JP2008120904A - Water-dispersible resin composition and coating containing the same - Google Patents
Water-dispersible resin composition and coating containing the same Download PDFInfo
- Publication number
- JP2008120904A JP2008120904A JP2006305352A JP2006305352A JP2008120904A JP 2008120904 A JP2008120904 A JP 2008120904A JP 2006305352 A JP2006305352 A JP 2006305352A JP 2006305352 A JP2006305352 A JP 2006305352A JP 2008120904 A JP2008120904 A JP 2008120904A
- Authority
- JP
- Japan
- Prior art keywords
- mass
- group
- water
- resin composition
- dispersible resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000011342 resin composition Substances 0.000 title claims abstract description 41
- 239000011248 coating agent Substances 0.000 title claims description 11
- 238000000576 coating method Methods 0.000 title claims description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 48
- 239000000178 monomer Substances 0.000 claims abstract description 37
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 34
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 15
- 229920001515 polyalkylene glycol Polymers 0.000 claims abstract description 13
- 125000003827 glycol group Chemical group 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 8
- 230000009477 glass transition Effects 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 26
- -1 polysiloxane Polymers 0.000 description 26
- 239000003973 paint Substances 0.000 description 21
- 238000011109 contamination Methods 0.000 description 14
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 150000003377 silicon compounds Chemical class 0.000 description 8
- 229920001223 polyethylene glycol Polymers 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 230000001603 reducing effect Effects 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 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
- 238000013461 design Methods 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-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
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 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
- 229920006362 Teflon® Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 125000003368 amide group Chemical group 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
- 239000002518 antifoaming agent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 239000003999 initiator 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
- 238000002156 mixing Methods 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000002904 solvent 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
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- NWPIOULNZLJZHU-UHFFFAOYSA-N (1,2,2,6,6-pentamethylpiperidin-4-yl) 2-methylprop-2-enoate Chemical compound CN1C(C)(C)CC(OC(=O)C(C)=C)CC1(C)C NWPIOULNZLJZHU-UHFFFAOYSA-N 0.000 description 1
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 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
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- JJRUAPNVLBABCN-UHFFFAOYSA-N 2-(ethenoxymethyl)oxirane Chemical compound C=COCC1CO1 JJRUAPNVLBABCN-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- OWHSTLLOZWTNTQ-UHFFFAOYSA-N 2-ethylhexyl 2-sulfanylacetate Chemical compound CCCCC(CC)COC(=O)CS OWHSTLLOZWTNTQ-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 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
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-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
- 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
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 241000047703 Nonion Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 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
- 239000004809 Teflon Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- ZRPMSGIYVIZJMH-UHFFFAOYSA-N acetonitrile;prop-2-enoic acid Chemical compound CC#N.OC(=O)C=C ZRPMSGIYVIZJMH-UHFFFAOYSA-N 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000001204 arachidyl 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])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 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
- 230000003796 beauty Effects 0.000 description 1
- 230000008901 benefit 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
- 230000015572 biosynthetic process Effects 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
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- HCOMFAYPHBFMKU-UHFFFAOYSA-N butanedihydrazide Chemical compound NNC(=O)CCC(=O)NN HCOMFAYPHBFMKU-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 229960004106 citric acid Drugs 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000356 contaminant Substances 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
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical group CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 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
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 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
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- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 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
- 239000008268 mayonnaise Substances 0.000 description 1
- 235000010746 mayonnaise Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 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 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
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- GSGDTSDELPUTKU-UHFFFAOYSA-N nonoxybenzene Chemical compound CCCCCCCCCOC1=CC=CC=C1 GSGDTSDELPUTKU-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 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
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000011158 quantitative evaluation Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
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- 230000009257 reactivity Effects 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 229940083575 sodium dodecyl sulfate Drugs 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
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- 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
- 238000005507 spraying Methods 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
- 229960001367 tartaric acid Drugs 0.000 description 1
- 230000002123 temporal effect Effects 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
- 238000012360 testing method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- FUSUHKVFWTUUBE-UHFFFAOYSA-N vinyl methyl ketone Natural products CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Abstract
Description
本発明は、耐候性、耐汚染性及び安定性に優れる水分散性樹脂組成物及びこれを含む塗料に関するものである。 The present invention relates to a water-dispersible resin composition excellent in weather resistance, stain resistance and stability, and a coating comprising the same.
現在、建物、構造物の美観保護のため、低汚染型の塗料、被覆材が一般的に塗装されている。その中で満足されるようなものは、殆どがケイ素系化合物を含有する溶剤系無機塗料、有機無機ハイブリッド樹脂由来のものであった。これは、富田らが示したように（非特許文献１を参照）、それら塗料で一般的に使用されるアルコキシル基含有オリゴマーが塗膜形成時に塗膜表面に移行し、加水分解、シロキサン結合を形成すると同時に親水性のシラノール基を効率的に発生させることで塗膜表面に親油性の汚染物質がなじみ難くなったり、降雨によるセルフクリーニングによって低汚染機能に優れ、美観維持ができるからである。 Currently, low-contamination paints and coating materials are generally applied to protect the beauty of buildings and structures. Most of them were derived from solvent-based inorganic paints and organic-inorganic hybrid resins containing silicon compounds. As shown by Tomita et al. (See Non-Patent Document 1), the alkoxyl group-containing oligomers generally used in these paints migrate to the surface of the paint film during the formation of the paint film, causing hydrolysis and siloxane bonding. This is because, by forming hydrophilic silanol groups efficiently at the same time as forming, it becomes difficult for a lipophilic contaminant to become familiar with the surface of the coating film, and self-cleaning due to rain is excellent in a low contamination function and can maintain aesthetics.
このように、低汚染性を発現させるために多量のアルコキシル基を必要とする低汚染型塗料に関しては、その官能基が水との反応性に富むことから水系樹脂を使用した塗料の設計は難しく、溶剤系樹脂を用いることが一般的であった。 Thus, for low-contamination paints that require a large amount of alkoxyl groups to develop low-contamination properties, it is difficult to design paints that use water-based resins because their functional groups are highly reactive with water. In general, a solvent-based resin is used.
このような背景のもと、アルコキシル基をポリアルキレングリコールと一部反応させることで、水系塗料用の低汚染化剤として機能させることが提案されている（例えば、特許文献１を参照）。この低汚染化剤を配合した塗料は、耐汚染性に優れているものの、経時安定性が悪いという問題がある。 Under such a background, it has been proposed to cause an alkoxyl group to partially react with a polyalkylene glycol so as to function as a low contamination agent for water-based paints (see, for example, Patent Document 1). A paint containing this low-contamination agent has a problem of poor stability over time although it is excellent in stain resistance.
反応性シリル基を有しガラス転移温度が−２０〜１０℃である合成エマルジョンと片末端がＯＨ基であるポリオキシアルキレン鎖を有し水酸基価が５〜１５０ＫＯＨｍｇ／ｇであるポリシロキサン化合物とを含む塗料も提案されている（例えば、特許文献２を参照）。この塗料では、上記特許文献１の塗料の耐汚染性に加えて経時安定性に優れる結果が得られているが、耐候性に劣るという問題がある。 A synthetic emulsion having a reactive silyl group and a glass transition temperature of −20 to 10 ° C. and a polysiloxane compound having a polyoxyalkylene chain having one end of an OH group and a hydroxyl value of 5 to 150 KOHmg / g The coating material containing is also proposed (for example, refer patent document 2). In this paint, in addition to the stain resistance of the paint of the above-mentioned Patent Document 1, a result that is excellent in stability over time is obtained, but there is a problem that it is inferior in weather resistance.
一方で、水性樹脂エマルジョンに対してアルコキシル基含有ケイ素系化合物を導入する方法が種々提案されており、塗料の低汚染化の有力な手段として研究されている。 On the other hand, various methods for introducing an alkoxyl group-containing silicon compound into an aqueous resin emulsion have been proposed and studied as an effective means for reducing the contamination of paints.
例えば、特許文献３では、加水分解性シリル基を持ったケイ素系化合物と不飽和単量体とを乳化重合により共重合させて得られる樹脂が提案されている。特に不飽和基を有するケイ素系化合物を共重合する場合、１％程度の少量のケイ素系化合物を導入し、耐水性、耐候性などの耐久性を付与するには有効な手段であるが、低汚染化のために１０％等多量のケイ素系化合物を導入しようとすると、内部架橋が進行し成膜性が損なわれたり、あるいは粒子間架橋が原因で安定性が損なわれる。そのため、実質、多量のケイ素系化合物を導入することが不可能であることから、上記低汚染化のための樹脂設計ができない。 For example, Patent Document 3 proposes a resin obtained by copolymerizing a silicon compound having a hydrolyzable silyl group and an unsaturated monomer by emulsion polymerization. Particularly when copolymerizing a silicon compound having an unsaturated group, it is an effective means for introducing a small amount of silicon compound of about 1% and imparting durability such as water resistance and weather resistance. If an attempt is made to introduce a large amount of silicon compound such as 10% for the purpose of contamination, the internal crosslinking proceeds and the film formability is impaired, or the stability is impaired due to interparticle crosslinking. For this reason, since it is impossible to introduce a large amount of silicon compound, it is impossible to design a resin for reducing the contamination.
特許文献４では、低汚染化を目的として、アルコキシル基含有ケイ素系化合物の存在下、不飽和単量体を乳化重合して得られる高分子ラテックスと、ヒドラジン誘導体とからなる塗料が提案されている。しかしながら、低汚染化に関与するアルコキシル基の残存率が低く、またそのケイ素系化合物に少なくとも１つ以上のアルキル基を有するため、その疎水基が原因で十分に低汚染化することができない。 Patent Document 4 proposes a paint comprising a polymer latex obtained by emulsion polymerization of an unsaturated monomer in the presence of an alkoxyl group-containing silicon compound and a hydrazine derivative for the purpose of reducing contamination. . However, the residual rate of alkoxyl groups involved in the reduction of contamination is low, and the silicon-based compound has at least one alkyl group, so that the contamination cannot be sufficiently reduced due to the hydrophobic group.
特許文献５では、実施例において末端がＯＨ基のポリアルキレングリコール鎖を有する非イオン性化合物（ここでは非イオン性界面活性剤）の存在下でエチレン性不飽和単量体を乳化重合させると同時にシリケートを別添する操作を行っている。しかしながら、特許文献５は耐候性付与が目的で三官能アルキルシリケート化合物を使用しており、その疎水基が原因で十分に低汚染化することができない。 In Patent Document 5, in the examples, an ethylenically unsaturated monomer is emulsion-polymerized in the presence of a nonionic compound having a polyalkylene glycol chain having an OH group at the end (here, a nonionic surfactant). An operation to attach a silicate is performed. However, Patent Document 5 uses a trifunctional alkyl silicate compound for the purpose of imparting weather resistance, and cannot sufficiently reduce contamination due to its hydrophobic group.
また、特許文献６は、四官能シリケート縮合物および部分加水分解物を低汚染化剤として用いる方法を提案しており、セルフクリーニングを付与するには良策と思われる。しかしながら、耐候性および低汚染化が未だ十分とは言えない。 Patent Document 6 proposes a method of using a tetrafunctional silicate condensate and a partial hydrolyzate as a low-contaminating agent, which seems to be a good measure for providing self-cleaning. However, it cannot be said that the weather resistance and the low contamination are still sufficient.
更に、特許文献７では、乳化重合中に四官能のシリケート化合物、部分加水分解物及びシリコン成分とシロキサン結合を形成可能なシランカップリング剤を使用することで耐候性、耐汚染性を向上させることが提案されている。しかしながら、四官能のシリケート化合物を使用しているため、重合中にゲル化したり、経時で増粘するなど不安定になる。 Furthermore, in Patent Document 7, the weather resistance and stain resistance are improved by using a tetrafunctional silicate compound, a partial hydrolyzate, and a silane coupling agent capable of forming a siloxane bond with a silicon component during emulsion polymerization. Has been proposed. However, since a tetrafunctional silicate compound is used, it becomes unstable such as gelation during polymerization or thickening with time.
したがって、本発明は、上記実情に鑑みてなされたものであり、安定性、耐候性及び耐汚染性に優れる水分散性樹脂組成物を提供することを目的とする。 Accordingly, the present invention has been made in view of the above circumstances, and an object thereof is to provide a water-dispersible resin composition that is excellent in stability, weather resistance and stain resistance.
そこで、本発明者らは水分散性樹脂組成物について鋭意検討を重ねた結果、不飽和基を有するシランカップリング剤を含む不飽和単量体組成物に対して、１〜３個の加水分解性アルコキシル基を有するアルキルアルコキシシラン化合物もしくはその加水分解物と、４個の加水分解性アルコキシル基を有するアルコキシシラン化合物もしくはその加水分解物と、末端がＯＨ基であるポリアルキレングリコール鎖を有する非イオン性化合物とが特定の割合で存在する下で、不飽和単量体組成物を乳化重合して得られる水分散性樹脂組成物が、安定性、耐候性及び耐汚染性に優れることを見出し、本発明を完成するに至った。 Accordingly, as a result of intensive studies on the water-dispersible resin composition, the present inventors have obtained 1 to 3 hydrolysiss with respect to an unsaturated monomer composition containing a silane coupling agent having an unsaturated group. Alkyl alkoxysilane compound having a functional alkoxyl group or a hydrolyzate thereof, an alkoxysilane compound having four hydrolyzable alkoxyl groups or a hydrolyzate thereof, and a non-ion having a polyalkylene glycol chain having a terminal OH group The water-dispersible resin composition obtained by emulsion polymerization of the unsaturated monomer composition in the presence of a specific compound in a specific ratio has been found to be excellent in stability, weather resistance and stain resistance, The present invention has been completed.
即ち、本発明は、不飽和単量体組成物（Ｘ）に対して、１〜３個の加水分解性アルコキシル基を有するアルキルアルコキシシラン化合物もしくはその加水分解物（Ａ）が０．１〜３０質量％、４個の加水分解性アルコキシル基を有するアルコキシシラン化合物もしくはその加水分解物（Ｂ）が０．１〜３０質量％及び末端がＯＨ基であるポリアルキレングリコール鎖を有する非イオン性化合物（Ｃ）が０．１〜５質量％存在する下で、不飽和単量体組成物（Ｘ）を乳化重合して得られる水分散性樹脂組成物であって、不飽和単量体組成物（Ｘ）が、不飽和基を有するシランカップリング剤を０．１〜２質量％含む水分散性樹脂組成物である。
１〜３個の加水分解性アルコキシル基を有するアルキルアルコキシシラン化合物もしくはその加水分解物（Ａ）と４個の加水分解性アルコキシル基を有するアルコキシシラン化合物もしくはその加水分解物（Ｂ）とは質量比で９０：１０〜２５：７５であることが好ましい。
また、不飽和基を有するシランカップリング剤を除いた不飽和単量体組成物（Ｘ）の理論ガラス転移温度は−２０℃以上であることが好ましい。
更に、本発明は、上記水分散性樹脂組成物を含む塗料である。
That is, in the present invention, the unsaturated alkoxyl monomer composition (X) contains 0.1 to 30 alkylalkoxysilane compounds having 1 to 3 hydrolyzable alkoxyl groups or hydrolysates thereof (A). Nonionic compound having a polyalkylene glycol chain of 0.1 to 30% by mass of an alkoxysilane compound having 4 hydrolyzable alkoxyl groups or a hydrolyzate thereof (B) and having an OH group at the end. C) is a water-dispersible resin composition obtained by emulsion polymerization of the unsaturated monomer composition (X) in the presence of 0.1 to 5% by mass, the unsaturated monomer composition ( X) is a water-dispersible resin composition containing 0.1 to 2% by mass of a silane coupling agent having an unsaturated group.
An alkyl alkoxysilane compound having 1 to 3 hydrolyzable alkoxyl groups or a hydrolyzate thereof (A) and an alkoxysilane compound having 4 hydrolyzable alkoxyl groups or a hydrolyzate thereof (B) are in a mass ratio. 90:10 to 25:75.
Moreover, it is preferable that the theoretical glass transition temperature of unsaturated monomer composition (X) except the silane coupling agent which has an unsaturated group is -20 degreeC or more.
Furthermore, this invention is a coating material containing the said water dispersible resin composition.
本発明によれば、安定性、耐候性及び耐汚染性に優れる水分散性樹脂組成物を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the water dispersible resin composition excellent in stability, a weather resistance, and stain resistance can be provided.
以下、本発明を詳細に説明する。
本発明による水分散性樹脂組成物は、１〜３個の加水分解性アルコキシル基を有するアルキルアルコキシシラン化合物もしくはその加水分解物（Ａ）と、４個の加水分解性アルコキシル基を有するアルコキシシラン化合物もしくはその加水分解物（Ｂ）と、末端がＯＨ基であるポリアルキレングリコール鎖を有する非イオン性化合物（Ｃ）との存在下で、不飽和基を有するシランカップリング剤を含む不飽和単量体組成物（Ｘ）を乳化重合することにより得られるものである。
Hereinafter, the present invention will be described in detail.
The water-dispersible resin composition according to the present invention comprises an alkylalkoxysilane compound having 1 to 3 hydrolyzable alkoxyl groups or a hydrolyzate thereof (A) and an alkoxysilane compound having 4 hydrolyzable alkoxyl groups. Alternatively, an unsaturated monomer containing a silane coupling agent having an unsaturated group in the presence of the hydrolyzate (B) and a nonionic compound (C) having a polyalkylene glycol chain having an OH group at the end. It is obtained by emulsion polymerization of the body composition (X).
本発明において（Ａ）成分として使用される１〜３個の加水分解性アルコキシル基を有するアルキルアルコキシシラン化合物は、以下の一般式で表される。
（Ｒ１）ａ−Ｓｉ−（ＯＲ２）４−ａ
式中、Ｒ１は炭素数１〜１０、好ましくは炭素数１〜４のアルキル基又はフェニル基であり、Ｒ２は炭素数１〜１０、好ましくは炭素数１〜４のアルキル基、アラキル基又はアリール基であり、ａは１〜３の整数である。Ｒ１の炭素数が１０を超えると反応性が低下する。Ｒ１の具体例としてはメチル基、エチル基、ｎ−プロピル基、ｉｓｏ−プロピル基などが挙げられる。尚、Ｒ１が２つ以上存在する場合、Ｒ１は同一であっても異なっていてもよい。Ｒ２の炭素数が１０を超えるとアルコキシル基の加水分解性や反応性が低下する。Ｒ２の具体例としてはメチル基、エチル基、ｎ−プロピル基、ｉｓｏ−プロピル基、ベンジル基、フェニル基などが挙げられる。尚、Ｒ２が２つ以上存在する場合、Ｒ２は同一であっても異なっていてもよい。また、（Ａ）成分として、上記アルキルアルコキシシラン化合物のアルコキシル基（ＯＲ２）が加水分解されたもの、即ち、上記一般式においてＲ２が水素原子である化合物を用いてもよい。Ｒ２が２つ以上存在するアルキルアルコキシシラン化合物の場合、その加水分解物は、すべてのＲ２が水素原子であってもよいし一部が水素原子であってもよい。
The alkylalkoxysilane compound having 1 to 3 hydrolyzable alkoxyl groups used as the component (A) in the present invention is represented by the following general formula.
(R 1 ) a -Si- (OR 2 ) 4-a
In the formula, R 1 is an alkyl group or phenyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, and R 2 is an alkyl group or aralkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms. Or it is an aryl group and a is an integer of 1-3. When the carbon number of R 1 exceeds 10, the reactivity decreases. Specific examples of R 1 include a methyl group, an ethyl group, an n-propyl group, and an iso-propyl group. In addition, when two or more R 1 exists, R 1 may be the same or different. The number of carbon atoms in R 2 is a hydrolyzable or reactive alkoxyl group is reduced more than 10. Specific examples of R 2 include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, a benzyl group, and a phenyl group. In addition, when two or more R 2 exists, R 2 may be the same or different. As the component (A), a compound obtained by hydrolyzing the alkoxyl group (OR 2 ) of the alkylalkoxysilane compound, that is, a compound in which R 2 is a hydrogen atom in the general formula may be used. In the case of an alkylalkoxysilane compound in which two or more R 2 are present, in the hydrolyzate, all R 2 may be hydrogen atoms or a part thereof may be hydrogen atoms.
不飽和単量体（Ｘ）を乳化重合させる際に、１〜３個の加水分解性アルコキシル基を有するアルキルアルコキシシラン化合物もしくはその加水分解物（Ａ）は不飽和単量体（Ｘ）に対して０．１〜３０質量％、好ましくは５〜２０質量％使用しなければならい。（Ａ）成分が０．１質量％未満であると、得られる水分散性樹脂組成物の耐候性が不十分となり、３０質量％を超えると耐汚染性が不十分となる。 When the unsaturated monomer (X) is subjected to emulsion polymerization, the alkylalkoxysilane compound having 1 to 3 hydrolyzable alkoxyl groups or the hydrolyzate (A) thereof is used with respect to the unsaturated monomer (X). 0.1 to 30% by mass, preferably 5 to 20% by mass. When the component (A) is less than 0.1% by mass, the resulting water-dispersible resin composition has insufficient weather resistance, and when it exceeds 30% by mass, the stain resistance becomes insufficient.
本発明において（Ｂ）成分として使用される４個の加水分解性アルコキシル基を有するアルコキシシラン化合物は、以下の一般式で表される。
Ｓｉ−（ＯＲ３）４
式中、Ｒ３は炭素数１〜１０、好ましくは炭素数１〜４のアルキル基、アラキル基又はアリール基である。Ｒ３の炭素数が１０を超えると、その電子供与性が高いためアルコキシル基の加水分解性が低下する。Ｒ３の具体例としてはメチル基、エチル基、ｎ−プロピル基、ｉｓｏ−プロピル基、ベンジル基、フェニル基などが挙げられる。尚、Ｒ３は同一であっても異なっていてもよい。また、（Ｂ）成分として、上記アルコキシシラン化合物のアルコキシル基（ＯＲ３）が加水分解されたもの、即ち、上記一般式においてＲ３のすべて又は一部が水素原子である化合物を用いてもよい。
The alkoxysilane compound having four hydrolyzable alkoxyl groups used as the component (B) in the present invention is represented by the following general formula.
Si- (OR 3 ) 4
Wherein, R 3 is 1 to 10 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, arachidyl group or an aryl group. When the carbon number of R 3 exceeds 10, the hydrolyzability of the alkoxyl group is lowered because of its high electron donating property. Specific examples of R 3 include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, a benzyl group, and a phenyl group. R 3 may be the same or different. Further, as the component (B), a compound in which the alkoxyl group (OR 3 ) of the alkoxysilane compound is hydrolyzed, that is, a compound in which all or a part of R 3 in the general formula is a hydrogen atom may be used. .
不飽和単量体（Ｘ）を乳化重合させる際に、４個の加水分解性アルコキシル基を有するアルコキシシラン化合物もしくはその加水分解物（Ｂ）は不飽和単量体（Ｘ）に対して０．１〜３０質量％、好ましくは５〜２０質量％使用しなければならない。（Ｂ）成分が０．１質量％未満であると、得られる水分散性樹脂組成物の耐汚染性が不十分となり、３０質量％を超えると重合安定性及び経時安定性が不十分となる。 When the unsaturated monomer (X) is subjected to emulsion polymerization, the alkoxysilane compound having four hydrolyzable alkoxyl groups or the hydrolyzate (B) thereof is added to the unsaturated monomer (X) in an amount of 0.8. 1-30% by weight, preferably 5-20% by weight, must be used. When the component (B) is less than 0.1% by mass, the resulting water-dispersible resin composition has insufficient stain resistance, and when it exceeds 30% by mass, the polymerization stability and stability over time are insufficient. .
本発明において、１〜３個の加水分解性アルコキシル基を有するアルキルアルコキシシラン化合物もしくはその加水分解物（Ａ）と４個の加水分解性アルコキシル基を有するアルコキシシラン化合物もしくはその加水分解物（Ｂ）との質量比は、９０：１０〜２５：７５であることが好ましく、６０：４０〜４０：６０であることが更に好ましい。（Ａ）成分が過剰であると、得られる水分散性樹脂組成物の耐汚染性が低下することがあり、一方、（Ｂ）成分が過剰であると、得られる水分散性樹脂組成物の重合安定性及び経時安定性が低下することがある。 In the present invention, an alkylalkoxysilane compound having 1 to 3 hydrolyzable alkoxyl groups or a hydrolyzate thereof (A) and an alkoxysilane compound having 4 hydrolyzable alkoxyl groups or a hydrolyzate thereof (B) The mass ratio is preferably 90:10 to 25:75, and more preferably 60:40 to 40:60. If the component (A) is excessive, the stain resistance of the resulting water-dispersible resin composition may be reduced. On the other hand, if the component (B) is excessive, the resulting water-dispersible resin composition Polymerization stability and stability over time may decrease.
本発明において（Ｃ）成分として使用されるポリアルキレングリコール鎖を有する非イオン性化合物は、末端がＯＨ基であることを必須とする。具体的にはポリエチレングリコール、ポリプロピレングリコール、ポリエチレングリコール−ポリプロピレングリコールブロックポリマーなどのポリアルキレングリコール、ポリエチレングリコールノニルフェニルエーテル、ポリエチレングリコールモノラウリルエーテルなどのポリエチレングリコールモノアルキルエーテル、ポリオキシエチレンステアレートなどのポリオキシエチレン脂肪酸エステル、２重結合を有するラジカル重合可能なポリアルキレングリコール鎖含有（メタ）アクリレートなども使用することができる。 In the present invention, the nonionic compound having a polyalkylene glycol chain used as the component (C) must have a terminal OH group. Specifically, polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polyethylene glycol-polypropylene glycol block polymers, polyethylene glycol monoalkyl ethers such as polyethylene glycol nonylphenyl ether, polyethylene glycol monolauryl ether, and polyoxyethylene stearates. Oxyethylene fatty acid esters, polyalkylene glycol chain-containing (meth) acrylates having a double bond and radical polymerization can also be used.
不飽和単量体（Ｘ）を乳化重合させる際に、末端がＯＨ基であるポリアルキレングリコール鎖を有する非イオン性化合物（Ｃ）は不飽和単量体（Ｘ）に対して０．１〜５質量％、好ましくは１〜３質量％使用しなければならない。（Ｃ）成分が０．１質量％未満であると、得られる水分散性樹脂組成物の安定性、耐汚染性が不十分となり、５質量％を超えると安定性、耐候性、耐汚染性が不十分となる。 When the unsaturated monomer (X) is subjected to emulsion polymerization, the nonionic compound (C) having a polyalkylene glycol chain having an OH group at the end is 0.1 to 0.1% of the unsaturated monomer (X). 5% by weight, preferably 1 to 3% by weight, must be used. When the component (C) is less than 0.1% by mass, the resulting water-dispersible resin composition has insufficient stability and stain resistance, and when it exceeds 5% by mass, the stability, weather resistance and stain resistance are increased. Is insufficient.
本発明において使用される不飽和単量体組成物（Ｘ）中に含まれる不飽和単量体としては、（メタ）アクリル酸アルキルエステル、少なくとも１個の重合可能な（メタ）アクロイル基を有するものを挙げることができる。（メタ）アクリル酸アルキルエステルの具体例としては、１〜１８個の炭素数の直鎖状、分岐鎖状もしくは環状のアルキル鎖を有する（メタ）アクリル酸エステル（メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｉｓｏ−ブチル（メタ）クリレート、ｔｅｒｔ−ブチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソボロニル（メタ）アクリレート等）が挙げられる。また、芳香族ビニル化合物（スチレン、α−メチルスチレン、ｐ−メチルスチレン、エチルビニルベンゼン等）、複素環式ビニル化合物（ビニルピロリドン等）、ヒドロキシアルキル（メタ）アクリレート（２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート等）、ポリアルキレンレングリコール（メタ）アクリレート（エチレングリコール（メタ）アクリレート、ブチレングリコール（メタ）アクリレート等）、アルキルアミノ（メタ）アクリレート（Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリレート等）、ビニルエステル化合物（蟻酸ビニル、酢酸ビニル、プロピオン酸ビニル、バーサチツク酸ビニル（商品名）等）、モノオレフィン化合物（エチレン、プロピレン、ブチレン、イソブチレン等）、共役ジオレフィン化合物（ブタジエン、イソプレン、クロロプレン等）、α，β−不飽和モノ又はジカルボン酸（アクリル酸、メタクリル酸、クロトン酸、シトラコン酸、イタコン酸、マレイン酸、無水マレイン酸、フマル酸等）、カルボキシル基含有ビニル化合物（フタル酸モノヒドロキシエチル（メタ）アクリレート、シュウ酸モノヒドロキシプロピル（メタ）アクリレート等）、アミンイミド基含有ビニル化合物（１，１，１−トリメチルアミンメタクリルイミドなど）、シアン化ビニル化合物（アクリロニトリル、メタクリロニトリル等）、アミド基もしくは置換アミド基含有α，β−エチレン性不飽和化合物（（メタ）アクリルアミド、Ｎ−メチルアクリルアミド、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリルアミド等）、カルボニル基含有α，β−エチレン性不飽和化合物（アクロレイン、ダイアセトンアクリルアミド、ビニルメチルケトン、ダイアセトンアクリレート、アセトニトリルアクリレート等）、スルホン酸基含有α，β−エチレン性不飽和化合物（スルホン酸アリル、ｐ−スチレンスルホン酸ナトリウム等）、エチレン性不飽和基含有紫外線吸収剤（２−（２‘−ヒドロキシ−５’−メタアクロイルオキシエチルフェニル）−２Ｈ−ベンゾトリアゾールなど）、エチレン性不飽和基含有光安定剤（１，２，２，６，６−ペンタメチル−４−ピペリジルメタクリレートなど）等の公知の重合性ビニル化合物も使用することができる。 The unsaturated monomer contained in the unsaturated monomer composition (X) used in the present invention has (meth) acrylic acid alkyl ester and at least one polymerizable (meth) acryloyl group. Things can be mentioned. Specific examples of the (meth) acrylic acid alkyl ester include (meth) acrylic acid esters having a linear, branched or cyclic alkyl chain having 1 to 18 carbon atoms (methyl (meth) acrylate, ethyl ( (Meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl ( (Meth) acrylate, isoboronyl (meth) acrylate, etc.). In addition, aromatic vinyl compounds (styrene, α-methylstyrene, p-methylstyrene, ethylvinylbenzene, etc.), heterocyclic vinyl compounds (vinylpyrrolidone, etc.), hydroxyalkyl (meth) acrylates (2-hydroxyethyl (meth)) Acrylate, 2-hydroxypropyl (meth) acrylate, etc.), polyalkylene glycol (meth) acrylate (ethylene glycol (meth) acrylate, butylene glycol (meth) acrylate, etc.), alkylamino (meth) acrylate (N, N-dimethyl) Aminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, etc.), vinyl ester compounds (vinyl formate, vinyl acetate, vinyl propionate, vinyl versatate (trade name), etc.), mono-olefin Compounds (ethylene, propylene, butylene, isobutylene, etc.), conjugated diolefin compounds (butadiene, isoprene, chloroprene, etc.), α, β-unsaturated mono- or dicarboxylic acids (acrylic acid, methacrylic acid, crotonic acid, citraconic acid, itaconic acid , Maleic acid, maleic anhydride, fumaric acid, etc.), carboxyl group-containing vinyl compounds (monohydroxyethyl (meth) acrylate, phthalate monohydroxypropyl (meth) acrylate, etc.), amineimide group-containing vinyl compounds (1,1 , 1-trimethylamine methacrylimide, etc.), vinyl cyanide compounds (acrylonitrile, methacrylonitrile, etc.), amide groups or substituted amide group-containing α, β-ethylenically unsaturated compounds ((meth) acrylamide, N-methylacrylamide, N N-dimethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, etc.), carbonyl group-containing α, β-ethylenically unsaturated compound (acrolein, diacetone acrylamide, vinyl methyl ketone, diacetone acrylate, acetonitrile Acrylate, etc.), sulfonic acid group-containing α, β-ethylenically unsaturated compounds (allyl sulfonate, sodium p-styrenesulfonate, etc.), ethylenically unsaturated group-containing ultraviolet absorber (2- (2′-hydroxy-5) '-Methacryloyloxyethylphenyl) -2H-benzotriazole, etc.), ethylenically unsaturated group-containing light stabilizers (1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, etc.) Vinyl compounds can also be used.
また、必要に応じて、乳化重合の際に架橋性モノマーを併用してもよい。このような架橋性モノマーとして、エポキシ基含有α，β−エチレン性不飽和化合物（グリシジル（メタ）アクリレート、３，４−エポキシシクロヘキシルメチル（メタ）アクリレート、グリシジルビニルエーテル、グリシジル（メタ）アリルエーテル、３，４−エポキシシクロヘキシル（メタ）アクリレート等）、多官能ビニル化合物（エチレングリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、アリル（メタ）アクリレート、ジビニルベンゼン、ジアリルフタレート等）等を導入し、それ自身同士の架橋をさせるか、活性水素基を持つエチレン性不飽和化合物成分と組み合わせて架橋させる、もしくは、カルボニル基含有α，β−エチレン性不飽和化合物（特にケト基含有のものに限る）を導入し、ポリヒドラジン化合物（特に２つ以上のヒドラジド基を有する化合物；シュウ酸ジヒドラジド、コハク酸ジヒドラジド、アジピン酸ジヒドラジド、ポリアクリル酸ヒドラジド等）などが挙げられる。 Moreover, you may use a crosslinkable monomer together in the case of emulsion polymerization as needed. Examples of such crosslinkable monomers include epoxy group-containing α, β-ethylenically unsaturated compounds (glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, glycidyl vinyl ether, glycidyl (meth) allyl ether, 3 , 4-epoxycyclohexyl (meth) acrylate, etc.), polyfunctional vinyl compounds (ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, allyl (meth) acrylate, divinylbenzene, diallyl phthalate, etc.)) And can be crosslinked with each other or combined with an ethylenically unsaturated compound component having an active hydrogen group, or a carbonyl group-containing α, β-ethylenically unsaturated compound (particularly a keto group-containing one). Limited) Li hydrazine compound (Compound particular having two or more hydrazide groups; oxalic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, polyacrylic acid hydrazide, etc.) and the like.
耐候性及び耐汚染性を向上させる観点から、不飽和単量体組成物（不飽和基を有するシランカップリング剤を除く）の理論ガラス転移温度（以下、Ｔｇと略すことがある）は−２０℃以上であることが好ましく、０℃〜６０℃であることが更に好ましい。なお、本発明において理論ガラス転移温度（絶対温度）は、下式から算出した値とする。
１／Ｔｇ＝Ｗ１／Ｔ１＋Ｗ２／Ｔ２＋・・・Ｗｎ／Ｔｎ
式中のＷ１、Ｗ２・・・Ｗｎは各不飽和単量体の質量％（＝（各不飽和単量体の配合量／全不飽和単量体の質量）×１００）であり、Ｔ１、Ｔ２・・・Ｔｎは、各不飽和単量体の単独重合体のガラス転移温度（絶対温度）である。ここで、各不飽和単量体の単独重合体のガラス転移温度は、Polymer Hand Book（Second Edition, J. Brandrup・E. H. Immergut 編）による値である。
From the viewpoint of improving the weather resistance and stain resistance, the theoretical glass transition temperature (hereinafter sometimes abbreviated as Tg) of the unsaturated monomer composition (excluding the silane coupling agent having an unsaturated group) is −20. It is preferable that it is more than 0 degreeC, and it is still more preferable that it is 0 degreeC-60 degreeC. In the present invention, the theoretical glass transition temperature (absolute temperature) is a value calculated from the following equation.
1 / Tg = W1 / T1 + W2 / T2 +... Wn / Tn
W1, W2... Wn in the formula is mass% of each unsaturated monomer (= (blending amount of each unsaturated monomer / mass of all unsaturated monomers) × 100), and T1, T2... Tn is the glass transition temperature (absolute temperature) of the homopolymer of each unsaturated monomer. Here, the glass transition temperature of the homopolymer of each unsaturated monomer is a value according to Polymer Hand Book (Second Edition, edited by J. Brandrup / EH Immergut).
また、本発明において使用される不飽和単量体組成物（Ｘ）には、０．１〜２質量％、好ましくは０．２〜１質量％の不飽和基を有するシランカップリング剤が含まれることを必須としている。不飽和単量体組成物（Ｘ）が不飽和基を有するシランカップリング剤が０．１質量％未満であると、得られる水分散性樹脂組成物の耐候性及び耐汚染性が不十分であり、２質量％を超えると重合安定性及び経時安定性が不十分となる。
このような不飽和基を有するシランカップリング剤の例としては、加水分解性アルコキシル基含有α，β−エチレン性不飽和化合物（ビニルトリエトキシシラン、ビニルトリス（β−メトキシエトキシ）シラン、γ−メタクリロキシプロピルトリメトキシシラン等）が挙げられる。
The unsaturated monomer composition (X) used in the present invention contains a silane coupling agent having an unsaturated group of 0.1 to 2% by mass, preferably 0.2 to 1% by mass. It is essential that When the unsaturated monomer composition (X) is less than 0.1% by mass of the silane coupling agent having an unsaturated group, the resulting water-dispersible resin composition has insufficient weather resistance and stain resistance. Yes, when it exceeds 2% by mass, the polymerization stability and the temporal stability become insufficient.
Examples of such silane coupling agents having an unsaturated group include hydrolyzable alkoxyl group-containing α, β-ethylenically unsaturated compounds (vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacrylic acid). And roxypropyltrimethoxysilane).
本発明による水分散性樹脂組成物は、乳化重合によって製造することができる。したがって、乳化重合に際しては、本発明の効果を損なわない範囲で、界面活性剤、重合開始剤、還元剤、連鎖移動剤等を適宜使用してもよい。このような界面活性剤は、乳化重合時の不飽和単量体の乳化安定性付与のための後添加など使用方法について特に制限されることはない。具体的にはドデシルベンゼンスルホン酸ナトリウム、ドデシル硫酸ナトリウム等のアニオン性界面活性剤、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンノニルフェニルエーテル等のノニオン性界面活性剤、セシルトリメチルアンモニウムブロミド、ラウリルピリジニウムクロリド等のカチオン性界面活性剤、ラウリルベダイン等の両性界面活性剤、反応性界面活性剤等が挙げられ、１種単独で使用してもよいし２種以上を混合して使用してもよい。 The water dispersible resin composition according to the present invention can be produced by emulsion polymerization. Therefore, in the emulsion polymerization, a surfactant, a polymerization initiator, a reducing agent, a chain transfer agent, and the like may be appropriately used as long as the effects of the present invention are not impaired. Such a surfactant is not particularly limited in terms of usage such as post-addition for imparting emulsion stability of an unsaturated monomer during emulsion polymerization. Specifically, anionic surfactants such as sodium dodecylbenzenesulfonate and sodium dodecylsulfate, nonionic surfactants such as polyoxyethylene lauryl ether and polyoxyethylene nonylphenyl ether, cesyltrimethylammonium bromide, laurylpyridinium chloride, etc. The cationic surfactants, amphoteric surfactants such as laurylbedine, reactive surfactants and the like may be mentioned, and these may be used alone or in admixture of two or more.
また、乳化重合において使用される重合開始剤としては、過硫酸カリウム、過硫酸アンモニウム等の過硫酸塩系開始剤、２，２’−アゾビス（２−メチルプロピオンアミジン）ジ塩酸塩等の水溶性アゾ系開始剤、ｔ−ブチルヒドロパーオキシド、クメンヒドロパーオキシド等の有機過酸化物類、過酸化水素等が挙げられる。これらの重合開始剤は１種単独で使用してもよいし２種以上を混合して使用してもよい。 The polymerization initiator used in emulsion polymerization includes persulfate initiators such as potassium persulfate and ammonium persulfate, and water-soluble azo such as 2,2′-azobis (2-methylpropionamidine) dihydrochloride. Examples thereof include system initiators, organic peroxides such as t-butyl hydroperoxide and cumene hydroperoxide, and hydrogen peroxide. These polymerization initiators may be used individually by 1 type, and 2 or more types may be mixed and used for them.
そして、場合に応じて、乳化重合において、これら重合開始剤と共に還元剤を使用できる。このような還元剤としては、アスコルビン酸、酒石酸、クエン酸、ブドウ糖、ホルムアルデヒドスルホキシラート金属塩等の還元性有機化合物、チオ硫酸ナトリウム、亜硫酸ナトリウム、重亜硫酸ナトリウム、メタ重亜硫酸ナトリウム等の還元性無機化合物等が挙げられる。 And according to the case, in emulsion polymerization, a reducing agent can be used with these polymerization initiators. Such reducing agents include reducing organic compounds such as ascorbic acid, tartaric acid, citric acid, glucose, formaldehyde sulfoxylate metal salts, reducing properties such as sodium thiosulfate, sodium sulfite, sodium bisulfite, and sodium metabisulfite. An inorganic compound etc. are mentioned.
更にまた、乳化重合においては、必要に応じて連鎖移動剤を使用できるが、耐候性などの物性上問題とならないように使用量を検討すべきで、その用途仕様に応じてコントロールする範囲内で使用できる。このような連鎖移動剤としては、ｎ−ドデシルメルカプタン、ｔｅｒｔ−ドデシルメルカプタン、ｎ−ブチルメルカプタン、２−エチルヘキシルチオグリコレート、２−メルカプトエタノール、β−メルカプトプロピオン酸等が挙げられる。 Furthermore, in emulsion polymerization, a chain transfer agent can be used as necessary, but the amount used should be examined so as not to cause problems in physical properties such as weather resistance, and within the range controlled according to the application specifications. Can be used. Examples of such chain transfer agents include n-dodecyl mercaptan, tert-dodecyl mercaptan, n-butyl mercaptan, 2-ethylhexyl thioglycolate, 2-mercaptoethanol, β-mercaptopropionic acid and the like.
この乳化重合は、通常、約５〜約１００℃、好ましくは約５０〜９０℃の温度条件下で行われる。反応時間は、特に制限されることはなく、各成分の配合量及び反応温度等に応じて適宜調整すればよい。 This emulsion polymerization is usually carried out under temperature conditions of about 5 to about 100 ° C, preferably about 50 to 90 ° C. The reaction time is not particularly limited and may be appropriately adjusted according to the blending amount of each component, the reaction temperature, and the like.
得られた水分散性樹脂組成物は、１種又はそれ以上の酸もしくは塩基の添加によって、その系のｐＨを４〜１０（特に、シリコン成分の安定性を考慮すると５〜８）に中和することが好ましい。ｐＨを上記範囲にすることでエマルジョンの表面電荷を高くし、安定性を付与することができる。使用する一般的な酸としては、酢酸、乳酸、塩酸、燐酸、硫酸などが挙げられる。また、使用する一般的な塩基としては、トリエチルアミン、アンモニア、ジエタノールアミン、ジエチルアミノエタノール等のアミン化合物、水酸化カリウム、水酸化ナトリウム、水酸化リチウム等のアルカリ金属水酸化物が挙げられる。 The resulting water-dispersible resin composition is neutralized to a pH of 4 to 10 (especially 5 to 8 considering the stability of the silicon component) by adding one or more acids or bases. It is preferable to do. By setting the pH within the above range, the surface charge of the emulsion can be increased and stability can be imparted. Common acids used include acetic acid, lactic acid, hydrochloric acid, phosphoric acid, sulfuric acid and the like. Examples of the general base used include amine compounds such as triethylamine, ammonia, diethanolamine and diethylaminoethanol, and alkali metal hydroxides such as potassium hydroxide, sodium hydroxide and lithium hydroxide.
本発明による塗料は、上記水分散性樹脂組成物を含むものである。本発明の塗料には、公知の添加剤、例えば、増粘剤、消泡剤、顔料、分散剤、光安定剤、紫外線吸収剤、防腐剤、造膜助剤などを適宜配合することができる。本発明による塗料は、建築塗料、サイジングボード用塗料、モルタル被覆材などの様々なコーティング剤として使用することができる。また、紙、繊維、金属など被覆できるものであれば制限なく使用することが可能であり、その手法に関しても限定されない。更に、本発明の塗料には、必要に応じて、シリコン成分の硬化促進剤として、有機・無機アミン類、無機・有機酸類、燐酸エステル類、有機錫化合物、有機シラン化合物、有機チタン化合物、有機ジルコニウム化合物なども添加してもよい。添加する手法に制限はなく、水分散性樹脂組成物を調製する際（乳化重合時）に添加してもよいし、乳化重合後に添加してもよいし、あるいは両方で添加してもよい。 The coating material by this invention contains the said water dispersible resin composition. Known additives such as thickeners, antifoaming agents, pigments, dispersants, light stabilizers, ultraviolet absorbers, preservatives, film-forming aids, and the like can be appropriately blended with the paint of the present invention. . The paint according to the present invention can be used as various coating agents such as architectural paints, sizing board paints, and mortar coatings. Further, any paper, fiber, metal, or the like that can be coated can be used without limitation, and the method is not limited. Furthermore, in the coating material of the present invention, organic / inorganic amines, inorganic / organic acids, phosphoric acid esters, organic tin compounds, organic silane compounds, organic titanium compounds, organic as organic silicone curing accelerators, if necessary A zirconium compound or the like may also be added. There is no restriction | limiting in the method to add, You may add at the time of preparing a water-dispersible resin composition (at the time of emulsion polymerization), you may add after emulsion polymerization, or you may add by both.
以下、実施例及び比較例により本発明を具体的に説明する。また、実施例及び比較例における物性の評価は、以下に示す方法により行った。 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. Further, physical properties in Examples and Comparative Examples were evaluated by the following methods.
（１）水分散性樹脂組成物の性状
（ｉ）不揮発分
予め質量が測定された水分散性樹脂組成物を１０５℃、１時間乾燥させ、揮発残分の質量を測定した。初期の質量と揮発残分の質量とから不揮発分の質量％を計算した。
（ｉｉ）粘度
ＢＭ型粘度計を用いて２３℃、６０ｒｐｍにおける粘度を測定した。
（ｉｉｉ）ｐＨ
ｐＨメーターを用いて測定した。
（ｉｖ）最低造膜温度（以下、ＭＦＴと略記することがある）
熱勾配式最低造膜温度測定装置にて測定した。
(1) Properties of Water Dispersible Resin Composition (i) Nonvolatile Content A water dispersible resin composition whose mass was measured in advance was dried at 105 ° C. for 1 hour, and the mass of volatile residue was measured. From the initial mass and the mass of the volatile residue, the mass% of the nonvolatile content was calculated.
(Ii) Viscosity Viscosity at 23 ° C. and 60 rpm was measured using a BM viscometer.
(Iii) pH
It measured using the pH meter.
(Iv) Minimum film forming temperature (hereinafter sometimes abbreviated as MFT)
It measured with the thermal gradient type minimum film-forming temperature measuring apparatus.
（２）高温安定性
水分散性樹脂組成物をマヨネーズ瓶に入れ、６０℃の条件下で７日間静置した後の粘度、ＭＦＴを測定し、粘度変化が２０％以内でＭＦＴ変化が１０％以内を○、それらを超えて変化したものを×とした。
(2) High temperature stability Viscosity and MFT were measured after placing the water-dispersible resin composition in a mayonnaise bottle and allowed to stand at 60 ° C. for 7 days. The viscosity change was within 20% and the MFT change was 10%. The inside was marked with ◯, and the thing that changed beyond them was marked with ×.
（３）耐候性及び耐汚染性の評価
（ｉ）グロス塗料の調製
脱イオン水 ８２．６質量部、増粘剤としてナトロゾール２５０ＨＲ（ハーキュレース製） ０．８質量部、中和剤としてアンモニア水 ０．２質量部、防腐剤としてアモルデンＦＳ−１４Ｄ（大和化学工業製） １．１質量部、分散剤としてポイズ５２１（花王製） ４．２質量部、消泡剤としてＳＮデフォーマー３７１（サンノプコ製） １．１質量部、酸化チタンとしてタイペークＣＲ−９７（石原産業製） ２１０質量部を容器中でホモディスパーを用いて約２０００ｒｐｍで撹拌しながら上記順に仕込み、更に約２０００ｒｐｍで１時間撹拌した。その後、１２０メッシュのテフロン（登録商標）メッシュで濾過し、合計３００質量部、固形分濃度７０質量％（酸化チタンを固形分として計算）のミルベースを得た。
別容器に、前記ミルベース ３００質量部、水分散性樹脂組成物 ６００質量部（不揮発分５０質量％の場合。不揮発分が５０質量％以外の場合には、水分散性樹脂組成物の不揮発分に応じて、同量の樹脂が含まれるように添加量を設定した。）、造膜助剤としてＣＳ−１２（チッソ製） ５４質量部、粘性調整剤としてアデカノールＵＨ−４２０（旭電化工業製） １質量部を仕込み、ホモディスパーを用いて約２０００ｒｐｍで１０分間撹拌した。その後、１５０メッシュのテフロン（登録商標）メッシュで濾過し、固形分濃度５３．４質量％、顔料濃度１５．５体積％（比重を酸化チタン；４．２、水分散性樹脂組成物；１．１として計算した）のグロス塗料 ９５５質量部を得た。
(3) Evaluation of weather resistance and stain resistance (i) Preparation of gloss paint Deionized water 82.6 parts by mass, Natrozole 250HR (made by Hercules) as a thickener 0.8 parts by mass, aqueous ammonia as a neutralizer 0 .2 parts by weight, Amorden FS-14D as a preservative (manufactured by Yamato Chemical Co., Ltd.) 1.1 parts by weight, Poise 521 (manufactured by Kao) as a dispersant, 4.2 parts by weight, SN deformer 371 (manufactured by San Nopco) as an antifoaming agent 1.1 parts by mass and 210 parts by mass of Typeke CR-97 (manufactured by Ishihara Sangyo) as titanium oxide were charged in the above order in a container using a homodisper at about 2000 rpm, and further stirred at about 2000 rpm for 1 hour. Then, it filtered with the 120 mesh Teflon (trademark) mesh, and obtained the mill base of a total of 300 mass parts and solid content concentration of 70 mass% (calculating titanium oxide as solid content).
In a separate container, 300 parts by mass of the mill base and 600 parts by mass of the water-dispersible resin composition (when the nonvolatile content is 50% by mass. When the nonvolatile content is other than 50% by mass, the nonvolatile content of the water-dispersible resin composition Accordingly, the addition amount was set so that the same amount of resin was included.), 54 parts by mass of CS-12 (manufactured by Chisso) as a film-forming aid, and Adecanol UH-420 (manufactured by Asahi Denka Kogyo) as a viscosity modifier 1 part by mass was charged and stirred at about 2000 rpm for 10 minutes using a homodisper. Thereafter, the mixture was filtered through a 150-mesh Teflon (registered trademark) mesh, the solid content concentration was 53.4% by mass, the pigment concentration was 15.5% by volume (specific gravity was titanium oxide; 4.2, water-dispersible resin composition; 955 parts by weight of a gloss paint (calculated as 1) was obtained.
（ｉｉ）塗板の調製
上記グロス塗料に水を添加して約８００ｍＰａ・ｓ（ＢＨ型粘度計、２０ｒｐｍ、２３℃）の粘度に調整した。この塗料を、シーラー処理が予め施されたフレキ板にスプレーを用いて１５０ｇ／ｍ２×２回吹きした後、２３℃、６５％ＲＨで１週間養生し塗板を得た。上記操作を繰り返して塗板を合計で２枚作製した。
(Ii) Preparation of coated plate Water was added to the gloss paint to adjust the viscosity to about 800 mPa · s (BH viscometer, 20 rpm, 23 ° C.). After spraying 150 g / m 2 × 2 times on a flexible plate that had been previously treated with a sealer, this paint was cured at 23 ° C. and 65% RH for 1 week to obtain a coated plate. The above operation was repeated to produce a total of two coated plates.
（ｉｉｉ）耐候性の評価
上記塗板のうちの１枚をメタリングウエザーメーター（スガ試験機）で試験し、５００ｈｒ照射後の光沢保持率を測定した。メタリングウエザーメーターの条件は、ブラックパネル温度６３℃、湿度５０％ＲＨ、照度１．５５ｋＷ／ｍ２、照射２時間→照射＋降雨２分（３サイクル）→結露２時間（雰囲気３０℃、９５％ＲＨ、塗板２５℃）の８時間サイクル試験とした。
(Iii) Evaluation of weather resistance One of the coated plates was tested with a metering weather meter (Suga test machine), and the gloss retention after irradiation for 500 hr was measured. The conditions of the metering weather meter are as follows: black panel temperature 63 ° C., humidity 50% RH, illuminance 1.55 kW / m 2 , irradiation 2 hours → irradiation + rainfall 2 minutes (3 cycles) → condensation 2 hours (atmosphere 30 ° C., 95 % RH, coated plate 25 ° C.).
（ｉｖ）耐汚染性の評価
上記塗板の残りの１枚を屋外に３ヶ月間暴露し、暴露前後の色差（ΔＥ）を測定した（兵庫県たつの市、南向き４５°）。
(Iv) Evaluation of stain resistance The remaining one of the coated plates was exposed outdoors for 3 months, and the color difference (ΔE) before and after exposure was measured (Tatsuno City, Hyogo Prefecture, 45 ° southward).
＜実施例１＞
撹拌機、温度計、環流凝縮機を備えた重合装置中に、脱イオン水 ２００質量部、（Ｃ）成分としてのエマルゲン１４７（ポリオキシエチレンラウリルエーテル、花王製）５質量部を入れ、窒素置換を十分に行った後、昇温した。内温を７５℃に保ちながら、（Ａ）成分としてのメチルトリメトキシシラン（以下、ＭＴＭＳと略記することがある） １００質量部、（Ｂ）成分としてのテトラエトキシシラン（以下、ＴＥＯＳと略記することがある） ７５質量部を加え、３０分間保持した。さらに、脱イオン水 ４５０質量部と、アクアロンＫＨ−１０（アニオン性反応性界面活性剤、第一工業製薬製） １０質量部と、（Ｘ）成分としてのメチルメタクリレート ２０７質量部、シクロヘキシルメタクリレート １００質量部及び２−エチルヘキシルアクリレート １９３質量部と、不飽和基を有するシランカップリング剤としてのγ−メタクリロキシプロピルトリメトキシシラン（以下、γ−ＭＰＴＭＳと略記することがある） ２質量部と、メタクリル酸 １０質量部とをホモミキサーにて予め混合乳化したものを用意し、この乳化物の５質量％を先の重合装置内に加えた。次いで、過硫酸カリウム ０．５質量部、脱イオン水 ３質量部を加えて重合を開始し、８０℃で１５分反応させた。さらに、先の乳化物の残り９５質量％と、２．５％過硫酸カリウム水溶液 ４０質量部とを内温８０℃に保ちながら４時間掛けて滴下した。さらに、８０℃で２時間反応させ、その後室温（２５℃）に冷却した。最後にアンモニア水でｐＨ６に調整し、実施例１の水分散性樹脂組成物を得た。尚、使用した不飽和単量体の理論Ｔｇは１０℃である。得られた水分散性樹脂組成物の性状は、不揮発分４３．８質量％、粘度（ＢＭ型粘度計、６０ｒｐｍ、２３℃）８０ｍＰａ・ｓ、ｐＨ６．０、ＭＦＴ４５℃であった。
<Example 1>
In a polymerization apparatus equipped with a stirrer, a thermometer, and a reflux condenser, 200 parts by mass of deionized water and 5 parts by mass of Emulgen 147 (polyoxyethylene lauryl ether, manufactured by Kao) as component (C) were placed, and the atmosphere was replaced with nitrogen. After sufficiently performing, the temperature was raised. While maintaining the internal temperature at 75 ° C., 100 parts by mass of methyltrimethoxysilane (hereinafter abbreviated as MTMS) as component (A), tetraethoxysilane (hereinafter abbreviated as TEOS) as component (B) 75 parts by weight was added and held for 30 minutes. Furthermore, 450 parts by mass of deionized water, 10 parts by mass of Aqualon KH-10 (anionic reactive surfactant, manufactured by Daiichi Kogyo Seiyaku), 207 parts by mass of methyl methacrylate as component (X), 100 parts by mass of cyclohexyl methacrylate Part and 2-ethylhexyl acrylate 193 parts by weight, γ-methacryloxypropyltrimethoxysilane (hereinafter sometimes abbreviated as γ-MPTMS) as a silane coupling agent having an unsaturated group, 2 parts by weight, and methacrylic acid What mixed and emulsified 10 mass parts beforehand with the homomixer was prepared, and 5 mass% of this emulsion was added in the previous polymerization apparatus. Next, 0.5 parts by mass of potassium persulfate and 3 parts by mass of deionized water were added to initiate polymerization, and the reaction was carried out at 80 ° C. for 15 minutes. Further, the remaining 95% by mass of the previous emulsion and 40 parts by mass of 2.5% potassium persulfate aqueous solution were added dropwise over 4 hours while maintaining the internal temperature at 80 ° C. Furthermore, it was made to react at 80 degreeC for 2 hours, and it cooled to room temperature (25 degreeC) after that. Finally, the pH was adjusted to 6 with aqueous ammonia to obtain a water-dispersible resin composition of Example 1. The theoretical Tg of the unsaturated monomer used is 10 ° C. The properties of the obtained water-dispersible resin composition were a non-volatile content of 43.8% by mass, a viscosity (BM type viscometer, 60 rpm, 23 ° C.), 80 mPa · s, pH 6.0, and MFT of 45 ° C.
＜実施例２＞
エマルゲン１４７の代わりに、ＰＥＧ＃２００（ポリエチレングリコール、日本油脂製）を用いる以外は、実施例１の操作に準じて実施例２の水分散性樹脂組成物を得た。
<Example 2>
A water-dispersible resin composition of Example 2 was obtained in accordance with the operation of Example 1 except that PEG # 200 (polyethylene glycol, manufactured by NOF Corporation) was used instead of Emulgen 147.
＜実施例３＞
メチルトリメトキシシラン１００質量部の代わりに、メチルトリメトキシシラン ５０質量部とジメチルジメトキシシラン ５０質量部とを用いる以外は、実施例１の操作に準じて実施例３の水分散性樹脂組成物を得た。
<Example 3>
The water-dispersible resin composition of Example 3 was prepared according to the procedure of Example 1 except that 50 parts by mass of methyltrimethoxysilane and 50 parts by mass of dimethyldimethoxysilane were used instead of 100 parts by mass of methyltrimethoxysilane. Obtained.
＜比較例１〜８＞
（Ａ）〜（Ｃ）成分及びシランカップリング剤を表１に示される配合に変える以外は、実施例１の操作に準じて比較例１〜８の水分散性樹脂組成物をそれぞれ得た。
<Comparative Examples 1-8>
The water-dispersible resin compositions of Comparative Examples 1 to 8 were obtained in the same manner as in Example 1 except that the components (A) to (C) and the silane coupling agent were changed to those shown in Table 1.
実施例１〜３及び比較例１〜８で得られた水分散性樹脂組成物の性状、高温安定性、耐候性および耐汚染性の評価結果を表２に示した。 Table 2 shows the evaluation results of the properties, high-temperature stability, weather resistance and stain resistance of the water-dispersible resin compositions obtained in Examples 1 to 3 and Comparative Examples 1 to 8.
表２から分かるように、加水分解性アルコキシル基を２あるいは３個持つアルキルアルコキシシラン化合物（ＭＴＭＳ、ＤＭＤＭＳ）と、加水分解性アルコキシル基を４個持つアルコキシシラン化合物（ＴＥＯＳ）と、末端がＯＨ基であるポリアルキレングリコール鎖を有する非イオン性化合物（ポリオキシエチレンラウリルエーテル、ポリエチレングリコール）との存在下で、不飽和基を有するシランカップリング剤（γ−ＭＰＴＭＳ）を一部含む不飽和単量体組成物を乳化重合して得られる実施例１〜３の水分散性樹脂組成物は、比較例１〜８の水分散性樹脂組成物と比べて、高温安定性、耐候性及び耐汚染性が優れている。 As can be seen from Table 2, an alkylalkoxysilane compound (MTMS, DMDMS) having 2 or 3 hydrolyzable alkoxyl groups, an alkoxysilane compound (TEOS) having 4 hydrolyzable alkoxyl groups, and an OH group at the end Unsaturated monomer containing a part of a silane coupling agent (γ-MPTMS) having an unsaturated group in the presence of a nonionic compound having a polyalkylene glycol chain (polyoxyethylene lauryl ether, polyethylene glycol) The water-dispersible resin compositions of Examples 1 to 3 obtained by emulsion polymerization of the body composition are higher in temperature stability, weather resistance and stain resistance than the water-dispersible resin compositions of Comparative Examples 1 to 8. Is excellent.
Claims (4)
不飽和単量体組成物（Ｘ）が、不飽和基を有するシランカップリング剤を０．１〜２質量％含むことを特徴とする水分散性樹脂組成物。 An alkylalkoxysilane compound having 1 to 3 hydrolyzable alkoxyl groups or a hydrolyzate thereof (A) is 0.1 to 30% by mass with respect to the unsaturated monomer composition (X). 0.1 to 30% by mass of the alkoxysilane compound having a hydrolyzable alkoxyl group or its hydrolyzate (B) and 0.1% of the nonionic compound (C) having a polyalkylene glycol chain having a terminal OH group A water-dispersible resin composition obtained by emulsion polymerization of an unsaturated monomer composition (X) in the presence of ˜5% by mass,
The water-dispersible resin composition, wherein the unsaturated monomer composition (X) contains 0.1 to 2% by mass of a silane coupling agent having an unsaturated group.
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