CN104876452B - A kind of preparation method of new nano self-cleaning glass - Google Patents
A kind of preparation method of new nano self-cleaning glass Download PDFInfo
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- CN104876452B CN104876452B CN201510064039.4A CN201510064039A CN104876452B CN 104876452 B CN104876452 B CN 104876452B CN 201510064039 A CN201510064039 A CN 201510064039A CN 104876452 B CN104876452 B CN 104876452B
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- 239000005348 self-cleaning glass Substances 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000011521 glass Substances 0.000 claims abstract description 76
- 238000004140 cleaning Methods 0.000 claims abstract description 73
- 238000005507 spraying Methods 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000004088 foaming agent Substances 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000003973 paint Substances 0.000 claims abstract description 4
- 239000011248 coating agent Substances 0.000 claims description 52
- 238000000576 coating method Methods 0.000 claims description 52
- 239000002904 solvent Substances 0.000 claims description 44
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 32
- -1 polysiloxane Polymers 0.000 claims description 31
- 229920001296 polysiloxane Polymers 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 19
- 239000007921 spray Substances 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000005329 float glass Substances 0.000 claims description 16
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000003513 alkali Substances 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
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- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 9
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- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
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- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- 238000002834 transmittance Methods 0.000 abstract description 8
- BQFCCCIRTOLPEF-UHFFFAOYSA-N chembl1976978 Chemical compound CC1=CC=CC=C1N=NC1=C(O)C=CC2=CC=CC=C12 BQFCCCIRTOLPEF-UHFFFAOYSA-N 0.000 abstract 2
- 230000002708 enhancing effect Effects 0.000 abstract 1
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- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 3
- 229960000907 methylthioninium chloride Drugs 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 238000006124 Pilkington process Methods 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
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- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical compound OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 description 1
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- CMGRCCOGISJTTQ-UHFFFAOYSA-N NOC(O)=C Chemical group NOC(O)=C CMGRCCOGISJTTQ-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
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- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
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- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical group OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
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- 125000003700 epoxy group Chemical group 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Surface Treatment Of Glass (AREA)
Abstract
The invention provides a kind of preparation method of the self-cleaning glass of new low-refraction, it comprises the following steps：1) by nano self-cleaning paint even application in glass surface；2) self-cleaning glass that step 1) obtains is dried under conditions of normal temperature or heating and obtains the self-cleaning glass with a nano self-cleaning film；3) the self-cleaning glass surface spraying solvent orange 2 A obtained in step 2), stand, remove the solvent orange 2 A for having dissolved nanometer pore-foaming agent, dry, nano concavo-convex structure is formed in the film layer.Self-cleaning glass prepared by the method for the present invention has the automatical cleaning ability improved and higher light transmittance, while also has the Superhydrophilic and anti-fog properties of enhancing, and applicability is wider.
Description
Technical Field
The invention belongs to the technical field of functional materials, relates to a preparation method of glass, and particularly relates to a preparation technology of self-cleaning glass with low refractive index.
Background
With the rapid development of the building industry in China, the glass curtain wall is favored by architects due to the advantages of wind resistance, rain resistance, heat preservation, heat insulation, noise prevention, air permeation resistance, decoration and the like. But its cleaning method is not changed. The manual cleaning is inconvenient and unsafe, in addition, the cleaning agent is used for a long time, not only the resources are wasted, but also the environment is polluted, and the environmental protection and saving guidelines advocated by the state at present are not met, so the research on the preparation of the self-cleaning glass becomes a hotspot.
The research shows that: under the irradiation of light, the titanium dioxide has the functions of super-hydrophilicity, photocatalysis (organic matter decomposition), negative oxygen ion release and the like, namely the self-cleaning function. The titanium dioxide self-cleaning function is applied to the glass curtain wall, so that the cleaning problem can be solved, the glass can be naturally cleaned by rain wash and regular running water wash, the service life of the self-cleaning glass can be prolonged for ten years, and experts predict that the glass which does not need to be manually cleaned can cause a large-scale cleaning revolution.
There are many methods for producing self-cleaning glass, such as chemical vapor deposition, magnetron sputtering, sol-gel methods, and the like. The titanium dioxide films prepared by the former two methods generally do not have good photocatalytic activity because the titanium dioxide films prepared by chemical vapor deposition and magnetron sputtering are generally amorphous or have a low anatase phase content and are dense and have a low specific surface area, so that the titanium dioxide films thus prepared have poor or no photocatalytic activity. The sol-gel method for preparing the titanium dioxide film on the surface of the glass has a plurality of outstanding advantages, but sodium ions in the glass are diffused into the newly prepared titanium dioxide film during heat treatment, so that the photocatalytic activity of the titanium dioxide film is greatly reduced. The reason is that the high concentration of sodium ions can prevent the formation of an optically active anatase phase, and the low concentration of sodium ions can form a composite center of photo-generated electrons or gaps on the surface or the body of the titanium dioxide film, so that the prepared titanium dioxide coated self-cleaning glass has low photocatalytic activity and poor self-cleaning capability.
CN200710118124.X discloses a preparation method of self-cleaning toughened glass, which is characterized in that a nano titanium dioxide composite coating is manufactured on the surface of cleaned glass, so that the self-cleaning capacity of the glass is improved, and the self-cleaning toughened glass which is induced and excited in multiple modes and has stable performance is provided. But it may have problems of low light transmittance, a self-cleaning effect to be improved, and the like.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a novel preparation method of self-cleaning glass with low refractive index, and the prepared self-cleaning glass has improved self-cleaning capability and higher light transmittance.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of novel self-cleaning glass with low refractive index comprises the following steps:
1) uniformly spraying the nano self-cleaning coating on the surface of the glass;
2) drying the self-cleaning glass obtained in the step 1) at normal temperature or under a heating condition to obtain self-cleaning glass with a nano self-cleaning film;
3) soaking the self-cleaning glass obtained in the step 2) in a solvent A to remove the nano pore-forming agent in the film layer, and drying to form a nano concave-convex structure on the film layer; or,
spraying a solvent A on the surface of the self-cleaning glass obtained in the step 2), standing, removing the solvent A in which the nano pore-foaming agent is dissolved, drying, and forming a nano concave-convex structure on the film layer;
wherein the nano self-cleaning coating comprises the following components: (a) silica nanoparticles; (b) a polysiloxane; (c) anatase titanium dioxide; (d) nano pore-foaming agent and (e) solvent B.
According to the invention, the content of each component in the coating is as follows by weight percent: (a)1 to 5 percent; (b)5 to 20 percent; (c)10 to 30 percent; (d)5 to 10 percent; (e)25 to 70 percent.
According to the invention, the solvent B is selected from one or more of methanol, absolute ethanol, ethanol with the mass concentration of 95%, isopropanol, acetone, butanol, butanone, butanediol, propylene glycol, ethylene glycol, isobutanol, 4-hydroxy-4-methyl-2-pentanone and N-methylpyrrolidone.
According to the invention, the polysiloxane is selected from linear polysiloxanes or branched polysiloxanes. Preferably, the resin composition has one or more hydrophilic functional groups such as a hydroxyl group, an amino group, a carboxyl group, an epoxy group, and a sulfonic acid group.
According to the invention, the nano-pore-forming agent is a compound which can be dissolved in acid liquor, alkali liquor or water and is selected from one of acid-soluble compounds, alkali-soluble compounds and neutral water-soluble compounds. The average particle size of the nano pore-foaming agent is 10-100 nm.
According to the invention, the solvent A is a substance capable of selectively dissolving the nano-pore-forming agent and is selected from water, dilute acid or dilute alkali. When the nano-porogen is a neutral water-soluble compound, solvent a may be selected from water. When the nano-pore-forming agent is an acid-soluble compound, the solvent A is selected from dilute acid, such as dilute hydrochloric acid, dilute sulfuric acid and the like. When the nano-porogen is an alkali soluble compound, the solvent A is selected from dilute alkali, such as 1-10 wt% NaOH, etc.
According to the invention, the concentration of the nano self-cleaning coating is 1-30g/L, preferably 2-25 g/L.
According to the invention, the coating material is sprayed at a speed of more than 0.5 m/s to less than 2.5 m/s, preferably 0.6-2.0 m/s.
According to the invention, the solvent A is sprayed at a speed of more than 1.0 m/s to less than 3.0 m/s, preferably 1.5-2.5 m/s.
According to the invention, the step 1) is also preceded by a step of cleaning and drying the glass.
According to the invention, the tempered glass produced by the method further comprises the following steps:
4) optionally, soaking the nano self-cleaning glass obtained in the step 3) in an acid solution for acid treatment; if the solvent A in the step 3) is diluted acid, the step can be completely omitted;
5) tempering the nano self-cleaning glass obtained in the step 4) at 600-700 ℃ for 550-650 seconds.
According to the invention, the concentration of the acid of step 4) is 0.001-4M, and the acid is an organic acid or an inorganic acid. Preferably, the organic acid is formic acid or acetic acid; the inorganic acid is hydrochloric acid, sulfuric acid or nitric acid.
According to the invention, the method produces float glass comprising the steps of:
1') the spraying of step 1) is carried out by: an online spraying device for spraying nano self-cleaning paint is additionally arranged across the float glass production line above the area between the tail end of an annealing furnace and an emergency transverse cutting machine of the float glass production line; directly and uniformly atomizing and spraying the nano self-cleaning coating on the non-tin surface of the glass with the temperature of 60-120 ℃ obtained at the tail end of an annealing kiln to form a coating of the nano self-cleaning coating on the non-tin surface of the glass;
2) drying the self-cleaning glass obtained in the step 1) at normal temperature or under a heating condition to obtain self-cleaning glass with a nano self-cleaning film;
3) soaking the self-cleaning glass obtained in the step 2) in a solvent A to remove the nano pore-forming agent in the film layer, and drying to form a nano concave-convex structure on the film layer; or,
spraying a solvent A on the surface of the self-cleaning glass obtained in the step 2), standing, removing the solvent A in which the nano pore-foaming agent is dissolved, drying, and forming a nano concave-convex structure on the film layer;
4') carrying out on-line production on the self-cleaning glass with the nano self-cleaning film with the nano concave-convex structure formed on the non-tin surface of the glass obtained in the step 3) according to the cold end production process of the float glass, and finally obtaining the nano self-cleaning glass.
According to the invention, the spray gun head of the online spraying equipment is vertical to the non-tin surface of the glass ribbon on the float glass production line, and the running direction of the spray gun head of the online spraying equipment and the running direction of the glass ribbon make horizontal reciprocating motion at an angle of about 90 degrees.
According to the invention, the distance between the spray gun head of the online spraying equipment and the non-tin surface of the glass ribbon on the float glass production line is 100-400 mm.
According to the invention, the speed range of the horizontal reciprocating motion of the running direction of the spray gun head of the on-line spraying equipment and the running direction of the glass ribbon which form an angle of about 90 degrees is 0.1-10 m/s.
According to the invention, the flow of the coating is 0.1-2L/min when the coating is sprayed by the spray gun head of the online spraying equipment; the pressure intensity of compressed air used by a spray gun of the on-line spraying equipment is 0.1-0.6 MPa.
The invention has the beneficial effects that:
the preparation method is simple and feasible, and the preparation of the self-cleaning glass with low refractive index is realized by improving the formula of the coating and a simple online treatment method on the basis of the existing method, and the prepared self-cleaning glass has improved self-cleaning capability and higher light transmittance.
In addition, the self-cleaning glass prepared by the method has enhanced super-hydrophilicity and antifogging property, and is wider in applicability.
Drawings
FIG. 1 shows the contact angle test results for the glass of example 6 of the present invention, wherein the contact angle of the prepared fresh sample is less than 10 degrees, and after UV illumination, the contact angle is close to 0 degree, and the sample is in a super-hydrophilic state.
Detailed Description
As described above, the present invention discloses a novel technology for preparing self-cleaning glass with low refractive index, and the method can prepare tempered glass, and specifically comprises the following steps:
(a) cleaning and drying steps of glass
Before the nano coating is sprayed on the surface of the glass, the surface of the glass is cleaned. The cleaning of the glass surface directly influences the quality of the self-cleaning glass product, and the film coating is carried out on the glass surface with the pollution of grease, dust and the like, so that the firmness of the film and the glass is influenced, and the self-cleaning effect is further influenced. The specific cleaning method can be as follows: polishing the surface of the glass by a rotating disc by using glass polishing powder (the mixing ratio of the polishing powder to deionized water is 1: 10) of about 400 meshes, washing dirt and the polishing powder on the surface of the glass by using water, and drying the water on the surface of the glass by using a fan with a filter screen to ensure that the surface of the glass is clean and free of any dust. For a substrate with special requirements, the glass surface can be cleaned, dried and purged by high-purity nitrogen.
(1) Uniformly spraying the nano self-cleaning coating on the surface of the clean glass obtained in the step (a), and adjusting the spraying speed and flow rate according to different requirements to obtain a self-cleaning nano coating with required thickness; the spraying speed is 0.5-2 m/s.
(2) And (2) airing the self-cleaning glass obtained in the step (1) under natural conditions or drying the surface of the self-cleaning glass by using an electric heating rod, so that the curing of the self-cleaning film layer is accelerated.
(3) Soaking the self-cleaning glass obtained in the step (2) in a solvent A to remove the nano pore-forming agent in the film layer, and drying to form a nano concave-convex structure on the film layer; or,
and (3) spraying a solvent A on the surface of the self-cleaning glass obtained in the step (2), standing, removing the solvent A in which the nano pore-foaming agent is dissolved, drying, and forming a nano concave-convex structure on the film layer.
(4) Optionally, soaking the nano self-cleaning glass obtained in the step (3) in an acid solution for acid treatment; if the solvent A in step 3) is chosen to be a dilute acid, this step can be omitted completely.
(5) The produced self-cleaning glass can utilize the instantaneous high temperature in the preparation process of toughened glass to realize the rapid crystallization of titanium dioxide on the surface of the glass while toughening. And (3) tempering the self-cleaning glass prepared in the step (4) at 600-700 ℃ for 550-650 seconds, so that the nano self-cleaning film layer is firmer after instantaneous high temperature, the service life of the self-cleaning coating is prolonged, and one-step forming of tempering and self-cleaning is realized. The method is simple, and simultaneously makes full use of the self energy during toughening treatment, thereby saving energy.
The nano self-cleaning coating comprises the following components: (a) silica nanoparticles; (b) a polysiloxane; (c) anatase titanium dioxide; (d) nano pore-foaming agent and (e) solvent B. The coating comprises the following components in percentage by weight: (a)1 to 5 percent; (b)5 to 20 percent; (c)10 to 30 percent; (d)5 to 10 percent; (e)25 to 70 percent.
The solvent B is selected from one or more of methanol, absolute ethanol, ethanol with the mass concentration of 95%, isopropanol, acetone, butanol, butanone, butanediol, propylene glycol, ethylene glycol, isobutanol, 4-hydroxy-4-methyl-2-pentanone and N-methylpyrrolidone.
One or more of an aqueous anti-scratch slip agent and a film former may also be included in the coating.
The anatase type nano titanium dioxide raw material has the particle size of 10-30nm, is a commercial product, and can be prepared by referring to the method disclosed in CN 03119113.4.
The particle size of the silica nanoparticles is 10-30nm, and the silica nanoparticles are commercially available products, namely silica nanoparticles which are conventionally used in the field.
The polysiloxane is selected from straight-chain polysiloxane and/or branched polysiloxane, and preferably has one or more of hydrophilic functional groups such as hydroxyl, amino, carboxyl, epoxy, sulfonic acid group and the like. The polysiloxane may have a structure represented by the general formula: (R)3SiO1/2)a(R2SiO2/2)b(RSiO3/2)c(SiO4/2)dWherein each R, which may be the same or different, is independently selected from the group consisting of alkyl, alkoxy, aryl, aryloxy, alkenyl, halogen, hydroxy, carboxy, epoxy, amino, sulfonic acid, and the like, said alkyl, alkoxy, aryl, aryloxy being optionally substituted with halogen, hydroxy, amino, oxyethylene chains. When the polysiloxane contains hydrophilic functional groups, the interfacial bonding force with the silica nanoparticles and anatase titanium dioxide can be promoted, so that the dispersibility is improved, and the polysiloxane also contributes to the improvement of the bonding force with glass based on the functional groups. Wherein a + b + c + d is 1, and a, b, c and d are numbers selected from 0 to 1. In general, linear polysiloxane can provide good leveling property to the coating, and branched polysiloxane can provide good hardness and wear resistance to the coating, and the combination effect of the two can be better. The polysiloxane may also be DR100, manufactured by Beijing Cusson glass technology, Inc.
The polysiloxane has a number average molecular weight of 1000-100000.
The nano pore-foaming agent is a pore-foaming agent which can be dissolved in acid liquor, alkali liquor or water and is selected from one or more of acid-soluble compounds, alkali-soluble compounds and neutral water-soluble compounds. The acid-soluble compound includes carbonates such as sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate, etc. The alkali-soluble compound includes a polymer containing a carboxyl group, a hydroxyl group, or the like, which is reactive with a base. The neutral water-soluble compound is selected from water-soluble salts such as potassium chloride, sodium chloride, etc., or water-soluble polymers such as water-soluble natural polymers, e.g., polysaccharides, starch, or synthetic polymers, e.g., polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, etc.
The average particle size of the nano-pore-foaming agent is 10-100 nm.
The nano-pore-forming agent is prepared according to a known conventional method, such as a spray drying method and the like.
The water-based anti-scraping slip agent is prepared by the chemical company Limited of Storocco, Guangzhou-8300PS or-8510, and the like.
The film forming agent is glycol ether or vinyl glycol butyl ether, etc.
The glycol ethers are one of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, etc.
The steps adopt the self-cleaning coating sprayed on the clean glass surface under the conditions of normal temperature and normal pressure to prepare the nano self-cleaning glass, and the particle size of the nano silicon dioxide and the nano titanium dioxide in the nano self-cleaning film layer is 10-30 nm. The self-cleaning film layer also has super-hydrophilicity under visible light, the contact angle between the surface of the newly prepared self-cleaning glass and water is less than 0 degree, a complete water film can be formed, and the self-cleaning glass has super-hydrophilicity and self-cleaning capability. In addition, the refractive index of the glass surface is 1.4 to 1.6. The glass is excellent in antifogging properties due to its reduced contact angle.
The nano self-cleaning glass obtained by the method has good photocatalytic property and photoinduced hydrophilicity under visible light, has stable performance and excellent light transmittance and anti-fogging performance, can be widely applied to glass curtain walls of high-rise buildings, automobile glass, street lamp lampshades, kitchen glass and anti-fogging glass, can avoid manual cleaning of indoor and outdoor glass of the high-rise buildings, saves manpower and material resources, reduces corrosion and damage to glass and building structures caused by using a cleaning agent for manual cleaning, and has an environment-friendly effect.
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
Example 1.
Polishing the glass surface by a rotating disk by using 400-mesh glass polishing powder, washing dirt and polishing powder on the glass surface by using water, naturally airing in a clean place, uniformly spraying the nano self-cleaning coating on the glass surface by using a spray gun (the speed is 1.2 m/s), and standing at room temperature for 5 minutes to obtain the self-cleaning glass coated with the self-cleaning film. And spraying a solvent A on the surface of the self-cleaning glass, standing, removing the solvent A in which the nano pore-foaming agent is dissolved, and drying to form a nano concave-convex structure on the film layer. And then the prepared self-cleaning glass is tempered for 650 seconds at 700 ℃, the treated self-cleaning glass not only keeps good super-hydrophilic characteristic, but also the titanium dioxide crystal form on the surface of the glass is not changed, and the adhesive force and the hardness of the film layer on the surface of the glass are improved. Through detection, the light transmittance of the glass is 95%, the contact angle of the glass is close to 0 degree, and the glass has excellent anti-fogging performance.
The nano self-cleaning coating in the embodiment comprises the following components in percentage by weight:
wherein the polysiloxane is linear polysiloxane with the number average molecular weight of about 2000; the nano pore-foaming agent is sodium carbonate with the particle size of about 25 nm; the solvent A is dilute hydrochloric acid; solvent B is 95% ethanol.
Example 2
Two pieces of 5cm x 5cm of the self-cleaning glass (with the light transmittance of 95%) in example 1 are soaked in a methylene blue solution with the concentration of 1mmol/l for 1 hour, the self-cleaning glass is taken out and the back of the self-cleaning glass is wiped dry, the self-cleaning glass is vertically placed in a dark place, the self-cleaning glass is placed under an ultraviolet lamp (45W) for irradiating for half an hour after the methylene blue solution is naturally dried, and then the light transmittance of the self-cleaning glass is tested to be 95%, which shows that the methylene blue on the surface of the self-cleaning glass is completely decomposed, and the self-cleaning glass has better photocatalytic performance.
Example 3
The self-cleaning glass in the example 2 after being irradiated by ultraviolet light for half an hour is continuously irradiated under an ultraviolet lamp of 500W for 24 hours, and the surface state is observed, so that the phenomena of color change and chalking are avoided.
Example 4
The nano self-cleaning coating in the embodiment 1 is uniformly sprayed on the surface of glass by a spray gun (the speed is 1.5 m/s), and the super-hydrophilic nano self-cleaning glass can be obtained by curing at normal temperature and normal pressure without high-temperature sintering, and the ageing resistance, the acid resistance, the alkali resistance and the adhesive force of a film layer all reach the national coating standard. The obtained nano self-cleaning glass is tempered for 550 seconds at 700 ℃, the self-cleaning glass after treatment not only keeps the original good super-hydrophilic performance and photocatalytic performance, but also improves the adhesive force and the aging resistance of the film layer.
Example 5
The nano self-cleaning coating of example 1 was uniformly sprayed on the glass surface (speed 0.5 m/s), after curing for 10 minutes under natural conditions, the self-cleaning film layer on the glass surface was heat-treated for 20 minutes by heating to 80 ℃ with an electric heating rod, and from the test results (see table 1), the heat-treatment temperature did not affect the appearance of the self-cleaning glass and the hydrophilicity of the self-cleaning film, and the adhesion force was not affected at all.
TABLE 1
| Test items | At normal temperature | Heating at 80 deg.C |
| Stain resistance | Level 0 | Level 0 |
| Contact angle (degree) | 0.5 | 0.52 |
| Adhesion force | 0 grade of cross-cut method | 0 grade of cross-cut method |
Example 6
(1) An online spraying device for spraying nano self-cleaning paint is additionally arranged across the float glass production line above the area between the tail end of an annealing furnace and an emergency transverse cutting machine of the float glass production line, a spray gun head of the online spraying device is vertical to the position 100mm above the non-tin surface of a glass belt on the float glass production line, and the running direction of the spray gun head of the online spraying device and the running direction of the glass belt form an angle of 90 degrees and horizontally reciprocate with the speed of 10 m/s; directly and uniformly atomizing and spraying the nano self-cleaning coating on the non-tin surface of the glass with the temperature of 120 ℃ obtained at the tail end of an annealing kiln to form a coating of the nano self-cleaning coating on the non-tin surface of the glass; wherein: the pressure of compressed air used by a spray gun of the online spraying equipment for spraying the nano self-cleaning coating is 0.6Mpa, and the flow rate of the sprayed nano self-cleaning coating is 0.5L/min; the spray gun of the on-line spraying equipment for spraying the nano self-cleaning coating sprays the atomized nano self-cleaning coating with the width of 100 mm.
(2) Drying the self-cleaning glass obtained in the step (1) at normal temperature or under a heating condition to obtain self-cleaning glass with a nano self-cleaning film;
(3) spraying a solvent A on the surface of the self-cleaning glass obtained in the step (2), standing, removing the solvent A in which the nano pore-foaming agent is dissolved, drying, and forming a nano concave-convex structure on the film layer;
(4') cutting the glass which is obtained in the step (3) and forms the nano self-cleaning coating on the non-tin surface of the glass after entering the cold end of the float glass production line to obtain the nano self-cleaning glass with the required size. And coating a preservative film before the obtained nano self-cleaning glass is boxed so as to ensure the integrity of the coating on the surface of the nano self-cleaning glass.
The super-hydrophilic nano self-cleaning glass obtained by spraying the nano self-cleaning coating at 120 ℃ has the advantages that the acid resistance, the alkali resistance and the adhesive force of a film layer are higher than those of the self-cleaning glass obtained by spraying the nano self-cleaning coating at room temperature, a water contact angle test is carried out on a small sample obtained after cutting the nano self-cleaning glass, the result is shown in figure 1, the contact angle between the surface of the nano self-cleaning glass and water is less than 10 degrees, the nano self-cleaning glass can reach 0 degree after being irradiated by UV light, and the nano self-cleaning glass.
The nano self-cleaning coating comprises the following components in percentage by weight:
aqueous scratch and slip resistant agent (from Storocco chemical Co., Ltd., Guangzhou)-8300PS)2％；
Wherein the polysiloxane is linear polysiloxane with the number average molecular weight of about 2000; the nano pore-foaming agent is sodium carbonate with the particle size of about 25 nm; the solvent A is dilute hydrochloric acid; solvent B is 95% ethanol.
Example 7
5 pieces of nano self-cleaning glass produced on line by the float method in the embodiment 6 are taken, the specification is 10cm multiplied by 10cm, the aging performance test is carried out according to GB/T1865-1997, after 2000 hours, a little scale exists on the surface of the self-cleaning glass film layer, after the self-cleaning glass film layer is cleaned by dilute hydrochloric acid, the contact angle test is carried out, and the result is 2 degrees. The film layer still exists, which shows that the nano self-cleaning glass has good aging resistance.
Example 8
The nano self-cleaning glass prepared in the embodiment 6 is scribed with lattices on the surface by adopting the national standard GB/T17748-1999, the surface film layer does not fall off, and the grade is 0.
Example 9
The nano self-cleaning glass produced on line by the float method in the embodiment 6 is toughened on line, the contact angle of the surface of the glass is not changed greatly, the crystal form is still anatase, and meanwhile, the composite film is enhanced by toughening treatment to be combined with the surface of the glass.
Example 10
In example 6, two pieces of nano self-cleaning glass prepared by on-line spraying and having the same size (25mm by 25mm) were used for the photocatalytic experiment (see table 2) at the residual temperature of the glass surface of 100 ℃, and the result of decomposing methyl orange per hour is as follows: 8.6%, the comparative sample was a room temperature spray sample, and the results were: 2.1 percent.
Description of the drawings: soaking glass with a self-cleaning nano film in 20mg/l methyl orange aqueous solution, after Ultraviolet (UV) irradiation for 1 hour, oxidizing and decomposing the methyl orange to reduce the content, particularly, accelerating the oxidation and the reduction of the methyl orange in the range of 100nm near the nano self-cleaning glass film due to the oxidation catalysis of the film, so as to reduce the concentration of the methyl orange solution, namely, the change of the concentration of the methyl orange solution carries the information of the photocatalytic oxidation performance of the nano self-cleaning glass film, measuring the change of the concentration of the methyl orange solution, and obtaining the photocatalytic performance data of the nano self-cleaning glass film through calculation.
TABLE 2
Claims (16)
1. A method for preparing self-cleaning glass with low refractive index comprises the following steps:
1) uniformly spraying the nano self-cleaning coating on the surface of the glass;
2) drying the self-cleaning glass obtained in the step 1) at normal temperature or under a heating condition to obtain self-cleaning glass with a nano self-cleaning film;
3) soaking the self-cleaning glass obtained in the step 2) in a solvent A to remove the nano pore-forming agent in the film, drying, and forming a nano concave-convex structure on the film; or,
spraying a solvent A on the surface of the self-cleaning glass obtained in the step 2), standing, removing the solvent A in which the nano pore-foaming agent is dissolved, drying, and forming a nano concave-convex structure on the film;
wherein the nano self-cleaning coating comprises the following components: (a) silica nanoparticles; (b) a polysiloxane; (c) anatase titanium dioxide; (d) nano pore-foaming agent and (e) solvent B;
the nano pore-foaming agent is one of the following compounds which can be dissolved in acid liquor or alkali liquor: acid-soluble compounds, alkali-soluble compounds; the average particle size of the nano pore-foaming agent is 10-100 nm;
the solvent A is a substance capable of selectively dissolving the nano pore-forming agent and is selected from dilute acid or dilute alkali; and when the nano-pore-forming agent is an acid-soluble compound, the solvent A is selected from dilute acid; when the nano-pore-forming agent is an alkali soluble compound, the solvent A is selected from dilute alkali;
the coating comprises the following components in percentage by weight: (a)1 to 5 percent; (b)5 to 20 percent; (c)10 to 30 percent; (d)5 to 10 percent; (e)25 to 70 percent;
the concentration of the nano self-cleaning coating is 2-25 g/L.
2. The method according to claim 1, wherein the solvent B is selected from methanol, absolute ethanol, ethanol with a mass concentration of 95%, isopropanol, acetone, butanol, butanone, butanediol, propylene glycol, ethylene glycol, isobutanol, 4-hydroxy-4-methyl-2-pentanone, and N-methylpyrrolidone.
3. The method according to claim 1, wherein the polysiloxane is selected from a linear polysiloxane or a branched polysiloxane; the polysiloxane has one or more of the following hydrophilic functional groups: hydroxyl, amino, carboxyl, epoxy and sulfonic acid.
4. The method of claim 1, wherein when the nano-porogen is an acid soluble compound, the solvent A is selected from diluted hydrochloric acid or diluted sulfuric acid; when the nano-porogen is an alkali soluble compound, the solvent A is selected from 1-10 wt% NaOH.
5. The method of claim 1, wherein the coating material is sprayed at a speed of greater than 0.5 m/s to less than 2.5 m/s.
6. The method of claim 5, wherein the coating material is sprayed at a speed of 0.6 to 2.0 m/s.
7. The production method according to claim 1, wherein the spraying speed of the solvent a is more than 1.0 m/s to less than 3.0 m/s.
8. The production method according to claim 7, wherein the spraying speed of the solvent A is 1.5 to 2.5 m/s.
9. The method for preparing the glass of claim 1, wherein the step 1) is further preceded by a step of cleaning and drying the glass.
10. The method according to any one of claims 1 to 9, wherein the tempered glass is produced by the method, which further comprises the steps of:
4) optionally, soaking the nano self-cleaning glass obtained in the step 3) in an acid solution for acid treatment; if the solvent A in the step 3) is diluted acid, the step can be completely omitted;
5) tempering the nano self-cleaning glass obtained in the step 4) at 600-700 ℃ for 550-650 seconds.
11. The method according to claim 10, wherein the acid of step 4) has a concentration of 0.001 to 4M, and the acid is an organic acid or an inorganic acid; the organic acid is formic acid or acetic acid; the inorganic acid is hydrochloric acid, sulfuric acid or nitric acid.
12. A method of manufacturing according to any one of claims 1 to 9, wherein the method produces float glass comprising the steps of:
1') the spraying of step 1) is carried out by: an online spraying device for spraying nano self-cleaning paint is additionally arranged across the float glass production line above the area between the tail end of an annealing furnace and an emergency transverse cutting machine of the float glass production line; directly and uniformly atomizing and spraying the nano self-cleaning coating on the non-tin surface of the glass with the temperature of 60-120 ℃ obtained at the tail end of an annealing kiln to form a coating of the nano self-cleaning coating on the non-tin surface of the glass;
2) drying the self-cleaning glass obtained in the step 1') at normal temperature or under a heating condition to obtain self-cleaning glass with a nano self-cleaning film;
3) soaking the self-cleaning glass obtained in the step 2) in a solvent A to remove the nano pore-forming agent in the film, drying, and forming a nano concave-convex structure on the film; or,
spraying a solvent A on the surface of the self-cleaning glass obtained in the step 2), standing, removing the solvent A in which the nano pore-foaming agent is dissolved, drying, and forming a nano concave-convex structure on the film;
4') carrying out on-line production on the self-cleaning glass with the nano self-cleaning film with the nano concave-convex structure formed on the non-tin surface of the glass obtained in the step 3) according to the cold end production process of the float glass, and finally obtaining the nano self-cleaning glass.
13. A method according to claim 12, wherein the lance head of the in-line coating apparatus is perpendicular to the non-tin surface of the glass ribbon on the float glass line and the travelling direction of the lance head of the in-line coating apparatus is reciprocated horizontally at an angle of 90 ° to the travelling direction of the glass ribbon.
14. A method according to claim 13, wherein the lance head of the in-line apparatus is positioned at a distance of from 100 to 400mm from the non-tin surface of the ribbon in the float glass line.
15. The production method according to claim 14, wherein the speed range at which the lance head of the inline coating apparatus horizontally reciprocates at an angle of 90 degrees to the running direction of the glass ribbon is 0.1 to 10 m/s.
16. The production method according to any one of claims 13 to 15, wherein a flow rate of the coating material at the time of spraying the coating material is 0.1 to 2L/min by a spray head of the inline spray apparatus; the pressure intensity of compressed air used by a spray gun of the on-line spraying equipment is 0.1-0.6 MPa.
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| CN108640491B (en) * | 2018-03-28 | 2021-05-25 | 无锡阿森那斯卫浴设备有限公司 | Manufacturing method of easy-to-clean toughened glass |
| CN108980771A (en) * | 2018-09-27 | 2018-12-11 | 华域视觉科技(上海)有限公司 | Photocatalytic self-cleaning car light and automobile |
| CN113292245B (en) * | 2020-02-24 | 2022-05-13 | 江苏秀强玻璃工艺股份有限公司 | Multifunctional relief glass and processing method thereof |
| CN111732890B (en) * | 2020-07-17 | 2021-08-17 | 徐州市威固特种玻璃有限公司 | Long-acting antifogging coating on glass surface and preparation method thereof |
| CN115259686A (en) * | 2022-08-11 | 2022-11-01 | 咸宁南玻节能玻璃有限公司 | Easy-to-clean glass and preparation method thereof |
| CN115403275A (en) * | 2022-09-26 | 2022-11-29 | 咸宁南玻节能玻璃有限公司 | Glass protection solution, preparation method of glass protection solution and film forming method of glass protection solution |
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