SG178152A1 - Aqueous emulsion type resin composition and coating materials containing same - Google Patents
Aqueous emulsion type resin composition and coating materials containing same Download PDFInfo
- Publication number
- SG178152A1 SG178152A1 SG2012006292A SG2012006292A SG178152A1 SG 178152 A1 SG178152 A1 SG 178152A1 SG 2012006292 A SG2012006292 A SG 2012006292A SG 2012006292 A SG2012006292 A SG 2012006292A SG 178152 A1 SG178152 A1 SG 178152A1
- Authority
- SG
- Singapore
- Prior art keywords
- weight
- parts
- resin composition
- emulsion resin
- unsaturated monomer
- Prior art date
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- 239000000839 emulsion Substances 0.000 title claims abstract description 58
- 239000011342 resin composition Substances 0.000 title claims abstract description 50
- 239000000463 material Substances 0.000 title claims abstract description 46
- 239000011248 coating agent Substances 0.000 title claims abstract description 23
- 238000000576 coating method Methods 0.000 title claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 41
- 239000000203 mixture Substances 0.000 claims abstract description 37
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004094 surface-active agent Substances 0.000 claims abstract description 21
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract 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 claims 1
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 15
- 230000007774 longterm Effects 0.000 abstract description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 42
- 238000006116 polymerization reaction Methods 0.000 description 38
- 238000012010 media fill test Methods 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 150000001875 compounds Chemical class 0.000 description 19
- 239000008367 deionised water Substances 0.000 description 17
- 229910021641 deionized water Inorganic materials 0.000 description 17
- -1 2-hydroxypropyl Chemical group 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 11
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 11
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 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
- 239000002253 acid Substances 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000000413 hydrolysate Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 230000002335 preservative effect Effects 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002562 thickening agent Substances 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
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- ABYZSYDGJGVCHS-ZETCQYMHSA-N (2s)-2-acetamido-n-(4-nitrophenyl)propanamide Chemical compound CC(=O)N[C@@H](C)C(=O)NC1=CC=C([N+]([O-])=O)C=C1 ABYZSYDGJGVCHS-ZETCQYMHSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- GKQHIYSTBXDYNQ-UHFFFAOYSA-M 1-dodecylpyridin-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+]1=CC=CC=C1 GKQHIYSTBXDYNQ-UHFFFAOYSA-M 0.000 description 1
- PRPINYUDVPFIRX-UHFFFAOYSA-N 1-naphthaleneacetic acid Chemical compound C1=CC=C2C(CC(=O)O)=CC=CC2=C1 PRPINYUDVPFIRX-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- NDAJNMAAXXIADY-UHFFFAOYSA-N 2-methylpropanimidamide Chemical compound CC(C)C(N)=N NDAJNMAAXXIADY-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229930194542 Keto Natural products 0.000 description 1
- 241000531897 Loma Species 0.000 description 1
- 241001328813 Methles Species 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- 102000014105 Semaphorin Human genes 0.000 description 1
- 108050003978 Semaphorin Proteins 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- OFCNXPDARWKPPY-UHFFFAOYSA-N allopurinol Chemical compound OC1=NC=NC2=C1C=NN2 OFCNXPDARWKPPY-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 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 1
- SWRGUMCEJHQWEE-UHFFFAOYSA-N ethanedihydrazide Chemical compound NNC(=O)C(=O)NN SWRGUMCEJHQWEE-UHFFFAOYSA-N 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 235000001727 glucose Nutrition 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229940094506 lauryl betaine Drugs 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
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- DVEKCXOJTLDBFE-UHFFFAOYSA-N n-dodecyl-n,n-dimethylglycinate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC([O-])=O DVEKCXOJTLDBFE-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000015424 sodium Nutrition 0.000 description 1
- 229940077386 sodium benzenesulfonate Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 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
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- 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 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 239000012720 thermal barrier coating Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
-
- 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
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- 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
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1806—C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate
-
- 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
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
- C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Paints Or Removers (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
AQUEOUS EMULSION RESIN COMPOSITION AND COATING MATERIALS CONTAINING SAMEThe aqueous emulsion resin composition of the present invention is obtained by emulsion polymerization of an unsaturated monomer composition comprising as essential components y-methacryloxypropyl trimethoxysilane as component. (A), cyclohexylmetbacrylate as component (B), and at least one unsaturated monomer selected from the group consisting of methyl methacrylate, butyl (meth)acrylat, and 2-ethy1hexyl. (meth)acrylate as component (C) in the presence of a free-radical reactive surfactant, The aqueous emulsion resin composition shows not only excellent weather and stain resistances but also excellent long-term storage stability, due to the synergistic action of these components (A) to (C).
Description
AQUEOUS EMULSION RESIN COMPOSITION AND COATING MATERIALS
CONTAINING SAME
[0001]
The present invention relates to an agueous emulsion regin composition and coating materials containing same.
[0002]
Buildings and structures are coated with coating materials excellent in weather resistance and stain resistance so that the beautiful appearances thereof can be maintained.
Aqueous emulsion resin compositions obtained by emulsion polymerization of an unsaturated monomer composition containing 0.1 to 2wt% of a silane coupling agent in the presence of an alkylalkozysilane compound having 1 to 3 hydrolyzable alkoxy groups or a hydrolysate thereof, an alkoxvsilane compound having four hydrolyzable alkoxyl groups or a hydrolysate thereof, and a nonionic compound having an
OH~-terminated polvalkylense glycol chain at a specific ratio have been proposed. {For example, see Patent Literature 1.)
The aqueous emulsion resin compesitions are excellent in weather resistance and stain resistance, but do not have sufficient long-term storage stability.
[0003] [Patent Literature 1] Japanese Patent Application Laid-Open No. 2008-120904
[0004]
Therefore, the problem to be zclved by the present invention is to provide an agusous emulsion resin composition with excellent weather resistance, stain resistance, and long-term storage stability and coating materials containing same.
[0005]
As a result of keen study, the inventors of the present application found that an aqueous emulsion resin composition obtained by emulsion polymerization of an unsaturated monomer composition having a specific constitution in the presence of a specific surfactant with excellent iong-term storage stability as well as weather resistance and stain resistance to complete the present invention.
Namely, the present invention relates to an agueous emulsion resin composition obtained by emulsion polymerization of an unsaturated monomer composition comprising (A} v-methacryloxypropyl trimethoxysilane, (B} cyclohexyl methacrylate, and (C) at least one unsaturated monomer selected from the group consisting of methyl methacrylate, butyl {methacrylate and Z-ethylhexyl {(methlacryvlate in the presence of a free-radical reactive surfactant, wherein the unsaturated monomer composition contains 0.1 to 2 wti of {A} v-methacryloxypropyl trimethoxysilane and 25 to 75 wit% of {B) cyclohexyl methacrylate.
[C006]
The present invention can provide an agueous emulsion resin composition excellent weather resistance, stain resistance, and long-term storage stability.
[0007]
The present invention will be explained in detail below.
The agueous emulsion resin composition of the present invention is obtained by emulsion polymerization of an unsaturated monomer composition comprising as essential components yv-methacryloxypropyl trimethoxysilane as component {A}, cyclohexyl methacrylate as component {B}, and at least one unsaturated monomer selected from the group consisting of methyl methacrylate, butyl {(methlascrylate and 2-ethyvlihexyl {meth}acrylate as component {CC} in the presence of a free-radical reactive surfactant. Not only weather resistance and stain resistance but also long-term storage stability can be significantly increased, due to the synergistic action of thege components (A) to {(€} in the present invention. [00081 v-Methacrvlioxzypropyltrimethoxysilanse as component {A} has three hydrolyzable alkoxyl groups and one unsaturated group and can impart excellent weather resistance and stain resistance to the agueous emulsion resin composition of the present invention, due to its high self-crosslinking properties. v-Methacryvlioxypropyltrimethoxysilane is contained eggentially in an amount of 0.1 to 2 wit%, preferably 0.2 to 1 wi? in the unsaturated monomer composition. If the content of v-methacryvlioxypropyl trimethoxysilane is less than 0.1 wtg, weather resistance and stain resistance are decreased. If it is more than 2 wt%, polymerization stability and film-forming properties are decreased. 0009]
Cyclohexyl methacrylate as component (B} can impart mainly weather resistance and stain resistance to the agueous emulsion resin composition of the present invention.
Cyelohexyl methacryviate is contained essentially in an amount of 25 toe 73 wi%, preferably 25 to 70 wt? in the unsaturated moncmeyr composition. If the content of cyclohexyl methacrylate is less than 25 wid, weather resistance and stain resistance ave decreased. If it is more than 75 wiki, polymerization stability and film-forming properties are decreasad.
[0010]
The unsaturated monomer as component (C} is at least one monomer selected from the group consisting of methyl methacrylate, butvl {(methlacrylate, and Z-sthyvihexyl {methlacrylate. Component {CC} can mainly impart weather resistance and stain resistance to the agueocus emulsion resin composition of the present invention.
Component {CC} is preferably contained in an amount of 30 to 70 wig, move preferably 35 to 68 wt % in the unsaturated monomer composition.
[0011]
Various unsaturated monomers other than components {A} to {(C} may be contained in the unsaturated monomer composition guch that the affects of the pregent invention are not reduced.
Thege unsaturated monomers include {methlacrylates having a linear, branched, or cyclic alkyl chain with I to 18 carbon atoms such as methyl acrylate, ethyl {(methlacrviate, iso-butyl {methlacrylate, tert-butyl {(methlacryvlate, cyclohexyl acrylate, lauryl (methacrylate, stearyl (methjlacrylate, and ischornyl {(methl)acrvlate; aromatic vinyl compounds such as styrene, o-methylstyrens, p-methylstyrens, and ethylivinyi benzene; heterocyclic vinyl compounds such as vinylpyrrolidone; hydroxyalkyl (methlacrylates such as 2-hydroxyethyl (methlacryvliate and 2-hydroxypropyl {methlacrylate; pelvalkylens glycol {methlacrylates such as ethylene glycol {(methjacryiate and butyiens givcol {mathlacyrylate; alkylamino {(methlacryvlates such as
N,N-dimaethylaminoethyl {(methlacryviate and
N,.N-dimethylaminopropyl {(methjlacrvlate; vinyl ester compounds such as vinyl formate, vinyl acetate, vinyl propionate, and versatic acid vinyl {trade name}; monoolefin compounds such as ethylene, propylene, butylene, and ischutylene; conjugated diglefin compounds such as butadiene, isoprene, and chloroprene;: o,f f~unsaturated meno-~ or dicarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, cliitraconic acid, itaconic acld, maleic acid, maleic anhydride, and fumaric acid: carboxyl group-containing vinyl compounds such as monchydroxyvethyl {methacrylate phthalate and monchydroxypropyl {methlacrylate oxalate; amineimide group~containing vinyl compounds such as 1,1, 1-trimethylamine methacrylimide; vinvli cvanide compounds such as acrylonitrile and methacryionitrile; o,p-ethylenically unsaturated compounds containing an amide or substituted amide group such as {methlacryviamide, N-methyvlacrvlamide, N,N-dimethyl {(methlacrvliamide, and N,N-dimethylaminopropyl {methlacryvliamide; carbonyl group-containing a, Pb-ethylenically unsaturated compounds such as acrolein, diacetone acrylamide, vinvl methyl ketone, and diacetone acryiate; sulfonic acid group-containing o,f-ethylenically ungaturated compounds such as allyl sulfonate and sodium p-styrene sulfonate; ethylenically unsaturated group-~containing ultraviolet absorbers such as 3-{3H-benzotriazol-2-yvl}-4-hydroxyphenetyl-methacrylate; ethylenically unsaturated group-containing light stabilizers such as 1.,2,2,6,6-pentamethyl-4-pyperidyl methacrylate; and silane coupling agents containing an unsaturated group other than v-methacryloxypropyl trimethoxysilane such as v-methacryloxypropyltriethoxysilane, vinyltriethoxysilane, and vinvitris{f-methoxyvethoxyisilane; and further include epoxy group-containing o,f-ethylenically unsaturated compounds such as glycidyl {meth)acrylate, 3. 4-epoxyoyelohexylimathyl {(methlacrylate, glycidyl winvl eather, glveidyl {meth)allyl ether, and 3, 4-epoxycoyclohexyl {methjlacrylate; multifunctional vinyl compounds such as ethylene glycol di{methlacrylate, trimethyviclpropane tri{methlacrylate, allyl (methacrylate, divinvibenzene, and diallyl phthalate, and the like.
Regarding an epoxy group~-containing o, f-ethylenically unsaturated compound and a multifunctional vinvi compound, the compounds per se can he crosslinked or can be crosslinked with an ethylenically unsaturated compound component having an active hydrogen group or a carbonvl group~containing o,P~-ethylenically unsaturated compound {especially that having a keto group) is introduced and they are crosslinked in combination with a compound,
especially that having two or more hydrazide groups, i1.e., a polvhydrazine compound such as oxalic dihydrazide, succinic dihyvdrazide, adipic dihydrazide, or polyacrylic hydrazide.
[0012]
Further, they can be crosslinked by adding a crosslinking compound without free-radical reactivity, for example, an alkyl silicate such as tetramethoxysilane, tetraethoxysilane, or methyltrimethoxysilane, a multifunctional epoxy compound such as ethylene glycol diglvcidyl ether, polyethylene glycol diglyveidyl ether, glyveercl polyglyeidyl ether, or bisphencol A glyveidyl ether or the like during or after emulsion pelymerization as necessary.
[0013]
In addition, the logical glass transition temperature {hereinafter, may be referred to as Tg) of the unsaturated monomer composition to be used preferably ranges from 0 to 50°C, considering prevention of blocking of coating film surfaces and film Forming properties. The logical glass transition temperature in the present invention ig a value caleulated using the formulae below.
L/Pg{K)=W/ T+ Wo/ Tor Wy/Ta+. WAT,
Tg{* Cl=Tg(K}~273
In the formula, Wy, W,, Wy, .. and W, represent the ratio {wt%} of each unsaturated monomer to the unsaturated monomer composition. Ti, TT, T;, .. and T, represent the glass transition temperature {absolute temperature {(K}) of a homopolymer of each unsaturated monomer. The glass transition temperature of a homopolymer of each unsaturated monomer is described in Polymer
Hand Book (Second Edition, edited by J. Brandrup -E.H.
Immergutb}. [00141
It is essential in the present invention to use a free-radical reactive surfactant in emulsion polymerization of components {4} to {LC} and other unsaturated monomers added as necessary. The free-radical reactive surfactant can mainly impart weather resistance and stain resistance to the agueous &
emulsion resin composition of the present invention. Any free~radical reactive surfactants may be used without limitation as long as they have free-vadical reactivity.
Specific examples thereof include ADEKA REASQCAP {registered trademark, manufactured by ADEKA Corporation}, SE~-L10N, SR-10,
SR-20, SR-30, ER-~20, ER~30, and AQUARON (registered trademarks, manufactured by DAI-ICHT XKOGYO SEIYAKU CO., LTD}, HS8-10, KH-5,
KH-1¢, and BLEMINOL {registered trademarks, manufactured by
Sanyo Chemical Industries, Ltd. }, §8-20 and EMULGEN {registered trademarks, manufactured by KAQ Corporation}, PD-104, PD-420,
PD-430, and the like,
The amount of free-radical reactive surfactant to be used ig preferably 0.5 to 5 wt¥ with respect to the unsaturated monomer composition to be used. If the amount of free-radical reactive surfactant to be used is too small, the polymerization stability may be reduced. On the other hand, if it is too large, water-proof properties may be reduced. Basically, it is egzential for these free-radical reactive surfactants to be added before or during emulsion polymerization so as to emulsify unsaturated monomers. However, post-addition thereof is allowed 20 as to impart stability to the emulsion that had been subjected to emulsion polymerization.
[0015]
Further, a surfactant without reactivity may be used in combination with the above free-radical reactive surfactant.
Examples of a surfactant without reactivity that can be used in combination include anionic surfactants such as dedscyl sodium benzene sulfonate and dedecyl sodium sulfate: nonionic surfactants such as polyoxyethylene lauryl ether and polyoxyethylene nonylphenyl ether; cationic surfactants such as cetyl trimethyl ammonium bromide and lauryl pyridinium chloride; and amphoteric surfactants such as lauryl betaine.
These surfactants without reactivity may be added before or during emulsion polymerization so as to emulsify unsaturated monomers or pest-addition thereof is allowed so as toe impart stability to the emulsion that had been subjected to emulsion polymerization,
[0016]
In addition, polymerization initiators that can be used in emulsion polymerization include persulfate-based initiators such as potassium persulfate and ammonium persulfate; water-soluble azo-type initiators such as 2, 2'-azobig{2-methylpropionamidine} dihydrochloride; organic peroxides such as t-butyl hydroperoxide and cumene hydroperoxide; hydrogen peroxide and the like. These initiators may be used alone or in combination of two or more thereof. In general, the amount of polymerization initiator to be used is 0.1 to 1 wi% with respect to the unsaturated monomer composition to be used.
[0017]
Further, reducing agents may be used together with these polymerization initiators in emulsion polymerization as necessary. These reducing agents include reducing organic compounds such as ascorbic acid, tartaric acid, citric acid, glucose, and formaldehyde sulfoxvliate metal salts; reducing inorganic compounds such as sodium thiosulfate, sodium sulfite, sodium bisulfite, and sodium metablisulfite; and the like. The amount of reducing agent to be used may be appropriately determined such that the effects of the present invention would not be reduced. [001s]
Inaddition, achain transfer agent may be used in emulsion polymerization as necessary. Examples of chain transfer agents include n-~dodecyimercaptan, tert-dedecylmercaptan, n-butylmercaptan, 2Z-ethylhexyl thioglvcolate, 2- mercaptoethanol, £~ mercaptopropionic acid, and the like. Ths amount of chain transfer agent to be used may be appropriately determined such that the effects of the present invention would not be reduced.
[0019]
Emulsion polymerization in the present invention is generally performed under temperature conditions of about 53°C &
to about 100°C, preferably about 50°C to 80°C. The reaction time is not particularly limited and can be appropriately changed, based on the amount of sach component contained, ths reaction temperature, and the like.
[0020]
Stability can be imparted to the agueous emulsion resin composition by adding an acid or base to the agueous emulsion resin composition obtained after emulsion polymerization to neutralize the pH thereof such that the pH becomes 4 to 10 and increasing the surface electric charge of the polymer. General acids that can be used include acetic acid, lactic acid, hydrochloric acid, phosphoric acid, sulfuric acid, and the like.
In addition, general bases that can be used include amine compounds such as triethylamine, ammonia, diethanolamine, diethyvlamincethanoel and alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, and lithium hydroxide.
[0021]
The coating materials of the present invention contain the above aguecus emulsion resin composition. A thickening agent, an antifoaming agent, a pigment {an extender, a color pigment, a hollow balloon, a thermal barrier pigment, and the like}, a dispersing agent, a wetting agent, a Light stabilizer, an ultraviolet absorber, a preservative, an antibacterial agent, and the like may be optionally added to the coating material of the present invention. The coating materials of the present invention may be used as various coating materials such as architectural paint, thermal barrier coating materials, heat-insulating coating materials, ccating materials for siding boards. road marking coating materials, and mortar coating materials. In addition, the coating materials of the praesent invention may be used for materials that can be coated, i.e., paper, fibers, metal, wood, ceramics, and the like. The coating technigue therefor is not limited.
[00221
The present invention will be explained in detail, with reference to Examples and Comparative swmamples. Physical properties of the emulsions obtained in the Examples and the
Comparative examples were evaluated by the methods described below.
[0023] {1} Properties of an agueous emulsion resin composition {1-1} Neonvelatile components
An aqueous emulsion resin composition whose weight had been measured was dried al 105°C for one hour to determine the weight of residue after evaporation. The ratio {wis} of nonvolatile components was calculated, based on the initial welght and the weight of the residues after evaporation. {1-2} Viscosity
The viscosity of an agueocus emulsion resin composition was measured at 23°C at 60 rpm using a BM-type viscometler. {1-3} pH
The pH of the aqueous emulsion resin composition was measured using a pH meter. {1-4} Minimum film forming temperature (hereinafter, may be referred to as MFT)
MFTs were determined using a device for measuring heat-gradient minimum film forming temperature. In addition, the MFT of an aqueous emulsion resin composition which had been left at 50°C for one month was determined in The same manner.
[0024] {2} Evaluation on long-term storage stability
The change rate of MFT was calculated, based on the initial
MFT of the agueocus emulsion resin composition and the MFT of the aguecus emulsion rasin composition which had been left, said
MPTs having been determined as in {1-4}. It was evaluated in accordance with evaluation standards below. (0: The change rate of MFT is 10% or less.
X: The change rate of MPT is more than 10%
[0025] {3} Evaluation on weather resistance and stain resistance
{3-1} Preparation of gloss coating materials 82.6 parts by weight of deionizedwater, 0.8 part by welght of NATROSOL 250HR (manufactured by Hercules Corporation} as a thickening agent, 0.2 part by weight of ammonia walter as a neutralizing agent, 1.1 parts by weight of AMORDEN PS5-14D {manufactured by Daiwa Chemical Industry Co., Ltd.) as a preservative, 4.2 parts by weight of POIZ 521 {manufactured by
KAO Corporation} as a dispersing agent, 1.1 parts by weight of
SN DEFORMER 371 (manufactured by SAN NOPCO LIMITED) as an antifoaming agent, and 210 parts by weight of TIPAQUE CR-97 {manufactured by ISHIHARA SANGYC KATIGHA, LTD.) as titanium oxide were fed into a container in this order, while agitated at about 2000 rpm using a homodisper. The mixture was further agitated at about 2000 rpm for one hour. Then, the mixture was filtered via a 120-mesh Teflon (registered trademark} mesh to obtain 300 parts by welght of a mill base having a solid content of 70 wt¥ {calculated, considering titanium oxide as a solid component}. 300 parts by weight of the obtained mill base, 600 parts by weight of the agueous emulsion resin composition {in the case where the weight ratio of the nonvolatile components was 50 wid: in other cases where the weight ratio of the nonvoiatile components was other than 50 wt%, the amount of the added resin was adjusted such that 300 paris by weight of the resin was contained in each composition, based on the welght of nonvolatile components), o parts by weight of C8-12 {manufactured by Chisso Corporation} as a film forming agent {a=MFT5X6}, and one part by weight of ADEKANCL UH-420 {manufactured by ADEKA Corporation) as a viscosity modifier were fed into another container and were agitated at about 2000 rpm for 10 minutes using a homodisper. Then, the mixture was filtered with 150-mesh Teflon {registered trademark) mesh fo obtain 955 parts by weight of a gloss coating material having a 80l1id content of 53.4 wi% and a pigment content of 15.5 vols {calculated, considering the specific gravity of titanium oxide to be 4.2 and the specific gravity of the agueocus emulsion resin composition to be 1.1}.
[0026] {3-2} Preparation of coated plates
The viscogity of the obtained gloss coating material was adjusted to about 300 mPa 5s {measured using a B-type viscometer at 20 rpm at 23°C) by adding water to the ceating material.
After a flexible board that had been subjected to a sealing treatment was sprayed with 150 g/m” of this coating material using a spraver twice, the coated material was cured at 23°C at 65% in RH for one week to obtain a coated board. This procedural process was repeated to prepare two coated boards in total.
[0027] {3-3} EBvaluation on weather resistance
One of the prepared coated hoards was tested using a
Metaling Weather Meter {Suga Test Instruments) and the gloss retention after irradiation for 400 hrs was determined. An eight bhour-cycle test comprising irradiation for two hours, irradiation for two minutes with water spraving {three cycles}, and dew condensation for two hours {in the atmosphere at 30°C, at 895% in RH, and at a temperature of the coated board of 25°C} on conditions of using the Metaling Weather Meter of a black panel temperature of 63°C, humidity of 50% in RBH, and an illumination intensity at 1.55 kW/m" was conducted. Weather resistance was evaluated in accordance with the standards below. (J: The gloss retention was 70% or higher.
A: The gloss retention was 50% or higher and less than 70%,
X: Phe gloss retention was less than 50%.
[0028] {3-4} Evaluation on stain resistances
Another coated board prepared was exposed to the cutside atmosphere for three months {Tatsuno City, Hyogo Prefecture, at 45° south latitude) and the color difference {AE} before and after the exposure was determined. The stain resistance was avaluated in sccoordance with the standards below. (0: AE was less than 4.
ON: AR was 4 or more and less than 8
KX: AE was 8 or more. [0g29e] <Example 1) 200 parts by weight of deionized water and 0.2 part by weight of ADEKA REASOAP SR-10 {anionic reactive surfactant, manufactured by ADEKA Corporation} were fed inte a polymerization apparatus equipped with an agitator, a thermometer, and a reflux condenser. After the space within the device was sufficiently filled with nitrogen, the temperature was raised to 75°C.
A mixture of 258 parts by weight of deionized water, 9.8 parts by weight of ADEKA REASQAPY SBR-10, 118 parts by weight of methyl methacrylate, 200 parts by weight of cyclohexyl methacrylate, 167 parts by weight of 2-ethylhexvl acrylate, 5 parts by weight of yv-methacryloxypropyl trimethoxysilane, and parts by weight of methacrylic acid that had been emulsified using a homemixer was prepared. One portion (5 wt%) of the emulsified material was added to the inside ¢f the polymerization apparatus, while the temperature in the polymerization apparatus was kept at 75°C.
Next, 0.2 part by weight of potassium persulfate was added to the inside of the polymerization apparatus toe initiate polymerization reaction, which was continued at 80°C for 15 minutes. The remaining portion {25% wii) of the emulsified material and 50 parts by weight of 2% agueocus potassium persulfate sclution were dropped into the polymerization apparatus over four hours. Further, they were reacted at 80°C for two hours and then were cooled to room temperature (25°C).
Finally, 3.5 parts by weight of ammonia water was added to adjust the pH to obtain an agueocus emulsion resin composition of
Example 1. The logical Tg of the unsaturated monomer composition in Example 1 was 15°C. Properties of the obtained agueous emulsion resin composition were as follows: nonvolatile components of 50.3 wits, viscosity {measured using a BM-type viscometer at 60 rpm at 23°C) of 170 mPa-s, pH of 9.0, MFT of 47°C,
[0830]
Example 20
The aqueous emulsion resin composition of Example 2 was obtained by the same procedural steps as those in Example 1, except that an emulsified material comprising 258 parts by weight of deionized water, 9.8 parts by weight of ADEKA REASOAP
SR-10, 22.5 parts by weight of methyl methacrylate, 300 parts by weight of cyclohexyl methacrylate, 160 parts by weight of 2-ethylhexyl acrylate, 2.5 parts by weight of v-methacryloxypropyl trimethoxysilane, 10 parts by weight of methacrylic acid, and 5 parts by weight of Z-hydroxyethyl methacrylate was used in place of the emulsified material of
Example 1. The logical Pg of the unsaturated monomer composition in Example 2 was 20°C. Properties of the obtained agqueous emulsion resin composition were as follows: nonvolatile components of 50.4 wt?, viscosity {measured using a BM-type viscometer at 60 rpm at 23°C) of 190 mPa-s, pH of 8.8, MFT of 46°C. 0031]
LExample 3)
The agusous emulsion resin composition of Example 3 was obtained by the same procedural steps as those in Example 1. except that an emulsified material comprising 235.5 parts by weight of deionized water, 9.8 parts by weight of ADEKA REASOAP
SR~-10, 55 parts by welght of methyl methacrylate, 150 parts by welght of cyclohexyl methacrylate, 150 parts by welght of n-butyl methacrylate, 128.5 parts of n-butyl acrylate, 1.5 parts by weight of v-methacryloxypropyl trimethoxysilane, 12.5 parts by weight of 80% acrylic acid, and 3 parts by weight of diacetone acrylamide was used in place of the emulsified material of Example 1 and after the emulsified material was cooled, a solution of 3.5 parts by weight of ammonia water and 2.6 parts by welght of adipic dihydrazide in 18 parts by welght of deionized water was added. The logical Tg of the unsaturated monomer composition in Example 3 was 20°C. Properties of the obtained agueous emulsion resin composition were as follows: nonvolatile components of 51.1 wid, viscosity {measured using a BM-type viscometer at 60 rpm at 23°C) of 330 mPa s, pHof 7.8,
MFT of 35°C. [00327
Example 4>
The agueocus emulsion resin composition of Example 4 was obtained by the same procedural steps as those in Example 1, except that AQUARON KH-10 (manufactured by DAI-ICHI KOGYO
SEIYAKY CO., LTD} was used in place of ADEKA REASCAP SR-10 in
Example 1. The logical Tg of the unsaturated monomer composition in Example 4 was 15°C. Properties of the obtained aqueous emulsion resin composition were as follows: nonvolatile components of 50.3 wt%, viscosity (measured using a BM-type viscometer at 60 rpm at 23°C} of 150 mPa-s, pH of 8.9, MFT of 48°C.
[0033] {Comparative example 1) 250 parts by weight of deionized water and 5 parts by weight of EMULGERN 147 {polyoxyethylene lauryl ether, manufactured by KAQ Corporation} were fed into a polymerization apparatus eguipped with an agitator, a thermometer, and a reflux condenser. After the space within the device was sufficiently filled with nitrogen, the temperature was raised to 75°C. 75 parts by weight of methyltrimethoxysilane (MIMS) and 50 parts by weight of tetraethoxysilane (TECS) were added, while the temperature in the polymerization apparatus was kept at 75°C and were left for 30 minutes. Further, a mixture of 440 parts by weight of deionized water, 10 parts by weight of AQUARCN KE-10, 223 parts by weight of methyl methacrylate, 75 parts by weight of cyclohexyl methacrylate, 190 parts by welght of 2-ethylhexyl acrviate, 2 parts by weight of y-methacryloxypropyl trimethoxysilane, and 10 parts by weight of methacrylic acid that had been emulsified using a homomixer was prepared. One portion {5 wt%} of the emulsified material was added to the inside of the polymerization apparatus, while the temperature in the polymerization apparatus was kept at 75°C.
Next, 0.2 part by weight of potassium persulfate was added to the inside of the polymerization apparatus to initiate polymerization reaction, which was continued at 80°C for 15 minutes. Further, the remaining portion {85 wt%}] of the emulsified material and 50 parts by welght of 23 agusous potassium persulfate solution were dropped into the polymarization apparatus over four hours, while the temperature in the polymerization apparatus was kept at 80°C. Further, they were reacted at 80°C for two hours and then were cooled to room temperature {25°C}. Finally, 3.5 parts by weight of ammonia water was added to adjust the pH to obtain an agueous emulsion resin gomposition of Comparative example 1. The logical Tg of the unsaturated monomer composition in Comparative example 1 was 10°C. Properties of the obtained agueous emulsion resin composition were as follows: nonvolatile components of 41.8 wid, viscosity {measured using a BM-type viscometer at 60 rpm at 23°C} of 60 mPa's, pH of 5.3, MFT of 38°C.
[0034]
Comparative example 22 200 parts by welght of deionized water and 0.2 part by weight of ADEKA REASQAP SR-10 were fed into a polymerization apparatus equipped with an agitator, a thermometer, and a reflux condenser. After the space within the apparatus was sufficiently filled with nitrogen, the temperature was ralsed to 75°C, A mixture of 260 parts by welght of deionized water, 9.8 parts by weight of ADEKA REASQOAP SR-14, 121 parts by weight of methyl methacrylate, 200 parts by welght of cyclohexyl methacrylate, 169 parts by weight of 2-ethylhexyl acrviate, and parts by weight of methacrylic acid that had been emulsified using a homomixer was prepared. One portion (5 wt} of the emulsified material was added to the inside of the polymerization apparatus, while the temperatures in the polymerization apparatus was kept at 75°C. is
Next, 0.2 part by weight of potassium persulfate was added toe the inside of the polymerization apparatus toe initiate polymerization reaction, which was continued at 80°C for 135 minutes. The remaining portion {95 wif) of the emulsified material and 50 parts by weight of 2% agueocus potassium persulfate solution were dropped into the polymerization apparatus over four hours, while the temperature in the polymerization apparatus was kept at 8¢°C. Further, they were reacted at 80°C for two hours and then were cooled to room temperature {25°C}. Finally, 3.5 parts by weight of ammonia water was added to adjust the pH to obtain an agueaous emulsion resin composition of Comparative example 2. The logical Tg of the unsaturated monomer composition in Comparative example 2 was 15°C. Properties of the obtained aqueous emulsion resin composition were as follows: nonvolatile components of 50.2 wid, viscosity (measured using a BM-type viscometer at 60 rpm at 23°CY of 150 wmPa-s, pH of 8.9, MFT of 45°C.
[0035] (Comparative examples 3)
The agueocus emulsion resin composition of Comparative example 3 was obtained by the same progedural steps as those in Comparative example 2, except that an emulsified material comprising 260 parts by weight of deionized water, 9.8 parts by weight of ADEKA REASCAP SR-10, 305.5 parts by weight of methyl methacrylate, 183 parts by weight of 2-ethylhexyl acrylate, 1.5 parts by weight of yv-methacryloxypropyl trimethoxysilane, and parts by weight of methacrylic acid was used in place of the emulsified material of Comparative example 2. The logical Tg of the unsaturated monomer composition in Comparative examples 3 was 153°C. Properties of the obtained agueous emulsion resin composition were as follows: nonvolatile components of 50.1 wt%, viscosity (measured using a BM-type viscometer at 60 rpm at 23°CY of 190 mPa -s, pH of 9.0, MFT of 42°C. [003s] <Comparative example 43> 189.4 parts by welght of deionized water and 8.8 part by weight of NEWREX R-25 {anionic nonreactive surfactant, manufactured by NOF CORPORATION) were fed into a polymerization apparatus equipped with an agitator, a thermometer, and a reflux condenser. After the space within the apparatus was sufficiently filled with nitrogen, the temperature was raised to 75°C. A nmixture of 230.6 parts by weight of deionized water, 39.2 parts by weight of NEWREX R-23, 131 parts by weight of methyl methacrviate, 200 parts by weight of cyclohexyl methacrylate, 154 parts by weight of 2-ethylhexyl acrylate, 5 parts by weight of v-methacryloxypropyl trimethoxysilane, and 10 parts by weight of methacrylic acid that had been emulsified using a homomixer was prepared. One portion {8 wtf} of the emulsified material was added to the inside of the polymerization apparatus, while the temperature in the polymerization apparatus was kept at 75°C,
Newt, 0.2 part by weight of potassium persulfate was added to the inside of the polymerization apparatus to initiate polymerization reaction, which was continued at 80°C for 15 minutes. The remaining portion (23 wit%}) of the emulsified material and 50 parts by weight of 2% agueosus potassium persulfate solution were dropped into the polymerization apparatus over four hours, while the temperature in the polymerization apparatus was kept at 80°C. Further, they ware reacted at 80°C for two hours and then were cooled to room temperature {25°C}. Finally. 3.5 parts by weight of ammonia water was added to adjust the pH to obtain an agueocus emulsion resin composition of Comparative example 4. The logical Tg of the unsaturated monomer composition in Comparative example 4 was 20°C. Properties of the obtained aguecus emulsion resin composition were as follows: nonvolatile components of 50.2 wid, viscosity {measured using a BM-iype viscometer at 60 rpm at 23°C) of 160 mPa-s, pH of 9.2, MFT of 48°C.
[0037]
LComparvative example 32
The agueous emulsion resin composition of Comparative example 5 was obtained by the same procedural steps as those is in Comparative example 2, except that an emulsified material comprising 260 parts by welght of deionized water, 9.8 parts by weight of ADEKA REASOAP SR-10, 200 parts by weight of cyvolohexyl methacrylate, 285 parts by weight of ethyl acrylate, parts by weight of v-methacryloxypropyl trimethoxysilane, and parts by weight of methacrylic acid was used in place of the emulsified material of Comparative example 2. The logical Tg of the unsaturated monomer composition in Comparative example 5 was 15°C. Properties of the obtained agusous emulsion resin composition were as follows: nonvolatile components of 49.9 wt%, viscosity {measured using a BM-type viscometer at 60 rpm at 23° CY of 160 mPa-s, pH of 8.9, MFT of 28°C.
[0038] {Comparative example &> 200 parts by weight of deionized water and 0.23 part by weight of ADEKA REASCAP SR-10 were fed into a polymerization apparatus equipped with an agitator, a thermometer, and a refiux condenser. After the space within the apparatus was sufficiently filled with nitrogen, the temperature was raised to 75°C. A mixture of 285 parts by weight of deionized water, 9.8 parts by weight of ADEKA REASQAP SR-10. 105 parts by weight of methyl methacrylate, 200 parts by weight of cyclohexyl methacrylate, 160 parte by weight of 2-ethylhenyl acrylate, 10 parts by weight of methacrylic acid, and 25 parts by weight of methacryloxypropyl trimethoxysilane that had been emulsified using a homomixer was prepared. One portion {5 wt%} of the emulsified material was added to the inside of the polymerization apparatus, while the temperature in the polymerization apparatus was kept at 75°C.
Next, 0.2 part by welght of potassium persulfate was added to the inside of the polymerization apparatus to initiate polymerization reaction, which was continued at 80°C for 15 minutes. The remaining portion {95 wit%} of the emulsified material and 50 parts by weight of 2% aqueous potassium persulfate solution were dropped into the polymerization apparatus over four hours, while the temperature in the is polymerization apparatus was kept at 80°C. Further, they were reacted at 830°C for two hours and then were cooled to room temperature (25°C). Finally, 3.5 paris by weight of ammonia water was added to adjust the pH to obtain an agueous emulsion resin composition of Comparative example 6. The logical Tg of the unsaturated monomer composition in Comparative example 6 was 15°C. Properties of the obtained agueous emulsion resin composition were as follows: nonvolatile components of 50.2 wid, viscosity {measured using a BM-type viscometer at 60 rpm at 23° CY of 140 wPa-g, pH of 8.9%, MFT of higher than $0°C.
[0039]
Comparative eaxampls 75
The same procedural steps as those in Comparative example 2 were conducted, except that an emulsified material comprising 260 parts by weight of deionized water, 9.8 parts by weight of
ADEKA REASCAR SR-10, 12.5 parts by weight of methyl methacrylate, 475% parts by weight of cyclchexyl methacrylate, 2.5 parts by weight of v-methacryloxypropyl trimethoxrysilane, and 10 parts by weight of methacrylic acid was used in place of the emulsified material of Comparative example 2, but coagulation occurred during the reaction to form a gel. The logical Tg of the unsaturated monomer composition in Comparative example 7 was 85°C. [00401
Evaluation results on weather registance, stain resistance, and long-term storage stability of the agueous emulsion resin compositions obtained in Examples I to 4 and
Comparative examples 1 to 7 are shown in Tables 1 and 2. The abbreviated term in the tables, i.e., “MMA” means methyl methacrylate, “2EHA” means Z-ethyvlhexyl acrylate, "MAa” means methacrylic acid, “2HEMA” means 2-hydroxyethyl methacrylate, “nBMAY means n~butyvl methacrylate, “"nBA” means n-butyl acrylate, “Aa” means acrylic acid, “DAA” means diacetone acrylamide,
PEEAY means ethyl acrylate, “MIMS” means methvitrimethoxysilane, and “TEOSY means tetraethoxysilane.
{Table 1] — "1 ” AA SSS — xample i Example 2 Evampie 3 i 2 i a inn a a Ak bb a. ° Exaile 4 : Tut \ 5.5 wih fevers sss egssessersansbees 1 om 00 wt ; fwk : i ¥ NasasssstLastassLdiis iLL i frome N ~ } 3 3 AANA AAA A A A A A A nn mmm on i Compensat B i ; i jrm—————— i Lampe i EB i AQ with i 80 wt i hit sm ! om 30 wth | wk ; : i Snnnnnns sn RAIA NAA 13s Fae is es i i Se
Po i BE at i aa 1 : TU e— Lo MMARIG wi MMA 4.5 wil MMA TT wk i Raa a y i oe : tA 3 { | RRMA A we L 2EHA 32 wil Do nmmaanw 0 MMaZiSano i i i SIA NE wilh . : { SA 33 oy, t
ST 1 : Po oaBAZETwts | WHA SRA WE ; Frente mE AE EA i Other unsaturated | i Bi : i 3 : i wid { 8 } i i monomers i Maa 2 with i . dha 2 wk i Aa lwih i i { SEMA 1 wal § ; : : SHEMA 1 wi% ! DAAm 1 wil { Mas & wih i
F : ! rr ERE A a RY { Fres-radical reactive ! { : i
VU surfactant 3 Praga { : surfactant sant i Present i Grasent { ; {
Hrasent i Frasent i : RR ORE A RR RRR Se i : : i Logiesl Tg 80) 3 HE : : i ” ] ie i 240 i 3 } £4 ¥ a0 5 i 3 ; i ad IN i \ i :
MFT (= Q) before being Co a 7 i i eft a7 | a 3 : i # i 4% : facets aannaanannanns, {
Long-term storage : 1
LE t : i i i stability © O : 0 O ; : i o i : SR } : : } ArrrrraaaaaaE a aaa
Went? OPTI TS {
Weather rosistance | 3 ; 0 i : : ! i : \ ; } : © ; © : rare be ba :
Trrtroes : nse aS = . + k 3 : {: Stain resistance Or ; i 3 : i : Qo i Go o 3 + § 3. { i : meme Ed re ee RAT i i i
{0042} {Table 2]
Comparative | Comparstive {| Comparative | Lomparstive {| Comparative | Comparative { Comparative i example Poexamnle 201 Loxavole 3 8 example d 1 examole § 1 example § i example 7} i Cumponent & ! 0.4 wih : = i 8.3 wih i Powik \ Twih { 5 wth P08 wii ! {Component 8 ! PE wt i 4G wil i = P40 wl bodowd 1 aval i a5 wil §
A i MMA : MMA i MBA i RAMA i § MMA i i
Lo “ 445 wi% 1 242wty 1 Bibw¥ 4 282wk Vo Mwts MMA : + Component po i ot i fe i arms t h : re i wa i i i ZEA i 2EHA i 2EHA i EHS § 2EHA Po 20wtE i i 38 wil {338 wih 38Bwih 1 308 wih} I RR £1 i § {Other \ : : i EA Hhwik | : : \ unsaturated Vo oMAa2at% | MAa2 wid | MAa Zw | Maa Zz wh Maa LoMAs 2 wii] MAa2wad }oraonomars i i ; : } wth § i ;
Frae-radical ! { { : i ; ! rasative ; Frasent ! Frasant i Present | Absent 3 Pregent 4 Frese i Fragant : i surfactant ; } i i ; ! ! i MTMES and TEOS : Present Absent. i Absent { Absent i Absent ; Absent { Absent ;
Ulogieal TRO | 0 i 15 i is i 20 i 15 ; 18 i as :
MFT (2 05 before | : : ; { {Higher thar ; : ;
MET 5 before 18 | £6 az ; 48 2a i ghe v har ; an ; being loft i | i i } i 80 i i : i i i \ i i i i i ; { i : i i
Long-term i : i ; © ; « : bh § * ; G i Q ; O i O i = i = i storage stability 3 | i i i ; i i
Lo bs bb ——————
Wanther : o EL 4 a Fa Lx ew {iresistancs i i i i i i i : Stain resistance | 0 \ a A ; Fal i X | SA i 2 i $1) Comparative example 5 was not evaluated because a coating film could not && prepared, due to an
MFT of higher than 80° C. *2: Comparative example 6 was not evaluated because a gel was formed during the reaction.
[0043]
It is shown that coating materials using the agueous emulsion resin compositions obtained in Examples 1 to 4 were excellent in weather resistance, stain resistance, and long-term storage stability. In contrast, it is shown that
Comparative example 1 corresponding to the water dispersion resin composition described in Patent publication 1 was excellent in weather resistance and staln resistance, but was poor in long-term storage stability. It was indicated that
Comparative example 2 was poor in weather resistance and stain resistance because it did not contain component {A}. It was indicated that Comparative example 3 was poor in weather registance and stain resistance because it did not contain component (BB). It was indicated that Comparative example 4 was poor in weather resistance and stain resistance because 1t did not use a free-radical reactive surfactant. It was indicated that Comparative example 5 was peor in weather resistance and stain resistance because it 4id not contain component {C}.
Comparative example 6 could not be evaluated because the amount of the contained component {A} was in excess, which resulted in significantly reduced film forming properties. Comparative example 7 could not be evaluated because the amount of the contained component {(B} was in excess, which resulted in reduced polymerization stability.
Claims (2)
- CLATME i. An aguecus emulsion resin composition obtained by emulsion polvmerization of an unsaturated monomer composition comprising {A} v-methacrvioxypropyl trimethowxysilans, {(B} cyclohexyl methacrylate, and (CC) at least one unsaturated monomer selected from the group consisting of methyl methacrylate, butyl {(methlacrylate and 2-sthyvlihexyl {methlacrylate in thes presence of a free-radical reactive surfactant, wherein the unsaturated monomer composition contains 0.1 to 2 wt% of (A} y-methacryloxypropyl trimaethoxysilane and 25 to 75 wtit of (B) cyclohexyl mathacrylate.
- 2. A coating material containing the agusous emulsion resin composition according to Claim 1.
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| JP2009194540A JP2011046783A (en) | 2009-08-25 | 2009-08-25 | Aqueous emulsion resin composition and coating obtained by blending the same |
| PCT/JP2010/064183 WO2011024759A1 (en) | 2009-08-25 | 2010-08-23 | Aqueous emulsion type resin composition and coating materials containing same |
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| JP7099692B2 (en) * | 2018-03-28 | 2022-07-12 | 日本カーバイド工業株式会社 | Paper coating (meth) acrylic resin emulsions, films, and laminates |
| JP6512352B2 (en) * | 2018-07-09 | 2019-05-15 | 日立化成株式会社 | Thermal radiation paint and light emitting diode (LED) illumination coated with the same, heat sink, back sheet for solar cell module |
| WO2020085263A1 (en) * | 2018-10-22 | 2020-04-30 | 株式会社日本触媒 | Aqueous dispersion, production method for aqueous dispersion, and use for aqueous dispersion |
| CN114044857B (en) * | 2021-12-02 | 2024-04-09 | 万华化学集团股份有限公司 | Preparation method of polyacrylate aqueous dispersion with carboxyl-rich surface, dispersion and application of polyacrylate aqueous dispersion |
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| JP2007197644A (en) * | 2006-01-30 | 2007-08-09 | Nippon Shokubai Co Ltd | alpha-(HYDROXYALKYL)ACRYLATE COPOLYMER |
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