CN107540241A - A kind of method that the controllable hydrophobic silica anti-reflection film of refractive index is prepared with phenyl triethoxysilane - Google Patents
A kind of method that the controllable hydrophobic silica anti-reflection film of refractive index is prepared with phenyl triethoxysilane Download PDFInfo
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- CN107540241A CN107540241A CN201710732173.6A CN201710732173A CN107540241A CN 107540241 A CN107540241 A CN 107540241A CN 201710732173 A CN201710732173 A CN 201710732173A CN 107540241 A CN107540241 A CN 107540241A
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- refractive index
- phenyl triethoxysilane
- reflection film
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Abstract
The invention provides a kind of the controllable hydrophobic SiO of refractive index is prepared using phenyl triethoxysilane2The method of anti-reflection film, by preparing phenyl triethoxysilane and tetraethyl orthosilicate hybrid collosol, and by certain preparation means, there is refractive index simultaneously on a glass substrate toward high regulation and control and hydrophobic SiO2Anti-reflection film, concretely comprise the following steps：Phenyl triethoxysilane and tetraethyl orthosilicate are hydridization precursor liquid, are dispersed in absolute ethyl alcohol, are hydrolyzed under the catalysis of ammoniacal liquor and polycondensation；By above-mentioned precursor liquid, with dip-coating method, plated film, film layer obtained by after heat treatment are 1.26 1.43 in hydrophobicity and the controllable scope of refractive index on a glass substrate after ageing certain time.
Description
Technical field
The invention belongs to use optics field of film preparation, particularly relate to a kind of prepared using phenyl triethoxysilane and reflect
The controllable hydrophobic SiO of rate2The method of anti-reflection film.
Background technology
SiO2Nowadays the reflection that anti-reflection film can effectively reduce light has been widely used in military, industry, agricultural, traffic thing
Stream, astrophysics and medical science etc., play more and more important effect, especially in high power in daily life
In terms of the optical fields such as laser system, flat-panel screens and solar cell.
In numerous preparation SiO2In the method for anti-reflection film, compared with chemical vapour deposition technique, physical vaporous deposition, plasma
Body facture and chemical method for etching, there is sol-gel process manufacture craft simply, under normal temperature and pressure to operate, resisting laser damage threshold
It is worth high, easy-regulating particle size and easily further the advantages that carrying out functionalization and turns into one of conventional method.
SiO prepared by sol-gel process base catalysis method2Anti-reflection film, it is by spherical SiO in film forming2Particle is on substrate
Random accumulation forms, and there is abundant hole between inside particles and particle, causes its film to have very high porosity, single
Layer film refractive index can as little as 1.23.But in actual use, for wideband anti-reflection film in response to more generally causing to make
With more and more higher is required, refractive index is 1.23 individual layer SiO2Anti-reflection film can not meet present situation in certain wave with 0 reflection, instead
And prepare the SiO for having graded index2Anti-reflection film is increasingly becoming focus.
In addition, SiO2The environment resistant problem of anti-reflection film is always SiO prepared by sol-gel process base catalysis method2Anti-reflection film
Problems faced, reason are SiO2There are substantial amounts of polar hydroxyl groups on anti-reflection film surface, in SiO2Anti-reflection film is in actual use, empty
Polar contaminants in gas are easily by SiO2The substantial amounts of polar group absorption in anti-reflection film surface, pollutant even can penetrate into hole
In, have a strong impact on the optical stability of film.
The content of the invention
For it is mentioned above the problem of, realizing the adjustable aspect of refractive index, main method has at present：In glass surface
The micro-structural that lithographic method prepares refractive index consecutive variations is learned, but this method requires high to condition and is difficult to reach, and is unfavorable for work
Industry metaplasia is produced；Or use template agent method first introduce chelating polymer template again high-temperature calcination remove template entered with increasing film porosity
And regulating and controlling refractive index, the method is cumbersome, and regulated and controled toward anti-reflection film low-refraction, and rarely technology prepares high folding
Penetrate the SiO of rate2Anti-reflection film.In SiO2In the environment resistant problem of anti-reflection film, hybrid inorganic-organic method, which can effectively be alleviated, suppresses SiO2
The problem of absorption of the anti-reflection film surface to polar contaminants.
The present invention uses phenyl triethoxysilane as modifying agent, and it is an object of the present invention to provide a kind of hydrophobicity is strong, and reflects
SiO of the rate toward top adjustment2Anti-reflection film and preparation method thereof, on the one hand solve in SiO2The surface hydroxyl occurred in anti-reflection film application
The problem of optical stability declines, service life shortens caused by polar contaminants in base absorption air, on the other hand may be used also
To provide certain basis for the preparation of wideband anti-reflection film.
To realize object above, the present invention adopts the following technical scheme that：
（1）The preparation of phenyl triethoxysilane and tetraethyl orthosilicate hybrid collosol：By modifying agent phenyl triethoxysilane, just
Silester, absolute ethyl alcohol, catalyst ammonia water and distilled water are 1.75-9.6 in mass ratio：8.3-15.8：100-200：0.1-
6.5：1-10 is mixed, and stirs 0.5-12 h at 25-50 DEG C in closed glass container, is aged 3-45 days at room temperature afterwards.
（2）Film preparation：Use dipping-pulling method with friction speed in substrate coating the glass substrate of clean dry,
0.5-3 h are heat-treated at 80-200 DEG C afterwards.
Described pull rate is 50-400 mm/min.
Hydrophobic SiO made from a kind of method described above2Anti-reflection film, by by modifying agent phenyl triethoxysilane and just
Silester hydridization, just can be by SiO2Anti-reflection film by it is hydrophilic be changed into it is hydrophobic, strengthen its optical stability, extend the life-span it is same
The a range of refractive indexes of Shi Shixian are controllable.
The remarkable advantage of the present invention is：This method is by adding modifying agent phenyl triethoxysilane when preparing colloidal sol
With regard to that can prepare while have hydrophobicity and the controllable SiO of refractive index2Anti-reflection film, the refractive index prepared different from conventional method are controllable
Anti-reflection film be refractive index toward low-key control, the present invention be modifying agent using phenyl triethoxysilane, phenyl group can be filled into
In the hole of anti-reflection film, by controlling phenyl loading to control porosity further to regulate and control refractive index, refractive index controlled range
1.26-1.43 to prepare high index of refraction and hydrophobic SiO2Anti-reflection film provides a kind of new method.
Brief description of the drawings
Fig. 1 is different quality than SiO made from raw material2The contact angle figure of anti-reflection film.
Embodiment
The comparative example and embodiment of the present invention is described below（Raw material is marketable material, and purity is pure for chemical pure or analysis
Grade）.
Comparative example 1
（1）By tetraethyl orthosilicate, absolute ethyl alcohol, distilled water and ammoniacal liquor in mass ratio 16.7：137.4：4：0.9 in closed glass
It is aged 6 days with 30 DEG C of h of magnetic agitation 2,25 DEG C of constant temperature in container.
（2）Dipping-pulling method is used with 100 mm/min pull rate plated films on substrate, afterwards at 120 DEG C at heat
Manage 2 h.
Embodiment 1
（1）Phenyl triethoxysilane, tetraethyl orthosilicate, absolute ethyl alcohol, distilled water and ammoniacal liquor in mass ratio 0.91：15.6：
137.4：4：0.9 is aged 6 days in closed glass container with 30 DEG C of h of magnetic agitation 3,25 DEG C of constant temperature.
（2）Dipping-pulling method is used with 100 mm/min pull rate plated films on substrate, afterwards at 100 DEG C at heat
Manage 2 h.
Embodiment 2
（1）Phenyl triethoxysilane, tetraethyl orthosilicate, absolute ethyl alcohol, distilled water and ammoniacal liquor in mass ratio 5.5：11.9：
137.4：4：0.9 is aged 10 days in closed glass container with 45 DEG C of h of magnetic agitation 2,25 DEG C of constant temperature.
（2）Dipping-pulling method is used with 100 mm/min pull rate plated films on substrate, afterwards at 150 DEG C at heat
Manage 1 h.
Embodiment 3
（1）Phenyl triethoxysilane, tetraethyl orthosilicate, absolute ethyl alcohol, distilled water and ammoniacal liquor in mass ratio 9.6：8.3：
137.4：4：0.9 is aged 25 days in closed glass container with 30 DEG C of h of magnetic agitation 8,25 DEG C of constant temperature.
（2）Dipping-pulling method is used with 100 mm/min pull rate plated films on substrate, afterwards at 200 DEG C at heat
Manage 0.5 h.
The different quality of table 1 than raw material under SiO2Centre wavelength, maximum transmission and the refractive index of anti-reflection film
Phenyl triethoxysilane can regulate and control SiO as modifying agent2The refractive index mechanism of anti-reflection film is, the phenyl group of introducing
Filling SiO can be played2The effect of hole between particle, regulate and control SiO2Particle hole and then regulation refractive index, realize refractive index
Control in higher range.SiO produced by the present invention2The modification scope of anti-reflection film refractive index is in 1.26-1.43.In titanium dioxide
In silicon anti-reflection film, because the refractive index of pure silicon dioxide is 1.46, the present invention can realize that regulation and control to 1.43, are achieved and significantly entered
Step.
Fig. 1 show SiO under different embodiments2The contact angle figure of anti-reflection film, it can be found that being not added with modifying agent from figure
SiO2Anti-reflection film is strongly hydrophilic, and contact angle is 22.6 o, after being modified by phenyl triethoxysilane, SiO2Anti-reflection film
Hydrophobicity have and improve to some extent.
Presently preferred embodiments of the present invention is the foregoing is only, as long as the equivalent change made according to this scope and modification,
The category present invention covers category.
Claims (6)
1. a kind of prepare the controllable hydrophobic SiO of refractive index with phenyl triethoxysilane2The method of anti-reflection film, it is characterised in that tool
Body step is as follows：
（1）The preparation of phenyl triethoxysilane and tetraethyl orthosilicate hybrid collosol：By modifying agent phenyl triethoxysilane, just
Silester, absolute ethyl alcohol, catalyst ammonia water and distilled water are 1.75-9.6 in mass ratio：8.3-15.8：100-200：0.1-
6.5：1-10 is mixed, and is hydrolyzed under the catalysis of ammoniacal liquor and polycondensation, is stirred in the glass container of closing at 25-50 DEG C
0.5-12 h, it is aged 3-45 days at room temperature afterwards；
（2）Dipping-pulling method is used then to be coated with film layer with 50-400 mm/min speed plated film on a glass substrate
Substrate, which is placed in 80-200 DEG C of baking oven, dries 0.5-3 h, and hydrophobic increasing of the refractive index in 1.26-1.43 is obtained after natural cooling
Permeable membrane.
2. according to claim 1 prepare the controllable SiO of refractive index with phenyl triethoxysilane2The method of anti-reflection film, its
It is characterised by, phenyl triethoxysilane, tetraethyl orthosilicate, absolute ethyl alcohol, distilled water and ammoniacal liquor 1.75-9.6 in mass ratio：
8.3-15.8：100-200：1-10：0.1-6.5.
3. according to claim 1 prepare the controllable hydrophobic SiO of refractive index with phenyl triethoxysilane2The side of anti-reflection film
Method, it is characterised in that step（1）Whipping temp is 25-50 DEG C, and the time is 0.5-12 h.
4. according to claim 1 prepare the controllable hydrophobic SiO of refractive index with phenyl triethoxysilane2The side of anti-reflection film
Method, it is characterised in that the constant temperature digestion time of mixed sols is 3-45 days, and thermostat temperature is 25 DEG C.
5. according to claim 1 prepare the controllable hydrophobic SiO of refractive index with phenyl triethoxysilane2The side of anti-reflection film
Method, it is characterised in that step（2）The speed of middle plated film is 50-400 mm/min.
6. according to claim 1 prepare the controllable hydrophobic SiO of refractive index with phenyl triethoxysilane2The side of anti-reflection film
Method, it is characterised in that step（2）Middle drying temperature is 80-200 DEG C, and drying time is 0.5-3 h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109957346A (en) * | 2019-03-26 | 2019-07-02 | 东莞奥得时精密电子有限公司 | Antifog laminating film and its material and technique |
| WO2023169539A1 (en) * | 2022-03-10 | 2023-09-14 | 福耀玻璃工业集团股份有限公司 | Hydrophobic anti-reflective glass for vehicle, fabrication method therefor, and laminated glass |
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| CN104609738A (en) * | 2013-11-01 | 2015-05-13 | 北京有色金属研究总院 | Method used for increasing silicon dioxide antireflection film hole stability |
| CN106431001A (en) * | 2016-10-12 | 2017-02-22 | 福建农林大学 | Method for preparing hydrophobic SiO2 antireflective coating with organic-inorganic hybrid method |
| CN106477909A (en) * | 2016-10-12 | 2017-03-08 | 福建农林大学 | One kind prepares hydrophobic SiO with dodecyl triethoxysilane2The method of anti-reflection film |
| CN106630668A (en) * | 2016-10-12 | 2017-05-10 | 福建农林大学 | Method for preparing SiO2 antireflection film with controllable refractive index by using propyltriethoxysilane |
| CN106800885A (en) * | 2016-12-21 | 2017-06-06 | 中国科学院兰州化学物理研究所 | A kind of large-scale preparation method of transparent hydrophobic/super-amphiphobic coating |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104609738A (en) * | 2013-11-01 | 2015-05-13 | 北京有色金属研究总院 | Method used for increasing silicon dioxide antireflection film hole stability |
| CN106431001A (en) * | 2016-10-12 | 2017-02-22 | 福建农林大学 | Method for preparing hydrophobic SiO2 antireflective coating with organic-inorganic hybrid method |
| CN106477909A (en) * | 2016-10-12 | 2017-03-08 | 福建农林大学 | One kind prepares hydrophobic SiO with dodecyl triethoxysilane2The method of anti-reflection film |
| CN106630668A (en) * | 2016-10-12 | 2017-05-10 | 福建农林大学 | Method for preparing SiO2 antireflection film with controllable refractive index by using propyltriethoxysilane |
| CN106800885A (en) * | 2016-12-21 | 2017-06-06 | 中国科学院兰州化学物理研究所 | A kind of large-scale preparation method of transparent hydrophobic/super-amphiphobic coating |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109957346A (en) * | 2019-03-26 | 2019-07-02 | 东莞奥得时精密电子有限公司 | Antifog laminating film and its material and technique |
| CN109957346B (en) * | 2019-03-26 | 2021-06-18 | 东莞奥得时精密电子有限公司 | Antifogging adhesive film and its material and technology |
| WO2023169539A1 (en) * | 2022-03-10 | 2023-09-14 | 福耀玻璃工业集团股份有限公司 | Hydrophobic anti-reflective glass for vehicle, fabrication method therefor, and laminated glass |
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Application publication date: 20180105 |