CN102701601A - Preparation technique of self-cleaning and mildew-proof bathroom glass - Google Patents
Preparation technique of self-cleaning and mildew-proof bathroom glass Download PDFInfo
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- CN102701601A CN102701601A CN2012101463603A CN201210146360A CN102701601A CN 102701601 A CN102701601 A CN 102701601A CN 2012101463603 A CN2012101463603 A CN 2012101463603A CN 201210146360 A CN201210146360 A CN 201210146360A CN 102701601 A CN102701601 A CN 102701601A
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Abstract
The invention discloses a preparation technique of self-cleaning and mildew-proof bathroom glass, bathroom-dedicated glass is used as a base plate, and a spray filming method is adopted to prepare the self-cleaning and mildew-proof bathroom glass, the preparation technique comprises the following steps: cleaning the glass, spraying and filming, drying the film and heat-treating the film. According to the development and industrialization of the self-cleaning and mildew-proof bathroom glass provided by the preparation technique, not only can a healthy and beautiful living space can be created for people, but also more unnecessary resource waste can be reduced, the service life of the bathroom glass can be prolonged, and the preparation technique has important social benefits, economic benefits and environmental benefits.
Description
Technical field
The present invention relates to a kind of automatically cleaning mildew-resistant bathroom glass preparation technology.
Technical background
Common bathroom glass in use unavoidably can be residual water stain with other bathing spots, long-term accumulation not only influences attractive in appearance but also can make a large amount of bacteria breeds, influences living environment and healthy.Frequent cleans to bathroom glass then can consume great amount of water resources, and a large amount of use dischargings of washing composition simultaneously also can cause secondary pollution to environment.On the other hand, behind the simple glass life-time service, owing to receive the erosion of aqueous vapor mildew phenomena can take place, surface staining forms rainbow, hickie or spray etc., and transparency is reduced, and is difficult to clean.Bathroom glass is owing to be in the moist environment for a long time, and the existence meeting of gases such as a large amount of steam and CO2 is this Signs of Mould of aggravation further, has a strong impact on the work-ing life of glass.
Self-cleaning glass must have two kinds of performances: photocatalytic and photic Superhydrophilic.The former is meant that glass surface has photo-catalysis capability under the irradiation of light, can decompose the organic pollutant molecule that is adsorbed on glass surface, makes it to be decomposed into small molecules, or even carbonic acid gas and water molecules; The latter is meant that under rayed glass surface can keep the ultra affinity with water for a long time, and water can not form the globule but the layer of even moisture film at glass surface, and like this, the pollutent of glass surface is taken together under the washing away of water.The most outstanding advantage of self-cleaning glass exactly can automatically cleane and need not to go to clean with washing composition or external force again, thereby has received the extensive concern of industry.
The preparation of self-cleaning glass is the film that has self-cleaning function at surface of ordinary glass plating one deck, and the TiO2 film becomes the most original and most widely used self-cleaning function material because of having photocatalysis to degrade organic matter characteristic and photic Superhydrophilic.The Hashimoto of Tokyo Univ Japan in 1972, discovery TiO2 electrodes such as Fujishima can make water decomposition under illumination condition, find that also TiO2 film surface after illumination has photocatalytic activity.These achievements have caused the numerous investigators' in the world attention once delivering, and the various countries scholar has launched the research of relevant TiO2 photocatalysis performance rapidly, and begins to be applied to industrial circle, and initial application mainly is sewage and air-polluting purification aspect at once.1997, Fujishima etc. found that further the TiO2 film also has photic Superhydrophilic.TiO2 film its hydrophilicity under UV-irradiation has bigger variation: water contacts with the TiO2 film surface, and contact angle is more than tens of degree during beginning; After receiving UV-irradiation, contact angle can diminish rapidly, reaches at last or near zero degree, presents super hydrophilicity; Stop irradiation, contact angle can progressively raise, if can become ultra hydrophily again through irradiation again.Chemical Vapor deposition process is the preparation method of the self-cleaning glass studying the earliest and on production line, use.Chemical vapour deposition is that chemical reaction is carried out on the substrate of flowing through (glass) surface, generates the film forming method of solid matter at glass surface with after the chemical substance gasification.Its advantage is that the film purity of preparation is high, compactness is good, forms good crystalline material easily; Be easy to realize the mass-producing continuous production, constant product quality.Adopt the CVD legal system to be equipped with the TiO2 film, deposition results often is three kinds of TiO2 crystal formation coexistences, because the TiO2 content of effective ingredient Detitanium-ore-type is low, wetting ability and photocatalytic are difficult to guarantee; The film of this method preparation is generally the non-nano structure simultaneously, and specific surface area is little, makes that also its efficient is lower.For remedying above-mentioned deficiency, the CVD method often improves performance through increasing the thickness mode, causes the loss of transmission of film.In addition, because equipment requirements is high, shortcomings such as cost is high, initial investment is big, very flexible, the product of CVD method had popularization on market, but because performance and cost factor, the market feedback effect is not very good.
Magnetron sputtering method is a kind of method of thin film physics vapour deposition; Be under the condition of the photoglow under the control of ring-type magnetic field; The positive ion that utilizes geseous discharge to produce quickens to become high energy particle under electric field action, bump solid film layer material surface; After carrying out energy and momentum-exchange, the atom of film material or molecule leave the surface and are deposited on film forming method on the glass substrate under bombardment.The film of magnetron sputtering method preparation has high quality, high-density, good sticking power and intensity, and the processing unit (plant) stable performance, is convenient to operation, and technology is controlled easily, produces good reproducibility, is applicable to deposited of large area, convenient continuous and semicontinuous production.But owing to being target with the titanium, the speed that generates the TiO2 film at glass surface is slow, and plated film efficient is low, influences production cost; The thickness of plated film does not reach to a certain degree simultaneously, makes the photocatalysis efficiency of film not reach application indexes, but the too thick visible light transmissivity that can influence glass again of plated film.Therefore, up to the present magnetron sputtering method still fails to be applied to mass production TiO2 film self-cleaning glass.
Sol-gel method is the automatically cleaning effect working method of self-cleaning glass preferably of industrialization at present and product.Sol-gel method is from solution, after solation, gelation, and a kind of method of preparation nanometer film under coldcondition.Advantage is: 1, low temperature also can obtain self-cleaning glass, and equipment is simple, and the initial investment cost is low; 2, the factors such as composition, pH value, temperature of reaction and time of drying through the adjustment material solution can realize the adjusting to micropore size, distribution and the arrangement situation of xln in material of material, obtain the thin-film material of ideal functionality; 3, raw material with molecularity dissolving, mix the material that also can evenly be formed multi-component reaction.Shortcoming is: what 1, obtain is amorphous structure; Must could prepare and have the anatase structured of good light catalytic performance through subsequent heat treatment, have the transformation efficiency problem, and the thermal treatment meeting cause grain growth; Reduce the specific surface area of film, thereby influence its automatically cleaning effect; 2, dipping lifts and usually causes the inhomogeneous of film surface structure, therefore rainbow phenomena occurs, and the transmittance of film is reduced; 3, the sticking power of rete and glass is relatively poor, influences the work-ing life of self-cleaning glass.
Take a broad view of domestic and international research in recent years, the technology of preparing of TiO2 film has had very much progress, and the utilization scope enlarges gradually, but still exists the scientific and technical difficult problem of several keys, makes its widespread use in industry receive very big restriction.These problems mainly comprise: (1) quantum yield is low, and photocatalysis efficiency is low; (2) solar energy utilization ratio is low, is that main photocatalyst can only absorb the ultraviolet part in the sunshine with TiO2, and can not makes full use of the visible light part; (3) present research mostly concentrates on the photocatalytic activity of film, has often ignored the photoinduction wetting ability, and these two kinds of performances of photocatalytic activity and photoinduction wetting ability cooperate with each other and reach good result; (4) load technology of film does not also reach and is both keeping high catalytic activity; Satisfy again under the prerequisite that the physicochemical property of certain material requires; On the differing materials surface evenly, supported catalyst securely, the weather resisteant when the TiO2 film combines with the bathroom glassy phase, wear resistance, erosion resistance, thermotolerance etc. are demanded urgently further promoting and improving.
The have its source in Na2O of glass surface of weathering of glass gets into film through pellicular water to the erosion process of glass, and the result makes pellicular water become alkaline solution, causes the corrosion to the glass skeleton.The content of Na2O is high more in the glass, be etched so that mouldy possibility big more; But, to use Na2O in the preparation process of glass inevitably as fusing assistant.Existing mold-proof method normally after the glass smelting moulding, before packing uses, manages to make Na2O that mouldy influence degree is reduced.Mildew-resistant mechanism mainly contains: the content of top layer Na2O is reduced in (1), thereby reduces pellicular water to glass attack speed; Like aeration; (2) isolated moisture like mildew-resistant powder method, holding paper method etc., makes moisture can not arrive glass surface, reduces the etchant of glass surface; (3) depressor effect like spray method, holding paper method etc., contains divalent-metal ion in " mist ", " paper ", stop Na+ from glass inside to surface transport; (4) sterilization like bactericidal assay, adds sterilant in glass ingredient, or at the glass surface spraying fungicide, the bacterium of glass surface can not be grown, and prevents mouldy; (5) reduce surface p H value,, can reduce glass surface " protective membrane " corrosion speed like mildew-resistant powder method, holding paper method etc.
At present, the glass fungus-proof measure generally adopted of China's sheet glass manufacturing enterprise mainly contains the holding paper method and sprays glass fungus-proof powder method.Owing to adopt to spray glass fungus-proof powder method to glass surface and have better anti-mold effect, employing sprays the glass fungus-proof powder and replaces traditional holding paper mildew-resistant method basically in the world.Though present mold-proof method all has certain anti-mold effect; But but exist the mildew-resistant time short; Be prone to cause problems such as cleaning difficulty, and in the glass use, all materials that play mildew-proof function all can be removed at formation powder trace on glass; Therefore, can't realize the mildew-resistant of glass in using.How mildew-resistant and the automatically cleaning with glass effectively combines have to be solved to reach good comprehensive performances.
Summary of the invention
The present invention is directed to above-mentioned defective,, a kind of automatically cleaning mildew-resistant bathroom glass of environmental protection is provided through adding inorganic airsetting material.
Technical scheme of the present invention is following:
A kind of automatically cleaning mildew-resistant bathroom glass preparation technology is substrate with the bathroom special glass, adopts the spraying film to prepare automatically cleaning mildew-resistant bathroom glass, it is characterized in that, comprises the steps:
(1) cleaning of glass is cleaned its surface before plated film, and selecting neutral synthetic washing agent, pickle solution and pure water for use is the liquid cleaning medium, uses the glass washer-drier to wash, and the glass after the washing is through the steam heating drying for standby;
(2) spraying plated film at glass surface spraying mildew-resistant liquid, secondly is that the TiO2 film is then adopted the sol-gel method preparation at first; Promptly according to the compositing formula of TiO2 base film colloidal sol of design; In liquid stirrers, obtain stable, uniform sol, under certain temperature and pressure, adopt the high-pressure atomization spray gun device that colloidal sol evenly is sprayed on the glass substrate with the certain speed operation; Because the Evaporation of polyreaction and solvent; Dissolved adhesiveness increases rapidly, constantly transforms to gel, obtains certain thickness TiO2 gel-film;
(3) drying of plated film deposits to the gel-film of glass surface through the gelatinization process of colloidal sol, solvent is also contained in inside, under specific temperature, adopts specific drying program, makes gel-film in the glass surface firm attachment;
(4) thermal treatment of plated film is sent into the gel-film behind the finish-drying in the heat treatment furnace, through control heat-treating atmosphere, heat-up rate, Heating temperature and heat-up time, obtains required function film glass.
Mildew-resistant liquid staple in the described step (2) adopts organic acid, cationic metal salt, tensio-active agent etc.
The compositing formula according to the TiO2 base film colloidal sol that designs in the described step (2) comprises titanium alkoxide, template, solvent, catalyzer, doping agent etc.
The exploitation and the industrialization of the automatically cleaning mildew-resistant bathroom glass of environmental protection provided by the invention; Not only can build healthy living space attractive in appearance for people; And can reduce a large amount of unnecessary wastings of resources; Prolong the work-ing life of bathroom glass, have important social benefit, economic benefit and environmental benefit, embody through the following aspects:
1, introduces organic formwork, construct special micro nano surface structure more easily, obtain Superhydrophilic, make the film of high-specific surface area, improve photocatalysis performance;
2, replace pulling film forming technology commonly used, adopt the spraying film-forming process, the uniform film of construction structure is avoided the rainbow effect;
3, introduce the inorganic oxide layer, improve the weathering resistance and the resistance to acids and bases of film;
4, self-cleaning film and mildew-resistant protective membrane are effectively combined, construct multi-functional environment-protection bathroom glass, can reach following technical indicator:
(1) good, the smooth surface of the rete transparency, non-ripple, nothing come off, no rainbow effect, visible light transmittance rate is greater than 80%;
(2) the photocatalytic degradation rate of TiO2 is greater than 90%;
(3) through doping vario-property, its excitation wavelength is widened to visible-range, improved the catalyzed degradation ability under the visible light TiO2;
(4) the water droplet contact angle θ of TiO2 film surface＜5 °;
(5) the rete wear resistance reaches the requirement of GB 5137.1;
(6) rete can soak 48h at 2～4%HCl solution or in 2～4%NaOH solution serious erosion not take place;
(7) in climatic chamber, carry out mouldy experiment, mouldy grade is more than the B level.
Embodiment
A kind of automatically cleaning mildew-resistant bathroom glass preparation technology is substrate with the bathroom special glass, adopts the spraying film to prepare automatically cleaning mildew-resistant bathroom glass, it is characterized in that, comprises the steps:
(1) cleaning of glass is cleaned its surface before plated film, and selecting neutral synthetic washing agent, pickle solution and pure water for use is the liquid cleaning medium, uses the glass washer-drier to wash, and the glass after the washing is through the steam heating drying for standby;
(2) spraying plated film at glass surface spraying mildew-resistant liquid, secondly is that the TiO2 film is then adopted the sol-gel method preparation at first; Promptly according to the compositing formula of TiO2 base film colloidal sol of design; In liquid stirrers, obtain stable, uniform sol, under certain temperature and pressure, adopt the high-pressure atomization spray gun device that colloidal sol evenly is sprayed on the glass substrate with the certain speed operation; Because the Evaporation of polyreaction and solvent; Dissolved adhesiveness increases rapidly, constantly transforms to gel, obtains certain thickness TiO2 gel-film;
(3) drying of plated film deposits to the gel-film of glass surface through the gelatinization process of colloidal sol, solvent is also contained in inside, under specific temperature, adopts specific drying program, makes gel-film in the glass surface firm attachment;
(4) thermal treatment of plated film is sent into the gel-film behind the finish-drying in the heat treatment furnace, through control heat-treating atmosphere, heat-up rate, Heating temperature and heat-up time, obtains required function film glass.
Mildew-resistant liquid staple in the described step (2) adopts organic acid, cationic metal salt, tensio-active agent etc.
The compositing formula according to the TiO2 base film colloidal sol that designs in the described step (2) comprises titanium alkoxide, template, solvent, catalyzer, doping agent etc.
Claims (3)
1. an automatically cleaning mildew-resistant bathroom glass preparation technology is substrate with the bathroom special glass, adopts the spraying film to prepare automatically cleaning mildew-resistant bathroom glass, it is characterized in that, comprises the steps:
(1) cleaning of glass is cleaned its surface before plated film, and selecting neutral synthetic washing agent, pickle solution and pure water for use is the liquid cleaning medium, uses the glass washer-drier to wash, and the glass after the washing is through the steam heating drying for standby;
(2) spraying plated film at glass surface spraying mildew-resistant liquid, secondly is that the TiO2 film is then adopted the sol-gel method preparation at first; Promptly according to the compositing formula of TiO2 base film colloidal sol of design; In liquid stirrers, obtain stable, uniform sol, under certain temperature and pressure, adopt the high-pressure atomization spray gun device that colloidal sol evenly is sprayed on the glass substrate with the certain speed operation; Because the Evaporation of polyreaction and solvent; Dissolved adhesiveness increases rapidly, constantly transforms to gel, obtains certain thickness TiO2 gel-film;
(3) drying of plated film deposits to the gel-film of glass surface through the gelatinization process of colloidal sol, solvent is also contained in inside, under specific temperature, adopts specific drying program, makes gel-film in the glass surface firm attachment;
(4) thermal treatment of plated film is sent into the gel-film behind the finish-drying in the heat treatment furnace, through control heat-treating atmosphere, heat-up rate, Heating temperature and heat-up time, obtains required function film glass.
2. according to claim 1 described a kind of automatically cleaning mildew-resistant bathroom glass preparation technology, it is characterized in that the mildew-resistant liquid staple in the described step (2) adopts organic acid, cationic metal salt, tensio-active agent etc.
3. according to claim 1 described a kind of automatically cleaning mildew-resistant bathroom glass preparation technology, it is characterized in that the compositing formula according to the TiO2 base film colloidal sol that designs in the described step (2) comprises titanium alkoxide, template, solvent, catalyzer, doping agent etc.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2012101463603A CN102701601A (en) | 2012-05-11 | 2012-05-11 | Preparation technique of self-cleaning and mildew-proof bathroom glass |
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| CN2012101463603A CN102701601A (en) | 2012-05-11 | 2012-05-11 | Preparation technique of self-cleaning and mildew-proof bathroom glass |
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| CN102701601A true CN102701601A (en) | 2012-10-03 |
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| CN2012101463603A Pending CN102701601A (en) | 2012-05-11 | 2012-05-11 | Preparation technique of self-cleaning and mildew-proof bathroom glass |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113246577A (en) * | 2021-05-06 | 2021-08-13 | 常熟明阳玻璃制品有限公司 | Production process of high-strength self-cleaning bathroom glass |
Citations (5)
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|---|---|---|---|---|
| CN1400185A (en) * | 2001-07-31 | 2003-03-05 | 武汉理工大学 | Method for preparing high-activity titanium dioxide film self-cleaning glass material |
| KR20040054263A (en) * | 2002-12-18 | 2004-06-25 | 이성호 | Development of Hydrophilic Glass for Automotive Windows |
| CN1817812A (en) * | 2005-02-07 | 2006-08-16 | 格兰特工程玻璃(中山)有限公司 | Production of self-cleaning glass |
| CN1872756A (en) * | 2006-06-13 | 2006-12-06 | 蒋建新 | Technique for fabricating Nano self-cleaning glass |
| CN102211877A (en) * | 2011-04-11 | 2011-10-12 | 河北大学 | Highly self-cleaning hydrophilic glass and preparation method |
-
2012
- 2012-05-11 CN CN2012101463603A patent/CN102701601A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1400185A (en) * | 2001-07-31 | 2003-03-05 | 武汉理工大学 | Method for preparing high-activity titanium dioxide film self-cleaning glass material |
| KR20040054263A (en) * | 2002-12-18 | 2004-06-25 | 이성호 | Development of Hydrophilic Glass for Automotive Windows |
| CN1817812A (en) * | 2005-02-07 | 2006-08-16 | 格兰特工程玻璃(中山)有限公司 | Production of self-cleaning glass |
| CN1872756A (en) * | 2006-06-13 | 2006-12-06 | 蒋建新 | Technique for fabricating Nano self-cleaning glass |
| CN102211877A (en) * | 2011-04-11 | 2011-10-12 | 河北大学 | Highly self-cleaning hydrophilic glass and preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 王承遇等: "《玻璃表面处理技术》", 31 July 2004, 化学工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113246577A (en) * | 2021-05-06 | 2021-08-13 | 常熟明阳玻璃制品有限公司 | Production process of high-strength self-cleaning bathroom glass |
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Application publication date: 20121003 |