CN117683461A - Preparation method of high-transparency super-wear-resistant self-cleaning antibacterial coating - Google Patents
Preparation method of high-transparency super-wear-resistant self-cleaning antibacterial coating Download PDFInfo
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- CN117683461A CN117683461A CN202311692001.2A CN202311692001A CN117683461A CN 117683461 A CN117683461 A CN 117683461A CN 202311692001 A CN202311692001 A CN 202311692001A CN 117683461 A CN117683461 A CN 117683461A
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- Prior art keywords
- inorganic nano
- wear
- nano particles
- polysiloxane
- transparency
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- 238000000576 coating method Methods 0.000 title claims abstract description 136
- 239000011248 coating agent Substances 0.000 title claims abstract description 135
- 238000004140 cleaning Methods 0.000 title claims abstract description 56
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002105 nanoparticle Substances 0.000 claims abstract description 121
- -1 polysiloxane Polymers 0.000 claims abstract description 92
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 60
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 238000005406 washing Methods 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 22
- 239000003960 organic solvent Substances 0.000 claims abstract description 22
- 239000000758 substrate Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000006184 cosolvent Substances 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 239000003607 modifier Substances 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910000077 silane Inorganic materials 0.000 claims abstract description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 7
- 239000010703 silicon Substances 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 24
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 22
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 22
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical group CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- 239000008096 xylene Substances 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 4
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 4
- 239000003973 paint Substances 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 claims description 4
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims description 3
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 claims description 3
- 239000003517 fume Substances 0.000 claims description 3
- 125000000962 organic group Chemical group 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 claims description 2
- 125000003396 thiol group Chemical class [H]S* 0.000 claims description 2
- OYGYKEULCAINCL-UHFFFAOYSA-N triethoxy(hexadecyl)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC OYGYKEULCAINCL-UHFFFAOYSA-N 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 239000011259 mixed solution Substances 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 39
- 238000002834 transmittance Methods 0.000 description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- 239000011521 glass Substances 0.000 description 24
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 18
- 239000004745 nonwoven fabric Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- 239000002245 particle Substances 0.000 description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 241000588724 Escherichia coli Species 0.000 description 7
- 241000191967 Staphylococcus aureus Species 0.000 description 7
- 238000005299 abrasion Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000005119 centrifugation Methods 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 230000001954 sterilising effect Effects 0.000 description 7
- 238000004659 sterilization and disinfection Methods 0.000 description 7
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 6
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 6
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 6
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical group CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- XKZQEUJIZUWRQQ-UHFFFAOYSA-N hexadecyl(trimethyl)silane Chemical compound CCCCCCCCCCCCCCCC[Si](C)(C)C XKZQEUJIZUWRQQ-UHFFFAOYSA-N 0.000 description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- GBCKRQRXNXQQPW-UHFFFAOYSA-N n,n-dimethylprop-2-en-1-amine Chemical compound CN(C)CC=C GBCKRQRXNXQQPW-UHFFFAOYSA-N 0.000 description 3
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 2
- 230000000051 modifying effect Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- SIJJORQTGHGGNV-UHFFFAOYSA-N triethyl(hexadecyl)silane Chemical compound CCCCCCCCCCCCCCCC[Si](CC)(CC)CC SIJJORQTGHGGNV-UHFFFAOYSA-N 0.000 description 2
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 description 1
- ICRYQIULEQOXIA-UHFFFAOYSA-N 3-chloropropoxyperoxysilane Chemical compound ClCCCOOO[SiH3] ICRYQIULEQOXIA-UHFFFAOYSA-N 0.000 description 1
- KXFMNTBKTQKJKR-UHFFFAOYSA-N C(C)O[SiH3].C(=O)(O)C=C Chemical compound C(C)O[SiH3].C(=O)(O)C=C KXFMNTBKTQKJKR-UHFFFAOYSA-N 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 description 1
- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical compound CCO[Si](C)OCC GAURFLBIDLSLQU-UHFFFAOYSA-N 0.000 description 1
- UYJVWFZJQXTYLG-UHFFFAOYSA-N diethoxy-ethyl-phenylsilane Chemical compound CCO[Si](CC)(OCC)C1=CC=CC=C1 UYJVWFZJQXTYLG-UHFFFAOYSA-N 0.000 description 1
- MNFGEHQPOWJJBH-UHFFFAOYSA-N diethoxy-methyl-phenylsilane Chemical compound CCO[Si](C)(OCC)C1=CC=CC=C1 MNFGEHQPOWJJBH-UHFFFAOYSA-N 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- HTSRFYSEWIPFNI-UHFFFAOYSA-N ethyl-dimethoxy-methylsilane Chemical compound CC[Si](C)(OC)OC HTSRFYSEWIPFNI-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- FABOKLHQXVRECE-UHFFFAOYSA-N phenyl(tripropoxy)silane Chemical compound CCCO[Si](OCCC)(OCCC)C1=CC=CC=C1 FABOKLHQXVRECE-UHFFFAOYSA-N 0.000 description 1
- VPLNCHFJAOKWBT-UHFFFAOYSA-N phenyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)C1=CC=CC=C1 VPLNCHFJAOKWBT-UHFFFAOYSA-N 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- INUOIYMEJLOQFN-UHFFFAOYSA-N tributoxy(phenyl)silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)C1=CC=CC=C1 INUOIYMEJLOQFN-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Plant Pathology (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a high-transparency super-wear-resistant self-cleaning antibacterial coating and a preparation method thereof. The method comprises the following steps: (1) Adding an alcohol solvent, a cosolvent, a catalyst and inorganic nano particles into a container, uniformly mixing, adding a silane modifier for reaction, and filtering, washing and drying to obtain the modified inorganic nano particles. (2) Adding an alcohol solvent, a cosolvent, modified inorganic nano particles, a silane coupling agent and an antibacterial organic silicon monomer into a container, uniformly mixing, adding a catalyst, filtering, washing and drying to obtain polysiloxane grafted with the inorganic nano particles. (3) And respectively or mixedly dissolving the polysiloxane doped with the inorganic nano particles and the flatting agent in an organic solvent, and obtaining the high-transparency wear-resistant self-cleaning antibacterial coating after the polysiloxane doped with the inorganic nano particles and the flatting agent are completely dissolved. (4) The high-transparency wear-resistant self-cleaning antibacterial coating is rubbed on the substrate step by step or by one step. The transparent wear-resistant coating prepared by the invention has good self-cleaning and antibacterial effects.
Description
Technical Field
The invention belongs to the field of antibacterial coatings, and particularly relates to a preparation method and application of a high-transparency super-wear-resistant self-cleaning antibacterial coating, in particular to a method for protecting the surface of a silicon-based optical panel by adopting the high-transparency super-wear-resistant self-cleaning coating.
Background
As global energy and environmental crisis become more severe, photovoltaic cells have grown and solar power plants have been built in succession. Most photovoltaic panels mainly work outdoors, and the surfaces of the panels are inevitably shielded by pollutants for a long time, so that the power generation efficiency of a power station is greatly influenced, and huge losses are caused. For the pollutants, if manual cleaning is selected, huge manpower and material resources are wasted, and the effect is not ideal, so that the development of the novel high-efficiency multifunctional self-cleaning coating for the photovoltaic panel is significant.
Inspired by the self-cleaning effect of the lotus leaf surface, the bionic principle is utilized to construct a micro-nano coarse structure while reducing the surface energy of the coating so as to improve the hydrophobicity of the coating, however, the method is not suitable for the high-transparency self-cleaning coating. It is known from Rayleigh scattering and Mie scattering theory that, in order to achieve good light transmittance, the surface roughness needs to be smaller than the wavelength of light in addition to ensuring light transmittance of the optical surface material. When the roughness is more than 100nm, scattering of light is remarkably enhanced, and thus light transmittance cannot be achieved by the roughness of the micrometer scale, which means that it is difficult to increase the hydrophobicity of the light-transmitting self-cleaning coating by increasing the surface roughness, and a balance must be struck between excellent optical transparency and hydrophobicity. Fluorine-containing species are often selected to modify the surface of the material due to their low surface tension, and although the resulting sample has improved hydrophobic properties, the presence of fluorine-containing species can pose a potential threat to the environment, causing ozone layer voids. Therefore use-CH 3 Instead of-FH 3 Has great significance on environmental protection, and the fluoridized material has high price and is not suitable for large-scale industrialized production, so the price is cheaper and environmental-friendly-CH is used 3 Materials as modifiers to reduce surface energy. However, although the application of the hydrophobic material in daily life is very common, many difficulties exist in preparation and application, and the prepared hydrophobic material has the defects of complex process, poor mechanical property, high preparation cost, poor weather resistance and the like.
Polymer/inorganic nanocomposite materials are attracting attention in various fields such as optics, chemical industry, biology, etc. The composite material formed by the particles and the polymer can not only play the respective roles of the particles and the polymer, but also can show the synergistic effect of the particles and the polymer in the whole material. When inorganic nano particles are filled in the polymer for composite modification, not only can the strength of the polymer be enhanced, but also the toughness of the material can be improved. In addition, a better fit point is found in the aspects of roughness and optical performance by controlling the addition amount and the particle size of the particles, so that the coating has higher hydrophobicity and good light transmittance, and the composite material formed by adding the inorganic nano particles has certain wear resistance.
According to the invention, through modifying the inorganic nano particles, active reactive groups are grafted on the surfaces of the inorganic nano particles, and firm chemical bonds are constructed among the inorganic nano particles, polysiloxane and flatting agent, so that the inorganic nano particles, the polysiloxane and the flatting agent are tightly connected. The aggregate attachment of the particles on the micro-scale maintains a lower roughness of the coating surface, wherein the polysiloxane and leveling agent mainly provide a low surface energy of the coating and bond with the surface of the inorganic nanoparticles, which can reduce the reflection of light, thereby providing the coating with high light transmittance. The organosilicon monomer in the coating is firmly connected with the substrate through the addition reaction to form Si-O-Si bond, so that excellent wear resistance is provided for the coating, and the unique microstructure and surface chemical composition of the organosilicon monomer endow the coating with good transparency and antibacterial self-cleaning capability. The coating prepared by the invention has wide application prospect on the surfaces of outdoor photovoltaic modules, curtain walls, electronic screens and laser amplifiers.
Disclosure of Invention
The invention aims to provide a preparation method of a high-transparency super-wear-resistant self-cleaning antibacterial coating. The method combines the surface chemical grafting modification of the inorganic nano particles to improve the compatibility of the nano particles and a matrix, and firmly combines the inorganic nano particles and an organosilicon monomer to the surface of a silicon-based material in a chemical bonding mode by an in-situ polymerization mode, so that the wettability and roughness of the inorganic nano particles on the surface of a substrate are controllably regulated, the phenomenon of reduced transparency of a coating is avoided, and the wear resistance and antibacterial performance of the coating are improved.
In order to achieve the aim of the invention, a preparation method of the high-transparency super-wear-resistant self-cleaning antibacterial coating comprises the following steps:
(1) Adding a certain amount of alcohol solvent, cosolvent, catalyst and inorganic nano particles into a container at a time at 25-40 ℃, wherein the concentration of the inorganic nano particles is controlled to be 1-1000 mg/mL, and the volume ratio of the alcohol solvent to the cosolvent is 0.1-10; after the reactants are uniformly mixed under the condition of the rotating speed of 50-1000 rpm, adding a silane modifier into a reaction system, wherein the mass dosage of the silane modifier is 0.5-40% of the total mass dosage of the inorganic nano particles; after the reaction for 0.5 to 30 hours, filtering and washing, and drying for 10 to 30 hours at the temperature of between 40 and 50 ℃ to obtain the modified inorganic nano particles.
(2) Adding a certain amount of alcohol solvent, cosolvent, modified inorganic nano-particles, silane coupling agent and antibacterial organic silicon monomer into a container at one time, wherein the mass dosage of the modified inorganic nano-particles is controlled to be 0.25-10% of the mass dosage of the whole system, and the volume ratio of the alcohol solvent to the cosolvent is 0.1-10; uniformly mixing the reactants under the condition of the rotating speed of 100 rpm-1000 rpm, adding a catalyst into the mixture, reacting for 10-30 hours at 60 ℃, filtering and washing, and drying for 10-30 hours at 40-50 ℃ to obtain polysiloxane grafted with inorganic nano particles.
(3) And respectively or mixedly dissolving polysiloxane doped with inorganic nano particles and a flatting agent in an organic solvent at the temperature of 25-40 ℃ and the rotating speed of 100-1000 rpm, wherein the concentration of the polysiloxane is controlled to be 5-30 wt percent, the mass concentration of the flatting agent is 10-20 wt percent, and after the polysiloxane doped with the inorganic nano particles and the flatting agent are completely dissolved, the high-transparency wear-resistant self-cleaning antibacterial coating is obtained.
(4) The high-transparency wear-resistant self-cleaning antibacterial coating is coated on a substrate step by step or by a one-step method, is cured for 10min in a fume hood at 20-80 ℃, and is cured for 1-2 h at a high temperature of 100-200 ℃, so that the high-transparency wear-resistant self-cleaning antibacterial coating can be successfully attached on the substrate to form the high-transparency wear-resistant self-cleaning antibacterial coating.
In the present invention, the inorganic nanoparticles can be obtained by the existing method, (1) SiO having a size in the range of 10nm to 50nm is synthesized by a hydrothermal method 2 、ZnO、Ag、Fe 3 O 4 An inorganic nanoparticle; (2) Direct purchase of commercially available SiO in this size range 2 、ZnO、Ag、Fe 3 O 4 An aqueous dispersion of nanoparticles.
In view of the modifying effect, dispersion stability, transmittance and antibacterial effect of the nanoparticle surface, it is preferable that the average size of the inorganic nanoparticles is controlled to 10nm to 30nm.
The alcohol solvent is one or more of methanol, ethanol, isopropanol, propylene glycol, butanol, 1, 4-butanediol, 1, 3-butanediol and glycerol.
The cosolvent is water, dimethyl sulfoxide and N, N-dimethylformamide.
The catalyst is an ammonia catalyst, including but not limited to ammonia monohydrate, hydrazine hydrate and the like, the ammonia catalyst is added dropwise, a pH meter is continuously used for monitoring the pH value when the ammonia catalyst is added dropwise, and the catalyst can be stopped to be added dropwise when the pH value reaches 10-11.
The uniformly mixing mode is magnetic stirring, and the time is 1-2 h.
The filtering and washing modes are as follows: the reaction system is put into a high-speed centrifuge for centrifugation, the centrifugation speed is 5000-8000 rpm, and the centrifugation time is 5-10 min; filtering and separating the mixture from the supernatant after centrifugation, performing ultrasonic dispersion on the mixture and water after separation, and putting the mixture and water into a high-speed centrifuge again for centrifugation, wherein the centrifugation speed is 5000-8000 rpm, and the centrifugation time is 5-10 min; repeating the steps for three times to obtain the product which is completely washed.
In the step (1), the silane modifier is gamma-glycidoxypropyl trimethoxy silane, gamma-glycidoxypropyl triethoxy silane, gamma-glycidoxypropyl methyl diethoxy silane, hexadecyl trimethoxy silane or hexadecyl triethoxy silane.
In the step (2), the silane coupling agent is selected from phenyl trimethoxy silane, phenyl triethoxy silane, phenyl tripropoxy silane, phenyl triisopropoxy silane, phenyl tri-n-butoxy silane, diphenyl dimethoxy silane, diphenyl diethoxy silane, methylphenyl dimethoxy silane, methylphenyl diethoxy silane, ethyl phenyl diethoxy silane, gamma-glycidyl ether oxypropyl trimethoxy silane, gamma-glycidyl ether oxypropyl triethoxy silane, gamma-glycidyl ether oxypropyl methyl diethoxy silane, dimethyl dimethoxy silane, dimethyl diethoxy silane and methyl ethyl dimethoxy silane.
In the step (2) of the present invention, the antibacterial silicone monomer is selected from at least one of the following: methyl triethoxysilane quaternary ammonium salt, methyl dimethoxysilane quaternary ammonium salt, N-dimethyldodecylaminopropyl trimethoxysilane ammonium chloride, N-allyldimethylamine and 3-chloropropyltrimethoxysilane, acrylate ethoxysilane, N-dimethyldodecylaminopropyl trimethoxysilane ammonium chloride, N-allyldimethylamine and 3-chloropropyltrimethoxysilane are preferable in view of actual antibacterial effect; the dosage of the catalyst is 0.2-10wt% of the mass of the silane coupling agent.
In step (2) of the present invention, the polysiloxane refers to a polymer in which the main chain is composed of repeating unit silicon-oxygen (Si-O) bonds, wherein an organic group is attached to a silicon atom.
In the step (3) of the invention, the leveling agent is amino modified polydimethylsiloxane, carboxyl modified polydimethylsiloxane, epoxy modified polydimethylsiloxane, isocyanate modified polydimethylsiloxane and mercapto modified polydimethylsiloxane.
In the step (3) of the invention, the respectively or mixed dissolution in the organic solvent means two ways of preparing the light-transmitting high-transparency wear-resistant self-cleaning paint, and the way 1 is as follows: taking a certain amount of polysiloxane doped with inorganic nano particles and a leveling agent at the temperature of 25-40 ℃, and respectively dissolving the polysiloxane and the leveling agent in an organic solvent with the same volume; mode 2: taking a certain amount of polysiloxane doped with inorganic nano particles and a leveling agent at the temperature of 25-40 ℃, and mixing and dissolving the polysiloxane and the leveling agent in an organic solvent with certain mass.
In the step (3), the organic solvent is one or more of methanol, ethanol, ethyl acetate, acetone, n-hexadecane, cyclohexane, tetrahydrofuran, dichloromethane, carbon tetrachloride, toluene and xylene.
In the step (4), the step-by-step or one-step wiping coating refers to two modes of coating the high-transparency wear-resistant self-cleaning coating, namely mode 1: a certain amount of organic solvent dissolved with polysiloxane doped with inorganic nano particles is taken and rubbed on a substrate, and then a certain amount of organic solvent dissolved with flatting agent is taken and rubbed on the substrate; mode 2: and taking a certain amount of organic solvent dissolved with polysiloxane doped with inorganic nano particles and a leveling agent, and wiping the organic solvent on a substrate.
In the step (4), the wiping mode is to dip the high-transparency wear-resistant self-cleaning paint with the volume of about 1-1000 mu L by using non-woven fabrics, and uniformly and thinly coat the high-transparency wear-resistant self-cleaning paint on a substrate at the speed of 1-5 m/s.
In the step (4), the substrate is made of silicon-based materials such as glass, silicon chips and the like, impurities attached to the substrate are required to be washed away in advance by using water, and the substrate can be used as the substrate after being dried at the temperature of 40-80 ℃.
In the present invention, the inorganic nanoparticle having a proper size has an excellent anti-reflection function, but since it has only hydrophilic hydroxyl groups on the surface, the surface characteristics of the inorganic nanoparticle are very single due to the too single groups, which greatly limits the application of the inorganic nanoparticle. By carrying out surface modification on the inorganic nano particles, the surfaces of the inorganic nano particles are grafted with the amphiphilic groups with reactivity through chemical reaction, so that the application range of the inorganic nano particles is greatly widened. Particularly, the invention adopts an in-situ polymerization mode, so that the inorganic nano particles are firmly and chemically combined with polysiloxane and a flatting agent through chemical bonds, the organic silicon and the inorganic nano particles have quite good compatibility, the agglomeration phenomenon of the inorganic nano particles in the coating is avoided, the high dispersion of the inorganic nano particles in the coating is realized, and the inorganic nano particles with certain mechanical strength provide a certain degree of wear resistance for the coating.
The inventor has intensively studied and found that the coating has ultrahigh hardness structurally due to the formation of a firm crosslinked network between the organosilicon and the inorganic nano-particles; the inorganic nano particles are uniformly and firmly connected with the polysiloxane and the flatting agent, the surface property of the coating is uniform and smooth, the inorganic nano particles are highly dispersed in the coating, the occurrence of diffuse reflection is radically stopped, and the light transmittance of the coating is enhanced, so that the coating has excellent transparency.
Compared with the prior art, the technical scheme of the invention has the following technical advantages: 1) The process is simple, the raw materials are easy to obtain, and the cost is low; 2) The coating is highly transparent, the light transmittance of the coated glass is up to 91.5% in the visible light range, the average light transmittance is 90.2%, and the light transmittance is superior to that of the glass substrate, so that the coated glass has good commercial application. (the highest light transmittance in the visible light range of glass is known as 91.4%, and the average light transmittance is known as 90.1%); 3) The coating is super wear-resistant, and can keep self-cleaning performance after being scratched by 1400 times of scissors; 4) The coating has ultrahigh adhesive force to the substrate, has certain tolerance to acid-base salt and long service life. 5) The invention connects the inorganic nano particles, polysiloxane and flatting agent together through chemical bonds, and simultaneously combines the performances of high transparency, super wear resistance and self cleaning, and has antibacterial performance.
Drawings
Fig. 1 is a SEM image comparison of the coating before and after 1500 scratches.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail hereinafter with reference to the accompanying drawings and examples, the specific examples described herein are only for explaining the present invention, and the scope of the present invention is not limited in any way to the above.
The invention enables the inorganic nano particles to form extremely stable covalent bonding with polysiloxane and flatting agent through chemical bond by in-situ polycondensation. Because of good compatibility between the organosilicon and the silicon dioxide particles, the agglomeration phenomenon of inorganic nano particles in the coating is avoided, the high dispersion of the inorganic nano particles in the coating is realized, the occurrence of diffuse reflection is greatly reduced, and the light transmittance of the coating is enhanced, so that the coating has excellent transparency. In the invention, because a firm cross-linked network is formed between the organosilicon monomers and the inorganic nano particles, the coating is endowed with ultra-high hardness structurally, and the inorganic nano particles with certain mechanical strength provide excellent wear resistance for the coating. In addition, the prepared transparent wear-resistant coating has good self-cleaning and antibacterial effects.
Example 1:
1g of silicon dioxide nano particles (20 nm) are dissolved in 30mL of ethanol water solution (the volume ratio of ethanol to water is 3:1) at 25 ℃, the pH value of a reaction system is adjusted to 10-11 by using ammonia monohydrate, after stirring for 1h under the condition that the rotating speed of a magnetic stirrer is 600rpm, 0.1g of gamma-glycidoxypropyl trimethoxysilane and 0.05g of hexadecyltrimethylsilane are added into the reaction system, stirring is carried out for 8h under the condition that the rotating speed of 600rpm is adopted, and centrifugal separation and washing are carried out on the product; drying at 45 ℃ for 10 hours to obtain the modified silica nano-particles.
0.0655g of modified silica nanoparticles was dissolved in 30mL of an aqueous solution of ethanol (volume ratio of ethanol to water: 3:1), to which 3.966g of phenyltrimethoxysilane, 2.404g of dimethyldimethoxysilane, 2.363g of gamma-glycidoxypropyl trimethoxysilane, 0.437g of N, N-dimethyldodecylaminopropyl trimethoxysilane ammonium chloride were added, and stirred at 600rpm for 1 hour, and the pH of the reaction system was adjusted to 10.5 using ammonia monohydrate. And (3) after reacting at 60 ℃ for 10 hours, centrifugally washing the product, and drying at 45 ℃ for 10 hours to obtain polysiloxane doped with modified silica nano particles.
0.5g of polysiloxane doped with modified silica nanoparticles and 1.5g of amino-modified polydimethylsiloxane were dissolved in 5g of xylene, respectively, at 25℃and mixed at 800rpm for 1 hour, and 50. Mu.L of xylene dissolved with polysiloxane doped with modified silica nanoparticles was dipped in using a nonwoven fabric and uniformly coated on a glass sheet at a rate of 3 m/s. And then dipping 50 mu L of dimethylbenzene dissolved with amino-modified polydimethylsiloxane by using non-woven fabrics, uniformly coating the dimethylbenzene on a glass sheet at the same speed, curing for 10min at 25 ℃, and then curing for 1h at 120 ℃ to obtain the high-transparency super-wear-resistant self-cleaning antibacterial coating. The water contact angle of the coating was measured by dynamic video contact angle, the light transmittance of the coating was measured at a wavelength range of 300-800nm using an ultraviolet-visible spectrophotometer, and the abrasion resistance of the coating was measured according to ASTM D4213-2008. The water contact angle of the prepared coating is 125 degrees, and the light transmittance after coating glass is 90.2 percent. The sterilization rates of the coating on escherichia coli and staphylococcus aureus are 97% and 95% respectively according to GB/T21866-2008.
Comparative example 1:
1g of silicon dioxide nano particles (10 nm) are dissolved in 30mL of ethanol water solution (the volume ratio of ethanol to water is 3:1) at 25 ℃, the pH value of a reaction system is adjusted to 10-11 by using ammonia monohydrate, after stirring for 1h under the condition that the rotating speed of a magnetic stirrer is 600rpm, 0.1g of gamma-glycidoxypropyl trimethoxysilane and 0.05g of hexadecyltrimethylsilane are added into the reaction system, stirring is carried out for 8h under the condition that the rotating speed of 600rpm is adopted, and centrifugal separation and washing are carried out on the product; drying at 45 ℃ for 10 hours to obtain the modified silica nano-particles.
0.0655g of modified silica nanoparticles was dissolved in 30mL of an aqueous solution of ethanol (volume ratio of ethanol to water: 3:1), to which 3.966g of phenyltrimethoxysilane, 2.404g of dimethyldimethoxysilane, 2.363g of gamma-glycidoxypropyl trimethoxysilane, 0.218g of N, N-dimethyldodecylaminopropyl trimethoxysilane ammonium chloride were added, and stirred at 600rpm for 1 hour, and the pH of the reaction system was adjusted to 10.5 using ammonia monohydrate. And (3) after reacting at 60 ℃ for 10 hours, centrifugally washing the product, and drying at 45 ℃ for 10 hours to obtain polysiloxane doped with modified silica nano particles.
0.5g of polysiloxane doped with modified silica nanoparticles and 1.5g of amino-modified polydimethylsiloxane were dissolved in 5g of xylene, respectively, at 25℃and mixed at 800rpm for 1 hour, and 50. Mu.L of xylene dissolved with polysiloxane doped with modified silica nanoparticles was dipped in using a nonwoven fabric and uniformly coated on a glass sheet at a rate of 3 m/s. And then dipping 50 mu L of dimethylbenzene dissolved with amino-modified polydimethylsiloxane by using non-woven fabrics, uniformly coating the dimethylbenzene on a glass sheet at the same speed, curing for 10min at 25 ℃, and then curing for 1h at 120 ℃ to obtain the high-transparency super-wear-resistant self-cleaning antibacterial coating. The water contact angle of the coating was measured by dynamic video contact angle, the light transmittance of the coating was measured at a wavelength range of 300-800nm using an ultraviolet-visible spectrophotometer, and the abrasion resistance of the coating was measured according to ASTM D4213-2008. The water contact angle of the prepared coating is 120 degrees, and the light transmittance after coating glass is 93.5 percent. The sterilization rates of the coating on escherichia coli and staphylococcus aureus are 93% and 92% respectively according to GB/T21866-2008.
Comparative example 2:
1g of silicon dioxide nano particles (30 nm) are dissolved in 30mL of ethanol water solution (the volume ratio of ethanol to water is 3:1) at 25 ℃, the pH value of a reaction system is adjusted to 10-11 by using ammonia monohydrate, after stirring for 1h under the condition that the rotating speed of a magnetic stirrer is 600rpm, 0.1g of gamma-glycidoxypropyl trimethoxysilane and 0.05g of hexadecyltrimethylsilane are added into the reaction system, stirring is carried out for 8h under the condition that the rotating speed of 600rpm is adopted, and centrifugal separation and washing are carried out on the product; drying at 45 ℃ for 10 hours to obtain the modified silica nano-particles.
0.0655g of modified silica nanoparticles was dissolved in 30mL of an aqueous solution of ethanol (volume ratio of ethanol to water: 3:1), to which 3.966g of phenyltrimethoxysilane, 2.404g of dimethyldimethoxysilane, 2.363g of gamma-glycidoxypropyl trimethoxysilane, 0.873g of N, N-dimethyldodecylaminopropyl trimethoxysilane ammonium chloride were added, and stirred at 600rpm for 1 hour, and the pH of the reaction system was adjusted to 10.5 using ammonia monohydrate. And (3) after reacting at 60 ℃ for 10 hours, centrifugally washing the product, and drying at 45 ℃ for 10 hours to obtain polysiloxane doped with modified silica nano particles.
0.5g of polysiloxane doped with modified silica nanoparticles and 1.5g of amino-modified polydimethylsiloxane were dissolved in 5g of xylene, respectively, at 25℃and mixed at 800rpm for 1 hour, and 50. Mu.L of xylene dissolved with polysiloxane doped with modified silica nanoparticles was dipped in using a nonwoven fabric and uniformly coated on a glass sheet at a rate of 3 m/s. And then dipping 50 mu L of dimethylbenzene dissolved with amino-modified polydimethylsiloxane by using non-woven fabrics, uniformly coating the dimethylbenzene on a glass sheet at the same speed, curing for 10min at 25 ℃, and then curing for 1h at 120 ℃ to obtain the high-transparency super-wear-resistant self-cleaning antibacterial coating. The water contact angle of the coating was measured by dynamic video contact angle, the light transmittance of the coating was measured at a wavelength range of 300-800nm using an ultraviolet-visible spectrophotometer, and the abrasion resistance of the coating was measured according to ASTM D4213-2008. The water contact angle of the prepared coating is 127 degrees, and the light transmittance after coating glass is 87.1 percent. The sterilization rates of the coating on escherichia coli and staphylococcus aureus are 97% and 95% respectively according to GB/T21866-2008.
Example 2:
2g of silicon dioxide nano particles (20 nm) are dissolved in 60mL of dimethyl sulfoxide solution of isopropanol (the volume ratio of the isopropanol to the dimethyl sulfoxide is 3:1) at 30 ℃, ammonia monohydrate is used for adjusting the pH value of a reaction system to 10-11, after stirring for 1h at the speed of a magnetic stirrer of 800rpm, 0.1g of gamma-glycidoxypropyl triethoxysilane and 0.05g of hexadecyl triethylsilane are added into the reaction system, stirring is carried out for 12h at the speed of 800rpm, and centrifugal separation and washing are carried out on the product; drying at 50 ℃ for 10 hours to obtain the modified silica nano-particles.
0.1310g of modified silica nanoparticles were dissolved in 60mL of a dimethyl sulfoxide solution of isopropyl alcohol (the volume ratio of isopropyl alcohol to dimethyl sulfoxide was 3:1), 3.966g of phenyltriethoxysilane, 2.404g of dimethyldiethoxysilane, 2.363g of gamma-glycidoxypropyl methyldiethoxysilane, 0.873g of N-allyldimethylamine were added thereto, and the mixture was stirred at 800rpm for 1 hour, and the pH of the reaction system was adjusted to 10.5 using ammonia monohydrate. And (3) after reacting for 15 hours at 60 ℃, centrifugally washing the product, and drying for 10 hours at 50 ℃ to obtain polysiloxane doped with modified silica nano particles.
1.0g of polysiloxane doped with modified silicon dioxide nano particles and 2.0g of epoxy modified polydimethylsiloxane are mixed and dissolved in 10g of tetrahydrofuran at 30 ℃, after being mixed for 1h at 1000rpm, 100 mu L of tetrahydrofuran dissolved with polysiloxane doped with modified silicon dioxide nano particles and epoxy modified polydimethylsiloxane are dipped in non-woven fabrics, uniformly coated on a glass sheet at a speed of 3m/s, cured for 10min at 45 ℃, and then cured for 1.5h at 150 ℃ to obtain the high-transparency super-wear-resistant self-cleaning antibacterial coating. The water contact angle of the coating was measured by dynamic video contact angle, the light transmittance of the coating was measured at a wavelength range of 300-800nm using an ultraviolet-visible spectrophotometer, and the abrasion resistance of the coating was measured according to ASTM D4213-2008. The water contact angle of the prepared coating is 140 degrees, and the light transmittance after coating glass is 83.4 percent. The sterilization rates of the coating on escherichia coli and staphylococcus aureus are 97% and 95% respectively according to GB/T21866-2008.
Example 3:
dissolving 0.5g of silica nano particles (20 nm) in 30mL of dimethyl sulfoxide solution of methanol (the volume ratio of the methanol to the dimethyl sulfoxide is 3:1) at 30 ℃, regulating the pH value of a reaction system to be 10-11 by using hydrazine hydrate, stirring for 1h under the condition that the rotating speed of a magnetic stirrer is 400rpm, adding 0.05g of gamma-glycidoxypropyl triethoxysilane and 0.025g of hexadecyl triethylsilane into the reaction system, stirring for 6h under the condition that the rotating speed of the magnetic stirrer is 400rpm, and centrifugally separating and washing a product; drying at 45 ℃ for 12 hours to obtain the modified silica nano-particles.
0.0655g of modified silica nanoparticles was dissolved in 30mL of a dimethyl sulfoxide solution of methanol (the volume ratio of methanol to dimethyl sulfoxide was 3:1), to which were added 3.966g of phenyltriethoxysilane, 2.404g of dimethyldiethoxysilane, 2.363g of gamma-glycidoxypropyl trimethoxysilane, 0.218g of 3-chloropropyl trioxysilane, and stirred at 600rpm for 1 hour, and the pH of the reaction system was adjusted to 10.5 using hydrazine hydrate. And (3) after reacting for 10 hours at 60 ℃, centrifugally washing the product, and drying for 12 hours at 45 ℃ to obtain polysiloxane doped with modified silica nano particles.
Mixing 0.5g of polysiloxane doped with modified silicon dioxide nano particles and 1.5g of isocyanato modified polydimethylsiloxane at 25 ℃ and dissolving in 10g of dichloromethane, mixing at 800rpm for 1h, dipping 100 mu L of dichloromethane dissolved with polysiloxane doped with modified silicon dioxide nano particles and isocyanato modified polydimethylsiloxane by using a non-woven fabric, uniformly coating the non-woven fabric on a glass sheet at a speed of 3m/s, curing at 25 ℃ for 10min, and then curing at 120 ℃ for 1.5h to obtain the high-transparency super-wear-resistant self-cleaning antibacterial coating. The water contact angle of the coating was measured by dynamic video contact angle, the light transmittance of the coating was measured at a wavelength range of 300-800nm using an ultraviolet-visible spectrophotometer, and the abrasion resistance of the coating was measured according to ASTM D4213-2008. The water contact angle of the prepared coating is 115 degrees, and the light transmittance after coating glass is 92.1 percent. The sterilization rates of the coating on escherichia coli and staphylococcus aureus are 93% and 91% respectively according to GB/T21866-2008.
Example 4:
1g of silver nano particles (20 nm) are dissolved in 30mL of aqueous solution of methanol (the volume ratio of the methanol to the water is 3:1) at 25 ℃, the pH value of a reaction system is adjusted to 10-11 by using hydrazine hydrate, after stirring for 1h under the condition that the rotating speed of a magnetic stirrer is 800rpm, 0.1g of gamma-glycidoxypropyl trimethoxysilane and 0.05g of hexadecyltrimethylsilane are added into the reaction system, stirring is carried out for 15h under the condition that the rotating speed of 800rpm is adopted, and centrifugal separation and washing are carried out on the product; drying at 50 ℃ for 14 hours to obtain the modified silver nano-particles.
0.0655g of modified silver nano particles are dissolved in 30mL of aqueous solution of methanol (the volume ratio of methanol to water is 3:1), 3.966g of phenyl trimethoxysilane, 2.404g of dimethyl dimethoxy silane, 2.363g of gamma-glycidoxypropyl trimethoxysilane and 0.437g of N, N-dimethyl dodecyl amino propyl trimethoxy silane ammonium chloride are added, and stirring is carried out for 1h under the condition of 800rpm, and the pH value of the reaction system is adjusted to 10.5 by using hydrazine hydrate. And (3) after reacting at 60 ℃ for 15 hours, centrifugally washing the product, and drying at 50 ℃ for 14 hours to obtain polysiloxane doped with modified silver nano particles.
After 0.5g of polysiloxane doped with modified silver nanoparticles and 1.5g of amino-modified polydimethylsiloxane were dissolved in 5g of tetrahydrofuran, respectively, at 30℃and mixed for 1 hour at 800rpm, 50. Mu.L of tetrahydrofuran dissolved with polysiloxane doped with modified silver nanoparticles was dipped with nonwoven fabric, and uniformly coated on a glass sheet at a speed of 3 m/s. And dipping 50 mu L of tetrahydrofuran dissolved with amino modified polydimethylsiloxane by using non-woven fabrics, uniformly coating the non-woven fabrics on a glass sheet at the same speed, curing for 10min at 45 ℃, and then curing for 1.5h at 150 ℃ to obtain the high-transparency super-wear-resistant self-cleaning antibacterial coating. The water contact angle of the coating was measured by dynamic video contact angle, the light transmittance of the coating was measured at a wavelength range of 300-800nm using an ultraviolet-visible spectrophotometer, and the abrasion resistance of the coating was measured according to ASTM D4213-2008. The water contact angle of the prepared coating is 123 degrees, and the light transmittance after coating glass is 89.2 percent. The sterilization rates of the coating on escherichia coli and staphylococcus aureus are 97% and 94% respectively according to GB/T21866-2008.
Example 5:
1g of ferroferric oxide nano particles (20 nm) are dissolved in 30mL of aqueous solution of butanediol (the volume ratio of butanediol to water is 3:1) at 30 ℃, ammonia monohydrate is used for adjusting the pH value of a reaction system to 10-11, after stirring for 1h at the speed of a magnetic stirrer of 800rpm, 0.1g of gamma-glycidoxypropyl trimethoxysilane and 0.05g of hexadecyltrimethylsilane are added into the reaction system, stirring is carried out for 12h at the speed of 800rpm, and centrifugal separation and washing are carried out on the product; and drying at 50 ℃ for 14 hours to obtain the modified ferroferric oxide nano-particles.
0.0655g of modified ferroferric oxide nano particles are dissolved in 30mL of aqueous solution of butanediol (the volume ratio of butanediol to water is 3:1), 3.966g of phenyl trimethoxysilane, 2.404g of dimethyl dimethoxy silane, 2.363g of gamma-glycidoxypropyl trimethoxysilane and 0.437g of N, N-dimethyl dodecyl amino propyl trimethoxy silane ammonium chloride are added into the mixture, the mixture is stirred for 1h at 800rpm, and the pH value of the reaction system is adjusted to 10.5 by using ammonia monohydrate. And (3) after reacting for 15 hours at 60 ℃, centrifugally washing the product, and drying for 14 hours at 50 ℃ to obtain polysiloxane doped with the modified ferroferric oxide nano particles.
After 0.5g of polysiloxane doped with modified ferroferric oxide nanoparticles and 1.5g of amino-modified polydimethylsiloxane were dissolved in 5g of tetrahydrofuran, respectively, at 30℃and mixed for 1 hour at 800rpm, 50. Mu.L of tetrahydrofuran dissolved with polysiloxane doped with modified ferroferric oxide nanoparticles was dipped in using nonwoven fabric, and uniformly coated on a glass sheet at a speed of 3 m/s. And then dipping 50 mu L of dimethylbenzene dissolved with amino-modified polydimethylsiloxane by using non-woven fabrics, uniformly coating the dimethylbenzene on a glass sheet at the same speed, curing for 10min at 45 ℃, and then curing for 1.5h at the temperature of 150 ℃ to obtain the high-transparency super-wear-resistant self-cleaning antibacterial coating. The water contact angle of the coating was measured by dynamic video contact angle, the light transmittance of the coating was measured at a wavelength range of 300-800nm using an ultraviolet-visible spectrophotometer, and the abrasion resistance of the coating was measured according to ASTM D4213-2008. The water contact angle of the prepared coating is 122 degrees, and the light transmittance after coating glass is 88.1 percent. The sterilization rates of the coating on escherichia coli and staphylococcus aureus are 96% and 94% respectively according to GB/T21866-2008.
TABLE 1
As shown in table 1, examples and comparative examples, the particle size, the amount and the kind of the inorganic nanoparticles are directly related to the contact angle and the transmittance of the coating, and in comparative example 1, the particle size of the inorganic nanoparticles is only 10nm, which greatly improves the transmittance of light, so that the transmittance is increased to 93.5%, but too small particle size reduces the roughness of the surface of the coating, affects the self-cleaning performance of the coating, and reduces the contact angle of the coating by only 120 °; in contrast, in comparative example 2, the particle diameter of the electrodeless nanoparticle was 30nm, and the transmittance was reduced to 87.1% although the contact angle of the coating layer was increased to 127 °; in example 2, the amount of electrodeless nanoparticles was doubled, so that the contact angle was greatly increased to 140 °, and the light transmittance was greatly reduced to 83.4%, which is inexpensiveness; in order to consider the self-cleaning and high transparency properties in combination, it is known that the particle size and the amount in example 1 are optimal; therefore, the particle size and the amount of the inorganic nanoparticles in example 1 were used in examples 4 and 5, and the types of the inorganic nanoparticles were changed, but it was apparent that the contact angle and the light transmittance were lower than those of example 1, and that the inorganic nanoparticles in example 1, namely, silica, were optimal.
As shown in fig. 1, a friction cycle test was performed for the coating of example 1: the sharp scissors and the coating form an angle of 45 degrees, and rapidly slide back and forth with force. Each hundred photographs were taken to record the appearance of the coating and to test the water contact angle. Fig. 1 shows SEM image comparison of the coating before and after 1500 scratches (left panel is the original coating, right panel is the coating after 1500 scratches);
Claims (10)
1. the preparation method of the high-transparency super-wear-resistant self-cleaning antibacterial coating is characterized by comprising the following steps of:
(1) Adding a certain amount of alcohol solvent, cosolvent, catalyst and inorganic nano particles into a container at a time at 25-40 ℃, wherein the concentration of the inorganic nano particles is controlled to be 1-1000 mg/mL, and the volume ratio of the alcohol solvent to the cosolvent is 0.1-10; after the reactants are uniformly mixed under the condition of the rotating speed of 50-1000 rpm, adding a silane modifier into a reaction system, wherein the mass dosage of the silane modifier is 0.5-40% of the total mass dosage of the inorganic nano particles; after reacting for 0.5-30 h, filtering, washing, and drying at 40-50 ℃ for 10-30 h to obtain modified inorganic nano particles;
(2) Adding a certain amount of alcohol solvent, cosolvent, modified inorganic nano-particles, silane coupling agent and antibacterial organic silicon monomer into a container at one time, wherein the mass dosage of the modified inorganic nano-particles is controlled to be 0.25-10% of the mass dosage of the whole system, and the volume ratio of the alcohol solvent to the cosolvent is 0.1-10; uniformly mixing the reactants at the rotating speed of 100 rpm-1000 rpm, adding a catalyst into the mixture, reacting for 10-30 hours at 60 ℃, filtering and washing, and drying for 10-30 hours at 40-50 ℃ to obtain polysiloxane grafted with inorganic nano particles;
(3) Respectively dissolving polysiloxane doped with inorganic nano particles and a leveling agent into an organic solvent at the temperature of 25-40 ℃ and the rotating speed of 100-1000 rpm, wherein the mass concentration of the polysiloxane is controlled to be 5-30 wt% of the total system, and the total system comprises the polysiloxane doped with the inorganic nano particles, the leveling agent and the organic solvent; the mass concentration of the leveling agent is 10-20wt%, and after the polysiloxane doped with inorganic nano particles and the leveling agent are completely dissolved, the high-transparency wear-resistant self-cleaning antibacterial coating is obtained;
(4) The high-transparency wear-resistant self-cleaning antibacterial coating is coated on a substrate in a stepwise manner, cured for 10min in a fume hood at 20-80 ℃, and cured for 1-2 h at a high temperature of 100-200 ℃, and the high-transparency wear-resistant self-cleaning antibacterial coating can be successfully attached on the substrate to form the high-transparency wear-resistant self-cleaning antibacterial coating.
2. The preparation method of the high-transparency super-wear-resistant self-cleaning antibacterial coating is characterized by comprising the following steps of:
(1) Adding a certain amount of alcohol solvent, cosolvent, catalyst and inorganic nano particles into a container at a time at 25-40 ℃, wherein the concentration of the inorganic nano particles is controlled to be 1-1000 mg/mL, and the volume ratio of the alcohol solvent to the cosolvent is 0.1-10; after the reactants are uniformly mixed under the condition of the rotating speed of 50-1000 rpm, adding a silane modifier into a reaction system, wherein the mass dosage of the silane modifier is 0.5-40% of the total mass dosage of the inorganic nano particles; after reacting for 0.5-30 h, filtering, washing, and drying at 40-50 ℃ for 10-30 h to obtain modified inorganic nano particles;
(2) Adding a certain amount of alcohol solvent, cosolvent, modified inorganic nano-particles, silane coupling agent and antibacterial organic silicon monomer into a container at one time, wherein the mass dosage of the modified inorganic nano-particles is controlled to be 0.25-10% of the mass dosage of the whole system, and the volume ratio of the alcohol solvent to the cosolvent is 0.1-10; uniformly mixing the reactants at the rotating speed of 100 rpm-1000 rpm, adding a catalyst into the mixture, reacting for 10-30 hours at 60 ℃, filtering and washing, and drying for 10-30 hours at 40-50 ℃ to obtain polysiloxane grafted with inorganic nano particles;
(3) Mixing polysiloxane doped with inorganic nano particles and a leveling agent at the temperature of between 25 and 40 ℃ and the rotating speed of between 100 and 1000rpm, and then dissolving the mixture in an organic solvent, wherein the concentration of the polysiloxane is controlled to be 5 to 30 weight percent of the total system, and the mass concentration of the leveling agent is controlled to be 10 to 20 weight percent, and obtaining the high-transparency wear-resistant self-cleaning antibacterial coating after the polysiloxane doped with the inorganic nano particles and the leveling agent are completely dissolved;
(4) The high-transparency wear-resistant self-cleaning antibacterial coating is rubbed on a substrate by a one-step method, is cured for 10min in a fume hood at 20-80 ℃ and is cured for 1-2 h at a high temperature of 100-200 ℃, and the high-transparency wear-resistant self-cleaning antibacterial coating can be successfully attached on the substrate to form the high-transparency wear-resistant self-cleaning antibacterial coating.
3. The method for preparing the high-transparency super-wear-resistant self-cleaning antibacterial coating as claimed in claim 1 or 2, which is characterized in that: in the step (1), the silane modifier is gamma-glycidoxypropyl trimethoxy silane, gamma-glycidoxypropyl triethoxy silane, gamma-glycidoxypropyl methyl diethoxy silane, hexadecyl trimethoxy silane or hexadecyl triethoxy silane.
4. The method for preparing the high-transparency super-wear-resistant self-cleaning antibacterial coating as claimed in claim 1 or 2, which is characterized in that: the dosage of the antibacterial organic silicon monomer in the step (2) is 0.2-10wt% of the mass of the silane coupling agent.
5. The method for preparing the high-transparency super-wear-resistant self-cleaning antibacterial coating as claimed in claim 1 or 2, which is characterized in that: in step (2), the polysiloxane refers to a polymer in which the main chain is composed of repeating unit silicon-oxygen (Si-O) bonds, wherein an organic group is attached to a silicon atom.
6. The method for preparing the high-transparency super-wear-resistant self-cleaning antibacterial coating as claimed in claim 1 or 2, which is characterized in that: the polysiloxane in the step (2) refers to a polymer in which the main chain is composed of repeating unit silicon-oxygen (Si-O) bonds, and an organic group is attached to a silicon atom; the leveling agent in the step (3) is amino modified polydimethylsiloxane, carboxyl modified polydimethylsiloxane, epoxy modified polydimethylsiloxane, isocyanate modified polydimethylsiloxane and mercapto modified polydimethylsiloxane, and the organic solvent in the step (3) is one or more of methanol, ethanol, ethyl acetate, acetone, n-hexadecane, cyclohexane, tetrahydrofuran, dichloromethane, carbon tetrachloride, benzene, toluene and xylene.
7. The method for preparing the high-transparency super-wear-resistant self-cleaning antibacterial coating, as claimed in claim 1, is characterized in that: in the step (3), the respectively dissolving in the organic solvent means two modes of preparing the light-transmitting high-transparency wear-resistant self-cleaning coating, taking a certain amount of polysiloxane doped with inorganic nano particles and a leveling agent at the temperature of 25-40 ℃, and respectively dissolving the polysiloxane and the leveling agent in the organic solvent with the same volume.
8. The method for preparing the high-transparency super-wear-resistant self-cleaning antibacterial coating, as claimed in claim 2, is characterized in that: in the step (3), the mixed solution in the organic solvent means two ways of preparing the light-transmitting high-transparency wear-resistant self-cleaning paint: taking a certain amount of polysiloxane doped with inorganic nano particles and a leveling agent at the temperature of 25-40 ℃, and mixing and dissolving the polysiloxane and the leveling agent in an organic solvent with certain mass.
9. The method for preparing the high-transparency super-wear-resistant self-cleaning antibacterial coating, as claimed in claim 1, is characterized in that: the step-by-step wiping means: a certain amount of organic solvent dissolved with polysiloxane doped with inorganic nano particles is taken and rubbed on a substrate, and then a certain amount of organic solvent dissolved with flatting agent is taken and rubbed on the substrate.
10. The method for preparing the high-transparency super-wear-resistant self-cleaning antibacterial coating, as claimed in claim 2, is characterized in that: the one-step wiping means: and taking a certain amount of organic solvent dissolved with polysiloxane doped with inorganic nano particles and a leveling agent, and wiping the organic solvent on a substrate.
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