CN106007394B - A kind of liquid hydrophilic glass film, hydrophilic glass and their preparation method - Google Patents
A kind of liquid hydrophilic glass film, hydrophilic glass and their preparation method Download PDFInfo
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- CN106007394B CN106007394B CN201610368255.2A CN201610368255A CN106007394B CN 106007394 B CN106007394 B CN 106007394B CN 201610368255 A CN201610368255 A CN 201610368255A CN 106007394 B CN106007394 B CN 106007394B
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- glass
- film
- hydrophilic glass
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- liquid
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Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/141—Preparation of hydrosols or aqueous dispersions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/213—SiO2
Abstract
The invention discloses a kind of liquid hydrophilic glass film, hydrophilic glass and their preparation methods.Method is: trimethoxy mercapto propyl silane is mixed with tetraalkyl orthosilicate, it stirs evenly, then ethyl alcohol is added and continues stirring at least 2 days, clear solution is obtained, water is added into clear solution, continues to stir, make trimethoxy mercapto propyl silane and tetraalkyl orthosilicate complete hydrolysis, liquid hydrophilic glass film is obtained, liquid hydrophilic glass film is coated in glass surface then drying, obtains hydrophilic glass.The method of the present invention carries out at room temperature, and simple process, glass-film is firmly combined with glass, good hydrophilic property, long service life compare simple process with existing method, it is low in cost, it is convenient for industrialized production, can be widely used for the fields such as glass curtain wall, glass pane, solar power station.
Description
Technical field
The present invention relates to a kind of preparation method of liquid hydrophilic glass film and resulting liquid hydrophilic glass films, further relate to one
Kind hydrophilic glass and preparation method thereof, belongs to nano coating automatically cleaning technical field.
Background technique
Industrial development leads to greenhouse effects, and pollution is also increasingly severe, and the environment of life faces many challenges, floats in air
Floating to have a large amount of pollutant, these pollutants can be adsorbed on the surface of constructure screen wall, automobile etc., seriously affect the life of people
Bioplasm amount, the self-cleaning function for increasing material become one of the main task of material worker.Self-cleaning surface mainly has at present
It is hydrophilic and high two kinds of hydrophobic high, wherein the application that high hydrophilic film material has comparison wide, such as one layer is coated on glass curtain wall surface
High hydrophilic film can reduce angle of wetting, can reduce the absorption of dust, and can use rain-out surface.Current technology is a kind of
It is to cover one layer of high hydrophilic film in glass surface high-temperature process, this method is at high cost.Another method is hydrophilic in surface sprinkling
Nanometer layer forms convex-concave structure, is allowed to shape for example, CN201510064039.4 coats SiO2/TiO2 nanometer layer in glass surface
At hydrophobic surface；CN102219391A octamethylcy-clotetrasiloxane, KOH, ethyl orthosilicate etc. are that hydrophobic coating is made in raw material；
CN105086537A prepares hydrophobic clean coating by the direct hydrolysis of ethyl orthosilicate, silane coupling agent, siliceous amine alkane, these
Method is although at low cost, but poor with glass matrix associativity, and the duration is short, and effect is relatively poor.
Summary of the invention
It is gained liquid the present invention provides the preparation method of liquid hydrophilic glass film for deficiency existing for current technology
Hydrophilic glass film, this method is easy to operate, at low cost, and gained glass-film good hydrophilic property, self-cleaning effect is good, with glass matrix
Associativity is good, and performance is stable, lasting.
The present invention also provides a kind of hydrophilic glass, which is covered with hydrophilic glass film of the present invention, hydrophilic
Property and self-cleaning ability enhancing.
The present invention also provides a kind of preparation method of hydrophilic glass, this method is easy to implement, is convenient for application.
Specific technical solution of the present invention is as follows:
A kind of preparation method of liquid hydrophilic glass film, method includes the following steps:
(1) trimethoxy mercapto propyl silane is mixed with tetraalkyl orthosilicate, is stirred evenly, ethyl alcohol is then added and continues to stir
It mixes at least 2 days, obtains clear solution；
(2) water is added in the clear solution of step (1), continues to stir, make trimethoxy mercapto propyl silane and positive silicic acid
Arrcostab complete hydrolysis obtains the SiO containing sulfydryl2Colloidal sol, SiO of the gained containing sulfydryl2Colloidal sol is liquid hydrophilic glass film.
In above-mentioned steps (1), the structural formula of raw material trimethoxy mercapto propyl silane is (CH3O)3SiC2H6SH。
In above-mentioned steps (1), first the silane reagent containing sulfydryl is mixed with tetraalkyl orthosilicate, is then existed in ethyl alcohol
Lower stirring hydrolyzes tetraalkyl orthosilicate slowly using the faintly acid of sulfydryl, prevents its hydrolysis rate too fast and generates reunion,
Preferably to form SiO2Network structure not only contributes to the combination with glass-film and glass matrix, it can also be ensured that glass
Film spreads over glass surface well, forms the glass-film of homogeneous transparent.In addition, passing through silane reagent and positive silicic acid containing sulfydryl
Arrcostab is sufficiently mixed stirring, and sulfydryl can uniformly enter SiO2In network structure, make glass-film self-cleaning effect more evenly
Effectively.
In above-mentioned steps (1), the tetraalkyl orthosilicate is ethyl orthosilicate, methyl orthosilicate or positive silicic acid propyl ester.
In above-mentioned steps (1), the volume ratio of trimethoxy mercapto propyl silane and tetraalkyl orthosilicate is 0.05-0.15:1.
In above-mentioned steps (1), the volume ratio of tetraalkyl orthosilicate and ethyl alcohol is 0.08-0.12:1.
In above-mentioned steps (1), after trimethoxy mercapto propyl silane is mixed with tetraalkyl orthosilicate, stirring at least 5h is added
Ethyl alcohol, so that raw material is uniformly mixed.
In above-mentioned steps (2), the volume ratio of water and ethyl orthosilicate is 0.8-1.2:1.Pass through the control of water, gained liquid
Glass-film uniformly, stablize, can easily glass surface formed layer of transparent glass-film, and be combined, the service life it is long.
In above-mentioned steps (2), after water is added, it is stirred at least 5 days.
Liquid hydrophilic glass film obtained is also within that scope of the present invention according to the method described above.The glass-film is liquid
State, spraying is convenient, good with glass associativity, can be in the hydrophilic film of glass surface one layer of homogeneous transparent of formation, automatically cleaning effect
Fruit is good, and performance is stable, lasting.
The present invention also provides a kind of hydrophilic glasses, are covered with one layer of SiO containing sulfydryl in glass surface2Film.Preferably,
The SiO containing sulfydryl2Film is by the way that liquid hydrophilic glass film of the invention is coated in glass surface and then dry shape
What formula was formed.Hydrophilic glass film of the present invention is firmly combined with glass, consistency of performance, stabilization, in visible-range completely through,
Form fully transparent glass-film.
Further, liquid hydrophilic glass film can be coated in glass table by the way of spraying, spin coating, dip-coating or printing
Face.
The present invention also provides a kind of preparation method of hydrophilic glass, this method glass surface coat one layer it is of the invention
Liquid hydrophilic glass film, up to hydrophilic glass after drying.
In above-mentioned preparation method, liquid hydrophilic glass film is coated in glass by the way of spraying, spin coating, dip-coating or printing
Surface.
The present invention is using the silane reagent containing sulfydryl as raw material, using the faintly acid of sulfydryl, first by ethyl orthosilicate in mercapto
It is slowly hydrolyzed in the presence of base, prevents hydrolytic process too fast and generate reunion, preferably to form SiO2Network structure, then again
Water is added to be fully hydrolyzed, glass-film homogeneous transparent obtained in this way, and glass matrix associativity is good, good hydrophilic property, very
It is easy to spread over glass surface, makes glass that there is good hydrophilic, self-cleaning effect, and effect is lasting stablizes, the service life is long.This hair
Bright glass-film is prepared at room temperature, and simple process and low cost is convenient for industrialized production, and can be widely used for glass curtain wall, window glass
The fields such as glass, solar power station.
Specific embodiment
Below by embodiment, the outstanding feature and marked improvement that the present invention is furture elucidated, following embodiments are only that
Illustrate the present invention and is never limited in the present invention.
Embodiment 1
(1) 0.5mL trimethoxy mercapto propyl silane is added in 5mL ethyl orthosilicate and is stirred 5 hours, 50mL is added later
Ethyl alcohol stirs 2 days, obtains the solution of homogeneous transparent；
(2) 5mL water is added in the solution of step (1) to stir 5 days, obtains the SiO containing sulfydryl2Colloidal sol, i.e. liquid parent
Waterglass film；
(3) above-mentioned liquid hydrophilic glass film is sprayed on glass surface, obtains hydrophilic glass after dry.The hydrophilic glass table
The glass-film homogeneous transparent in face is smooth, flawless.
Embodiment 2
(1) 0.25mL trimethoxy mercapto propyl silane is added in 5mL methyl orthosilicate and is stirred 5 hours, is added later
50mL ethyl alcohol stirs 2 days, obtains the solution of homogeneous transparent；
(2) 5.5mL water is added in the solution of step (1) to stir 5 days, obtains the SiO containing sulfydryl2Colloidal sol, i.e. liquid
Hydrophilic glass film；
(3) above-mentioned liquid hydrophilic glass film is spin-coated on glass surface, obtains hydrophilic glass after dry.The hydrophilic glass table
The glass-film homogeneous transparent in face is smooth, flawless.
Embodiment 3
(1) 0.75mL trimethoxy mercapto propyl silane is added in 5mL positive silicic acid propyl ester and is stirred 5 hours, is added later
50mL ethyl alcohol stirs 2 days, obtains the solution of homogeneous transparent；
(2) 4mL water is added in the solution of step (1) to stir 5 days, obtains the SiO containing sulfydryl2Colloidal sol, i.e. liquid parent
Waterglass film；
(3) above-mentioned liquid hydrophilic glass film is sprayed on glass surface, obtains hydrophilic glass after dry.The hydrophilic glass table
The glass-film homogeneous transparent in face is smooth, flawless.
Embodiment 4
(1) 0.75mL trimethoxy mercapto propyl silane is added in 5mL ethyl orthosilicate and is stirred 5 hours, is added later
50mL ethyl alcohol stirs 2 days, obtains the solution of homogeneous transparent；
(2) 6mL water is added in the solution of step (1) to stir 5 days, obtains the SiO containing sulfydryl2Colloidal sol, i.e. liquid parent
Waterglass film；
(3) above-mentioned liquid hydrophilic glass film is sprayed on glass surface, obtains hydrophilic glass after dry.The hydrophilic glass table
The glass-film homogeneous transparent in face is smooth, flawless.
Comparative example 1
(1) with embodiment 4；
(2) 50mL water is added in the solution of step (1) to stir 5 days, obtains the SiO containing sulfydryl2Colloidal sol；
(3) by the above-mentioned SiO containing sulfydryl2Colloidal sol is sprayed on glass surface, obtains the glass for being covered with glass-film after dry.
It cracks after the glass-film of the glass surface is dry.
Comparative example 2
(1) 0.75mL trimethoxy mercapto propyl silane is added in 5mL ethyl orthosilicate and is stirred 5 hours, is added later
50mL ethyl alcohol stirs 2 hours, obtains the solution of homogeneous transparent；
(2) 4mL water is added in the solution of step (1) to stir 5 days, obtains the SiO containing sulfydryl2Colloidal sol；
(3) by the above-mentioned SiO containing sulfydryl2Colloidal sol is sprayed on glass surface, is formed after dry in glass surface transparent
SiO2Glass-film, the glass-film do not crack.
Comparative example 3
(1) 5mL methyl orthosilicate is added in 0.1mL trimethoxy mercapto propyl silane to stir 5 hours, 50mL second is added later
Alcohol stirs 2 days, obtains the solution of homogeneous transparent；
(2) 5mL water is added in the solution of step (1) to stir 5 days, obtains the SiO containing sulfydryl2Colloidal sol；
(3) by the above-mentioned SiO containing sulfydryl2Colloidal sol is sprayed on glass surface, the SiO formed after dry in glass surface2Glass
Glass film cracking.
Application examples
Above-described embodiment and the glass-film of comparative example are subjected to hydrophily verification test respectively, to detect the hydrophilic of glass-film
And self-cleaning performance, the method is as follows:
It is visually observed after the glass-film of each embodiment and comparative example is placed 2 months, 2 months under same outdoor environment
The dust of embodiment 1-4 glass surface is obviously fewer than comparative example 1-3, after surface dirt is removed, is seen with 400 times of microscopes
Glass surface is examined, it is found that the glass-film of the glass surface of embodiment 1-4 is still smooth, flawless, the glass-film of comparative example 2 has gently
Micro- slight crack occurs, and the glass-film slight crack of comparative example 1 and 3 is clearly.
Angle of wetting test is carried out to the glass-film of embodiment 1-4 and comparative example 1-3, wherein the glass-film of embodiment 1-4
Angle of wetting is 180 °, i.e., water droplet is paved completely, good hydrophilic property, and the angle of wetting of the glass-film of comparative example 1-3 is 90 °, than implementing
The glass-film hydrophily of example is weaker.
Claims (8)
1. a kind of preparation method of liquid hydrophilic glass film, it is characterized in that the following steps are included:
(1) trimethoxy mercapto propyl silane is mixed with ethyl orthosilicate, is stirred evenly, ethyl alcohol is then added and continues stirring at least
2 days, obtain clear solution；
(2) water is added in the clear solution of step (1), continues to stir, make trimethoxy mercapto propyl silane and ethyl orthosilicate
Complete hydrolysis obtains the SiO containing sulfydryl2Colloidal sol, SiO of the gained containing sulfydryl2Colloidal sol is liquid hydrophilic glass film；
In step (1), the volume ratio of trimethoxy mercapto propyl silane and ethyl orthosilicate is 0.05-0.15:1；In step (1),
The volume ratio of ethyl orthosilicate and ethyl alcohol is 0.08-0.12:1；
In step (2), the volume ratio of water and ethyl orthosilicate is 0.8-1.2:1.
2. preparation method according to claim 1, it is characterized in that: in step (1), trimethoxy mercapto propyl silane and positive silicon
After acetoacetic ester mixing, stirring at least 5h adds ethyl alcohol；In step (2), after water is added, it is stirred at least 5 days.
3. a kind of preparation method of liquid hydrophilic glass film, it is characterized in that the following steps are included:
0.25mL trimethoxy mercapto propyl silane is added in 5mL methyl orthosilicate and is stirred 5 hours, 50mL ethyl alcohol is added later and stirs
It mixes 2 days, obtains the solution of homogeneous transparent；
5.5mL water is added in the solution of step (1) to stir 5 days, obtains the SiO containing sulfydryl2Colloidal sol, i.e. liquid hydrophilic glass
Film.
4. a kind of preparation method of liquid hydrophilic glass film, it is characterized in that the following steps are included:
0.75mL trimethoxy mercapto propyl silane is added in 5mL positive silicic acid propyl ester and is stirred 5 hours, 50mL ethyl alcohol is added later and stirs
It mixes 2 days, obtains the solution of homogeneous transparent；
4mL water is added in the solution of step (1) to stir 5 days, obtains the SiO containing sulfydryl2Colloidal sol, i.e. liquid hydrophilic glass film.
5. liquid hydrophilic glass made from the preparation method according to liquid hydrophilic glass film of any of claims 1-4
Film.
6. a kind of hydrophilic glass, it is characterized in that: being covered with one layer of SiO containing sulfydryl in glass surface2Film, it is described containing sulfydryl
SiO2Film is formed by way of liquid hydrophilic glass film described in claim 5 is coated in glass surface and then drying
's.
7. a kind of preparation method of hydrophilic glass, it is characterized in that: coating the parent of liquid described in one layer of claim 5 in glass surface
Waterglass film, up to hydrophilic glass after drying.
8. preparation method according to claim 7, it is characterized in that: liquid hydrophilic glass film using spraying, spin coating, dip-coating or
The mode of printing is coated in glass surface.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610368255.2A CN106007394B (en) | 2016-05-30 | 2016-05-30 | A kind of liquid hydrophilic glass film, hydrophilic glass and their preparation method |
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| CN201610368255.2A CN106007394B (en) | 2016-05-30 | 2016-05-30 | A kind of liquid hydrophilic glass film, hydrophilic glass and their preparation method |
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| CN106007394B true CN106007394B (en) | 2018-12-18 |
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| CN106946469A (en) * | 2017-02-28 | 2017-07-14 | 山东工业陶瓷研究设计院有限公司 | Anti-reflection coating easy to clean and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105176179A (en) * | 2015-08-31 | 2015-12-23 | 福州富兰机电技术开发有限公司 | Modified silica sol, and preparation method and application thereof |
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| CN105176179A (en) * | 2015-08-31 | 2015-12-23 | 福州富兰机电技术开发有限公司 | Modified silica sol, and preparation method and application thereof |
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