CN102774085B - Hydrophobic substrate and preparation method thereof - Google Patents
Hydrophobic substrate and preparation method thereof Download PDFInfo
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- CN102774085B CN102774085B CN201210225678.0A CN201210225678A CN102774085B CN 102774085 B CN102774085 B CN 102774085B CN 201210225678 A CN201210225678 A CN 201210225678A CN 102774085 B CN102774085 B CN 102774085B
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- substrate
- surface energy
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- energy coat
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Abstract
A kind of hydrophobic substrate and preparation method thereof.Described hydrophobic substrate includes: substrate and the low surface energy coat being positioned on described substrate surface, and the material of described low surface energy coat includes methoxy silane.The manufacture method of described hydrophobic substrate, including: substrate is provided；Forming low surface energy coat on the substrate, the material of described low surface energy coat includes methoxy silane.The present invention both can avoid the low surface energy coat corrosion to substrate, can reduce again production cost.
Description
Technical field
The present invention relates to hydrophobic technical field, particularly relate to a kind of hydrophobic substrate and preparation method thereof.
Background technology
Hydrophobic surface generally refers to the surface of solids contact angle with the water surface more than 120 °.Due to hydrophobic surface
The least with the contact area of water droplet, water droplet easily tumbles from surface.Therefore, hydrophobic surface not only has
Self-cleaning function, but also have anti-electric spread lead, anticorrosion, waterproof, antifog, gas defence, snow defence,
Frost protection, anti-stick, the function such as anti-pollution, thus at building, textile clothing, liquid conveying, biology
Medical science, article of everyday use all have a wide range of applications with fields such as packaging, transport facility and microanalysiss
Prospect.
In general, the hydrophobic performance of object depends on the low-surface energy substance modified on its surface.
Fig. 1 shows a kind of Hydrophobic glass plate of the prior art.With reference to shown in Fig. 1, described Hydrophobic glass plate
Including: glass 10 and the low surface energy coat 20 being positioned at described glass 10 surface, described low surface energy coat
20 are made up of fluorine-containing siloxanes.Effect due to described low surface energy coat 20 so that whole hydrophobic glass
The surface of glass plate presents hydrophobic characteristic.
But, owing to low surface energy coat 20 comprising fluorine element, therefore when low surface energy coat 20 is at glass
During upper residence time long enough, described fluorine element will the surface of etching glass 10, thus affect this and dredge
The normal use of waterglass plate.
Similarly, when above-mentioned low surface energy coat 20 is used for metal surface or frosting, equally can corruption
Erosion metal or the surface of plastics.
Additionally, the price comparison of fluorine-containing low surface energy coat 20 is expensive, finally improve production cost.
Summary of the invention
The problem that the present invention solves is to provide a kind of hydrophobic substrate and preparation method thereof, both can avoid low table
The face energy coating corrosion to substrate, can reduce again production cost.
For solving the problems referred to above, the invention provides a kind of hydrophobic substrate, described in: substrate and being positioned at
Low surface energy coat on substrate surface, the material of described low surface energy coat includes methoxy silane.
Alternatively, the material of described substrate is glass, plastics or metal.
Alternatively, the thickness range of described low surface energy coat is 10nm ~ 500nm.
Alternatively, the material of described low surface energy coat is hexadecyl trimethoxy silane
(Hexadecyltrimethoxysilane, HDTMS).
For solving the problems referred to above, present invention also offers the manufacture method of a kind of hydrophobic substrate, including:
Substrate is provided；
Forming low surface energy coat on the substrate, the material of described low surface energy coat includes methoxyl group
Silane.
Alternatively, before forming described low surface energy coat, also include: described substrate is carried out
Process.
Alternatively, described substrate is carried out process to include: use acetone, isopropyl acetone and deionized water
Mixed solution described substrate is carried out ultrasonic waves for cleaning.
Alternatively, before forming described low surface energy coat, also include: the substrate after cleaning is carried out
Roughening processes.
Alternatively, described roughening processes and uses Fluohydric acid. or salpeter solution to realize.
Alternatively, the weight percentage ranges of described Fluohydric acid. or nitric acid is 5wt% ~ 20wt%；Roughening
The time range processed is 30 minutes ~ 120 minutes；The temperature range that roughening processes is 20 DEG C ~ 80 DEG C.
Alternatively, after described roughening processes and before forming described low surface energy coat, also include:
Deionized water is used to clean described substrate.
Alternatively, the step forming low surface energy coat on the substrate includes:
Hexadecyl trimethoxy silane is provided；
In hexadecyl trimethoxy silane, add ethanol form solution；
Described solution is carried out acidification；
Solution after acidification is stirred；
By the way of infiltration, spin coating or sprinkling, described solution is formed at described substrate surface.
Alternatively, described solution is carried out acidification to include: in described solution, add acetic acid, hydrochloric acid
Or at least one in nitric acid, make the pH value of described solution be positioned at 4.5 ~ 5.5 scopes.
Alternatively, the time of described stir process is more than or equal to 60 minutes.
Alternatively, when using pattern of invasion that described solution is formed at described substrate surface, by described base
The end, is placed in described solution, and standing time is 30 minutes ~ 60 minutes.
Alternatively, in described solution, the mass percent of hexadecyl trimethoxy silane is 3%～5%.
Alternatively, after forming described low surface energy coat, also include: by described low surface energy coat
Dry, and carry out cured.
Alternatively, the time range of described cured is 30 minutes ~ 60 minutes, and temperature range is
100℃~150℃。
Alternatively, described offer substrate includes providing substrate of glass, plastic-substrates or metallic substrates.
Compared with prior art, technical solution of the present invention has the advantage that
1) in described hydrophobic substrate, the material of low surface energy coat includes methoxy silane, does not include fluorine element,
Even if thus use for a long time, described low surface energy coat also will not corrode substrate, may finally ensure to dredge
The normal use of water base plate.Additionally, the price comparison of described low surface energy coat is cheap, thus reduce
Production cost.
2) in alternative, described low surface energy coat is HDTMS, meeting after hydrolyzing due to HDTMS
Produce three active groups, relative to general siloxanes, can have with substrate generation chemical reaction
Higher mechanical performance.Additionally, described HDTMS has the double effects of water and oil repellant.
Accompanying drawing explanation
Fig. 1 is the structural representation of a kind of Hydrophobic glass plate in prior art；
Fig. 2 is the schematic flow sheet of the manufacture method of hydrophobic substrate in embodiment of the present invention；
Fig. 3 is the schematic flow sheet forming low surface energy coat in embodiment of the present invention；
Fig. 4 is the structural representation of hydrophobic substrate in embodiment of the present invention.
Detailed description of the invention
Understandable, below in conjunction with the accompanying drawings for enabling the above-mentioned purpose of the present invention, feature and advantage to become apparent from
The detailed description of the invention of the present invention is described in detail.
Elaborate a lot of detail in the following description so that fully understanding the present invention, but this
Bright other can also be used to be different from alternate manner described here implement, therefore the present invention is not by following
The restriction of disclosed specific embodiment.
The most as described in the background section, in prior art, low surface energy coat includes fluorine element, thus leads
Cause corrosion substrate and relatively costly defect.
For drawbacks described above, inventor providing a kind of hydrophobic substrate and preparation method thereof, it uses and does not wrap
Include the methoxy silane of fluorine element as low surface energy coat, even if thus using for a long time, described low table
Substrate coating also can will not be corroded in face, may finally ensure the normal use of hydrophobic substrate.Additionally, it is described
The price comparison of low surface energy coat is cheap, thus reduces production cost.
It is described in detail below in conjunction with the accompanying drawings.
With reference to shown in Fig. 2, present embodiments provide for the manufacture method of a kind of hydrophobic substrate, including:
Step S1, it is provided that substrate；
Step S2, is carried out described substrate processing；
Step S3, is roughened the substrate after cleaning；
Step S4, forms low surface energy coat on the substrate；
Step S5, dries described low surface energy coat, and carries out cured.
Step S1 is first carried out, it is provided that substrate.
Described substrate can be substrate of glass, it is also possible to be the metallic substrates of any metal material, it is also possible to
It it is plastic-substrates etc..
The present embodiment is not intended to the concrete shape of substrate, size and thickness.
Then perform step S2, be carried out processing.
The present embodiment can use the mixed solution of acetone, isopropyl acetone and deionized water to carry out described substrate
Ultrasonic waves for cleaning, its detailed process does not repeats them here known to for those skilled in the art being.
It should be noted that in other embodiments of the invention, it is also possible to adopt and clean base in other ways
The end, it is not intended to protection scope of the present invention.
By described cleaning treatment, the impurity of substrate surface can be removed, it is ensured that obtain clean substrate,
Do not make the carrying out of described impurity effect subsequent step.
Then step S3, is roughened.
The present embodiment can use Fluohydric acid. (HF) or nitric acid (HNO3) solution realize roughening process.
Described Fluohydric acid. or salpeter solution can react with substrate, so that substrate surface is relatively rough.
Specifically, described substrate can be immersed directly in Fluohydric acid. or salpeter solution by this example.Its
In, the weight percentage ranges of described Fluohydric acid. or nitric acid can be 5wt% ~ 20wt%；Roughening processes
Time range can be 30 minutes ~ 120 minutes；The temperature range that roughening processes can be
20℃~80℃。
Processed by described roughening, the wettability of substrate can be increased, increase follow-up at substrate surface
The fastness of the film layer formed and uniformity.
Additionally, after being roughened, it is also possible to use deionized water to clean described substrate, to go
The acid solution remained except described substrate surface.
Then perform step S4, form low surface energy coat.
The material of low surface energy coat described in the present embodiment includes methoxy silane, is specifically as follows
HDTMS。
When using HDTMS to constitute low surface energy coat, have the advantage that
A, HDTMS do not include fluorine element, though the long-time and base of glass, metal or plastic material
The end, contacts, and also will not corrode substrate；
Can produce three active groups after B, HDTMS hydrolysis, described active group can occur with substrate
Chemical reaction so that the adhesiveness of HDTMS and substrate is the best, thus improves service life；
C, it is provided simultaneously with the double effects of water and oil repellant due to HDTMS, therefore can ensure that making obtains
Hydrophobic substrate not only water repellent but also refuse oil；
D, HDTMS's is cheap, such that it is able to reduce the production cost of hydrophobic substrate.
Specifically, before HDTMS is by hydrolyzing
After becoming hydrolysisThus HDTMS can have three silicone hydroxyl (from structural formula the most also
Can only have three silicone hydroxyl), this silicone hydroxyl reacts with suprabasil hydroxyl as active group, therefore
HDTMS is the best with the adhesion of substrate.
Additionally, surface energy will be caused too high when carbochain is too short in low-surface-energy material, do not have hydrophobic effect
Really；Link breakdown, less stable then it is susceptible to when carbochain is long.The present embodiment is selected HDTMS
As low-surface-energy material, the carbon chain lengths of HDTMS is moderate, thus both can play hydrophobic effect, and
Stability is relatively good.
With reference to shown in Fig. 3, the step forming low surface energy coat in the present embodiment on the substrate is permissible
Including:
Step S41, it is provided that hexadecyl trimethoxy silane；
Step S42, adds ethanol in hexadecyl trimethoxy silane and forms solution；
Step S43, carries out acidification to described solution；
Step S44, is stirred the solution after acidification；
Step S45, is formed at described substrate surface by described solution by the way of infiltration, spin coating or sprinkling.
First, it is provided that chemical structural formula is CH3(CH2)15Si(OCH3)3HDTMS.
Then, inventor studies discovery HDTMS and is soluble in ethanol, therefore adds second in HDTMS
Alcohol, such that it is able to obtain comprising the solution of HDTMS.
HDTMS both can be placed in ethanol solution by the present embodiment, it is also possible to is poured into by ethanol solution
In HDTMS.
Specifically, in described solution, the mass percent of hexadecyl trimethoxy silane may range from
3%～5%.
Then, described solution is carried out acidification, so that HDTMS is hydrolyzed, and generate activity
Group hydroxy.
Specifically, described solution adds at least one in acetic acid, hydrochloric acid or nitric acid, until making molten
The pH value of liquid is positioned between 4.5 ~ 5.5, such as: the pH value of solution is 4.5,5.0 or 5.5.
Then, the solution after acidification is stirred, so that HDTMS hydrolysis is abundant and equal
Even.
Specifically, the solution after acidification is put in agitating device, this solution is carried out 60 minutes with
On stirring.
Then, after treating that above-mentioned solution has been prepared, it is possible to be formed at described substrate surface, with
As low surface energy coat.
Specifically, by any one in infiltration, spin coating or spray pattern, described solution can be formed
At described substrate surface.
When using pattern of invasion that described solution is formed at described substrate surface, described substrate is placed on
In described solution, relatively more abundant in order to ensure to react, standing time can be 30 minutes ~ 60 minutes, such as:
30 minutes, 40 minutes, 50 minutes or 60 minutes.This operation can be carried out the most at normal temperatures, it is not necessary to
Other devices, simple to operate, and can guarantee that low surface energy coat is the most uniform in the distribution of substrate surface.
When using spin coating or spray pattern that described solution is formed at described substrate surface, required time ratio
Shorter, efficiency comparison is high, simultaneously it is also ensured that the uniformity that is distributed at substrate surface of low surface energy coat.
So far, low surface energy coat is defined at substrate surface.The thickness of described low surface energy coat is point
Sub-rank, is specifically as follows 10nm ~ 500nm, such as: 10nm, 50nm, 100nm, 250nm or 500nm.
Then perform step S5, described low surface energy coat is dried, and carries out cured.
The present embodiment, after forming described low surface energy coat, is first dried in room temperature.
After described low surface energy coat is dried, it is possible to carry out cured.Specifically, described solid
The time range that change processes can be 30 minutes ~ 60 minutes, such as: 30 minutes, 40 minutes, 50 minutes
Or 60 minutes；Temperature range can be 100 DEG C ~ 150 DEG C, such as: 100 DEG C, 110 DEG C, 120 DEG C, 130 DEG C,
140 DEG C or 150 DEG C.
By described cured, the low surface energy coat set at substrate surface can be increased, prevent low
Coming off of surface energy coat.
It should be noted that in other embodiments of the invention, in order to simplify step, ensureing at base
On the premise of basal surface can form low surface energy coat, described cleaning treatment, roughening process or at solidification
Step corresponding to reason all can be omitted.
The technics comparing of the present embodiment is simple, makes the table of substrate by forming HDTMS at substrate surface
Face is hydrophobicity, due to use HDTMS as low surface energy coat, even if thus use for a long time,
Described low surface energy coat also will not corrode substrate, may finally ensure the normal use of hydrophobic substrate；Again
Owing to the price comparison of HDTMS is cheap, thus reduce production cost.
Correspondingly, with reference to shown in Fig. 4, present embodiment additionally provides a kind of hydrophobic substrate, including:
Substrate 100；
It is positioned at the low surface energy coat 200 on described substrate 100 surface, described low surface energy coat 200
Material includes methoxy silane.
Wherein, the material of described substrate 100 can be glass, plastics or metal.
Wherein, the thickness range of described low surface energy coat 200 can be 10nm ~ 500nm, such as: 10nm,
50nm, 100nm, 250nm or 500nm.
Specifically, the material of described low surface energy coat 200 can be hexadecyl trimethoxy silane.
Described hydrophobic substrate specifically can use preceding method to make, and does not repeats them here.
In the hydrophobic substrate that the present embodiment makes, employing HDTMS is as low surface energy coat, even if thus
Long-time use, described low surface energy coat also will not corrode substrate, may finally ensure hydrophobic substrate
Normal use.Additionally, the price comparison of described low surface energy coat is cheap, thus reduce production cost,
It is beneficial to the large-scale popularization and application of hydrophobic substrate.
Although the present invention discloses as above with preferred embodiment, but the present invention is not limited to this.Any ability
Field technique personnel, without departing from the spirit and scope of the present invention, all can make various changes or modifications, because of
This protection scope of the present invention should be as the criterion with claim limited range.
Claims (8)
1. the manufacture method of a hydrophobic substrate, it is characterised in that including:
Thering is provided substrate, described substrate is substrate of glass；
Described substrate is roughened, described roughening processes and uses Fluohydric acid. or salpeter solution to realize, the weight percentage ranges of described Fluohydric acid. or nitric acid is 5wt%～20wt%, the time range that described roughening processes is 30 minutes～120 minutes, and the temperature range that described roughening processes is 20 DEG C～80 DEG C；And
Forming low surface energy coat on the substrate, the material of described low surface energy coat includes methoxy silane, and the step forming low surface energy coat on the substrate includes:
Hexadecyl trimethoxy silane is provided；
Adding ethanol in hexadecyl trimethoxy silane and form solution, in described solution, the mass percent of hexadecyl trimethoxy silane is 3%～5%；
In described solution, add at least one in acetic acid, hydrochloric acid or nitric acid, make the pH value of described solution be positioned at 4.5～5.5 scopes, so that hexadecyl trimethoxy silane is hydrolyzed；
Solution after acidification is stirred；And
By the way of infiltration, spin coating or sprinkling, the solution after stir process is formed at described substrate surface.
2. the manufacture method of hydrophobic substrate as claimed in claim 1, it is characterised in that before roughening processes, also include: be carried out described substrate processing.
3. the manufacture method of hydrophobic substrate as claimed in claim 2, it is characterised in that described substrate is carried out process and includes: use the mixed solution of acetone, isopropyl acetone and deionized water that described substrate is carried out ultrasonic waves for cleaning.
4. the manufacture method of hydrophobic substrate as claimed in claim 1, it is characterised in that after described roughening processes and before forming described low surface energy coat, also include: use deionized water to clean described substrate.
5. the manufacture method of hydrophobic substrate as claimed in claim 1, it is characterised in that the time of described stir process is more than or equal to 60 minutes.
6. the manufacture method of hydrophobic substrate as claimed in claim 1, it is characterised in that when using pattern of invasion that the solution after stir process is formed at described substrate surface, described substrate being placed in described solution, standing time is 30 minutes～60 minutes.
7. the manufacture method of hydrophobic substrate as claimed in claim 1, it is characterised in that after forming described low surface energy coat, also include: described low surface energy coat is dried, and carry out cured.
8. the manufacture method of hydrophobic substrate as claimed in claim 7, it is characterised in that the time range of described cured is 30 minutes～60 minutes, and temperature range is 100 DEG C～150 DEG C.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210225678.0A CN102774085B (en) | 2012-06-29 | 2012-06-29 | Hydrophobic substrate and preparation method thereof |
| PCT/CN2013/078043 WO2014000651A1 (en) | 2012-06-29 | 2013-06-26 | Optical assembly, manufacturing method therefor, and photovoltaic device |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210225678.0A CN102774085B (en) | 2012-06-29 | 2012-06-29 | Hydrophobic substrate and preparation method thereof |
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| CN102774085A CN102774085A (en) | 2012-11-14 |
| CN102774085B true CN102774085B (en) | 2016-08-24 |
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| CN104021879B (en) * | 2013-09-18 | 2017-02-01 | 天津工业大学 | Preparation method for carbon nanotube flexible transparent conductive thin film |
| CN103951277B (en) * | 2014-05-04 | 2015-11-25 | 江南大学 | A kind of super lyophoby anti-reflective glass upper layer and preparation method thereof |
| CN108855259A (en) * | 2018-06-05 | 2018-11-23 | 中国科学院苏州生物医学工程技术研究所 | A kind of surface modifying method of micro-array chip |
| CN108675646B (en) * | 2018-07-23 | 2021-08-31 | 北方夜视技术股份有限公司 | Microporous optical element with highly roughened channel interior surface and method of making same |
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| CN102321974B (en) * | 2011-07-14 | 2012-12-19 | 陕西科技大学 | Preparation method of superhydrophobic ultraviolet resistant textile |
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