CN101492544B - Transparent self-cleaning film, preparation and uses thereof - Google Patents
Transparent self-cleaning film, preparation and uses thereof Download PDFInfo
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- CN101492544B CN101492544B CN2008100569182A CN200810056918A CN101492544B CN 101492544 B CN101492544 B CN 101492544B CN 2008100569182 A CN2008100569182 A CN 2008100569182A CN 200810056918 A CN200810056918 A CN 200810056918A CN 101492544 B CN101492544 B CN 101492544B
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Abstract
The invention discloses a transparent self-cleaning film, a preparation method and the application thereof. The method is as follows: 0.03-3 (parts by weight) of ortho-silicate ester, 4-9.5 of ethanol, 0.01-2 of ammonia and 0-1 of water are blended, stirred, formed to film and dried, and is put into a chemical solution with formula I general formula for self-assembly to obtain the film; and also the components can be even blended, and then a substrate is put into coating liquid and stands for film. In formula I, R1 is C1-C24 alkyl, aryl or fluorating group; R2 is C1-C6 alkyl; X is halogen or C1-C6 oxyl; N is 0, 1 or 2. The water contact angle of the film reach more 150 degrees, the lag angle is less than 20 degrees, the transmittance of the film is more than 0.90, the mechanical strength is higher and the self-cleaning is good. The preparation method has simple technique, low energy consumption and has good industry application prospect. R1Si(R2)nX<3-n> is formula I.
Description
Skill this area
The present invention relates to a kind of transparent self-cleaning film and preparation method thereof and application.
Background technology
Have superhydrophobic property coating (with the contact angle of water greater than 150 °, and lagging angle is less) produce and life in great application prospect is all arranged.Because the less contact area of these film surfaces and water, thus on super hydrophobic surface, just can not take place to have chemical reaction that water could take place and with water formation chemical bond.Corresponding image surface is to the absorption of snow and rainwater, and the oxidation and the various phenomenons such as examining resistance of rubbing on surface can reduce or stop accordingly at super hydrophobic surface.Just they have everybody usually said self-cleaning function.Super-hydrophobicization door and window, material of construction and exterior coating with self-cleaning function is the effective way that solves sleet adhesion and contamination by dust.
Recently, the researchist has invented various methods and has prepared super hydrophobic surface, main method has template, phase separation method, crystallization process, plasma etching method, sol-gel method, soft etching and electrochemical deposition method or the like, its mainly prepare thought be construct the surface (micro-nano) micro-rough structure reach make the surface super thin character.Along with going deep into of recently super-hydrophobic research, more and more show out the drawback and the fatal shortcoming thereof that obtain micro-nano compound structure by the microtexture on the whole bag of tricks regulation and control surface especially.Although have the film or the surperficial contact angle and the low lag-effect that has greater than 150 ° of the compound microtexture of micro-nano, but general such film or surface do not possess the transparency, physical strength extreme difference and come off easily, and the problems referred to above have restricted the popularization of super-hydrophobic practical application greatly.Meanwhile, along with everybody to the deepening continuously of automatically cleaning phenomenon research, key the manifesting gradually of low lag-effect (water droplet is difficult for adhering to from the teeth outwards easily from the film surface landing).Do not have under 150 ° the situation of surpassing at contact angle, lower lagging angle also can make little water droplet be easy to break away from from film surface, thereby has reached hydrophobic, self-cleaning purpose.The transparency, physical strength and the low hysteresis that is to say self-cleaning film is the key issue that needs to be resolved hurrily.
Summary of the invention
The purpose of this invention is to provide a kind of transparent self-cleaning film and simple preparation method thereof, overcome preparation method's complicacy of super-hydrophobic coat in the past, low mechanical strength and high energy consumption and be difficult to be applied to difficult problems such as suitability for industrialized production have solved above technological difficulties with simple preparation method.
The purpose of this invention is to provide a kind of transparent self-cleaning film and preparation method thereof and application.
The method for preparing transparent self-cleaning film provided by the invention comprises the steps:
1) the positive silicon ester of 0.01-3 parts by weight, the ethanol of 4-9.5 parts by weight, the ammoniacal liquor of 0.01-2 parts by weight and the water of 0-1 parts by weight are mixed, stir the back film forming, obtain being coated with the substrate of mixed solution;
2) the above-mentioned substrate that is coated with mixed solution is placed the ethanolic soln self-assembly with formula I structure general formula, obtain transparent self-cleaning film;
R
1Si (R
2)
nX
3-nFormula I
In the above-mentioned formula I general structure, R
1Be alkyl, aryl or fluorinated groups;
Wherein, R
1During for alkyl, can be the C1-C24 alkyl of straight or branched, preferably have the alkyl of 1-18 carbonatoms; R
1During for aryl, for replace or unsubstituted, comprise five yuan, the carbocyclic ring or the heterocyclic group of hexa-atomic or ten-ring system, it is connected with Siliciumatom by the alkyl of the straight or branched of a covalent linkage or 1-8 carbon atom; R
1During for the fluoro group, be fluoridized alkyl or aryl, the perhaps alkyl or phenyl that is replaced by fluorine for the hydrogen on 1-8 the carbon atom that begins from the end of group;
R
2Alkyl for the straight or branched of C1-C6;
X is a hydrolysable group, can be halogen, preferred chlorine, and the perhaps-oxyl of C1-C6, the-oxyl of preferred C1-C3 is as methoxyl group, oxyethyl group or isopropoxy;
N is 0,1 or 2, if n is 0 or 1 o'clock, X can be identical or different group;
The concentration of the ethanolic soln of above-mentioned formula I structure general formula is 0.001-5mol/L, and the mass percent concentration of ammoniacal liquor is 25-28%.
In the step 1) of aforesaid method, positive silicon ester is a synthon, and ethanol is disperse phase, and ammoniacal liquor is catalyzer, and water is as aid dispersion phase or promotor.Whipping temp is 0-100 ℃, and churning time is 0.1-4h, and drying temperature is 20-300 ℃, and the film of various routines is applicable to this method, as crystal pulling method, dipping method etc.; Step 2) in, the time of self-assembly is 0.1-20h, and the temperature of self-assembly is 20-300 ℃.The substrate that is used for preparing film in this method can be a kind of of glass, polyethylene, acrylonitrile-butadiene-styrene copolymer, polypropylene, polyvinyl chloride, polystyrene, polycarbonate, polysulfones, nylon, pottery, metal, vinyl cyanide/styrol copolymer, ADC resin (allyl diglycol carbonates), polyethylene terephthalate, copolyesters, Chlorinated Polypropylene III, polymethylmethacrylate, polynorbornene resin or cyclic olefine copolymer.
In order to make follow-up self-assembling reaction carry out more fully, make the performance of gained film more excellent, in above-mentioned steps 1) drying step after, the above-mentioned substrate that is coated with mixed solution can be placed concentration is 1x10
-4-1g/cm
3Use 0.1Mw/cm in the ozone environment
2-1W/cm
2Uviolizing 0.1-4 hour.In addition, after the self-assembly step,, also thin-film ultrasonic can be cleaned 1-20 minute for further improving the performance of film.
The above-mentioned method for preparing transparent self-cleaning film provided by the invention, also can carry out as follows:
1) 25% the ammoniacal liquor of the ethanol of the positive silicon ester of 0.01-3 parts by weight, 4-9.5 parts by weight, 0.01-2 parts by weight and the water of 0-1 parts by weight are mixed, stir;
2) in the system of step 1), add the ethanolic soln of compound, continue to stir with formula I general structure, after leaving standstill, film forming;
R
1Si (R
2)
nX
3-nFormula I
In the above-mentioned formula I general structure, R
1Be alkyl, aryl or fluorinated groups;
Wherein, R
1During for alkyl, can be the C1-C24 alkyl of straight or branched, preferably have the alkyl of 1-18 carbon atom; R
1During for aryl, for replace or unsubstituted, comprise five yuan, the carbocyclic ring or the heterocyclic group of hexa-atomic or ten-ring system, it is connected with Siliciumatom by the alkyl of the straight or branched of a covalent linkage or 1-8 carbon atom; R
1During for the fluoro group, be fluoridized alkyl or aryl, the perhaps alkyl or phenyl that is replaced by fluorine for the hydrogen on 1-8 the carbon atom that begins from the end of group;
R
2Alkyl for the straight or branched of C1-C6;
X is a hydrolysable group, can be halogen, preferred chlorine, and the perhaps-oxyl of C1-C6, the-oxyl of preferred C1-C3 is as methoxyl group, oxyethyl group or isopropoxy;
N is 0,1 or 2, if n is 0 or 1 o'clock, X can be identical or different group;
The concentration of the ethanolic soln of above-mentioned formula I structure general formula is 0.001-5mol/L, and the mass percent concentration of ammoniacal liquor is 25-28%.
In the step 1) of aforesaid method, positive silicon ester is a synthon, and ethanol is disperse phase, and ammoniacal liquor is catalyzer, and water is as aid dispersion phase or promotor.Whipping temp is 0-100 ℃, and churning time is 0.1-4 hour; Step 2) in, whipping temp is 0-100 ℃, and churning time is 0.1-24 hour, and time of repose is 0.1-5 hour.The film of various routines is applicable to this method, as crystal pulling method, dipping method or spin-coating method etc.
The transparent self-cleaning film and the application of this film in preparation automatically cleaning material that utilize aforesaid method provided by the invention to obtain also belong to protection scope of the present invention.
Transparent self-cleaning film provided by the invention, its water contact angle reaches more than 150 °, and lagging angle is less than 20 °, and the film transmittance is all more than 0.90, its physical strength is 1H-3H, efficiently solves the bad mechanical strength of super-hydrophobic coat and does not possess transparent problem.This film is not hung any globule after the flowing water flushing, has good automatically cleaning characteristic, can be coated on the various material surfaces such as door and window and vehicle glass and rear vision mirror, building, dress ornament, make it have self-cleaning functions such as waterproof, antifouling, frost protection, anti-accumulated snow.Preparation method provided by the invention, technology is simple, overcomes complicated process of preparation, the high energy consumption of existing method and is difficult to the difficult problem of industrial applications, has better industrial application prospect.
Embodiment
The present invention will be further described below in conjunction with specific embodiment, but the present invention is not limited to following examples.
The transparent self-cleaning film that utilizes method provided by the invention to obtain, its physical strength height, pencil hardness can reach 1H-3H; Through scanning electron microscopic observation, film is formed by the build-up of particles of 5-100nm, and thickness is 5-500nm.
In following examples, the consumption of each material all by weight, the mass percent concentration of used ammoniacal liquor is 25%.
Embodiment 1, preparation transparent self-cleaning film
Get methyl silicate (Si (OCH
3)
4) 1 part, 7.5 parts of dehydrated alcohols, 1 part of ammoniacal liquor, 0.5 part in water, with said mixture at room temperature vigorous stirring 3h to even;
Make it be covered with thin film by dipping, behind the at room temperature dry 5h of film, be placed in the ethanolic soln that concentration is the 0.5mol/L monomethyl trichlorosilane, behind 60 ℃ of self-assembly 2h, promptly get transparent self-cleaning film in the polyvinyl primary coat.
The water contact angle of this film can reach 120 °, and roll angle is 20 °, and transmittance is 0.93.
Embodiment 2, preparation transparent self-cleaning film
Get methyl silicate (Si (OCH
3)
4) 2 parts, 6.5 parts of dehydrated alcohols, 0.5 part of ammoniacal liquor, 1 part in water, with said mixture at 40 ℃ of following vigorous stirring 2h to even;
Then, directly add the dodecyl Trimethoxy silane, control its concentration, continue to stir 1h, shelve 5h, film behind dry 5h under 50 ℃, promptly get transparent self-cleaning film at 1mol/L.
The water contact angle of this film can reach 130 °, and roll angle is 20 °, and transmittance is 0.95.
Embodiment 3, preparation transparent self-cleaning film
Get tetraethoxy (Si (OC
2H
5)
4) 1 part, 8 parts of dehydrated alcohols, 0.5 part of ammoniacal liquor, 0.5 part in water, with said mixture at 80 ℃ of following vigorous stirring 1.5h to even.
Make it apply the last layer film in ceramic bases by dipping, film places irradiation 3h under the ultraviolet lamp behind dry 0.5h under 80 ℃, be placed at last in the ethanolic soln of octyl trichlorosilane (1mol/L), behind 80 ℃ of self-assembly 4h, ultrasonic cleaning 5-15 minute, promptly get transparent self-cleaning film.
The water contact angle of this film can reach 148 °, and roll angle is 10 °, and transmittance is 0.94.
Embodiment 4, preparation transparent self-cleaning film
Get tetraethoxy (Si (OC
2H
5)
4) 1 part, 7.5 parts of dehydrated alcohols, 1 part of ammoniacal liquor, 0.5 part in water, with said mixture at room temperature vigorous stirring 4h to even.
Make it apply the last layer film by dipping in polypropylene substrate, film is behind dry 0.5h under 100 ℃, be placed in the ethanolic soln of monomethyl trichlorosilane (1.5 mol/L), behind 100 ℃ of self-assembly 0.1h ultrasonic cleaning 5-15 minute, promptly get transparent self-cleaning film.
The water contact angle of this film can reach 120 °, and roll angle is 30 °, and transmittance is 0.98.
Embodiment 5, preparation transparent self-cleaning film
Get tetraethoxy (Si (OC
2H
5)
4) 0.2 part, 9.5 parts of dehydrated alcohols, 0.2 part of ammoniacal liquor, 0.1 part in water, with said mixture at 100 ℃ of following vigorous stirring 0.5h to even.
Make it apply the last layer film by dipping in metal base, film is behind dry 0.5h under 140 ℃, be placed in the ethanolic soln of octadecyl chlorodimethyl silane (0.05 mol/L), behind 70 ℃ of self-assembly 0.1h ultrasonic cleaning 5-15 minute, promptly get transparent self-cleaning film.
The water contact angle of this film can reach 150 °, and roll angle is 15 °, and transmittance is 0.99.
Embodiment 6, preparation transparent self-cleaning film
Tetraethoxy (Si (OC
2H
5)
4) 1.5 parts, 7.2 parts of dehydrated alcohols, 0.8 part of ammoniacal liquor, 0.5 part in water, with above-mentioned mixture at 50 ℃ of following vigorous stirring 1h to even.
Make it apply the last layer film by dipping in the ABS substrate, film is behind dry 0.5h under 1 80 ℃, be placed in the ethanolic soln of octadecyl chlorodimethyl silane (0.05 mol/L), behind 150 ℃ of self-assembly 0.1h ultrasonic cleaning 5-15 minute, promptly get transparent self-cleaning film.
The water contact angle of this film can reach 138 °, and roll angle is 15 °, and transmittance is 0.96.
Embodiment 7, preparation transparent self-cleaning film
Get methyl silicate (Si (OCH
3)
4) 3 parts, 5 parts of dehydrated alcohols, 1.5 parts of ammoniacal liquor, 0.5 part in water, with said mixture at room temperature vigorous stirring 2h to even.
Directly add methyltrimethoxy silane then, its concentration is controlled at 1mol/L, stirs 1h, shelves 2h, films behind dry 5h under 110 ℃, promptly gets transparent self-cleaning film.
The water contact angle of this film can reach 148 °, and roll angle is 10 °, and transmittance is 0.94.
Embodiment 8, preparation transparent self-cleaning film
Tetraethoxy (Si (OC
2H
5)
4) 0.8 part, 8.2 parts of dehydrated alcohols, 0.5 part of ammoniacal liquor, 0.5 part in water, with above-mentioned mixture at 60 ℃ of following vigorous stirring 4h to even.
Directly add 13 fluoro-1,1,2 then, 2-tetrahydrochysene octyldimethyl chlorosilane, its concentration is controlled at 0.1mol/L, stirs 1h, shelves 2h, films behind dry 5h under 80 ℃, promptly gets transparent self-cleaning film.
The water contact angle of this film can reach 152 °, and roll angle is 4 °, and transmittance is 0.95.
Embodiment 9, preparation transparent self-cleaning film
Tetraethoxy (Si (OC
2H
5)
4) 1.5 parts, 7 parts of dehydrated alcohols, 1.5 parts of ammoniacal liquor, with above-mentioned mixture at room temperature vigorous stirring 2.5h to even.
Make it be covered with thin film in polystyrene-based primary coat by dipping, film is placed in the ethanolic soln of monomethyl trichlorosilane (1.5M) behind dry 0.5h under 100 ℃, and ultrasonic cleaning promptly got transparent self-cleaning film after 5 minutes behind 200 ℃ of self-assembly 0.1h.
The water contact angle of this film can reach 142 °, and roll angle is 10 °, and transmittance is 0.97.
Claims (8)
1. a method for preparing transparent self-cleaning film on substrate comprises the steps:
1) ethanol of the positive silicon ester of 0.01-3 parts by weight, 4-9.5 parts by weight, the ammoniacal liquor of 0.01-2 parts by weight and the water of 0-1 parts by weight are mixed, stir back film forming on substrate, drying obtains being coated with the substrate of mixed solution;
2) the described substrate that is coated with mixed solution is placed the ethanolic soln self-assembly with formula I structure general formula, obtain being grown in on-chip transparent self-cleaning film;
R
1Si (R
2)
nX
3-nFormula I
Wherein, in the described formula I general structure, R
1A kind of in the alkyl of C1-C24 or the fluorinated groups;
Described fluorinated groups is fluoridized alkyl or aryl, perhaps the alkyl that is replaced by fluorine for the hydrogen on 1-8 the carbon atom that begins from the end of group;
R
2Alkyl for C1-C6;
X is the-oxyl of halogen or C1-C6;
N is 0,1 or 2;
The concentration of the ethanolic soln of described formula I structure general formula is 0.001-5mol/L;
In the described step 1), whipping temp is 0-100 ℃, and churning time is 0.1-4h.
2. method according to claim 1 is characterized in that: described step 2), the time of self-assembly is 0.1-20h, and the temperature of self-assembly is 20-300 ℃.
3. method according to claim 1 and 2 is characterized in that: in the described step 1), described drying temperature is 20-300 ℃, and be 0.1-6h time of drying.
4. method according to claim 1 and 2 is characterized in that: in the described step 1), the mass percent concentration of ammoniacal liquor is 25-28%; Substrate is a kind of in glass, polyethylene, acrylonitrile-butadiene-styrene copolymer, polypropylene, polyvinyl chloride, polystyrene, polycarbonate, polysulfones, nylon, pottery, metal, vinyl cyanide/styrol copolymer, ADC resin, polyethylene terephthalate, copolyesters, Chlorinated Polypropylene III, polymethylmethacrylate, polynorbornene resin or the cyclic olefine copolymer;
In the described formula I general structure, R
1Alkyl for C1-C18; X is chlorine, methoxyl group, oxyethyl group or isopropoxy.
5. method according to claim 1 and 2 is characterized in that: after described step 1), 1 * 10
-4-1g/cm
3Under the concentration of ozone atmosphere, use 0.1Mw/cm
2-1W/cm
2Described substrate 0.1-4 hour of being coated with mixed solution of uviolizing.
6. a method for preparing transparent self-cleaning film on substrate comprises the steps:
1) the positive silicon ester of 0.01-3 parts by weight, the ethanol of 4-9.5 parts by weight, the ammoniacal liquor of 0.01-2 parts by weight and the water of 0-1 parts by weight are mixed, stir;
2) add the ethanolic soln of the compound with formula I general structure in the system of step 1), stir, obtain coating liquid, substrate is placed described coating liquid, leave standstill, film forming obtains being grown in on-chip transparent self-cleaning film;
R
1Si (R
2)
nX
3-nFormula I
Wherein, in the described formula I general structure, R
1A kind of in the alkyl of C1-C24 or the fluorinated groups;
Described fluorinated groups is fluoridized alkyl or aryl, perhaps the alkyl that is replaced by fluorine for the hydrogen on 1-8 the carbon atom that begins from the end of group;
R
2Alkyl for C1-C6;
X is the-oxyl of halogen or C1-C6;
N is 0,1 or 2;
The concentration of the ethanolic soln of described formula I structure general formula is 0.001-5mol/L;
In the described step 1), whipping temp is 0-100 ℃; Described step 2) in, whipping temp is 0-100 ℃;
In the described step 1), churning time is 0.1-4 hour; Described step 2) in, churning time is 0.1-24 hour, and time of repose is 0.1-5 hour.
7. method according to claim 6 is characterized in that: in the described step 1), the mass percent concentration of ammoniacal liquor is 25-28%;
In the described formula I general structure, R
1Alkyl for C1-C18; X is chlorine, methoxyl group, oxyethyl group or isopropoxy.
8. the transparent self-cleaning film that obtains of the arbitrary described method of claim 1-5 and claim 6-7.
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| CN102732149A (en) * | 2011-04-01 | 2012-10-17 | 河南思可达光伏材料股份有限公司 | Antifouling antireflection nano-paint, its preparation method and application |
| CN103182369B (en) * | 2013-02-26 | 2014-08-27 | 中南林业科技大学 | Method for preparing super-hydrophobic film with hybrid multi-stage structure on metal matrix |
| CN104449088A (en) * | 2014-12-09 | 2015-03-25 | 苏州明轩地坪涂料有限公司 | Damp-proof resin coating |
| CN110183881A (en) * | 2019-05-22 | 2019-08-30 | 苏州清飙科技有限公司 | A kind of glass coating material, self-cleaning glass and preparation method thereof |
| CN112724511B (en) * | 2020-12-22 | 2022-07-12 | 上海日之升科技有限公司 | Easy-to-clean mildew-proof PP composite material and preparation method thereof |
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| CN1544324A (en) * | 2003-11-20 | 2004-11-10 | 中国科学院上海技术物理研究所 | Silica dioxide aerogel membrane material preparation method |
| JP2006076068A (en) * | 2004-09-08 | 2006-03-23 | Central Glass Co Ltd | Easily washable article for member used in water using area in house and its manufacturing method |
| CN1843999A (en) * | 2006-04-21 | 2006-10-11 | 中国科学院上海光学精密机械研究所 | Method for plating composite anti-reflection film on silicon dioxide crystal |
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2008
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1544324A (en) * | 2003-11-20 | 2004-11-10 | 中国科学院上海技术物理研究所 | Silica dioxide aerogel membrane material preparation method |
| JP2006076068A (en) * | 2004-09-08 | 2006-03-23 | Central Glass Co Ltd | Easily washable article for member used in water using area in house and its manufacturing method |
| CN1843999A (en) * | 2006-04-21 | 2006-10-11 | 中国科学院上海光学精密机械研究所 | Method for plating composite anti-reflection film on silicon dioxide crystal |
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