CN102774085A - Hydrophobic base plate and manufacturing method thereof - Google Patents
Hydrophobic base plate and manufacturing method thereof Download PDFInfo
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- CN102774085A CN102774085A CN2012102256780A CN201210225678A CN102774085A CN 102774085 A CN102774085 A CN 102774085A CN 2012102256780 A CN2012102256780 A CN 2012102256780A CN 201210225678 A CN201210225678 A CN 201210225678A CN 102774085 A CN102774085 A CN 102774085A
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Abstract
Disclosed are a hydrophobic base plate and a manufacturing method thereof. The hydrophobic base plate comprises a substrate and a low surface energy coating which is located on the surface of the substrate, and materials of the low surface energy coating include methoxy-silane. The manufacturing method of the hydrophobic base plate includes that the substrate is provided, the low surface energy coating is formed on the substrate, and the materials of the low surface energy coating include methoxy-silane. By means of the hydrophobic base plate and the manufacturing method thereof, the low surface energy coating is prevented from corroding the substrate, and the production costs can be lowered.
Description
Technical field
The present invention relates to hydrophobic technical field, relate in particular to a kind of hydrophobic substrate and preparation method thereof.
Background technology
The contact angle that hydrophobic surface generally is meant the surface of solids and water is greater than 120 ° surface.Because the contact area of hydrophobic surface and water droplet is very little, water droplet very easily tumbles from the surface.Therefore; Hydrophobic surface not only has self-cleaning function; But also have anti-electric current conduction, anticorrosion, waterproof, antifog, gas defence, snow defence, frost protection, anti-ly stick, function such as anti-pollution, thereby carry at building, textile clothing, liquid, biomedical, commodity and fields such as packing, transport facility and micro-analysis all are with a wide range of applications.
In general, the hydrophobic performance of object depends on its surface and goes up the low-surface-energy material of modifying.
Fig. 1 shows a kind of Hydrophobic glass plate of the prior art.With reference to shown in Figure 1, said Hydrophobic glass plate comprises: glass 10 and the low surface energy coat 20 that is positioned at said glass 10 surfaces, said low surface energy coat 20 is made up of fluorine-containing siloxanes.Because the effect of said low surface energy coat 20 makes the surface of whole Hydrophobic glass plate present hydrophobic characteristic.
But, owing to comprise fluorine element in the low surface energy coat 20, therefore when low surface energy coat 20 in time of stop on glass during long enough, the surface that said fluorine element just can etching glass 10, thus influence the normal use of this Hydrophobic glass plate.
Similarly, when above-mentioned low surface energy coat 20 is used for metal surface or frosting, the surface of understanding corroding metal or plastics equally.
In addition, the price comparison of fluorine-containing low surface energy coat 20 is expensive, has finally improved production cost.
Summary of the invention
The problem that the present invention solves provides a kind of hydrophobic substrate and preparation method thereof, both can avoid the corrosion of low surface energy coat to substrate, can reduce production costs again.
For addressing the above problem, the invention provides a kind of hydrophobic substrate, comprising: substrate and be positioned at the low surface energy coat on the said substrate surface, the material of said low surface energy coat comprises methoxy silane.
Alternatively, the material of said substrate is glass, plastics or metal.
Alternatively, the thickness range of said low surface energy coat is 10nm ~ 500nm.
Alternatively, the material of said low surface energy coat be the cetyl trimethoxy silane (Hexadecyltrimethoxysilane, HDTMS).
For addressing the above problem, the present invention also provides a kind of preparation method of hydrophobic substrate, comprising:
Substrate is provided;
In said substrate, form low surface energy coat, the material of said low surface energy coat comprises methoxy silane.
Alternatively, before forming said low surface energy coat, also comprise: clean is carried out in said substrate.
Alternatively, clean being carried out in said substrate comprises: adopt the mixed solution of acetone, isopropyl acetone and deionized water that ultrasonic waves for cleaning is carried out in said substrate.
Alternatively, before forming said low surface energy coat, also comprise: roughened is carried out in the substrate to after cleaning.
Alternatively, said roughened adopts hydrofluoric acid or salpeter solution to realize.
Alternatively, the weight percentage ranges of said hydrofluoric acid or nitric acid is 5wt% ~ 20wt%; The time range of roughened is 30 minutes ~ 120 minutes; The temperature range of roughened is 20 ℃ ~ 80 ℃.
Alternatively, after the said roughened and before forming said low surface energy coat, also comprise: adopt the said substrate of washed with de-ionized water.
Alternatively, the step of formation low surface energy coat comprises in said substrate:
The cetyl trimethoxy silane is provided;
In the cetyl trimethoxy silane, add ethanol and form solution;
Said solution is carried out acidification;
Solution after the acidification is carried out stir process;
Mode through infiltration, spin coating or sprinkling is formed on said substrate surface with said solution.
Alternatively, said solution is carried out acidification comprise: in said solution, add at least a in acetate, hydrochloric acid or the nitric acid, make the pH value of said solution be positioned at 4.5 ~ 5.5 scopes.
Alternatively, the time of said stir process was more than or equal to 60 minutes.
Alternatively, when adopting pattern of invasion that said solution is formed on said substrate surface, said substrate is placed in the said solution, be 30 minutes ~ 60 minutes standing time.
Alternatively, the mass percent of cetyl trimethoxy silane is 3%～5% in the said solution.
Alternatively, after forming said low surface energy coat, also comprise: said low surface energy coat is dried, and be cured processing.
Alternatively, the time range of said cured is 30 minutes ~ 60 minutes, and temperature range is 100 ℃ ~ 150 ℃.
Alternatively, saidly provide substrate to comprise substrate of glass, plastic-substrates or metallic substrates are provided.
Compared with prior art, technical scheme of the present invention has the following advantages:
1) material of low surface energy coat comprises methoxy silane in the said hydrophobic substrate, does not comprise fluorine element, thereby even long-time the use, said low surface energy coat can not corrode substrate yet, finally can guarantee the normal use of hydrophobic substrate.In addition, the price comparison of said low surface energy coat is cheap, thereby has reduced production cost.
2) in the possibility, said low surface energy coat is HDTMS owing to can produce three active groups after the HDTMS hydrolysis, can with substrate generation chemical reaction, with respect to general siloxanes, have stronger mechanical performance.In addition, said HDTMS has the double effects of water and oil repellant.
Description of drawings
Fig. 1 is the structural representation of a kind of Hydrophobic glass plate in the prior art;
Fig. 2 is the schematic flow sheet of the preparation method of hydrophobic substrate in the embodiment of the present invention;
Fig. 3 is the schematic flow sheet that forms low surface energy coat in the embodiment of the present invention;
Fig. 4 is the structural representation of hydrophobic substrate in the embodiment of the present invention.
The specific embodiment
For make above-mentioned purpose of the present invention, feature and advantage can be more obviously understandable, does detailed explanation below in conjunction with the accompanying drawing specific embodiments of the invention.
Set forth a lot of details in the following description so that make much of the present invention, implement but the present invention can also adopt other to be different from alternate manner described here, so the present invention has not received the restriction of following disclosed specific embodiment.
Said as the background technology part, low surface energy coat comprises fluorine element in the prior art, thereby causes corroding substrate and the higher defective of cost.
To above-mentioned defective; The inventor provides a kind of hydrophobic substrate and preparation method thereof, and it adopts the methoxy silane that does not comprise fluorine element as low surface energy coat, thereby even long-time the use; Said low surface energy coat can not corrode substrate yet, finally can guarantee the normal use of hydrophobic substrate.In addition, the price comparison of said low surface energy coat is cheap, thereby has reduced production cost.
Be elaborated below in conjunction with accompanying drawing.
With reference to shown in Figure 2, this embodiment provides a kind of preparation method of hydrophobic substrate, comprising:
Step S1 provides substrate;
Step S2 carries out clean to said substrate;
Step S3 carries out roughened to the substrate after cleaning;
Step S4 forms low surface energy coat in said substrate;
Step S5 dries said low surface energy coat, and is cured processing.
At first execution in step S1 provides substrate.
Said substrate can be a substrate of glass, also can be the metallic substrates of any metal material, can also be plastic-substrates etc.
Present embodiment does not limit concrete shape, size and the thickness of substrate.
Then execution in step S2 carries out clean.
Present embodiment can adopt the mixed solution of acetone, isopropyl acetone and deionized water that ultrasonic waves for cleaning is carried out in said substrate, and its detailed process is known for those skilled in the art, repeats no more at this.
Need to prove that in other embodiments of the invention, can also adopt other modes to clean substrate, it does not limit protection scope of the present invention.
Through said clean, can remove the impurity of substrate surface, guarantee to obtain clean substrate, do not make the carrying out of said impurity effect subsequent step.
Then step S3 carries out roughened.
Present embodiment can adopt hydrofluoric acid (HF) or nitric acid (HNO
3) solution realization roughened.Said hydrofluoric acid or salpeter solution can react with substrate, thereby make substrate surface more coarse.
Particularly, can said substrate directly be immersed in hydrofluoric acid or the salpeter solution in this instance.Wherein, the weight percentage ranges of said hydrofluoric acid or nitric acid can be 5wt% ~ 20wt%; The time range of roughened can be 30 minutes ~ 120 minutes; The temperature range of roughened can be 20 ℃ ~ 80 ℃.
Through said roughened, can increase the wettability of substrate, increase the fastness and the uniformity of the follow-up rete that forms at substrate surface.
In addition, after carrying out roughened, can also adopt the said substrate of washed with de-ionized water, to remove the residual acid solution of said substrate surface.
Then execution in step S4 forms low surface energy coat.
The material of low surface energy coat described in the present embodiment comprises methoxy silane, specifically can be HDTMS.
When adopting HDTMS to constitute low surface energy coat, have the following advantages:
Do not comprise fluorine element among A, the HDTMS,, can not corrode substrate yet even contact with the substrate of glass, metal or plastic material for a long time;
Can produce three active groups after B, the HDTMS hydrolysis, said active group can with substrate generation chemical reaction, make that the adhesiveness of HDTMS and substrate is very good, thereby improved service life;
C, because HDTMS possesses the double effects of water and oil repellant simultaneously, therefore can guarantee to make the hydrophobic substrate that obtains not only refuses water but also refuse oil;
D, HDTMS's is cheap, thereby can reduce the production cost of hydrophobic substrate.Particularly;
of HDTMS before by hydrolysis becomes
after the hydrolysis thereby HDTMS can have three silicon hydroxyls (three silicon hydroxyls at most also can only be arranged) from structural formula; This silicon hydroxyl reacts as active group and suprabasil hydroxyl, so the adhesion of HDTMS and substrate is very good.
In addition, when carbochain is too short in the low-surface-energy material, will cause the surface ability too high, not have hydrophobic effect; The link fracture then takes place when carbochain is long easily, less stable.Select for use HDTMS as low-surface-energy material in the present embodiment, the carbon chain lengths of HDTMS is moderate, thereby both can play hydrophobic effect, and stability is also relatively good.
With reference to shown in Figure 3, the step that in said substrate, forms low surface energy coat in the present embodiment can comprise:
Step S41 provides the cetyl trimethoxy silane;
Step S42 adds ethanol and forms solution in the cetyl trimethoxy silane;
Step S43 carries out acidification to said solution;
Step S44 carries out stir process to the solution after the acidification;
Step S45, the mode through infiltration, spin coating or sprinkling is formed on said substrate surface with said solution.
At first, chemical structural formula being provided is CH
3(CH
2)
15Si (OCH
3)
3HDTMS.
Then, the inventor discovers that HDTMS is soluble in ethanol, therefore in HDTMS, adds ethanol, thereby can obtain comprising the solution of HDTMS.
Present embodiment both can place ethanolic solution with HDTMS, also can ethanolic solution be poured among the HDTMS.
Particularly, the mass percent scope of cetyl trimethoxy silane can be 3%～5% in the said solution.
Then, said solution is carried out acidification,, and generate the active group hydroxyl so that HDTMS is hydrolyzed.
Particularly, in said solution, add at least a in acetate, hydrochloric acid or the nitric acid, be positioned between 4.5 ~ 5.5 until the pH value that makes solution, as: the pH value of solution is 4.5,5.0 or 5.5.
Then, the solution after the acidification is carried out stir process, so that the HDTMS hydrolysis is abundant and even.
Particularly, the solution after the acidification is put into agitating device, this solution is carried out the stirring more than 60 minutes.
Then, treat that the preparation of above-mentioned solution is accomplished after, just can it be formed on said substrate surface, with as low surface energy coat.
Particularly, can said solution be formed on said substrate surface through in infiltration, spin coating or the spray pattern any.
When adopting pattern of invasion that said solution is formed on said substrate surface, said substrate is placed in the said solution, more abundant in order to guarantee reaction, can be 30 minutes ~ 60 minutes standing time, as: 30 minutes, 40 minutes, 50 minutes or 60 minutes.This operation can directly be carried out at normal temperatures, need not other devices, and is simple to operate, and can guarantee that low surface energy coat is very even in the distribution of substrate surface.
When adopting spin coating or spray pattern that said solution is formed on said substrate surface, required time is shorter, and efficient also can guarantee the uniformity that low surface energy coat distributes at substrate surface simultaneously than higher.
So far, formed low surface energy coat at substrate surface.The thickness of said low surface energy coat is the molecule rank, specifically can be 10nm ~ 500nm, as: 10nm, 50nm, 100nm, 250nm or 500nm.
Then execution in step S5 dries said low surface energy coat, and is cured processing.
Present embodiment at first dries it in room temperature after forming said low surface energy coat.
After said low surface energy coat dried, just can be cured processing.Particularly, the time range of said cured can be 30 minutes ~ 60 minutes, as: 30 minutes, 40 minutes, 50 minutes or 60 minutes; Temperature range can be 100 ℃ ~ 150 ℃, as: 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ or 150 ℃.
Through said cured, can increase the set of low surface energy coat at substrate surface, prevent coming off of low surface energy coat.
Need to prove that in other embodiments of the invention, in order to simplify step, can form under the prerequisite of low surface energy coat at substrate surface guaranteeing, the pairing step of said clean, roughened or cured all can be omitted.
The technology of present embodiment is fairly simple; Make the surface of substrate be hydrophobicity through forming HDTMS at substrate surface; Owing to adopt HDTMS as low surface energy coat; Even thereby long-time the use, said low surface energy coat can not corrode substrate yet, finally can guarantee the normal use of hydrophobic substrate; Again because the price comparison of HDTMS is cheap, thereby reduced production cost.
Correspondingly, with reference to shown in Figure 4, this embodiment also provides a kind of hydrophobic substrate, comprising:
Substrate 100;
Be positioned at said substrate 100 lip-deep low surface energy coats 200, the material of said low surface energy coat 200 comprises methoxy silane.
Wherein, the material of said substrate 100 can be glass, plastics or metal.
Wherein, the thickness range of said low surface energy coat 200 can be 10nm ~ 500nm, as: 10nm, 50nm, 100nm, 250nm or 500nm.
Particularly, the material of said low surface energy coat 200 can be the cetyl trimethoxy silane.
Said hydrophobic substrate specifically can adopt preceding method to make, and repeats no more at this.
Adopt HDTMS as low surface energy coat in the hydrophobic substrate that present embodiment is made, thereby even long-time the use, said low surface energy coat can not corrode substrate yet, finally can guarantee the normal use of hydrophobic substrate.In addition, the price comparison of said low surface energy coat is cheap, thereby has reduced production cost, is beneficial to hydrophobic substrate and applies on a large scale.
Though the present invention discloses as above with preferred embodiment, the present invention is defined in this.Any those skilled in the art are not breaking away from the spirit and scope of the present invention, all can do various changes and modification, so protection scope of the present invention should be as the criterion with claim institute restricted portion.
Claims (19)
1. a hydrophobic substrate is characterized in that, comprising: substrate and be positioned at the low surface energy coat on the said substrate surface, the material of said low surface energy coat comprises methoxy silane.
2. hydrophobic substrate as claimed in claim 1 is characterized in that, the material of said substrate is glass, plastics or metal.
3. hydrophobic substrate as claimed in claim 1 is characterized in that, the thickness range of said low surface energy coat is 10nm ~ 500nm.
4. hydrophobic substrate as claimed in claim 1 is characterized in that, the material of said low surface energy coat is the cetyl trimethoxy silane.
5. the preparation method of a hydrophobic substrate is characterized in that, comprising:
Substrate is provided;
In said substrate, form low surface energy coat, the material of said low surface energy coat comprises methoxy silane.
6. the preparation method of hydrophobic substrate as claimed in claim 5 is characterized in that, before forming said low surface energy coat, also comprises: clean is carried out in said substrate.
7. the preparation method of hydrophobic substrate as claimed in claim 6 is characterized in that, clean is carried out in said substrate comprise: adopt the mixed solution of acetone, isopropyl acetone and deionized water that ultrasonic waves for cleaning is carried out in said substrate.
8. the preparation method of hydrophobic substrate as claimed in claim 6 is characterized in that, before forming said low surface energy coat, also comprises: roughened is carried out in the substrate to after cleaning.
9. the preparation method of hydrophobic substrate as claimed in claim 8 is characterized in that, said roughened adopts hydrofluoric acid or salpeter solution to realize.
10. the preparation method of hydrophobic substrate as claimed in claim 9 is characterized in that, the weight percentage ranges of said hydrofluoric acid or nitric acid is 5wt% ~ 20wt%; The time range of roughened is 30 minutes ~ 120 minutes; The temperature range of roughened is 20 ℃ ~ 80 ℃.
11. the preparation method of hydrophobic substrate as claimed in claim 8 is characterized in that, after the said roughened and before forming said low surface energy coat, also comprises: adopt the said substrate of washed with de-ionized water.
12. the preparation method of hydrophobic substrate as claimed in claim 5 is characterized in that, the step that in said substrate, forms low surface energy coat comprises:
The cetyl trimethoxy silane is provided;
In the cetyl trimethoxy silane, add ethanol and form solution;
Said solution is carried out acidification;
Solution after the acidification is carried out stir process;
Mode through infiltration, spin coating or sprinkling is formed on said substrate surface with said solution.
13. the preparation method of hydrophobic substrate as claimed in claim 12 is characterized in that, said solution is carried out acidification comprise: in said solution, add at least a in acetate, hydrochloric acid or the nitric acid, make the pH value of said solution be positioned at 4.5 ~ 5.5 scopes.
14. the preparation method of hydrophobic substrate as claimed in claim 12 is characterized in that, the time of said stir process was more than or equal to 60 minutes.
15. the preparation method of hydrophobic substrate as claimed in claim 12 is characterized in that, when adopting pattern of invasion that said solution is formed on said substrate surface, said substrate is placed in the said solution, be 30 minutes ~ 60 minutes standing time.
16. the preparation method of hydrophobic substrate as claimed in claim 12 is characterized in that, the mass percent of cetyl trimethoxy silane is 3%～5% in the said solution.
17. the preparation method of hydrophobic substrate as claimed in claim 5 is characterized in that, after forming said low surface energy coat, also comprises: said low surface energy coat is dried, and be cured processing.
18. the preparation method of hydrophobic substrate as claimed in claim 17 is characterized in that, the time range of said cured is 30 minutes ~ 60 minutes, and temperature range is 100 ℃ ~ 150 ℃.
19. the preparation method of hydrophobic substrate as claimed in claim 5 is characterized in that, saidly provides substrate to comprise substrate of glass, plastic-substrates or metallic substrates are provided.
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| 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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| CN201210225678.0A CN102774085B (en) | 2012-06-29 | 2012-06-29 | Hydrophobic substrate and preparation method thereof |
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| CN103951277A (en) * | 2014-05-04 | 2014-07-30 | 江南大学 | Super-lyophobic anti-reflection glass surface layer and preparation method thereof |
| CN104021879A (en) * | 2013-09-18 | 2014-09-03 | 天津工业大学 | Preparation method for strong-adhesion-force carbon nanotube flexible transparent conductive thin film and adhesion force detection method |
| CN108675646A (en) * | 2018-07-23 | 2018-10-19 | 北方夜视技术股份有限公司 | Micropore optical element and preparation method thereof with large roughness channel inner surface |
| 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 |
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Cited By (7)
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| CN104021879A (en) * | 2013-09-18 | 2014-09-03 | 天津工业大学 | Preparation method for strong-adhesion-force carbon nanotube flexible transparent conductive thin film and adhesion force detection method |
| CN104021879B (en) * | 2013-09-18 | 2017-02-01 | 天津工业大学 | Preparation method for carbon nanotube flexible transparent conductive thin film |
| CN103951277A (en) * | 2014-05-04 | 2014-07-30 | 江南大学 | Super-lyophobic anti-reflection glass surface layer and preparation method thereof |
| 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 |
| CN108675646A (en) * | 2018-07-23 | 2018-10-19 | 北方夜视技术股份有限公司 | Micropore optical element and preparation method thereof with large roughness channel inner surface |
| 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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