,將反應液投入大量的甲基乙基酮中使樹脂析出。將此樹脂進一步以甲基乙基酮洗淨數次,將未反應的馬來酸酐除去。減壓乾燥後,將所得之馬來酸酐改性聚烯烴樹脂280g及氯仿2520g置入設有攪拌器之高壓釜中,進行約5分鐘的氮氣置換後,於110℃加熱使樹脂充分溶解。然後,加入過氧化-2-乙基己酸叔丁酯1.4g,吹送預定量之氯氣。藉由將係反應溶劑之氯仿予以減壓餾去使其乾燥,獲得氯含有率為18質量%,重量平均分子量為100000,利用DSC測定之熔點為85℃,馬來酸酐之含量為0.9質量%之酸改性氯化聚烯烴樹脂的固體(CPO-1)。
實施例1(水性樹脂組成物(a)之製造)
將在製造例1獲得之酸改性聚烯烴樹脂100g、甲基丙烯酸環己酯46g、甲基丙烯酸月桂酯46g、甲基丙烯酸-2-羥乙酯4g、甲基丙烯酸-4-羥丁酯4g、聚氧乙烯苯乙烯化苯醚(第一工業製藥(股)公司製、商品名「Noigen EA-197」、非離子性界面活性劑)15g及二辛基磺酸基琥珀酸鈉(第一工業製藥(股)公司製、商品名「Neocol P」、陰離子性界面活性劑)1.5g置入設有冷卻器、溫度計、攪拌機及滴加漏斗之2公升4口燒瓶中,以保持在100℃的狀態使其充分溶解。將N,N-二甲基乙醇胺3.2g加入此溶液中,並攪拌15分鐘。接著,在激烈攪拌的狀態下,將預先以95℃加熱好之去離子水500g從滴加漏斗滴加30分鐘,使酸改性聚烯烴樹脂轉相乳化。將此乳化液冷卻至80℃後,藉由將氮氣流入使系統內進行充分地氮氣置換。然後,以保持在80℃的狀態下添加將過硫酸銨0.6g溶解於去離子水30g所
成之水溶液,並在氮氣流下開始聚合。在氮氣流下以80℃反應8小時,之後進行冷卻,獲得樹脂濃度(固體成分)為30質量%,樹脂粒子之平均粒徑為140nm的水性樹脂組成物(a)。又,(甲基)丙烯酸酯共聚物(B)的理論Tg為-14.1℃。
實施例2(水性樹脂組成物(b之製造)
除了將各成分之種類變更為表1的組成以外係以與實施例1同樣的方法進行,獲得樹脂濃度(固體成分)為30質量%,樹脂粒子之平均粒徑為160nm的水性樹脂組成物(b)。又,(甲基)丙烯酸酯共聚物(B)的理論Tg為46.5℃。
實施例3(水性樹脂組成物(c)之製造)
除了將各成分的量變更為表1的組成以外係以與實施例1同樣的方法進行,獲得樹脂濃度(固體成分)為30質量%,樹脂粒子之平均粒徑為180nm的水性樹脂組成物(c)。又,(甲基)丙烯酸酯共聚物(B)的理論Tg為-14.1℃。
實施例4(水性樹脂組成物(d)之製造)
除了將各成分的量變更為表1的組成以外係以與實施例1同樣的方法進行,獲得樹脂濃度(固體成分)為30質量%,樹脂粒子之平均粒徑為100nm的水性樹脂組成物(d)。又,(甲基)丙烯酸酯共聚物(B)的理論Tg為-14.1℃。
實施例5(水性樹脂組成物(e)之製造)
除了將各成分之種類變更為表1的組成以外係以與實施例1同樣的方法進行,獲得樹脂濃度(固體成分)為30質量%,樹脂粒子之平均粒徑為140nm的水性樹脂組成物(e)。又,(甲基)丙烯酸酯共聚物(B)的理論Tg為-35.1℃。
實施例6(水性樹脂組成物(f)之製造)
除了將各成分之種類變更為表1的組成以外係以與實施例1同樣的方法進行,獲得樹脂濃度(固體成分)為30質量%,樹脂粒子之平均粒徑為130nm的水性樹脂組成物(f)。又,(甲基)丙烯酸酯共聚物(B)的理論Tg為46.5℃。
實施例7(水性樹脂組成物(g)之製造)
除了將各成分之種類變更為表1的組成以外係以與實施例1同樣的方法進行,獲得樹脂濃度(固體成分)為30質量%,樹脂粒子之平均粒徑為180nm的水性樹脂組成物(g)。又,(甲基)丙烯酸酯共聚物(B)的理論Tg為25.6℃。
實施例8(水性樹脂組成物(h)之製造)
除了將各成分之種類變更為表1的組成以外係以與實施例1同樣的方法進行,獲得樹脂濃度(固體成分)為30質量%,樹脂粒子之平均粒徑為180nm的水性樹脂組成物(h)。又,(甲基)丙烯酸酯共聚物(B)的理論Tg為-7.9℃。
實施例9(水性樹脂組成物(i)之製造)
除了將各成分之種類變更為表1的組成以外係以與實施例1同樣的方法進行,獲得樹脂濃度(固體成分)為30質量%,樹脂粒子之平均粒徑為150nm的水性樹脂組成物(i)。又,(甲基)丙烯酸酯共聚物(B)的理論Tg為-15.2℃。
實施例10(水性樹脂組成物(j)之製造)
除了將各成分之種類變更為表1的組成以外係以與實施例1同樣的方法進行,獲得樹脂濃度(固體成分)為30質量%,樹脂粒子之平均粒徑為110nm的水性樹脂組成物(j)。又,(甲基)丙烯酸酯共聚物(B)的理論Tg為-37.9℃。
比較例1(水性樹脂組成物(k)之製造)
將在製造例1獲得之酸改性聚烯烴100g、甲苯90g、異丙醇90g及聚氧乙烯苯乙烯化苯醚(第一工業製藥(股)公司製、商品名「Noigen EA-197」、非離子性界面活性劑)15g置入設有冷卻器、溫度計、攪拌機及滴加漏斗之2公升4口燒瓶中,以保持在100℃的狀態使其充分溶解。將N,N-二甲基乙醇胺3.2g加入此溶液中,並攪拌15分鐘。接著,在激烈攪拌的狀態下,將預先以95℃加熱好之去離子水300g從滴加漏斗滴加30分鐘,使酸改性聚烯烴轉相乳化。將此乳化液冷卻至60℃,藉由在減壓下予以脫溶劑而獲得樹脂濃度(固體成分)為30質量%,樹脂粒子之平均粒徑為130nm的水性樹脂組成物(k)。
比較例2(水性樹脂組成物(l)之製造)
除了將各成分之種類變更為表1的組成以外係以與實施例1同樣的方法進行,獲得樹脂濃度(固體成分)為30質量%,樹脂粒子之平均粒徑為130nm的水性樹脂組成物(l)。又,(甲基)丙烯酸酯共聚物(B)的理論Tg為78.9℃。
比較例3(水性樹脂組成物(m)之製造)
除了將各成分之種類變更為表1的組成以外係以與實施例1同樣的方法進行,獲得樹脂濃度(固體成分)為30質量%,樹脂粒子之平均粒徑為180nm的水性樹脂組成物(m)。又,(甲基)丙烯酸酯共聚物(B)的理論Tg為21.2℃。
表1中各記號的意義如下。LMA:甲基丙烯酸月桂酯(Tg=-65℃)、SMA:甲基丙烯酸十八酯(Tg=38℃)、CHMA:甲基丙烯酸環己酯(Tg=66℃)、MMA:甲基丙烯酸甲酯(Tg=105℃)、EHMA:甲基丙烯酸-2-乙基己酯(Tg=-10℃)、HEMA:甲基丙烯酸-2-羥乙酯(Tg=55℃)、4HBA:丙烯酸-4-羥丁酯(Tg=-40℃)、DMAA:二甲基丙烯醯胺(Tg=119℃)、苯乙烯(Tg=100℃)。
使用在上述實施例1~10及比較例1~3中所得之水性樹脂組成物(a)~(m)針對以下特性進行評價。其結果如表1所示。
(1)密接性
在水性樹脂組成物100g中添加作為成膜助劑之丙二醇單甲醚2g、及作為潤濕劑之「Dinol 604」(Air Products Japan(股)公司製)2g,並以磁攪拌器攪拌30分鐘。將此乳劑以使乾燥塗膜厚成為10μm的方式進行噴霧塗佈於經異丙醇洗淨之聚丙烯板(日本試驗面板公司製)。在80℃下乾燥3分鐘後,將作為保護膜之2K胺甲酸脂塗料(關西塗料公司製之RETANPG White III)以成為40~50μm的方式進行噴霧塗佈。在80℃×30分鐘之乾燥後,在25℃×相對濕度60%的環境下放置24小時,並將其作為試驗板。在此試驗板上以1mm的間隔製作到達基底的100個方格,在其上壓接玻璃紙膠帶並以相對於塗面為90度的角度重複進行3次剝除,將沒有剝離的情況評價為○,將在第3次剝除時發生剝離的情況評價為△,並將在第2次剝除為止之前就剝離的情況評價為×。
(2)耐水性
將以上述(1)的方法獲得之試驗板浸漬於40℃的溫水240小時後,以與上述(1)同樣的方法對密接性進行評價。再確認塗膜的外觀是否發生起泡(塗膜之翻翹、膨起)。將沒有剝離、起泡的情況評價為○,將沒有剝離但有起泡的情況評價為△,並將剝離的情況評價為×。
(3)剝離強度
除了將保護膜進行100μm噴霧塗佈以外,以與上述(1)同樣的方法製得試驗板後,在25℃×相對濕度60%的環境下再放置48小時,並將其作為試驗板。在此試驗板上以1cm的間隔製作條狀的剝離片,在拉伸試驗機(A&D公司製之
TENSILONRTG-1310)以50mm/分的速度進行50mm、180°的剝離試驗。將拉伸時的應力定義為剝離強度,並將5次試驗的平均值作為測定結果。
(4)相容性
各自將「Superflex 150HS」(第一工業製藥(股)公司製之聚胺甲酸酯乳劑、固體成分38質量%)及「Primal 2133」(Rohm & Haas Japan(股)公司製之丙烯酸聚合物乳劑、固體成分41.5質量%)以相對於水性樹脂組成物之固體成分為1:1之質量比的方式予以混合,並將該混合物以50μm塗抹器塗佈於玻璃板,在80℃下乾燥30分鐘。以目視觀察乾燥後之玻璃板的狀態,將2種塗膜皆透明的情況評價為○,將任1種的塗膜中有發生混濁的情況評價為△,並將2種塗膜中皆發生混濁的情況評價為×。
(5)高樹脂含量穩定性
將在上述實施例及比較例得到之水性樹脂組成物濃縮至樹脂濃度45質量%,並從外觀確認其流動性。將有流動性的情況評價為○,並將增稠顯著且沒有流動性的情況評價為×。
[表2結果之考察]
如從表2可見,上述實施例1~10中獲得之水性樹脂組成物(a)~(j)在80℃煅燒中表現與係聚烯烴單獨分散體之水性樹脂組成物(k)同樣高的剝離強度而且耐水性、及高樹脂含量下的穩定性亦優異。反觀酸改性聚烯烴與(甲基)丙烯酸酯共聚物間的比、組成落在本發明之範圍外的情況,剝離強度降低而且對於聚烯烴基材的密接性、耐水性亦變差。
Claims (11)
- 一種水性樹脂組成物,含有酸改性聚烯烴樹脂(A)及(甲基)丙烯酸酯共聚物(B),其特徵為:酸改性聚烯烴樹脂(A)中以0.5~10質量%的範圍含有不飽和羧酸或其酸酐,(甲基)丙烯酸酯共聚物(B),就共聚合成分而言,含有酯部分係碳數12以上之烴基之(甲基)丙烯酸酯(B1)以及酯部分係碳數11以下之烴基之(甲基)丙烯酸酯(B2),相對於酸改性聚烯烴樹脂(A)100質量份,(甲基)丙烯酸酯共聚物(B)的含量落在80~250質量份的範圍內。
- 如請求項1之水性樹脂組成物,其中,(甲基)丙烯酸酯共聚物(B)更含有選自於由含有極性基之(甲基)丙烯酸酯、(甲基)丙烯酸及(甲基)丙烯醯胺構成之群組中之1種以上的含極性基之單體(B3)。
- 如請求項1或2之水性樹脂組成物,含有界面活性劑及鹼性化合物中之任一者或兩者。
- 如請求項1或2之水性樹脂組成物,其中,(甲基)丙烯酸酯共聚物(B)含有之酯部分係碳數12以上的烴基的(甲基)丙烯酸酯(B1)與酯部分係碳數11以下的烴基的(甲基)丙烯酸酯(B2)之質量比係落在70/30~20/80的範圍內。
- 如請求項1或2之水性樹脂組成物,其中,(甲基)丙烯酸酯共聚物(B)之玻璃轉移溫度(Tg)落在-40℃~80℃的範圍內。
- 如請求項1或2之水性樹脂組成物,其中,酸改性聚烯烴樹脂(A)利用示差掃描型熱量計(DSC)測得之熔點為90℃以下。
- 一種聚烯烴基材用塗料,含有如請求項1至6中任一項之水性樹脂組成物。
- 一種聚烯烴基材用印墨,含有如請求項1至6中任一項之水性樹脂組成物。
- 一種聚烯烴基材用黏接劑,含有如請求項1至6中任一項之水性樹脂組成物。
- 一種聚烯烴基材用密封劑,含有如請求項1至6中任一項之水性樹脂組成物。
- 一種聚烯烴基材塗佈用底漆,含有如請求項1至6中任一項之水性樹脂組成物。
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