CN1186413C - Nano uvioresistant polyurethane paint - Google Patents
Nano uvioresistant polyurethane paint Download PDFInfo
- Publication number
- CN1186413C CN1186413C CNB01128269XA CN01128269A CN1186413C CN 1186413 C CN1186413 C CN 1186413C CN B01128269X A CNB01128269X A CN B01128269XA CN 01128269 A CN01128269 A CN 01128269A CN 1186413 C CN1186413 C CN 1186413C
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- Prior art keywords
- nano
- efka
- polyurethane paint
- oxide
- ultraviolet
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Links
- 239000003973 paint Substances 0.000 title claims abstract description 68
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 66
- 239000004814 polyurethane Substances 0.000 title claims abstract description 65
- 239000000057 synthetic resin Substances 0.000 claims abstract description 61
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 61
- 239000002270 dispersing agent Substances 0.000 claims abstract description 43
- 239000002904 solvent Substances 0.000 claims abstract description 29
- 239000002002 slurry Substances 0.000 claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 10
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 5
- 229920001225 polyester resin Polymers 0.000 claims abstract description 5
- 239000004645 polyester resin Substances 0.000 claims abstract description 5
- 239000012948 isocyanate Substances 0.000 claims abstract description 3
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 3
- 229920002521 macromolecule Polymers 0.000 claims description 42
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 18
- -1 amide salt Chemical class 0.000 claims description 15
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 8
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Natural products CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 6
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003921 oil Substances 0.000 claims description 6
- 150000002576 ketones Chemical class 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000004576 sand Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 claims description 4
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 claims description 4
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229920000728 polyester Chemical class 0.000 claims description 4
- 229920000570 polyether Chemical class 0.000 claims description 4
- 229920000098 polyolefin Polymers 0.000 claims description 4
- FIABMSNMLZUWQH-UHFFFAOYSA-N propyl 2-methoxyacetate Chemical compound CCCOC(=O)COC FIABMSNMLZUWQH-UHFFFAOYSA-N 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 150000003505 terpenes Chemical class 0.000 claims description 3
- 235000007586 terpenes Nutrition 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 229920002732 Polyanhydride Polymers 0.000 claims description 2
- 229920002125 Sokalan® Chemical class 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical class O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 229920000058 polyacrylate Chemical class 0.000 claims description 2
- 239000004584 polyacrylic acid Chemical class 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 239000011164 primary particle Substances 0.000 claims description 2
- 150000003673 urethanes Chemical class 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 239000013078 crystal Substances 0.000 claims 1
- 229920001610 polycaprolactone Polymers 0.000 claims 1
- 238000004381 surface treatment Methods 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 2
- 230000006750 UV protection Effects 0.000 abstract 1
- 239000011247 coating layer Substances 0.000 abstract 1
- 230000000007 visual effect Effects 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 35
- 239000011248 coating agent Substances 0.000 description 32
- 239000011527 polyurethane coating Substances 0.000 description 23
- 239000007787 solid Substances 0.000 description 21
- 239000000523 sample Substances 0.000 description 19
- 239000011521 glass Substances 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 238000007605 air drying Methods 0.000 description 8
- 239000008199 coating composition Substances 0.000 description 8
- 238000011160 research Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000004154 testing of material Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 7
- 229940112824 paste Drugs 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 239000007822 coupling agent Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229960001866 silicon dioxide Drugs 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000005639 Lauric acid Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 239000004848 polyfunctional curative Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 125000006414 CCl Chemical group ClC* 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- ZCZSIDMEHXZRLG-UHFFFAOYSA-N Heptyl acetate Chemical compound CCCCCCCOC(C)=O ZCZSIDMEHXZRLG-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 2
- 229940082004 sodium laurate Drugs 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- FGLBSLMDCBOPQK-UHFFFAOYSA-N 2-nitropropane Chemical compound CC(C)[N+]([O-])=O FGLBSLMDCBOPQK-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- VHYDRYKWJJEOET-UHFFFAOYSA-N OC1=C(C(=O)C2=CC=CC=C2)C=CC(=C1)C1=CC=C(C=C1)OC Chemical compound OC1=C(C(=O)C2=CC=CC=C2)C=CC(=C1)C1=CC=C(C=C1)OC VHYDRYKWJJEOET-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229920004482 WACKER® Polymers 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical class O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 150000002168 ethanoic acid esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 125000006838 isophorone group Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229940017144 n-butyl lactate Drugs 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011297 pine tar Substances 0.000 description 1
- 229940068124 pine tar Drugs 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 239000000516 sunscreening agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229940052228 zinc oxide paste Drugs 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
The present invention relates to ultraviolet-resistant nanometer polyurethane paint which is composed of modified synthetic resin and a solidifying agent which are matched with each other for use, the synthetic resin is one or more of hydroxy-acrylic resin and hydroxy polyester resin; the solidifying agent is a solidifying agent of isocyanate. The present invention is characterized in that the modified synthetic resin is composed of 0.1 to 10% of nanometer oxide, 0.01 to 5% of macromolecular dispersing agent, 40 to 80% of synthetic resin and a solvent as the rest. In the present invention, a method of previously preparing nanometer slurry is first used for preparing the ultraviolet-resistant nanometer polyurethane paint, so that the nanometer materials can be more easily dispersed in the paint and therefore, the ultraviolet-resistant nanometer polyurethane paint has simple preparation process, and as a result, the problem of the compatibility among the nanophase materials, the solvent and the resin component is very well solved so that the ultraviolet-resistant nanometer polyurethane paint can be more stably stored. The ultraviolet-resistant nanometer polyurethane paint prepared by the method has the advantages of good stability of storage and good performance of ultraviolet resistance; the ultraviolet-resistant nanometer polyurethane paint is non-transparent in a UVA range and a UVB range of ultraviolet light and is transparent in a range of visual light; a coating layer of the ultraviolet-resistant nanometer polyurethane paint, which has the thickness of 10 mu m can shield 94% of ultraviolet rays.
Description
Technical field:
The present invention relates to coating technology, a kind of polyurethane coating with anti-ultraviolet function is provided especially.
Background technology:
Ultraviolet ray is a kind of hertzian wave shorter than visible wavelength, and its wavelength is between 200～400nm.(200～280nm), UVC represents with symbol can be divided into short wave ultraviolet again by the wavelength size; (280～320nm), UVB represents ultraviolet B radiation with symbol; (320～400nm), UVA represents long wave ultraviolet with symbol.Ultraviolet wavelength is short more, and energy is strong more, and is big more to the destruction of organic coating, timber, plastics, paper etc.
Table 1 light wavelength and energy
Wavelength/nm 200 300 400 500 700 800
Luminous energy/kJmol
-1598 397 301 238 171 146
Dissociable key name O-H C-H C-C C-Cl N-N O-O
Ionic dissociation energy/kJmol
-1462 413 347 326 158 138
As shown in Table 1, the energy of the light wave of longer wavelength only can make molecule produce vibration and rotate and generate heat, and ultraviolet ray can be to C-H, C-C, C-Cl etc. in the organism, and the material with identical bond energy produces destruction.Sun-screening agent in the past, uvioresistant additive great majority are organism, as benzophenone series, benzotriazole system, salicylate system etc.Disclosed improved ultraviolet radiation absorbing composition of Chinese patent CN1111504A and method, employed organic ultraviolet radiation adsorber have 2-hydroxyl-4 p-methoxy-phenyl benzophenone, para-amino benzoic acid, Whitfield's ointment 2-ethylhexyl etc.Japanese Patent JP flat 4-333662 discloses the ultraviolet absorber that the phenyl methanone derivatives is used for cloth.These organic uvioresistant additives have certain toxicity, if be used as the uvioresistant additive in coating, along with the prolongation of paint film Exposure to Sunlight time, its ultraviolet screener performance can reduce ultimate failure gradually.
Because the development of nanometer material science technology is used some nano inoganic particle that the ultraviolet screener performance is arranged as the uvioresistant additive, has become one of focus of research.Nano-TiO
2The crystalline optical property is obeyed famous Reyleith scanttering light scattering theory, can see through visible light and shorter (200～400nm) the UV-light of scattering wavelength.Show this TiO thus
2Ability with the transparency and scatters ultraviolet.General T iO
2Also has the ultraviolet ability of certain absorption.But nano-TiO
2Particle diameter is littler, and activity is bigger, and it is stronger therefore to absorb ultraviolet ability.It can scattering can absorb ultraviolet ray again, shielding ultraviolet rays very capable.Nano inorganic oxide has characteristics such as nontoxic, heat-resisting, long-acting, that compatibility is good as the uvioresistant additive.
Do not find as yet with the patent of nano material preparation uvioresistant paint at present, and the patent of report preparation of nanomaterials is more.A kind of SnO is disclosed as the flat 2-194063 of Japanese Patent JP
2, ZrO
2, SiO
2, Al
2O
3The preparation method of multiple coating superfine titanic oxide powder; It is the method that main raw material prepares nano titanium oxide that Chinese patent CN1146976A discloses with metatitanic acid; Chinese patent CN1192992A discloses with H
2TiO
3Be raw material, urea prepares the method for nano titanium oxide for the precipitation from homogeneous solution agent; The flat 2-289506 of Japanese Patent JP reports that a kind of specific surface area is 20～30m
2/ g, absorption of UV is that 90% nano zine oxide can be used for makeup; The flat 2-194063 of Japanese Patent JP has reported that a kind of nano titanium oxide that coats tindioxide and zirconium dioxide has good uv-shielding capacity.
The technology contents of invention:
The objective of the invention is to prepare a kind of nano uvioresistant polyurethane paint with satisfactory stability and good uv-shielding capacity.
The invention provides a kind of nano uvioresistant polyurethane paint, constitute by matching used modified synthetic resin and solidifying agent two-pack, synthetic resins refers to one or more of Hydroxylated acrylic resin, hydroxy polyester resin, solidifying agent refers to the isocyanates solidifying agent, it is characterized in that: described modified synthetic resin is by the solvent composition of 0.1-10% nano-oxide, 0.01-5% macromolecule dispersing agent, 40-80% synthetic resins, surplus; Nano-oxide is preferably 0.5-5% in the described modified synthetic resin; Macromolecule dispersing agent is preferably 0.3-1.5%.
Wherein:
Nano-oxide refers to nano titanium oxide and/or the nano zine oxide of mean particle size below 100nm of primary particle;
Macromolecule dispersing agent is selected from one or more of the ketone macromolecular compound of polyolefins, polyolefine salt, polycarboxylic acid, polycarboxylic acid salt, polyacrylic acid, polyacrylate, polyester, polyester salt, polyamide-based, polymeric amide salt, polyurethanes, urethane salt, polyethers, polyethers salt, polyanhydrides, polysiloxane-based, polyoxyethylene, polyoxypropylene class, Malaysia acids, maleic anhydride class, poly-ε-in oneself;
Solvent is selected from one or more of aliphatic hydrocarbon, aromatic hydrocarbon, ester class, ketone, terpene, replacement hydro carbons.
In the nano uvioresistant polyurethane paint of the present invention, nano titanium oxide better is a rutile-type, can be not surface treated; Can handle through inorganic surfaces, handle as one or more coatings of silicon-dioxide, aluminium sesquioxide, zirconium dioxide, zinc oxide, tindioxide; Can be through organic surface-treated, as one or more surface-treateds with stearic acid, oleic acid, lauric acid or their metallic salt, dimethyl silicone oil, siloxanes coupling agent, titanate coupling agent; Also can handle through inorganic and organic compound surface.Nano zine oxide can be not surface treated; Can handle through inorganic surfaces, handle as one or more coatings of titanium dioxide, silicon-dioxide, aluminium sesquioxide, zirconium dioxide, tindioxide; Can be through organic surface-treated, as carry out that one or more coatings of stearic acid, oleic acid, lauric acid or their metallic salt, dimethyl silicone oil, siloxanes coupling agent, titanate coupling agent handle; Also can handle through inorganic and organic compound surface.
In the nano uvioresistant polyurethane paint of the present invention, the macromolecular compound dispersion agent can be Disperbyk103, Disperbyk106, Disperbyk107, Disperbyk110, Disperbyk111, Disperbyk115, Disperbyk130, Disperbyk160, Disperbyk162, Disperbyk163, Disperbyk164, Disperbyk2000, Anti-Terra-P, Anti-Terra-202, Anti-Terra-204, Anti-Terra-206, Anti-Terra-207, Anti-Terra-P, the Byk-P104S of German Bi Ke (BYK) chemical company; The Solsperse3000 of Avecia company, Solsperse13940, Solsperse17000, Solsperse24000, Solsperse28000, Solsperse32000, Solsperse32500, Solsperse34750, Solsperse41090; The TEXAPHOR of Henkel (Henkel) company
963, TEXAPHOR
963S, TEXAPHOR
3061, TEXAPHOR
3073, TEXAPHOR
3241, TEXAPHOR
3112, TEXAPHOR
3250, TEXAPHOR
3287; Moral modest (DEUCHEM) enterprise stock company limited 902,923,923S, DP-981, DP-983, DP-S81,904,904S; EFKA-44, EFKA-54, EFKA-63, EFKA-64, EFKA-65, EFKA-66, EFKA-46, EFKA-47, EFKA-48, EFKA-49, EFKA-701, EFKA-745, EFKA-764, EFKA-766, the EFKA-Polymer4010 of Holland EFKA auxiliary agent company (EFKA); Dispers700, Dispers610, Dispers610S, Dispers630S, the Dispers710 of enlightening height (Tego) chemical company; Hypersol LA707, Hypersol L4708, Hypersol L4742, Hypersol L4744, the Hypersol P496 of Denmark KVK (Kemisk Vaerk Koege) company; The Elvacite type dispersant A B1010 of company of Du Pont (Du Pont), AB1015, AB1020, AB1030.
Macromolecule dispersing agent is the Disperbyk103 of German Bi Ke chemical company preferably, Disperbyk106, Disperbyk107, Disperbyk110, Disperbyk111, Disperbyk115, Disperbyk130, Disperbyk160, Disperbyk162, Disperbyk163, Disperbyk164, Disperbyk2000, Anti-Terra-P, Anti-Terra-202, Anti-Terra-204, Anti-Terra-206, Anti-Terra-207, Anti-Terra-P, Byk-P104S; The Solsperse3000 of Avecia company, Solsperse13940, Solsperse17000, Solsperse24000, Solsperse28000, Solsperse32000, Solsperse32500, Solsperse34750; EFKA-44, EFKA-54, EFKA-63, EFKA-64, EFKA-65, EFKA-66, EFKA-46, EFKA-47, EFKA-48, EFKA-49, EFKA-701, EFKA-745, EFKA-764, EFKA-766, the EFKA-Polymer 4010 of Holland EFKA (EFKA) auxiliary agent company; The Hypersol L4707 of Denmark KVK company, Hypersol L4708, Hypersol L4742, Hypersol LA744, Hypersol P4963; The Elvacite type dispersant A B1010 of E.I.Du Pont Company (Du Pont), AB1015, AB1020, AB1030.
In the nano uvioresistant polyurethane paint of the present invention, aliphatic solvents refers to sherwood oil, No. 200 solvent oils, raffinates oil, butane, Skellysolve A, iso-pentane, isohexane, normal hexane, normal heptane, isoheptane, octane, octane-iso; Aromatic hydrocarbon solvent refers to benzene,toluene,xylene, Three methyl Benzene, Solvesso100, Solvesso150, Solvesso200, solvent naphtha, ethylbenzene, isopropyl benzene; Ketones solvent refers to acetone, methylethylketone, mibk, pimelinketone, isophorone, diacetone alcohol, metacetone, methyl propyl ketone, esters solvent and refers to vinyl acetic monomer, n-butyl acetate, isobutyl acetate, capryl acetate, acetic acid heptyl ester, acetic acid ester in the last of the ten Heavenly stems, n-Butyl lactate, methoxyacetic acid propyl ester; Terpene type solvent refers to turps, pine tar, kautschin, replacement varsol and refers to trichloroethane, 2-nitropropane.
Solvent is No. 200 solvent oils, Skellysolve A, iso-pentane, isohexane, normal hexane, normal heptane, isoheptane, toluene, dimethylbenzene, Three methyl Benzene, Solvesso100, Solvesso150, Solvesso200, solvent naphtha, methylethylketone, mibk, pimelinketone, isophorones, is vinyl acetic monomer, n-butyl acetate, isobutyl acetate, methoxyacetic acid propyl ester, trichloroethane preferably.
In the nano uvioresistant polyurethane paint of the present invention,, can be selected from the Desmophen of Bayer (Bayer) company as the synthetic resins in the modified synthetic resin component of nano uvioresistant polyurethane paint
A VPLS2180FE, Desmophen
A365/1, Desmophen
A VPLS 2009/1 FE, Desmophen
RD181/1 75X, Desmophen
A450 MPA/X, Desmophen
A575 FE, Desmophen
VPLS 2971, Desmophen
670BA, Desmophen
1652, Desmophen
A160, Desmophen
650, Desmophen
651, the FX-1560 of Deuchem Co., Ltd., FX-1660, FX-2460A, FX-2820, FX-2970A, FX-2970B, FX-3070, FX-3360, FX-4365, F-45, TN-4366, TN-4543, PE-8043; Can be selected from the Desmodur of Bayer (Bayer) company as the curing agent component of nano uvioresistant polyurethane paint
N75, Desmodur
N100, Desmodur
N3390, Desmodur
N3300, Desmodur
VPLS2010/1, Desmodur
VPLS 2103, Desmodur
Z4470; The Tolonate of France inferior (Rhodia) company in sieve ground
TMHDB-75MX, Tolonate
TMHDT-90; The CORONATE 2604 of Japanese polyurethane Co., Ltd., CORONATE HX-T, CORONATE 2384, CORONATE HK.The proportioning of modified synthetic resin component and curing agent component is NCO: OH=0.8～1.3: 1 (mol ratio).
The present invention also provides the preparation method of above-mentioned nano uvioresistant polyurethane paint, it is characterized in that process is as follows:
At first macromolecule dispersing agent is added in the solvent, add nano-oxide then, 400-2000rpm high speed dispersion 2-60 minute; The slurry of gained ground in ball mill or sand mill or ball mill 20 minutes-24 hours, made the nano-oxide slurry; Consist of, in 100% weight, nano-oxide 10-60% weight, macromolecule dispersing agent 0.5-10.5% weight, the solvent of surplus;
Above-mentioned nano-oxide slurry is mixed with synthetic resin solution on demand, fully disperse this mixture, make the modified synthetic resin component of nano uvioresistant polyurethane paint after filtering with high speed dispersor or grinding plant; Supporting with a certain proportion of curing agent component, promptly form nano uvioresistant polyurethane paint.
Among the preparation method of nano uvioresistant polyurethane paint of the present invention, the first step slurrying solvent for use is preferably identical with second step preparation nano uvioresistant polyurethane paint solvent for use.Nanometer slurry and synthetic resins blended equipment are the mixing equipment that uses in the paint manufacturing process, comprise high speed dispersor, sand mill, ball mill and ball mill.
The present invention has proposed to adopt the method for prefabricated nanometer slurry to prepare nano uvioresistant polyurethane paint first, make nano material easier dispersion in coating, nano material and solvent have been solved well, the compatibility issue of resin Composition, it is more stable that nano uvioresistant polyurethane paint is stored, and preparation technology is simpler.Nano uvioresistant polyurethane paint excellent storage stability with this method preparation, uvioresistant performance is good, nano uvioresistant polyurethane paint is opaque at UV-light UVA and UVB scope, at visible-range is transparent, the ultraviolet ray of the nano uvioresistant polyurethane coating maskable 94% that 10 μ m are thick.
Nano uvioresistant polyurethane paint of the present invention can be used for the uvioresistant protection of metal, plastics, woodenware, paper, fabric etc., also can be used for the weathering resistance protection of various finish paints.
Description of drawings:
Fig. 1 is the relation of the different nano-oxide content of nano uvioresistant polyurethane coating and ultraviolet ray and visible light transmissivity.
Embodiment:
Unless outside specializing among the present invention, related ratio all is weight percentage.
The evaluation of nano uvioresistant polyurethane paint: dried film thickness is measured with the 6000FN1 type thickness tester of U.S. DeFelsko company, gets 5 mean values, and measuring error is at ± 2 μ m.With day island proper Tianjin company UV-265 ultraviolet spectrophotometer test different coating sample at the light penetration at 300nm, 360nm, 560nm place, with typical case's sign as the light penetration of UVB, UVA, three kinds of wavelength band of visible light.To the ultraviolet ray of certain wavelength, rate of ultraviolet shield=1-transmitance.The test of all coating sample light penetrations all with uncoated glass slide of the same race as reference sample.The parallel sample of every kind of nano uvioresistant polyurethane coating and contrast coating is 5, and its transmitance is the mean value of 5 parallel samples.
Embodiment 1
In the 300ml beaker, take by weighing mibk 95g, normal hexane 5g, add 0.28g macromolecule dispersing agent Dispers630S, 0.28g Dispers610S, the rutile type nano titanic oxide 11.17g that adds 50nm aluminium sesquioxide, silicon-dioxide, the composite coated processing of zirconium dioxide again, 1000rpm disperseed 10 minutes, used ball mill grinding then 1 hour, make the nano titanium oxide weight ratio and be 10% nano titanium dioxide paste, the total amount of its macromolecule dispersing agent is 0.5%.
Embodiment 2
In the 300ml beaker, take by weighing removal xylene 70g, pimelinketone 20g, turps 10g, add 2.71g macromolecule dispersing agent Solsperse32000,2.71g macromolecule dispersing agent Solsperse32500, add the rutile type nano titanic oxide 45.18g that 100nm Zinic stearas coating is handled again, 800rpm disperseed 15 minutes, ground 6 hours with sand mill then, make the nano titanium oxide weight ratio and be 30% nano titanium dioxide paste, the total amount of its macromolecule dispersing agent is 3.6%.
Embodiment 3
In the 300ml beaker, take by weighing solvent oil 5g, methylethylketone 45g No. 200, add 3.25g macromolecule dispersing agent Disperbyk106, add 90nm rutile type nano titanic oxide 65.09g again, 1800rpm disperseed 20 minutes, used ball mill grinding then 24 hours, make the nano titanium oxide weight ratio and be 55% nano titanium dioxide paste, the weight ratio of its macromolecule dispersing agent Disperbyk106 is 2.7%.
Embodiment 4
In the 300ml beaker, take by weighing vinyl acetic monomer 80g, isophorone 20g, add 3.32g macromolecule dispersing agent Hypersol L4708,3.32g Hypersol P4707, the nano zine oxide 11.85g that adds 15nm silicon-dioxide, aluminium sesquioxide, the composite coated processing of titanate coupling agent KR-TTS (U.S. Kenrich petroleum chemistry company) again, 400rpm disperseed 40 minutes, ground 20 minutes with sand mill then, make the nano zine oxide weight ratio and be 10% nano zine oxide slurry, the total amount of its macromolecule dispersing agent is 5.6%.
Embodiment 5
In the 300ml beaker, take by weighing 95g methoxyacetic acid propyl ester, 5g Solvesso100, adding macromolecule dispersing agent AB1020 is 11.11g, the nano zine oxide 47.61g that adds the composite coated processing of 30nm dimethyl silicone oil and silane coupling agent GF-56 (German Wacker company) again, 800rpm disperseed 15 minutes, ground 6 hours with ball mill then, make the nano zine oxide weight ratio and be 30% nano zine oxide slurry, the weight ratio of its macromolecule dispersing agent AB1020 is 7%.
Embodiment 6
In the 300ml beaker, take by weighing isobutyl acetate 10g, n-butyl acetate 40g, adding macromolecule dispersing agent Disperbyk110 is 15.2g, add the nano zine oxide 79.59g that 90nm lauric acid coating is handled again, 1500rpm disperseed 60 minutes, ground 2 hours with ball mill then, make the nano zine oxide weight ratio and be 55% nano zine oxide slurry, the weight ratio of its macromolecule dispersing agent Disperbyk110 is 10.5%.
Embodiment 7
In the 300ml beaker, take by weighing toluene 40g, trichloroethane 10g, add macromolecule dispersing agent TEXAPHOR
3241 is 0.85g, adds nano titanium oxide 16.95g, the nano zine oxide 16.95g that 90nm sodium laurate coating is handled that 90nm sodium laurate coating is handled again, and 1800rpm disperseed 60 minutes.Ground 10 hours with ball mill then, make the nano-oxide weight ratio and be 40% nano-oxide slurry.Macromolecule dispersing agent TEXAPHOR in this nano-oxide slurry
3241 weight ratio is 1%.
Embodiment 8
The preparation method is with embodiment 4, adjust the add-on of nano zine oxide and macromolecule dispersing agent Hypersol LA708 and Hypersol P4707, wherein macromolecule dispersing agent Hypersol LA708 and Hypersol P4707 and ratio between the two are with embodiment 4, making the total amount of macromolecule dispersing agent in the nano zine oxide slurry of preparation is 1%, and the weight ratio of nano zine oxide is 10%.
Embodiment 9
The preparation method is with embodiment 4, adjust the add-on of nano zine oxide and macromolecule dispersing agent Hypersol L4708 and Hypersol P4707, wherein macromolecule dispersing agent Hypersol L4708 and Hypersol P4707 and ratio between the two are with embodiment 4, making the total amount of macromolecule dispersing agent in the nano zine oxide slurry of preparation is 10%, and the weight ratio of nano zine oxide is 10%.
Embodiment 10
In the beaker of 300ml, claim 50g Hydroxylated acrylic resin FX-2820 (solid content is 60%, and the hydroxy radical content of solid resin is 2.8%).Add the 40% nanometer thing slurry 0.47g that embodiment 7 methods are made, the synthetic resins that adds the nanometer slurry disperseed 10 minutes with GFJ0.4 high speed dispersor (Shanghai modern environment engineering and technological research institute) 1000rpm, was prepared into the modified synthetic resin component of nano uvioresistant polyurethane paint after filtering with 200 order copper mesh; Curing agent component is Desmudur
N75 (solid content is 75%, and NCO content is 16.4%).Two components are pressed NCO: OH=0.8: 1 (mol ratio) proportioning promptly needs to add 10.16g Desmudur in the modified synthetic resin component
N75, stir the QXG line rod spreader (Tianjin material-testing machine factory) that uses 10 μ m～50 μ m in the back and go up this nano uvioresistant polyurethane paint of coating in the glass slide (harbour, Qinhuangdao medical glass factory) of 76mm * 26mm * 0.5mm, the sample Air drying of coating composition 7 days, making build is the coating sample of 10 ± 2 μ m.
Embodiment 11
In the beaker of 300ml, claim 50g hydroxy polyester resin TN4366 (solid content is 60%, and the hydroxy radical content of solid resin is 2%).Add the 55% nano zine oxide slurry 2.2g that embodiment 6 methods are made, the synthetic resins liquid that adds the nanometer slurry disperseed 10 minutes with GFJ0.4 high speed dispersor (Shanghai modern environment engineering and technological research institute) 1000rpm, was prepared into the modified synthetic resin component of nano uvioresistant polyurethane paint after filtering with 200 order copper mesh; Curing agent component is Tolonate
TMHDT-90 (solid content is 90%, and NCO content is 19.8%).Two components are pressed NCO: OH=1.3: 1 (mol ratio) proportioning promptly needs to add 9.73gTolonate in the modified synthetic resin component
TMHDT-90, stir the QXG line rod spreader (Tianjin material-testing machine factory) that uses 10 μ m～50 μ m in the back and go up this nano uvioresistant polyurethane paint of coating in the glass slide (harbour, Qinhuangdao medical glass factory) of 76mm * 26mm * 0.5mm, the sample Air drying of coating composition 7 days, making build is the coating sample of 10 ± 2 μ m.
Embodiment 12
In the beaker of 300ml, claim 50g Hydroxylated acrylic resin Desmophen
A160 (solid content is 60%, and hydroxy radical content is 1.6%).Add the 55% nano titanium dioxide paste 8.15g that embodiment 3 methods are made, the synthetic resins liquid that adds the nanometer slurry disperseed 10 minutes with GFJ0.4 high speed dispersor (Shanghai modern environment engineering and technological research institute) 1000rpm, was prepared into the modified synthetic resin component of nano uvioresistant polyurethane paint after filtering with 200 order copper mesh; Curing agent component is CORONATE HX-T (solid content is 77%, and NCO content is 16.2%).Two components are pressed NCO: OH=1.1: 1 (mol ratio) proportioning, promptly need in the modified synthetic resin component, to add 13.42g CORONATE HX-T, stir the QXG line rod spreader (Tianjin material-testing machine factory) that uses 10 μ m～50 μ m in the back and go up this nano uvioresistant polyurethane paint of coating in the glass slide (harbour, Qinhuangdao medical glass factory) of 76mm * 26mm * 0.5mm, the sample Air drying of coating composition 7 days, making build is the coating sample of 10 ± 2 μ m.
Embodiment 13
In the beaker of 300ml, claim 50g Hydroxylated acrylic resin FX-2970A (solid content is 70%, and the hydroxy radical content of solid resin is 2.9%).Add the 10% interior meter zinc oxide paste 12.6g that embodiment 4 methods are made, the synthetic resins liquid that adds the nanometer slurry disperseed 10 minutes with GFJ0.4 high speed dispersor (Shanghai modern environment engineering and technological research institute) 1000rpm, was prepared into the modified synthetic resin component of nano uvioresistant polyurethane paint after filtering with 200 order copper mesh; Curing agent component is CORONATE 2384 (solid content is 77%, and NCO content is 16.3%).Two components are pressed NCO: OH=1.2: 1 (mol ratio) proportioning, promptly need in the modified synthetic resin component, to add 18.46g CORONATE 2384, stir the QXG line rod spreader (Tianjin material-testing machine factory) that uses 10 μ m～50 μ m in the back and go up this nano uvioresistant polyurethane paint of coating in the glass slide (harbour, Qinhuangdao medical glass factory) of 76mm * 26mm * 0.5mm, the sample Air drying of coating composition 7 days, making build is the coating sample of 10 ± 2 μ m.
Embodiment 14
The preparation method is with embodiment 13, and just when the preparation nano uvioresistant polyurethane paint, 10% nano zine oxide that the nano-oxide slurry uses embodiment 8 methods to make is starched, and other is constant.
Embodiment 15
The preparation method is with embodiment 13, and just when the preparation nano uvioresistant polyurethane paint, 10% nano zine oxide that the nano-oxide slurry uses embodiment 9 methods to make is starched, and other is constant.
Embodiment 16
In the beaker of 300ml, claim 50g Hydroxylated acrylic resin Desmophen
A365/1 (solid content is 65%, and hydroxy radical content is 2.9%).Add the 30% nano titanium dioxide paste 1.6g that embodiment 2 methods are made, the synthetic resins liquid that adds the nanometer slurry disperseed 10 minutes with GFJ0.4 high speed dispersor (Shanghai modern environment engineering and technological research institute) 1500rpm, was prepared into the modified synthetic resin component of nano uvioresistant polyurethane paint after filtering with 200 order copper mesh; Curing agent component is Desmodur
N3390 (solid content is 90%, and NCO content is 19.6%).Two components are pressed NCO: OH=0.9: 1 (mol ratio) proportioning promptly needs to add 16.45g Desmodur in the modified synthetic resin component
N3390, stir the QXG line rod spreader (Tianjin material-testing machine factory) that uses 10 μ m～50 μ m in the back and go up this nano uvioresistant polyurethane paint of coating in the glass slide (harbour, Qinhuangdao medical glass factory) of 76mm * 26mm * 0.5mm, the sample Air drying of coating composition 7 days, making build is the coating sample of 10 ± 2 μ m.
Embodiment 17
In the beaker of 300ml, claim 50g hydroxy polyester resin 670BA (solid content is 80%, and hydroxy radical content is 3.4%).Add the 30% nano titanium dioxide paste 1.5g that embodiment 2 methods are made, add the 30% nano zine oxide slurry 1.5g that embodiment 5 methods are made, the synthetic resins liquid that adds the nanometer slurry disperseed 10 minutes with GFJ0.4 high speed dispersor (Shanghai modern environment engineering and technological research institute) 1500rpm, was prepared into the modified synthetic resin component of nano uvioresistant polyurethane paint after filtering with 200 order copper mesh; Curing agent component is Tolonate
TMHDB-75MX (solid content is 75%, and NCO content is 16.4%).Two components are pressed NCO: OH=1: 1 (mol ratio) proportioning promptly needs to add 25.61g Tolonate in the modified synthetic resin component
TMHDB-75MX, stir the QXG line rod spreader (Tianjin material-testing machine factory) that uses 10 μ m～50 μ m in the back and go up this nano uvioresistant polyurethane paint of coating in the glass slide (harbour, Qinhuangdao medical glass factory) of 76mm * 26mm * 0.5mm, the sample Air drying of coating composition 7 days, making build is the coating sample of 10 ± 2 μ m.
Embodiment 18
In the beaker of 300ml, claim 50g Hydroxylated acrylic resin FX-2820 (solid content is 60%, and the hydroxy radical content of solid resin is 2.8%).Add the 10% nano titanium dioxide paste 25g that embodiment 1 method is made, the synthetic resins liquid that adds the nanometer slurry disperseed 10 minutes with GFJ0.4 high speed dispersor (Shanghai modern environment engineering and technological research institute) 1000rpm, was prepared into the modified synthetic resin component of nano uvioresistant polyurethane paint after filtering with 200 order copper mesh; Curing agent component is Desmudur
N75 (solid content is 75%, and NCO content is 16.4%).Two components are pressed NCO: OH=0.8: 1 (mol ratio) proportioning promptly needs to add 10.16g Desmudur in the modified synthetic resin component
N75, stir the QXG line rod spreader (Tianjin material-testing machine factory) that uses 10 μ m～50 μ m in the back and go up this nano uvioresistant polyurethane paint of coating in the glass slide (harbour, Qinhuangdao medical glass factory) of 76mm * 26mm * 0.5mm, the sample Air drying of coating composition 7 days, making build is the coating sample of 10 ± 2 μ m.
Comparative example 1
Claim 50g Hydroxylated acrylic resin FX-2820 (solid content is 60%, and the hydroxy radical content of solid resin is 2.8%) in the beaker of 300ml, this Hydroxylated acrylic resin liquid is the synthetic resins component; Curing agent component is Desmudur
N75 (solid content is 75%, and NCO content is 16.4%).Two components are pressed NCO: OH=1: 1 (mol ratio) proportioning promptly needs to add 12.65g Desmudur in the synthetic resins component
N75, stir the QXG line rod spreader (Tianjin material-testing machine factory) that uses 10 μ m～50 μ m in the back and go up this polyurethane coating of coating in the glass slide (harbour, Qinhuangdao medical glass factory) of 76mm * 26mm * 0.5mm, the sample Air drying of coating composition 7 days, making build is the contrast coating sample of 10 ± 2 μ m.
The nano uvioresistant polyurethane coating of the different nano-oxide content of table 1 and the performance that contrasts coating
| The kind of nano-oxide | Synthetic resins content in the modified synthetic resin, % | Nano-oxide content in the modified synthetic resin, % | Macromolecule dispersing agent content in the modified synthetic resin, % | Hardener dose (NCO: OH, mol ratio) | The coating transmitance, % | |||
| 300nm | 360nm | 560nm | ||||||
| Embodiment 10 | Nano titanium oxide and nano zine oxide | 59.44 | 0.37 | 0.01 | 0.8∶1 | 4.25 | 4.84 | 91.27 |
| Embodiment 11 | Nano zine oxide | 57.47 | 2.32 | 0.44 | 1.3∶1 | 2.54 | 2.35 | 82.66 |
| Embodiment 12 | Nano titanium oxide | 51.59 | 7.71 | 0.38 | 1.1∶1 | 0.03 | 0.02 | 75.45 |
| Comparative example 1 | 1∶1 | 92.45 | 93.58 | 97.20 | ||||
As shown in Table 1, be 10 μ m at build, the nano uvioresistant polyurethane coating is 95.75～99.97% to the rate of ultraviolet shield of 300nm; And the polyurethane coating that does not have a nano-oxide is 7.55% to the rate of ultraviolet shield of 300nm.Corresponding nano uvioresistant polyurethane coating is 13 times of polyurethane coating that do not have nano-oxide approximately to the rate of ultraviolet shield of 300nm.
At build is 10 μ m, and the nano uvioresistant polyurethane coating is 95.16～99.98% to the rate of ultraviolet shield of 360nm; And the polyurethane coating that does not have a nano-oxide is 6.42% to the rate of ultraviolet shield of 360nm.Corresponding nano uvioresistant polyurethane coating is 15 times of polyurethane coating that do not have nano-oxide to the rate of ultraviolet shield of 360nm.
The nano uvioresistant polyurethane coating 75.45～91.27%, is transparent in the transmitance at visible light 560nm place.
In addition, the nano-oxide content of the nano uvioresistant polyurethane paint of embodiment 11 is in the 0.5-5% scope, the rate of ultraviolet shield of nano uvioresistant polyurethane coating is more than 97%, and the transmitance of visible light is more than 80%, ultraviolet shield effectiveness and visible light transparent very good.The nano-oxide content of the nano uvioresistant polyurethane paint of embodiment 10 exceeds the 0.5-5% scope, the rate of ultraviolet shield of nano uvioresistant polyurethane coating is more than 95%, the transmitance of visible light is 91.27%, though visible light is transparent good, ultraviolet shielding effect reduces.The nano-oxide content of the nano uvioresistant polyurethane paint of embodiment 12 exceeds the 0.5-5% scope, the rate of ultraviolet shield of nano uvioresistant polyurethane coating is more than 99%, the transmitance of visible light is 75.45%, though ultraviolet shielding effect is good, the transparency of visible light reduces.
The performance of the nano uvioresistant polyurethane paint of the different macromolecule dispersing agent content of table 2
| The kind of nano-oxide | Synthetic resins content in the modified synthetic resin, % | Nano-oxide content in the modified synthetic resin, % | Macromolecule dispersing agent content in the modified synthetic resin, % | Hardener dose (NCO: OH, mol ratio) | The coating transmitance, % | |||
| 300nm | 360nm | 560nm | ||||||
| Embodiment 13 | Nano zine oxide | 55.91 | 2.01 | 1.13 | 1.2∶1 | 2.87 | 2.65 | 84.45 |
| Embodiment 14 | Nano zine oxide | 55.91 | 2.01 | 0.2 | 1.2∶1 | 4.89 | 5.73 | 80.15 |
| Embodiment 15 | Nano zine oxide | 55.91 | 2.01 | 2.01 | 1.2∶1 | 5.32 | 4.55 | 82.86 |
Table 2 is performances of the nano uvioresistant polyurethane paint of different macromolecule dispersing agent content.As known from Table 2, the macromolecule dispersing agent weight ratio is 1.13% in the modified synthetic resin of embodiment 13, in the 0.3-1.5% scope, this nano uvioresistant polyurethane coating is greater than the nano uvioresistant polyurethane coating of embodiment 14 and embodiment 15 to the ultraviolet shielding rate of 300nm and 360nm, and the transparency will be got well.
The performance of the nano uvioresistant polyurethane paint of the different synthetic resins content of table 3
| The kind of nano-oxide | Synthetic resins content in the modified synthetic resin, % | Nano-oxide content in the modified synthetic resin, % | Macromolecule dispersing agent content in the modified synthetic resin, % | Hardener dose (NCO: OH, mol ratio) | The coating transmitance, % | |||
| 300nm | 360nm | 560nm | ||||||
| Embodiment 16 | Nano titanium oxide | 62.98 | 0.93 | 0.11 | 0.9∶1 | 3.81 | 3.64 | 90.35 |
| Embodiment 17 | Nano titanium oxide and nano zine oxide | 75.47 | 1.7 | 0.3 | 1∶1 | 3.45 | 3.34 | 86.56 |
| Implement 18 | Nano titanium oxide | 40 | 3.33 | 0.17 | 0.8∶1 | 0.89 | 0.56 | 80.35 |
Table 3 is performances of the nano uvioresistant polyurethane paint of different synthetic resins content.As can be seen from Table 3, the weight ratio of synthetic resins is in 40～80% scopes in the modification synthesizing propylene acid resin, the nano uvioresistant polyurethane coating of gained to the ultraviolet shielding rate of 300nm and 360nm more than 96%, and visible light is had the extraordinary transparency, to the visible light transmissivity of 560nm greater than 80%.
Fig. 1 is the relation of the different nano-oxide content of nano uvioresistant polyurethane coating and ultraviolet ray and visible light transmissivity.Has good especially uv-shielding capacity by Fig. 1 nano uvioresistant polyurethane coating that contains nano-oxide that can visually see.
Claims (9)
1, a kind of nano uvioresistant polyurethane paint, constitute by matching used modified synthetic resin and solidifying agent two-pack, synthetic resins refers to one or more of Hydroxylated acrylic resin, hydroxy polyester resin, solidifying agent refers to the isocyanates solidifying agent, it is characterized in that: described modified synthetic resin is by the solvent composition of 0.1-10% nano-oxide, 0.01-5% macromolecule dispersing agent, 40-80% synthetic resins, surplus;
Wherein:
Nano-oxide refers to nano titanium oxide and/or the nano zine oxide of mean particle size below 100nm of primary particle;
Macromolecule dispersing agent is selected from one or more of ketone macromolecular compound in polyolefins, polyolefine salt, polycarboxylic acid, polycarboxylic acid salt, polyacrylic acid, polyacrylate, polyester, polyester salt, polyamide-based, polymeric amide salt, polyurethanes, urethane salt, polyethers, polyethers salt, polyanhydrides, polysiloxane-based, polyoxyethylene, polyoxypropylene class, Malaysia acids, maleic anhydride class, the poly epsilon caprolactone;
Solvent is selected from one or more of aliphatic hydrocarbon, aromatic hydrocarbon, ester class, ketone, terpene, replacement hydro carbons;
The proportioning of modified synthetic resin and solidifying agent is pressed NCO: OH=0.8～1.3: 1 mol ratios.
2, according to the described nano uvioresistant polyurethane paint of claim 1, it is characterized in that: described nano-oxide is through surface treatment.
3, according to the described nano uvioresistant polyurethane paint of claim 1, it is characterized in that: the crystal formation of described nano titanium oxide is a rutile-type.
4, according to claim 1,2 or 3 described nano uvioresistant polyurethane paints, it is characterized in that: the content of described nano-oxide is 0.5-5%.
5, according to the described nano uvioresistant polyurethane paint of claim 1, it is characterized in that: described macromolecule dispersing agent is selected from the Disperbyk103 of German Bi Ke chemical company, Disperbyk106, Disperbyk107, Disperbyk110, Disperbyk111, Disperbyk115, Disperbyk130, Disperbyk160, Disperbyk162, Disperbyk163, Disperbyk164, Disperbyk2000, Anti-Terra-P, Anti-Terra-202, Anti-Terra-204, Anti-Terra-206, Anti-Terra-207, Anti-Terra-P, Byk-P104S; The Solsperse3000 of Avecia company, Solsperse13940, Solsperse17000, Solsperse24000, Solsperse28000, Solsperse32000, Solsperse32500, Solsperse34750, Solsperse41090; The TEXAPHOR of Henkel Corp.
963, TEXAPHOR
963S, TEXAPHOR
3061, TEXAPHOR
3073, TEXAPHOR
3241, TEXAPHOR
3112, TEXAPHOR
3250, TEXAPHOR
3287; Deuchem Co., Ltd. 902,923,923S, DP-981, DP-983, DP-S81,904,904S; EFKA-44, EFKA-54, EFKA-63, EFKA-64, EFKA-65, EFKA-66, EFKA-46, EFKA-47, EFKA-48, EFKA-49, EFKA-701, EFKA-745, EFKA-764, EFKA-766, the EFKA-Polymer4010 of Holland EFKA auxiliary agent company; The Dispers700 of Di Gao chemical company, Dispers610, Dispers610S, Dispers630S, Dispers710; The Hypersol L4707 of Denmark KVK company, Hypersol L4708, Hypersol L4742, Hypersol L4744, Hypersol P496; The Elvacite type dispersant A B1010 of E.I.Du Pont Company, AB1015, AB1020, AB1030.
6, according to claim 1 or 5 described nano uvioresistant polyurethane paints, it is characterized in that: the content of described macromolecule dispersing agent is 0.3-1.5%.
7, according to the described nano uvioresistant polyurethane paint of claim 1, it is characterized in that: described solvent is No. 200 solvent oils, Skellysolve A, iso-pentane, isohexane, normal hexane, normal heptane, isoheptane, toluene, dimethylbenzene, Three methyl Benzene, Solvesso100, Solvesso150, Solvesso200, solvent naphtha, methylethylketone, mibk, pimelinketone, isophorone, vinyl acetic monomer, n-butyl acetate, isobutyl acetate, methoxyacetic acid propyl ester, trichloroethane.
8, the preparation method of the described nano uvioresistant polyurethane paint of a kind of claim 1 is characterized in that process is as follows:
At first macromolecule dispersing agent is added in the solvent, add nano-oxide then, 400-2000rpm high speed dispersion 2-60 minute; The slurry of gained ground in ball mill or sand mill or ball mill 20 minutes-24 hours, made the nano-oxide slurry; Consist of, in 100% weight, nano-oxide 10-60% weight, macromolecule dispersing agent 0.5-10.5% weight, the solvent of surplus;
Above-mentioned nano-oxide slurry is mixed with synthetic resin solution, fully disperse this mixture, make the modified synthetic resin component of nano uvioresistant polyurethane paint after filtering with high speed dispersor or grinding plant; Supporting with curing agent component, promptly form nano uvioresistant polyurethane paint.
9. by the preparation method of the described nano uvioresistant polyurethane paint of claim 8, it is characterized in that the first step slurrying solvent for use is identical with second step preparation nano uvioresistant polyurethane paint solvent for use.
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| CNB01128269XA CN1186413C (en) | 2001-10-12 | 2001-10-12 | Nano uvioresistant polyurethane paint |
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| CN1300246C (en) * | 2003-12-19 | 2007-02-14 | 上海交通大学 | Method for preparing uvioresistant polyester by nanometer titania generated in situ |
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| CN104017489B (en) * | 2014-05-29 | 2016-04-06 | 中国石油大学(华东) | A kind of nano-titanium dioxide modified acrylic polyurethane finish paint and preparation method thereof |
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| CN109796861A (en) * | 2017-11-17 | 2019-05-24 | 沙冰娟 | A kind of preparation method of modified nano zinc oxide-polyurethane composite coating |
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| US20210009819A1 (en) * | 2019-07-09 | 2021-01-14 | The Boeing Company | Coatings for sterilization with uv light |
| CN111303754B (en) * | 2020-04-17 | 2021-05-04 | 中国科学院长春应用化学研究所 | Scratch-resistant wear-resistant polyurethane transparent coating with high adhesive force |
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| CN114716900A (en) * | 2022-04-21 | 2022-07-08 | 苏州皇冠涂料科技发展有限公司 | High-hardness wear-resistant PU (polyurethane) coating |
| CN116496684A (en) * | 2023-03-15 | 2023-07-28 | 沈阳派尔化学有限公司 | Preparation method of lead-free environment-friendly high-weather-resistance flexible polyurethane paint for roads and bridges |
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