US20010025080A1 - Method for producing water based coating compositions - Google Patents
Method for producing water based coating compositions Download PDFInfo
- Publication number
- US20010025080A1 US20010025080A1 US09/753,843 US75384301A US2001025080A1 US 20010025080 A1 US20010025080 A1 US 20010025080A1 US 75384301 A US75384301 A US 75384301A US 2001025080 A1 US2001025080 A1 US 2001025080A1
- Authority
- US
- United States
- Prior art keywords
- water based
- coating composition
- condensation reaction
- resin coating
- tin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000008199 coating composition Substances 0.000 title claims abstract description 70
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 129
- 239000002245 particle Substances 0.000 claims abstract description 95
- 239000000203 mixture Substances 0.000 claims abstract description 64
- 238000006482 condensation reaction Methods 0.000 claims abstract description 50
- 239000000725 suspension Substances 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 24
- 238000004132 cross linking Methods 0.000 claims abstract description 19
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract description 11
- 239000004971 Cross linker Substances 0.000 claims abstract description 10
- 125000005372 silanol group Chemical group 0.000 claims abstract description 8
- 239000000839 emulsion Substances 0.000 claims description 46
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical class [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 claims description 31
- 230000007062 hydrolysis Effects 0.000 claims description 16
- 238000006460 hydrolysis reaction Methods 0.000 claims description 16
- 230000036961 partial effect Effects 0.000 claims description 16
- 239000007859 condensation product Substances 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 9
- 229920000180 alkyd Polymers 0.000 claims description 9
- 229910000077 silane Inorganic materials 0.000 claims description 9
- 239000004925 Acrylic resin Substances 0.000 claims description 7
- 229920000178 Acrylic resin Polymers 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- JQZRVMZHTADUSY-UHFFFAOYSA-L di(octanoyloxy)tin Chemical group [Sn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O JQZRVMZHTADUSY-UHFFFAOYSA-L 0.000 claims description 7
- 150000007524 organic acids Chemical class 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- 230000001804 emulsifying effect Effects 0.000 claims description 6
- 239000003822 epoxy resin Substances 0.000 claims description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 229920003180 amino resin Polymers 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 229920001225 polyester resin Polymers 0.000 claims description 3
- 239000004645 polyester resin Substances 0.000 claims description 3
- 229920005749 polyurethane resin Polymers 0.000 claims description 3
- 229920002050 silicone resin Polymers 0.000 claims description 3
- 238000000576 coating method Methods 0.000 abstract description 19
- 238000005299 abrasion Methods 0.000 abstract description 6
- -1 3-chloropropyl Chemical group 0.000 description 43
- 238000009833 condensation Methods 0.000 description 21
- 230000005494 condensation Effects 0.000 description 21
- 239000003973 paint Substances 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- 238000004945 emulsification Methods 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 239000000084 colloidal system Substances 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 description 4
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 4
- 230000000717 retained effect Effects 0.000 description 4
- 238000006748 scratching Methods 0.000 description 4
- 230000002393 scratching effect Effects 0.000 description 4
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 4
- 125000004066 1-hydroxyethyl group Chemical group [H]OC([H])([*])C([H])([H])[H] 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- MWRSABPHNREIIX-UHFFFAOYSA-N 9,9-dimethyldecan-1-ol Chemical compound CC(C)(C)CCCCCCCCO MWRSABPHNREIIX-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-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
- 239000004593 Epoxy Substances 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- YGHFDTDSFZTYBW-UHFFFAOYSA-N O-silylhydroxylamine Chemical class NO[SiH3] YGHFDTDSFZTYBW-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000005388 dimethylhydrogensiloxy group Chemical group 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical group CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- UQMGAWUIVYDWBP-UHFFFAOYSA-N silyl acetate Chemical class CC(=O)O[SiH3] UQMGAWUIVYDWBP-UHFFFAOYSA-N 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- OGZPYBBKQGPQNU-DABLZPOSSA-N (e)-n-[bis[[(e)-butan-2-ylideneamino]oxy]-methylsilyl]oxybutan-2-imine Chemical compound CC\C(C)=N\O[Si](C)(O\N=C(/C)CC)O\N=C(/C)CC OGZPYBBKQGPQNU-DABLZPOSSA-N 0.000 description 1
- UAZLASMTBCLJKO-UHFFFAOYSA-N 2-decylbenzenesulfonic acid Chemical compound CCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O UAZLASMTBCLJKO-UHFFFAOYSA-N 0.000 description 1
- BOZRCGLDOHDZBP-UHFFFAOYSA-N 2-ethylhexanoic acid;tin Chemical compound [Sn].CCCCC(CC)C(O)=O BOZRCGLDOHDZBP-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
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 1
- JBDMKOVTOUIKFI-UHFFFAOYSA-N 3-[methoxy(dimethyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(C)CCCOC(=O)C(C)=C JBDMKOVTOUIKFI-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-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
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- KXJLGCBCRCSXQF-UHFFFAOYSA-N [diacetyloxy(ethyl)silyl] acetate Chemical compound CC(=O)O[Si](CC)(OC(C)=O)OC(C)=O KXJLGCBCRCSXQF-UHFFFAOYSA-N 0.000 description 1
- TVJPBVNWVPUZBM-UHFFFAOYSA-N [diacetyloxy(methyl)silyl] acetate Chemical compound CC(=O)O[Si](C)(OC(C)=O)OC(C)=O TVJPBVNWVPUZBM-UHFFFAOYSA-N 0.000 description 1
- NBJODVYWAQLZOC-UHFFFAOYSA-L [dibutyl(octanoyloxy)stannyl] octanoate Chemical compound CCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCC NBJODVYWAQLZOC-UHFFFAOYSA-L 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 125000002344 aminooxy group Chemical group [H]N([H])O[*] 0.000 description 1
- SROUPOMLWHGKPN-UHFFFAOYSA-L bis(7,7-dimethyloctanoyloxy)tin Chemical compound [Sn+2].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O SROUPOMLWHGKPN-UHFFFAOYSA-L 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- SLQTWNAJXFHMHM-UHFFFAOYSA-N dimethoxy-methyl-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](C)(OC)OC)CCC2OC21 SLQTWNAJXFHMHM-UHFFFAOYSA-N 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- LMQORFSQFKHATF-UHFFFAOYSA-N dimethoxy-methyl-[4-(oxiran-2-yl)butyl]silane Chemical compound CO[Si](C)(OC)CCCCC1CO1 LMQORFSQFKHATF-UHFFFAOYSA-N 0.000 description 1
- HPDHLPPVRQGVAB-UHFFFAOYSA-N dimethoxy-methyl-[8-(oxiran-2-yl)octyl]silane Chemical compound CO[Si](C)(OC)CCCCCCCCC1CO1 HPDHLPPVRQGVAB-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 1
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000009503 electrostatic coating Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 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
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- XWHJQTQOUDOZGR-UHFFFAOYSA-N hex-1-enyl(trimethoxy)silane Chemical compound CCCCC=C[Si](OC)(OC)OC XWHJQTQOUDOZGR-UHFFFAOYSA-N 0.000 description 1
- DEQLTFPCJRGSHW-UHFFFAOYSA-N hexadecylbenzene Chemical compound CCCCCCCCCCCCCCCCC1=CC=CC=C1 DEQLTFPCJRGSHW-UHFFFAOYSA-N 0.000 description 1
- KTUVYMAZYSSBKC-UHFFFAOYSA-N hexyl benzenesulfonate Chemical compound CCCCCCOS(=O)(=O)C1=CC=CC=C1 KTUVYMAZYSSBKC-UHFFFAOYSA-N 0.000 description 1
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- GVMDZMPQYYHMSV-UHFFFAOYSA-N octyl benzenesulfonate Chemical compound CCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVMDZMPQYYHMSV-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000001367 organochlorosilanes Chemical class 0.000 description 1
- 125000003544 oxime group Chemical group 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000008054 sulfonate salts Chemical class 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- OQNGNXKLDCKIIH-UHFFFAOYSA-N tetradecyl benzenesulfonate Chemical compound CCCCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 OQNGNXKLDCKIIH-UHFFFAOYSA-N 0.000 description 1
- INETXKGLHYNTHK-AQWWNALJSA-N tetrakis[(e)-butan-2-ylideneamino] silicate Chemical compound CC\C(C)=N\O[Si](O\N=C(/C)CC)(O\N=C(/C)CC)O\N=C(/C)CC INETXKGLHYNTHK-AQWWNALJSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- YZVRVDPMGYFCGL-UHFFFAOYSA-N triacetyloxysilyl acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)OC(C)=O YZVRVDPMGYFCGL-UHFFFAOYSA-N 0.000 description 1
- HHPPHUYKUOAWJV-UHFFFAOYSA-N triethoxy-[4-(oxiran-2-yl)butyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCCC1CO1 HHPPHUYKUOAWJV-UHFFFAOYSA-N 0.000 description 1
- BQOPVYVBEXOUFE-UHFFFAOYSA-N triethoxy-[8-(oxiran-2-yl)octyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCCCCCCC1CO1 BQOPVYVBEXOUFE-UHFFFAOYSA-N 0.000 description 1
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 description 1
- HILHCDFHSDUYNX-UHFFFAOYSA-N trimethoxy(pentyl)silane Chemical compound CCCCC[Si](OC)(OC)OC HILHCDFHSDUYNX-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- LTOKKZDSYQQAHL-UHFFFAOYSA-N trimethoxy-[4-(oxiran-2-yl)butyl]silane Chemical compound CO[Si](OC)(OC)CCCCC1CO1 LTOKKZDSYQQAHL-UHFFFAOYSA-N 0.000 description 1
- UEFJJFILJJDEFC-UHFFFAOYSA-N trimethoxy-[8-(oxiran-2-yl)octyl]silane Chemical compound CO[Si](OC)(OC)CCCCCCCCC1CO1 UEFJJFILJJDEFC-UHFFFAOYSA-N 0.000 description 1
- OLTVTFUBQOLTND-UHFFFAOYSA-N tris(2-methoxyethoxy)-methylsilane Chemical compound COCCO[Si](C)(OCCOC)OCCOC OLTVTFUBQOLTND-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
Definitions
- This invention relates to a method for producing water based coating compositions. More particularly, the invention is directed to an efficient method for producing water based coating compositions that have the ability to form highly scratch and abrasion resistant matte coatings in which crosslinked silicone particles are well dispersed.
- Japanese Laid Open (Kokai or Unexamined) Patent Application Number Hei 11-140191 (140,191/1999) teaches that waterborne crosslinked silicone particle suspensions of crosslinked silicone particles, nonionic surfactant, ionic surfactant, and water, can be blended into water based coating compositions.
- a problem with preparing water based coating compositions using waterborne crosslinked silicone particle suspensions is that the application of the resulting water based coating compositions produces matte coatings that have unacceptable scratch and abrasion resistance.
- the object of this invention is to provide an efficient method for producing water based coating compositions that are able to form highly scratch and abrasion resistant matte coatings in which crosslinked silicone particles are well dispersed.
- the method involves producing water based coating compositions by the addition to a water based coating composition of a waterborne suspension of crosslinked silicone particles that have an average diameter of 0.1 to 200 ⁇ m.
- the method for producing water based coating compositions is characterized in that the suspension is a waterborne suspension of crosslinked silicone particles afforded by effecting crosslinking of a condensation reaction crosslinkable silicone composition comprising (A) an organopolysiloxane that contains at least two silanol groups in each molecule, (B) a crosslinker, and (C) a condensation reaction catalyst.
- the crosslinking is effected in the emulsified composition in an aqueous solution of an anionic surfactant.
- the water based coating compositions comprise a coating resin component emulsified in water.
- the water based coating composition should have the ability to form a coating or film upon drying or curing of the coating resin component when water is removed after its application.
- the nature of the composition is not otherwise critical.
- the water based coating composition can be exemplified by ambient temperature curing water based coating compositions, ambient temperature drying water based coating compositions, and water based coating compositions that cure upon the application of heat.
- the coatings of this invention can be used in the protection of substrate surfaces, altering the appearance of substrate surfaces, or changing the character of substrate surfaces, ranging from pigmented paints to varnishes and unpigmented coatings.
- the water based coating composition can for example comprise a water based polyurethane resin coating composition, a water based alkyd resin coating composition, a water based epoxy resin coating composition, a water based acrylic resin coating composition, a water based silicone modified epoxy resin coating composition, a water based silicone modified polyester resin coating composition, a water based silicone resin coating composition, or a water based amino alkyd resin coating composition of an amino resin and an alkyd resin.
- the method for making water based coating compositions begins with preparation of a waterborne crosslinked silicone particle suspension containing crosslinked silicone particles having an average particle size of 0.1 to 200 ⁇ m. This is accomplished by the crosslinking of a condensation reaction crosslinkable silicone composition which comprises (A) an organopolysiloxane that contains at least two silanol groups in each molecule, (B) a crosslinker, and (C) a condensation reaction catalyst. Crosslinking is carried out in an aqueous solution of an anionic surfactant with the condensation reaction crosslinkable silicone composition (A)-(C) being present in an emulsified state.
- Organopolysiloxane (A) is the main or base component of the condensation reaction crosslinkable silicone composition and it should contain at least two silanol groups in each molecule.
- the silanol groups in component (A) are preferably present in the molecular chain terminal positions.
- Silicon bonded organic groups in component (A) can be exemplified by substituted and unsubstituted monovalent hydrocarbyl groups among which are alkyl groups such as methyl, ethyl, propyl, and butyl; alkenyl groups such as vinyl and allyl; aryl groups such as phenyl; aralkyl groups such as benzyl and phenethyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; and halogenated alkyl groups such as 3-chloropropyl and 3,3,3-trifluoropropyl.
- alkyl groups such as methyl, ethyl, propyl, and butyl
- alkenyl groups such as vinyl and allyl
- aryl groups such as phenyl
- aralkyl groups such as benzyl and phenethyl
- cycloalkyl groups such as cyclopentyl and cyclohe
- the molecular structure of component (A) can be, for example, straight chain, partially branched straight chain, branched chain, or network. Preferably, it is straight chain or partially branched straight chain. While the viscosity of component (A) at 25° C. is not critical, it is preferably 5 to 1,000,000 mPa ⁇ s, more preferably 5 to 10,000 mPa ⁇ s, and particularly preferably 5 to 1,000 mPa ⁇ s. The physical properties of the obtained crosslinked silicone particles become increasingly impaired as the viscosity of component (A) at 25° C. declines below the lower limit of these ranges. The ability to emulsify the composition in water is compromised when the upper limit of the ranges is exceeded.
- the crosslinker (B) is the component that functions to crosslink the condensation reaction crosslinkable silicone composition, and this is accomplished by condensing with silanol groups in component (A).
- the crosslinker (B) can be (i) a silane that contains at least three silicon bonded hydrolyzable groups in each molecule, or partial hydrolysis and condensation products of such a silane, or crosslinker (B) can be (ii) an organopolysiloxane that contains at least three silicon bonded hydrogen atoms in each molecule.
- the silicon bonded hydrolyzable groups in component (B)(i) can be alkoxy groups such as methoxy, ethoxy, or methoxyethoxy; oxime groups such as methyl ethyl ketoxime; acetoxy groups; or aminoxy groups.
- the silane or siloxane comprising component (B)(i) can be exemplified by alkoxysilanes such as methyltrimethoxysilane, ethyltrimethoxysilane, methyl tris(methoxyethoxy)silane, tetramethoxysilane, and tetraethoxysilane, and the partial hydrolysis and condensation products of these alkoxy silanes; oxime silanes such as methyltris(methyl ethyl ketoxime)silane, ethyltris(methyl ethyl ketoxime)silane, and tetra(methyl ethyl ketoxime)silane, and the partial hydrolysis and condensation products of these oxime silanes; acetoxy silanes such as methyltriacetoxysilane, ethyltriacetoxysilane, and tetra acetoxysilane, and the partial hydrolysis and condensation products of these
- the silicon bonded organic groups present in component (B)(ii) can be exemplified by substituted and unsubstituted monovalent hydrocarbyl groups, among which are alkyl groups such as methyl, ethyl, propyl, and butyl; alkenyl groups such as vinyl and allyl; aryl groups such as phenyl; aralkyl groups such as benzyl and phenethyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; and halogenated alkyl groups such as 3-chloropropyl and 3,3,3-trifluoropropyl.
- alkyl groups such as methyl, ethyl, propyl, and butyl
- alkenyl groups such as vinyl and allyl
- aryl groups such as phenyl
- aralkyl groups such as benzyl and phenethyl
- cycloalkyl groups such as cyclopent
- the molecular structure of component (B)(ii) can be straight chain, partially branched straight chain, branched chain, network, or cyclic.
- Organopolysiloxanes encompassed by component (B)(ii) can be exemplified by trimethylsiloxy endblocked methylhydrogen polysiloxanes, trimethylsiloxy endblocked dimethylsiloxane/methylhydrogen siloxane copolymers, dimethylhydrogensiloxy endblocked dimethylsiloxane/methylhydrogen siloxane copolymers, cyclic methylhydrogen polysiloxanes, and by organopolysiloxanes afforded by replacing all or part of the methyl groups in any of the preceding siloxanes with other alkyl groups such as ethyl or with aryl groups such as phenyl.
- Component (B) should be present in the condensation reaction crosslinkable silicone composition in an amount sufficient to crosslink the condensation reaction crosslinkable silicone composition. In more specific terms, it is present preferably at 0.1 to 50 weight parts per 100 weight parts of component (A).
- the content of component (B) below the lower limit of the range runs the risk of failing to obtain an acceptable crosslinking of the condensation reaction crosslinkable silicone composition, while a content of component (B) above the upper limit of the range runs the risk of impairing the physical properties of crosslinked silicone particles obtained.
- the condensation reaction crosslinkable silicone composition may optionally contain a component (D), which component (D) can be an organoalkoxysilane containing an alkyl group of five or more carbon atoms, a (meth)acrylic group, an epoxy group, a mercapto group, an amino group, or an alkenyl group.
- component (D) can also be a partial hydrolysis and condensation product of such organoalkoxysilanes.
- Optional component (D) can be exemplified by alkyl group containing alkoxysilanes such as pentyltrimethoxysilane, hexyltrimethoxysilane, and octyltrimethoxysilane; (meth)acryl functional alkoxysilanes such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-methacryloxypropyldimethylmethoxysilane; epoxy functional alkoxysilanes among which are compositions such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyl dimethoxysilane, 2-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl) ethylmethyl dimethoxysilane, 4-oxiranylbutyltrimethoxy
- component (D) in the condensation reaction crosslinkable silicone composition is not critical, component (D) is preferably used in an amount that provides 0.1 to 10 weight percent of (D) in the condensation reaction crosslinkable silicone composition, and more preferably 05 to 5 weight percent of (D) in the condensation reaction crosslinkable silicone composition.
- a content of component (D) below the lower limit of the range runs the risk of producing crosslinked silicone particles with a poor adherence for organic resins.
- a content of component (D) above the upper limit of the range runs the risk of impairing the physical properties of the crosslinked silicone particles obtained.
- the condensation reaction crosslinkable silicone composition may also contain other components among which are reinforcing fillers such as precipitated silica, fumed silica, calcined silica, and fumed titanium oxide; nonreinforcing fillers such as quartz powder, diatomaceous earth, abestos, aluminosilicate, iron oxide, zinc oxide, and calcium carbonate; fillers treated with organsilicon compounds such as organochlorosilanes, organoalkoxysilanes, organosilazanes, or organsiloxane oligomers; pigments; epoxy and/or amino functional organic compounds; heat stabilizers; flame retardants; plasticizers; and noncrosslinkable organopolysiloxanes.
- reinforcing fillers such as precipitated silica, fumed silica, calcined silica, and fumed titanium oxide
- nonreinforcing fillers such as quartz powder, diatomaceous earth, abestos, aluminosilicate, iron oxide, zinc
- the anionic surfactant emulsification of the condensation reaction crosslinkable silicone composition in water is carried out using an emulsifying device such as a colloid mill, homomixer, or homogenizer.
- an emulsifying device such as a colloid mill, homomixer, or homogenizer.
- the absence of the condensation catalyst (C) from the condensation reaction crosslinkable silicone composition enables thorough emulsification and even application of some heating during emulsification.
- thorough emulsification of the condensation reaction crosslinkable silicone composition in water can be achieved, which in turn enables a small average particle size to be obtained, making possible production of crosslinked silicone particles with little variation in size.
- the anionic surfactant used for emulsifying the condensation reaction crosslinkable silicone composition in water can be an alkylbenzene sulfonate salt such as hexylbenzene sulfonate, octylbenzene sulfonate, decylbenzene sulfonate, dodecylbenzene sulfonate, cetylbenzene sulfonate, and myristylbenzene sulfonate; sulfonate salts such as alkylnaphthalene sulfonates, sulfosuccinates, n-olefin sulfonates, and N-acyl sulfonates; carboxylate salts such as soaps, N-acylamino acid salts, polyoxyethylene carboxylates, polyoxyethylene alkyl ether carboxylates, and acylated peptides; sulfate ester salts
- the anionic surfactant is used in an amount that provides 0.05 to 20 weight percent, preferably 0.1 to 10 weight percent anionic surfactant in the emulsion of the condensation reaction crosslinkable silicone composition.
- the use of an anionic surfactant in an amount below the lower limit of the range runs the risk of the resulting emulsion having reduced stability.
- the use of anionic surfactant in excess of the upper limit of the range runs the rise of imposing limitations on application of crosslinked silicone particles obtained.
- the average particle size of emulsion particles be 0.1 to 500 ⁇ m when the condensation reaction crosslinkable silicone composition is being emulsified in water. It is difficult to prepare an emulsion with an average particle size below the lower limit of the range, while an emulsion in which the average particle size exceeds the upper limit of the range has poor stability.
- the content of the condensation reaction crosslinkable silicone composition in the emulsion is 10 to 90 weight percent, preferably 20 to 80 weight percent, in the emulsion.
- a condensation reaction crosslinkable silicone composition content below the lower limit of the range impairs dewatering of the emulsion and recovery of crosslinked silicone particles, and can result in limitations on applications of the waterborne crosslinked silicone particle suspension.
- a composition content in excess of the upper limit of the range risks impairing the handling characteristics of the resulting waterborne crosslinked silicone particle suspension.
- a characteristic feature of the invention is the addition of a tin (II) salt of an organic acid containing no more than ten carbon atoms to the emulsion as the condensation reaction catalyst (C).
- a tin (II) salt of an organic acid containing no more than ten carbon atoms to the emulsion as the condensation reaction catalyst (C).
- the use of an organotin compound or a tin (II) salt of an organic acid with more than ten carbon atoms encounters problems of inadequate crosslinking in the condensation reaction crosslinkable silicone composition, and failure of crosslinking to occur.
- the preferred tin (II) salt of an organic acid containing no more than ten carbon atoms is preferably a tin (II) salt of a saturated aliphatic acid containing no more than ten carbon atoms, such as tin (II) acetate, tin (II) 2-ethylhexanoate, tin (II) neodecanoate, tin (II) 2,4-pentadionate, and tin (II) octanoate. Tin (II) octanoate is especially preferred.
- the invention encompasses direct addition of tin (II) salt of organic acid catalyst, hereafter referred to as tin (II) salt, to the emulsion of the condensation reaction crosslinkable silicone composition
- the tin (II) salt is preferably added to the emulsion of the condensation reaction crosslinkable silicone composition in the form of a separate emulsion prepared in advance by emulsification of the tin (II) salt in water using an emulsifying agent.
- the use of an emulsion of tin (II) salt results in a substantial acceleration of the crosslinking reaction in the condensation reaction crosslinkable silicone composition, and enables production of crosslinked silicone particles with uniform particle size.
- the emulsion of tin (II) salt can be prepared by direct emulsification of tin (II) salt in water using an anionic surfactant.
- the tin (II) salt can be diluted in an organic solvent and then emulsified in water using an anionic surfactant.
- the anionic surfactant used for emulsification of the tin (II) salt can be the same type of anionic surfactant as mentioned above.
- the anionic surfactant is used for emulsification of the tin (II) salt in an amount of 0.01 to 1,000 weight parts per 100 weight parts of the tin (II) salt.
- the organic solvent should be a ketone such as acetone and methyl ethyl ketone, or an alcohol containing no more than 4 carbon atoms such as methanol, ethanol, n-propanol, isopropanol, and tert-butanol. Lower alcohols are preferred.
- the tin (II) salt emulsion can be prepared using an emulsifying device such as a colloid mill or homogenizer.
- the amount of tin (II) salt is not critical, but it is preferably added at 0.01 to 20 weight parts, particularly 0.1 to 10 weight parts, in each case per 100 weight parts of the condensation reaction crosslinkable silicone composition. Addition of the tin (II) salt in an amount below the lower limit of the range runs the risk of failing to obtain an adequate acceleration of crosslinking in the condensation reaction crosslinkable silicone composition. Addition of the tin (II) salt in excess of the upper limit of the range runs the risk of compromising the physical properties of the crosslinked silicone particles obtained.
- tin (II) salt to the emulsion of the condensation reaction crosslinkable silicone composition serves to accelerate the crosslinking reaction in the condensation reaction crosslinkable silicone composition.
- crosslinking will still proceed slowly when the temperature of the emulsion is too low.
- the stability of the emulsion will be reduced when its temperature is too high. Therefore, the temperature of addition of the tin (II) salt is preferably from 5 to 70° C.
- Crosslinked silicone particles prepared according to the invention should have a spherical shape and an average particle size of 0.1 to 500 ⁇ m.
- the crosslinked silicone particles have the capacity to impart an excellent impact resistance and blocking resistance to organic resins.
- the crosslinked silicone particles should have a type A durometer hardness of 10-95, as determined by Japanese Industrial Standard (JIS) K 6253-1997, preferably a hardness of 20-90, to avoid scratching or abrasion of organic resin film surfaces produced when the film is rubbed.
- Water based coating compositions according to the invention can be prepared simply by intermixing a water based coating composition with a separately prepared waterborne dispersion of cured condensation curable silicone particles.
- Water based coating compositions can also be prepared by producing the coating resin component in a waterborne dispersion of cured condensation curable silicone particles.
- a water based coating composition having a high total solids concentration it is preferred to use a waterborne dispersion of cured condensation curable silicone particles that has a high concentration of cured condensation curable silicone particles, or to produce the coating resin component in the waterborne dispersion of cured condensation curable silicone particles.
- the level of addition of the waterborne crosslinked silicone particle suspension with respect to the water based coating composition is not critical, but the waterborne crosslinked silicone particle suspension is preferably used in an amount that provides 0.01 to 10 weight parts of crosslinked silicone particles from the suspension per 100 weight parts of solids in the coating composition.
- Water based coating compositions according to the invention may contain other components in addition to the water based dispersion of cured condensation curable silicone particles, such as inorganic particles, thickeners, and pigments.
- Water based coating compositions according to the invention can be applied by coating methods used in the application of organic solvent based coating compositions, such as spray coating, electrostatic coating, immersion coating, curtain flow coating, roll coating, and shower coating.
- a crosslinked silicone sheet with a thickness of 1 mm was prepared by maintaining a condensation catalyst containing condensation crosslinking silicone composition for one week at 25° C. to effect crosslinking.
- Type A durometer hardness was measured on the crosslinked silicone according to the protocol of JIS K 6253-1997 using a micro hardness testing device of H. W. Wallace Co.
- the average particle size was determined for a waterborne crosslinked silicone particle dispersion using a laser diffraction instrument for measuring particle size distributions.
- the instrument was a Model LA-500 of Horiba Seisakusho.
- the median diameter i.e., the particle diameter corresponding to 50 percent of the cumulative distribution, was measured with the instrument and was used as the average particle size of the crosslinked silicone particles.
- the average particle size of the condensation catalyst emulsion was measured using a laser scattering submicron particle analyzer.
- the device was a Model N4 instrument of Coulter Electronics.
- condensation catalyst emulsion having an average particle size of 1.2 ⁇ m.
- the condensation catalyst emulsion was prepared by emulsification of one weight part tin (II) octanoate in an aqueous solution of 9.75 weight parts of pure water and 0.25 weight part sodium polyoxyethylene lauryl sulfate anionic surfactant.
- suspension (A) The combined emulsion mixture was allowed to stand for one day which resulted in the production of a uniform and gel free waterborne suspension of crosslinked silicone particles.
- the composition was designated suspension (A).
- suspension (A) was filtered through a 200 mesh screen, the amount of retained crosslinked silicone particles was no more than 0.1 weight percent of the total amount filtered.
- the crosslinked silicone particles in suspension (A) were rubbery and had a type A durometer hardness of 60 and an average particle size of 2 ⁇ m.
- a condensation catalyst emulsion having an average particle size of approximately 1.2 ⁇ m was added to the emulsion of condensation reaction crosslinkable silicone composition.
- the condensation catalyst emulsion was prepared by emulsification of one weight part of tin (II) octanoate in an aqueous solution of 9.75 weight parts of pure water and 0.25 weight part of sodium polyoxyethylene lauryl sulfate anionic surfactant.
- the combined emulsions were allowed to stand for one day which resulted in production of a uniform and gel free waterborne suspension of crosslinked silicone particles designated suspension (B).
- suspension (B) When suspension (B) was filtered through a 200 mesh screen, the amount of crosslinked silicone particles retained on the screen was no more than 0.1 weight percent of the total amount filtered.
- the crosslinked silicone particles in suspension (B) were rubbery and had a type A durometer hardness of 60 and an average particle size of 2 ⁇ m.
- a composition (I) was prepared by mixing 20 weight parts of a dimethylhydrogensiloxy endblocked methylhydrogen polysiloxane with a viscosity of 10 mPa ⁇ s, 5 weight parts of 3-glycidoxypropyltrimethoxysilane, and 95 weight parts of a dimethylpolysiloxane with the formula HO((CH 3 ) 2 SiO) 35 H.
- a composition (II) was prepared by mixing 5 weight parts of 3-glycidoxypropyltrimethoxysilane, 1.0 weight part of dibutyltin dioctoate, and 95 weight parts of a dimethylpolysiloxane with the formula HO((CH 3 ) 2 SiO) 35 H.
- compositions (I) and (II) were placed in separate holding tanks, and the tanks were cooled to ⁇ 10° C.
- 500 weight parts of composition (I) and 500 weight parts of composition (II) were mixed to homogeneity by passage through a static mixer manufactured by Tokushu Kika Kabushiki Kaisha. The mixture was transferred to a high speed stirred mixer, and 9,000 weight parts of ion exchanged water, and 20 weight parts of ethylene oxide adduct of trimethylnonanol, a nonionic surfactant sold under the name Tergitol® TMN-6 by Union Carbide Corporation, were poured into the mixer at the same time.
- the emulsion was mixed with a condensation catalyst emulsion having an average particle size of 1.2 ⁇ m.
- the condensation catalyst emulsion was prepared by emulsifying one weight part of tin (II) octanoate in an aqueous solution of 9.75 weight parts of pure water and 0.25 weight part of sodium polyoxyethylene lauryl sulfate anionic surfactant.
- the composition was allowed to stand for 1 day resulting in a uniform and gel free waterborne suspension of crosslinked silicone particles designated suspension (D).
- Each waterborne crosslinked silicone particle suspension (A)-(D) prepared and described in Reference Examples 1-4 was added to a water based urethane resin paint manufactured by Kansai Paint Co., Ltd., and to a water based acrylic resin paint also manufactured by Kansai Paint Co., Ltd..
- the suspensions were added in an amount to provide 1.5 weight parts of crosslinked silicone particles for each 100 weight parts of solids in the respective paint.
- addition of the suspension to the paint was followed by shaking 50 times to yield a water based coating composition.
- Each of the water based coating compositions were applied to a polyethylene terephthalate (PET) film and dried by heating for 10 minutes at 100° C. to produce a paint film with a thickness of 15 ⁇ m.
- PET polyethylene terephthalate
- the method of the invention for producing water based coating compositions provides very efficiently produce water based coating compositions that can form highly scratch and abrasion resistant coatings in which the crosslinked silicone particles are thoroughly dispersed.
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Abstract
An efficient method is provided for producing water based coating compositions that are capable of forming highly scratch and abrasion resistant matte coatings in which crosslinked silicone particles are well dispersed. The method involves addition to a water based coating composition of a waterborne suspension of crosslinked silicone particles having an average diameter of 0.1-200 μm. The method is characterized in that the suspension is a waterborne crosslinked silicone particle suspension provided by effecting crosslinking of a condensation reaction crosslinkable silicone composition comprising (A) an organopolysiloxane containing at least two silanol groups in each molecule, (B) a crosslinker, and (C) a condensation reaction catalyst. The crosslinking is effected in the emulsified composition in an aqueous solution of an anionic surfactant.
Description
- Not applicable.
- Not applicable.
- Not applicable.
- This invention relates to a method for producing water based coating compositions. More particularly, the invention is directed to an efficient method for producing water based coating compositions that have the ability to form highly scratch and abrasion resistant matte coatings in which crosslinked silicone particles are well dispersed.
- Japanese Laid Open (Kokai or Unexamined) Patent Application Number Hei 2-113079 (113,079/1990)/EP 0 365 009 A2 (Apr. 25, 1990), discloses blending crosslinked silicone particles into coating compositions to produce coating compositions that form matte coatings.
- Since a uniform dispersion is not obtained when crosslinked silicone particles are blended into a water based coating composition, Japanese Laid Open (Kokai or Unexamined) Patent Application Number Hei 5-9409 (9,409/1993)/U.S. Pat. No. 5,708,057 (Jan. 13, 1998), teaches a method for preparing water based coating compositions in which crosslinked silicone particles are blended as a waterborne suspension into water based coating compositions.
- Japanese Laid Open (Kokai or Unexamined) Patent Application Number Hei 11-140191 (140,191/1999) teaches that waterborne crosslinked silicone particle suspensions of crosslinked silicone particles, nonionic surfactant, ionic surfactant, and water, can be blended into water based coating compositions.
- A problem with preparing water based coating compositions using waterborne crosslinked silicone particle suspensions is that the application of the resulting water based coating compositions produces matte coatings that have unacceptable scratch and abrasion resistance.
- Therefore, the object of this invention is to provide an efficient method for producing water based coating compositions that are able to form highly scratch and abrasion resistant matte coatings in which crosslinked silicone particles are well dispersed.
- In particular, the method involves producing water based coating compositions by the addition to a water based coating composition of a waterborne suspension of crosslinked silicone particles that have an average diameter of 0.1 to 200 μm. Furthermore, the method for producing water based coating compositions is characterized in that the suspension is a waterborne suspension of crosslinked silicone particles afforded by effecting crosslinking of a condensation reaction crosslinkable silicone composition comprising (A) an organopolysiloxane that contains at least two silanol groups in each molecule, (B) a crosslinker, and (C) a condensation reaction catalyst. The crosslinking is effected in the emulsified composition in an aqueous solution of an anionic surfactant.
- These and other features of the invention will become apparent from a consideration of the detailed description.
- Not applicable.
- The water based coating compositions comprise a coating resin component emulsified in water. The water based coating composition should have the ability to form a coating or film upon drying or curing of the coating resin component when water is removed after its application. The nature of the composition is not otherwise critical.
- The water based coating composition can be exemplified by ambient temperature curing water based coating compositions, ambient temperature drying water based coating compositions, and water based coating compositions that cure upon the application of heat. The coatings of this invention can be used in the protection of substrate surfaces, altering the appearance of substrate surfaces, or changing the character of substrate surfaces, ranging from pigmented paints to varnishes and unpigmented coatings. The water based coating composition can for example comprise a water based polyurethane resin coating composition, a water based alkyd resin coating composition, a water based epoxy resin coating composition, a water based acrylic resin coating composition, a water based silicone modified epoxy resin coating composition, a water based silicone modified polyester resin coating composition, a water based silicone resin coating composition, or a water based amino alkyd resin coating composition of an amino resin and an alkyd resin.
- The method for making water based coating compositions begins with preparation of a waterborne crosslinked silicone particle suspension containing crosslinked silicone particles having an average particle size of 0.1 to 200 μm. This is accomplished by the crosslinking of a condensation reaction crosslinkable silicone composition which comprises (A) an organopolysiloxane that contains at least two silanol groups in each molecule, (B) a crosslinker, and (C) a condensation reaction catalyst. Crosslinking is carried out in an aqueous solution of an anionic surfactant with the condensation reaction crosslinkable silicone composition (A)-(C) being present in an emulsified state.
- Organopolysiloxane (A) is the main or base component of the condensation reaction crosslinkable silicone composition and it should contain at least two silanol groups in each molecule. The silanol groups in component (A) are preferably present in the molecular chain terminal positions. Silicon bonded organic groups in component (A) can be exemplified by substituted and unsubstituted monovalent hydrocarbyl groups among which are alkyl groups such as methyl, ethyl, propyl, and butyl; alkenyl groups such as vinyl and allyl; aryl groups such as phenyl; aralkyl groups such as benzyl and phenethyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; and halogenated alkyl groups such as 3-chloropropyl and 3,3,3-trifluoropropyl.
- The molecular structure of component (A) can be, for example, straight chain, partially branched straight chain, branched chain, or network. Preferably, it is straight chain or partially branched straight chain. While the viscosity of component (A) at 25° C. is not critical, it is preferably 5 to 1,000,000 mPa·s, more preferably 5 to 10,000 mPa·s, and particularly preferably 5 to 1,000 mPa·s. The physical properties of the obtained crosslinked silicone particles become increasingly impaired as the viscosity of component (A) at 25° C. declines below the lower limit of these ranges. The ability to emulsify the composition in water is compromised when the upper limit of the ranges is exceeded.
- The crosslinker (B) is the component that functions to crosslink the condensation reaction crosslinkable silicone composition, and this is accomplished by condensing with silanol groups in component (A). The crosslinker (B) can be (i) a silane that contains at least three silicon bonded hydrolyzable groups in each molecule, or partial hydrolysis and condensation products of such a silane, or crosslinker (B) can be (ii) an organopolysiloxane that contains at least three silicon bonded hydrogen atoms in each molecule.
- The silicon bonded hydrolyzable groups in component (B)(i) can be alkoxy groups such as methoxy, ethoxy, or methoxyethoxy; oxime groups such as methyl ethyl ketoxime; acetoxy groups; or aminoxy groups. The silane or siloxane comprising component (B)(i) can be exemplified by alkoxysilanes such as methyltrimethoxysilane, ethyltrimethoxysilane, methyl tris(methoxyethoxy)silane, tetramethoxysilane, and tetraethoxysilane, and the partial hydrolysis and condensation products of these alkoxy silanes; oxime silanes such as methyltris(methyl ethyl ketoxime)silane, ethyltris(methyl ethyl ketoxime)silane, and tetra(methyl ethyl ketoxime)silane, and the partial hydrolysis and condensation products of these oxime silanes; acetoxy silanes such as methyltriacetoxysilane, ethyltriacetoxysilane, and tetra acetoxysilane, and the partial hydrolysis and condensation products of these acetoxysilanes; and aminoxy silanes such as methyltris(trimethylaminoxy)silane, ethyltris(trimethylaminoxy)silane, and tetra(trimethylaminoxy)silane, and the partial hydrolysis and condensation products of these aminoxy silanes. Alkoxy silanes and their partial hydrolysis and condensation products are preferred, and alkyl polysilicates afforded by the partial hydrolysis and condensation of tetraalkoxysilanes are particularly preferred.
- The silicon bonded organic groups present in component (B)(ii) can be exemplified by substituted and unsubstituted monovalent hydrocarbyl groups, among which are alkyl groups such as methyl, ethyl, propyl, and butyl; alkenyl groups such as vinyl and allyl; aryl groups such as phenyl; aralkyl groups such as benzyl and phenethyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; and halogenated alkyl groups such as 3-chloropropyl and 3,3,3-trifluoropropyl. The molecular structure of component (B)(ii) can be straight chain, partially branched straight chain, branched chain, network, or cyclic. Organopolysiloxanes encompassed by component (B)(ii) can be exemplified by trimethylsiloxy endblocked methylhydrogen polysiloxanes, trimethylsiloxy endblocked dimethylsiloxane/methylhydrogen siloxane copolymers, dimethylhydrogensiloxy endblocked dimethylsiloxane/methylhydrogen siloxane copolymers, cyclic methylhydrogen polysiloxanes, and by organopolysiloxanes afforded by replacing all or part of the methyl groups in any of the preceding siloxanes with other alkyl groups such as ethyl or with aryl groups such as phenyl.
- Component (B) should be present in the condensation reaction crosslinkable silicone composition in an amount sufficient to crosslink the condensation reaction crosslinkable silicone composition. In more specific terms, it is present preferably at 0.1 to 50 weight parts per 100 weight parts of component (A). The content of component (B) below the lower limit of the range runs the risk of failing to obtain an acceptable crosslinking of the condensation reaction crosslinkable silicone composition, while a content of component (B) above the upper limit of the range runs the risk of impairing the physical properties of crosslinked silicone particles obtained.
- The condensation reaction crosslinkable silicone composition may optionally contain a component (D), which component (D) can be an organoalkoxysilane containing an alkyl group of five or more carbon atoms, a (meth)acrylic group, an epoxy group, a mercapto group, an amino group, or an alkenyl group. Component (D) can also be a partial hydrolysis and condensation product of such organoalkoxysilanes. Optional component (D) can be exemplified by alkyl group containing alkoxysilanes such as pentyltrimethoxysilane, hexyltrimethoxysilane, and octyltrimethoxysilane; (meth)acryl functional alkoxysilanes such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-methacryloxypropyldimethylmethoxysilane; epoxy functional alkoxysilanes among which are compositions such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyl dimethoxysilane, 2-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl) ethylmethyl dimethoxysilane, 4-oxiranylbutyltrimethoxysilane, 4-oxiranylbutyltriethoxysilane, 4-oxiranylbutylmethyldimethoxysilane, 8-oxiranyloctyltrimethoxysilane, 8-oxiranyloctyltriethoxysilane, and 8-oxiranyloctylmethyldimethoxysilane; mercapto functional alkoxysilanes such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropylmethyldimethoxysilane; amino functional alkoxysilanes such as 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyl dimethoxysilane, and 3-anilinopropyltrimethoxysilane; and alkenyl functional alkoxysilanes such as vinyltrimethoxysilane, allyltrimethoxysilane, and hexenyltrimethoxysilane. The partial hydrolysis and condensation products of any of these compounds can also be employed as optional component (D).
- While the content of component (D) in the condensation reaction crosslinkable silicone composition is not critical, component (D) is preferably used in an amount that provides 0.1 to 10 weight percent of (D) in the condensation reaction crosslinkable silicone composition, and more preferably 05 to 5 weight percent of (D) in the condensation reaction crosslinkable silicone composition. A content of component (D) below the lower limit of the range runs the risk of producing crosslinked silicone particles with a poor adherence for organic resins. A content of component (D) above the upper limit of the range runs the risk of impairing the physical properties of the crosslinked silicone particles obtained.
- The condensation reaction crosslinkable silicone composition may also contain other components among which are reinforcing fillers such as precipitated silica, fumed silica, calcined silica, and fumed titanium oxide; nonreinforcing fillers such as quartz powder, diatomaceous earth, abestos, aluminosilicate, iron oxide, zinc oxide, and calcium carbonate; fillers treated with organsilicon compounds such as organochlorosilanes, organoalkoxysilanes, organosilazanes, or organsiloxane oligomers; pigments; epoxy and/or amino functional organic compounds; heat stabilizers; flame retardants; plasticizers; and noncrosslinkable organopolysiloxanes.
- The anionic surfactant emulsification of the condensation reaction crosslinkable silicone composition in water is carried out using an emulsifying device such as a colloid mill, homomixer, or homogenizer. The absence of the condensation catalyst (C) from the condensation reaction crosslinkable silicone composition enables thorough emulsification and even application of some heating during emulsification. As a consequence, thorough emulsification of the condensation reaction crosslinkable silicone composition in water can be achieved, which in turn enables a small average particle size to be obtained, making possible production of crosslinked silicone particles with little variation in size.
- The anionic surfactant used for emulsifying the condensation reaction crosslinkable silicone composition in water can be an alkylbenzene sulfonate salt such as hexylbenzene sulfonate, octylbenzene sulfonate, decylbenzene sulfonate, dodecylbenzene sulfonate, cetylbenzene sulfonate, and myristylbenzene sulfonate; sulfonate salts such as alkylnaphthalene sulfonates, sulfosuccinates, n-olefin sulfonates, and N-acyl sulfonates; carboxylate salts such as soaps, N-acylamino acid salts, polyoxyethylene carboxylates, polyoxyethylene alkyl ether carboxylates, and acylated peptides; sulfate ester salts such as sulfated oils, salts of alkyl sulfates, salts of alkyl ether sulfates, salts of polyoxyethylene sulfates, salts of sulfates of polyoxyethylene alkylaryl ethers, and salts of alkylamide sulfates; salts of alkyl phosphates, salts of polyoxyethylene phosphates, salts of polyoxyethylene alkyl ether phosphates, salts of polyoxyethylene alkylaryl ether phosphates; and mixtures thereof.
- The anionic surfactant is used in an amount that provides 0.05 to 20 weight percent, preferably 0.1 to 10 weight percent anionic surfactant in the emulsion of the condensation reaction crosslinkable silicone composition. The use of an anionic surfactant in an amount below the lower limit of the range runs the risk of the resulting emulsion having reduced stability. The use of anionic surfactant in excess of the upper limit of the range runs the rise of imposing limitations on application of crosslinked silicone particles obtained.
- To obtain compositions suitable for use according to the invention, it is necessary that the average particle size of emulsion particles be 0.1 to 500 μm when the condensation reaction crosslinkable silicone composition is being emulsified in water. It is difficult to prepare an emulsion with an average particle size below the lower limit of the range, while an emulsion in which the average particle size exceeds the upper limit of the range has poor stability. The content of the condensation reaction crosslinkable silicone composition in the emulsion is 10 to 90 weight percent, preferably 20 to 80 weight percent, in the emulsion. A condensation reaction crosslinkable silicone composition content below the lower limit of the range impairs dewatering of the emulsion and recovery of crosslinked silicone particles, and can result in limitations on applications of the waterborne crosslinked silicone particle suspension. A composition content in excess of the upper limit of the range risks impairing the handling characteristics of the resulting waterborne crosslinked silicone particle suspension.
- A characteristic feature of the invention is the addition of a tin (II) salt of an organic acid containing no more than ten carbon atoms to the emulsion as the condensation reaction catalyst (C). The use of an organotin compound or a tin (II) salt of an organic acid with more than ten carbon atoms encounters problems of inadequate crosslinking in the condensation reaction crosslinkable silicone composition, and failure of crosslinking to occur. The preferred tin (II) salt of an organic acid containing no more than ten carbon atoms is preferably a tin (II) salt of a saturated aliphatic acid containing no more than ten carbon atoms, such as tin (II) acetate, tin (II) 2-ethylhexanoate, tin (II) neodecanoate, tin (II) 2,4-pentadionate, and tin (II) octanoate. Tin (II) octanoate is especially preferred.
- While the invention encompasses direct addition of tin (II) salt of organic acid catalyst, hereafter referred to as tin (II) salt, to the emulsion of the condensation reaction crosslinkable silicone composition, the tin (II) salt is preferably added to the emulsion of the condensation reaction crosslinkable silicone composition in the form of a separate emulsion prepared in advance by emulsification of the tin (II) salt in water using an emulsifying agent. The use of an emulsion of tin (II) salt results in a substantial acceleration of the crosslinking reaction in the condensation reaction crosslinkable silicone composition, and enables production of crosslinked silicone particles with uniform particle size. The emulsion of tin (II) salt can be prepared by direct emulsification of tin (II) salt in water using an anionic surfactant.
- When it is desired to prepare a uniform emulsion of the tin (II) salt, the tin (II) salt can be diluted in an organic solvent and then emulsified in water using an anionic surfactant. The anionic surfactant used for emulsification of the tin (II) salt can be the same type of anionic surfactant as mentioned above. The anionic surfactant is used for emulsification of the tin (II) salt in an amount of 0.01 to 1,000 weight parts per 100 weight parts of the tin (II) salt. When the tin (II) salt is to be preliminarily diluted in an organic solvent, the organic solvent should be a ketone such as acetone and methyl ethyl ketone, or an alcohol containing no more than 4 carbon atoms such as methanol, ethanol, n-propanol, isopropanol, and tert-butanol. Lower alcohols are preferred. The tin (II) salt emulsion can be prepared using an emulsifying device such as a colloid mill or homogenizer.
- The amount of tin (II) salt is not critical, but it is preferably added at 0.01 to 20 weight parts, particularly 0.1 to 10 weight parts, in each case per 100 weight parts of the condensation reaction crosslinkable silicone composition. Addition of the tin (II) salt in an amount below the lower limit of the range runs the risk of failing to obtain an adequate acceleration of crosslinking in the condensation reaction crosslinkable silicone composition. Addition of the tin (II) salt in excess of the upper limit of the range runs the risk of compromising the physical properties of the crosslinked silicone particles obtained.
- The addition of tin (II) salt to the emulsion of the condensation reaction crosslinkable silicone composition serves to accelerate the crosslinking reaction in the condensation reaction crosslinkable silicone composition. However, crosslinking will still proceed slowly when the temperature of the emulsion is too low. Conversely, the stability of the emulsion will be reduced when its temperature is too high. Therefore, the temperature of addition of the tin (II) salt is preferably from 5 to 70° C.
- Crosslinked silicone particles prepared according to the invention should have a spherical shape and an average particle size of 0.1 to 500 μm. The crosslinked silicone particles have the capacity to impart an excellent impact resistance and blocking resistance to organic resins. In addition, the crosslinked silicone particles should have a type A durometer hardness of 10-95, as determined by Japanese Industrial Standard (JIS) K 6253-1997, preferably a hardness of 20-90, to avoid scratching or abrasion of organic resin film surfaces produced when the film is rubbed.
- Water based coating compositions according to the invention can be prepared simply by intermixing a water based coating composition with a separately prepared waterborne dispersion of cured condensation curable silicone particles. Water based coating compositions can also be prepared by producing the coating resin component in a waterborne dispersion of cured condensation curable silicone particles. When a water based coating composition having a high total solids concentration is desired, it is preferred to use a waterborne dispersion of cured condensation curable silicone particles that has a high concentration of cured condensation curable silicone particles, or to produce the coating resin component in the waterborne dispersion of cured condensation curable silicone particles. The level of addition of the waterborne crosslinked silicone particle suspension with respect to the water based coating composition is not critical, but the waterborne crosslinked silicone particle suspension is preferably used in an amount that provides 0.01 to 10 weight parts of crosslinked silicone particles from the suspension per 100 weight parts of solids in the coating composition.
- Water based coating compositions according to the invention may contain other components in addition to the water based dispersion of cured condensation curable silicone particles, such as inorganic particles, thickeners, and pigments.
- Water based coating compositions according to the invention can be applied by coating methods used in the application of organic solvent based coating compositions, such as spray coating, electrostatic coating, immersion coating, curtain flow coating, roll coating, and shower coating.
- The following working examples are set forth in order to illustrate this invention in more detail. Viscosity values in the examples were measured at 25° C., and properties of the crosslinked silicone particles were measured using the following methods. Durometer of Crosslinked Silicone Particles
- A crosslinked silicone sheet with a thickness of 1 mm was prepared by maintaining a condensation catalyst containing condensation crosslinking silicone composition for one week at 25° C. to effect crosslinking. Type A durometer hardness was measured on the crosslinked silicone according to the protocol of JIS K 6253-1997 using a micro hardness testing device of H. W. Wallace Co.
- Average Particle Size of Crosslinked Silicone Particles
- The average particle size was determined for a waterborne crosslinked silicone particle dispersion using a laser diffraction instrument for measuring particle size distributions. The instrument was a Model LA-500 of Horiba Seisakusho. The median diameter, i.e., the particle diameter corresponding to 50 percent of the cumulative distribution, was measured with the instrument and was used as the average particle size of the crosslinked silicone particles.
- Average Particle Size of the Condensation Catalyst Emulsion
- The average particle size of the condensation catalyst emulsion was measured using a laser scattering submicron particle analyzer. The device was a Model N4 instrument of Coulter Electronics.
- 84.7 weight parts of adimethylpolysiloxane with the formula HO((CH 3)2SiO)11H, 10.5 weight parts of ethyl polysilicate of the formula (C2H5O)12Si5O4 produced by partial hydrolysis and condensation of tetraethoxysilane, and 4.8 weight parts of 3-glycidoxypropyltrimethoxysilane, were mixed to homogeneity. The mixture was emulsified in an aqueous solution of 30 weight parts of pure water and one weight part of sodium polyoxyethylene lauryl sulfate anionic surfactant. The mixture was further emulsified to homogeneity using a colloid mill, and diluted with 58 weight parts of pure water to produce an emulsion of a condensation reaction crosslinkable silicone composition.
- To the emulsion was added a condensation catalyst emulsion having an average particle size of 1.2 μm. The condensation catalyst emulsion was prepared by emulsification of one weight part tin (II) octanoate in an aqueous solution of 9.75 weight parts of pure water and 0.25 weight part sodium polyoxyethylene lauryl sulfate anionic surfactant.
- The combined emulsion mixture was allowed to stand for one day which resulted in the production of a uniform and gel free waterborne suspension of crosslinked silicone particles. The composition was designated suspension (A). When suspension (A) was filtered through a 200 mesh screen, the amount of retained crosslinked silicone particles was no more than 0.1 weight percent of the total amount filtered. The crosslinked silicone particles in suspension (A) were rubbery and had a type A durometer hardness of 60 and an average particle size of 2 μm.
- 84.7 weight parts of a dimethylpolysiloxane with the formula HO((CH 3)2SiO)11H, 10.5 weight parts of ethyl polysilicate with the formula (C2H5O)12Si5O4 produced by partial hydrolysis and condensation of tetraethoxysilane, and 4.8 weight parts of allyltrimethoxysilane were mixed to homogeneity. The mixture was emulsified in an aqueous solution of 30 weight parts of pure water and one weight part of sodium polyoxyethylene lauryl sulfate anionic surfactant. The mixture was further emulsified to homogeneity using a colloid mill, and diluted with 58 weight parts of pure water to produce an emulsion of condensation reaction crosslinkable silicone composition.
- A condensation catalyst emulsion having an average particle size of approximately 1.2 μm was added to the emulsion of condensation reaction crosslinkable silicone composition. The condensation catalyst emulsion was prepared by emulsification of one weight part of tin (II) octanoate in an aqueous solution of 9.75 weight parts of pure water and 0.25 weight part of sodium polyoxyethylene lauryl sulfate anionic surfactant. The combined emulsions were allowed to stand for one day which resulted in production of a uniform and gel free waterborne suspension of crosslinked silicone particles designated suspension (B). When suspension (B) was filtered through a 200 mesh screen, the amount of crosslinked silicone particles retained on the screen was no more than 0.1 weight percent of the total amount filtered. The crosslinked silicone particles in suspension (B) were rubbery and had a type A durometer hardness of 60 and an average particle size of 2 μm.
- A composition (I) was prepared by mixing 20 weight parts of a dimethylhydrogensiloxy endblocked methylhydrogen polysiloxane with a viscosity of 10 mPa·s, 5 weight parts of 3-glycidoxypropyltrimethoxysilane, and 95 weight parts of a dimethylpolysiloxane with the formula HO((CH 3)2SiO)35H.
- A composition (II) was prepared by mixing 5 weight parts of 3-glycidoxypropyltrimethoxysilane, 1.0 weight part of dibutyltin dioctoate, and 95 weight parts of a dimethylpolysiloxane with the formula HO((CH 3)2SiO)35H.
- Compositions (I) and (II) were placed in separate holding tanks, and the tanks were cooled to −10° C. 500 weight parts of composition (I) and 500 weight parts of composition (II) were mixed to homogeneity by passage through a static mixer manufactured by Tokushu Kika Kabushiki Kaisha. The mixture was transferred to a high speed stirred mixer, and 9,000 weight parts of ion exchanged water, and 20 weight parts of ethylene oxide adduct of trimethylnonanol, a nonionic surfactant sold under the name Tergitol® TMN-6 by Union Carbide Corporation, were poured into the mixer at the same time. Stirring was carried out at 1,400 rpm, followed by passage through a colloid mill, to prepare an emulsion of condensation reaction crosslinkable silicone composition. The emulsion was maintained for two days at room temperature to produce a waterborne suspension of crosslinked silicone particles designated suspension (C). When suspension (C) was filtered through a 200 mesh screen, the amount of crosslinked silicone particles retained on the screen was 0.5 weight percent of the total amount filtered. The crosslinked silicone particles in suspension (C) were rubbery and had an A durometer hardness of 42 and an average particle size of 3 μm.
- 84.7 weight parts of a dimethylpolysiloxane with the formula HO((CH 3)2SiO)11H, 10.5 weight parts of ethyl polysilicate with the formula (C2H5O)12Si5O4 produced by partial hydrolysis and condensation of tetraethoxysilane, and 4.8 weight parts of 3-glycidoxypropyltrimethoxysilane were mixed to homogeneity. The mixture was emulsified in an aqueous solution of 30 weight parts of pure water and 0.5 weight part ethylene oxide adduct on trimethylnonanol, a nonionic surfactant sold under the name Tergitol® TMN-6 by Union Carbide Corporation. The composition was further emulsified to homogeneity using a colloid mill and then diluted with 58 weight parts of pure water producing an emulsion of a condensation reaction crosslinkable silicone composition.
- 0.5 weight part of sodium polyoxyethylene lauryl sulfate anionic surfactant was added to the emulsion. The emulsion was mixed with a condensation catalyst emulsion having an average particle size of 1.2 μm. The condensation catalyst emulsion was prepared by emulsifying one weight part of tin (II) octanoate in an aqueous solution of 9.75 weight parts of pure water and 0.25 weight part of sodium polyoxyethylene lauryl sulfate anionic surfactant. The composition was allowed to stand for 1 day resulting in a uniform and gel free waterborne suspension of crosslinked silicone particles designated suspension (D). When suspension (D) was filtered through a 200 mesh screen, the amount of crosslinked silicone particles retained on the screen was 1.9 weight percent of the total amount filtered. Crosslinked silicone particles in suspension (D) were rubbery and had an A durometer hardness of 60 and an average particle size of 4 μm.
- Each waterborne crosslinked silicone particle suspension (A)-(D) prepared and described in Reference Examples 1-4 was added to a water based urethane resin paint manufactured by Kansai Paint Co., Ltd., and to a water based acrylic resin paint also manufactured by Kansai Paint Co., Ltd.. The suspensions were added in an amount to provide 1.5 weight parts of crosslinked silicone particles for each 100 weight parts of solids in the respective paint. In each case, addition of the suspension to the paint was followed by shaking 50 times to yield a water based coating composition. Each of the water based coating compositions were applied to a polyethylene terephthalate (PET) film and dried by heating for 10 minutes at 100° C. to produce a paint film with a thickness of 15 μm.
- Using a light microscope at 1000 × magnification, each paint film was examined for the existence of pinholes due to escape of crosslinked silicone particles from the paint film surface, and for the occurrence of crosslinked silicone particles which had segregated to the paint film surface. A value of + was assigned to films with an absence of pinholes and crosslinked silicone particles segregated to the coating film surface; and a value of × was assigned when either or both of these phenomena were observed. Table 1 shows the evaluation of the paint films.
TABLE 1 Comparative Comparative Example 1 Example 2 Example 1 Example 2 waterborne cross- A B C D linked silicone particle suspension urethane resin + + x x acrylic resin + + x x - The flattening performance of each paint film surface was also evaluated using the scale + for strong flattening activity and particle aggregates of no more than 30 μm; Δ for some flattening activity present and particle aggregates of no more than 30 μm; and × for little flattening activity. Table 2 shows this evaluation of the paint films.
TABLE 2 Comparative Comparative Example 1 Example 2 Example 1 Example 2 waterborne cross- A B C D linked silicone particle suspension urethane resin + + + Δ acrylic resin + + Δ Δ - The occurrence of scratching of the paint film surfaces was evaluated after each paint film surface had been rubbed five times with a piece of polypropylene resin. The occurrence of scratching was evaluated using the scale + for no scratching of the paint film; Δ for small scratches in the paint film; and × for large scratches in the paint film. Table 3 shows the results of this evaluation of the paint films.
TABLE 3 Comparative Comparative Example 1 Example 2 Example 1 Example 2 waterborne cross- A B C D linked silicone particle suspension urethane resin + + x x acrylic resin + + Δ Δ - In view of the above, it can be seen that the method of the invention for producing water based coating compositions provides very efficiently produce water based coating compositions that can form highly scratch and abrasion resistant coatings in which the crosslinked silicone particles are thoroughly dispersed.
- Other variations may be made in compounds, compositions, and methods described herein without departing from the essential features of the invention. The embodiments of the invention specifically illustrated herein are exemplary only and not intended as limitations on their scope except as defined in the appended claims.
Claims (18)
1. A method of making a water based coating composition comprising adding a waterborne suspension of crosslinked silicone particles that have an average diameter of 0.1-200 μm to a water based coating composition, the waterborne suspension of crosslinked silicone particles being prepared by crosslinking a condensation reaction crosslinkable silicone composition containing (A) an organopolysiloxane having at least two silanol groups in its molecule, (B) a crosslinker, and (C) a condensation reaction catalyst, crosslinking being carried out in an emulsion containing (A)-(C) and an aqueous solution of an anionic surfactant.
2. A method according to in which condensation reaction catalyst (C) is the last component added to the emulsion.
claim 1
3. A method according to in which condensation reaction catalyst (C) is an emulsion prepared by emulsifying a tin (II) salt of organic acid having no more than 10 carbon atoms in water using an anionic surfactant.
claim 1
4. A method according to in which the average particle size of the tin (II) salt in the emulsion is no more than 10 μm.
claim 3
5. A method according to wherein the tin (II) salt is tin (II) octanoate.
claim 4
6. A method according to wherein crosslinker (B) is a silane having at least three silicon bonded hydrolyzable groups in its molecule or a partial hydrolysis and condensation product thereof.
claim 1
7. A method according to wherein the condensation reaction crosslinkable silicone composition contains (D) an organoalkoxysilane having an alkyl group of at least five carbon atoms, a (meth)acrylic group, an epoxy group, a mercapto group, an amino group, an alkenyl group, or partial hydrolysis and condensation products thereof.
claim 1
8. A method according to wherein the water based coating composition is selected from the group consisting of a water based polyurethane resin coating composition, a water based alkyd resin coating composition, a water based epoxy resin coating composition, a water based acrylic resin coating composition, a water based silicone modified epoxy resin coating composition, a water based silicone modified polyester resin coating composition, a water based silicone resin coating composition, and a water based amino alkyd resin coating composition of an amino resin and an alkyd resin.
claim 1
9. A water based coating composition prepared according to the method in .
claim 8
10. A method of making a water based coating composition comprising adding a waterborne suspension of crosslinked silicone particles that have an average diameter of 0.1-200 μm to a water based coating composition, the waterborne suspension of crosslinked silicone particles being prepared by crosslinking a condensation reaction crosslinkable silicone composition containing (A) an organopolysiloxane having at least two silanol groups in its molecule, (B) a crosslinker, and (C) a condensation reaction catalyst, crosslinking being carried out in an emulsion containing (A)-(C) and an aqueous solution of an anionic surfactant, condensation reaction catalyst (C) being a tin (II) salt of an organic acid having no more than 10 carbon atoms.
11. A method according to in which condensation reaction catalyst (C) is the last component added to the emulsion.
claim 10
12. A method according to in which condensation reaction catalyst (C) is an emulsion prepared by emulsifying a tin (II) salt of organic acid having no more than 10 carbon atoms in water using an anionic surfactant.
claim 10
13. A method according to in which the average particle size of the tin (II) salt in the emulsion is no more than 10 μm.
claim 12
14. A method according to wherein the tin (II) salt is tin (II) octanoate.
claim 13
15. A method according to wherein crosslinker (B) is a silane having at least three silicon bonded hydrolyzable groups in its molecule or a partial hydrolysis and condensation product thereof.
claim 10
16. A method according to wherein the condensation reaction crosslinkable silicone composition contains (D) an organoalkoxysilane having an alkyl group of at least five carbon atoms, a (meth)acrylic group, an epoxy group, a mercapto group, an amino group, an alkenyl group, or partial hydrolysis and condensation products thereof.
claim 10
17. A method according to wherein the water based coating composition is selected from the group consisting of a water based polyurethane resin coating composition, a water based alkyd resin coating composition, a water based epoxy resin coating composition, a water based acrylic resin coating composition, a water based silicone modified epoxy resin coating composition, a water based silicone modified polyester resin coating composition, a water based silicone resin coating composition, and a water based amino alkyd resin coating composition of an amino resin and an alkyd resin.
claim 10
18. A water based coating composition prepared according to the method in .
claim 17
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| JPH086069B2 (en) | 1988-10-20 | 1996-01-24 | 東レ・ダウコーニング・シリコーン株式会社 | Paint composition |
| FR2649115B1 (en) * | 1989-06-29 | 1994-10-28 | Rhone Poulenc Chimie | AQUEOUS DISPERSION BASED ON SILICON OILS AND ORGANIC (CO) POLYMER CROSSLINKING TO AN ELASTOMER BY REMOVAL OF WATER |
| JP2787737B2 (en) * | 1991-06-28 | 1998-08-20 | 東レ・ダウコーニング・シリコーン 株式会社 | Method for producing aqueous coating composition |
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| JPH1161010A (en) * | 1997-08-26 | 1999-03-05 | Toray Dow Corning Silicone Co Ltd | Coating composition |
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- 2001-01-03 US US09/753,843 patent/US6433041B2/en not_active Expired - Lifetime
- 2001-02-01 EP EP01300923A patent/EP1132443B1/en not_active Expired - Lifetime
- 2001-02-01 DE DE60102850T patent/DE60102850T2/en not_active Expired - Lifetime
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| US7125585B2 (en) * | 2002-09-26 | 2006-10-24 | Goldschmidt Gmbh | Siloxane compounds and their use as homogenizer in release agents with matting effect for producing moldings from plastics with matt surfaces |
| US20140371358A1 (en) * | 2013-06-17 | 2014-12-18 | Toshiba Tec Kabushiki Kaisha | Inkjet ink |
| US9963604B2 (en) * | 2013-06-17 | 2018-05-08 | Toshiba Tec Kabushiki Kaisha | Inkjet ink |
| WO2020232058A1 (en) * | 2019-05-15 | 2020-11-19 | Ampacet Corporation | Matte finish for plastics |
| US20230174791A1 (en) * | 2020-04-30 | 2023-06-08 | Flooring Technologies Ltd. | Composition for Matting and Reducing Anti-Fingerprint Effects of Surfaces on Carrier Materials |
| EP3928860A1 (en) * | 2020-06-24 | 2021-12-29 | Universität des Saarlandes | Microparticles; method for producing microparticles, use of the microparticles and component |
| WO2021259672A1 (en) * | 2020-06-24 | 2021-12-30 | Universität des Saarlandes | Method for producing microparticles, microparticles, use of the microparticles, and component |
| CN114058252A (en) * | 2021-12-31 | 2022-02-18 | 福建龙兴九源科技股份有限公司 | Water-based woodenware coating and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| DE60102850T2 (en) | 2005-04-21 |
| EP1132443A9 (en) | 2001-10-31 |
| JP2001240803A (en) | 2001-09-04 |
| EP1132443A2 (en) | 2001-09-12 |
| DE60102850D1 (en) | 2004-05-27 |
| EP1132443A3 (en) | 2003-03-19 |
| EP1132443B1 (en) | 2004-04-21 |
| US6433041B2 (en) | 2002-08-13 |
| JP4693953B2 (en) | 2011-06-01 |
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