CN1597810A - Antifogging antibacterial multifunctional coating and preparation method and application thereof - Google Patents
Antifogging antibacterial multifunctional coating and preparation method and application thereof Download PDFInfo
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- CN1597810A CN1597810A CN 03157178 CN03157178A CN1597810A CN 1597810 A CN1597810 A CN 1597810A CN 03157178 CN03157178 CN 03157178 CN 03157178 A CN03157178 A CN 03157178A CN 1597810 A CN1597810 A CN 1597810A
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- 238000000576 coating method Methods 0.000 title claims abstract description 68
- 239000011248 coating agent Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 230000000844 anti-bacterial effect Effects 0.000 title abstract 3
- 239000000243 solution Substances 0.000 claims abstract description 44
- 230000003115 biocidal effect Effects 0.000 claims abstract description 30
- 229910052709 silver Inorganic materials 0.000 claims abstract description 15
- 239000004332 silver Substances 0.000 claims abstract description 15
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011521 glass Substances 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- 239000010949 copper Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 229920003023 plastic Polymers 0.000 claims abstract description 8
- 239000004033 plastic Substances 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 239000010936 titanium Substances 0.000 claims abstract description 8
- 150000003751 zinc Chemical class 0.000 claims abstract description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000032683 aging Effects 0.000 claims abstract description 6
- 229920000642 polymer Polymers 0.000 claims abstract description 6
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
- 239000007822 coupling agent Substances 0.000 claims abstract description 5
- 239000000413 hydrolysate Substances 0.000 claims abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 5
- 230000007062 hydrolysis Effects 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 45
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 39
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 29
- 239000003960 organic solvent Substances 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 150000007530 organic bases Chemical class 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- 238000013019 agitation Methods 0.000 claims description 14
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 14
- 239000011707 mineral Substances 0.000 claims description 14
- -1 silver halide Chemical class 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 11
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 10
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 6
- 238000003483 aging Methods 0.000 claims description 5
- 230000001699 photocatalysis Effects 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 238000007146 photocatalysis Methods 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 229960004418 trolamine Drugs 0.000 claims description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical group CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 229920002319 Poly(methyl acrylate) Polymers 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 2
- 239000004568 cement Substances 0.000 claims description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims description 2
- 229920002521 macromolecule Polymers 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 abstract description 9
- 238000004332 deodorization Methods 0.000 abstract description 4
- 239000006087 Silane Coupling Agent Substances 0.000 abstract description 2
- 239000008204 material by function Substances 0.000 abstract description 2
- 239000003973 paint Substances 0.000 abstract description 2
- 230000002265 prevention Effects 0.000 abstract 2
- 229910003082 TiO2-SiO2 Inorganic materials 0.000 abstract 1
- 239000000919 ceramic Substances 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000003344 environmental pollutant Substances 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 238000006303 photolysis reaction Methods 0.000 abstract 1
- 230000015843 photosynthesis, light reaction Effects 0.000 abstract 1
- 231100000719 pollutant Toxicity 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 1
- 239000012686 silicon precursor Substances 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 230000008901 benefit Effects 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 101710134784 Agnoprotein Proteins 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 231100000614 poison Toxicity 0.000 description 3
- 230000007096 poisonous effect Effects 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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Abstract
The invention belongs to the field of functional materials, and particularly relates to an antifogging and antibacterial multifunctional coating, and a preparation method and application thereof. (1) Preparing TiO by controlling hydrolysis of titanium precursor at 0-150 DEG C2Sol; (2) to TiO 22Adding a silicon precursor into the sol, and hydrolyzing at room temperature to 90 ℃ to obtain TiO2－SiO2Mixing sol; (3) adding a solution of a silane coupling agent and a solution of a high molecular polymer, and aging to obtain the antifogging and antibacterial multifunctional coating. Introducing silver, copper or zinc salt into the sol system in step (2) or step (3). The coating TiO is2+SiO280-100 parts of mixed sol, 0-2 parts of aqueous solution of silver, copper or zinc salt, 0-5 parts of coupling agent or hydrolysate thereof and 0-15 parts of high molecular polymer solution. The paint can be used on the surfaces of glass, plastic, ceramics and the like to enable the surfaces to have multiple functions of fog prevention, mildew prevention, deodorization, pollutant photolysis, antibiosis, self-cleaning and the like.
Description
Technical field
The invention belongs to field of functional materials, particularly a series of multifunctional coatings and its production and use with antifog, antibiotic, mildew-resistant, deodorization, photocatalytic degradation pollutent and self-cleaning function.
Background technology
At present, domestic anti-fog coating is mainly by acrylic polymer and colloidal state SiO
2As main solid phase moiety.In this class coating, there are a large amount of volatility very strong poisonous organic solvent such as dimethylbenzene, the first isobutyl ketone, toluene, methyl alcohol etc. are poisonous and the solvent of pungent smell arranged.The existence of these deleterious solvents and a large amount of organic polymers all can pollute and injure environment and human body.[up-to-date coating variety prescription and technology collection, Xie Fangcheng, Liu Guojie chief editor, China Light Industry Press, 1996].Simultaneously, anti-fog coating commonly used at present generally requires to adopt the process for photocuring [coating of thermal curing method or ultraviolet lighting in the curing of film, Zhou Xueliang chief editor Chemical Industry Press fine chemistry industry publishing centre, 2002], this is from having limited the use of such coating in numerous occasions to a great extent.
Summary of the invention
But one of purpose of the present invention provides fast filming at room temperature, has the antifog antibiotic multifunction coating of multi-efficiencies such as antifog, antibiotic, photochemical catalysis and automatically cleaning simultaneously.
Another object of the present invention provides a kind of preparation method of antifog antibiotic multifunction coating.
A further object of the present invention provides the purposes of antifog antibiotic multifunction coating.
Antifog antibiotic multifunction coating of the present invention, in weight part, this system component is:
TiO
2+ SiO
280～100 parts of mixed solss
0～2 part of silver, copper or zinc solution
0～5 part of coupling agent or its hydrolysate
0～15 part of macromolecule polymer solution
Described TiO
2+ SiO
2Comprise water, organic solvent, organic bases, mineral acid, TiO in the mixed sols
2And SiO
2Composition.
In weight part TiO
2+ SiO
2Consisting of of mixed sols:
0.1～95 part in water
5～97 parts of organic solvents
TiO
20.01～2 parts
SiO
20.1～3 parts
0～0.1 part of silver, copper or zinc salt
0～3 part of organic bases
0.01～2 part of mineral acid
TiO wherein
2+ SiO
2TiO in the mixed sols
2Colloidal sol is by the precursor of titanium such as Ti (OC
3H
7)
4, Ti (OC
4H
9)
4, TiCl
4Or TiOSO
4Solution etc. join that in the mixing solutions of the water of organic bases or mineral acid and organic solvent hydrolysis obtains; TiO
2+ SiO
2Colloidal sol is at TiO by methyl silicate or tetraethyl silicate
2Hydrolysis obtains in the colloidal sol.
Organic bases in the described mixed sols is Tetramethylammonium hydroxide, urea, diethanolamine or trolamine etc.
Described mineral acid is hydrochloric acid, sulfuric acid or nitric acid etc.
Described organic solvent is ethanol, propyl alcohol, Virahol, butanols, ethyl cellosolve or ethylene glycol butyl ether etc.
Described silver salt is mainly difficulty soluble salt or the soluble salt of silver and the soluble salt of copper or zinc of silver such as silver halide or Sulfuric acid disilver salt.
Coupling agent described in coating is formed is silane coupling agent such as γ-mercaptopropyl trimethoxysilane, γ-epoxypropyl Trimethoxy silane, γ-An Bingjisanyiyangjiguiwan, γ-chloropropyl triethoxysilane, tetraethyl silicate, methyl silicate or their any mixture etc.
Described high molecular polymer is polymethyl acrylate class, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, poly-epoxidized ethylene or their any mixture etc.
Preparation method's step of antifog antibiotic multifunction coating of the present invention comprises:
(1) preparation TiO
2Colloidal sol
After the mineral acid of getting 0～5 part organic bases or 0.1～2 part is dissolved in the mixing solutions of 55～95 parts the water of arbitrary proportion and organic solvent, continue stirred for several minute after, make it to mix fully.Under vigorous stirring, to the organic solution of the precursor of the aqueous solution of the precursor that wherein adds 5～40 parts of titaniums or titanium, 0～150 ℃ of constant temperature continues to stir 0.5～20 hour, makes the precursor hydrolysis of titanium obtain TiO again
2Colloidal sol is treated behind the colloidal sol naturally cooling standby;
(2) TiO
2+ SiO
2The preparation of colloidal sol
Get in the organic solvent that 5～40 parts tetraethyl silicate or methyl silicate be dissolved in 60～95 parts prepare silicon acetoacetic ester or methyl silicate solution.Under agitation with the TiO of 2～50 parts of steps (1) preparations
2Colloidal sol joins in the mixing solutions of 20～96 parts the water of arbitrary proportion and organic solvent, after continuing stirred for several minute, again 2～40 parts tetraethyl silicate or methyl silicate solution are added wherein, after continuing stirred for several minute, room temperature～90 ℃, constant temperature continues to stir 0.5～20 hour, naturally cools to room temperature.
(3) antifog antibiotic multifunction coating
The silane coupler solution or its hydrolysate that under agitation in the mixed sols that 80～100 parts step (2) obtains, add 0～5 part, 0～15 part high polymeric solution, continue to stir under the room temperature after 1～24 hour ageing can obtain having antibiotic, photocatalysis Decomposition pollutent and antifog multifunctional coating.
The aqueous solution that in step (2) or step (3), further adds 0～2 part silver, copper or zinc salt.
Antifog antibiotic multifunction coating of the present invention can be used for the protection on glass, pottery, plastics, metal or cement wall surface, makes these material surfaces have numerous functions such as antifog, antibiotic, deodorization, photocatalysis Decomposition pollutent and automatically cleaning.
In the present invention, we are with inorganic TiO
2And SiO
2As the main body composition that solid phase is formed, compare with traditional anti-fog coating, have diverse in function, toxicity is little, environmental hazard is low advantage.In addition, the solvent that antifog antibiotic multifunction coating involved in the present invention uses mainly is hypotoxic alcohol and water, also has clear superiority from the angle of environmental protection.
Compare with traditional anti-fog coating, coating involved in the present invention has the advantage of fast filming under the room temperature, can not heat or the occasion of ultraviolet lighting applicable to many.Except above-mentioned advantage, because TiO in the system
2The existence of small-particle and silver, copper or zinc salt etc., coating of the present invention also has good photocatalytic and good antimicrobial property and self-cleaning function.
Advantage of the present invention and positively effect:
Coating of the present invention is compared with traditional anti-fog coating, has increased antibiotic, deodorization, mildew-resistant and photocatalysis Decomposition pollutent and self-cleaning multi-functional.Simultaneously, having of material light catalysis property is beneficial under the luminous environment, the keeping for a long time and the cleaning on film surface of paint film anti-fog performance.
Coating of the present invention is compared with traditional anti-fog coating, does not need harsh condition of cure to need conditions such as thermofixation or ultraviolet light polymerization as traditional anti-fog coating.The anti-fog coating of the present invention's preparation at room temperature gets final product fast filming.Therefore, the multifunctional type anti-fog coating of the present invention's preparation has the wider advantage of use range.
The solvent that relates among the present invention mainly is an ethanol, water etc.With a large amount of poisonous organic solvent such as dimethylbenzene that use in the traditional anti-fog coating, toluene, mibk, methyl alcohol etc. compare that to have toxicity low, eco-friendly advantage.
The usage quantity of the organic polymer among the present invention is significantly less than traditional anti-fog coating, and this is also favourable to the toxicity that reduces coating of the present invention.The more important thing is that the environmental pollution that brings is relatively very little because the antifog composition among the present invention is mainly inorganics.
Coating of the present invention is compared with traditional anti-fog coating, adopts the antifog multifunctional coating of the present invention's preparation, is possessing under the situation of original performance, and it is little to have usage quantity, does not influence original material color, the advantage of proterties such as transparency.
The present invention prepares antifog antibiotic multifunction coating and has simple to operately, and preparation condition such as is easy to reach at advantage; Simultaneously, place between antifog, antibiotic, the self-cleaning function coating that adopts the present invention to prepare has often, performance does not have the characteristics of considerable change, and stability is high.
Description of drawings
Fig. 1. antifog, antibiotic, the stereoscan photograph of self-cleaning function coating after the substrate of glass film forming of preparation in the embodiment of the invention 1;
Fig. 2. the antifog multifunctional coating that waits of preparation is after the substrate of glass film forming in the embodiment of the invention 3, and the contact angle of film surface and water is with the variation of storage period;
Fig. 3. the antifog multifunctional coating of preparation is after the substrate of glass film forming in the embodiment of the invention 7, and when sunny side was placed, contact angle was with the variation of storage period;
Fig. 4. the situation of antifog multifunctional coating photocatalytic degradation azoic dyestuff tropeolin-D after the substrate of glass film forming of preparation in the embodiment of the invention 4;
Fig. 5. the practical function of the antifog multifunctional coating of preparation on glass port followed the tracks of detected result in the embodiment of the invention 2; The left side: window glass; The right is covered with antifog, the window glass of antibiotic multifunction film.
Below in conjunction with embodiment technical scheme of the present invention is further described.
Embodiment
Embodiment 1
Get weight part and be 5 parts Tetramethylammonium hydroxide and be dissolved in the mixed solvent that 75 parts of volume ratios are 1: 3 ethyl cellosolve and deionized water, under vigorous stirring to the TiOSO that wherein adds 20 parts
4The aqueous solution, continue to stir after 30 minutes, be heated to 100 ℃ of constant temperature 1 hour.Naturally cooling obtains TiO
2Colloidal sol.The tetraethyl silicate of getting 20 parts dissolves back preparation ethyl silicate solution in 80 parts ethanol.Under agitation, with 10 parts TiO
2Colloidal sol adds in the mixing solutions that 80 parts volume ratio is 2: 1 ethyl cellosolve and deionized water, after continuing stirred for several minute, again 10 parts ethyl silicate solution is added wherein, continue to stir after 10 minutes, constant temperature stirred 3 hours after being warmed up to 80 ℃, obtained TiO after naturally cooling to room temperature
2+ SiO
2Mixed sols, the consisting of of this colloidal sol: (weight part meter) water 61.41; Organic solvent 36.97; SiO
20.56; TiO
20.25; Organic bases 0.50; Mineral acid 0.31.Stir down, with 3 parts γ-glycidoxy Trimethoxy silane hydrolysate, 3 parts of polyacrylate solution add 94 parts TiO
2-SiO
2In the mixed sols, continue to stir the antifog antibiotic multifunction coating that promptly obtains can be used for external coatings such as glass, pottery, plastics after 5 hours under the room temperature.
Embodiment 2
After getting weight part and be in the deionized water that 3 parts urea is dissolved in 92 parts, under vigorous stirring to the TiOSO that wherein adds 5 parts
4The aqueous solution, continue to stir after 10 minutes, be heated to 80 ℃ of constant temperature and stir after 4 hours, naturally cooling obtains TiO
2Colloidal sol.The tetraethyl silicate of getting 10 parts dissolves back preparation ethyl silicate solution in 90 parts ethyl cellosolve.Under agitation, with 20 parts TiO
2Colloidal sol adds 50 parts of volume ratios and is in 1: 1 the deionized water and alcohol mixed solution, continue stirred for several minute after, again to the ethyl silicate solution that wherein adds 30 parts, continue stirred for several minute after, be warmed up to 60 ℃ of constant temperature and stir after 1 hour, naturally cooling obtains TiO
2～SiO
2Mixed sols.TiO
2～SiO
2Mixed sols consist of (weight part meter) water 46.61; Organic solvent 51.74; SiO
20.84; TiO
20.10; Organic bases 0.6; Mineral acid 0.11.Under induction stirring, to 95 parts TiO
2～SiO
2After adding 5 parts of γ-An Bingjisanyiyangjiguiwan acetone solns in the mixed sols, room temperature continues to stir the antifog antibiotic multifunction coating that can obtain can be used for external coatings such as glass, pottery, plastics in 24 hours.
Embodiment 3
The urea of getting weight part and be 4 parts is dissolved in 78 parts of deionized waters, under vigorous stirring to the TiCl that wherein adds 18 parts
4Ethanolic soln continues to stir after 5 minutes, is heated to 40 ℃ of constant temperature 8 hours.Naturally cooling obtains TiO
2Colloidal sol.The tetraethyl silicate of getting 40 parts dissolves back preparation ethyl silicate solution in 60 parts ethanol.Under agitation, with the TiO of 50 parts of preparations
2Colloidal sol adds in 45 parts the deionized water, continues stir about after 5 minutes, again to wherein adding 5 parts of ethyl silicate solutions, continues to stir after 20 minutes, be warmed up to 70 ℃ after constant temperature stirred 3 hours, naturally cool to room temperature.TiO
2～SiO
2Mixed sols consist of (weight part meter) water 91.06; Organic solvent 4.77; SiO
20.28; TiO
20.67; Organic bases 2; Mineral acid 1.22.Ageing TiO
2～SiO
2Mixed sols can obtain can be used for the antifog antibiotic multifunction coating of external coatings such as glass, pottery, plastics in 24 hours.
Embodiment 4
Get weight part and be 0.7 part trolamine and be dissolved in the mixed solvent that 69.3 parts of volume ratios are 1: 2 ethyl cellosolve and deionized water, under vigorous stirring to wherein add 30 parts TiOSO
4Ethanolic soln continues to stir after 20 minutes, is heated to 90 ℃ of constant temperature and stirs 4 hours, and naturally cooling obtains TiO
2Colloidal sol.Get in the ethanol that 5.1 parts tetraethyl silicate is dissolved in 94.9 parts and prepare ethyl silicate solution.Under agitation, with the TiO of 30 parts of preparations
2Colloidal sol adds in the mixed solvent that 63 parts of volume ratios are 1: 4 ethyl cellosolve and deionized water, after continuing stirred for several minute,, continue stirred for several minute again to wherein adding 7 parts of ethyl silicate solutions, constant temperature stirred 3 hours after being warmed up to 30 ℃, and naturally cooling obtains TiO
2～SiO
2Mixed sols.TiO
2～SiO
2Mixed sols consist of (weight part meter) water 65.23; Organic solvent 34.35; SiO
20.1; TiO
20.05; Organic bases 0.21; Mineral acid 0.06.Get 93 parts TiO
2-SiO
2Mixed sols is under agitation to wherein adding 1 part 10
-2The AgNO of mol/L
3The aqueous solution, 1 part γ-chloropropyl triethoxysilane ethanolic soln, the polyvinyl alcohol water solution of 10 parts of 5wt% continues to stir the antifog antibiotic multifunction coating that can obtain can be used for external coatings such as glass, pottery, plastics after 12 hours under the room temperature.
Get 1 part concentrated nitric acid and be dissolved in the mixing solutions that 59 parts volume ratio is 1: 16 deionized water and organic solvent, to the aqueous isopropanol that wherein adds 40 parts of tetrabutyl titanates, 0～5 ℃ continues to stir 5 hours under vigorous stirring.Naturally be placed into room temperature.Get in the ethanol that 14 parts tetraethyl silicate is dissolved in 86 parts and prepare ethyl silicate solution.Under vigorous stirring, with 20 parts of TiO
2Behind the ethyl cellosolve that the colloidal sol adding is 38 parts, again to wherein adding 2 part 10
-2The AgNO of mol/L
3The aqueous solution continued to stir after 10 minutes, again to the ethyl silicate solution that wherein adds 40 parts, continued under the room temperature to stir after 20 hours to obtain TiO
2-SiO
2Mixed sols.TiO
2-SiO
2Mixed sols consist of (weight part meter) water 1.52; Organic solvent 95.74; SiO
21.57; TiO
21.04; Organic bases 0; Mineral acid 0.13; Silver Nitrate 0.0085.Under agitation, to 95 parts TiO
2-SiO
2The polyvinyl alcohol solution that adds 5 parts in the mixed sols continues to stir the antifog antibiotic multifunction coating that can obtain can be used for external coatings such as glass, pottery, plastics in 5 hours.
Embodiment 6
Get weight part and be in the deionized water that 0.8 part diethanolamine is dissolved in 94.2 parts, under vigorous stirring, to the TiCl that wherein adds 5 parts
4The aqueous solution continues to stir after 10 minutes, is heated to 60 ℃ of constant temperature 7 hours.Naturally cooling.30 parts tetraethyl silicate are dissolved in 70 parts the ethanol and prepare ethyl silicate solution.Under agitation, with 50 parts TiO
2Colloidal sol adds in 45 parts the ethyl cellosolve, continue stirred for several minute after, again to the ethyl silicate solution that wherein adds 5 parts, be warmed up to 40 ℃ and continue to stir and naturally cool to room temperature after 10 hours and can obtain TiO
2-SiO
2Mixed sols.TiO
2-SiO
2Mixed sols consist of (weight part meter) water 48.78; Organic solvent 49.83; SiQ
20.42; TiO
20.2; Organic bases 0.4; Mineral acid 0.37; Get 99 parts TiO
2-SiO
2Mixed sols under agitation to wherein adding 0.5 part polyacrylate solution and 0.5 part gamma-amino propoxy-triethoxyl silane, continues to stir ageing after 24 hours under the room temperature.
Embodiment 7
Getting weight part and be 2.5 parts tetramethyl-aqua ammonia, to be dissolved in 72.5 parts of volume ratios be in 1: 1 the deionized water and ethanol mixed solvent, under vigorous stirring, to the TiOSO that wherein adds 25 parts
4The aqueous solution continues to stir after 10 minutes, is heated to 40 ℃ of constant temperature 3 hours.Naturally cooling.Get in the acetone that 40 parts tetraethyl silicate is dissolved in 60 parts and prepare ethyl silicate solution.Under agitation, with 50 parts TiO
2Colloidal sol adds in the mixed solvent that 30 parts of volume ratios are 1: 1 ethyl cellosolve and deionized water, continues to stir after 15 minutes, again to the ethyl silicate solution that wherein adds 20 parts, continues under the room temperature to stir can obtain TiO in 10 hours
2-SiO
2Mixed sols.TiO
2-SiO
2Mixed sols consist of (weight part meter) water 46.06; Organic solvent 49.56; SiO
22.24; TiO
20.4; Organic bases 1.25; Mineral acid 0.49.Get 99.38 parts TiO
2-SiO
2Mixed sols is under agitation to the AgNO that wherein adds 0.5 part 0.1mol/L
3The tetraethyl silicate ethanolic soln of solution and 0.2 part, the aqueous solution of 2 parts of polyvinylpyrrolidones, 40 ℃ continue to stir ageings after 24 hours down.
Claims (10)
1. antifog antibiotic multifunction coating, it is characterized in that: in weight part, this system component is:
TiO
2+ SiO
280～100 parts of mixed solss
0～2 part of silver, copper or zinc solution
0～5 part of coupling agent or its hydrolysate
0～15 part of macromolecule polymer solution.
2. coating as claimed in claim 1 is characterized in that: described TiO
2+ SiO
2Mixed sols consists of in weight part:
0.1～95 part in water
5～97 parts of organic solvents
TiO
20.01～2 parts
SiO
20.1～3 parts
0～0.1 part of silver, copper or zinc salt
0～3 part of organic bases
0.01～2 part of mineral acid.
3. coating as claimed in claim 2 is characterized in that: described organic bases is Tetramethylammonium hydroxide, urea, diethanolamine or trolamine.
4. coating as claimed in claim 2 is characterized in that: described organic solvent is ethanol, propyl alcohol, Virahol, butanols, ethyl cellosolve or ethylene glycol butyl ether.
5. coating as claimed in claim 1 or 2 is characterized in that: described silver salt is the difficulty soluble salt of silver such as the soluble salt of silver halide or Sulfuric acid disilver salt and silver; Described mantoquita is the soluble salt of copper; Described zinc salt is the soluble salt of zinc.
6. coating as claimed in claim 1 is characterized in that: described coupling agent is γ-mercaptopropyl trimethoxysilane, γ-epoxypropyl Trimethoxy silane, γ-An Bingjisanyiyangjiguiwan, γ-chloropropyl triethoxysilane, tetraethyl silicate, methyl silicate or their any mixture.
7. coating as claimed in claim 1 is characterized in that: described high molecular polymer is polymethyl acrylate class, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, poly-epoxidized ethylene or their any mixture.
8. preparation method as each described antifog antibiotic multifunction coating of claim 1～7, it is characterized in that: described method steps comprises:
(1) preparation TiO
2Colloidal sol
The mineral acid of getting 0～5 part organic bases or 0.1～2 part is dissolved in the mixing solutions of the water of 55～95 parts of arbitrary proportions and organic solvent, stirs, and mixes fully; Under vigorous stirring, to the organic solution of the precursor of the aqueous solution of the precursor that wherein adds 5～40 parts of titaniums or titanium, 0～150 ℃ of constant temperature continues to stir, and makes the precursor hydrolysis of titanium obtain TiO again
2Colloidal sol is treated behind the colloidal sol naturally cooling standby;
(2) TiO
2+ SiO
2The preparation of colloidal sol
Get in the organic solvent that 5～40 parts tetraethyl silicate or methyl silicate be dissolved in 60～95 parts prepare silicon acetoacetic ester or methyl silicate solution; Under agitation with the TiO of 2～50 parts of steps (1) preparations
2Colloidal sol adds in the mixing solutions of 20～96 parts the water of arbitrary proportion and organic solvent, continues to stir, and 2～40 parts tetraethyl silicate or methyl silicate solution is added wherein again, continue to stir, and room temperature～90 ℃, constant temperature stirs, and naturally cools to room temperature;
(3) antifog antibiotic multifunction coating
The silane coupler solution or its hydrolysate that under agitation in the mixed sols that 80～100 parts step (2) obtains, add 0～5 part, 0～15 part high polymeric solution, continue under the room temperature to stir, ageing promptly obtains having antibiotic, photocatalysis Decomposition pollutent and antifog multifunctional coating.
9. method as claimed in claim 8 is characterized in that: the aqueous solution that further adds 0～2 part silver, copper or zinc salt in step (2) or step (3).
10. purposes as each described antifog antibiotic multifunction coating of claim 1～7, it is characterized in that: described antifog antibiotic multifunction coating is used for the protection on glass, pottery, plastics, metal or cement wall surface.
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|---|---|---|---|
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|---|---|---|---|
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