JP5288680B2 - Water-based coating composition and coating film obtained from the coating composition - Google Patents
Water-based coating composition and coating film obtained from the coating composition Download PDFInfo
- Publication number
- JP5288680B2 JP5288680B2 JP2005105243A JP2005105243A JP5288680B2 JP 5288680 B2 JP5288680 B2 JP 5288680B2 JP 2005105243 A JP2005105243 A JP 2005105243A JP 2005105243 A JP2005105243 A JP 2005105243A JP 5288680 B2 JP5288680 B2 JP 5288680B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- water
- weight
- composition
- parts
- 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.)
- Expired - Fee Related
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 49
- 238000000576 coating method Methods 0.000 title claims description 34
- 239000011248 coating agent Substances 0.000 title claims description 31
- 239000008199 coating composition Substances 0.000 title description 12
- 239000003973 paint Substances 0.000 claims description 51
- 239000000178 monomer Substances 0.000 claims description 43
- 150000001875 compounds Chemical class 0.000 claims description 42
- 239000000839 emulsion Substances 0.000 claims description 40
- -1 polyoxy Polymers 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 36
- 238000006116 polymerization reaction Methods 0.000 claims description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 229920002554 vinyl polymer Polymers 0.000 claims description 14
- 239000000057 synthetic resin Substances 0.000 claims description 13
- 229920003002 synthetic resin Polymers 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000005370 alkoxysilyl group Chemical group 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 150000003606 tin compounds Chemical class 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- OLOQHZSCBTUIGQ-UHFFFAOYSA-L 2,2-dibutyl-1,3,2-oxathiastannolan-5-one Chemical compound CCCC[Sn]1(CCCC)OC(=O)CS1 OLOQHZSCBTUIGQ-UHFFFAOYSA-L 0.000 claims description 2
- UNIWFCPQNWBLKG-UHFFFAOYSA-L [[9-methyl-2-(7-methyloctyl)-2-(sulfanylmethyl)decanoyl]oxy-dioctylstannyl] 9-methyl-2-(7-methyloctyl)-2-(sulfanylmethyl)decanoate Chemical compound C(CCCCCC(C)C)C(C(=O)[O-])(CS)CCCCCCC(C)C.C(CCCCCCC)[Sn+2]CCCCCCCC.C(CCCCCC(C)C)C(C(=O)[O-])(CS)CCCCCCC(C)C UNIWFCPQNWBLKG-UHFFFAOYSA-L 0.000 claims description 2
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 claims description 2
- UHGHZQYYPSGQDA-UHFFFAOYSA-L dibutyltin(2+);9-methyl-2-(7-methyloctyl)-2-(sulfanylmethyl)decanoate Chemical compound CCCC[Sn+2]CCCC.CC(C)CCCCCCC(CS)(C([O-])=O)CCCCCCC(C)C.CC(C)CCCCCCC(CS)(C([O-])=O)CCCCCCC(C)C UHGHZQYYPSGQDA-UHFFFAOYSA-L 0.000 claims description 2
- HKPPFWSHODSGMF-UHFFFAOYSA-L dimethyltin(2+);2-sulfanyldecanoate Chemical class C[Sn+2]C.CCCCCCCCC(S)C([O-])=O.CCCCCCCCC(S)C([O-])=O HKPPFWSHODSGMF-UHFFFAOYSA-L 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 125000001302 tertiary amino group Chemical group 0.000 claims 2
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 description 19
- 238000004519 manufacturing process Methods 0.000 description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 11
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 230000007062 hydrolysis Effects 0.000 description 8
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 8
- 230000007423 decrease Effects 0.000 description 7
- 239000002202 Polyethylene glycol Substances 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 150000002902 organometallic compounds Chemical class 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 239000004480 active ingredient Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 229920001515 polyalkylene glycol Polymers 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- 229920001451 polypropylene glycol Polymers 0.000 description 5
- 239000000344 soap Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 4
- 239000012024 dehydrating agents Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 4
- RYYXDZDBXNUPOG-UHFFFAOYSA-N 4,5,6,7-tetrahydro-1,3-benzothiazole-2,6-diamine;dihydrochloride Chemical compound Cl.Cl.C1C(N)CCC2=C1SC(N)=N2 RYYXDZDBXNUPOG-UHFFFAOYSA-N 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010556 emulsion polymerization method Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 150000003512 tertiary amines Chemical group 0.000 description 3
- 239000004408 titanium dioxide Substances 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
- ADAKRBAJFHTIEW-UHFFFAOYSA-N 1-chloro-4-isocyanatobenzene Chemical compound ClC1=CC=C(N=C=O)C=C1 ADAKRBAJFHTIEW-UHFFFAOYSA-N 0.000 description 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 2
- XDQWJFXZTAWJST-UHFFFAOYSA-N 3-triethoxysilylpropyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C=C XDQWJFXZTAWJST-UHFFFAOYSA-N 0.000 description 2
- HGEKXQRHZRDGKO-UHFFFAOYSA-N 3-tripropoxysilylpropyl prop-2-enoate Chemical compound CCCO[Si](OCCC)(OCCC)CCCOC(=O)C=C HGEKXQRHZRDGKO-UHFFFAOYSA-N 0.000 description 2
- VLJQDHDVZJXNQL-UHFFFAOYSA-N 4-methyl-n-(oxomethylidene)benzenesulfonamide Chemical compound CC1=CC=C(S(=O)(=O)N=C=O)C=C1 VLJQDHDVZJXNQL-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
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- 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
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000003545 alkoxy 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
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000010425 asbestos Substances 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000002563 ionic surfactant Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- UJYAZVSPFMJCLW-UHFFFAOYSA-N n-(oxomethylidene)benzenesulfonamide Chemical compound O=C=NS(=O)(=O)C1=CC=CC=C1 UJYAZVSPFMJCLW-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 125000006353 oxyethylene group Chemical group 0.000 description 2
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 2
- 229910052895 riebeckite Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000010454 slate Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
- 229920006163 vinyl copolymer Polymers 0.000 description 2
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 1
- OZDOQMMXEACZAA-NRFIWDAESA-L (z)-4-butoxy-4-oxobut-2-enoate;dibutyltin(2+) Chemical compound CCCCOC(=O)\C=C/C(=O)O[Sn](CCCC)(CCCC)OC(=O)\C=C/C(=O)OCCCC OZDOQMMXEACZAA-NRFIWDAESA-L 0.000 description 1
- NDQXKKFRNOPRDW-UHFFFAOYSA-N 1,1,1-triethoxyethane Chemical compound CCOC(C)(OCC)OCC NDQXKKFRNOPRDW-UHFFFAOYSA-N 0.000 description 1
- HDPNBNXLBDFELL-UHFFFAOYSA-N 1,1,1-trimethoxyethane Chemical compound COC(C)(OC)OC HDPNBNXLBDFELL-UHFFFAOYSA-N 0.000 description 1
- UEVZIKFSVBYKAC-UHFFFAOYSA-N 1-(1,1-dibutoxyethoxy)butane Chemical compound CCCCOC(C)(OCCCC)OCCCC UEVZIKFSVBYKAC-UHFFFAOYSA-N 0.000 description 1
- SGJBIFUEFLWXJY-UHFFFAOYSA-N 1-(dibutoxymethoxy)butane Chemical compound CCCCOC(OCCCC)OCCCC SGJBIFUEFLWXJY-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- FTALTLPZDVFJSS-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl prop-2-enoate Chemical compound CCOCCOCCOC(=O)C=C FTALTLPZDVFJSS-UHFFFAOYSA-N 0.000 description 1
- OLQFXOWPTQTLDP-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCO OLQFXOWPTQTLDP-UHFFFAOYSA-N 0.000 description 1
- DAVVKEZTUOGEAK-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethyl 2-methylprop-2-enoate Chemical compound COCCOCCOC(=O)C(C)=C DAVVKEZTUOGEAK-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- TXHZNLCKXHJYNX-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound COCCOCCOCCOCCOCCOCCOCCOCCOCCOC(=O)C(C)=C TXHZNLCKXHJYNX-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical compound OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 1
- XLLXMBCBJGATSP-UHFFFAOYSA-N 2-phenylethenol Chemical compound OC=CC1=CC=CC=C1 XLLXMBCBJGATSP-UHFFFAOYSA-N 0.000 description 1
- BUJVPKZRXOTBGA-UHFFFAOYSA-N 2-trimethoxysilylethyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCOC(=O)C=C BUJVPKZRXOTBGA-UHFFFAOYSA-N 0.000 description 1
- MBNRBJNIYVXSQV-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propane-1-thiol Chemical compound CCO[Si](C)(OCC)CCCS MBNRBJNIYVXSQV-UHFFFAOYSA-N 0.000 description 1
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-M 3-mercaptopropionate Chemical compound [O-]C(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-M 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
- JMGZKPMMFXFSGK-UHFFFAOYSA-N 3-tri(propan-2-yloxy)silylpropyl prop-2-enoate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)CCCOC(=O)C=C JMGZKPMMFXFSGK-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- LNQVOBNVXUVSEA-UHFFFAOYSA-N 4,5-dihydro-1h-imidazol-3-ium;dodecanoate Chemical compound C1CN=C[NH2+]1.CCCCCCCCCCCC([O-])=O LNQVOBNVXUVSEA-UHFFFAOYSA-N 0.000 description 1
- COCLLEMEIJQBAG-UHFFFAOYSA-N 8-methylnonyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C(C)=C COCLLEMEIJQBAG-UHFFFAOYSA-N 0.000 description 1
- 102100026788 ATP synthase subunit C lysine N-methyltransferase Human genes 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- DEVXQDKRGJCZMV-UHFFFAOYSA-K Aluminum acetoacetate Chemical compound [Al+3].CC(=O)CC([O-])=O.CC(=O)CC([O-])=O.CC(=O)CC([O-])=O DEVXQDKRGJCZMV-UHFFFAOYSA-K 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 102100024522 Bladder cancer-associated protein Human genes 0.000 description 1
- 101150110835 Blcap gene Proteins 0.000 description 1
- GKEKEUVQLNJSGA-XGVHMZQUSA-L C(CCCCC(C)C)C([C@H]([C@H]([C@@H]([C@H](C(=O)[S-])O)O)O)O)(O)CCCCCC(C)C.C(CCC)[Sn+2]CCCC.C(CCCCC(C)C)C([C@H]([C@H]([C@@H]([C@H](C(=O)[S-])O)O)O)O)(O)CCCCCC(C)C Chemical compound C(CCCCC(C)C)C([C@H]([C@H]([C@@H]([C@H](C(=O)[S-])O)O)O)O)(O)CCCCCC(C)C.C(CCC)[Sn+2]CCCC.C(CCCCC(C)C)C([C@H]([C@H]([C@@H]([C@H](C(=O)[S-])O)O)O)O)(O)CCCCCC(C)C GKEKEUVQLNJSGA-XGVHMZQUSA-L 0.000 description 1
- FKHQDZOAPWTUCI-XGVHMZQUSA-L C(CCCCC(C)C)C([C@H]([C@H]([C@@H]([C@H](C(=O)[S-])O)O)O)O)(O)CCCCCC(C)C.C(CCCCCCC)[Sn+2]CCCCCCCC.C(CCCCC(C)C)C([C@H]([C@H]([C@@H]([C@H](C(=O)[S-])O)O)O)O)(O)CCCCCC(C)C Chemical compound C(CCCCC(C)C)C([C@H]([C@H]([C@@H]([C@H](C(=O)[S-])O)O)O)O)(O)CCCCCC(C)C.C(CCCCCCC)[Sn+2]CCCCCCCC.C(CCCCC(C)C)C([C@H]([C@H]([C@@H]([C@H](C(=O)[S-])O)O)O)O)(O)CCCCCC(C)C FKHQDZOAPWTUCI-XGVHMZQUSA-L 0.000 description 1
- 239000004380 Cholic acid Substances 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- 101000833848 Homo sapiens ATP synthase subunit C lysine N-methyltransferase Proteins 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical class SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 101100493740 Oryza sativa subsp. japonica BC10 gene Proteins 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- YVHDRFKHKGNLNW-UHFFFAOYSA-L [dibutyl(octadecanoyloxy)stannyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCCCCCCCC YVHDRFKHKGNLNW-UHFFFAOYSA-L 0.000 description 1
- RMKZLFMHXZAGTM-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl prop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C=C RMKZLFMHXZAGTM-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000005215 alkyl 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
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- MQPPCKJJFDNPHJ-UHFFFAOYSA-K aluminum;3-oxohexanoate Chemical compound [Al+3].CCCC(=O)CC([O-])=O.CCCC(=O)CC([O-])=O.CCCC(=O)CC([O-])=O MQPPCKJJFDNPHJ-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229940064004 antiseptic throat preparations Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- AYXKWPPGXCOLLI-UHFFFAOYSA-N azanium;2-(2-methylprop-2-enoyloxy)ethanesulfonate Chemical compound [NH4+].CC(=C)C(=O)OCCS([O-])(=O)=O AYXKWPPGXCOLLI-UHFFFAOYSA-N 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 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
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- 229960002645 boric acid Drugs 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000004148 curcumin Substances 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- WCRDXYSYPCEIAK-UHFFFAOYSA-N dibutylstannane Chemical compound CCCC[SnH2]CCCC WCRDXYSYPCEIAK-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- NBZNVCBJBGDRJI-KKUWAICFSA-L dibutyltin(2+);(z)-4-(2-ethylhexoxy)-4-oxobut-2-enoate Chemical compound CCCCC(CC)COC(=O)\C=C/C(=O)O[Sn](CCCC)(CCCC)OC(=O)\C=C/C(=O)OCC(CC)CCCC NBZNVCBJBGDRJI-KKUWAICFSA-L 0.000 description 1
- OSGZEAQLLRZGHT-VGKOASNMSA-L dibutyltin(2+);(z)-4-ethoxy-4-oxobut-2-enoate Chemical compound CCOC(=O)\C=C/C(=O)O[Sn](CCCC)(CCCC)OC(=O)\C=C/C(=O)OCC OSGZEAQLLRZGHT-VGKOASNMSA-L 0.000 description 1
- IESWIBSMHJCJAG-UHFFFAOYSA-L dibutyltin(2+);8-methyl-2-(6-methylheptyl)-2-sulfanylnonanoate Chemical compound CCCC[Sn+2]CCCC.CC(C)CCCCCC(S)(C([O-])=O)CCCCCC(C)C.CC(C)CCCCCC(S)(C([O-])=O)CCCCCC(C)C IESWIBSMHJCJAG-UHFFFAOYSA-L 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000001804 emulsifying effect Effects 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
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- MABAWBWRUSBLKQ-UHFFFAOYSA-N ethenyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)C=C MABAWBWRUSBLKQ-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- DECIPOUIJURFOJ-UHFFFAOYSA-N ethoxyquin Chemical compound N1C(C)(C)C=C(C)C2=CC(OCC)=CC=C21 DECIPOUIJURFOJ-UHFFFAOYSA-N 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000011381 foam concrete Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000010438 granite Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- GSGDTSDELPUTKU-UHFFFAOYSA-N nonoxybenzene Chemical compound CCCCCCCCCOC1=CC=CC=C1 GSGDTSDELPUTKU-UHFFFAOYSA-N 0.000 description 1
- JFOJYGMDZRCSPA-UHFFFAOYSA-J octadecanoate;tin(4+) Chemical compound [Sn+4].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O JFOJYGMDZRCSPA-UHFFFAOYSA-J 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000011178 precast concrete Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- XWIHRGFIPXWGEF-UHFFFAOYSA-N propafenone hydrochloride Chemical class Cl.CCCNCC(O)COC1=CC=CC=C1C(=O)CCC1=CC=CC=C1 XWIHRGFIPXWGEF-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- DEWNCLAWVNEDHG-UHFFFAOYSA-M sodium;2-(2-methylprop-2-enoyloxy)ethanesulfonate Chemical compound [Na+].CC(=C)C(=O)OCCS([O-])(=O)=O DEWNCLAWVNEDHG-UHFFFAOYSA-M 0.000 description 1
- IWPBANVNTNWEBT-UHFFFAOYSA-M sodium;2-(6-methylheptyl)benzenesulfonate Chemical compound [Na+].CC(C)CCCCCC1=CC=CC=C1S([O-])(=O)=O IWPBANVNTNWEBT-UHFFFAOYSA-M 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
- KEROTHRUZYBWCY-UHFFFAOYSA-N tridecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C(C)=C KEROTHRUZYBWCY-UHFFFAOYSA-N 0.000 description 1
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical group CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 description 1
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
Description
本発明は、高い耐汚染性を発現し、その効果を塗料可使時間の間、維持することが可能な水性塗料用組成物および該塗料組成物から得られる塗膜に関する。 The present invention relates to an aqueous coating composition capable of expressing high stain resistance and maintaining the effect during the paint usable time, and a coating film obtained from the coating composition.
近年、塗料の分野においても、公害対策あるいは省資源の観点より、有機溶剤を使用するものから、水溶性あるいは水分散樹脂への転換が試みられている。しかし、水性塗料は溶剤系塗料に比べ、塗膜性能が劣る傾向にあった。このような状況下、水性塗料においても溶剤系塗料と同等の塗膜物性が要求され、特に耐汚染性といった高度な性能付与が要求されている。 In recent years, in the field of paints, from the viewpoint of pollution control or resource saving, attempts have been made to switch from using organic solvents to water-soluble or water-dispersed resins. However, water-based paints tended to be inferior in coating film performance compared to solvent-based paints. Under such circumstances, water-based paints are also required to have the same coating film properties as solvent-based paints, and in particular, it is required to provide high performance such as stain resistance.
また、塗料への耐汚染性付与方法としては、塗料中にオルガノシリケートを配合する方法が知られている（例えば特許文献１参照）。
この方法により、形成した塗膜の親水性が向上し、油性の汚染物質の付着防止に効果があり、また、付着した汚染物質を降雨等の水滴で洗い流すことが可能である。しかしながら、上記方法を水性塗料に適用した場合、オルガノシリケートの水性塗料への混和性が悪く、表面光沢が低下するという問題があった。
これに対して、オルガノシリケートの水性塗料への混和性を改良する方法として、オルガノシリケートと乳化剤の混合物を添加する方法が開示されている（例えば特許文献２参照）。
As a method for imparting stain resistance to a paint, a method of blending an organosilicate in the paint is known (for example, see Patent Document 1).
By this method, the hydrophilicity of the formed coating film is improved, and it is effective in preventing the adhesion of oily contaminants, and the adhered contaminants can be washed away with water droplets such as rain. However, when the above method is applied to an aqueous paint, there is a problem that the miscibility of the organosilicate into the aqueous paint is poor and the surface gloss is lowered.
On the other hand, a method of adding a mixture of an organosilicate and an emulsifier is disclosed as a method for improving the miscibility of an organosilicate in an aqueous paint (see, for example, Patent Document 2).
この方法により、水性塗料との混和性は改善され、表面光沢の極端な低下は解決された。しかし、オルガノシリケートは加水分解しやすく、加水分解が進んだオルガノシリケートを含む塗料を塗布した場合、塗膜の耐汚染性が得られない問題があった。耐汚染性が発現するかは塗布前の塗料を見ただけでは区別が付かず、オルガノシリケートを配合した後の経過時間で経験的に推測することが行われていた。しかし、塗料の種類によってこの時間はかなり違うのが実状である。
本願は、オルガノシリケートの加水分解を防いで塗料の可使時間を保持し、耐汚染性が発現しなくなった塗料は使用できない、あるいは使用するのをためらう様な状態とすることを特徴としたものである。
This application is characterized by preventing the hydrolysis of organosilicates, maintaining the pot life, and making paints that no longer exhibit stain resistance not usable or hesitate to use. It is.
本発明が解決しようとする課題は、可使時間内の塗膜表面親水性を維持しつつ、表面親水性能が低下した塗料では、その使用が困難な状態となる水性塗料組成物を提供することである。 The problem to be solved by the present invention is to provide an aqueous coating composition that is difficult to use in a paint having reduced surface hydrophilic performance while maintaining the coating surface hydrophilicity within the pot life. It is.
分子内に加水分解性基に結合したケイ素基と特定の第３級アミン単位を少なくとも1つ有するエマルション、オルガノシリケート化合物、有機金属化合物を組み合わせた塗料組成物を用いることで、ポットライフが特定時間保持でき、耐汚染性を安定的に付与できる方法を見出した。 By using a coating composition that combines an emulsion having at least one silicon group bonded to a hydrolyzable group in the molecule and a specific tertiary amine unit, an organosilicate compound, and an organometallic compound, the pot life is specified for a specific time. The present inventors have found a method that can be retained and can stably impart stain resistance.
すなわち本願は、
・主鎖が実質的にビニル系重合体からなり、分子内に加水分解性基に結合したケイ素基と下記一般式（１）で表される第３級アミン単位を少なくとも1つ有する合成樹脂エマルション（Ａ）と一般式（２）で示されるオルガノシリケート化合物またはその部分加水分解縮合物（Ｂ）および有機金属化合物（Ｃ）からなる水性塗料用組成物。
一般式（１）
That is, this application
A synthetic resin emulsion whose main chain consists essentially of a vinyl polymer and has at least one tertiary amine unit represented by the following general formula (1) and a silicon group bonded to a hydrolyzable group in the molecule A composition for water-based paints comprising the organosilicate compound represented by (A) and the general formula (2) or a partially hydrolyzed condensate (B) thereof and an organometallic compound (C).
General formula (1)
（式中、Ｒ1、Ｒ2はいずれも炭素数１〜１０のアルキル基、ＸはＯもしくはＮＨ、ｍは２〜１０の整数を示す。）
Ｓｉ−（ＯＲ）4・・・・一般式（２）
（式中、Ｒは同じかまたは異なり炭素数１〜４のアルキル基である）（請求項１）。
・前記エマルション（Ａ）１００重量部に対して、オルガノシリケート化合物またはその部分加水分解縮合物（Ｂ）を０．１から１００重量部配合してなることを特徴とする請求項１に記載の水性塗料用組成物（請求項２）。
・前記エマルション（Ａ）がポリオキシアルキレン基含有重合体のエマルションであることを特徴とする請求項１または２のいずれか１項に記載の水性塗料用組成物（請求項３）。
・前記有機金属化合物（Ｃ）が有機錫化合物であることを特徴とする請求項１から３のいずれか１項に記載の水性塗料用組成物（請求項４）。
・前記有機金属化合物（Ｃ）が一般式（３）で示される含硫黄有機錫化合物であることを特徴とする請求項１から４のいずれか1項に記載の水性塗料用組成物。
（Ｒ1）（Ｒ2）Ｓｎ（Ｓ−Ｒ3）（Ｓ−Ｒ4）・・・一般式（３）
（式中、Ｒ1、Ｒ2は同じかまたは異なり炭素数１〜８の直鎖あるいは分岐したアルキル基、Ｒ3、Ｒ4は直鎖あるいは分岐した炭素数１〜２０のアルキル基、アルケニル基から選ばれる炭化水素基である）（請求項５）。
・前記（Ｂ）成分と（Ｃ）成分と、さらに分子中にポリオキシアルキレン基を有する化合物（Ｄ）を予め混合してなる混合物を前記（Ａ）成分に配合してなることを特徴とする請求項１から５のいずれか1項に記載の水性塗料用組成物（請求項６）。
・請求項１〜６のいずれか１項に記載の水性塗料組成物から得られる塗膜（請求項７）。
以上の構成によるものである。
(Wherein R 1 and R 2 are all alkyl groups having 1 to 10 carbon atoms, X is O or NH, and m is an integer of 2 to 10)
Si- (OR) 4 ... General formula (2)
(Wherein R is the same or different and is an alkyl group having 1 to 4 carbon atoms) (Claim 1).
The aqueous composition according to claim 1, wherein 0.1 to 100 parts by weight of an organosilicate compound or a partially hydrolyzed condensate (B) thereof is blended with 100 parts by weight of the emulsion (A). A coating composition (claim 2).
The aqueous emulsion composition according to claim 1 or 2, wherein the emulsion (A) is an emulsion of a polyoxyalkylene group-containing polymer.
The composition for water-based paint according to any one of claims 1 to 3, wherein the organometallic compound (C) is an organic tin compound (claim 4).
The composition for water-based paint according to any one of claims 1 to 4, wherein the organometallic compound (C) is a sulfur-containing organotin compound represented by the general formula (3).
(R 1 ) (R 2 ) Sn (S—R 3 ) (S—R 4 ) (3)
Wherein R 1 and R 2 are the same or different and are linear or branched alkyl groups having 1 to 8 carbon atoms, R 3 and R 4 are linear or branched alkyl groups having 1 to 20 carbon atoms and alkenyl groups. (Claim 5).
A mixture obtained by previously mixing the component (B), the component (C), and a compound (D) having a polyoxyalkylene group in the molecule is added to the component (A). The composition for water-based paints of any one of Claim 1 to 5 (Claim 6).
-The coating film obtained from the water-based coating composition of any one of Claims 1-6 (Claim 7).
This is due to the above configuration.
本発明の耐汚染性水性塗料組成物は、優れた耐汚染性および高い光沢を有する塗膜を形成することができる。また、可視時間の間は、混合直後と同様に塗膜表面親水性を維持することが可能で、一方、ポットライフ２４時間後には塗料が使用をためらうような状態となり、上記特性の発現程度が劣る塗料を用いない様にすることが可能となる。 The stain-resistant water-based coating composition of the present invention can form a coating film having excellent stain resistance and high gloss. Further, during the visible time, it is possible to maintain the coating surface hydrophilicity immediately after mixing, while the paint becomes hesitant to use after 24 hours of pot life, and the degree of expression of the above characteristics is increased. It becomes possible not to use inferior paint.
塗料の塗布作業では朝の作業前に一日の必要塗料の量を予測し、触媒その他の混合を行うことが通常行われている。まれに前日調合して残った塗料を使うと、オルガノシリケートの加水分解が進んで、耐汚染性が異なる部分がでて美観上問題となる場合があった。本願発明はこの様な問題を未然に防ぐことが可能である。
本願は、オルガノシリケートの急速な加水分解・縮合を防いで塗料の可使時間を保持し、加水分解・縮合が進みすぎ、耐汚染性が発現しないあるいは耐汚染性能が低くなった塗料は使用できない、あるいは使用するのをためらう様な状態とすることができる。
この様な状況となるには、塗装作業手順からみて、作業当日朝に調合した塗料をその日一日は安定的に使用でき、翌日には使わないようにすればよいので、調合後の安定性期間（使用するのを判断する期間）としては、２４時間が目安として考えられる。なるべくなら２０時間、あるいは１５時間が好ましい。
In the paint application work, it is usual to predict the amount of paint required per day before the morning work and to mix the catalyst and other materials. In rare cases, when the paint left after the previous day was used, the hydrolysis of the organosilicate progressed, and there was a case where a part with different stain resistance appeared, which was an aesthetic problem. The present invention can prevent such a problem in advance.
This application prevents the rapid hydrolysis / condensation of organosilicates, maintains the pot life, and the hydrolysis / condensation proceeds so much that the paint does not exhibit stain resistance or has poor stain resistance performance. Or, it can be in a state of hesitation in using it.
In order to achieve such a situation, it is necessary to use the paint prepared in the morning on the day of the work in a stable manner on the day and not to use it on the next day. As a guideline), 24 hours can be considered as a guide. If possible, 20 hours or 15 hours are preferable.
以下に本発明をその実施の形態に基づき詳細に説明する。
（合成樹脂エマルジョン）
本発明の合成樹脂エマルション（Ａ）成分は、その主鎖が実質的にビニル系単量体及び必要に応じてその他単量体を共重合した主鎖からなる。
ここで、「主鎖がビニル系共重合体鎖からなる」とは、ビニル基、ビニリデン基のように、重合性炭素炭素二重結合を化合物あるいは重合性二重結合を有する化合物と他の化合物との共重合体ブロックがビニル系共重合体（Ａ）の主鎖を構成していることを意味する。
Hereinafter, the present invention will be described in detail based on an embodiment thereof.
(Synthetic resin emulsion)
The synthetic resin emulsion (A) component of the present invention consists of a main chain in which the main chain is substantially copolymerized with a vinyl monomer and, if necessary, other monomers.
Here, “the main chain is composed of a vinyl copolymer chain” means that a compound having a polymerizable carbon-carbon double bond or a compound having a polymerizable double bond and other compounds, such as a vinyl group and a vinylidene group. This means that the copolymer block constitutes the main chain of the vinyl copolymer (A).
前記加水分解性基と結合したケイ素基の加水分解性基は、ハロゲン基、アルコキシ基等がある。その中で、反応の制御の簡便さからアルコキシ基が有用である。
前記合成樹脂エマルション（Ａ）成分は、たとえば重合性二重結合および炭素原子に結合した加水分解性シリル基を含有する単量体（ａ）、下記一般式（１）で表される第３級アミン単位含有単量体（ｂ）、その他の単量体（ｃ）を重合することによって製造することができる。
Examples of the hydrolyzable group of the silicon group bonded to the hydrolyzable group include a halogen group and an alkoxy group. Among them, an alkoxy group is useful because of easy control of the reaction.
The synthetic resin emulsion (A) component is, for example, a monomer (a) containing a polymerizable double bond and a hydrolyzable silyl group bonded to a carbon atom, a tertiary class represented by the following general formula (1) It can be produced by polymerizing the amine unit-containing monomer (b) and the other monomer (c).
一般式（１） General formula (1)
（式中、Ｒ1、Ｒ2はいずれも炭素数１〜１０のアルキル基、ＸはＯもしくはＮＨ、ｎは２〜１０の整数を示す。）。 (In the formula, R 1 and R 2 are all alkyl groups having 1 to 10 carbon atoms, X is O or NH, and n is an integer of 2 to 10).
加水分解性シリル基を含有する単量体としては、取扱いの容易さ、価格の点および反応副生成物が生じにくい点から、アルコキシシリル基含有ビニル系モノマーが好ましい。アルコシキシシリル基含有ビニルモノマーの具体例としては、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（２−メトキシエトキシ）シラン、ビニルトリイソプロポキシシラン、γ−（メタ）アクリロキシプロピルトリメトキシシラン、γ−（メタ）アクリロキシプロピルトリエトキシシラン、γ−（メタ）アクリロキシプロピルトリ−ｎ−プロポキシシラン、γ−（メタ）アクリロキシプロピルトリイソプロポキシシラン、ビニルトリアセトキシシラン、β−（メタ）アクリロキシエチルトリメトキシシラン等が挙げられる。これらの加水分解性シリル基含有ビニル系単量体は、１種を単独で用いてもよいし、また２種以上を併用しても良い。 As the monomer containing a hydrolyzable silyl group, an alkoxysilyl group-containing vinyl monomer is preferable from the viewpoint of ease of handling, cost, and the difficulty of producing a reaction byproduct. Specific examples of vinyloxy group-containing vinyl monomers include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltriisopropoxysilane, and γ- (meth) acryloxypropyltrimethoxysilane. , Γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropyltri-n-propoxysilane, γ- (meth) acryloxypropyltriisopropoxysilane, vinyltriacetoxysilane, β- (meth ) Acryloxyethyltrimethoxysilane and the like. These hydrolyzable silyl group-containing vinyl monomers may be used alone or in combination of two or more.
水性塗料にした場合の貯蔵安定性の点からγ−（メタ）アクリロキシプロピルトリエトキシシラン、γ−（メタ）アクリロキシプロピルトリ−ｎ−プロポキシシラン、γ−（メタ）アクリロキシプロピルトリイソプロポキシシランが特に好ましい。
加水分解性シリル基含有単量体は、全単量体１００重量部中に０．１〜５０重量部用いて共重合されることが望ましい。０．１重量部未満では耐水性、耐久性が低下し、５０重量部を越えるとエマルジョンが不安定となり、０．５〜２０重量部がより好ましい。
上記のように得られたアルコキシシリル基含有アクリル系エマルジョンは、本発明のアルコキシシラン化合物の加水分解・縮合を促進する化合物（Ｃ）成分が混合された場合、架橋反応が進行し、耐水性・耐候性が良好な塗膜となる。
Γ- (Meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropyltri-n-propoxysilane, γ- (meth) acryloxypropyltriisopropoxy from the viewpoint of storage stability in the case of water-based paint Silane is particularly preferred.
The hydrolyzable silyl group-containing monomer is desirably copolymerized using 0.1 to 50 parts by weight in 100 parts by weight of all monomers. If it is less than 0.1 parts by weight, the water resistance and durability are lowered, and if it exceeds 50 parts by weight, the emulsion becomes unstable, and 0.5 to 20 parts by weight is more preferable.
When the compound (C) that promotes hydrolysis / condensation of the alkoxysilane compound of the present invention is mixed with the alkoxysilyl group-containing acrylic emulsion obtained as described above, the crosslinking reaction proceeds, and the water resistance / The coating film has good weather resistance.
下記一般式（１）で表される第３級アミン単位含有単量体（ｂ）としては、
一般式（１）
As the tertiary amine unit-containing monomer (b) represented by the following general formula (1),
General formula (1)
（式中、Ｒ1、Ｒ2はいずれも炭素数１〜１０のアルキル基、ＸはＯもしくはＮＨ、ｍは２〜１０の整数を示す。）で表される構造を有するものであれば特に制限はないが、合成の容易さの点から、２−（Ｎ，Ｎ−ジメチルアミノ）エチルアクリレート、２−（Ｎ，Ｎ−ジメチルアミノ）エチルメタクリレート、３−（Ｎ，Ｎ―ジメチルアミノ）プロピルアクリルアミド等が挙げられる。 (In the formula, R 1 and R 2 are both alkyl groups having 1 to 10 carbon atoms, X is O or NH, and m is an integer of 2 to 10). Although not limited, 2- (N, N-dimethylamino) ethyl acrylate, 2- (N, N-dimethylamino) ethyl methacrylate, 3- (N, N-dimethylamino) propyl are preferred from the viewpoint of ease of synthesis. Examples include acrylamide.
前記単量体（ｂ）の使用量の合計は、用いる単量体（ａ）の種類および使用量に応じて適宜調整すればよいが、通常用いる重合成分全量の０.１〜１０％、さらには０.２〜５％、特には０.３〜３％が好ましい。 The total amount of the monomer (b) used may be appropriately adjusted according to the type and amount of the monomer (a) used, but is 0.1 to 10% of the total amount of the polymerization components used normally, Is preferably 0.2 to 5%, particularly preferably 0.3 to 3%.
使用量が０．１％未満の場合には、本発明の目的とする効果の発現が不充分であり、１０％を超える場合には、得られるエマルションの安定性が損なわれる場合がある。 When the amount used is less than 0.1%, the intended effect of the present invention is not sufficiently exhibited, and when it exceeds 10%, the stability of the resulting emulsion may be impaired.
その他の単量体（ｃ）としては、特に限定はないが、具体例としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−ブチルアクリレート、ｉｓｏ−ブチルアクリレート、ｔｅｒｔ−ブチルアクリレート、ベンジル（メタ）アクリレート、シクロヘキシルアクリレート、ｎ−ブチルメタクリレート、ｉｓｏ−ブチルメタクリレート、ｔｅｒｔ−ブチルメタクリレート、２−エチルヘキシルメタクリレート、イソデシルメタクリレート、ラウリルメタクリレート、トリデシルメタクリレート、ステアリルメタクリレート、シクロヘキシルメタクリレート、イソボニルメタクリレートなどの（メタ）アクリレート系単量体； スチレン、α−メチルスチレン、クロロスチレン、ビニルトルエンなどの芳香族炭化水素系ビニル単量体；酢酸ビニル、プロピオン酸ビニルなどのビニル化合物；（メタ）アクリロニトリルなどのニトリル基含有ビニル系単量体；グリシジル（メタ）アクリレートなどのエポキシ基含有ビニル系単量体；２−ヒドロキシプロピル（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、２−ヒドロキシエチルビニルエーテル、ヒドロキシスチレン、アロニクス５７００（東亜合成化学（株）製）、ｐｌａｃｃｅｌＦＡ−１、ｐｌａｃｃｅｌＦＡ−４、ｐｌａｃｃｅｌＦＭ−１、ｐｌａｃｃｅｌＦＭ−４（以上、ダイセル化学（株）製）、ＨＥ−１０、ＨＥ−２０、ＨＰ−１０、ＨＰ−２０（以上、（株）日本触媒製）、ブレンマーＰＥＰシリーズ、ブレンマーＮＫＨ−５０５０、ブレンマーＧＬＭ（以上日本油脂（株）製）、水酸基含有ビニル系変性ヒドロキシアルキルビニル系モノマーなどの水酸基含有ビニル系単量体；東亜合成化学（株）製のマクロモノマーであるＡＳ−６、ＡＮ−６、ＡＡ−６、ＡＢ−６、ＡＫ−５などの化合物、ビニルメチルエーテル、プロピレン、ブタジエン等が挙げられる。 Other monomers (c) are not particularly limited, but specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, benzyl (Meth) acrylate, cyclohexyl acrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, etc. (Meth) acrylate monomer; aromatic hydrocarbon vinyl such as styrene, α-methylstyrene, chlorostyrene, vinyltoluene Vinyl compounds such as vinyl acetate and vinyl propionate; nitrile group-containing vinyl monomers such as (meth) acrylonitrile; epoxy group-containing vinyl monomers such as glycidyl (meth) acrylate; 2-hydroxypropyl (meth) Acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl vinyl ether, hydroxystyrene, Aronics 5700 (manufactured by Toa Gosei Kagaku Co., Ltd.), placFA-1, placFA-4, placceFM-1, placceFM-4 (above, Daicel Chemical Industries, Ltd.), HE-10, HE-20, HP-10, HP-20 (above, manufactured by Nippon Shokubai Co., Ltd.), Blemmer PEP series, Blemmer NKH-5050, Blemmer GLM (above Nippon Oil & Fats (above) Co., Ltd.), water Hydroxyl group-containing vinyl monomers such as group-containing vinyl-modified hydroxyalkyl vinyl monomers; AS-6, AN-6, AA-6, AB-6, AK- which are macromonomers manufactured by Toa Synthetic Chemical Co., Ltd. 5 and the like, vinyl methyl ether, propylene, butadiene and the like.
更に、エマルジョンの安定性を向上させることが可能な親水性を有するビニル系単量体も使用可能である。使用可能な親水性基を有するビニル系単量体としては、スチレンスルホン酸ナトリウム、２−スルホエチルメタクリレートナトリウム、２−スルホエチルメタクリレートアンモニウム、ポリオキシアルキレン鎖を有するビニル系単量体が挙げられる。 Furthermore, a hydrophilic vinyl monomer capable of improving the stability of the emulsion can also be used. Examples of the vinyl monomer having a hydrophilic group that can be used include sodium styrenesulfonate, sodium 2-sulfoethyl methacrylate, 2-sulfoethyl methacrylate ammonium, and vinyl monomers having a polyoxyalkylene chain.
ポリオキシアルキレン鎖を有するビニル系単量体に限定はないが、ポリオキアルキレン鎖を有するアクリル酸エステル又はメタクリル酸エステルが好ましく、具体例としては日本油脂（株）製ブレンマーＰＥ−９０、ＰＥ−２００、ＰＥ−３５０、ＡＥ−９０、ＡＥ−２００、ＡＥ−３５０、ＰＰ−５００、ＰＰ−８００、ＰＰ−１０００、ＡＰ−４００、ＡＰ−５５０、ＡＰ−８００、７００ＰＥＰ−３５０Ｂ、１０ＰＥＰ−５５０Ｂ、５５ＰＥＴ−４００、３０ＰＥＴ−８００、５５ＰＥＴ−８００、３０ＰＰＴ−８００、５０ＰＰＴ−８００、７０ＰＰＴ−８００、ＰＭＥ−１００、ＰＭＥ−２００、ＰＭＥ−４００、ＰＭＥ−１０００、ＰＭＥ−４０００、ＡＭＥ−４００、５０ＰＯＥＰ−８００Ｂ、５０ＡＯＥＰ−８００Ｂ、ＡＥＰ、ＡＥＴ、ＡＰＴ、ＰＬＥ、ＡＬＥ、ＰＳＥ、ＡＳＥ、ＰＫＥ、ＡＫＥ、ＰＮＥ、ＡＮＥ、ＰＮＰ、ＡＮＰ、ＰＮＥＰ−６００、共栄社化学（株）製ライトエステル１３０ＭＡ、０４１ＭＡ、ＭＴＧ、ライトアクリレートＥＣ−Ａ、ＭＴＧ−Ａ、１３０Ａ、ＤＰＭ−Ａ、Ｐ−２００Ａ、ＮＰ−４ＥＡ、ＮＰ−８ＥＡ、ＥＨＤＧ−Ａ、日本乳化剤（株）製ＭＡ−３０、ＭＡ−５０、ＭＡ−１００、ＭＡ−１５０、ＲＭＡ−１１２０、ＲＭＡ−５６４、ＲＭＡ−５６８、ＲＭＡ−５０６、ＭＰＧ１３０−ＭＡ、Ａｎｔｏｘ ＭＳ−６０、ＭＰＧ−１３０ＭＡ、ＲＭＡ−１５０Ｍ、ＲＭＡ−３００Ｍ、ＲＭＡ−４５０Ｍ、ＲＡ−１０２０、ＲＡ−１１２０、ＲＡ−１８２０、新中村化学工業（株）製ＮＫ−ＥＳＴＥＲ Ｍ−２０Ｇ、Ｍ−４０Ｇ、Ｍ−９０Ｇ、Ｍ−２３０Ｇ、ＡＭＰ−１０Ｇ、ＡＭＰ−２０Ｇ、ＡＭＰ−６０Ｇ、ＡＭ−９０Ｇ、ＬＡ、三洋化成（株）製エレミノールＲＳ−３０などがあげられる。 Although there is no limitation in the vinyl-type monomer which has a polyoxyalkylene chain, the acrylic acid ester or methacrylic acid ester which has a polyoxyalkylene chain is preferable, and as a specific example, Nippon Oil & Fats Co., Ltd. Blemmer PE-90, PE- 200, PE-350, AE-90, AE-200, AE-350, PP-500, PP-800, PP-1000, AP-400, AP-550, AP-800, 700PEP-350B, 10PEP-550B, 55PET-400, 30PET-800, 55PET-800, 30PPT-800, 50PPT-800, 70PPT-800, PME-100, PME-200, PME-400, PME-1000, PME-4000, AME-400, 50POEP- 800B, 50AOEP-800B, AE , AET, APT, PLE, ALE, PSE, ASE, PKE, AKE, PNE, ANE, PNP, ANP, PNEP-600, Kyoeisha Chemical Co., Ltd. light ester 130MA, 041MA, MTG, light acrylate EC-A, MTG -A, 130A, DPM-A, P-200A, NP-4EA, NP-8EA, EHDG-A, MA-30 manufactured by Nippon Emulsifier Co., Ltd., MA-50, MA-100, MA-150, RMA-1120 , RMA-564, RMA-568, RMA-506, MPG130-MA, Antox MS-60, MPG-130MA, RMA-150M, RMA-300M, RMA-450M, RA-1020, RA-1120, RA-1820, NK-ESTER M-20G, M-40G, M manufactured by Shin-Nakamura Chemical Co., Ltd. 90G, M-230G, AMP-10G, AMP-20G, AMP-60G, AM-90G, LA, Sanyo Chemical Industries Co., Ltd. ELEMINOL RS-30 and the like.
ポリエチレングリコールジ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、トリアリルシアヌレート、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などの重合性の不飽和結合を２つ以上有する単量体を使用することも可能である。この場合、生成した粒子内部に架橋を有する構造となり、形成した塗膜の耐水性が向上する。 Uses a monomer having two or more polymerizable unsaturated bonds such as polyethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, triallyl cyanurate, allyl (meth) acrylate, divinylbenzene, diallyl phthalate It is also possible to do. In this case, the generated particles have a structure having cross-linking, and the water resistance of the formed coating film is improved.
本発明に使用できるアクリル樹脂エマルジョンは、通常の方法を採用することで得ることができるが、エマルジョンの粒子径および安定性を考慮すると乳化重合法が好ましい。
前記乳化重合法には特に限定がなく、たとえばバッチ重合法、モノマー滴下重合法、乳化モノマー滴下重合法などの各種乳化重合法の中から適宜選択して採用することができるが、本発明においては、特に製造時のエマルジョンの安定性を確保する上で、モノマー滴下重合法および乳化モノマー滴下重合法が好ましい。
The acrylic resin emulsion that can be used in the present invention can be obtained by adopting a usual method, but an emulsion polymerization method is preferred in consideration of the particle size and stability of the emulsion.
The emulsion polymerization method is not particularly limited, and can be appropriately selected from various emulsion polymerization methods such as a batch polymerization method, a monomer dropping polymerization method, and an emulsion monomer dropping polymerization method. In particular, in order to ensure the stability of the emulsion at the time of production, a monomer dropping polymerization method and an emulsion monomer dropping polymerization method are preferred.
乳化重合に際しては、通常用いられるイオン性または非イオン性の界面活性剤を用いることができる。 In emulsion polymerization, commonly used ionic or nonionic surfactants can be used.
イオン性界面活性剤としては、たとえばポリオキシエチレンノニルフェニルエーテルサルフェート、ポリオキシエチレンアリルエーテルサルフェート、オクチルフェノキシエトキシエチルスルホネート、ポリオキシエチレントリデシルエーテルサルフェートなどのポリオキシエチレン鎖を有するアニオン性界面活性剤；ラウリルスルホン酸ナトリウム、ドデシルベンゼンスルホン酸ナトリウム、イソオクチルベンゼンスルホン酸ナトリウムなどのスルホン酸塩；イミダゾリンラウレート、アンモニウムハイドロオキサイドなどのアンモニウム塩などが代表例として挙げられるが、これらの中では、ポリオキシエチレン鎖を有するアニオン性界面活性剤が好ましい。 Examples of the ionic surfactant include an anionic surfactant having a polyoxyethylene chain such as polyoxyethylene nonylphenyl ether sulfate, polyoxyethylene allyl ether sulfate, octylphenoxyethoxyethyl sulfonate, polyoxyethylene tridecyl ether sulfate, and the like. Sulfonic acid salts such as sodium lauryl sulfonate, sodium dodecylbenzene sulfonate and sodium isooctylbenzene sulfonate; ammonium salts such as imidazoline laurate and ammonium hydroxide are typical examples. An anionic surfactant having an oxyethylene chain is preferred.
また、非イオン性界面活性剤としては、たとえばポリエチレングリコールノニルフェニルエーテル；ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンラウリルエーテルなどのポリオキシエチレン類；Ｌ−７７、Ｌ−７２０、Ｌ−５４１０、Ｌ−７６０２、Ｌ−７６０７（以上、ユニオンカーバイド社製）などのシリコーンを含む非イオン系の界面活性剤などが代表例として挙げられる。 Examples of the nonionic surfactant include polyethylene glycol nonylphenyl ether; polyoxyethylenes such as polyoxyethylene nonylphenyl ether and polyoxyethylene lauryl ether; L-77, L-720, L-5410, L Representative examples include nonionic surfactants containing silicone such as −7602 and L-7607 (manufactured by Union Carbide).
本発明においては、界面活性剤として１分子中に重合性二重結合を有する反応性界面活性剤を用いることが耐水性、耐候性の点で好ましい。また、特に分子内にポリオキシアルキレン基を有する反応性界面活性剤を用いた場合には、機械的安定性を向上させることができる。 In the present invention, it is preferable to use a reactive surfactant having a polymerizable double bond in one molecule as the surfactant in terms of water resistance and weather resistance. In particular, when a reactive surfactant having a polyoxyalkylene group in the molecule is used, the mechanical stability can be improved.
かかる反応性界面活性剤の具体例としては、例えば、旭電化工業（株）製アデカリアソープＥＲ−１０、ＥＲ−２０、ＥＲ−３０、ＥＲ−４０、ＳＲ−１０、ＳＲ−２０、ＳＲ−１０２５、ＮＥ−１０、ＮＥ−２０、ＮＥ−３０、ＮＥ−４０、ＳＥ−１０Ｎ）、日本乳化剤（株）製Ａｎｔｏｘ−ＭＳ−６０、ＲＭＡ−１１２０、ＲＭＡ−５６４、ＲＭＡ−５６８、ＲＭＡ−５０６、第一工業製薬（株）製アクアロンＫＨ−０５、ＫＨ−１０、ＲＮ−２０、ＲＮ−３０、ＲＮ−５０、ＲＮ−２０２５、ＨＳ−１０、ＨＳ−２０、ＨＳ−１０２５、ＢＣ０５、ＢＣ１０、ＢＣ０５１５、ＢＣ１０２５、三洋化成工業（株）製エレミノールＪＳ−２、エレミノールＲＳ−３０、花王（株）製ラテムルＳ−１８０、Ｓ−１８０Ａ、ＰＤ−１０４、ＰＤ−４２０、ＰＤ−４３０などが挙げられる。 Specific examples of such reactive surfactants include, for example, Adeka Soap ER-10, ER-20, ER-30, ER-40, SR-10, SR-20, SR- manufactured by Asahi Denka Kogyo Co., Ltd. 1025, NE-10, NE-20, NE-30, NE-40, SE-10N), Nippon Emulsifier Co., Ltd. Antox-MS-60, RMA-1120, RMA-564, RMA-568, RMA-506 , Aqualon KH-05, KH-10, RN-20, RN-30, RN-50, RN-2025, HS-10, HS-20, HS-1025, BC05, BC10, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. BC0515, BC1025, Sanyo Chemical Industries Co., Ltd. Eleminol JS-2, Eleminol RS-30, Kao Co., Ltd. Latemul S-180, S-180A, PD-104, PD 420, such as PD-430 and the like.
なかでも、環境への配慮から、非アルキルフェノール系のものが望ましい。
前記界面活性剤は、単独または２種以上を混合して用いることができ、その使用量は、単量体全量１００重量部に対して１０重量部以下、好ましくは０．５〜８重量部である。
Of these, non-alkylphenol-based ones are desirable in consideration of the environment.
The surfactants can be used alone or in admixture of two or more, and the amount used is 10 parts by weight or less, preferably 0.5 to 8 parts by weight based on 100 parts by weight of the total amount of monomers. is there.
重合開始剤としては、特に限定はないが、重合をより安定に行なうために、重合開始剤としてレドックス系を用いることが望ましい。また、重合中の混合液の安定性を保持し、重合を安定に行なうためには、温度は７０℃以下、好ましくは４０〜６５℃であり、ｐＨは５〜９に調整することが好ましい。 Although there is no limitation in particular as a polymerization initiator, In order to perform superposition | polymerization more stably, it is desirable to use a redox system as a polymerization initiator. Further, in order to maintain the stability of the mixed solution during the polymerization and perform the polymerization stably, the temperature is 70 ° C. or lower, preferably 40 to 65 ° C., and the pH is preferably adjusted to 5 to 9.
前記レドックス系に用いる開始剤として、例えば、過硫酸カリウム、過硫酸アンモニウム、過酸化水素、ｔ−ブチルハイドロパーオキサイド、ベンゾイルパーオキサイド、クメンハイドロパーオキサイドなどがあげられ、これらに組み合わせる還元剤としては、酸性亜硫酸ナトリウム、ロンガリット、Ｂｒｕｇｇｏｌｉｔｅ ＦＦ−６（ＢｒｕｇｇａｍａｎｎＣｈｅｍｉｃａｌＵＳ製）、二酸化チオ尿素、Ｌ−アスコルビン酸などがあげられる。特に、ｔ−ブチルハイドロパーオキサイド、ベンゾイルパーオキサイド、クメンハイドロパーオキサイド等の有機過酸化物とロンガリット、Ｂｒｕｇｇｏｌｉｔｅ ＦＦ−６または二酸化チオ尿素との組み合わせが好ましい。 Examples of the initiator used in the redox system include potassium persulfate, ammonium persulfate, hydrogen peroxide, t-butyl hydroperoxide, benzoyl peroxide, cumene hydroperoxide, and the like. Examples thereof include acidic sodium sulfite, Rongalite, Bruggolite FF-6 (manufactured by Bruggamann Chemical US), thiourea dioxide, L-ascorbic acid and the like. In particular, a combination of an organic peroxide such as t-butyl hydroperoxide, benzoyl peroxide, cumene hydroperoxide and the like and Rongalite, Bruggolite FF-6 or thiourea dioxide is preferable.
なお、還元剤は、環境への配慮からホルムアルデヒド発生のないＢｒｕｇｇｏｌｉｔｅ ＦＦ−６、二酸化チオ尿素が特に好ましい。 Note that the reducing agent is particularly preferably Bruggolite FF-6 or thiourea dioxide which does not generate formaldehyde in consideration of the environment.
前記重合開始剤の使用量は、単量体全量１００重量部に対して０．０１〜１０部、好ましくは０．０５〜５重量部である。かかる重合開始剤の使用量が０．０１重量部未満である場合には、重合が進行しにくくなることがあり、１０重量部を超える場合には、生成する重合体の分子量が低下する傾向がある。 The amount of the polymerization initiator used is 0.01 to 10 parts, preferably 0.05 to 5 parts by weight based on 100 parts by weight of the total amount of monomers. When the amount of the polymerization initiator used is less than 0.01 parts by weight, the polymerization may be difficult to proceed. When the amount exceeds 10 parts by weight, the molecular weight of the produced polymer tends to decrease. is there.
また、重合開始剤の触媒活性を安定的に付与するために、硫酸鉄などの２価の鉄イオンを含む化合物とエチレンジアミン四酢酸二ナトリウムなどのキレート化剤を用いてもよい。かかるキレート化剤の使用量は、単量体全量１００重量部に対して０．０００１〜１重量部、好ましくは０．００１〜０．５重量部である。 In order to stably impart the catalytic activity of the polymerization initiator, a compound containing a divalent iron ion such as iron sulfate and a chelating agent such as disodium ethylenediaminetetraacetate may be used. The amount of the chelating agent used is 0.0001 to 1 part by weight, preferably 0.001 to 0.5 part by weight, based on 100 parts by weight of the total amount of monomers.
重合体の分子量を調節するために連鎖移動剤の添加も可能である。連鎖移動剤としては公知のもの、例えば、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、γ−メルカプトプロピルトリメトキシシラン、γ−メルカプトプロピルトリエトキシシラン、γ−メルカプトプロピルメチルジメトキシシラン、γ−メルカプトプロピルメチルジエトキシシラン等のメルカプタン系化合物、クロロホルム、四塩化炭素等の有機ハロゲン化物、スルフィドベンゼン、イソプロピルベンゼン、塩化第二鉄等が挙げられる。 Chain transfer agents can be added to control the molecular weight of the polymer. Known chain transfer agents such as n-dodecyl mercaptan, tert-dodecyl mercaptan, n-butyl mercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, Examples include mercaptan compounds such as γ-mercaptopropylmethyldiethoxysilane, organic halides such as chloroform and carbon tetrachloride, sulfide benzene, isopropylbenzene, and ferric chloride.
アクリル樹脂エマルジョン中の樹脂固形分濃度は、２０〜７０重量％が好ましく、さらに好ましくは３０〜６０重量％となるように調整する。かかる樹脂固形分濃度が７０重量％を超える場合には、系の濃度が著しく上昇するため、重合反応に伴なう発熱を除去することが困難になったり、重合器からの取り出しに長時間を要するようになる傾向がある。また、樹脂固形分濃度が２０重量％未満である場合には、重合操作の面では何ら問題は生じないものの、１回の重合操作によって生じる樹脂量が少なく、経済面で不利となる。 The resin solid content concentration in the acrylic resin emulsion is preferably 20 to 70% by weight, and more preferably 30 to 60% by weight. When the resin solid content concentration exceeds 70% by weight, the concentration of the system increases remarkably, making it difficult to remove the heat generated by the polymerization reaction or taking a long time to remove from the polymerization vessel. There is a tendency to become necessary. Further, when the resin solid content concentration is less than 20% by weight, there is no problem in terms of polymerization operation, but the amount of resin produced by one polymerization operation is small, which is disadvantageous in terms of economy.
なお、本発明に用いられるアクリル樹脂エマルジョンは、平均粒子径が０．０２〜１．０μｍ程度が好ましい。平均粒子径は、重合初期に仕込む乳化剤の量で調整することが可能である。 The acrylic resin emulsion used in the present invention preferably has an average particle size of about 0.02 to 1.0 μm. The average particle size can be adjusted by the amount of the emulsifier charged in the initial stage of polymerization.
（オルガノシリケート）
本発明で使用可能なオルガノシリケート化合物（Ａ）としては、加水分解性珪素基を含有する化合物であり、下記一般式（２）として現される化合物又はその部分分解縮合物である。
Ｓｉ−（ＯＲ）4・・・・一般式（２）
（式中Ｒは同じか又は異なり炭素数１〜４のアルキル基である）
具体的化合物としては、テトラメトキシシラン、テトラエトキシシラン、テトラ−ｎ−プロポキシシラン、テトラ−ｉ−プロポキシシラン、テトラ−ｎ−ブトキシシラン、テトラ−ｉ−ブトキシシラン、テトラ−ｔ−ブトキシシラン及びそれらの部分加水分解・縮合物が例示できる。中でもメチルシリケート５１、エチルシリケート４５、エチルシリケート４０、エチルシリケート４８（以上、コルコート（株）製）、シリケート４５、シリケート４０（以上、多摩化学工業（株）製）が望ましい。上記化合物は１種単独でもよく、２種以上を併用しても良い。
(Organosilicate)
The organosilicate compound (A) usable in the present invention is a compound containing a hydrolyzable silicon group, and is a compound represented by the following general formula (2) or a partial decomposition condensate thereof.
Si- (OR) 4 ... General formula (2)
(Wherein R is the same or different and is an alkyl group having 1 to 4 carbon atoms)
Specific compounds include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane and the like The partial hydrolysis-condensation product can be illustrated. Of these, methyl silicate 51, ethyl silicate 45, ethyl silicate 40, ethyl silicate 48 (manufactured by Colcoat Co., Ltd.), silicate 45, and silicate 40 (manufactured by Tama Chemical Industry Co., Ltd.) are preferable. The said compound may be single 1 type, and may use 2 or more types together.
また、同一分子中に異なったアルコキシシリル基を含有するオルガノシリケートも使用可能である。例えば、メチルエチルシリケート、メチルプロピルシリケート、メチルブチルシリケート、エチルプロピルシリケート、プロピルブチルシリケートなどである。これら置換基の比率が０〜１００％の間で任意に変更可能である。また、これらのシリケートの部分加水分解・縮合物も使用可能であると記述したが、縮合度は１〜２０程度が好ましい。更に好ましい縮合度の範囲は、３〜１５である。上記オルガノシリケート化合物ではアルコキシシリル基の炭素数は１〜４の化合物を例示しているが、炭素数が少なくなるほど反応性が向上することは一般的に知られている。 Organosilicates containing different alkoxysilyl groups in the same molecule can also be used. For example, methyl ethyl silicate, methyl propyl silicate, methyl butyl silicate, ethyl propyl silicate, propyl butyl silicate and the like. The ratio of these substituents can be arbitrarily changed between 0 to 100%. Moreover, although it described that the partial hydrolysis and condensate of these silicates can also be used, about 1-20 are preferable for a condensation degree. A more preferable range of the condensation degree is 3-15. In the organosilicate compound, compounds having 1 to 4 carbon atoms in the alkoxysilyl group are exemplified, but it is generally known that the reactivity improves as the carbon number decreases.
水性塗料へ添加した場合、炭素数が小さいオルガノシリケート、例えば、メチルシリケートを用いた場合、反応性が高く、塗料のゲル化までの時間、すなわち、ポットライフが短くなる。これに対し、炭素数が大きいブチルシリケートを用いた場合、耐汚染性付与率が低下し、ポットライフが長くなる。この耐汚染性とポットライフのバランスを考えると、アルコキシシリル基のアルキル部は炭素数が１と炭素数が２、３又は４が混在している場合、炭素数が２と炭素数が３又は４が混在していることが好ましく、平均として炭素数１．５〜２．８が好ましい。即ち、メチルシリケートとエチルシリケートの等モル混合物もしくは同一分子中にメチル基とエチル基を同数有するシリケートは炭素数１．５と計算できる。 When added to a water-based paint, an organosilicate having a small number of carbon atoms, such as methyl silicate, is highly reactive, and the time until gelation of the paint, that is, the pot life is shortened. On the other hand, when butyl silicate having a large number of carbon atoms is used, the stain resistance imparting rate is lowered and the pot life is lengthened. Considering the balance between the contamination resistance and the pot life, when the alkyl part of the alkoxysilyl group has 1 carbon and 2, 3 or 4 carbons, the carbon number is 2 and the carbon number is 3 or 4 is preferably mixed, and an average of 1.5 to 2.8 carbon atoms is preferable. That is, an equimolar mixture of methyl silicate and ethyl silicate, or a silicate having the same number of methyl groups and ethyl groups in the same molecule can be calculated as 1.5 carbon atoms.
（有機金属化合物）
本発明における（Ｃ）成分である有機金属化合物の具体例としては、例えば、エチルアセトアセテ−トアルミニウムジイソプロピレ−ト、アルミニウムトリス（アセチルアセテート）、アルミニウムトリス（エチルアセトアセテート）、アルミニウムモノアセチルアセトネ−トビス（エチルアセトアセテート）、アルキルアセチルアセテ−トアルミニウムジイソプロピレ−トなどの有機アルミ化合物；有機錫化合物；有機チタネート化合物；有機亜鉛化合物等の有機金属化合物が挙げられる。これらは、単独で用いてもよく、２種以上併用してもよい。
(Organic metal compound)
Specific examples of the organometallic compound (C) in the present invention include, for example, ethyl acetoacetate aluminum diisopropylate, aluminum tris (acetyl acetate), aluminum tris (ethyl acetoacetate), aluminum monoacetyl Organic aluminum compounds such as acetonatobis (ethyl acetoacetate) and alkyl acetyl acetate aluminum diisopropylate; organic tin compounds; organic titanate compounds; and organic metal compounds such as organic zinc compounds. These may be used alone or in combination of two or more.
なかでも親水性の発現しやすさから有機錫化合物がよく、例えば、ジオクチル錫ビス（２−エチルヘキシルマレ−ト）、ジオクチル錫オキサイドまたはジブチル錫オキサイドとシリケ−トとの縮合物、ジブチル錫ジオクトエ−ト、ジブチル錫ジラウレ−ト、ジブチル錫ジステアレ−ト、ジブチル錫ジアセチルアセトナ−ト、ジブチル錫ビス（エチルマレ−ト）、ジブチル錫ビス（ブチルマレ−ト）、ジブチル錫ビス（２−エチルヘキシルマレ−ト）、ジブチル錫ビス（オレイルマレ−ト）、スタナスオクトエ−ト、ステアリン酸錫、ジ−ｎ−ブチル錫ラルレ−トオキサイドがある。また、分子内にＳ原子有する錫化合物としては、ジブチル錫ビスイソノニル−３―メルカプトプロピオネ−ト、ジオクチル錫ビスイソノニル−３−メルカプトプロピオネ−ト、オクチルブチル錫ビスイソノニル−３−メルカプトプロピオネ−ト、ジブチル錫ビスイソオクチルチオグルコレ−ト、ジオクチル錫ビスイソオクチルチオグルコレ−ト、オクチルブチル錫ビスイソオクチルチオグルコレ−トなどが挙げられる。 Of these, organotin compounds are preferred because they are easily expressed with hydrophilicity. , Dibutyltin dilaurate, dibutyltin distearate, dibutyltin diacetylacetonate, dibutyltin bis (ethyl maleate), dibutyltin bis (butyl maleate), dibutyltin bis (2-ethylhexyl maleate) ), Dibutyltin bis (oleyl maleate), stannous octoate, tin stearate, and di-n-butyltin rallate oxide. Examples of tin compounds having S atoms in the molecule include dibutyltin bisisononyl-3-mercaptopropionate, dioctyltin bisisononyl-3-mercaptopropionate, octylbutyltin bisisononyl-3-mercaptopropionate, Examples thereof include dibutyltin bisisooctylthiogluconate, dioctyltin bisisooctylthiogluconate, and octylbutyltin bisisooctylthiogluconate.
更に、ジブチル錫チオグリコレート、ジブチル錫ビスイソノニル３−メルカプトプロピオネート、ジブチル錫ビスイソオクチルチオグリコレート、ジブチル錫ビス２−エチルヘキシルチオグリコレート、ジメチル錫ビスドデシルメルカプチド、ジブチル錫ビスドデシルメルカプチド、ジオクチル錫ビスドデシルメルカプチド、ジメチル錫ビス（オクチルチオグルコール酸エステル）塩などが接触角とポットライフのバランスがとりやすく好ましい。 Further, dibutyltin thioglycolate, dibutyltin bisisononyl 3-mercaptopropionate, dibutyltin bisisooctylthioglycolate, dibutyltin bis2-ethylhexylthioglycolate, dimethyltin bisdodecyl mercaptide, dibutyltin bisdodecyl mercaptide Dioctyltin bisdodecyl mercaptide, dimethyltin bis (octylthioglycolate) salt, and the like are preferable because the contact angle and the pot life are easily balanced.
特に、水中での安定性およびポットライフ後の塗料を用いても接触角が低下するという点から、成分が一般式（３）で示される含硫黄有機錫化合物
（Ｒ1）（Ｒ2）Ｓｎ（Ｓ−Ｒ3）（Ｓ−Ｒ4）・・・一般式（３）
（式中、Ｒ1、Ｒ2は同じかまたは異なり炭素数１〜８の直鎖あるいは分岐したアルキル基、Ｒ3、Ｒ4は直鎖あるいは分岐した炭素数１〜２０のアルキル基、アルケニル基などの炭化水素基である）であることが好ましく、具体的にはジブチル錫ビスドデシルメルカプチド、ジオクチル錫ビスドデシルメルカプチドなどが挙げられる。
これらは、単独で用いてもよく、２種以上を併用してもよい。
In particular, the sulfur-containing organotin compound (R 1 ) (R 2 ) Sn represented by the general formula (3) is used because the contact angle is lowered even when using a paint after pot life after stability in water. (S-R 3) (S -R 4) ··· formula (3)
Wherein R 1 and R 2 are the same or different and are linear or branched alkyl groups having 1 to 8 carbon atoms, R 3 and R 4 are linear or branched alkyl groups having 1 to 20 carbon atoms and alkenyl groups. It is preferably a hydrocarbon group such as dibutyltin bisdodecyl mercaptide, dioctyltin bisdodecyl mercaptide and the like.
These may be used alone or in combination of two or more.
（Ｃ）成分はオルガノシリケート化合物（Ａ）１００重量部に対し、０．０５〜２０重量部配合することができ、好ましくは０．０５〜１０重量部、更に好ましくは０．１〜１０重量部である。配合量が０．０５重量部未満では、耐汚染性付与の効果が低く、２０重量部を超えると配合物の安定性が低下する。水性塗料に添加した場合に（Ｃ）の存在量が多くなり、塗膜の耐候性が低下する。 Component (C) can be blended in an amount of 0.05 to 20 parts by weight, preferably 0.05 to 10 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the organosilicate compound (A). It is. When the blending amount is less than 0.05 parts by weight, the effect of imparting stain resistance is low, and when it exceeds 20 parts by weight, the stability of the blend decreases. When added to a water-based paint, the amount of (C) present increases, and the weather resistance of the coating film decreases.
（ポリオキシアルキレン基含有化合物）
本発明におけるポリオキシアルキレン基含有化合物（Ｄ）は、親水性基部位として機能し、前記（Ｂ）および（Ｃ）成分を水性塗料中に均一に分散するができる。
ポリオキシアルキレン基の具体例としては、ポリオキシエチレン基、ポリオキシプロピレン基、オキシエチレン基とオキシプロピレン基がブロックまたはランダム結合したポリオキシアルキレン基、前記ポリオキシエチレン基、ポリオキシプロピレン基、ポリオキシアルキレン基に、さらにオキシオキシブチレン基がブロックまたはランダム結合で含まれている基などが挙げられる。
(Polyoxyalkylene group-containing compound)
The polyoxyalkylene group-containing compound (D) in the present invention functions as a hydrophilic group site, and can uniformly disperse the components (B) and (C) in the aqueous paint.
Specific examples of the polyoxyalkylene group include a polyoxyethylene group, a polyoxypropylene group, a polyoxyalkylene group in which an oxyethylene group and an oxypropylene group are blocked or randomly bonded, the polyoxyethylene group, the polyoxypropylene group, and the polyoxyalkylene group. Examples of the oxyalkylene group further include a group in which an oxyoxybutylene group is contained in a block or random bond.
なかでも、上記オルガノシリケート化合物（Ｂ）との相溶性がよく、得られる耐汚染性付与組成物が均一溶液となりやすくなることから、ポリオキシプロピレン基が特に好ましい。さらに、ポリオキシアルキレン基を含有する化合物としては、種々の有機基を併せ持つ化合物を使用でき、その具体例を以下に例示する。 Of these, a polyoxypropylene group is particularly preferred because it has good compatibility with the organosilicate compound (B) and the resulting stain resistance-imparting composition tends to be a uniform solution. Furthermore, as the compound containing a polyoxyalkylene group, compounds having various organic groups can be used, and specific examples thereof are exemplified below.
水酸基を含有する化合物の具体例としては、各種付加量のポリエチレングリコールやポリプロピレングリコール等のポリアルキレングリコール誘導体やプロノン１０２、プロノン２０１等プロノンシリーズに代表されるブロック型（以上、日本油脂（株）製）、ユニオールＤＡ−４００、ユニオールＤＢ−４００、ユニオールＤＢ−５３０（以上、日本油脂（株）製）等のビスフェノールＡ誘導体等が挙げられる。 Specific examples of the compound containing a hydroxyl group include polyalkylene glycol derivatives such as various addition amounts of polyethylene glycol and polypropylene glycol, and block types represented by the Pronon series such as Pronon 102 and Pronon 201 (Nippon Yushi Co., Ltd.) Bisphenol A derivatives, such as UNIOR DA-400, UNIOR DB-400, UNIOR DB-530 (manufactured by NOF Corporation), and the like.
エーテル基を含有する化合物の具体例としては、ポリエチレングリコールオレイルエーテルやポリエチレングリコールジメチルエーテル等の各種ポリアルキレングリコールアルキルエーテルが挙げられる。 Specific examples of the compound containing an ether group include various polyalkylene glycol alkyl ethers such as polyethylene glycol oleyl ether and polyethylene glycol dimethyl ether.
エステル基を含有する化合物の具体例としては、ポリエチレングリコールモノオクチルエステルやポリプロピレングリコールモノステアリルエステル、ポリプロピレングリコールジステアリルエステル等のポリアルキレングリコールアルキルエステル等が挙げられる。 Specific examples of the compound containing an ester group include polyalkylene glycol alkyl esters such as polyethylene glycol monooctyl ester, polypropylene glycol monostearyl ester, and polypropylene glycol distearyl ester.
アリル基を含有する化合物の具体例としては、ユニオックスＰＫＡ−５００６やユニオールＰＫＡ−５０１４、ユニオールＰＫＡ−５０１７（以上、日本油脂（株）製）等の各種ポリアルキレングリコールアリルエーテルが挙げられる。 Specific examples of the compound containing an allyl group include various polyalkylene glycol allyl ethers such as UNIOX PKA-5006, UNIOR PKA-5014 and UNIOR PKA-5017 (manufactured by NOF Corporation).
（メタ）アクリル基を含有する化合物の具体例としては、ブレンマーＰＰシリーズやブレンマーＰＭＥシリーズ、ブレンマーＰＤＥシリーズ（以上、日本油脂（株）製）等のポリアルキレングリコール（メタ）アクリレートが挙げられる。 Specific examples of the compound containing a (meth) acrylic group include polyalkylene glycol (meth) acrylates such as Blemmer PP series, Blemmer PME series, and Blemmer PDE series (hereinafter, manufactured by NOF Corporation).
（ブロック）イソシアネート基を含有する化合物の具体例としては、バイヒジュール３１００、バイヒジュール２３３６、バイヒジュールＬＳ２１５０／ｌ、バイヒジュールＢＬ１１６、バイヒジュールＢＬ５１４０、バイヒジュールＢＬ５２３５、バイヒジュールＴＰＬＳ２１８６、バイヒドロールＴＰＬＳ２１５３（以上、住化バイエルウレタン（株）製）、タケネートＷＤ−２２０、タケネートＷＤ−２４０、タケネートＷＤ−７２０、タケネートＷＤ−７２５、タケネートＷＤ−７２６、タケネートＷＤ−７３０、タケネートＷＢ−７００、タケネートＷＢ−７２０、タケネートＷＢ−７３０、タケネートＷＢ−９２０（以上、三井武田ケミカル（株）製）、アクアネート１００、アクアネート１１０、アクアネート２００、アクアネート２１０、アクアネート１２０（以上、日本ポリウレタン工業（株）製）、デュラネートＷＢ４０−１００、デュラネートＷＢ４０−８０Ｄ、デュラネートＷＴ２０−１００、デュラネートＷＴ３０−１００（以上、旭化成（株）製）等が挙げられる。 Specific examples of the compound containing a (block) isocyanate group include Bihydur 3100, Bihydur 2336, Bihydur LS2150 / 1, Bihydur BL116, Bihydur BL5140, Bihydur BL5235, Bihydur TPLS2186, Bihydrol TPLS2153 (above, Sumika Bayer Urethane Co., Ltd.) Made), Takenate WD-220, Takenate WD-240, Takenate WD-720, Takenate WD-725, Takenate WD-726, Takenate WD-730, Takenate WB-700, Takenate WB-720, Takenate WB-730, Takenate WB -920 (Mitsui Takeda Chemical Co., Ltd.), Aquanate 100, Aquanate 110, Aquanate 200, Aqua 210, Aquanate 120 (manufactured by Nippon Polyurethane Industry Co., Ltd.), Duranate WB40-100, Duranate WB40-80D, Duranate WT20-100, Duranate WT30-100 (above, manufactured by Asahi Kasei Corporation) and the like. It is done.
エポキシ基を含有する化合物の具体例としては、デナコールＥＸ−６１１、ＥＸ−６１２、ＥＸ−６１４、ＥＸ−６１４Ｂ、ＥＸ−６２２、ＥＸ−５１２、ＥＸ−５２１、ＥＸ−４１１、ＥＸ−４２１、ＥＸ−３０１、ＥＸ−３１３、ＥＸ−３１４、ＥＸ−３２１、ＥＸ−２１１、ＥＸ−８１０、ＥＸ−８１１、ＥＸ−８５１、ＥＸ−８２１、ＥＸ−８３０、ＥＸ−８３２、ＥＸ−８４１、ＥＸ−８６１、ＥＸ−９１１、ＥＸ−９４１、ＥＸ−９２０、ＥＸ−９２１、ＥＸ−９３１、ＥＸ−１４５、ＥＸ−１７１、ＥＸ−７０１（以上、ナガセケムテックス（株）製）、エポライト４０Ｅ、エポライト１００Ｅ、エポライト２００Ｅ、エポライト４００Ｅ、エポライト７０Ｐ、エポライト２００Ｐ、エポライト４００Ｐ、エポライト１５００ＮＰ、エポライト８０ＭＦ、エポライト１００ＭＦ（以上、共栄社化学（株）製）、ＳＲ−ＮＰＧ、ＳＲ−１６Ｈ、ＳＲ−ＴＭＰ、ＳＲ−ＴＰＧ、ＳＲ−４ＰＧ、ＳＲ−２ＥＧ、ＳＲ−８ＥＧ、ＳＲ−８ＥＧＳ、ＳＲ−ＧＬＧ、ＳＲ−ＤＧＥ、ＳＲ−４ＧＬ、ＳＲ−４ＧＬＳ（以上、阪本薬品工業（株）製）、エピオールＢＥ−２００、Ｇ−１００、Ｅ−１００、Ｅ−４００、Ｅ−１０００、Ｐ−２００、ＮＰＧ−１００、ＴＭＰ−１００、エピオールＯＨ（以上、日本油脂（株）製）等が挙げられる。 Specific examples of the compound containing an epoxy group include Denacol EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX -301, EX-313, EX-314, EX-321, EX-211, EX-810, EX-811, EX-851, EX-821, EX-830, EX-832, EX-841, EX-861 EX-911, EX-941, EX-920, EX-921, EX-931, EX-145, EX-171, EX-701 (manufactured by Nagase ChemteX Corporation), Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 70P, Epolite 200P, Epolite 400P, Epolite 1500 P, Epolite 80MF, Epolite 100MF (above, manufactured by Kyoeisha Chemical Co., Ltd.), SR-NPG, SR-16H, SR-TMP, SR-TPG, SR-4PG, SR-2EG, SR-8EG, SR-8EGS, SR-GLG, SR-DGE, SR-4GL, SR-4GLS (manufactured by Sakamoto Pharmaceutical Co., Ltd.), Epiol BE-200, G-100, E-100, E-400, E-1000, P- 200, NPG-100, TMP-100, Epiol OH (manufactured by NOF Corporation) and the like.
カルボジイミド基を含有する化合物の具体例としては、カルボジライトＶ−０２、Ｖ−０４、Ｖ−０６、Ｖ−０２−Ｌ２、Ｅ−０１、Ｅ−０２、Ｅ−０３、Ｅ−０４、Ｅ−０５（以上、日清紡績（株）製）等が挙げられる。
また、水を含まないものとしてＶ−０２Ｂ、Ｖ−０４Ｂ、Ｅｌａｓｔｏｓｔａｂ Ｈ０１（以上、日清紡績（株）製）などがある。
本発明の耐汚染性付与組成物中には反応性官能基とオルガノシリケートとを共存させるため水を含まない方が好ましく、水を含有している場合はこれらを脱水して用いるか、または水を含まないものを用いるのが望ましい。
Specific examples of the compound containing a carbodiimide group include carbodilite V-02, V-04, V-06, V-02-L2, E-01, E-02, E-03, E-04, and E-05. (Above, manufactured by Nisshinbo Industries, Inc.).
Examples of water-free products include V-02B, V-04B, and Elastostab H01 (manufactured by Nisshinbo Industries, Inc.).
In the stain resistance-imparting composition of the present invention, it is preferable not to contain water in order to allow the reactive functional group and the organosilicate to coexist. When water is contained, these are used after dehydration or water. It is desirable to use those that do not contain.
アルコキシシリル基を含有する化合物の具体例としては、Ａ−１２３０、ＭＡＣ−２１０１、ＭＡＣ−２３０１（日本ユニカー（株）製）等が挙げられる。 Specific examples of the compound containing an alkoxysilyl group include A-1230, MAC-2101, MAC-2301 (manufactured by Nippon Unicar Co., Ltd.) and the like.
オキサゾリン基を含有する化合物の具体例としては、（株）日本触媒製エポクロスＷＳ−５００、Ｋ−２０１０Ｅ、Ｋ−２０２０Ｅ、Ｋ−２０３０Ｅ、Ｋ−１０１０Ｅ、Ｋ−１０２０Ｅ、Ｋ−１０３０Ｅ（以上、（株）日本触媒製）等が挙げられる。これらは、水溶液またはエマルジョンとして市販されているため、脱水して使用するのが望ましい。 Specific examples of the compound containing an oxazoline group include EPOCROS WS-500, K-2010E, K-2020E, K-2030E, K-1010E, K-1020E, K-1030E (manufactured by Nippon Shokubai Co., Ltd.) (Manufactured by Nippon Shokubai Co., Ltd.). Since these are commercially available as aqueous solutions or emulsions, it is desirable to use them after dehydration.
これらは、単独で用いてもよく、２種以上を併用してもよい。
上記ポリオキシアルキレン基含有化合物の使用量は、オルガノシリケート化合物（Ａ）１００重量部に対し、５〜３００部、更には１０〜１５０部が好ましい。５重量部未満では、耐汚染性付与組成物が水性塗料中に均一に分散せず、形成した塗膜の光沢値が低下し、また、３００重量部以上用いた場合、形成した塗膜の初期タック、硬度が低下する傾向がある。
These may be used alone or in combination of two or more.
The amount of the polyoxyalkylene group-containing compound used is preferably 5 to 300 parts, more preferably 10 to 150 parts, per 100 parts by weight of the organosilicate compound (A). If the amount is less than 5 parts by weight, the stain resistance imparting composition is not uniformly dispersed in the water-based paint, and the gloss value of the formed coating film is lowered. Tack and hardness tend to decrease.
（脱水剤）
オルガノシリケートに脱水作用があるため、通常、汚染付与組成物中では脱水剤（Ｇ）は必要としないが、特に水との反応性が高いオルガノシリケートや水溶性および／または水分散製硬化剤を用いる場合には、脱水剤を配合することが好ましい。
(Dehydrating agent)
Since organosilicate has a dehydrating action, a dehydrating agent (G) is not usually required in a stain-imparting composition, but an organosilicate or a water-soluble and / or water-dispersed curing agent that is particularly highly reactive with water is used. When using, it is preferable to mix | blend a dehydrating agent.
脱水剤としては、例えば、オルソ蟻酸トリメチル、オルソ蟻酸トリエチルもしくはオルソ蟻酸トリブチル等のオルソ蟻酸トリアルキル；オルソ酢酸トリメチル、オルソ酢酸トリエチルもしくはオルソ酢酸トリブチル等のオルソ酢酸トリアルキル；またはオルソほう酸トリメチル、オルソほう酸トリエチル、オルソほう酸トリブチル等のオルソほう酸トリアルキル等のオルソカルボン酸エステル。 Examples of the dehydrating agent include trialkyl orthoformate such as trimethyl orthoformate, triethyl orthoformate or tributyl orthoformate; trialkyl orthoacetate such as trimethyl orthoacetate, triethyl orthoacetate or tributyl orthoacetate; or trimethyl orthoborate and orthoboric acid. Orthocarboxylic acid esters such as trialkyl orthoborate such as triethyl and tributyl orthoborate.
また、ベンゼンスルフォニルイソシアネート、トシルイソシアネート、フェニルイソシアネート、ｐ−クロロフェニルイソシアネート、などのイソシアネート類があるが、好ましくは、ベンゼンスルフォニルイソシアネート、トシルイソシアネート、フェニルイソシアネートまたはｐ−クロロフェニルイソシアネートなどのような、種々のモノイソシアネート類などである。 In addition, there are isocyanates such as benzenesulfonyl isocyanate, tosyl isocyanate, phenyl isocyanate, p-chlorophenyl isocyanate, etc., but various monovalents such as benzenesulfonyl isocyanate, tosyl isocyanate, phenyl isocyanate or p-chlorophenyl isocyanate are preferable. Isocyanates and the like.
本発明の合成樹脂エマルジョンに、必要に応じて、通常塗料に用いられる顔料（二酸化チタン、炭酸カルシウム、炭酸バリウム、カオリンなどの白色顔料、カーボン、ベンガラ、シアニンブルーなどの有色系顔料）が使用できる。二酸化チタンは顔料のなかでも最も使用量が多く重要である。アルミナ、ジルコニアにより表面処理された二酸化チタンを用いることにより光沢、耐候性が向上する。また、造膜助剤、コロイダルシリカ、可塑剤、溶剤、分散剤、増粘剤、消泡剤、防腐剤、防かび剤、防藻剤、紫外線吸収剤、光安定剤などの通常の塗料用成分として使用される添加剤を配合することもできる。 In the synthetic resin emulsion of the present invention, pigments (white pigments such as titanium dioxide, calcium carbonate, barium carbonate, and kaolin, and colored pigments such as carbon, bengara, and cyanine blue) that are commonly used in paints can be used as necessary. . Titanium dioxide is the most used and important among the pigments. Gloss and weather resistance are improved by using titanium dioxide surface-treated with alumina or zirconia. Also for ordinary coatings such as film-forming aids, colloidal silica, plasticizers, solvents, dispersants, thickeners, antifoaming agents, antiseptics, fungicides, algaeproofing agents, ultraviolet absorbers, light stabilizers, etc. Additives used as ingredients can also be blended.
（塗料用組成物の配合方法）
本発明における塗料用組成物の配合方法としては、合成樹脂エマルション（Ａ）からなる水性塗料にオルガノシリケート化合物（Ｂ）と有機金属化合物（Ｃ）を添加すればよいが、予め（Ｂ）成分と（Ｃ）成分を混合した後に、塗装直前に水性塗料に添加する方法がよい。この方法では塗料を塗布した際の塗膜の物性変化が少なくて好ましい。また、（Ｂ）成分と（Ｃ）成分を混合する際に、さらに（Ｄ）成分を配合しておくことが特に好ましい。この方法であれば、安定して優れた耐汚染性と高い光沢を有する塗膜を形成させることが可能である。
(Method of blending paint composition)
As a blending method of the coating composition in the present invention, the organosilicate compound (B) and the organometallic compound (C) may be added to the aqueous coating composition comprising the synthetic resin emulsion (A). (C) After mixing a component, the method of adding to a water-based coating material just before coating is good. This method is preferable because there is little change in physical properties of the coating film when the coating is applied. Moreover, when mixing (B) component and (C) component, it is especially preferable to mix | blend (D) component further. With this method, it is possible to stably form a coating film having excellent stain resistance and high gloss.
上記（Ｂ）、（Ｃ）、（Ｄ）成分を混合する場合、単純に混合・撹拌するだけでも可能であるが、物性に影響を与えない程度に加熱することでも対処可能である。１００℃以上の高温にした場合や水分が混入した場合は、（Ａ）成分の縮合反応の進行し増粘・ゲル化する可能性もある。また、ゲル化しないまでも水性塗料に添加し形成した塗膜の耐汚染性低下・光沢低下等の機能低下する場合があり、注意が必要である。 When the components (B), (C), and (D) are mixed, it is possible to simply mix and stir, but it is also possible to cope with heating to such an extent that physical properties are not affected. When the temperature is higher than 100 ° C. or when moisture is mixed, the condensation reaction of the component (A) may proceed to increase the viscosity or gel. In addition, even if it does not gel, it may be deteriorated in functions such as a decrease in stain resistance and a decrease in gloss of the coating film formed by adding to the water-based paint.
本発明の耐汚染性が付与された水性塗料は、例えば建築内外装用、メタリックベースあるいはメタリックベース上のクリアーなどの自動車用、アルミニウム、ステンレスなどの金属直塗用、スレート、コンクリート、瓦、モルタル、石膏ボード、石綿スレート、アスベストボード、プレキャストコンクリート、軽量気泡コンクリート、硅酸カルシウム板、タイル、レンガなどの窯業系直塗用、ガラス用、天然大理石、御影石等の石材用の塗料あるいは上面処理剤として用いられる。また、直塗用だけでなく、水系あるいは溶剤系プライマー上、アクリルゴム上、複層仕上塗材のトップコート、可とう形改修用仕上塗材のトップコート、コンクリート等の無機系基材に水系あるいは溶剤系浸透性吸水防止材上の塗装にも用いられる。 The water-based paint imparted with stain resistance of the present invention is, for example, for interior and exterior of buildings, for automobiles such as metallic base or clear on metallic base, for direct coating of metals such as aluminum and stainless steel, slate, concrete, roof tile, mortar, Gypsum board, asbestos slate, asbestos board, precast concrete, lightweight cellular concrete, calcium oxalate board, tiles, bricks and other ceramics direct coating, glass, natural marble, granite and other stone paints or top treatments Used. In addition to direct coating, water-based or solvent-based primer, acrylic rubber, multi-layer finish top coat, flexible top finish coat, water-based inorganic base materials such as concrete Alternatively, it can be used for coating on a solvent-based permeable water absorption preventing material.
以下に、本発明を実施例に基づいて説明するが、本発明はこれによって限定されるものではない。
（アルコキシシリル基含有アクリルエマルジョンの製造例１）
撹拌機、還流冷却器、窒素ガス導入管および滴下ロートを備えた反応容器に、脱イオン水２００重量部、Ｎｅｗｃｏｌ−７０７ＳＦ（日本乳化剤（株）製）１．０重量部、炭酸水素ナトリウム０．０５重量部を仕込み、窒素ガスを導入しつつ５０℃に昇温した。
Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto.
(Production example 1 of alkoxysilyl group-containing acrylic emulsion)
In a reaction vessel equipped with a stirrer, reflux condenser, nitrogen gas inlet tube and dropping funnel, 200 parts by weight of deionized water, 1.0 part by weight of Newcol-707SF (manufactured by Nippon Emulsifier Co., Ltd.), 0. 05 parts by weight were charged, and the temperature was raised to 50 ° C. while introducing nitrogen gas.
昇温後、表１（製造例１）のコア部に示すモノマー混合物のうちの２０重量部、ｔ−ブチルハイドロパーオキサイド０．１４重量部、Ｂｒｕｇｇｏｌｉｔｅ ＦＦ−６（ＢｒｕｇｇａｍａｎｎＣｈｅｍｉｃａｌＵＳ製）０．２重量部を添加し、３０分間初期重合を行った。上記モノマー混合物の残り１８０重量部にアデカリアソープＳＲ−１０２５（旭電化工業（株）製：有効成分１００％）１１．２重量部、アデカリアソープＥＲ−２０（旭電化工業（株）製：有効成分７５％）１．８重量部、および脱イオン水６４重量部を加え乳化したモノマー乳化液とｔ−ブチルハイドロパーオキサイド０．１６重量部、Ｂｒｕｇｇｏｌｉｔｅ ＦＦ−６ ０．０９部を１００分かけて等速追加した。追加終了後、１時間後重合を行った。 After the temperature rise, 20 parts by weight of the monomer mixture shown in the core part of Table 1 (Production Example 1), 0.14 parts by weight of t-butyl hydroperoxide, 0.2 parts by weight of Bruggolite FF-6 (manufactured by Bruggamann Chemical US) Was added and initial polymerization was performed for 30 minutes. ADEKA rear soap SR-1025 (Asahi Denka Kogyo Co., Ltd .: active ingredient 100%) 11.2 parts by weight, Adeka Soap ER-20 (Asahi Denka Kogyo Co., Ltd.): (Active ingredient 75%) 1.8 parts by weight and monomer emulsion obtained by adding 64 parts by weight of deionized water, 0.16 parts by weight of t-butyl hydroperoxide, 0.09 part of Bruggolite FF-6 over 100 minutes Added at a constant speed. Polymerization was performed after 1 hour after the addition was completed.
さらに、表１（製造例１）のシェル部に示すモノマー混合物２００重量部にアデカリアソープＳＲ−１０２５ １２．６重量部、アデカリアソープＥＲ−２０ １．９重量部、および脱イオン水６４重量部を加え乳化したモノマー乳化液とｔ−ブチルハイドロパーオキサイド０．２０重量部、Ｂｒｕｇｇｏｌｉｔｅ ＦＦ−６ ０．１部を、１１０分かけて等速追加した。追加終了後、１時間後重合を行った。得られた合成樹脂のエマルジョンに炭酸水素ナトリウム１．５部を添加後、脱イオン水で固形部５０％に調整した。 Furthermore, 200 parts by weight of the monomer mixture shown in the shell part of Table 1 (Production Example 1), 12.6 parts by weight of Adeka Soap SR-1025, 1.9 parts by weight of Adeka Soap ER-20, and 64 parts by weight of deionized water A monomer emulsion emulsified by adding parts, 0.20 parts by weight of t-butyl hydroperoxide, and 0.1 part of Bruggolite FF-6 were added at a constant rate over 110 minutes. Polymerization was performed after 1 hour after the addition was completed. After adding 1.5 parts of sodium hydrogen carbonate to the resulting synthetic resin emulsion, the solid part was adjusted to 50% with deionized water.
（アルコキシシリル基含有アクリルエマルジョンの製造例２〜４および６、７）
表１中のモノマー組成を変更する以外は、製造例１と同様の方法により乳化重合し、固形分５０％の合成樹脂エマルション（製造例２〜４および６、７）を得た。
(Production Examples 2 to 4 and 6, 7 of alkoxysilyl group-containing acrylic emulsion)
Except for changing the monomer composition in Table 1, emulsion polymerization was carried out in the same manner as in Production Example 1 to obtain synthetic resin emulsions (Production Examples 2 to 4, 6 and 7) having a solid content of 50%.
（アルコキシシリル基含有アクリルエマルジョンの製造例５）
撹拌機、還流冷却器、窒素ガス導入管および滴下ロートを備えた反応容器に、脱イオン水２００重量部、Ｎｅｗｃｏｌ−７０７ＳＦ（日本乳化剤（株）製：有効成分３０％）１．０重量部、炭酸水素ナトリウム０．０５重量部を仕込み、窒素ガスを導入しつつ５０℃に昇温した。
(Production Example 5 of alkoxysilyl group-containing acrylic emulsion)
In a reaction vessel equipped with a stirrer, reflux condenser, nitrogen gas inlet tube and dropping funnel, 200 parts by weight of deionized water, 1.0 part by weight of Newcol-707SF (manufactured by Nippon Emulsifier Co., Ltd .: active ingredient 30%), Sodium hydrogen carbonate 0.05 part by weight was charged, and the temperature was raised to 50 ° C. while introducing nitrogen gas.
昇温後、表１（製造例５）のコア部に示すモノマー混合物のうちの２０重量部、ｔ−ブチルハイドロパーオキサイド０．１４重量部、ロンガリット０．４重量部を添加し、３０分間初期重合を行った。上記モノマー混合物の残り２６０重量部にアクアロンＢＣ０５１５（第一工業製薬（株）製：有効成分１５％）９．７重量部、アクアロンＲＮ２０２５（第一工業製薬（株）製：有効成分２０％）２．７重量部および脱イオン水６６重量部を加え乳化したモノマー乳化液とｔ−ブチルハイドロパーオキサイド０．２０重量部を１４５分かけて等速追加した。追加終了後、１時間後重合を行った。 After the temperature increase, 20 parts by weight of the monomer mixture shown in the core part of Table 1 (Production Example 5), 0.14 parts by weight of t-butyl hydroperoxide, and 0.4 parts by weight of Rongalite were added, and the initial period was 30 minutes Polymerization was performed. The remaining 260 parts by weight of the monomer mixture is 9.7 parts by weight of Aqualon BC0515 (Daiichi Kogyo Seiyaku Co., Ltd .: active ingredient 15%), Aqualon RN2025 (Daiichi Kogyo Seiyaku Co., Ltd .: active ingredient 20%) 2 .7 parts by weight and 66 parts by weight of deionized water and emulsified monomer emulsion and 0.20 parts by weight of t-butyl hydroperoxide were added at a constant rate over 145 minutes. Polymerization was performed after 1 hour after the addition was completed.
さらに、表１（製造例５）のシェル部に示すモノマー混合物１２０重量部にアクアロンＢＣ０５１５ ６．０重量部、アクアロンＲＮ２０２５ １．６重量部および脱イオン水２７重量部を加え乳化したモノマー乳化液とｔ−ブチルハイドロパーオキサイド０．１５重量部を６５分かけて等速追加した。追加終了後、１時間後重合を行った。得られた合成樹脂のエマルジョンに炭酸水素ナトリウム１．５部を添加後、脱イオン水で固形部５０％に調整した（製造例５）。 Further, a monomer emulsion obtained by emulsifying by adding 6.0 parts by weight of Aqualon BC0515, 1.6 parts by weight of Aqualon RN2025 and 27 parts by weight of deionized water to 120 parts by weight of the monomer mixture shown in the shell part of Table 1 (Production Example 5), 0.15 parts by weight of t-butyl hydroperoxide was added at a constant rate over 65 minutes. Polymerization was performed after 1 hour after the addition was completed. After adding 1.5 parts of sodium hydrogencarbonate to the obtained synthetic resin emulsion, the solid part was adjusted to 50% with deionized water (Production Example 5).
（塗料の作成）
合成した樹脂エマルジョンを用い、表２の顔料ペーストを用いて、表３に示す配合処方（重量部）で塗料を作製した。（ＡＳ−１〜７）。
(Creation of paint)
Using the synthesized resin emulsion, a paint was prepared using the pigment paste of Table 2 and the formulation (parts by weight) shown in Table 3. (AS-1-7).
（硬化剤配合物の製造方法１〜３）
撹拌機、還流冷却器、窒素ガス導入管を備えた容器に表４に示す成分を（Ｄ）、（Ｂ）、（Ｃ）の順序で撹拌しながら、投入した（表４中のその他成分を用いる場合には、（Ｄ）成分の後に投入した）。投入終了後、３０分撹拌し、表４の硬化剤配合物ＣＴ−１〜３を得た。
(Manufacturing method 1-3 of a hardening | curing agent compound)
While stirring the components shown in Table 4 in the order of (D), (B), and (C) in a vessel equipped with a stirrer, a reflux condenser, and a nitrogen gas introduction pipe (the other components in Table 4 were added). When used, it was added after the component (D)). After completion of the addition, the mixture was stirred for 30 minutes to obtain curing agent formulations CT-1 to 3 shown in Table 4.
シリケート４５： エチルシリケート部分加水分解縮合物（シリカ残量比率４５％）（多摩化学工業（株）製）
エチルシリケート４０： エチルシリケート部分加水分解縮合物（シリカ残量比率４０％）（コルコート（株）製）
ユニオールＤＢ−５３０：ポリプロピレングリコールビスフェノールＡエーテル（日本油脂（株）製）
カルボジライトＶ−０４Ｂ： 水溶性ポリカルボジイミド（日清紡積（株）製）
ＳＲ−ＴＰＧ： ポリプロピレングリコールジグリシジルエーテル（阪本薬品工業（株）製）。
Silicate 45: ethyl silicate partial hydrolysis condensate (silica residual ratio 45%) (manufactured by Tama Chemical Co., Ltd.)
Ethyl silicate 40: Ethyl silicate partial hydrolysis condensate (silica residual ratio 40%) (manufactured by Colcoat Co., Ltd.)
UNIOR DB-530: Polypropylene glycol bisphenol A ether (manufactured by NOF Corporation)
Carbodilite V-04B: Water-soluble polycarbodiimide (manufactured by Nisshinbo Co., Ltd.)
SR-TPG: Polypropylene glycol diglycidyl ether (manufactured by Sakamoto Pharmaceutical Co., Ltd.).
（物性評価）
・塗膜の作製
表３に示す配合にて作製した水性塗料に硬化剤配合物（ＣＴ−１〜３）を添加、攪拌し、添加、攪拌後すぐ、３時間後、６時間後の塗料をそれぞれ６ミルのアプリケーターでガラス板に塗装し、７日間室温で養生した。表５に物性評価結果を示す。
・塗膜の水接触角の測定
耐汚染性の指標となる塗膜の水接触角を接触角測定機（協和界面科学（株）製：ＣＡ−Ｓ１５０型）を用い測定した。評価は、上記作製サンプルを養生後、水に７日間浸漬後に実施した。
(Evaluation of the physical properties)
-Preparation of coating film Addition and agitation of the hardener formulation (CT-1 to 3) to the aqueous paint prepared by the composition shown in Table 3, and immediately after the addition and stirring, the paint after 3 hours and after 6 hours. Each was coated on a glass plate with a 6 mil applicator and cured at room temperature for 7 days. Table 5 shows the physical property evaluation results.
-Measurement of water contact angle of coating film The water contact angle of the coating film, which is an index of stain resistance, was measured using a contact angle measuring machine (Kyowa Interface Science Co., Ltd .: CA-S150 type). The evaluation was carried out after curing the prepared sample and immersing it in water for 7 days.
・ポットライフ２４時間後の塗料状態
上記塗料にアルミホイルを軽くかぶせ、室温にて２４時間放置した。放置後の塗料の状態を目視にて観察した。
Ａ：ゲル化している状態
Ｂ：増粘が激しく、流動性がほとんどない状態
Ｃ：変化がない、あるいはやや増粘した状態であるが、塗装が可能な状態
・６０°光沢
上記養生サンプル（添加後すぐ）の６０°光沢を光沢計Ｍｕｌｔｉ Ｇｒｏｓｓ２６８（（株）ミノルタ製）にて測定した。
-Paint state after 24 hours of pot life The above paint was lightly covered with aluminum foil and allowed to stand at room temperature for 24 hours. The state of the paint after standing was visually observed.
A: Gelled state B: Vigorous thickening, almost no fluidity C: No change or slightly thickened state, but paintable, 60 ° gloss above curing sample (added) 60 ° gloss immediately after) was measured with a gloss meter Multi Gross268 (manufactured by Minolta Co., Ltd.).
本発明の水性塗料組成物は、優れた耐汚染性を有し、且つ、ポットライフ２４時間後には塗料が実質的に使用をためらうような状態となる。また、例えば実施例で示されているように、ポットライフ６時間後においても水接触角が上昇することなく、親水性を保持した塗膜を形成する。形成した塗膜は耐水性、耐候性、付着性を向上させることができる。
The aqueous coating composition of the present invention has excellent stain resistance, and after 24 hours in the pot life, the coating is substantially hesitant to use. For example, as shown in the Examples, a coating film having hydrophilicity is formed without increasing the water contact angle even after 6 hours of pot life. The formed coating film can improve water resistance, weather resistance, and adhesion.
Claims (6)
一般式（２）で示されるオルガノシリケート化合物またはその部分加水分解縮合物（Ｂ）、
ジブチル錫ビスイソノニル−３−メルカプトプロピオネート、ジオクチル錫ビスイソノニル−３−メルカプトプロピオネート、オクチルブチル錫ビスイソノニル−３−メルカプトプロピオネート、ジブチル錫ビスイソオクチルチオグルコレート、ジオクチル錫ビスイソオクチルチオグルコレート、オクチルブチル錫ビスイソオクチルチオグルコレート、ジブチル錫チオグリコレート、ジブチル錫ビス２−エチルヘキシルチオグリコレート、ジメチル錫ビスドデシルメルカプチド、ジブチル錫ビスドデシルメルカプチド、ジオクチル錫ビスドデシルメルカプチド、及び、ジメチル錫ビス（オクチルチオグルコール酸エステル）塩からなる群より選択される、分子内にＳ原子を有する有機錫化合物（Ｃ）、および、
水酸基、エーテル基、エステル基、アリル基、（メタ）アクリル基、（ブロック）イソシアネート基、エポキシ基、カルボジイミド基、アルコキシシリル基、及びオキサゾリン基からなる群より選択される１種以上を有するポリオキシアルキレン化合物（Ｄ）、
からなり、
合成樹脂エマルション（Ａ）は、前記一般式（１）で表される第３級アミン単位を含有する単量体（ｂ）を重合成分全量の０．３〜３．０重量％用いてなる合成樹脂エマルションである、水性塗料用組成物。
一般式（１）
（式中、Ｒ1、Ｒ2はいずれも炭素数１〜１０のアルキル基、ＸはＯもしくはＮＨ、ｍは２〜１０の整数を示す。）
Ｓｉ−（ＯＲ）4・・・・一般式（２）
（式中、Ｒは同じかまたは異なり炭素数１〜４のアルキル基である） A synthetic resin emulsion whose main chain is substantially composed of a vinyl polymer and has at least one tertiary amine unit represented by the following general formula (1) and a silicon group bonded to a hydrolyzable group in the molecule ( A),
An organosilicate compound represented by the general formula (2) or a partially hydrolyzed condensate thereof (B),
Dibutyltin bisisononyl-3-mercaptopropionate, dioctyltin bisisononyl-3-mercaptopropionate, octylbutyltin bisisononyl-3-mercaptopropionate, dibutyltin bisisooctylthioglucorate, dioctyltin bisisooctylthiogluco Octylbutyltin bisisooctylthioglycolate, dibutyltin thioglycolate, dibutyltin bis-2-ethylhexylthioglycolate, dimethyltin bisdodecyl mercaptide, dibutyltin bisdodecyl mercaptide, dioctyltin bisdodecyl mercaptide, and An organic tin compound (C) having an S atom in the molecule, selected from the group consisting of dimethyltin bis (octylthioglycolate) salts , and
A polyoxy having at least one selected from the group consisting of a hydroxyl group, an ether group, an ester group, an allyl group, a (meth) acryl group, a (block) isocyanate group, an epoxy group, a carbodiimide group, an alkoxysilyl group, and an oxazoline group Alkylene compound (D),
Consists of
Synthetic resin emulsion (A) is a synthetic resin emulsion comprising 0.3 to 3.0% by weight of the total amount of the polymerization components of monomer (b) containing a tertiary amine unit represented by general formula (1). An aqueous paint composition, which is a resin emulsion.
General formula (1)
(Wherein R 1 and R 2 are all alkyl groups having 1 to 10 carbon atoms, X is O or NH, and m is an integer of 2 to 10)
Si- (OR) 4 ... General formula (2)
(Wherein R is the same or different and is an alkyl group having 1 to 4 carbon atoms)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005105243A JP5288680B2 (en) | 2005-03-31 | 2005-03-31 | Water-based coating composition and coating film obtained from the coating composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005105243A JP5288680B2 (en) | 2005-03-31 | 2005-03-31 | Water-based coating composition and coating film obtained from the coating composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2006282879A JP2006282879A (en) | 2006-10-19 |
| JP5288680B2 true JP5288680B2 (en) | 2013-09-11 |
Family
ID=37405124
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005105243A Expired - Fee Related JP5288680B2 (en) | 2005-03-31 | 2005-03-31 | Water-based coating composition and coating film obtained from the coating composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5288680B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5205006B2 (en) * | 2007-08-08 | 2013-06-05 | 株式会社カネカ | COATING METHOD AND COATED PRODUCT USING CURABLE COMPOSITION |
| JP5298228B2 (en) * | 2012-07-27 | 2013-09-25 | 株式会社カネカ | COATING METHOD AND COATED PRODUCT USING CURABLE COMPOSITION |
| JP6853726B2 (en) * | 2017-04-27 | 2021-03-31 | 株式会社日本触媒 | Resin composition for paint |
| JP2019189713A (en) * | 2018-04-23 | 2019-10-31 | 横浜ゴム株式会社 | Primer composition |
| KR102148742B1 (en) * | 2018-10-08 | 2020-08-27 | (주)제이씨콥스 | Eco-friendly automotive undercoat acrylic emulsion composition for winter |
Family Cites Families (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05331408A (en) * | 1992-06-02 | 1993-12-14 | Kanegafuchi Chem Ind Co Ltd | Curing composition for aqueous dispersion-type coating and its production |
| JPH0616735A (en) * | 1992-06-30 | 1994-01-25 | Kanegafuchi Chem Ind Co Ltd | Aqueous dispersion type composition |
| JP3390796B2 (en) * | 1992-07-07 | 2003-03-31 | 鐘淵化学工業株式会社 | Aqueous dispersion type composition and method for producing the same |
| JP3412916B2 (en) * | 1993-07-22 | 2003-06-03 | 鐘淵化学工業株式会社 | Curable composition for paint |
| JP3314319B2 (en) * | 1994-07-11 | 2002-08-12 | 鐘淵化学工業株式会社 | Room temperature curable composition |
| JP3423830B2 (en) * | 1996-02-16 | 2003-07-07 | 鐘淵化学工業株式会社 | Resin composition for water-based paint and method for forming coating film excellent in stain resistance |
| JP4510990B2 (en) * | 2000-03-30 | 2010-07-28 | 株式会社カネカ | Paint composition and water-based paint, and blending method thereof |
| JP4531922B2 (en) * | 2000-04-12 | 2010-08-25 | 株式会社カネカ | Water-based paint composition |
| JP2002363485A (en) * | 2001-04-05 | 2002-12-18 | Kanegafuchi Chem Ind Co Ltd | Curing composition for floor paint, method for forming coating film for floor, and floor coated with the composition or by method for forming the coating film for floor |
| JP2003226833A (en) * | 2001-04-09 | 2003-08-15 | Kanegafuchi Chem Ind Co Ltd | Curable composition for topcoat coating material and coated material |
| JP4652638B2 (en) * | 2001-09-20 | 2011-03-16 | 株式会社カネカ | Water dispersion curing agent composition |
| JP2003119424A (en) * | 2001-10-17 | 2003-04-23 | Kanegafuchi Chem Ind Co Ltd | Composition for imparting antifouling property, coating composition and coated film obtained from the coating composition |
| JP4256606B2 (en) * | 2001-11-09 | 2009-04-22 | 株式会社カネカ | Aqueous two-component paint composition |
| JP2004123982A (en) * | 2002-10-04 | 2004-04-22 | Kanegafuchi Chem Ind Co Ltd | Coating curing composition for floor |
| JP2005015676A (en) * | 2003-06-27 | 2005-01-20 | Kaneka Corp | Composition affording antifouling property, coating composition using the same and coated film using the coating composition |
| JP4836423B2 (en) * | 2004-06-28 | 2011-12-14 | 株式会社カネカ | Contamination resistance imparting composition, coating composition, and coating film obtained from the composition |
| JP5199530B2 (en) * | 2004-12-08 | 2013-05-15 | 株式会社カネカ | Contamination resistance imparting composition, coating composition, and coating film obtained from the coating composition |
| JP5403847B2 (en) * | 2005-01-05 | 2014-01-29 | 株式会社カネカ | Contamination resistance imparting composition, coating composition, and coating film obtained from the coating composition |
-
2005
- 2005-03-31 JP JP2005105243A patent/JP5288680B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2006282879A (en) | 2006-10-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5205006B2 (en) | COATING METHOD AND COATED PRODUCT USING CURABLE COMPOSITION | |
| JP5555449B2 (en) | Resin composition for water-based paint, paint comprising the resin composition for water-based paint | |
| JP2005015676A (en) | Composition affording antifouling property, coating composition using the same and coated film using the coating composition | |
| JPH08259892A (en) | Resin composition for aqueous coating and formation of coating film excellent in stain resistance | |
| JP5288680B2 (en) | Water-based coating composition and coating film obtained from the coating composition | |
| JP5043555B2 (en) | Curable composition | |
| JP5144890B2 (en) | Contamination resistance imparting composition, coating composition, and coating film obtained from the coating composition | |
| JP4890824B2 (en) | Coating composition, coating film obtained from the composition, and method for producing the coating composition | |
| JP2010013634A (en) | Aqueous coating resin composition | |
| JP2003119424A (en) | Composition for imparting antifouling property, coating composition and coated film obtained from the coating composition | |
| JP5199530B2 (en) | Contamination resistance imparting composition, coating composition, and coating film obtained from the coating composition | |
| JP5469871B2 (en) | Resin composition for water-based paint, paint comprising the resin composition for water-based paint, and method for coating the paint | |
| JPH08295826A (en) | Resin composition for aqueous coating and formation of coating film excellent in stain resistance | |
| JPH09221611A (en) | Resin composition for water base paint and formation of coating film having excellent stain resistance | |
| JP5636024B2 (en) | Contamination resistance imparting composition, coating composition, and coating film obtained from the coating composition | |
| JP5860608B2 (en) | Resin composition for water-based paint, paint comprising the resin composition for water-based paint | |
| JP4836423B2 (en) | Contamination resistance imparting composition, coating composition, and coating film obtained from the composition | |
| JP5667849B2 (en) | Aqueous resin composition | |
| JP5154305B2 (en) | Aqueous one-pack type antifouling resin composition for paint and coating film obtained from the paint resin composition | |
| JP5288679B2 (en) | Contamination resistance imparting composition, coating composition, and coating film obtained from the coating composition | |
| JP5492430B2 (en) | Aqueous one-pack type antifouling resin composition for paint and coating film obtained from the paint resin composition | |
| JP4780955B2 (en) | Contamination resistance imparting composition, coating composition, and coating film obtained from the coating composition | |
| JP5139632B2 (en) | Method for producing aqueous coating composition | |
| JP5403847B2 (en) | Contamination resistance imparting composition, coating composition, and coating film obtained from the coating composition | |
| JP5298228B2 (en) | COATING METHOD AND COATED PRODUCT USING CURABLE COMPOSITION |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20080122 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110712 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110906 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20110906 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120619 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120808 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20130514 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20130604 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5288680 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |