JP6837226B2 - Water-based paint composition - Google Patents
Water-based paint composition Download PDFInfo
- Publication number
- JP6837226B2 JP6837226B2 JP2016224627A JP2016224627A JP6837226B2 JP 6837226 B2 JP6837226 B2 JP 6837226B2 JP 2016224627 A JP2016224627 A JP 2016224627A JP 2016224627 A JP2016224627 A JP 2016224627A JP 6837226 B2 JP6837226 B2 JP 6837226B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- weight
- carbon atoms
- gloss
- coating composition
- 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.)
- Active
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 89
- 239000000203 mixture Substances 0.000 title description 24
- 239000003973 paint Substances 0.000 title description 11
- 229920001296 polysiloxane Polymers 0.000 claims description 52
- 239000000839 emulsion Substances 0.000 claims description 38
- 239000008199 coating composition Substances 0.000 claims description 29
- 125000003277 amino group Chemical group 0.000 claims description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 230000007062 hydrolysis Effects 0.000 claims description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002736 nonionic surfactant Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 4
- AHYFYQKMYMKPKD-UHFFFAOYSA-N 3-ethoxysilylpropan-1-amine Chemical compound CCO[SiH2]CCCN AHYFYQKMYMKPKD-UHFFFAOYSA-N 0.000 claims description 3
- BYIMSFXYUSZVLI-UHFFFAOYSA-N 3-methoxysilylpropan-1-amine Chemical compound CO[SiH2]CCCN BYIMSFXYUSZVLI-UHFFFAOYSA-N 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 150000003973 alkyl amines Chemical group 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 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 claims description 3
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 claims 1
- 239000011248 coating agent Substances 0.000 description 37
- 238000000576 coating method Methods 0.000 description 37
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 16
- 230000003373 anti-fouling effect Effects 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- -1 Polyoxyethylene Polymers 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 229920001451 polypropylene glycol Polymers 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002932 luster Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 5
- 238000004220 aggregation Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 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 4
- FDCJDKXCCYFOCV-UHFFFAOYSA-N 1-hexadecoxyhexadecane Chemical compound CCCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCC FDCJDKXCCYFOCV-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 150000005215 alkyl ethers Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 125000006353 oxyethylene group Chemical group 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 229920002050 silicone resin Polymers 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 230000001154 acute effect Effects 0.000 description 2
- 231100000570 acute poisoning Toxicity 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000005370 alkoxysilyl group Chemical group 0.000 description 2
- 231100000739 chronic poisoning Toxicity 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000008235 industrial water Substances 0.000 description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000008213 purified water Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 2
- 229920006310 Asahi-Kasei Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- FNYLWPVRPXGIIP-UHFFFAOYSA-N Triamterene Chemical compound NC1=NC2=NC(N)=NC(N)=C2N=C1C1=CC=CC=C1 FNYLWPVRPXGIIP-UHFFFAOYSA-N 0.000 description 1
- 229920004482 WACKER® Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229920013822 aminosilicone Polymers 0.000 description 1
- 239000013011 aqueous formulation Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- XGZGKDQVCBHSGI-UHFFFAOYSA-N butyl(triethoxy)silane Chemical compound CCCC[Si](OCC)(OCC)OCC XGZGKDQVCBHSGI-UHFFFAOYSA-N 0.000 description 1
- SXPLZNMUBFBFIA-UHFFFAOYSA-N butyl(trimethoxy)silane Chemical compound CCCC[Si](OC)(OC)OC SXPLZNMUBFBFIA-UHFFFAOYSA-N 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- KQAHMVLQCSALSX-UHFFFAOYSA-N decyl(trimethoxy)silane Chemical compound CCCCCCCCCC[Si](OC)(OC)OC KQAHMVLQCSALSX-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- ZMAPKOCENOWQRE-UHFFFAOYSA-N diethoxy(diethyl)silane Chemical compound CCO[Si](CC)(CC)OCC ZMAPKOCENOWQRE-UHFFFAOYSA-N 0.000 description 1
- VSYLGGHSEIWGJV-UHFFFAOYSA-N diethyl(dimethoxy)silane Chemical compound CC[Si](CC)(OC)OC VSYLGGHSEIWGJV-UHFFFAOYSA-N 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- NHYFIJRXGOQNFS-UHFFFAOYSA-N dimethoxy-bis(2-methylpropyl)silane Chemical compound CC(C)C[Si](OC)(CC(C)C)OC NHYFIJRXGOQNFS-UHFFFAOYSA-N 0.000 description 1
- VHPUZTHRFWIGAW-UHFFFAOYSA-N dimethoxy-di(propan-2-yl)silane Chemical compound CO[Si](OC)(C(C)C)C(C)C VHPUZTHRFWIGAW-UHFFFAOYSA-N 0.000 description 1
- YGUFXEJWPRRAEK-UHFFFAOYSA-N dodecyl(triethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OCC)(OCC)OCC YGUFXEJWPRRAEK-UHFFFAOYSA-N 0.000 description 1
- SCPWMSBAGXEGPW-UHFFFAOYSA-N dodecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OC)(OC)OC SCPWMSBAGXEGPW-UHFFFAOYSA-N 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- DFJDZTPFNSXNAX-UHFFFAOYSA-N ethoxy(triethyl)silane Chemical compound CCO[Si](CC)(CC)CC DFJDZTPFNSXNAX-UHFFFAOYSA-N 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-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
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000013101 initial test Methods 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- HOVAGTYPODGVJG-ZFYZTMLRSA-N methyl alpha-D-glucopyranoside Chemical compound CO[C@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O HOVAGTYPODGVJG-ZFYZTMLRSA-N 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- SLYCYWCVSGPDFR-UHFFFAOYSA-N octadecyltrimethoxysilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OC)(OC)OC SLYCYWCVSGPDFR-UHFFFAOYSA-N 0.000 description 1
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012169 petroleum derived wax Substances 0.000 description 1
- 235000019381 petroleum wax Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- ALVYUZIFSCKIFP-UHFFFAOYSA-N triethoxy(2-methylpropyl)silane Chemical compound CCO[Si](CC(C)C)(OCC)OCC ALVYUZIFSCKIFP-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- OYGYKEULCAINCL-UHFFFAOYSA-N triethoxy(hexadecyl)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC OYGYKEULCAINCL-UHFFFAOYSA-N 0.000 description 1
- WUMSTCDLAYQDNO-UHFFFAOYSA-N triethoxy(hexyl)silane Chemical compound CCCCCC[Si](OCC)(OCC)OCC WUMSTCDLAYQDNO-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- FZMJEGJVKFTGMU-UHFFFAOYSA-N triethoxy(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC FZMJEGJVKFTGMU-UHFFFAOYSA-N 0.000 description 1
- BJDLPDPRMYAOCM-UHFFFAOYSA-N triethoxy(propan-2-yl)silane Chemical compound CCO[Si](OCC)(OCC)C(C)C BJDLPDPRMYAOCM-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- SVKDNKCAGJVMMY-UHFFFAOYSA-N triethoxy(tetradecyl)silane Chemical compound CCCCCCCCCCCCCC[Si](OCC)(OCC)OCC SVKDNKCAGJVMMY-UHFFFAOYSA-N 0.000 description 1
- HUZZQXYTKNNCOU-UHFFFAOYSA-N triethyl(methoxy)silane Chemical compound CC[Si](CC)(CC)OC HUZZQXYTKNNCOU-UHFFFAOYSA-N 0.000 description 1
- XYJRNCYWTVGEEG-UHFFFAOYSA-N trimethoxy(2-methylpropyl)silane Chemical compound CO[Si](OC)(OC)CC(C)C XYJRNCYWTVGEEG-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
- LGROXJWYRXANBB-UHFFFAOYSA-N trimethoxy(propan-2-yl)silane Chemical compound CO[Si](OC)(OC)C(C)C LGROXJWYRXANBB-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- AXNJHBYHBDPTQF-UHFFFAOYSA-N trimethoxy(tetradecyl)silane Chemical compound CCCCCCCCCCCCCC[Si](OC)(OC)OC AXNJHBYHBDPTQF-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Description
本発明は、車両のガラスや車体本体などの所望の物品の表面に塗布することにより、被塗布物の表面の艶を出し、溶剤として水を含有する水系塗料組成物に関するものである。 The present invention relates to a water-based coating composition that glosses the surface of an object to be coated by applying it to the surface of a desired article such as vehicle glass or a vehicle body, and contains water as a solvent.
従来、自動車などの車両用の艶出し剤として、カルナバロウや石油ワックスを主体としたワックス類や、ジメチルシリコーンやアミノシリコーンなどの変性シリコーン、またはシリコーンレジンなどのシリコーン類を主成分としているが、ワックス類は効果の持続性が乏しく、シリコーン類は汚染されやすかったり反応性硬化物の製剤化が困難であったりした。 Conventionally, waxes mainly composed of carnauba wax and petroleum wax, modified silicones such as dimethyl silicone and aminosilicone, and silicones such as silicone resin are mainly used as polishes for vehicles such as automobiles. The effects of the types were poor, and the silicones were easily contaminated and it was difficult to formulate the reactive cured product.
近年では、シラザン類やアルコキシシランなどを有機溶媒中に分散・溶解させたものを、スプレーや手塗り等で被塗布物に処理し、乾燥過程でガラス状の効果被膜を形成させ、撥水性、艶及び耐久性にすぐれた塗料が知られている。 In recent years, silazanes, alkoxysilanes, etc. are dispersed and dissolved in an organic solvent and treated with a spray or hand coating to form a glass-like effect film during the drying process, resulting in water repellency. Paints with excellent luster and durability are known.
例えば、特許文献１において、メチルトリメトキシシランなどのアルコキシシランを塩酸などの酸により加水分解して縮合したシリコーン樹脂、α―メチル−Ｄ−グルコシド、界面活性剤、水などを混合して乳化剤とした艶出し剤が開示されている。 For example, in Patent Document 1, a silicone resin obtained by hydrolyzing and condensing an alkoxysilane such as methyltrimethoxysilane with an acid such as hydrochloric acid, α-methyl-D-glucoside, a surfactant, water and the like are mixed and used as an emulsifier. The polish is disclosed.
しかしながら、引用文献１の組成物では、塗膜作成後に塗膜の艶や撥水性等の耐久性に関して必ずしも良好とはいえず課題があった。 However, the composition of Cited Document 1 has a problem that the durability such as gloss and water repellency of the coating film is not always good after the coating film is formed.
また、引用文献１の組成物では、有機溶媒を含有している例もあり、塗工作業を行う現場の環境改善がより求められるようになってきており、有機溶剤を含有しない塗料組成物が求められている課題もあった。 Further, in the composition of Cited Document 1, there is an example in which an organic solvent is contained, and there is an increasing demand for improvement of the environment at the site where the coating work is performed. There were also issues that were sought.
そこで、本発明において、組成物としての保存安定に優れ、作成される塗膜に艶、撥水性、防汚性を付与し、耐久性に優れる水系塗料組成物を提供することを目的とする。 Therefore, it is an object of the present invention to provide a water-based coating composition which is excellent in storage stability as a composition, imparts luster, water repellency and antifouling property to the produced coating film, and is excellent in durability.
本発明者らは、コーティング組成物について鋭意研究を重ね、シリカ粒子の比表面積及び表面処理剤の種類を特定し、アルコキシシランのうちアミノ基を有する化合物を処方することにより、組成物として保存安定性に優れ、艶、撥水性及び防汚性を付与し、耐空性にも優れる塗膜を作成することができることを見出し、これらの知見に基づいて本発明に至った。 The present inventors have conducted extensive research on the coating composition, specified the specific surface area of the silica particles and the type of surface treatment agent, and formulated a compound having an amino group among the alkoxysilanes to store and stabilize the composition. It has been found that a coating film having excellent properties, gloss, water repellency and antifouling properties, and excellent air resistance can be produced, and the present invention has been made based on these findings.
〔１〕すなわち、本発明は、
（ａ−１）下記一般式（１）で表されるアルコキシシランと、
Ｘｎ−Ｓｉ−（ＯＹ）4-ｎ・・・・・・・（１）
（式中Ｘは炭素数１〜１８のアルキル基、Ｙは炭素数１〜４のアルキル基、ｎは１〜３の整数である）
（ａ−２）前記アルコキシシランの加水分解縮合物であるオルガノポリシロキサンと、
（ａ−３）非イオン性界面活性剤と、
（ａ−４）水を含有する
（Ａ）シリコーン乳化物と、
（Ｂ）下記一般式（２）で表されるアミノ基含有アルコキシシランと、
Ｚ−Ｓｉ（−Ｘ）ｍ−（ＯＹ）3-ｍ・・・・・・・（２）
（式中Ｚは１級から３級から選ばれる少なくとも１つのアミンを有するアルキルアミン鎖、Ｘは炭素数１〜４のアルキル基、Ｙは炭素数１〜４のアルキル基、ｍは０〜２の整数である）
（Ｃ）水
を含有し、
前記（Ａ）が０．０５〜１０重量％であり、前記（Ｂ）が０．０５〜０．１重量％であり、
炭化水素系、芳香族系、エステル系、アルコール系、ケトン系から選ばれる少なくとも一つの有機溶剤を配合していないことを特徴とする水系塗料組成物である。
[1] That is, the present invention
(A-1) Alkoxysilane represented by the following general formula (1) and
Xn-Si- (OY) 4-n ... (1)
(In the formula, X is an alkyl group having 1 to 18 carbon atoms, Y is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 3 carbon atoms).
(A-2) Organopolysiloxane, which is a hydrolysis condensate of the alkoxysilane,
(A-3) Nonionic surfactant and
(A-4) Water-containing (A) silicone emulsion and
(B) Amino group-containing alkoxysilane represented by the following general formula (2) and
Z-Si (-X) m- (OY) 3-m ... (2)
(Z in the formula is an alkylamine chain having at least one amine selected from primary to tertiary, X is an alkyl group having 1 to 4 carbon atoms, Y is an alkyl group having 1 to 4 carbon atoms, and m is 0 to 2. Is an integer of)
(C) containing water,
The (A) is 0.05 to 10% by weight, and the (B) is 0.05 to 0.1% by weight.
It is a water-based coating composition characterized in that it does not contain at least one organic solvent selected from hydrocarbon-based, aromatic-based, ester-based, alcohol-based, and ketone-based.
〔２〕そして、前記アミノ基含有アルコキシシランが、３−アミノプロピルメトキシシラン、３−アミノプロピルエトキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルメチルジメトキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルトリメトキシシラン、Ｎ−フェニル−３−アミノプロピルトリメトキシシランから選ばれる少なくとも１種であることを特徴とする前記〔１〕に記載の撥水性コーティング組成物である。 [2] The amino group-containing alkoxysilanes are 3-aminopropylmethoxysilane, 3-aminopropylethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, and N-2- (amino). The water-repellent coating composition according to the above [1], which is at least one selected from ethyl) -3-aminopropyltrimethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane.
本発明によれば、組成物として保存安定性に優れ、艶、撥水性及び防汚性を付与し、耐空性にも優れる塗膜を作成することができる。 According to the present invention, it is possible to prepare a coating film having excellent storage stability as a composition, imparting luster, water repellency and antifouling property, and also having excellent airworthiness.
以下、本発明の水系塗料組成物に関する実施形態について詳しく説明する。なお、説明中における範囲を示す表記は、上限と下限を含有するものである。 Hereinafter, embodiments relating to the water-based coating composition of the present invention will be described in detail. The notation indicating the range in the description includes the upper limit and the lower limit.
本発明の塗膜組成物は、（Ａ）シリコーン乳化物と、（Ｂ）特定のアミノ基含有アルコキシシランと、（Ｃ）水を含有している。少なくともこれら成分を配合した組成物により、後述するように、組成物としての保存安定性に優れ、塗膜作製後に処理表面の艶、撥水性や防汚性に優れた性能を示す塗膜を作成できる。 The coating film composition of the present invention contains (A) a silicone emulsion, (B) a specific amino group-containing alkoxysilane, and (C) water. As will be described later, a composition containing at least these components produces a coating film that has excellent storage stability as a composition and that exhibits excellent performance such as gloss, water repellency, and antifouling property on the treated surface after preparation of the coating film. it can.
（Ａ）シリコーン乳化物は、（ａ−１）特定のアルコキシシランと、（ａ−２）前記アルコキシシランの加水分解縮合物であるオルガノポリシロキサンと、（ａ−３）非イオン性界面活性剤と、（ａ−４）水を含有してなるエマルジョンである。（Ａ）シリコーン乳化物に関して、後述する条件に合致するように、各成分を自ら調整するなどして処方することもできるし、市販品を購入することもできる。 The (A) silicone emulsion comprises (a-1) a specific alkoxysilane, (a-2) an organopolysiloxane which is a hydrolysis condensate of the alkoxysilane, and (a-3) a nonionic surfactant. And (a-4) an emulsion containing water. (A) Regarding the silicone emulsion, each component can be adjusted by itself so as to meet the conditions described later, or a commercially available product can be purchased.
本発明に含有される（ａ−１）アルコキシシランは、下記の一般式（１）で表される化合物である。
Ｘｎ−Ｓｉ−（ＯＹ）4-ｎ・・・・・・・（１）
（式中Ｘは炭素数１〜１８のアルキル基、Ｙは炭素数１〜４のアルキル基、ｎは１〜３の整数である）
当該アルコキシシランによれば、塗布する基材と結合し、塗膜に艶、親水性、防汚性を付与することができる。なお、一般式（１）におけるＸ，Ｙは、一般式（２）におけるＸ，Ｙは独立している。
The alkoxysilane (a-1) contained in the present invention is a compound represented by the following general formula (1).
Xn-Si- (OY) 4-n ... (1)
(In the formula, X is an alkyl group having 1 to 18 carbon atoms, Y is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 3 carbon atoms).
According to the alkoxysilane, it can be bonded to the base material to be coated to impart gloss, hydrophilicity and antifouling property to the coating film. Note that X and Y in the general formula (1) are independent of X and Y in the general formula (2).
当該アルコシシランとしては、例えば、１官能のトリメチルメトキシシラン、トリエチルメトキシシラン、トリメチルエトキシシラン、トリエチルエトキシシランなどや、２官能のジメチルジメトキシシラン、ジエチルジメトキシシラン、ジイソプロピルジメトキシシラン、ジイソブチルジメトキシシラン、ジメチルジエトキシシラン、ジエチルジエトキシシランなどや、３官能のメチルトリメトキシシラン、エチルトリメトキシシラン、ｎ−プロピルトリメトキシシラン、イソプロピルトリメトキシシラン、ｎ−ブチルトリメトキシシラン、イソブチルトリメトキシシラン、ｎ−ヘキシルトリメトキシシラン、ｎ−オクチルトリメトキシシラン、ｎ−デシルトリメトキシシラン、ｎ−ドデシルトリメトキシシラン、ｎ−テトラデシルトリメトキシシラン、ｎ−ヘキサデシルトリメトキシシラン、ｎ−オクタデシルトリメトキシシラン、メチルトリエトキシシラン、エチルトリエトキシシラン、ｎ−プロピルトリエトキシシラン、イソプロピルトリエトキシシラン、ｎ−ブチルトリエトキシシラン、イソブチルトリエトキシシラン、ｎ−ヘキシルトリエトキシシラン、ｎ−オクチルトリエトキシシラン、ｎ−デシルトリエトキシシラン、ｎ−ドデシルトリエトキシシラン、ｎ−テトラデシルトリエトキシシラン、ｎ−ヘキサデシルトリエトキシシラン、ｎ−オクタデシルトリエトキシシランなどが好ましく、３官能の上記アルコシシランがさらに好ましい。このうちの１種又は２種以上を組み合わせて使用することができる。 Examples of the arcocisilane include monofunctional trimethylmethoxysilane, triethylmethoxysilane, trimethylethoxysilane, and triethylethoxysilane, and bifunctional dimethyldimethoxysilane, diethyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, and dimethyldiethoxy. Silane, diethyldiethoxysilane, etc., trifunctional methyltrimethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, isopropyltrimethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, n-hexyltri Methoxysilane, n-octyltrimethoxysilane, n-decyltrimethoxysilane, n-dodecyltrimethoxysilane, n-tetradecyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-octadecyltrimethoxysilane, methyltriethoxy Silane, ethyltriethoxysilane, n-propyltriethoxysilane, isopropyltriethoxysilane, n-butyltriethoxysilane, isobutyltriethoxysilane, n-hexyltriethoxysilane, n-octyltriethoxysilane, n-decyltriethoxy. Silane, n-dodecyltriethoxysilane, n-tetradecyltriethoxysilane, n-hexadecyltriethoxysilane, n-octadecyltriethoxysilane and the like are preferable, and the trifunctional arcocisilane is more preferable. One of them or two or more of them can be used in combination.
また、（Ａ）シリコーン乳化物における（ａ−１）一般式（１）で表されるアルコキシシランの含有割合は、１〜３０重量％であることが好ましく、２〜２５重量％であることが好ましい。（ａ−１）一般式（１）で表されるアルコキシシランの含有割合がこの範囲であると、塗布する基材の表面に艶、撥水性、防汚性を付与し、さらに、加水分解による凝集も生じにくくなり保存安定性を向上させることができる。 Further, the content ratio of the alkoxysilane represented by the general formula (1) in the (A) silicone emulsion is preferably 1 to 30% by weight, preferably 2 to 25% by weight. preferable. (A-1) When the content ratio of the alkoxysilane represented by the general formula (1) is within this range, gloss, water repellency, and antifouling property are imparted to the surface of the base material to be coated, and further, by hydrolysis. Aggregation is less likely to occur and storage stability can be improved.
本発明に含有される（ａ−２）前記アルコキシシランの加水分解縮合物であるオルガノポリシロキサンは、（ａ−１）一般式（１）で表されるアルコキシシランの加水分解物を脱水縮合により形成された重合物である。 The organopolysiloxane (a-2) which is a hydrolyzate of the alkoxysilane contained in the present invention is obtained by dehydrating and condensing the hydrolyzate of the alkoxysilane represented by (a-1) the general formula (1). It is a polymer formed.
当該オルガノポリシロキサンは、重合平均分子量として、２００〜１００００が好ましく、３００〜６０００が好ましい。当該オルガノポリシロキサンの重合平均分子量がこの範囲にあると、塗布する基材の表面に艶、撥水性、防汚性を付与し、さらに、加水分解による凝集も生じにくくなり保存安定性を向上させることができる。なお、当該オルガノポリシロキサンの重合平均分子量を測定する方法として、ＧＰＣ法（ゲル浸透クロマトグラフィー）にて、展開溶媒としてトルエンなどを用いて、標準ポリスチレン換算として算出されることが好ましい。 The organopolysiloxane has a polymerization average molecular weight of preferably 200 to 10000, preferably 300 to 6000. When the polymerization average molecular weight of the organopolysiloxane is in this range, gloss, water repellency, and antifouling property are imparted to the surface of the base material to be applied, and aggregation due to hydrolysis is less likely to occur, which improves storage stability. be able to. As a method for measuring the polymerization average molecular weight of the organopolysiloxane, it is preferable to calculate it in terms of standard polystyrene by using the GPC method (gel permeation chromatography) using toluene or the like as a developing solvent.
また、（Ａ）シリコーン乳化物における（ａ−２）前記アルコキシシランの加水分解縮合物であるオルガノポリシロキサンの含有割合は、１〜３０重量％であることが好ましく、１〜２０重量％であることが好ましい。当該オルガノポリシロキサンの含有割合がこの範囲であると、塗布する基材の表面に艶、撥水性、防汚性を付与し、さらに、加水分解による凝集も生じにくくなり保存安定性を向上させることができる。 The content of (a-2) organopolysiloxane, which is a hydrolyzed condensate of the alkoxysilane, in the (A) silicone emulsion is preferably 1 to 30% by weight, preferably 1 to 20% by weight. Is preferable. When the content ratio of the organopolysiloxane is in this range, gloss, water repellency, and antifouling property are imparted to the surface of the base material to be applied, and further, aggregation due to hydrolysis is less likely to occur, and storage stability is improved. Can be done.
本発明に含有される（ａ−３）非イオン性界面活性剤は、直鎖状又は分岐鎖を有するアルキル鎖の炭素数が１２〜２０と、−ＣＨ2ＣＨ2Ｏ−で表されるオキシエチレンユニットまたは−ＣＨ2ＣＨ（ＣＨ3）Ｏ−で表されるオキシプロピレンユニットの少なくとも一方から構成されてなるポリオキシエチレン（ＰＯＥ）アルキルエーテル、ポリオキシプロピレン（ＰＯＰ）アルキルエーテル、ポリオキシエチレン（ＰＯＥ）ポリオキシプロピレン（ＰＯＰ）アルキルエーテルなどの界面活性剤である。オキシエチレンユニット及びオキシプロピレンユニットとしては、１〜１００、好ましくは１〜５０、さらに好ましくは１〜２０含むことが好ましい。非イオン性界面活性剤中に、オキシエチレンユニット及びオキシプロピレンユニットがともに存在する場合、オキシエチレンユニット及びオキシプロピレンユニットはそれぞれランダム又はブロックで結合することができる。 The (a-3) nonionic surfactant contained in the present invention has an alkyl chain having a linear or branched chain having 12 to 20 carbon atoms and an oxy represented by −CH 2 CH 2 O−. Polyoxyethylene (POE) alkyl ether, polyoxypropylene (POP) alkyl ether, polyoxyethylene (polyoxyethylene (POP) alkyl ether, which is composed of at least one of an ethylene unit or an oxypropylene unit represented by -CH 2 CH (CH 3) O-. POE) A surfactant such as polyoxypropylene (POP) alkyl ether. The oxyethylene unit and the oxypropylene unit preferably contain 1 to 100, preferably 1 to 50, and more preferably 1 to 20. When both the oxyethylene unit and the oxypropylene unit are present in the nonionic surfactant, the oxyethylene unit and the oxypropylene unit can be bonded at random or in a block, respectively.
（ａ−３）非イオン性界面活性剤の具体例としては、ＰＯＥ（７）ラウリルエーテル、ＰＯＥ（９）ラウリルエーテル、ＰＯＥ（１１）ラウリルエーテル、ＰＯＥ（１０）セチルエーテル、ＰＯＥ（１５）セチルエーテル、ＰＯＥ（２０）セチルエーテル、ＰＯＥ（５）オレイルエーテル、ＰＯＥ（１０）オレイルエーテル、ＰＯＥ（２０）オレイルエーテル、ＰＯＰ（５）ラウリルエーテル、ＰＯＰ（７）セチルエーテル、ＰＯＰ（１０）オレイルエーテル、ＰＯＥ（３）ＰＯＰ（５）ラウリルエーテルなどが挙げられる。なお、ＰＯＥ、ＰＯＰのカッコ内の数値は、オキシエチレンユニット、オキシプロピレンユニットのユニット数を示している。 Specific examples of the (a-3) nonionic surfactant include POE (7) lauryl ether, POE (9) lauryl ether, POE (11) lauryl ether, POE (10) cetyl ether, and POE (15) cetyl. Ether, POE (20) cetyl ether, POE (5) oleyl ether, POE (10) oleyl ether, POE (20) oleyl ether, POP (5) lauryl ether, POP (7) cetyl ether, POP (10) oleyl ether , POE (3) POP (5) lauryl ether and the like. The numerical values in parentheses of POE and POP indicate the number of oxyethylene units and oxypropylene units.
また、（Ａ）シリコーン乳化物における（ａ−３）非イオン性界面活性剤の含有割合は、１〜１０重量％であることが好ましく、２〜８重量％であることが好ましい。（ａ−３）非イオン性界面活性剤の含有割合がこの範囲であると、（Ａ）シリコーン乳化物の乳化安定性を維持することができる。 The content of the (a-3) nonionic surfactant in the (A) silicone emulsion is preferably 1 to 10% by weight, preferably 2 to 8% by weight. When the content ratio of (a-3) nonionic surfactant is in this range, the emulsion stability of (A) silicone emulsion can be maintained.
本発明に含有される（ａ−４）水は、（Ａ）シリコーン乳化物をエマルジョンとするためのものである。（ａ−４）水としては、精製水、イオン交換水、工業用水など任意の水を使用することができる。また、水に含有される微量成分も（Ａ）シリコーン乳化物のエマルジョン形成や塗膜作製時の硬化性に影響を及ぼさない範囲で含有されていてもよい。 The water (a-4) contained in the present invention is for making (A) a silicone emulsion into an emulsion. As the water (a-4), any water such as purified water, ion-exchanged water, and industrial water can be used. Further, the trace component contained in water may also be contained within a range that does not affect the curability at the time of forming an emulsion of (A) silicone emulsion or preparing a coating film.
また、（Ａ）シリコーン乳化物における（ａ−４）水の含有割合は、３０〜７０重量％であることが好ましく、４０〜６０重量％であることが好ましい。（ａ−４）水の含有割合がこの範囲であると、（Ａ）シリコーン乳化物の乳化安定性を維持することができる。 The water content of (a-4) in the (A) silicone emulsion is preferably 30 to 70% by weight, preferably 40 to 60% by weight. When the content ratio of (a-4) water is in this range, the emulsion stability of (A) silicone emulsion can be maintained.
そして、本発明の水系塗料組成物における（Ａ）シリコーン乳化物の含有割合は、０．０５〜１０重量％であることが好ましく、１〜５重量％であることが好ましい。（Ａ）シリコーン乳化物の含有割合がこの範囲であると、被塗布物の艶、撥水性、防汚性を継続的に維持することができる。 The content ratio of the silicone emulsion (A) in the water-based coating composition of the present invention is preferably 0.05 to 10% by weight, preferably 1 to 5% by weight. When the content ratio of the silicone emulsion (A) is in this range, the luster, water repellency, and antifouling property of the object to be coated can be continuously maintained.
本発明に含有される（Ｂ）アミノ基含有アルコキシシランは、下記の一般式（２）で表される化合物である。
Ｚ−Ｓｉ（−Ｘ）ｍ−（ＯＹ）3-ｍ・・・・・・・（２）
（式中Ｚは１級から３級から選ばれる少なくとも１つのアミンを有するアルキルアミン鎖、Ｘは炭素数１〜４のアルキル基、Ｙは炭素数１〜４のアルキル基、ｍは０〜２の整数である）
当該アミノ基含有アルコキシシランによれば、本発明の水系塗料組成物を塗布することにより（Ａ）シリコーン乳化物のエマルジョンが破壊されたときに、（ａ−１）一般式（１）で表されるアルコキシシラン及び（ａ−２）前記アルコキシシランの加水分解縮合物であるオルガノポリシロキサンにおけるアルコキシル基の加水分解をアミノ基により促進することができ、強固な塗膜を形成することができる一方で、塗膜組成物においては（Ａ）シリコーン乳化物との反応が極めて生じにくいために保存安定性に優れるという効果を奏する。そして、（Ｂ）一般式（２）で表されるアミノ基含有アルコキシシランにより塗膜作成中に加水分解縮合反応が進行するので、（Ａ）シリコーン乳化物における（ａ−２）オルガノポリシロキサンの縮合度がそれほど高くないものでも使用することができるので粘度が低く取り扱い易く、（Ａ）シリコーン乳化物の作製、本発明の水系塗料組成物を作製するときにも混合しやすく、塗膜作成時にも均一な塗膜を作製することができるという効果も奏する。なお、一般式（２）におけるＸ，Ｙは、一般式（１）におけるＸ，Ｙは独立している。
The (B) amino group-containing alkoxysilane contained in the present invention is a compound represented by the following general formula (2).
Z-Si (-X) m- (OY) 3-m ... (2)
(Z in the formula is an alkylamine chain having at least one amine selected from primary to tertiary, X is an alkyl group having 1 to 4 carbon atoms, Y is an alkyl group having 1 to 4 carbon atoms, and m is 0 to 2. Is an integer of)
According to the amino group-containing alkoxysilane, when the emulsion of (A) silicone emulsion is destroyed by applying the aqueous coating composition of the present invention, it is represented by (a-1) the general formula (1). Alkoxysilane and (a-2) Hydrolysis of the alkoxyl group in organopolysiloxane, which is a hydrolysis condensate of the alkoxysilane, can be promoted by an amino group, and a strong coating film can be formed. In the coating composition, the reaction with the (A) silicone emulsion is extremely unlikely to occur, so that the effect of excellent storage stability is obtained. Then, since the hydrolysis condensation reaction proceeds during the preparation of the coating film by the amino group-containing alkoxysilane represented by (B) the general formula (2), the (a-2) organopolysiloxane in the (A) silicone emulsion Since it can be used even if the degree of condensation is not so high, it has low viscosity and is easy to handle, and it is easy to mix when (A) a silicone emulsion is prepared or the aqueous coating composition of the present invention is prepared, and when a coating film is prepared. It also has the effect of being able to produce a uniform coating film. Note that X and Y in the general formula (2) are independent of X and Y in the general formula (1).
当該アミノ基含有アルコシシランとしては、例えば、３−アミノプロピルメトキシシラン、３−アミノプロピルエトキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルメチルジメトキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルトリメトキシシラン、Ｎ−フェニル−３−アミノプロピルトリメトキシシランが好ましい。このうちの１種又は２種以上を組み合わせて使用することができる。 Examples of the amino group-containing arcocisilane include 3-aminopropylmethoxysilane, 3-aminopropylethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, and N-2- (aminoethyl)-. 3-Aminopropyltrimethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane are preferred. One of them or two or more of them can be used in combination.
また、本発明の水系塗料組成物における（Ｂ）当該アミノ基含有アルコキシシランの含有割合は、０．０５〜０．１重量％であることが好ましい。当該アルコキシシランの含有割合がこの範囲であると、被塗布物の艶、撥水性、防汚性を継続的に維持することができる。 Further, the content ratio of (B) the amino group-containing alkoxysilane in the water-based coating composition of the present invention is preferably 0.05 to 0.1% by weight. When the content ratio of the alkoxysilane is in this range, the luster, water repellency, and antifouling property of the object to be coated can be continuously maintained.
（Ａ）シリコーン乳化物と（Ｂ）一般式（２）で表されるアミノ基含有アルコキシシランとの配合比は、（Ｂ）一般式（２）で表されるアミノ基含有アルコキシシランが、（Ａ）シリコーン乳化物に対して、０．５〜２０重量％で配合されることが好ましく、さらに１〜１０重量％で配合されることが好ましい。（Ａ）シリコーン乳化物と（Ｂ）一般式（２）で表されるアミノ基含有アルコキシシランとの配合割合がこの範囲であると、加水分解による凝集も生じにくくなり保存安定性を向上させることができるとともに、被塗布物の艶、撥水性、防汚性を継続的に維持することができる。 The blending ratio of the silicone emulsion (A) and the amino group-containing alkoxysilane represented by (B) the general formula (2) is as follows: (B) The amino group-containing alkoxysilane represented by the general formula (2) is ( A) It is preferably blended in an amount of 0.5 to 20% by weight, more preferably 1 to 10% by weight, based on the silicone emulsion. When the blending ratio of (A) silicone emulsion and (B) amino group-containing alkoxysilane represented by the general formula (2) is within this range, aggregation due to hydrolysis is less likely to occur and storage stability is improved. At the same time, the luster, water repellency, and stain resistance of the object to be coated can be continuously maintained.
本発明に含有される（Ｃ）水は、（ａ−４）水とは別途配合されるものであり、（Ａ）シリコーン乳化物、（Ｂ）一般式（２）で表されるアミノ基含有アルコキシシランを均一分散させるための溶剤である。（Ｃ）水としては、（ａ−４）水と同様に、精製水、イオン交換水、工業用水など任意の水を使用することができる。また、水に含有される微量成分も塗膜作製時の硬化性に影響を及ぼさない範囲で含有されていてもよい。 The water (C) contained in the present invention is formulated separately from the water (a-4) and contains (A) a silicone emulsion and (B) an amino group represented by the general formula (2). It is a solvent for uniformly dispersing alkoxysilane. As the water (C), any water such as purified water, ion-exchanged water, and industrial water can be used as in the case of (a-4) water. Further, the trace component contained in water may also be contained within a range that does not affect the curability at the time of producing the coating film.
また、本発明の水系塗料組成物における（Ｃ）水の含有割合は、８９．９〜９９．４５重量％であることが好ましく、９４．９〜９８．９５重量％であることが好ましい。当該水の含有割合がこの範囲であると、加水分解による凝集も生じにくくなり保存安定性を向上させることができるとともに、後述する有機溶剤を含有しないので塗工作業を行う作業者が有機溶剤による急性又は慢性の中毒に侵されることを防ぐことができる。 The water content of (C) in the water-based coating composition of the present invention is preferably 89.9 to 99.45% by weight, preferably 94.9 to 98.95% by weight. When the content ratio of the water is within this range, aggregation due to hydrolysis is less likely to occur and storage stability can be improved, and since the organic solvent described later is not contained, the worker performing the coating work uses the organic solvent. It can prevent acute or chronic poisoning.
本発明における水系塗料組成物は、ｎ−ヘキサン、シクロヘキサン、シクロヘキセンなどの炭化水素系溶剤、トルエン、ベンゼン、キシレンなどの芳香族系溶剤、酢酸エチルなどのエステル系溶剤、メタノール、エタノール、イソプロパノールなどのアルコール系溶剤、メチルエチルケトン、メチルイソブチルケトンなどのケトン系溶剤などの有機溶剤を配合していない。これらの有機溶剤を配合していないことにより、ディーラーなどの施工工場において、塗工作業を行う作業者が有機溶剤による急性又は慢性の中毒に侵されることを防ぐことができる。なお、アルコキシシラン等のアルコキシル基の加水分解により生じるメタノールやエタノールなどのアルコール系溶剤は反応により生じたものであるので、配合したものではない。 The water-based coating composition in the present invention includes hydrocarbon solvents such as n-hexane, cyclohexane and cyclohexene, aromatic solvents such as toluene, benzene and xylene, ester solvents such as ethyl acetate, methanol, ethanol and isopropanol. It does not contain organic solvents such as alcohol solvents, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. By not blending these organic solvents, it is possible to prevent workers who perform coating work from being affected by acute or chronic poisoning due to organic solvents in a construction factory such as a dealer. Alcohol-based solvents such as methanol and ethanol produced by hydrolysis of an alkoxyl group such as alkoxysilane are produced by a reaction and are not blended.
本発明の水系塗料組成物は、各成分を配合後、室温で撹拌して調製される。アルコキシシラン、アミノ基含有アルコキシシラン、シリカ粒子と、アルコールの配合に際し、任意の順番で配合することもできるし、同時に配合することもできる。 The water-based coating composition of the present invention is prepared by mixing each component and then stirring at room temperature. Alkoxysilane, amino group-containing alkoxysilane, and silica particles can be blended in any order or at the same time when the alcohol is blended.
そして、本発明の水系塗料組成物は、必要に応じて、紫外線吸収剤、粘度調整剤、着色剤、防腐剤、ｐＨ調整剤などを添加することができる。 Then, the water-based coating composition of the present invention can be added with an ultraviolet absorber, a viscosity regulator, a colorant, a preservative, a pH adjuster and the like, if necessary.
本発明の水系塗料組成物は、ガラスや樹脂、金属やセラミックスなどを対象基材にすることが好ましい。 The water-based coating composition of the present invention preferably uses glass, resin, metal, ceramics, or the like as the target base material.
本発明の水系塗料組成物を各基材に処理する方法は、特に限定されず、スピンコート、ディップコート、ロールコート、フローコート、スプレーコートなどで処理してもよいし、スポンジや布などの治具を用いた手塗などで処理してもよい。その後、溶剤として使用される当該アルコールを自然乾燥させることで塗膜を作成することができ、加熱乾燥による後処理は必要でない。 The method for treating each base material of the water-based coating composition of the present invention is not particularly limited, and may be treated with a spin coat, a dip coat, a roll coat, a flow coat, a spray coat, or the like, or a sponge, a cloth, or the like. It may be processed by hand coating using a jig or the like. After that, a coating film can be formed by naturally drying the alcohol used as a solvent, and post-treatment by heat drying is not required.
以下、本発明の実施例について具体的に説明する。なお、本発明は以下の実施例に限定されるものではない。 Hereinafter, examples of the present invention will be specifically described. The present invention is not limited to the following examples.
（調整例１）
攪拌気、加熱装置、還流冷却装置及び滴下漏斗を備えたフラスコにメチルトリメトキシシラン（信越化学工業社製、商品名：ＫＢＭ１３）１３６ｇ、メタノール２０ｇおよびメチルトリクロロシランを塩酸濃度が２０ｐｐｍとなるように仕込み、攪拌しながら水１０ｇを滴下漏斗により徐々に滴下した。そして、約７０度の還流温度で２時間反応を継続して加水分解縮合反応を行った。反応後、未反応の水分等を分液して減圧下でメタノール等の揮発溶剤を留去して、未反応のトリメトキシシランも含有するオルガノポリシロキサン９４ｇを得た。得られたオルガノポリシロキサンの重合平均分子量３０００であった。そして、この未反応のトリメトキシシランも含有するオルガノポリシロキサン９０ｇに、非イオン系界面活性剤であるＰＯＥ（１５）セチルエーテル３ｇを加えて４０℃程度に加温し、その後、ホモミキサーを用いて５０００ｒｐｍにて攪拌を行い、そこへ加温した水９３ｇを徐々に添加し、４０〜４５℃で３０分攪拌を行い、５０％水溶液のシリコーン乳化物（Ａ−１）を得た。
(Adjustment example 1)
Methyltrimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name: KBM13) 136 g, methanol 20 g and methyltrichlorosilane so as to have a hydrochloric acid concentration of 20 ppm in a flask equipped with a stirrer, a heating device, a reflux cooling device and a dropping funnel. 10 g of water was gradually added dropwise with a dropping funnel while charging and stirring. Then, the reaction was continued for 2 hours at a reflux temperature of about 70 ° C. to carry out a hydrolysis condensation reaction. After the reaction, unreacted water and the like were separated and a volatile solvent such as methanol was distilled off under reduced pressure to obtain 94 g of an organopolysiloxane containing unreacted trimethoxysilane. The polymerization average molecular weight of the obtained organopolysiloxane was 3000. Then, to 90 g of the organopolysiloxane containing the unreacted trimethoxysilane, 3 g of POE (15) cetyl ether, which is a nonionic surfactant, is added and heated to about 40 ° C., and then a homomixer is used. The mixture was stirred at 5000 rpm, 93 g of warmed water was gradually added thereto, and the mixture was stirred at 40 to 45 ° C. for 30 minutes to obtain a 50% aqueous aqueous solution of silicone emulsion (A-1).
（実施例１）
シリコーン乳化物（Ａ−１）０．５重量％、Ｎ−２−（アミノエチル）−３−アミノプロピルトリメトキシシラン（信越化学工業社製、商品名：ＫＢＭ６０３）０．１重量％、水９９．４重量％からなる水系塗料組成物を得た。
(Example 1)
Silicone emulsion (A-1) 0.5% by weight, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM603) 0.1% by weight, water 99 A water-based coating composition consisting of .4% by weight was obtained.
（実施例２）
シリコーン乳化物（Ａ−１）１重量％、Ｎ−２−（アミノエチル）−３−アミノプロピルトリメトキシシラン（信越化学工業社製、商品名：ＫＢＭ６０３）０．１重量％、水９８．９重量％からなる水系塗料組成物を得た。
(Example 2)
Silicone emulsion (A-1) 1% by weight, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM603) 0.1% by weight, water 98.9 An aqueous coating composition consisting of% by weight was obtained.
（実施例３）
シリコーン乳化物（Ａ−１）５重量％、３−アミノプロピルトリメトキシシラン（信越化学工業社製、商品名：ＫＢＭ９０３）０．０５重量％、水９４．９５重量％からなる水系塗料組成物を得た。
(Example 3)
A water-based paint composition consisting of 5% by weight of silicone emulsion (A-1), 0.05% by weight of 3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM903), and 94.95% by weight of water. Obtained.
（実施例４）
シリコーン乳化物（Ａ−１）１０重量％、３−アミノプロピルトリメトキシシラン（信越化学工業社製、商品名：ＫＢＭ９０３）０．０５重量％、水８９．９５重量％からなる水系塗料組成物を得た。
(Example 4)
A water-based paint composition consisting of 10% by weight of silicone emulsion (A-1), 0.05% by weight of 3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM903), and 89.95% by weight of water. Obtained.
（比較例１）
シリコーン乳化物（Ａ−１）２重量％、水９８重量％からなる水系塗料組成物を得た。
(Comparative Example 1)
A water-based coating composition composed of 2% by weight of silicone emulsion (A-1) and 98% by weight of water was obtained.
（比較例２）
ジメチルシリコーン（東レダウコーニング社製、商品名：ＳＭ７０３６ＥＸ）４重量％、水９６重量％からなる水系塗料組成物を得た。
(Comparative Example 2)
A water-based coating composition composed of 4% by weight of dimethyl silicone (manufactured by Dow Corning Toray Co., Ltd., trade name: SM7036EX) and 96% by weight of water was obtained.
（比較例３）
アミノ変性シリコーン（旭化成ワッカー社製、商品名：ＮＰ２６１１）４重量％、水９６重量％からなる水系塗料組成物を得た。
(Comparative Example 3)
A water-based coating composition composed of 4% by weight of amino-modified silicone (manufactured by Asahi Kasei Wacker, trade name: NP2611) and 96% by weight of water was obtained.
（比較例４）
シリコーンレジン（信越化学工業社製、商品名：Ｘ−５２−８００５）２重量％、水９８重量％からなる水系塗料組成物を得た。
(Comparative Example 4)
A water-based coating composition composed of 2% by weight of a silicone resin (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-52-8005) and 98% by weight of water was obtained.
（比較例５）
シランオリゴマー（信越化学工業社製、商品名：ＫＲ５００）１重量％、チタン系触媒（信越化学工業社製、商品名：Ｄ２５）０．０３重量％、イソパラフィン（エクソンモービル社製、商品名：アイソバーＧ）９８．９７重量％からなる塗料組成物を得た。
(Comparative Example 5)
Silane oligomer (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KR500) 1% by weight, titanium-based catalyst (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: D25) 0.03% by weight, isoparaffin (manufactured by ExxonMobil, trade name: Isobar) G) A coating composition consisting of 98.97% by weight was obtained.
（組成物の保存安定性）
実施例１〜４に記載の水系塗料組成物及び比較例１〜５に記載の水系塗料組成物等を、５０℃環境下で２週間静置した後の状態を目視にて確認した。析出物の発生、ゲル化が見られないものを○と評価し、析出物の発生、ゲル化が見られるものを×と評価し、○である組成物を良好と判断した。
(Storage stability of composition)
The state of the water-based paint composition according to Examples 1 to 4 and the water-based paint composition according to Comparative Examples 1 to 5 after being allowed to stand in an environment of 50 ° C. for 2 weeks was visually confirmed. Those in which no precipitation or gelation was observed were evaluated as ◯, those in which precipitation or gelation was observed were evaluated as x, and the composition of ◯ was judged to be good.
（試験片の作成）
自動車の車体用めっき鋼板材片に、アクリル−メラミン系樹脂からなる自動車用塗料をベースコートとトップコートの積層形態で焼付けとそうして塗装板を作成した後、これをけいそう土で研磨し、水洗風乾して基材を作製した。実施例１〜４に記載の水系塗料組成物及び比較例１〜５に記載の水系塗料組成物等を、ネル布を用いて、基材に処理して、別の新しいクロスにてムラが残らないように拭き上げた。それを室温にて１日間室温にて自然乾燥及び養生して塗膜を付した試験片を作製した。
(Creation of test piece)
An automobile paint made of acrylic-melamine resin is baked on a piece of plated steel sheet for an automobile body in a laminated form of a base coat and a top coat to create a painted plate, which is then polished with diatomaceous earth. The substrate was prepared by washing with water and air-drying. The water-based paint composition according to Examples 1 to 4 and the water-based paint composition according to Comparative Examples 1 to 5 are treated on a base material using a flannel cloth, and unevenness remains with another new cloth. I wiped it so that it wasn't there. It was air-dried and cured at room temperature for 1 day at room temperature to prepare a test piece with a coating film.
これらの塗膜を付した試験片を用いて、艶、撥水性及び防汚性の評価を行い、また、基材に塗料組成物を拭き上げたときの仕上げも目視にて評価を行った。拭き仕上げについて、基材に塗布後に目視にてムラが生じなかったものを○と評価し、目視にてムラが残るものを×と評価し、○である組成物を良好と判断した。 Using the test pieces with these coating films, gloss, water repellency and antifouling property were evaluated, and the finish when the coating composition was wiped on the base material was also visually evaluated. Regarding the wiping finish, those in which no unevenness was visually observed after being applied to the base material were evaluated as ◯, those in which unevenness remained visually were evaluated as ×, and the composition of ◯ was judged to be good.
艶については、試験片の作製直後である初期時と屋外曝露にて３ヶ月経過した時に、日本電色社製のＧＬＯＳＳ ＭＥＴＥＲを用いて６０°光沢を測定して評価した。
具体的には、初期時において、試験片表面を６０°での光沢を測定し、塗布する前の基材の光沢の値を用いて下記一般式（３）に基づき光沢の増加割合を算出した。
光沢増加率（％）＝（処理後の光沢値−処理前の光沢値）／処理前の光沢値×１００・・・・（３）
こうして得られた光沢増加率が、１５％以上のものを○、１０％以上１５％未満のものを△、１０％未満のものを×と評価し、○である塗膜を良好と判断した。
The gloss was evaluated by measuring the gloss at 60 ° using GLOSS METER manufactured by Nippon Denshoku Co., Ltd. at the initial stage immediately after the preparation of the test piece and after 3 months of outdoor exposure.
Specifically, at the initial stage, the gloss of the surface of the test piece was measured at 60 °, and the rate of increase in gloss was calculated based on the following general formula (3) using the value of the gloss of the base material before coating. ..
Gloss increase rate (%) = (gloss value after treatment-gloss value before treatment) / gloss value before treatment x 100 ... (3)
Those having a gloss increase rate of 15% or more were evaluated as ◯, those having a gloss increase rate of 10% or more and less than 15% were evaluated as Δ, and those having a gloss increase rate of less than 10% were evaluated as ◯, and the coating film having a ◯ was judged to be good.
また、３ヶ月経過した時において、試験片表面を６０°での光沢を測定し、初期時の光沢値を用いて下記一般式（４）に基づき光沢の維持割合を算出した。
光沢維持率（％）＝（初期時の光沢値−３ヶ月経過時の光沢値）／初期時の光沢値×１００・・・・（４）
こうして得られた光沢維持率が、９５％以上１００％以下のものを○、９０％以上９５％未満のものを△、９０％未満のものを×と評価し、○である塗膜を良好と判断した。
Further, after 3 months had passed, the gloss on the surface of the test piece was measured at 60 °, and the gloss maintenance ratio was calculated based on the following general formula (4) using the initial gloss value.
Gloss retention rate (%) = (Initial gloss value-Gloss value after 3 months) / Initial gloss value x 100 ... (4)
A coating film having a gloss retention rate of 95% or more and 100% or less is evaluated as ◯, a coating film having a gloss retention rate of 90% or more and less than 95% is evaluated as Δ, and a coating film having a gloss retention rate of less than 90% is evaluated as good. It was judged.
撥水性については、試験片の作製直後である初期時と屋外曝露にて３ヶ月経過した時に、協和界面科学社製のＤｒｏｐＭａｓｔｅｒを用いて、当該塗膜表面における水に対する接触角をθ／２法により５点測定しその平均値を求めた。こうして得られた接触角が、１０５°以上のものを◎、１００％以上１０５％未満のものを○、９５％以上１００％未満のものを△、９５％未満のものを×と評価し、◎及び○である塗膜を良好と判断した。 Regarding water repellency, the contact angle with water on the surface of the coating film was determined by the θ / 2 method using a DropMaster manufactured by Kyowa Interface Science Co., Ltd. at the initial stage immediately after the preparation of the test piece and after 3 months of outdoor exposure. 5 points were measured and the average value was calculated. Those having a contact angle of 105 ° or more are evaluated as ⊚, those having a contact angle of 100% or more and less than 105% are evaluated as ◯, those having a contact angle of 95% or more and less than 100% are evaluated as Δ, and those having a contact angle of less than 95% are evaluated as ×. And the coating film of ○ was judged to be good.
防汚性については、試験片の作製直後である初期時と屋外曝露にて３ヶ月経過した時に、コニカミノルタ社製の色差計（ＣＲ−４１０）を用いて測定し、Ｌ，ａ，ｂより△Ｅ(色差)を算出し、初期時から３ヶ月経過時までの間にどの程度色味が変化したかと
いう色差をもって、３ヶ月間の汚れ具合として評価した。△Ｅ(色差)が３未満のものを
○、△Ｅ(色差)が３以上４未満のものを△、４以上のものを×と評価し、○である塗膜
を良好と判断した。
The antifouling property was measured using a color difference meter (CR-410) manufactured by Konica Minolta Co., Ltd. at the initial stage immediately after the preparation of the test piece and after 3 months of outdoor exposure. ΔE (color difference) was calculated, and the degree of stain was evaluated as the degree of stain for 3 months based on the color difference of how much the color changed from the initial time to the time when 3 months passed. Those having ΔE (color difference) of less than 3 were evaluated as ◯, those having ΔE (color difference) of 3 or more and less than 4 were evaluated as Δ, and those having ΔE (color difference) of 4 or more were evaluated as ×, and the coating film having ◯ was judged to be good.
得られた水系塗料組成物及び塗料組成物、及びそれらの組成物により作成された塗膜の物性評価の結果を、一覧にして表１に示す。 Table 1 shows a list of the obtained water-based paint composition, the paint composition, and the results of physical property evaluation of the coating film prepared by those compositions.
表１に示すように、実施例１〜４の水系塗料組成物は、析出物の発生もゲル化も起こらず保存安定性に優れており、基材へ塗布したときの拭き仕上げもムラなく均一に塗布することできた。また、その組成物により作成された塗膜において、塗膜形成後には目視で明らかな艶を発現し、３ヶ月屋外にて曝露した後でもその光沢を維持することができた。そして、撥水性において、初期撥水性が１０５°を超える接触角となり撥水性を示し、３ヶ月屋外にて曝露した後でも撥水性に関してもほとんど劣化することなく１０５°を超える接触角となり撥水性を維持した。そして防汚性についても、３ヶ月屋外にて曝露した後の試験片は初期時の試験片から大きく色差が増加しておらず汚れにくいことが明らかとなった。一方、（Ａ）シリコーン乳化物と、（Ｂ）一般式（２）で表されるアミノ基含有アルコキシシランを共に配合されていない比較例に関して、３ヶ月屋外にて曝露した後では艶、撥水性、防汚性の少なくとも一つの項目において、実施例に比べて劣る項目があり、総合的に市販可能な水準に届かず良好とは言なかった。 As shown in Table 1, the water-based coating compositions of Examples 1 to 4 have excellent storage stability without the formation of precipitates or gelation, and the wiping finish when applied to the substrate is uniform evenly. Could be applied to. Further, in the coating film prepared by the composition, a visually clear gloss was developed after the coating film was formed, and the gloss could be maintained even after being exposed outdoors for 3 months. In terms of water repellency, the initial water repellency becomes a contact angle exceeding 105 ° and exhibits water repellency, and even after being exposed outdoors for 3 months, the water repellency becomes a contact angle exceeding 105 ° with almost no deterioration, and the water repellency is improved. Maintained. Regarding the antifouling property, it was clarified that the test piece after being exposed outdoors for 3 months did not have a large color difference from the initial test piece and was not easily soiled. On the other hand, with respect to a comparative example in which (A) a silicone emulsion and (B) an amino group-containing alkoxysilane represented by the general formula (2) are not blended together, gloss and water repellency are obtained after 3 months of outdoor exposure. In at least one item of antifouling property, there was an item inferior to that of the examples, and it was not said that it was good because it did not reach the level that can be marketed comprehensively.
このように、（Ａ）シリコーン乳化物と、（Ｂ）一般式（２）で表されるアミノ基含有アルコキシシランを共に配合された水系の処方において、（Ｂ）一般式（２）で表されるアミノ基含有アルコキシシランのアミノ基が、（Ａ）シリコーン乳化物に含まれるアルコキシシリル基及び自身のアルコキシシリル基と加水分解を行い、また、塗膜中の組み込まれるために強固な塗膜を形成することができるために、艶、撥水性、防汚性に優れた塗膜を作製することができることが分かった。 As described above, in the aqueous formulation in which (A) the silicone emulsion and (B) the amino group-containing alkoxysilane represented by the general formula (2) are both blended, it is represented by (B) the general formula (2). The amino group of the amino group-containing alkoxysilane is hydrolyzed with the alkoxysilyl group contained in (A) the silicone emulsion and its own alkoxysilyl group, and a strong coating film is formed because it is incorporated into the coating film. It was found that a coating film having excellent luster, water repellency, and antifouling property can be produced because it can be formed.
Claims (2)
Ｘｎ−Ｓｉ−（ＯＹ）4-ｎ・・・・・・・（１）
（式中Ｘは炭素数１〜１８のアルキル基、Ｙは炭素数１〜４のアルキル基、ｎは１〜３の整数である）
（ａ−２）前記アルコキシシランの加水分解縮合物であるオルガノポリシロキサンと、
（ａ−３）非イオン性界面活性剤と、
（ａ−４）水を含有する
（Ａ）シリコーン乳化物と、
（Ｂ）下記一般式（２）で表されるアミノ基含有アルコキシシランと、
Ｚ−Ｓｉ（−Ｘ）ｍ−（ＯＹ）3-ｍ・・・・・・・（２）
（式中Ｚは１級から３級から選ばれる少なくとも１つのアミンを有するアルキルアミン鎖、Ｘは炭素数１〜４のアルキル基、Ｙは炭素数１〜４のアルキル基、ｍは０〜２の整数である）
（Ｃ）水
を含有し、
前記（Ａ）が０．０５〜１０重量％であり、前記（Ｂ）が０．０５〜０．１重量％であり、
炭化水素系、芳香族系、エステル系、アルコール系、ケトン系から選ばれる少なくとも一つの有機溶剤を配合していないことを特徴とする水系塗料組成物。 (A-1) Alkoxysilane represented by the following general formula (1) and
Xn-Si- (OY) 4-n ... (1)
(In the formula, X is an alkyl group having 1 to 18 carbon atoms, Y is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 3 carbon atoms).
(A-2) Organopolysiloxane, which is a hydrolysis condensate of the alkoxysilane,
(A-3) Nonionic surfactant and
(A-4) Water-containing (A) silicone emulsion and
(B) Amino group-containing alkoxysilane represented by the following general formula (2) and
Z-Si (-X) m- (OY) 3-m ... (2)
(Z in the formula is an alkylamine chain having at least one amine selected from primary to tertiary, X is an alkyl group having 1 to 4 carbon atoms, Y is an alkyl group having 1 to 4 carbon atoms, and m is 0 to 2. Is an integer of)
(C) containing water,
The (A) is 0.05 to 10% by weight, and the (B) is 0.05 to 0.1% by weight.
A water-based coating composition characterized in that it does not contain at least one organic solvent selected from hydrocarbon-based, aromatic-based, ester-based, alcohol-based, and ketone-based.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016224627A JP6837226B2 (en) | 2016-11-18 | 2016-11-18 | Water-based paint composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016224627A JP6837226B2 (en) | 2016-11-18 | 2016-11-18 | Water-based paint composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2018080291A JP2018080291A (en) | 2018-05-24 |
| JP6837226B2 true JP6837226B2 (en) | 2021-03-03 |
Family
ID=62197091
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2016224627A Active JP6837226B2 (en) | 2016-11-18 | 2016-11-18 | Water-based paint composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6837226B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6864353B2 (en) * | 2017-05-31 | 2021-04-28 | 石原ケミカル株式会社 | Water-based composition for painted surface |
| EP4007790A1 (en) | 2019-08-02 | 2022-06-08 | 3M Innovative Properties Company | Composition including a polyorganosiloxane and an amino-functional silane and method of using the same |
| US20230406760A1 (en) | 2020-11-10 | 2023-12-21 | 3M Innovative Properties Company | Process for making a coated article |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2614462B2 (en) * | 1987-10-05 | 1997-05-28 | 東レ・ダウコーニング・シリコーン株式会社 | Rubber surface treatment composition |
| JP2529020B2 (en) * | 1990-08-14 | 1996-08-28 | 信越化学工業株式会社 | Keratin fiber shrinkproof treatment method and treated product |
| JP2005015727A (en) * | 2003-06-30 | 2005-01-20 | Kansai Paint Co Ltd | Water-repellent film-forming composition and coating method using it |
| JP2005144666A (en) * | 2003-11-11 | 2005-06-09 | Shiga Pref Gov | Manufacturing method of organic/inorganic composite |
-
2016
- 2016-11-18 JP JP2016224627A patent/JP6837226B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2018080291A (en) | 2018-05-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6004607B2 (en) | Aqueous silane based on bis (trialkoxysilylalkyl) amine | |
| JP6197118B2 (en) | Curable silsesquioxane polymers, compositions, articles, and methods | |
| EP1773917B1 (en) | Block condensates of organofunctional siloxanes,their preparation and use, and their properties | |
| JP6864353B2 (en) | Water-based composition for painted surface | |
| US7019069B2 (en) | Silicone resin composition for water repellent coating | |
| TW557320B (en) | Ambient temperature curing coating composition | |
| US20140069293A1 (en) | Aqueous silane systems based on tris(alkoxysilylalkyl)amines and the use thereof | |
| CN112703241B (en) | Two-component coating composition | |
| JP2008516019A (en) | Polyether-functional siloxanes, polyether siloxane-containing compositions, methods for making the siloxanes, and uses of the siloxanes | |
| JPH0748560A (en) | Coating composition | |
| JP6837226B2 (en) | Water-based paint composition | |
| JP2013523923A (en) | Formulations suitable for use as anti-graffiti coatings with improved wetting properties | |
| JP2014205743A (en) | Inorganic coating composition and coated article thereof | |
| WO2008072616A1 (en) | Wipe-up-type hydrophilizing agent, method for formation of hydrophilic protective film, and hydrophilic protective film | |
| JP2012116969A (en) | Coating composition | |
| CA2336510A1 (en) | Methoxy-functional organopolysiloxanes, their preparation and use | |
| JP7307468B2 (en) | Aqueous composition for painted surfaces | |
| JP2011006653A (en) | Substrate with cured film | |
| JP7152010B2 (en) | Aqueous composition for painted surfaces | |
| WO2019022087A1 (en) | Coating-forming composition | |
| TW201811943A (en) | Protective coating composition with anti-skid function, coating product and preparation method thereof | |
| JP6802953B2 (en) | Water repellent coating composition | |
| JPH0431475A (en) | Film-forming material composition | |
| JP5241076B2 (en) | Forming method of coating film | |
| JPH0586194A (en) | Composition of polysiloxane resin containing cationic functional group, coating composition made by using it, and production of the resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20190702 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20200714 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20200805 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20200819 |
|
| 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: 20210107 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20210126 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6837226 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |