CN1827237A - Hydrophobic structure of substrate surface and its preparation method - Google Patents

Abstract

A hydrophobic structure of substrate surface and its preparation method, mainly coat organic-inorganic mixing material on the surface of the substrate, form the rough layer of nanometer on the surface of the substrate through the high-temperature sintering, and coat the low surface energy material, form the hydrophobic coating on the surface of the rough layer of nanometer; therefore, the hydrophobic structure has the advantages of excellent hydrophobicity, abrasion resistance, high transparency, high hardness, uniform particles and the like, the preparation method can simplify the working procedure, save the cost, effectively process and the like, and further improves the overall competitiveness of the industry.

Description

Hydrophobic structure of substrate surface and its preparation method

technical field

The present invention relates to a hydrophobic structure and its preparation method, in particular to a hydrophobic structure formed on the surface of a base material and its preparation method.

Background technique

In recent years, due to people's requirements for thinning and miniaturization of daily necessities, most industries have entered the era of nanotechnology. In addition to the household appliances around the life, the function and application of self-cleaning (self-cleaning) products have also greatly increased the market demand for general civilian products to reduce maintenance costs and improve product quality, making self-cleaning coatings The development of materials has attracted much attention in the market. The use of self-cleaning coating materials, such as coatings for building glass curtains, kitchen bathrooms, etc., can reduce maintenance costs; self-cleaning hydrophobic coatings applied to solar cells, satellite antenna surfaces, and car front glass can improve product quality and efficiency; applied to ships and aircraft shells can reduce fuel consumption and exhaust pollution caused by resistance. In the research of self-cleaning coating materials, the lotus effect (Lotus Effect) of forming an air cushion by confining air molecules on the rough surface, coupled with the surface characteristics of low surface energy materials, can make the water droplet contact angle of coating materials greater than 100°, Thus reducing the adhesion of water droplets and oil droplets.

In the structural design of self-cleaning coating materials in the prior art, multi-layer composite structures are mostly used to achieve the function of hydrophobic self-cleaning. The multilayer structure has different characteristics such as adhesion, rough surface structure, and ultra-low surface energy. However, most of the superhydrophobic structures currently face the problems of poor adhesion, insufficient hardness, poor transparency, and insufficient durability.

For example, US Pat. Nos. 5,413,865, 5,674,625, and 6,623,863 disclose the use of a sol-gel (sol-gel) method to prepare an inorganic solution, which is coated to form a rough surface. In the above method, except for the cumbersome process of preparing two or more solutions for sol-gel, the remaining processes, such as the formation and drying of the gel, need to be laboriously controlled to prevent phase separation. And the hydrophobic angle of its products is insufficient. The sol-gel coating liquid system is essentially a loose structure. In the process of solvent removal for thicker films, if the control is not proper, the film is easily broken due to surface tension imbalance, or the precipitated metal oxides are aggregated (gelation ), it is impossible to obtain nanoscale structured films.

U.S. Patent No. 5,250,322 and No. 6,623,863 disclose the use of sol-gel method and the mixing of silicone compound and fluorosilicon compound to form a hydrophobic surface, but this method has the problem of poor adhesion. US Patent No. 5,296,282 increases the roughness by adding filaments. However, this manufacturing method will cause discontinuity of the rough structure, which will result in insufficient hydrophobicity.

US Patent No. 5,693,236 discloses that the outer layer of the needle-like structure material is coated with a layer of hydrophobic substance, mixed with an adhesive, and then coated on the substrate to achieve a superhydrophobic effect. However, its manufacturing cost is relatively high, because the needle-like structure material is relatively expensive, and the particle size of the needle-like structure is relatively large, which easily leads to an opaque or low-transparency surface.

US Patent No. 6,306,506 discloses the use of argon (Ar) plasma to roughen the surface. This process is relatively complicated and difficult to control, and the required cost is expensive.

To sum up, the technical bottleneck of the existing hydrophobic nano-rough surface manufacturing lies in: since the interface of each layer in the multilayer structure is mostly combined with materials of different properties (polymers, inorganic oxides, low surface energy molecules), it is impossible to fabricate Rough surfaces with different characteristics such as adhesion, rough surface structure, ultra-low surface energy, etc., especially molecules with low surface energy characteristics usually have relatively poor adhesion; in addition, the fluorine currently used on self-cleaning surfaces is resin or hydrophobic With the combination of siloxane coupling agent or polymer without rough structure, the hydrophobic performance of a single material can only reach a water drop contact angle of about 90°, and cannot reach the hydrophobic characteristics of a water drop contact angle above 100°; generally, the sol-gel method is used The micron-scale rough surface produced cannot have sufficient hardness without high-temperature sintering, so it is prone to brittle cracks under long-term use; moreover, since the wavelength of visible light is about 400nm, micron-scale powder or sol- The rough surface made by gel technology is easy to cause visible light to be unable to penetrate or scatter, so how to make nano-scale continuous phase rough surface structure without affecting the light transmittance is a major technical challenge; low surface energy materials In addition to low surface energy, it also has disadvantages such as chemical inactivity and difficulty in bonding, so that the existing technology cannot achieve excellent light transmittance, good bonding characteristics or long-term product durability.

Due to the above problems in the prior art, in order to meet the market demand for self-cleaning coating materials, it is hoped to develop a hydrophobic structure with excellent hydrophobicity, high hardness, high transparency and wear resistance and its preparation method to solve the above problems. The various shortcomings of the prior art are actually problems to be solved urgently at present.

Contents of the invention

In order to overcome the disadvantages of the above-mentioned prior art, the main purpose of the present invention is to provide a hydrophobic [A1] structure on the surface of the substrate and its preparation method, which provides high hardness characteristics of the hydrophobic structure.

The second object of the present invention is to provide a hydrophobic structure on the surface of the substrate and its preparation method, so as to provide high transparency of the hydrophobic structure.

Another object of the present invention is to provide a hydrophobic structure on the surface of a substrate and a method for preparing the same, so as to provide the wear resistance of the hydrophobic structure.

Another object of the present invention is to provide a hydrophobic structure on the surface of a substrate and a method for preparing the same, so as to provide excellent hydrophobicity of the hydrophobic structure.

In order to achieve the above and other purposes, the present invention provides a hydrophobic structure on the surface of a substrate, the structure comprising: a nano-rough layer formed on the surface of the substrate, which is formed by sintering mixed nano-inorganic and organic substances at high temperature; and A hydrophobic coating is formed on the surface of the nano-rough layer.

The aforementioned nano-inorganic substance is a metal oxide. Preferably, the metal oxide is one selected from silicon oxides such as silicon dioxide, titanium oxides such as titanium dioxide, and zirconium oxides such as zirconium dioxide.

The inter-particles of the nano-inorganic substance have a continuous phase structure and are bonded by chemical bonds of organic substances such as silicon-oxygen bonds. The interface between the nano-rough layer and the surface of the substrate is bonded by chemical bonds of organic matter such as silicon-oxygen bonds. The interface between the nano-rough layer and the hydrophobic coating is bonded by organic chemical bonds such as silicon-oxygen bonds.

The average roughness of the nano-rough layer is between 1nm and 100nm. The thickness of the nano-rough layer is between 1nm and 150nm, preferably between 1nm and 100nm. The particle size of the nano-inorganic substance is between 10nm and 100nm, preferably between 10nm and 50nm.

The hydrophobic coating is made of low surface energy materials. It is preferably one of the polymers containing fluorine and silicon, such as alkyl group-containing chlorosilanes, fluoroalkyl group-containing trichlorosilanes, fluoroalkyl fluoroalkyl group-containing trialkoxysilanes, fluoroalkyl group-containing triacyloxysilanes, fluoroalkyl group-containing triisocyanatesilanes, alkane One of alkyl group-containing alkoxysilanes, alkyl group-containing acyloxysilanes and alkyl group-containing isocyanatesilanes.

The present invention also provides a method for preparing a hydrophobic structure on the surface of a substrate, the method comprising: providing a substrate, an organic-inorganic hybrid material and a low surface energy material; coating the organic-inorganic hybrid material on the surface of the substrate, and sintering at a high temperature to form a nano-rough layer on the surface of the substrate; and coating a low surface energy material to form a hydrophobic coating on the surface of the nano-rough layer.

The above-mentioned organic-inorganic hybrid material is a mixture of nano-inorganic substances and organic polymers. Preferably, the nano-inorganic substance can be one of metal oxide and inorganic compound. The metal oxide may be selected from one of silicon oxides such as silicon dioxide, titanium oxides such as titanium dioxide, and zirconium oxides such as zirconium dioxide. The inorganic compound is selected from one of trimethylethoxysilane (TMOS), tetraethoxysilane (TEOS) and triethoxytitanium (TEOTi). The particle size of the nano-inorganic substance is between 10nm and 100nm, preferably between 10nm and 50nm.

The organic polymer is a polymer compound with alkenyl groups, and its molecular weight ranges from 500 to 100,000, preferably from 5,000 to 75,000, and most preferably from 10,000 to 55,000. The polymer compound is selected from one of polyvinylpyr[A2]rolidone and polyvinyl alcohol. The organic-inorganic hybrid material contains 1 to 50% by weight of organic polymer. The wet film thickness of the organic-inorganic hybrid material coated on the surface of the substrate is between 100 nm and 1000 nm, preferably between 100 nm and 500 nm.

The nano-inorganic substance controls its oxide particle size through acidity and alkalinity, and forms a microphase separation structure with an organic polymer through sol-gel reaction. The pH control can be between pH 3 to 13, preferably between pH 7 to 13.

The high temperature sintering temperature is between 300°C and 800°C. Preferably, it is achieved by baking at a temperature between 300°C and 600°C.

The low surface energy material is one of polymers containing fluorine and silicon. Preferably, the polymer is selected from the group consisting of alkyl group-containing chlorosilanes, fluoroalkyl group-containing trichlorosilanes, fluoroalkyl-containing trialkoxysilanes ( fluoroalkylgroup-containing trialkoxysilanes), fluoroalkyl group-containing triacyloxysilanes, fluoroalkyl group-containing triisocyanatesilanes, alkyl-containing alkoxysilanes ( One of alkyl group-containing alkoxysilanes), alkyl group-containing acyloxysilanes and alkyl group-containing isocyanate silanes.

The substrate is selected from one of glass substrates, ceramic substrates or metal substrates. A room temperature curing step of about 20 hours may also be included before the high temperature sintering.

In the hydrophobic structure prepared by the method of the present invention, the interface of the inorganic compound is bonded by a chemical bond, and the chemical bond is a silicon-oxygen bond. The nano-inorganic matter is a continuous phase structure, therefore, the hydrophobic structure of the present invention has the advantages of excellent hydrophobicity, wear resistance, high transparency, high hardness and particle uniformity, and its preparation method can simplify the process and cost economy Advantages such as modernization and efficient processing, and then improve the overall competitiveness of the industry. On the other hand, the hydrophobic structure of the present invention is made by utilizing the composite properties of the nanocomposite material, so the rigidity of the inorganic material can be improved while the toughness of the organic material can also be improved.

Description of drawings

FIG. 1 is an electron micrograph (SEM) of the hydrophobic structure prepared in Example 1.

FIG. 2 is an atomic force microscope image (AFM) of the hydrophobic structure prepared in Example 1.

3 is a scanning electron microscope image (SEM) of the hydrophobic structure prepared in Example 2.

FIG. 4 is a scanning electron microscope image (SEM) of the hydrophobic structure prepared in Example 3.

Detailed ways

The characteristics and functions of the present invention will be further described in detail below by means of specific examples. But the implementation details are only used to illustrate the characteristics of the present invention, rather than to limit the scope of the present invention.

Example

The manufacture method of nano-rough layer and its coating method:

At room temperature, 125 grams of ethanol, 15 grams of tetraethoxysilane (tetraethoxysilane) and 4.15 grams (36 wt %) of ammonium hydroxide were placed in a double-neck round bottom flask in a molar ratio of 38:1:2.37, And it was stirred evenly for 30 minutes to make it a transparent solution. Next, under the condition of 90° C., a reflux reaction was performed for 8 hours. After the reaction was completed, it was placed at room temperature and stirred continuously for 20 hours to obtain an inorganic powder dispersion.

Separately, 10 g of polyvinyl pyrrolidone (polyvinyl pyrrolidone; molecular weight: 55,000) and 190 g of ethanol were stirred at room temperature for 30 minutes to completely dissolve to prepare an organic solution.

Next, according to the volume ratio of 7:3, the inorganic solution and the organic solution were uniformly stirred at room temperature for 60 minutes, so as to generate the organic-inorganic mixed solution required for coating.

Spin coating was performed once on a glass test piece by using a spin coater at a rotation speed of 1100 rpm, a spin time of 15 sec, and suction of 1.5 ml of the organic-inorganic mixed solution each time. Next, the test piece was left at room temperature for 20 hours to perform room temperature curing.

Next, place the cured glass specimen in a high-temperature oven, and heat it from 25°C to 100°C, and maintain it at 100°C for 1 hour; then heat it from 100°C to 600°C, and then cool it naturally to room temperature to form Glass sheet with nanorough layer. The above-mentioned heating step is achieved by increasing the temperature by 1.5° C. per minute.

Manufacturing method of hydrophobic coating and coating method of low surface energy material:

At room temperature, 23.7 grams of isopropylalcohol, 1 gram of n-heptadecafluorodecyltrimethoxysilane (heptadecafluorodecyltrimethoxysilane), 0.3 grams of pure water and 75 mg of nitric acid (0.1N), and stir it uniformly for 2 hours to carry out the hydrolysis reaction.

After the reaction was completed, 5 grams of 4A molecular sieves were added for dehydration and condensation polymerization, and left at room temperature for 18 hours. After the reaction is completed, filter the molecular sieve with filter paper to form a fluoroalkane silicon compound solution (FAS solution).

Using a spin coater with a rotation speed of 1100rpm and a spin time of 15sec, draw 1.5ml of FAS solution each time and drop it on a glass sheet with a nano-rough layer. Spin coating is carried out on the glass test piece at an interval of 5 minutes between each coating. 3 times.

Place the coated glass sheet in an oven and bake at 140° C. for 1 hour. The taken-out test piece is the base material with hydrophobic structure. The scanning electron microscope image (SEM) of the formed hydrophobic structure including the nano-rough layer and the hydrophobic coating is shown in FIG. 1 , and the atomic force microscope image (AFM) is shown in FIG. 2 . It can be seen from FIG. 1 and FIG. 2 that according to the method of the present invention, it is confirmed that a nano-scale hydrophobic structure can be formed on the substrate, and the nano-rough layer of the hydrophobic structure is a continuous phase.

Example 2

Repeat the steps of Example 1, replacing polyvinylpyrrolidone (polyvinyl pyrrolidone) with a molecular weight of 10,000, and the rest of the steps are the same as in Example 1. The SEM results are shown in Figure 3.

Example 3

At room temperature, 50 grams of ethanol, 5 grams of tetraethoxysilane (tetraethoxysilane) and 3.027 grams (36 wt %) of concentrated hydrochloric acid were successively placed in a double-neck round bottom bottle, and stirred evenly with a magnet for 19 hours, An inorganic solution is prepared.

Separately, 10 g of polyvinyl pyrrolidone (polyvinyl pyrrolidone; molecular weight: 55,000) and 190 g of ethanol were stirred at room temperature for 30 minutes to completely dissolve to prepare an organic solution.

Next, the inorganic solution and the organic solution were uniformly stirred at room temperature for 60 minutes according to a volume ratio of 7:3, so as to generate an organic-inorganic mixed solution required for coating.

Spin coating was performed once on a glass test piece by using a spin coater at a rotation speed of 1100 rpm, a spin time of 15 sec, and suction of 1.5 ml of the organic-inorganic mixed solution each time. Next, the test piece was left at room temperature for 20 hours to perform room temperature curing.

Next, place the cured glass specimen in a high-temperature oven, and heat it from 25°C to 100°C, and keep it at 100°C for 1 hour; then heat it from 100°C to 600°C, and then cool it naturally to room temperature A glass sheet with a nanorough layer is formed. The above-mentioned heating step is achieved by increasing the temperature by 1.5° C. per minute.

Manufacturing method of low surface energy material and its coating method:

At room temperature, 23.7 grams of isopropylalcohol, 1 gram of n-heptadecafluorodecyltrimethoxysilane (heptadecafluorodecyltrimethoxysilane), 0.3 grams of pure water and 75 mg of nitric acid (0.1N), and stir it uniformly for 2 hours to carry out the hydrolysis reaction.

After the reaction was completed, 5 grams of 4A molecular sieves were added for dehydration, condensation polymerization, and left at room temperature for 18 hours. After the reaction is completed, filter the molecular sieve with filter paper to form a fluoroalkane silicon compound solution (FAS solution).

Using a spin coater with a rotation speed of 1100rpm and a spin time of 15sec, draw 1.5ml of FAS solution each time and drop it on a glass sheet with a nano-rough layer. Spin coating is carried out on the glass test piece at an interval of 5 minutes between each coating. 3 times.

Place the coated glass sheet in an oven and bake at 140° C. for 1 hour. The taken-out test piece is the base material with hydrophobic structure. The SEM results are shown in Figure 4.

Characteristic Analysis of Hydrophobic Structure:

The test pieces of Examples 1, 2, and 3 were tested for contact angle, transparency, and pencil hardness by the following methods, and the test results are shown in Table 1.

Contact Angle Test - ASTM C 813-90

Keep the substrate level (the test piece needs to be flat, not twisted, and free of dirt). Drop a water droplet (deionized water or pure water, 2 μL) from the microneedle (as close to the surface as possible). When the water droplet touches the surface, the tip of the needle is still inside the water droplet (the center above the water droplet), and slowly move away from the needle. Barrel (the syringe cannot be retracted and moved violently, otherwise it will cause changes in the volume/position of water droplets). Measure the contact angles on the left and right sides of the water droplet, twice each, for a total of four data. On the surface of the same substrate, find four different positions, repeat the above steps, and measure, a total of 20 data, and calculate the average value.

Transparency Test - ASTM D 1747-97

The size of the test piece is 50mm*100mm, and the visible light transmittance (%) of the test piece is measured with a colorimeter with an integrating sphere. At a temperature of 45±5°C, place the test piece in the device, keep the test piece (A) and Blank (B) at a distance of 230mm from the light source, and use the CNS 10986 UV irradiation device to irradiate for 1000 hours. Then measure the visible light transmittance (%). The difference (absolute value) of the visible light transmittance (%) before and after the test was calculated.

Pencil hardness test ASTM 3363-92a

Place the test piece for more than 16 hours at an ambient temperature of 23±2°C and a relative humidity of 50±5%. Sharpen the pencil with a pencil sharpener to a pointy, smooth, oval shape. Then use sandpaper to grind the pencil head in the vertical direction to make it flat, undamaged, round, and non-cracked (5-6mm). Start with the hardest pencil for testing. Make the pencil and the substrate at 45 degrees, push forward (away from your own direction) with your hands (or fixed on the electric auxiliary pusher), and then push back (toward your own direction) with downward force, and the applied force It needs to be fixed, the length should be at least 6.5mm, and the speed should be 0.5 to 1mm/s. Test until the pencil cannot draw through the coating and touch the substrate (distance > 3mm, use a magnifying glass to assist; if the pencil head is damaged during the process, it needs to be tested again). The hardness of the hardest pencil that cannot trace the coating is the hardness of the coating. Repeat the test at least once until the result is the same.

Table 1 Test Methods water contact angle oil contact angle transparency hardness Example 1 135 88 93 9H Example 2 105 -- 91 9H Example 3 102 -- 92 9H

As can be seen from Table 1, the hydrophobic structure of the surface of the substrate produced by the inventive method has good hydrophobicity (water contact angle greater than 90°), and its transparency and hardness are also stronger than other existing products. excellent.

Claims (50)

1. the hydrophobic structure of a substrate surface is characterized in that, this structure comprises:

The nanometer rough layer is formed on this substrate surface, is to be formed through high temperature sintering by the nano-inorganic substance and the organic matter that mix; And

Hydrophobic coating is formed on this nanometer rough layer surface.

2. hydrophobic structure as claimed in claim 1 is characterized in that this nano-inorganic substance is a metal oxide.

3. hydrophobic structure as claimed in claim 2 is characterized in that, this metal oxide be selected from silicon oxide, titanium oxide and Zirconium oxide one of them.

4. hydrophobic structure as claimed in claim 3 is characterized in that, this silicon oxide is a silicon.

5. hydrophobic structure as claimed in claim 3 is characterized in that this titanium oxide is a titanium dioxide.

6. hydrophobic structure as claimed in claim 3 is characterized in that this Zirconium oxide is a zirconium dioxide.

7. hydrophobic structure as claimed in claim 1 is characterized in that, is the continuous phase structure between the particle of this nano-inorganic substance, and by the chemical bond bond of inorganic matter.

8. hydrophobic structure as claimed in claim 1 is characterized in that, the interface of this nanometer rough layer and this substrate surface is the chemical bond bond by inorganic matter.

9. hydrophobic structure as claimed in claim 1 is characterized in that, the interface of this nanometer rough layer and this hydrophobic coating is by organic chemical bond bond.

10. as claim 7,8 or 9 described hydrophobic structures, it is characterized in that this chemical bond is a silicon oxygen key.

11. hydrophobic structure as claimed in claim 1 is characterized in that, the mean roughness of this nanometer rough layer is between between the 1nm to 100nm.

12. hydrophobic structure as claimed in claim 1 is characterized in that, the thickness of this nanometer rough layer is between between the 1nm to 150nm.

13. hydrophobic structure as claimed in claim 12 is characterized in that, this thickness is between between the 1nm to 100nm.

14. hydrophobic structure as claimed in claim 1 is characterized in that, the particle diameter of this nano-inorganic substance is between between the 10nm to 100nm.

15. hydrophobic structure as claimed in claim 14 is characterized in that, this particle diameter is between between the 10nm to 50nm.

16. hydrophobic structure as claimed in claim 1 is characterized in that, this hydrophobic coating is made of low-surface-energy material.

17. hydrophobic structure as claimed in claim 16 is characterized in that, this low-surface-energy material be selected from fluorine-containing or silicon macromolecule one of them.

18. hydrophobic structure as claimed in claim 17, it is characterized in that, this macromolecule be selected from chlorine silicon hydride compounds, the trichlorine silicon hydride compounds that contains fluoroalkyl, the three alcoxyl silicon hydride compounds that contain fluoroalkyl, the trigalloyl siloxanes compound that contains fluoroalkyl, the triisocyanate silicon hydride compounds that contains fluoroalkyl, the alcoxyl silicon hydride compounds that contains alkyl that contain alkyl, contain the acyl-oxygen silicon hydride compounds of alkyl or contain alkyl isocyanates silicon hydride compounds one of them.

19. hydrophobic structure as claimed in claim 1 is characterized in that, this base material be selected from glass baseplate, ceramic base material or metal base one of them.

20. the hydrophobic structure method for making of a substrate surface is characterized in that, this method for making comprises:

Base material, organic and inorganic blending material and low-surface-energy material are provided;

Be coated with organic and inorganic blending material at this substrate surface, and form a nanometer rough layer at this substrate surface through high temperature sintering; And

The coating low-surface-energy material forms hydrophobic coating on this nanometer rough layer surface.

21. method for making as claimed in claim 20 is characterized in that, this organic and inorganic blending material is to mix nano-inorganic substance and organic polymer.

22. method for making as claimed in claim 21 is characterized in that, this nano-inorganic substance be metal oxide and inorganic compound one of them.

23. method for making as claimed in claim 22 is characterized in that, this metal oxide be selected from silicon oxide, titanium oxide or Zirconium oxide one of them.

24. method for making as claimed in claim 23 is characterized in that, this silicon oxide is a silicon.

25. method for making as claimed in claim 23 is characterized in that, this titanium oxide is a titanium dioxide.

26. method for making as claimed in claim 23 is characterized in that, this Zirconium oxide is a zirconium dioxide.

27. method for making as claimed in claim 22 is characterized in that, this inorganic compound be selected from trimethyl ethyoxyl silicon alkane, tetraethoxy silicon alkane or triethoxy titanium one of them.

28. method for making as claimed in claim 21 is characterized in that, the particle diameter of this nano-inorganic substance is between between the 10nm to 100nm.

29. method for making as claimed in claim 28 is characterized in that, this particle diameter is between between the 10nm to 50nm.

30. method for making as claimed in claim 21 is characterized in that, this organic polymer is the macromolecular compound with thiazolinyl, and its molecular weight ranges is 500 to 100000.

31. method for making as claimed in claim 30 is characterized in that, this molecular weight ranges is 5000 to 75000.

32. method for making as claimed in claim 31 is characterized in that, this molecular weight ranges is 10000 to 55000.

33. method for making as claimed in claim 30 is characterized in that, this macromolecular compound be selected from polyvinylpyrrolidone or polyvinyl alcohol one of them.

34. method for making as claimed in claim 21 is characterized in that, this organic and inorganic blending material contains the organic polymer of 1 to 50 weight %.

35. method for making as claimed in claim 21 is characterized in that, this organic and inorganic blending material is coated the wet-film thickness of substrate surface between between the 100nm to 1000nm.

36. method for making as claimed in claim 35 is characterized in that, this thickness is between between the 100nm to 500nm.

37. method for making as claimed in claim 21 is characterized in that, this nano-inorganic substance is to control its oxide diameter sizes via acid-base value, forms micro phase separation structure through producing solgel reaction with organic polymer.

38. method for making as claimed in claim 37 is characterized in that, this acid-base value control is between pH 3 to 13.

39. method for making as claimed in claim 38 is characterized in that, this acid-base value control is between pH 7 to 13.

40. method for making as claimed in claim 38 is characterized in that, the temperature of this high temperature sintering is between 300 ℃ to 800 ℃.

41. method for making as claimed in claim 38 is characterized in that, this temperature is between 300 ℃ to 600 ℃.

42. method for making as claimed in claim 20 is characterized in that, the mean roughness of this nanometer rough layer is between between the 1nm to 100nm.

43. method for making as claimed in claim 20 is characterized in that, the thickness of this nanometer rough layer is between between the 1nm to 150nm.

44. method for making as claimed in claim 43 is characterized in that, this thickness is between between the 1nm to 100nm.

45. method for making as claimed in claim 20 is characterized in that, this low-surface-energy material be selected from fluorine-containing or silicon macromolecule one of them.

46. method for making as claimed in claim 45, it is characterized in that, this macromolecule be selected from chlorine silicon hydride compounds, the trichlorine silicon hydride compounds that contains fluoroalkyl, the three alcoxyl silicon hydride compounds that contain fluoroalkyl, the trigalloyl siloxanes compound that contains fluoroalkyl, the triisocyanate silicon hydride compounds that contains fluoroalkyl, the alcoxyl silicon hydride compounds that contains alkyl that contain alkyl, contain the acyl-oxygen silicon hydride compounds of alkyl or contain alkyl isocyanates silicon hydride compounds one of them.

47. method for making as claimed in claim 20 is characterized in that, this base material be selected from glass baseplate, ceramic base material or metal base one of them.

48. method for making as claimed in claim 43 is characterized in that, before high temperature sintering, also comprises the step of carrying out room temperature curing.

49. method for making as claimed in claim 48 is characterized in that, this room temperature curing is to carry out 20 hours.

50. method for making as claimed in claim 48 is characterized in that, the step of this high temperature sintering is to reach with the baking of the temperature between 300 ℃ to 600 ℃.

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