CN113736292A - Inorganic nano long-acting antifogging self-cleaning coating and preparation method and application thereof - Google Patents
Inorganic nano long-acting antifogging self-cleaning coating and preparation method and application thereof Download PDFInfo
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- CN113736292A CN113736292A CN202111062750.8A CN202111062750A CN113736292A CN 113736292 A CN113736292 A CN 113736292A CN 202111062750 A CN202111062750 A CN 202111062750A CN 113736292 A CN113736292 A CN 113736292A
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- 238000000576 coating method Methods 0.000 title claims abstract description 138
- 239000011248 coating agent Substances 0.000 title claims abstract description 133
- 238000004140 cleaning Methods 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 81
- -1 modified magnesium-aluminum compound Chemical class 0.000 claims abstract description 34
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 15
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 150000007524 organic acids Chemical class 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 229910000077 silane Inorganic materials 0.000 claims abstract description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 44
- 238000003756 stirring Methods 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 10
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 9
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 9
- 238000010526 radical polymerization reaction Methods 0.000 claims description 9
- 238000005507 spraying Methods 0.000 claims description 9
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 8
- 229920000570 polyether Polymers 0.000 claims description 8
- 238000009736 wetting Methods 0.000 claims description 8
- DUYKOAQJUCADEC-UHFFFAOYSA-N [SiH4].N1=NN=CC=C1 Chemical compound [SiH4].N1=NN=CC=C1 DUYKOAQJUCADEC-UHFFFAOYSA-N 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 239000004111 Potassium silicate Substances 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052912 lithium silicate Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical group [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 4
- 235000019353 potassium silicate Nutrition 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- 230000001680 brushing effect Effects 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 150000004760 silicates Chemical class 0.000 claims description 2
- 239000000344 soap Substances 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 3
- AZXHPAFVHQFRFN-UHFFFAOYSA-N O.[Mg].[AlH3] Chemical compound O.[Mg].[AlH3] AZXHPAFVHQFRFN-UHFFFAOYSA-N 0.000 claims 1
- 229910020489 SiO3 Inorganic materials 0.000 claims 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims 1
- 239000000391 magnesium silicate Substances 0.000 claims 1
- 229910052919 magnesium silicate Inorganic materials 0.000 claims 1
- 235000019792 magnesium silicate Nutrition 0.000 claims 1
- WAWKNSMGOFSHHT-UHFFFAOYSA-N morpholine silane Chemical compound [SiH4].N1CCOCC1 WAWKNSMGOFSHHT-UHFFFAOYSA-N 0.000 claims 1
- 239000002086 nanomaterial Substances 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 7
- 238000004132 cross linking Methods 0.000 abstract description 4
- 210000003298 dental enamel Anatomy 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000011521 glass Substances 0.000 description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- PSNPEOOEWZZFPJ-UHFFFAOYSA-N alumane;yttrium Chemical compound [AlH3].[Y] PSNPEOOEWZZFPJ-UHFFFAOYSA-N 0.000 description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- 235000009781 Myrtillocactus geometrizans Nutrition 0.000 description 6
- 240000009125 Myrtillocactus geometrizans Species 0.000 description 6
- IDONJQWIJAPFEQ-UHFFFAOYSA-N [SiH4].S1SCC=C1.N1=CN=CN=C1 Chemical compound [SiH4].S1SCC=C1.N1=CN=CN=C1 IDONJQWIJAPFEQ-UHFFFAOYSA-N 0.000 description 6
- 239000001273 butane Substances 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 230000002209 hydrophobic effect Effects 0.000 description 6
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 210000001595 mastoid Anatomy 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 3
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006184 cosolvent Substances 0.000 description 2
- 239000000416 hydrocolloid Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical class CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- QDQXIBQGXNTLDB-UHFFFAOYSA-N [3-[bis(2-hydroxyethyl)amino]-2-hydroxypropyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)CN(CCO)CCO QDQXIBQGXNTLDB-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- XFBXDGLHUSUNMG-UHFFFAOYSA-N alumane;hydrate Chemical compound O.[AlH3] XFBXDGLHUSUNMG-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002186 photoactivation Effects 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
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- 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
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- 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
- C09D7/20—Diluents or solvents
-
- 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
-
- 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
- C09D7/63—Additives non-macromolecular organic
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides an inorganic nano long-acting antifogging self-cleaning coating and a preparation method and application thereof. The silicate modified by special silane has excellent film-forming property and stronger hydrophilic property; the composite organic acid metal salt of rare earth metal and aluminum has the advantages that silicate crosslinking film forming is promoted, the crosslinking density and the water resistance and chemical resistance of the coating are improved, meanwhile, the rare earth metal and the aluminum are inserted and embedded in the thin coating to form a firm feather-shaped and complex micro-nano structure, and a super-hydrophilic condition is formed; the polyhydroxy multi-hydrogen bond modified magnesium-aluminum compound is introduced to be bonded with silicate to form a firm hydrophilic group, and a super-hydrophilic interface is formed by matching with the physical structure of the ultrathin coating, so that liquid is quickly wetted and spread on the interface, and the magnesium-aluminum compound has the self-cleaning capability when meeting water. According to the invention, through the mutual matching of the raw materials, the coating forms an enamel surface with a long-acting wear-resistant super-hydrophilic inorganic micro-nano structure, the hardness of which is 9H and the hydrophilic angle of which is less than 5 degrees.
Description
Technical Field
The invention relates to the technical field of coating preparation, in particular to an inorganic nano long-acting antifogging self-cleaning coating and a preparation method and application thereof.
Background
Under daily environment, various material surfaces repel water to different degrees, and the water cannot form a uniform and continuous water film on the surfaces, so that the material surfaces need to be subjected to super-hydrophilic treatment. The super-hydrophilic treatment is further classified into inorganic coating treatment, organic coating treatment and organic-inorganic composite coating treatment. The super-hydrophilic surface with a water contact angle of less than 5 degrees is obtained by processing the surface of the material through the endowed coating, and the forming action mechanism of the super-hydrophilic surface is different. The method comprises the steps of forming photoactivation super-hydrophilicity by utilizing a photocatalytic substance, forming a low-surface-energy super-hydrophilicity water film by utilizing the slow release of a surfactant and the water fusion of an attachment surface, and forming a super-hydrophilicity surface by modifying a surface bonding hydrophilic group and a micro-nano mastoid structure. Although various super-hydrophilic coatings are applied to various industrial or commercial fields, mainly relating to the aspects of antifogging, self-cleaning antifouling, biological medicine and the like, most of the super-hydrophilic coatings have short service life and high cost, various defects of the super-hydrophilic coatings are not completely solved, and the super-hydrophilic coatings with high comprehensive performance are not produced and applied on a large scale like other characteristic coatings, so that the research on a super-hydrophilic coating with high comprehensive performance is very urgent at present.
The Chinese patent with the publication number of CN 109135487A discloses a composition and a preparation method of an organic silicon modified acrylic resin super-hydrophilic low-temperature antifogging coating containing quaternary ammonium sulfonate. The method is characterized in that gamma-methacryloxypropyltrimethoxysilane is used for modifying acrylic acid to obtain organic silicon modified acrylic resin, and then a surfactant 2-acrylamide-2-methylpropanesulfonic Acid (AMPS) and quaternary ammonium sulfonate salt of 3- (bis (2-hydroxyethyl) amino) -2-hydroxypropyl methacrylate (D-GMA) are compounded to prepare the organic super-hydrophilic coating. The organosilicon modified acrylic resin film-forming material obtained by silane modification has good water resistance and chemical resistance, particularly has excellent adhesive force performance for PC base materials, and can be combined with water to form a low-surface-energy aqueous solution due to the slow release of a surfactant on the surface, so that water is quickly wetted and spread on the surface of a coating to form a uniform and continuous water film, and an antifogging effect is achieved. However, the surfactant is carried away by water or detergent to cause loss, the hydrophilic effect is weakened, the hydrophilic effect is restored to the hydrophobic state until the surfactant is completely consumed, and generally the initial antifogging effect of the coating is better, but the timeliness is extremely short.
The Chinese patent publication No. CN 102241939A discloses a preparation method of an organic-inorganic hybrid super-hydrophilic coating. The method comprises the steps of firstly adopting a sol-gel method, carrying out hydrolytic polycondensation on silane coupling agent and ethyl orthosilicate to obtain modified silica sol, and then carrying out free radical polymerization on the modified silica sol and reactive hydrophilic monomer to obtain the organic-inorganic hybrid super-hydrophilic coating. The surface of the coating not only has a large number of hydrophilic groups, but also has high surface roughness formed by a large number of silicon dioxide particle clusters, and a super-hydrophilic surface is easy to form. However, the organic chain segment is introduced in a large amount, the weather resistance of the coating is poor, the hydrophilic group is easy to break, the hardness of the coating is not high enough, the rough micro-nano structure is easy to wear, and the hydrophobic state is easy to recover.
The chinese patent publication No. CN 1687249a discloses a method for preparing a super-hydrophilic coating. The method utilizes proper temperature and ultraviolet irradiation to firmly form a film of titanium dioxide hydrocolloid coated on the surface of a base material, and then the titanium dioxide hydrocolloid is dried at proper temperature and irradiated by ultraviolet light to ensure that the coating has the photo-activated super-hydrophilic property. After being irradiated by ultraviolet light, the titanium dioxide generates strong and stable super-hydrophilic characteristics. Active oxygen free radicals are generated on the photocatalytic surface and can react to generate oxygen radical cavities, water is easily adsorbed in the oxygen radical cavities to become chemically adsorbed water, and a micro-nano mastoid structure on the surface of titanium dioxide exists to form a super-hydrophilic surface. However, the hydroxyl group and the oxy-hole on titanium dioxide are unstable, and when no ultraviolet light source is irradiated, the hydroxyl group in the oxy-hole is rapidly replaced by oxygen in the air, and the hydrophobic state is restored.
In conclusion, the existing antifogging coating has the following defects:
(1) the most commonly used antifogging coating at present adopts the surfactant for slow release to achieve the purpose of super-hydrophilicity, the hydrophilic effect is quickly weakened due to the loss of the surfactant, the coating returns to a hydrophobic state, and the aging is short;
(2) adding a photocatalytic substance into the coating, achieving the purpose of super-hydrophilicity through photoinactivation, easily returning to a hydrophobic state when illumination is stopped or heavy oil stains are dried on the surface, and having different aging periods;
(3) the micro-nano structure is manufactured on the surface of the coating, the surface is modified by using the hydrophilic material to achieve the purpose of super-hydrophilicity, the micro-nano structure is not firm and is easy to wear, and the surface can be restored to a hydrophobic state due to aging loss of the hydrophilic modification material, so that rapid failure is caused.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide an inorganic nano long-acting antifogging self-cleaning coating, a preparation method and application thereof.
The purpose of the invention is realized by the following scheme:
the first aspect of the invention provides a preparation method of an inorganic nano long-acting anti-fog self-cleaning coating, which comprises the following steps:
step one, 0.1-15 parts by mass of polyhydroxy multi-hydrogen bond modified magnesium aluminum compound is fully dissolved in 11-50 parts by mass of deionized water, and the mixture is stirred at 50-90 ℃ and kept warm for 2-5h to obtain a hydrate with high viscosity; adding 5-56 parts of special silane modified silicate into a high-viscosity hydrate, controlling the pH to be 11-13 by taking organic amine AMP-95 or DMAE as a pH regulator under the stirring conditions of 1500-3000r/min at the temperature of 60-120 ℃, and reacting for 2-4h to obtain a reactive hydrophilic monomer;
adding 9-55 parts by mass of the reactive hydrophilic monomer obtained in the step one, 2-32 parts by mass of ethyl silicate and 0.01-2 parts by mass of triazine silane into 11-32 parts by mass of deionized water, and carrying out free radical polymerization at the temperature of 50-90 ℃ for 1-6 hours to prepare a polyhydroxy multi-hydrogen bond hydrophilic inorganic film-forming material; the polyhydroxy multi-hydrogen bond hydrophilic inorganic film-forming material contains-OH, -H and-NH2、-SO3A silicon-bonded monomer of an H hydrophilic group;
thirdly, taking 13-70 parts by mass of the inorganic film forming material obtained in the second step, adding 9-55 parts by mass of water, stirring at a high speed at the water bath temperature of 75-90 ℃, slowly dropwise adding 2-16 parts by mass of the composite organic acid metal salt of rare earth metal and aluminum, and after dropwise adding, keeping the temperature for 0.5-3 h to evaporate ethanol contained in the composite organic acid metal salt of rare earth metal and aluminum so as to stably store the subsequent coating;
and step four, standing and cooling the material prepared in the step three by 10 to 80 parts by mass to normal temperature, then stirring at high speed at normal temperature, and adding 0.1 to 9 parts of ethylene glycol monobutyl ether and 0.1 to 3 parts of polyether modified siloxane wetting and leveling agent to prepare the aqueous inorganic nano long-acting antifogging self-cleaning coating.
Preferably, in the first step, the magnesium aluminum silicate compound is SiO-containing3、-OH、-H、-NH2Magnesium aluminium hydrate of at least one of the bonds, e.g. magnesium aluminium silicate compound may be MgAl2SiO6·3H2O。
Preferably, the silane modified silicate is potassium silicate, sodium silicate or lithium silicate, and the silane is a tape
—OC2H5The silane of (1). For example, the silane is N-morpholine methyl triethoxysilane, and the silane-modified silicate is prepared by the following method: slowly dripping 0.1-15 parts of N-morpholine methyl triethoxysilane into 10-60 parts of potassium silicate, sodium silicate or lithium silicate solution under the condition of stirring, dripping 0.01-0.5 part of formic acid to promote the hydrolysis of the N-morpholine methyl triethoxysilane after dripping is finished, and further reacting with the potassium silicate, the sodium silicate or the lithium silicate to prepare morpholine silane modified silicate.
Preferably, the structural formula of the triazine silane is as follows:
Preferably, the rare earth metal in the composite organic acid metal salt of the rare earth metal and aluminum is yttrium, cerium, cobalt or manganese.
Preferably, the complex organic acid metal salt is selected from oxides, salts and organic acid soaps of metals of cobalt, manganese and aluminum.
The second aspect of the invention provides an inorganic nano long-acting anti-fog self-cleaning coating, which is prepared by the preparation method of the inorganic nano long-acting anti-fog self-cleaning coating.
The third aspect of the invention provides an application of an inorganic nano long-acting antifogging self-cleaning coating, wherein the application is that the inorganic nano long-acting antifogging self-cleaning coating is used for preparing an inorganic nano super-hydrophilic coating on the surface of an inorganic substrate, and the preparation method comprises the following steps: carrying out surface pretreatment on an inorganic substrate; and (3) coating the water-based inorganic nano super-hydrophilic coating on the pretreated inorganic substrate by adopting a spraying, dipping or brushing method, wherein the thickness of a wet film of the coating is 8-55 mu m, and baking for 3-20 min at the temperature of 120-280 ℃ to obtain the high-hardness inorganic nano super-hydrophilic thin coating.
Preferably, the adhesion force of the inorganic nano super-hydrophilic coating to an inorganic substrate is 0 grade, the hardness is greater than 9H, and the contact angle of the inorganic nano super-hydrophilic coating to water is less than 5 degrees. The water droplets quickly wet out and spread at the coating interface and form a uniform water film within 3 seconds. And (3) painting handwriting on the coating interface by using an oil marking pen, and automatically floating the font after dropping water, or erasing the font by lightly wiping the font by using a wet cloth.
Preferably, the inorganic substrate is a substrate of glass, metal, or the like. The pretreatment method of the inorganic substrate comprises ultrasonic cleaning, surface flame or plasma treatment
In the preparation process, firstly, polyhydroxy poly-hydrogen bond modified magnesium-aluminum compound and special silane modified silicate are adopted to graft hydroxyl and hydrogen bond onto the silicate through the bridge of the special silane at a specific temperature and a specific pH value, so that the silicate has more bonded hydrophilic groups. Then, the triazine silane is used for grafting the ethyl silicate hydrolysate in the deionized water to the bonded hydrophilic group silicate through hydroxyl polymerization, so that the bonded hydrophilic group silicate has a silicate compound with a three-dimensional structure of polyhydroxy multiple hydrogen bonds, and hydrophilic groups exist more firmly. Finally, the inorganic nano super-hydrophilic coating is compounded by matching with the composite organic acid metal salt of rare earth metal and aluminum and the cosolvent. Coating the mixture on a pretreated substrate by adopting a spraying, dipping or brushing method at a specified temperature and timeBaking and curing to form a compact firm film with excellent water resistance and chemical resistance. The surface of the coating not only has a large number of hydrophilic groups-OH, -H, -NH2or-SO3H, the composite organic acid metal salt of the rare earth metal and the aluminum can promote the silicate to be crosslinked and formed into a film so as to improve the water resistance and the chemical resistance, and the introduced rare earth metal and the introduced aluminum are inserted and embedded in the coating to form a microcosmic hard rough micro-nano mastoid structure and a firmer feather-shaped structure, which are the main reasons for forming the long-acting wear-resistant super-hydrophilic effect.
Compared with the prior art, the invention has the following beneficial effects:
1. the inorganic nano long-acting antifogging self-cleaning coating has excellent film-forming property and stronger hydrophilic property through morpholine silane modified silicate.
2. In the inorganic nano long-acting antifogging self-cleaning coating, the composite organic acid metal salt of rare earth metal and aluminum has the advantages of promoting silicate crosslinking film formation, improving the crosslinking density and the water resistance and chemical resistance of the coating, and simultaneously, the rare earth metal and the aluminum are inserted and embedded in the thin coating to form a firm pinnate and complex micro-nano structure to form a super-hydrophilic condition.
3. In the inorganic nano long-acting antifogging self-cleaning coating, the magnesium aluminum silicate compound is introduced and bonded with silicate to form a firm hydrophilic group, and a super-hydrophilic interface is formed by matching with the physical structure of the ultrathin coating, so that liquid is quickly wetted and spread on the interface, and the inorganic nano long-acting antifogging self-cleaning coating has the capability of self-cleaning when meeting water.
4. In the inorganic nano long-acting antifogging self-cleaning coating, water is used as a solvent, and ethylene glycol monobutyl ether is used as a cosolvent, so that the compatibility of various materials is improved, and the leveling is facilitated.
5. According to the invention, through the mutual matching of the raw materials, the coating forms a long-acting wear-resistant super-hydrophilic inorganic micro-nano structure enamel surface with the hardness of 9H and the hydrophilic angle of less than 5 degrees on the surface of an inorganic substrate.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be obvious to those skilled in the art that various changes and modifications can be made without departing from the spirit of the invention. All falling within the scope of the present invention.
The hydrophilicity test, coating hardness, and substrate adhesion test methods are as follows:
the super-hydrophilic coating was measured by dropping water on the surface of the coating using a contact angle measuring instrument model OCA-40 from Dataphysics, germany, and the contact angle with water was measured and the water drop spread rapidly on the surface of the coating. Using a pencil hardness tester, the coated surface was scratched 3 times with a 9H Mitsubishi pencil from Japan under a force of 1kg without damaging the coated surface. 35 square grids of 1 mm by 1 mm were scribed on the coating surface using a scriber. A250-type scotch tape produced by American 3M company is flatly adhered on a square grid without leaving a wire gap, and then the scotch tape is lifted at the fastest speed of 60 degrees, no coating is peeled off at the edge of a scratch, and the adhesion with a base material is evaluated as 0 grade.
Example 1
A preparation method of an inorganic nano long-acting antifogging self-cleaning coating comprises the following steps:
(1) 0.5g of magnesium aluminum silicate compound MgAl2SiO6·3H2Fully dissolving O in 100g of deionized water, stirring and preserving heat for 2 hours at 60 ℃ to obtain a hydrate with high viscosity; adding 35g of morpholine silane modified lithium silicate into a high-viscosity hydrate, controlling the pH to be 12 by taking organic amine AMP-95 as a pH regulator under the stirring conditions of 1500r/min and 80 ℃, and reacting for 2h to obtain a reactive hydrophilic monomer;
(2) and (2) adding the product obtained in the step (1), 12g of ethyl silicate and 2.82g of s-triazine dithiol silane into 46.36g of deionized water, and carrying out free radical polymerization reaction for 3 hours at the temperature of 80 ℃ to prepare the polyhydroxy multi-hydrogen bond hydrophilic silicate film-forming material.
(3) Adding the silicate film-forming material obtained in the step (2) and 8.6g of yttrium aluminum acetylacetonate trihydrate compound into 32.72g of water, and preserving the heat for 1.5 hours at the water bath temperature of 80 ℃ to evaporate ethanol contained in the yttrium aluminum acetylacetonate trihydrate compound so as to stably store the subsequent coating;
(4) and (3) standing and cooling the material prepared in the step (3) to normal temperature, and then adding 5.21g of ethylene glycol monobutyl ether and 0.6g of polyether modified siloxane wetting and leveling agent to prepare the aqueous inorganic nano long-acting antifogging self-cleaning coating.
(5) And (3) sequentially carrying out surface pretreatment on the sample glass by using acetone and distilled water, and airing. And adjusting the flame to be blue flame by using a butane flame gun, and quickly scanning the glass surface of the sample wafer once. Spraying the water-based inorganic nano super-hydrophilic coating on a glass sample by adopting a two-fluid spray gun with the caliber of 0.4, wherein the thickness of a wet film of the coating is about 5 mu m, and drying for 20min at the temperature of 230 ℃ to obtain a high-hardness inorganic nano super-hydrophilic thin coating.
(6) The super-hydrophilic coating was tested using a contact angle tester model OCA-40 from Dataphysics, germany, and the contact angle with water was found to be 6 °. The pencil hardness of the coating is 9H, and the adhesion with the base material is 0 grade.
Example 2
(1) 0.5g of magnesium aluminum silicate compound MgAl2SiO6·3H2Fully dissolving O in 100g of deionized water, stirring and preserving heat for 2 hours at 60 ℃ to obtain a hydrate with high viscosity; adding 42g of morpholine silane modified lithium silicate into a high-viscosity hydrate, controlling the pH to be 12 by taking organic amine AMP-95 as a pH regulator under the stirring conditions of 80 ℃ and 1200r/min, and reacting for 2h to obtain a reactive hydrophilic monomer;
(2) and (2) adding the product obtained in the step (1), 10g of ethyl silicate and 2.82g of s-triazine dithiol silane into 52.81g of deionized water, and carrying out free radical polymerization reaction for 3.5h at the temperature of 75 ℃ to prepare the polyhydroxy-multiple hydrogen bond hydrophilic silicate film-forming material.
(3) Adding the silicate film-forming material obtained in the step (2) and 8.6g of yttrium aluminum acetylacetonate trihydrate compound into 28.57g of water, and preserving the heat for 1.5h at the water bath temperature of 80 ℃ to evaporate ethanol contained in the yttrium aluminum acetylacetonate trihydrate compound so as to stably store a subsequent coating;
(4) and (3) standing and cooling the material prepared in the step (3) to normal temperature, and then adding 5.21g of ethylene glycol monobutyl ether and 0.6g of polyether modified siloxane wetting and leveling agent to prepare the aqueous inorganic nano long-acting antifogging self-cleaning coating.
(5) And (3) sequentially carrying out surface pretreatment on the sample glass by using acetone and distilled water, and airing. And adjusting the flame to be blue flame by using a butane flame gun, and quickly scanning the glass surface of the sample wafer once. Spraying the water-based inorganic nano super-hydrophilic coating on a glass sample by adopting a two-fluid spray gun with the caliber of 0.4, wherein the thickness of a wet film of the coating is about 5 mu m, and drying for 30min at the temperature of 250 ℃ to obtain a high-hardness inorganic nano super-hydrophilic thin coating.
(6) The super-hydrophilic coating is tested by adopting an OCA-40 type contact angle tester of Germany Datophysics company, and the contact angle of the super-hydrophilic coating with water is 2 degrees, the pencil hardness of the coating is 9H, and the adhesion force with a base material is 0 grade.
Example 3
(1) 0.6g of magnesium aluminum silicate compound MgAl2SiO6·3H2Fully dissolving O in 100g of deionized water, stirring and preserving heat for 2 hours at 60 ℃ to obtain a hydrate with high viscosity; adding 47g of morpholine silane modified lithium silicate into a high-viscosity hydrate, controlling the pH to be 11 by taking organic amine AMP-95 as a pH regulator under the stirring conditions of 1500r/min and 80 ℃, and reacting for 3 hours to obtain a reactive hydrophilic monomer;
(2) adding the product obtained in the step (1), 15g of ethyl silicate and 3.16g of s-triazine dithiol silane into 55.62g of deionized water, and carrying out free radical polymerization reaction for 3 hours at the temperature of 80 ℃ to prepare the polyhydroxy-multiple hydrogen bond hydrophilic silicate film-forming material.
(3) Adding the silicate film-forming material obtained in the step (2) and 12g of yttrium aluminum acetylacetonate trihydrate compound into 33.11g of water, and preserving the heat for 1.5 hours at the water bath temperature of 80 ℃ to evaporate ethanol contained in the yttrium aluminum acetylacetonate trihydrate compound so as to stably store the subsequent coating;
(4) and (4) standing and cooling the material prepared in the step (3) to normal temperature, and then adding 6.2g of ethylene glycol monobutyl ether and 0.8g of polyether modified siloxane wetting and leveling agent to prepare the aqueous inorganic nano long-acting antifogging self-cleaning coating.
(5) And (3) sequentially carrying out surface pretreatment on the sample glass by using acetone and distilled water, and airing. And adjusting the flame to be blue flame by using a butane flame gun, and quickly scanning the glass surface of the sample wafer once. Spraying the water-based inorganic nano super-hydrophilic coating on a glass sample by adopting a two-fluid spray gun with the caliber of 0.4, wherein the thickness of a wet film of the coating is about 5 mu m, and drying for 30min at the temperature of 230 ℃ to obtain a high-hardness inorganic nano super-hydrophilic thin coating.
(6) The super-hydrophilic coating is tested by adopting an OCA-40 type contact angle tester of Germany Datophysics company, and the contact angle of the super-hydrophilic coating with water is 5 degrees, the pencil hardness of the coating is 9H, and the adhesion force with a base material is 0 grade.
Example 4
(1) 0.5g of magnesium aluminum silicate compound MgAl2SiO6·3H2Fully dissolving O in 120g of deionized water, stirring and preserving heat for 2 hours at the temperature of 60 ℃ to obtain a hydrate with high viscosity; adding 42g of morpholine silane modified lithium silicate into a high-viscosity hydrate, controlling the pH to be 12 by taking organic amine AMP-95 as a pH regulator under the stirring conditions of 1500r/min and 80 ℃, and reacting for 2h to obtain a reactive hydrophilic monomer;
(2) adding the product obtained in the step (1), 15g of ethyl silicate and 2.82g of s-triazine dithiol silane into 56.47g of deionized water, and carrying out free radical polymerization reaction for 3h at the temperature of 80 ℃ to prepare the polyhydroxy-multiple hydrogen bond hydrophilic silicate film-forming material.
(3) Adding the silicate film-forming material obtained in the step (2) and 12g of yttrium aluminum acetylacetonate trihydrate compound into 33.11g of water, and preserving the heat for 1.5 hours at the water bath temperature of 80 ℃ to evaporate ethanol contained in the yttrium aluminum acetylacetonate trihydrate compound so as to stably store the subsequent coating;
(4) and (3) standing and cooling the material prepared in the step (3) to normal temperature, and then adding 5.21g of ethylene glycol monobutyl ether and 0.6g of polyether modified siloxane wetting and leveling agent to prepare the aqueous inorganic nano long-acting antifogging self-cleaning coating.
(5) And (3) sequentially carrying out surface pretreatment on the sample glass by using acetone and distilled water, and airing. And adjusting the flame to be blue flame by using a butane flame gun, and quickly scanning the glass surface of the sample wafer once. Spraying the water-based inorganic nano super-hydrophilic coating on a glass sample by adopting a two-fluid spray gun with the caliber of 0.4, wherein the thickness of a wet film of the coating is about 5 mu m, and drying for 30min at the temperature of 250 ℃ to obtain a high-hardness inorganic nano super-hydrophilic thin coating.
(6) The super-hydrophilic coating is tested by adopting an OCA-40 type contact angle tester of Germany Datophysics company, and the contact angle of the super-hydrophilic coating with water is 5 degrees, the pencil hardness of the coating is 9H, and the adhesion force with a base material is 0 grade.
Example 5
(1) 0.5g of magnesium aluminum silicate compound MgAl2SiO6·3H2Fully dissolving O in 100g of deionized water, stirring and preserving heat for 2 hours at 60 ℃ to obtain a hydrate with high viscosity; adding 42g of morpholine silane modified lithium silicate into a high-viscosity hydrate, controlling the pH to be 12 by taking organic amine AMP-95 as a pH regulator under the stirring conditions of 1500r/min and 80 ℃, and reacting for 2h to obtain a reactive hydrophilic monomer;
(2) and (2) adding the product obtained in the step (1), 12g of ethyl silicate, 2.82g of s-triazine dithiol silane and 1.2g of aminoethyl aminopropyl trimethoxy silane into 58.32g of deionized water, and carrying out free radical polymerization reaction for 3.5h at the temperature of 75 ℃ to prepare the polyhydroxy multi-hydrogen bond hydrophilic silicate film-forming material.
(3) Adding the silicate film-forming material obtained in the step (2) and 8.6g of yttrium aluminum acetylacetonate trihydrate compound into 32.72g of water, and preserving the heat for 1.5 hours at the water bath temperature of 80 ℃ to evaporate ethanol contained in the yttrium aluminum acetylacetonate trihydrate compound so as to stably store the subsequent coating;
(4) and (3) standing and cooling the material prepared in the step (3) to normal temperature, and then adding 5.21g of ethylene glycol monobutyl ether and 0.6g of polyether modified siloxane wetting and leveling agent to prepare the aqueous inorganic nano long-acting antifogging self-cleaning coating.
(5) And (3) sequentially carrying out surface pretreatment on the sample glass by using acetone and distilled water, and airing. And adjusting the flame to be blue flame by using a butane flame gun, and quickly scanning the glass surface of the sample wafer once. Spraying the water-based inorganic nano super-hydrophilic coating on a glass sample by adopting a two-fluid spray gun with the caliber of 0.4, wherein the thickness of a wet film of the coating is about 5 mu m, and drying for 20min at the temperature of 250 ℃ to obtain a high-hardness inorganic nano super-hydrophilic thin coating.
(6) The super-hydrophilic coating is tested by adopting an OCA-40 type contact angle tester of Germany Datophysics company, and the contact angle of the super-hydrophilic coating with water is 5 degrees, the pencil hardness of the coating is 9H, and the adhesion force with a base material is 0 grade.
Example 6
(1) 0.5g of magnesium aluminum silicate compound MgAl2SiO6·3H2Fully dissolving O in 120g of deionized water, stirring and preserving heat for 2 hours at the temperature of 60 ℃ to obtain a hydrate with high viscosity; adding 42g of morpholine silane modified lithium silicate into a high-viscosity hydrate, controlling the pH to be 11 by taking organic amine AMP-95 as a pH regulator under the stirring conditions of 80 ℃ and 1200r/min, and reacting for 3h to obtain a reactive hydrophilic monomer;
(2) adding the product obtained in the step (1), 15g of ethyl silicate and 3.16g of s-triazine dithiol silane into 56.47g of deionized water, and carrying out free radical polymerization reaction for 3.5h at the temperature of 75 ℃ to prepare the polyhydroxy-multiple hydrogen bond hydrophilic silicate film-forming material.
(3) Adding the silicate film-forming material obtained in the step (2) and 8.6g of yttrium aluminum acetylacetonate trihydrate compound into 32.72g of water, and preserving the heat for 1.5 hours at the water bath temperature of 80 ℃ to evaporate ethanol contained in the yttrium aluminum acetylacetonate trihydrate compound so as to stably store the subsequent coating;
(4) and (3) standing and cooling the material prepared in the step (3) to normal temperature, and then adding 6.2g of ethylene glycol monobutyl ether, 0.6g of polyether modified siloxane wetting and leveling agent and 0.3g of alkynediol wetting agent to prepare the aqueous inorganic nano long-acting antifogging self-cleaning coating.
(5) And (3) sequentially carrying out surface pretreatment on the sample glass by using acetone and distilled water, and airing. And adjusting the flame to be blue flame by using a butane flame gun, and quickly scanning the glass surface of the sample wafer once. Spraying the water-based inorganic nano super-hydrophilic coating on a glass sample by adopting a two-fluid spray gun with the caliber of 0.4, wherein the thickness of a wet film of the coating is about 5 mu m, and drying for 30min at the temperature of 250 ℃ to obtain a high-hardness inorganic nano super-hydrophilic thin coating.
(6) The super-hydrophilic coating is tested by adopting an OCA-40 type contact angle tester of Germany Datophysics company, and the contact angle of the super-hydrophilic coating with water is 3 degrees, the pencil hardness of the coating is 9H, and the adhesion force with a base material is 0 grade.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the present application may be combined with each other arbitrarily without conflict.
Claims (9)
1. A preparation method of an inorganic nano long-acting antifogging self-cleaning coating is characterized by comprising the following steps:
step one, fully dissolving 0.1-15 parts of magnesium aluminum silicate compound in deionized water by mass parts to obtain a hydrate with high viscosity; adding 5-56 parts of morpholine silane modified silicate into a high-viscosity hydrate, heating and stirring, adjusting the pH to be alkaline by using organic amine, and reacting to obtain a reactive hydrophilic monomer;
adding 9-55 parts by mass of the reactive hydrophilic monomer obtained in the step one, 2-32 parts by mass of ethyl silicate and 0.01-2 parts by mass of triazine silane into deionized water, and carrying out free radical polymerization under a heating condition to prepare a polyhydroxy multi-hydrogen bond hydrophilic silicate film-forming material;
step three, taking 13-98 parts by mass of the silicate film forming material obtained in the step two, adding the silicate film forming material into water, dropwise adding 2-16 parts of the composite organic acid metal salt of rare earth metal and aluminum under heating and stirring, and preserving heat after dropwise adding is finished to evaporate out ethanol contained in the composite organic acid metal salt of rare earth metal and aluminum;
and step four, standing and cooling 10-80 parts by mass of the material prepared in the step three to normal temperature, stirring at the normal temperature at the rotating speed of 1200-1500r/min, and adding 0.1-9 parts of ethylene glycol monobutyl ether and 0.1-3 parts of polyether modified siloxane wetting and leveling agent to prepare the water-based inorganic nano long-acting antifogging self-cleaning coating.
2. The method for preparing the inorganic nano long-acting antifogging self-cleaning coating according to claim 1, wherein in step one, the magnesium silicate is aluminizedThe compound is a compound containing-SiO3、-OH、-H、-NH2Magnesium aluminum hydrate of at least one of the bonds.
3. The method for preparing the inorganic nano long-acting antifogging self-cleaning coating according to claim 1, wherein in the first step, the morpholine silane modified silicate is potassium silicate, sodium silicate or lithium silicate, and the morpholine silane is a tape
—OC2H5The silane of (1).
4. The preparation method of the inorganic nano long-acting antifogging self-cleaning coating according to claim 1, wherein in the second step, the polyhydroxy polyhydrogen bonding hydrophilic silicate film-forming material is a material containing-OH, -H, -NH2、-SH、
Silicates of hydrophilic groups; the structural general formula of the triazine silane is as follows:
5. The preparation method of the inorganic nano long-acting antifogging self-cleaning coating according to claim 1, characterized in that, in the third step, in the composite organic acid metal salt of rare earth metal and aluminum, the rare earth metal is yttrium, cerium, cobalt or manganese.
6. The preparation method of the inorganic nano long-acting antifogging self-cleaning coating according to claim 5, characterized in that the composite organic acid metal salt is selected from oxides, salts and organic acid soaps of metals of cobalt, manganese and aluminum.
7. An inorganic nano long-acting antifogging self-cleaning coating, characterized in that, the coating is prepared by the preparation method of the inorganic nano long-acting antifogging self-cleaning coating according to any one of claims 1 to 6.
8. The application of the inorganic nano long-acting antifogging self-cleaning coating is characterized in that the inorganic nano long-acting antifogging self-cleaning coating is used for preparing an inorganic nano super-hydrophilic coating on the surface of an inorganic substrate, and the preparation method comprises the following steps: carrying out surface pretreatment on an inorganic substrate; and (3) coating the water-based inorganic nano long-acting antifogging self-cleaning coating on the pretreated inorganic substrate by adopting a spraying, dipping or brushing method, wherein the thickness of a wet film of the coating is 8-55 mu m, and baking for 3-20 min at the temperature of 120-280 ℃ to obtain the high-hardness inorganic nano super-hydrophilic coating.
9. The application of the inorganic nano long-acting antifogging self-cleaning coating according to claim 8, characterized in that the adhesion of the inorganic nano super-hydrophilic coating to the inorganic substrate is 0 grade, the hardness is more than 9H, and the contact angle with water is less than 5 °.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115304942A (en) * | 2022-08-16 | 2022-11-08 | 上海保耐舒新材料技术有限公司 | Water-based long-acting antifogging self-cleaning coating and preparation method thereof |
| CN115503267A (en) * | 2022-10-20 | 2022-12-23 | 深圳市宏海福新材料有限公司 | Wear-resistant antifog polarizer and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102241939A (en) * | 2011-05-17 | 2011-11-16 | 华南理工大学 | Organic-inorganic hybrid super-hydrophilic coating as well as preparation method and application thereof |
| US20110283916A1 (en) * | 2009-02-07 | 2011-11-24 | Cognis Ip Management Gmbh | Solvent-Free Water-Soluble Silane-Modified Silicates |
| CN104761153A (en) * | 2015-04-07 | 2015-07-08 | 泉州三欣新材料科技有限公司 | Super-hydrophilic anti-fog coating for glass and preparation method thereof |
| CN107227050A (en) * | 2017-08-08 | 2017-10-03 | 伍淼 | Superhydrophilic self-cleaning antifogging coating and preparation method thereof |
| CN108659244A (en) * | 2018-04-25 | 2018-10-16 | 成都思博特科技有限公司 | A kind of preparation method of transparent substrate surface hydrophily anti-fog coating |
-
2021
- 2021-09-10 CN CN202111062750.8A patent/CN113736292A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110283916A1 (en) * | 2009-02-07 | 2011-11-24 | Cognis Ip Management Gmbh | Solvent-Free Water-Soluble Silane-Modified Silicates |
| CN102307952A (en) * | 2009-02-07 | 2012-01-04 | 考格尼斯知识产权管理有限责任公司 | Solvent-free Water-soluable silane-modified silicates |
| CN102241939A (en) * | 2011-05-17 | 2011-11-16 | 华南理工大学 | Organic-inorganic hybrid super-hydrophilic coating as well as preparation method and application thereof |
| CN104761153A (en) * | 2015-04-07 | 2015-07-08 | 泉州三欣新材料科技有限公司 | Super-hydrophilic anti-fog coating for glass and preparation method thereof |
| CN107227050A (en) * | 2017-08-08 | 2017-10-03 | 伍淼 | Superhydrophilic self-cleaning antifogging coating and preparation method thereof |
| CN108659244A (en) * | 2018-04-25 | 2018-10-16 | 成都思博特科技有限公司 | A kind of preparation method of transparent substrate surface hydrophily anti-fog coating |
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| CN115304942A (en) * | 2022-08-16 | 2022-11-08 | 上海保耐舒新材料技术有限公司 | Water-based long-acting antifogging self-cleaning coating and preparation method thereof |
| CN115503267A (en) * | 2022-10-20 | 2022-12-23 | 深圳市宏海福新材料有限公司 | Wear-resistant antifog polarizer and preparation method thereof |
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Application publication date: 20211203 |