CN104877401A - Preparation method and application of glass coating liquid - Google Patents
Preparation method and application of glass coating liquid Download PDFInfo
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- CN104877401A CN104877401A CN201510271484.8A CN201510271484A CN104877401A CN 104877401 A CN104877401 A CN 104877401A CN 201510271484 A CN201510271484 A CN 201510271484A CN 104877401 A CN104877401 A CN 104877401A
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Abstract
The invention relates to a preparation method and application of a glass coating liquid. The preparation method is characterized by comprising the following steps: conducting ion exchange on alkali metal silicate to obtain activated silicic acid; adding a calcium or magnesium salt catalyst into activated silicic acid; adjusting the acid-alkali property of activated silicic acid containing the calcium or magnesium salt catalyst by utilizing alkali metal silicate; carrying out hydro-thermal treatment to ensure that activated silicic acid with the adjusted acid-alkali property is condensed and converted into a silicon dioxide hydrosol adopting a reticular structure. Under the condition that the pH value is 8.0-8.5, a condensation reaction on activated silicic acid is completed at 60-75 DEG C within 3-12 hours; after the condensation reaction is completed, calcium-magnesium ions are removed through separation, so that the glass coating liquid formed through further ion exchange does not contain metal irons, and is high in storage stability; when a coating layer is dry, the size of the coating layer is slightly changed, and micro-cracks are avoided; no thickening or gelatinizing phenomenon occurs when an acidic silica sol, namely the silicon dioxide hydrosol, is stored at ordinary temperature for 12 months or below 60 DEG C for 2 months, so that the acidic silica sol can be applied as a solar cell glass anti-reflection coating liquid.
Description
Technical field
The present invention relates to a kind of preparation method and application of glass coating liquid, particularly excellent storage stability and film layer are without the preparation method of silica glass coating liquid of cracking and the application as solar cell glass antireflective coating liquid, belong to inorganic chemical industry and field of new.
Background technology
Silica sol particles has larger surfactivity, can be miscible with organic polymer through surface modification, is widely used in the industries such as coating, precision casting, refractory materials and electronic industry.Silicon dioxide gel can be divided into acidity, alkalescence and neutral silicon sol by its pH value scope.
The usual preparation technology of acidic silicasol is by commercial water glass solution dilution, so carries out exchange with Zeo-karb and obtains active silicic acid; By silicic acid with base extraction to alkalescence, then be heated and carry out condensation reaction and concentrated, obtained alkaline silica sol; Finally by alkaline silica sol again through resin cation exchange, add appropriate acid further and regulate, obtain acidic silicasol.
due toacidic silicasol is in metastable condition, and the slow gel of meeting in put procedure, stationary phase is shorter, and the acidic silicasol gel trend that concentration is high is more obvious.In addition, there is crack splitting in the rete that acidic silicasol coating is formed, and when thicknesses of layers is larger, rete instant of complete cracking powder phenomenon-tion even occurs.
Common silica sol particle is spherical particle structure, and the gel film that coating is formed along with very large volumetric shrinkage, is thus easy to cause that rete is crack to be split in drying process.Early stage solution is generally control rete rate of drying and controlling diaphragm layer thickness to reduce internal stress, but improvement effect is limited.The measure that modern times take is the silicon sol preparing high-crosslinking-degree or high-polymerization degree, and spherical silicon dioxide particle is interconnected formation wire or cancellated colloidal sol in advance, thus reduces the volumetric shrinkage of film in film forming drying process.Such as, US Patent No. 5221497 (1993-06-22) and US5597512 (1997-01-28) disclose a kind of acicular silica colloidal sol and preparation method thereof, in active silicic acid, add calcium or magnesium salts, the mol ratio controlling calcium or magnesium salts and silicon-dioxide is 0.0015-0.0085:1; Then by sodium hydroxide or aqueous ethanolamine adjustment silicic acid sol extremely alkalescence, the mol ratio controlling alkalimetal oxide and silicon-dioxide is 0.005-0.05:1; Hydrothermal treatment consists makes silicic acid condensation be converted into acicular structure silica hydrosol, fundamentally improves membranous layer property and decreases crack splitting, and gained alkaline silica sol can be stored storage at 6 months or 60 DEG C at normal temperatures and gel not occur in 1 month.And find in application practice, only within 1 month, just there is obvious retrogradation and gelatin phenomenon if it stored in acid condition, can not demand of industrial production be met.
Summary of the invention
The object of the invention is to provide a kind of preparation method of glass coating liquid, the technical scheme taked adds calcium or magnesium salts catalyzer in the active silicic acid obtained in alkalimetal silicate ion-exchange, with the acid-basicity of alkalimetal silicate adjustment active silicic acid, then hydrothermal treatment consists makes active silicic acid condensation be converted into reticulated structure silica hydrosol.The condensation reaction of active silicic acid of the present invention completes in 3-12h under 60-75 DEG C and pH8.0-8.5, be separated after condensation reaction completes and remove calcium ions and magnesium ions, not containing metal ion in the glass coating liquid that further ion-exchange is formed, there is good storage stability, when film layer is dry, volume change is little, rete does not have crack splitting, and acidic silicasol is stored 2 moonsets at storage at normal temperature and retrogradation or gelatin phenomenon are not occurred at 12 months or 60 DEG C.
Glass coating liquid preparation process of the present invention and concrete steps are:
(1) SiO is prepared
2mass percentage concentration is the sodium silicate solution of 3%-5%, with strong-acid ion exchange resin process to solution PH 2.5-3.5, make sodium silicate aqueous solution be converted into active silicic acid solution, described sodium silicate solution is that the water-soluble dilution of water glass solution of solid Starso or modulus 2-4 forms;
(2) under agitation in active silicic acid solution, calcium or magnesium salts catalyst solution is added, the mol ratio controlling calcium or Mg catalyst and silicic acid is 0.009-0.015:1, make calcium or the dispersed formation clear solution of magnesium ion, described calcium or magnesium salts are its nitrate, hydrochloride or acetate;
(3) under agitation SiO is added to containing in the active silicic acid solution of catalyzer
2the alkali metal silicate solutions of mass percentage concentration 3%-5%, regulator solution potential of hydrogen, to pH8.0-8.5, is then carried out condensation reaction 3-12h, is obtained SiO at 60-75 DEG C
2the alkaline silica sol of mass percentage concentration 5%-10%, described alkalimetal silicate is water glass, potassium silicate, lithium silicate or its mixture;
(4) under agitation in above alkaline silica sol, add the oxalate solution that mass percentage concentration is 3%-6%, the mol ratio controlling oxalate and calcium or Mg catalyst is 1-3; 1, to precipitate removing calcium or Mg catalyst, described oxalate is ammonium oxalate, potassium oxalate, sodium oxalate or lithium oxalate;
(5) by the hybrid resin process of the silicon sol strongly-acid and strong alkali ion exchange resin of sloughing calcium or Mg catalyst, remove positively charged ion residual in silicon sol and negatively charged ion, make silicon sol pH2.5-3.5;
(6) acidified silica sol is to pH1.8-2.5 further, and at 60 DEG C, vacuum concentration is to SiO
2mass percentage concentration reaches 25%, silicon sol median size 20-30nm.
The present invention adopts alkalimetal silicate to adjust the acid-basicity of active silicic acid, and when can avoid adopting sodium hydroxide or thanomin, silicon sol local potential of hydrogen uneven generation gel crystal seed, makes silicon sol stablize and not easily gel occur.Owing to adding calcium or the raising of Mg catalyst concentration, the condensation reaction of active silicic acid can complete rapidly at lesser temps with close under neutrallty condition.
Another object of the present invention is that to improve solar cell glass transmission rate, concrete steps are using glass coating liquid of the present invention as the application of solar battery glass antireflective coating liquid:
(1) be less than in the coating chamber of RH50% at control temperature 20 DEG C and relative humidity, glass coating liquid deionized water is diluted to SiO
2mass percentage concentration 5%;
(2) add in three roller coating equipments after being filtered by glass coating liquid, colloidal sol is attached on coating roll equably, and adjustment coating equipment rotating speed, controls wet-film thickness about 2000nm;
(3) by glass coating liquid roller coat on the solar cell glass print cleaned up, through 80-150 DEG C of zone heating solidification 3-6 minute, obtain general hepatic solar cell coated glass;
(4) the coating process parameter of optimizing regulation three roller coating equipment, makes the build of solar cell coated glass control at 140nm-180nm, and the average transmittance controlled before and after plated film in 380nm-1100nm wavelength region increases 2.5%-3.5%;
(5) by the solar cell glass print of plated film tempering process 3-6 minute in 500-720 DEG C of annealing furnace, by rete sintering at glass surface, film surface is smooth and split without crack, can meet crystal-silicon solar cell glass production application requiring.
Thicknesses of layers is tested: produce F20 type film thickness determinator with filmtrics company of the U.S. and measure, design thicknesses of layers 140nm-180nm.
Transmittance is tested: according to ISO 9050-2003, adopts PerkinElmer company to produce Lambda950 spectrophotometer, and the transmittance of test 250nm-1100nm wavelength region, gets the mean value of 4 different positions transmittances.
Salt fog is aging: foundation IEC 61215 standard, sample is put into 35 DEG C of salt fog ageing ovens, with 5% sodium chloride solution spraying, regularly takes out and surveys transmittance, designs the aging rear transmittance reduction of salt fog in 96 hours and is less than 1.0%.
Hydrothermal aging: foundation IEC 61215 standard, puts into the hydrothermal aging case of 85 DEG C and relative humidity 85%, regularly takes out and survey transmittance by sample, after designing 1000 hours hydrothermal agings, transmittance reduction is less than 1.0%.
Wet freeze aging: according to IEC 61215 standard, being put into by sample and wetly freezing ageing oven, being down to-40 DEG C, regularly taking out and survey transmittance from 85 DEG C and relative humidity 85%, design cycle number of times 10 times is wet to be frozen aging rear transmittance and reduces and be less than 1.0%.
Film hardness is tested: do not make rete occur the most hard pencil hardness of more than 3mm cut, design pencil hardness 5H.
Washability is tested: with tap water, washing composition, cotton, sponge and plastic composition test, regular taking-up surveys transmittance, tests 25 times, and before and after test, transmittance reduction is less than 1.0%.
Advantage of the present invention and beneficial effect are embodied in:
(1) the present invention adopts alkalimetal silicate to replace the acid-basicity of sodium hydroxide or thanomin adjustment active silicic acid, can avoid silicon sol local potential of hydrogen uneven generation gel crystal seed, and can avoid introducing the anionic group affecting collosol stability;
(2) the present invention adopts ion-exchange to remove calcium in silicon sol or magnesium salts catalyzer and charged ion, improves the package stability of acidic silicasol;
(3) the silica sol particle polymerization degree of the present invention is high and have plane reticular structure, and when rete is dry, volume change is little, does not have crack splitting, can reach solar battery glass antireflective coating liquid application requiring.
Embodiment
Embodiment 1
Commercial solid water glass is dissolved in deionized water, preparation 2000g SiO
2the sodium silicate solution (0.5mol/L) of mass percentage concentration 3%, exchanges process with strong-acid ion exchange resin, then washes resin with deionized water, obtain the active silicic acid solution of pH3.5; Under agitation add the ca nitrate soln 15mL of 1mol/L, be uniformly mixed 10min and obtain clear solution; The sodium silicate solution under agitation adding 0.5mol/L is about 30mL, and regulator solution potential of hydrogen, to pH8.0-8.5, is then evaporated and carries out condensation reaction 3-5h, obtaining SiO at 75 DEG C
2the alkaline silica sol 1015g of mass percentage concentration 6%; In alkaline silica sol, under agitation add the ammonium oxalate solution 62g(0.03mol that mass percentage concentration is 6%), cross the calcium oxalate precipitation filtering formation; Use the hybrid resin process of strongly-acid and strong alkali ion exchange resin further, remove ammonium, sodium, calcium positively charged ion and oxalate anion residual in silicon sol, then wash with deionized water, obtain the acidic silicasol 1100g of PH3.5; With rare oxalic acid solution acidified silica sol to pH 2.5, at 60 DEG C, vacuum concentration is to SiO
2mass percentage concentration reaches 25%, records silicon sol median size 20-30nm, stores storage at 12 months or 60 DEG C retrogradation or gelatin phenomenon do not occur for 2 months under normal temperature.
Above glass coating liquid is spent and is dried uply diluted to SiO
2mass percentage concentration is 5%, in the coating chamber of temperature 20 DEG C with relative humidity 50%, with three roller coating equipments by its roller coat on the solar cell glass of 10 300mm*300mm*3.2mm, 3 minutes are solidified through 80-150 DEG C of zone heating, obtain blueing purple solar cell coated glass, record thicknesses of layers 165nm, be 94.8% at the average transmittance of 380-1100nm wavelength region, before and after plated film, transmittance increases by 3.2 %.By it on solar energy glass tempering production line, the anti-reflection film of solar cell glass print that obtains for 3 minutes at about 700 DEG C tempering of glass tempering process routinely, film surface is level and smooth, splits without crack, hardness 6H, ageing resistance reaches IEC 61215 standard set quota.
Embodiment 2
Be the industrial waterglass deionized water preparation 2000g SiO of 2.2 by commercially available modulus
2the sodium silicate solution (0.5mol/L) of mass percentage concentration 3%, exchanges process with strong-acid ion exchange resin, then washes resin with deionized water, obtain the active silicic acid solution of PH2.5; Under agitation add the magnesium nitrate solution 10mL of 1mol/L, be uniformly mixed 15min and obtain clear solution; The potassium silicate solution under agitation adding 0.5mol/L is about 30mL, and regulator solution potential of hydrogen, to pH8.0-8.5, is then evaporated and carries out condensation reaction 8-10h, obtaining SiO at 65 DEG C
2the alkaline silica sol 1015g of mass percentage concentration 6%; In alkaline silica sol, under agitation add the ammonium oxalate solution 62g(0.03mol that mass percentage concentration is 6%), cross the calcium oxalate precipitation filtering formation; Use the hybrid resin process of strongly-acid and strong alkali ion exchange resin further, remove ammonium, potassium, magnesium cation and oxalate anion residual in silicon sol, then wash with deionized water, obtain the acidic silicasol 1100g of pH2.5; With dilute phosphoric acid solution acidified silica sol to pH 1.8, at 60 DEG C, vacuum concentration is to SiO
2mass percentage concentration reaches 25%, records silicon sol median size 20-30nm, stores storage at 12 months or 60 DEG C retrogradation or gelatin phenomenon do not occur for 2 months under normal temperature.
Above glass coating liquid is spent and is dried uply diluted to SiO
2mass percentage concentration is 5%, in the coating chamber of temperature 20 DEG C with relative humidity 50%, with three roller coating equipments by its roller coat on the solar cell glass of 10 300mm*300mm*3.2mm, 3 minutes are solidified through 80-150 DEG C of zone heating, obtain blueing purple solar cell coated glass, record thicknesses of layers 175nm, be 94.6% at the average transmittance of 380-1100nm wavelength region, before and after plated film, transmittance increases by 3.0 %.By it on solar energy glass tempering production line, the anti-reflection film of solar cell glass print that obtains for 3 minutes at about 700 DEG C tempering of glass tempering process routinely, film surface is level and smooth, splits without crack, hardness 6H, ageing resistance reaches IEC 61215 standard set quota.
Claims (7)
1. the preparation method of a glass coating liquid, it is characterized in that in the active silicic acid obtained in alkalimetal silicate ion-exchange, adding calcium or magnesium salts catalyzer, with the acid-basicity of alkalimetal silicate adjustment active silicic acid, then hydrothermal treatment consists makes active silicic acid condensation be converted into reticulated structure silica hydrosol, be separated after condensation reaction completes and remove calcium ions and magnesium ions, not containing metallic impurity in the glass coating liquid that further ion-exchange is formed, there is good storage stability, when film layer is dry, volume change is little, rete does not have crack splitting, acidic silicasol storage at normal temperature is stored at 12 months or 60 DEG C and retrogradation or gelatin phenomenon was not occurred in 2 months.
2., by the preparation method of glass coating liquid described in claim 1, it is characterized in that the mol ratio of calcium or magnesium salts catalyzer and the silicic acid added is 0.009-0.015:1, described calcium or magnesium salts are its nitrate, hydrochloride or acetate.
3., by the preparation method of glass coating liquid described in claim 1, it is characterized in that SiO in the alkali metal silicate solutions added in active silicic acid solution
2mass percentage concentration is 3%-5%, by its regulator solution potential of hydrogen to pH8.0-8.5, then at 60-75 DEG C, carries out condensation reaction 3-12h, obtains SiO
2the alkaline silica sol of mass percentage concentration 5%-10%, described alkalimetal silicate is water glass, potassium silicate, lithium silicate or its mixture.
4. by the preparation method of glass coating liquid described in claim 1, it is characterized in that condensation reaction completes in backward alkaline silica sol and add the oxalate solution that mass percentage concentration is 3%-6%, the mol ratio controlling oxalic acid and calcium or magnesium salts catalyzer is 1-3:1, and described oxalate is ammonium oxalate, potassium oxalate, sodium oxalate or lithium oxalate.
5. by the preparation method of glass coating liquid described in claim 1, it is characterized in that the hybrid resin process silicon sol of use strongly-acid and strong alkali ion exchange resin further, remove positively charged ion residual in silicon sol and negatively charged ion, make silicon sol pH2.5-3.5.
6., by the preparation method of glass coating liquid described in claim 1, it is characterized in that further acidified silica sol is to pH1.8-2.5, at 60 DEG C, vacuum concentration is to SiO
2mass percentage concentration reaches 25%, and silicon sol median size is 20-30nm.
7. the application of glass coating liquid described in a claim 1, it is characterized in that as solar cell glass antireflective coating liquid, by its roller coat on the solar cell glass print cleaned up, through 80-150 DEG C of zone heating solidification 3-6 minute, obtain general hepatic solar cell coated glass, build controls at 140nm-180nm, average transmittance before and after plated film in 380nm-1100nm wavelength region increases 2.5%-3.5%, by the solar cell glass print of plated film tempering process 3-6 minute in 500 DEG C of-720 DEG C of annealing furnaces, by rete sintering at glass surface, film surface is smooth, split without crack, crystal-silicon solar cell production application requirement can be met.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106497160A (en) * | 2016-10-29 | 2017-03-15 | 袁春华 | A kind of method of utilization Fructus Ananadis comosi sauced for high stability coating liquid |
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| CN1036547A (en) * | 1988-03-16 | 1989-10-25 | 日产化学工业株式会社 | Stable silica sol and manufacture method thereof |
| CN101626979A (en) * | 2007-02-01 | 2010-01-13 | 日产化学工业株式会社 | Process for producing silica sol of long and thin shape |
| CN101844877A (en) * | 2010-05-29 | 2010-09-29 | 无锡海达安全玻璃有限公司 | Processing method for high anti-reflective glass for packaging solar battery pack |
| US20140013674A1 (en) * | 2011-12-28 | 2014-01-16 | Jgc Catalysts And Chemicals Ltd. | High Purity Silica Sol and its Production Method |
| CN104276766A (en) * | 2014-10-07 | 2015-01-14 | 天津市职业大学 | Production method of solar cell glass antireflection/light conversion dual-function coating solution |
-
2015
- 2015-05-25 CN CN201510271484.8A patent/CN104877401A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1036547A (en) * | 1988-03-16 | 1989-10-25 | 日产化学工业株式会社 | Stable silica sol and manufacture method thereof |
| CN101626979A (en) * | 2007-02-01 | 2010-01-13 | 日产化学工业株式会社 | Process for producing silica sol of long and thin shape |
| CN101844877A (en) * | 2010-05-29 | 2010-09-29 | 无锡海达安全玻璃有限公司 | Processing method for high anti-reflective glass for packaging solar battery pack |
| US20140013674A1 (en) * | 2011-12-28 | 2014-01-16 | Jgc Catalysts And Chemicals Ltd. | High Purity Silica Sol and its Production Method |
| CN104276766A (en) * | 2014-10-07 | 2015-01-14 | 天津市职业大学 | Production method of solar cell glass antireflection/light conversion dual-function coating solution |
Non-Patent Citations (1)
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| 柳云骐 等: "《材料化学》", 28 February 2013, 中国石油大学出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106497160A (en) * | 2016-10-29 | 2017-03-15 | 袁春华 | A kind of method of utilization Fructus Ananadis comosi sauced for high stability coating liquid |
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