CN1911846B - Nanometer self-cleaning composition - Google Patents
Nanometer self-cleaning composition Download PDFInfo
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- CN1911846B CN1911846B CN200610040983A CN200610040983A CN1911846B CN 1911846 B CN1911846 B CN 1911846B CN 200610040983 A CN200610040983 A CN 200610040983A CN 200610040983 A CN200610040983 A CN 200610040983A CN 1911846 B CN1911846 B CN 1911846B
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Abstract
The present invention discloses one kind of nanometer self-cleaning composition and its making process. The nanometer self-cleaning composition consists of nanometer titania 9-23 weight portions, nanometer silica 0.3-0.75 weight portions, nanometer metal additive 0.4-2.4 weight portions, surfactant 0.1-1.0 weight portions, deionized water 63.75-77 weight portions and organic solvent 11-13.5 weight portions. The nanometer self-cleaning composition is used in making self-cleaning glass mainly. Its making process includes the following steps: adding surfactant into deionized water, adding nanometer titania and nanometer metal additive, adding organic solvent, adding silica, and stirring. The making process is simple and has no environmental pollution.
Description
[technical field]
The present invention relates to a kind of nanometer self-cleaning composition, belong to technical field of nano material.
[background technology]
Most of self-cleaning product combination thing all is main raw material(s) with titanium dioxide.Titanium dioxide is a kind of white or pale yellow powder, and is water insoluble, also is insoluble to diluted acid.Titanium dioxide has three kinds of crystal formations: anatase type, rutile-type, brookite type.The brookite type instability does not still have industrial use; Rutile-type and Detitanium-ore-type all belong to tetragonal system, but because of the crystal formation difference, so different crystalline habits is arranged.
Rutile-type is elongated paired two-ling, and each rutile unit cell contains 2 titania molecule, links to each other with two seamed edges.
Detitanium-ore-type then occurs with octahedral form, and oxygen is positioned at octahedral drift angle, and each sharp titanium structure cell contains 4 titania molecule, links to each other with eight seamed edges.Detitanium-ore-type is (more than 700 degree) at high temperature, can be transformed into rutile-type, discharge the energy of 7.5 * 4.1868KJ/mol simultaneously.This conversion process also is subjected to some acceleration or suppresses the promotor of crystal formation conversion or the influence of inhibitor except temperature influence, and conversion is irreversible.Anatase titanium dioxide is generally in 400 degree left and right sides crystallizations.
Detitanium-ore-type has lot of advantages, and photoetch does not take place, and resistance to acids and bases is good, and chemical property is stable, and to biological nontoxic, the source is abundant, and energy gap is bigger, and the current potential of photohole is 3.2eV, and very strong oxidisability is arranged.It is a kind of photocatalytic semiconductor antiseptic-germicide, as a kind of N-type semiconductor, its energy gap is equivalent to the energy of wavelength 400nm light, can absorb the optical radiation that energy is higher than its energy gap at wavelength under less than the illumination of 400nm, produces transition of electron, valence electron is excited to conduction band, form hole one electron pair, and give medium on every side, bring out photochemical reaction transmission ofenergy, having photo-catalysis capability, is at present special ideal photocatalyst material.
Self-cleaning glass is glass with clean again, and multiple production technique is arranged, as sol-gel technology, off-line magnetron sputtering or vacuum deposition process, online CVD (chemical vapour deposition) and various dip-coating, spraying coating process.Make the production technique difference of self-cleaning glass, its required material combination composition formula is also inequality.Although the membranous layer ingredient of glass with clean mostly mainly contains titanium dioxide in analyzing, used titaniferous starting material are different when making self-cleaning composition.
Domestic many documents were all reported employing catalytic self-cleaning composition or self-cleaning film, as Chinese patent 03130468.0,00109176.X, 02147089.8,02805882.2,03814201.5,00808643.5,03817836.2,03803822.6 etc., they have all used organic titanium salt and/or silicone resin to be starting material, organic titanium salt comprises isopropyl titanate, titanium ethanolate, titanium tetraethoxide, four n-propyl alcohol titaniums, four propyl carbinol titaniums, the butyl titanium isopropylate, four (2-Ethyl Hexanol) titanium etc., and need add a large amount of organic solvents when dissolving these organic titanium salts and/or silicone resin, these organic titanium salts and/or silicone resin at high temperature resolve into titanium dioxide or silicon-dioxide, and organic solvent and its by product will recycle through complicated retrieving arrangement, otherwise can pollute environment.
Chinese patent 01131337.4 discloses a kind of preparation method of metal composite titanium dioxide nano particle, with the titanium tetrachloride is raw material, add transition metal salts such as iron, nickel, silver, add ammoniacal liquor, oxalate, thiosulphate etc. as complexing agent, utilize hydrothermal method, prepare the metal composite titanium dioxide nano particle that contains transition metal ion 0.005-5 weight part, titanium dioxide 95-100 weight part.
Chinese patent 01115626.0 discloses a kind of titania nano-paint and preparation method thereof, under the normal temperature, titanium dioxide nano-particle colloidal sol, organosilicon binding agent and solvent is even, wherein titanium dioxide nano-particle content is 0.5～30 grams per liter of coating system total amount, organosilicon caking agent content is 0.2～1 times of content of titanium dioxide in the coating system, makes the titania coating that is used to form photocatalytic transparent hydrophilic coating.Above-mentioned solvent preferably makes the mixed system of water and methyl alcohol, and alcohol is shared that ratio is not less than 50%.
Compare with Chinese patent 01131337.4,01115626.0, the invention discloses a kind of, preparation technology more simple nanometer self-cleaning composition free of contamination substantially environment.Employed titanium dioxide, silicon-dioxide, metal additive are nano level in manufacturing processed, help the homodisperse of raw material in solvent, help improving the self-cleaning property and the photocatalysis performance of self-cleaning composition, also help the tack and the compactness of the rete that utilizes the glass with clean that this self-cleaning composition makes.This nanometer self-cleaning composition is applicable to online production glass with clean on the floatation glass production line, is specially adapted to by high temperature pyrolysis spraying method online production glass with clean.
[summary of the invention]
First technical problem to be solved by this invention is to provide a kind of, preparation technology more simple nanometer self-cleaning composition free of contamination substantially to environment.
Second technical problem to be solved by this invention is to provide a kind of manufacture method of nanometer self-cleaning composition.
The present invention solves above-mentioned first technical problem by the following technical programs: a kind of nanometer self-cleaning composition, and this self-cleaning composition comprises: nano titanium oxide 9-23 weight part; Nano silicon 0.3-0.75 weight part; Nanometer metal additive 0.4-2.4 weight part; Tensio-active agent 0.1-1.0 weight part; Deionized water 63.75-77 weight part; Organic solvent 11-13.5 weight part.
This nanometer self-cleaning composition is applicable to online production glass with clean on the floatation glass production line, is specially adapted to by high temperature pyrolysis spraying method online production glass with clean.
Titanium dioxide is main raw material(s), because Detitanium-ore-type has very strong photocatalysis performance, and price is relatively cheap, so the present invention advises using the titanium dioxide of Detitanium-ore-type, uses Detitanium-ore-type can produce the best self-cleaning composition of photocatalysis performance; Certainly, rutile-type also has suitable photo-catalysis capability, so it is feasible adding a certain proportion of rutile-type in Detitanium-ore-type, but the shared ratio of suggestion rutile-type does not surpass 40%, and the titanium dioxide nano-particle of indication of the present invention is Detitanium-ore-type, rutile-type or the mixing crystal formation of the two.
In addition, the size of the TiO 2 particles that suggestion is used is nano level, and median size is 5-25nm, is preferably 8-17nm; This nanometer particle size all is vital to the photochemical catalysis effect of glass with clean, the compactness of rete.So the present invention also recommends to use nano silicon and nanometer metal additive.
Nano silicon is selected from one or more in nanometer titanium dioxide silicon emulsion, nano-silica powder end, liquid nanometer silicon-dioxide, the silicon oxide monocrystal nanowire.It at first can improve the wetting ability of glass with clean rete, reduces hydrophilic angle; Film strength be can also increase, stability and wearability improved.In addition, in the high temperature pyrolysis spraying process, it can also promote adhering between self-cleaning composition and the hot glass sheet matrix, has improved the sedimentation effect of self-cleaning composition to a certain extent, has reduced production cost.
Nanometer metal additive comprises one or more in cerium oxide, zinc oxide, aluminum oxide, zirconium white, cupric oxide, Praseodymium trioxide, Neodymium trioxide, lanthanum trioxide, platinum oxide, rhodium oxide, iridium oxide, palladous oxide, gold trioxide, the ruthenium oxide.
Structure, abundant transition of electron energy level is arranged, very responsive to photoabsorption, and has a stronger oxidation activity, therefore aspect photochemical catalytic oxidation, activity is stronger, particularly the photocatalyst that is combined into nano TiO 2, better effects if. and produce a large amount of negative oxygen ions, can improve indoor air environment. platinum oxide, zinc oxide, cupric oxide etc. have similar effect.
Add metal oxides such as zirconium white, Praseodymium trioxide, Neodymium trioxide, iridium oxide, also can improve the photochemical catalysis effect to a certain extent, also can improve water-repellancy, alkali-resistivity, wearability, wearing quality; Add-on does not have corresponding effect very little; Add-on is too many, the composition gelling easily takes place or condense deterioration of film outward appearance or photocatalysis reduction.The present invention advises using the 0.4-2.4 weight part of self-cleaning composition gross weight.
Tensio-active agent is nonionogenic tenside, nonionic poly-hydroxy tensio-active agent, aqueous wetting agent.It can reduce the surface tension between nano-metal-oxide and the solvent, and it mainly acts on is exactly to improve dispersion or the suspension effect of above-mentioned nano-metal-oxide particle in solution.
Solvent partly comprises inorganic solvent and organic solvent.Inorganic solvent is a deionized water, and organic solvent is selected from a kind of in methyl chloride, Virahol, bromo propane, bromic ether, methyl alcohol, chloric ethane, the methyl bromide.Deionized water 63.75-77 weight part; Organic solvent 11-13.5 weight part.Solvent is equivalent to the carrier of above-mentioned various metal oxides, under the drive of solvent and atomizing gas, above-mentioned nano-metal-oxide particle is sprayed onto the glass pane surface of heat.And the organic solvent in the solvent only accounts for the 1/5-1/7 of deionized water, the discharge of the by product when having significantly reduced the volatilization of organic solvent and organic metal salt high temperature pyrolysis, and whole technology has all strengthened environment protecting.
The present invention solves above-mentioned second technical problem by the following technical programs: a kind of manufacture method of nanometer self-cleaning composition, and the manufacture method of said composition may further comprise the steps:
1. the tensio-active agent that in the deionized water of 63.75-77 weight part, adds the 0.1-1.0 weight part;
2. in 1., add the nano titanium oxide of 9-23 weight part, the nanometer metal additive of 0.4-2.4 weight part;
3. and then add the organic solvent of 11-13.5 weight part;
4. in adding the nano silicon of 0.3-0.75 weight part 3. again.
In the manufacturing processed of said composition or after each step finishes, all will be through stirring, churning time was controlled at 5-60 minute.
This nanometer self-cleaning composition manufacture method simply is suitable for, environmentally safe basically.
This nanometer self-cleaning composition is mainly used in the manufacturing glass with clean, particularly online manufacturing glass with clean.
Further specify, this nanometer self-cleaning composition is used for online manufacturing and has hydrophilic, degradable organic pollutant and obnoxious flavour, purifies air, deodorizing, mildew-resistant, antifog, antibiotic, attrition resistant glass with clean.
Used substrate glass comprises system mirror level glass, automotive grade glass, architectural grade glass among the present invention.It can be colourless transparent glass; Also can be various colored glass, as green glass, blue glass, smoked glass, cranberry glass etc.
Because the used starting material of nanometer self-cleaning composition among the present invention have directly used TiO 2 particles, silicon-dioxide, metal additive etc., and the organic salt of organo-metallic salt, silicone resin and other metals that does not use titanium is as starting material; And methyl alcohol in solvent about only the 1/5-1/7 of the ionized water that accounts for, the discharge of the by product when having significantly reduced the volatilization of organic solvent and organic metal salt high temperature pyrolysis, whole technology has all strengthened environment protecting.Compare with other disclosed documents and materials, preparation technology of the present invention is relatively simple, suitable.
The present invention's starting material such as employed titanium dioxide, silicon-dioxide, metal additive in the manufacturing processed of nanometer self-cleaning composition are Nano grade, and median size is 5-25nm, is preferably 8-17nm; This nanometer particle size all is vital to the photochemical catalysis effect of glass with clean, the compactness of rete.
The glass with clean that utilizes this self-cleaning composition to produce is widely used, and can be applied to fields such as system mirror glass, vehicle glass, automobile rearview mirror, buildings glass, glass curtain wall, upholstery glass, shower room glass, glass partition, glass door, urban public utilities, billboard.
[embodiment]
In the deionized water of 69 weight parts, add the tensio-active agent of 0.5 weight part, stirred 5 minutes; Add the nano-titania particle of 17 weight parts, the nano-cerium oxide of 1.9 weight parts and the mixture of nano zine oxide then, stirred 40 minutes; And then add the organic solvent of 11.1 weight parts, stirred 5-15 minute; The nano silicon that adds 0.5 weight part again stirred 60 minutes, can obtain nanometer self-cleaning composition.
With above-mentioned self-cleaning composition, under atomizing gas drives, spray to the glass pane surface of heat by reciprocating type spray gun, the surface temperature of sheet glass is 400-630 ℃, spray tip is 19cm to the distance of sheet glass, the transfer pressure of atomizing gas is 0.45MPa, and the flow of raw material nozzles is 1.0L/min.
Claims (9)
1. nanometer self-cleaning composition, it is characterized in that: this self-cleaning composition comprises
Nano titanium oxide 9-23 weight part
Nano silicon 0.3-0.75 weight part
Nanometer metal additive 0.4-2.4 weight part
Tensio-active agent 0.1-1.0 weight part
Deionized water 63.75-77 weight part
Organic solvent 11-13.5 weight part,
Above-mentioned each component is 100 weight parts in gross weight.
2. nanometer self-cleaning composition as claimed in claim 1 is characterized in that: nano-titania particle is Detitanium-ore-type, rutile-type or the mixing crystal formation of the two.
3. nanometer self-cleaning composition as claimed in claim 1 is characterized in that: nano silicon is at least a in nano-silica powder end, the silicon oxide monocrystal nanowire.
4. nanometer self-cleaning composition as claimed in claim 1 is characterized in that: this nanometer metal additive comprises at least a in cerium oxide, zinc oxide, aluminum oxide, zirconium white, cupric oxide, Praseodymium trioxide, Neodymium trioxide, lanthanum trioxide, platinum oxide, rhodium oxide, iridium oxide, palladous oxide, gold trioxide, the ruthenium oxide.
5. nanometer self-cleaning composition as claimed in claim 1 is characterized in that: tensio-active agent is a nonionic poly-hydroxy tensio-active agent.
6. nanometer self-cleaning composition as claimed in claim 1 is characterized in that: organic solvent is selected from a kind of in methyl chloride, Virahol, bromo propane, bromic ether, methyl alcohol, chloric ethane, the methyl bromide.
7. the manufacture method of a nanometer self-cleaning composition, it is characterized in that: the manufacture method of said composition may further comprise the steps:
1. the tensio-active agent that in the deionized water of 63.75-77 weight part, adds the 0.1-1.0 weight part;
2. in 1., add the nano titanium oxide of 9-23 weight part, the nanometer metal additive of 0.4-2.4 weight part;
3. and then add the organic solvent of 11-13.5 weight part;
4. in adding the nano silicon of 0.3-0.75 weight part 3. again, stir and get final product.
8. the manufacture method of nanometer self-cleaning composition as claimed in claim 7 is characterized in that: in its manufacturing step or after each step end, need to stir 5-60 minute.
9. the manufacture method of nanometer self-cleaning composition as claimed in claim 7, it is characterized in that: deionized water 69 weight parts wherein, tensio-active agent 0.5 weight part, nano titanium oxide 17 weight parts, nanometer metal additive 1.9 weight parts, organic solvent 11.1 weight parts, nano silicon 0.5 weight part.
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| CN200610040983A CN1911846B (en) | 2006-08-15 | 2006-08-15 | Nanometer self-cleaning composition |
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| CN200610040983A CN1911846B (en) | 2006-08-15 | 2006-08-15 | Nanometer self-cleaning composition |
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| CN1911846B true CN1911846B (en) | 2010-05-12 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102560325A (en) * | 2012-02-23 | 2012-07-11 | 常州天合光能有限公司 | Method for preparing nanometer titanium dioxide (TiO2) self-cleaning film |
| CN107162420A (en) * | 2017-06-21 | 2017-09-15 | 合肥市旺友门窗有限公司 | A kind of nano mildew-proof glass and preparation method thereof |
| CN111826007A (en) * | 2020-07-29 | 2020-10-27 | 广州市达三江科技有限公司 | Long-acting self-cleaning composition for glass surface |
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| CN1380369A (en) * | 2002-05-16 | 2002-11-20 | 复旦大学 | Water high-weatherability nano external wall paint and its preparation method |
| CN1382521A (en) * | 2001-04-25 | 2002-12-04 | 中国科学院理化技术研究所 | Metal composite titanium dioxide nano particle and preparation method and application thereof |
| CN1384165A (en) * | 2001-04-28 | 2002-12-11 | 中国科学院化学研究所 | Titania nano-paint for forming photocatalytic transparent hydrophilic coating and its prepn |
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| CN1417147A (en) * | 2002-11-26 | 2003-05-14 | 复旦大学 | Low-temperature prepn process of self-cleaning nano Tio2 glass |
| US6576589B1 (en) * | 1999-09-20 | 2003-06-10 | Lg Electronics Inc. | Method for making anatase type titanium dioxide photocatalyst |
| EP1431351A1 (en) * | 2002-12-17 | 2004-06-23 | MERCK PATENT GmbH | Spherical inorganic absorption pigments |
| CN1788794A (en) * | 2004-12-13 | 2006-06-21 | 谢家忠 | Nanometer photo-catalytic sterilizing and air-cleaning agent |
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2006
- 2006-08-15 CN CN200610040983A patent/CN1911846B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6576589B1 (en) * | 1999-09-20 | 2003-06-10 | Lg Electronics Inc. | Method for making anatase type titanium dioxide photocatalyst |
| CN1382521A (en) * | 2001-04-25 | 2002-12-04 | 中国科学院理化技术研究所 | Metal composite titanium dioxide nano particle and preparation method and application thereof |
| CN1384165A (en) * | 2001-04-28 | 2002-12-11 | 中国科学院化学研究所 | Titania nano-paint for forming photocatalytic transparent hydrophilic coating and its prepn |
| CN1394918A (en) * | 2001-07-06 | 2003-02-05 | 韩巍 | Nano Water dispersion medium composition, its preparation method and application |
| CN1380369A (en) * | 2002-05-16 | 2002-11-20 | 复旦大学 | Water high-weatherability nano external wall paint and its preparation method |
| CN1417147A (en) * | 2002-11-26 | 2003-05-14 | 复旦大学 | Low-temperature prepn process of self-cleaning nano Tio2 glass |
| EP1431351A1 (en) * | 2002-12-17 | 2004-06-23 | MERCK PATENT GmbH | Spherical inorganic absorption pigments |
| CN1788794A (en) * | 2004-12-13 | 2006-06-21 | 谢家忠 | Nanometer photo-catalytic sterilizing and air-cleaning agent |
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| CN1911846A (en) | 2007-02-14 |
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