A method for rapidly constructing a patterned lubricating coating

Abstract

The present invention discloses a preparation method for rapidly constructing a patterned lubricating coating, which comprises the following steps: S1: subjecting the cleaned and dried substrate material to surface activation treatment; S2: placing the substrate material after hydroxyl activation treatment into a dryer, performing vacuum treatment, introducing a flexible molecular chain liquid, and carrying out hydroxyl capping or chlorine capping; S3: heating in the vacuum dryer to rapidly volatilize the flexible molecular chain liquid, depositing a layer of flexible polymer molecular chains on the surface of the activated substrate to form a stable lubricating layer; S4: laminating the lubricated surface with a patterned template and irradiating under ultraviolet light to obtain the corresponding patterned lubricating coating. The process of the present invention is extremely simple and easy to master, and the required production conditions are easily achievable. The lubricating surface constructed by chemical bond action can improve the performance stability and mechanical properties of the coating, and can effectively solve the problems of easy oil leakage and poor mechanical stability of the patterned lubricating coating constructed by perfusion of lubricating fluid.

Description

Technical Field

[0001] The present invention belongs to the technical field of lubricating coating preparation, and particularly relates to a preparation method for rapidly constructing different patterned lubricating coatings. Background Art

[0002] Lubricating coatings with unique wettability and low contact hysteresis performance have important applications in fields such as biosensors, food, aerospace, etc. Especially in the field of biosensors, the patterned characteristics of lubricating coatings can provide more possibilities for the development of biosensors with complex functions and modular functions based on lubricating coatings. The introduced patterned lubricating coatings can be used to develop visual biosensors, which can improve the detection efficiency and certain accuracy of the sensors, reduce the test cost to a certain extent, and also reduce the input of human resources to a certain extent.

[0003] Among the existing patterned lubricating coatings, the required patterns are mainly etched by laser to obtain a patterned template. Then, through complex processes such as spin coating, baking, exposure of the patterned template, baking, development, and finally hard baking, a surface with simple patterning can be obtained, and then lubricating oil is poured onto the surface to obtain a lubricating coating with a certain pattern. The lubricating surface constructed by this technology can achieve patterning to a certain extent, but the technological process is too complex and the control of the exposure time is very strict, which is not very operable for large-scale manufacturing. At the same time, there are also certain difficulties in modifying functional biomolecules (such as nucleic acids, proteins, DNA, etc., target substances) on the surface of the lubricating coating in the later stage. The lubricating fluid in the lubricating surface cannot be stably adsorbed in the patterned microstructures, and is easy to evaporate or flow away, resulting in the failure of the lubricating performance, thus limiting the practical application of biosensors.

[0004] Through the above analysis, the problems and defects existing in the prior art are as follows:

[0005] (1) The technological process for preparing patterns is too complex, and the lubricating fluid is easy to evaporate and flow away in the patterned structure, resulting in the failure of the lubricating performance, thus affecting the stability of the lubricating coating;

[0006] (2) It is relatively difficult to modify target substances of biomolecular information with biological recognition (such as nucleic acids, proteins, DNA, etc.) on the patterned surface filled with lubricating fluid, which poses a certain difficulty to the development of biosensors with a patterned lubricating surface. Summary of the Invention

[0007] Aiming at the problems existing in the prior art, the present invention provides a preparation method for rapidly constructing a patterned lubricating coating.

[0008] To solve the technical problems of the present invention, the present invention adopts the following technical solutions:

[0009] A method for rapidly constructing a patterned lubricating coating comprises the following steps:

[0010] S1: performing surface activation treatment on the cleaned and dried substrate material, wherein the substrate material will have more hydroxyl groups after the activation treatment;

[0011] S2: placing the substrate material after hydroxyl activation treatment into a dryer, performing vacuum treatment, introducing a flexible molecular chain liquid, and performing hydroxyl end-capping or chlorine end-capping;

[0012] S3: by heating the vacuum dryer to make the flexible molecular chain liquid evaporate quickly, a layer of flexible polymer molecular chains is deposited on the surface of the activated substrate to form a stable lubricating layer;

[0013] S4: Laying the lubricating surface and the patterned template together and irradiating them under ultraviolet light, so that the wettability of some parts changes, and obtaining a corresponding patterned lubricating coating.

[0014] Technical principle of the present invention: The present invention is to activate the surface of the base material to make the surface rich in active hydroxyl (-OH) groups, and then use the vapor deposition method to graft flexible polymer chains on the surface, so that chemical covalent bonds can be formed between the two, thereby forming a stable lubricating coating on the surface. The grafting density of the polymer molecular chain is controlled by controlling the surface hydroxylation time and regulating the time and temperature of the vapor deposition of polydimethylsiloxane. After the rapid preparation of the surface lubricating coating is completed, a photochemical modification liquid is dripped between the lubricating coating and the patterned pattern template under the irradiation of ultraviolet light, and a lubricating surface with a corresponding pattern can be quickly obtained. Compared with the existing patterned lubricating coatings, the invention shows good lubrication performance and patterning controllability, greatly reduces the patterning process flow, and can effectively improve the utilization rate of the patterned lubricating coating.

[0015] Furthermore, in step S1, the surface of the substrate material is activated by plasma.

[0016] Furthermore, the substrate material is subjected to surface activation treatment for 2 minutes.

[0017] Furthermore, the flexible molecular chain liquid in step S2 is a polydimethylsiloxane solution.

[0018] Furthermore, the amount of the polydimethylsiloxane solution is 50 μL.

[0019] Furthermore, in step S3, the temperature of heating the dryer to make the polydimethylsiloxane solution volatilize quickly is 25-60° C., and the reaction time is 30-60 min.

[0020] Further, in step S4, when the lubricating surface is attached to the patterned template, a photoinitiator solution is added.

[0021] Further, preparation of the photoinitiator solution: Ammonium persulfate is dissolved in deionized water to prepare a 30 wt% photoinitiator solution.

[0022] Further, the dosage of the photoinitiator solution is 100 μL.

[0023] Further, the irradiation time under ultraviolet light in step S4 is 10 - 30 min, and the intensity of the ultraviolet light is 100 W / m 2 .

[0024] The technical effects or advantages of the technical solution to be protected by the present invention:

[0025] (1) The present invention is based on the chemical vapor deposition method to rapidly prepare a lubricating coating. This method can prepare a uniform polymer-based lubricating surface on the surface of the substrate material, has relatively low process requirements, short time, and can achieve large-scale production. On the basis of completing the preparation of the lubricating surface, according to our actual needs, a patterned template is prepared. By introducing a photoinitiator, under ultraviolet light irradiation, the covalent bond formed between the polymer molecules and the hydroxyl groups on the surface of the substrate material can be rapidly broken to obtain a patterned lubricating surface with different wettabilities.

[0026] (2) The lubricating surface constructed by chemical bond action in the present invention can improve the performance stability and mechanical properties of the coating, and can effectively solve the problems of easy oil leakage and poor mechanical stability of the patterned lubricating coating constructed by perfusion of lubricating fluid. The process of the present invention is extremely simple and easy to master, the required production conditions are easy to achieve, and the production costs of polydimethylsiloxane and ultraviolet light irradiation equipment are low, having good economic benefits and being able to achieve large-scale application.

[0027] (3) The expected benefits and commercial value after the transformation of the technical solution of the present invention are:

[0028] Biosensors have good application prospects in medicine and food detection. In most disease detections, biosensors play an important role, which is conducive to early detection and treatment in clinical medicine and can give timely signal feedback on the disease changes of patients. By developing biosensors based on patterned lubricating surfaces, visual results can be obtained for the signals emitted by diseases. This not only facilitates the analysis of the condition but also enables patients to have a more intuitive understanding of their life and health status. The lubricating coating has a certain anti-fouling effect, which can effectively ensure the specific binding of bioinformation molecules and improve the accuracy of biosensors. From the perspective of hospital clinical tests, due to the complexity of test objects and test substances, the test probes of biosensors will be contaminated, resulting in false positive test results. In order to reduce the occurrence of these situations, hospitals generally need to conduct multiple tests to ensure the reliability of the results. We reduce the occurrence of false positives by testing (taking 15 times as a group of results) and replacing the test probes multiple times (taking 15 times as a group of results), which is a serious waste of human and material resources in hospitals. Moreover, multiple tests require the cooperation of patients multiple times, which increases the medical costs of patients. Therefore, if the biosensors developed based on patterned lubricating coatings can be applied in clinical medicine, generally an effective visual detection result can be obtained at one time, which can save at least 90% of the patient's test costs, and the readability of the visual results can reduce the input of human and material resources of hospital testers by at least 70%. In addition, biosensors can effectively detect the residues of microbial toxins, additives, pesticides, veterinary drugs, hormones, etc. in food, which is quite practical. Biosensors based on patterned lubricating surfaces should also have great economic value in food testing. Description of the Drawings

[0029] Figure 1 is a flowchart of a preparation method for rapidly constructing a patterned lubricating coating provided by an embodiment of the present invention;

[0030] Figure 2 is a static contact angle diagram of surface activation of silicon wafers and glass slides and construction of a lubricating surface with polydimethylsiloxane provided by an embodiment of the present invention;

[0031] Figure 3 is a dynamic sliding angle diagram of surface activation of silicon wafers and glass slides and construction of a lubricating surface with polydimethylsiloxane provided by an embodiment of the present invention;

[0032] Figure 4 is a patterned template diagram for the preparation of a patterned lubricating coating provided by an embodiment of the present invention;

[0033] Figure 5 is an array diagram showing different wettabilities of a patterned lubricating surface applied to the surface of a silicon wafer provided by Embodiment 1 of the present invention;

[0034] Figure 6 It is an array diagram showing different wettabilities on the surface of a glass sheet by applying the patterned lubricating surface provided in the second embodiment of the present invention. Detailed implementation manners

[0035] In order to make the objectives, technical solutions and advantages of the present invention clearer and more understandable, the present invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0036] I. Explanation of the embodiment. This part is an explanatory embodiment that expands on the technical solution of the claims to enable those skilled in the art to fully understand how the present invention is specifically implemented.

[0037] As Figure 1 shown, the embodiment of the present invention provides a preparation method for quickly constructing a patterned lubricating coating, including the following steps:

[0038] S1: Surface activation treatment (mainly plasma treatment) is performed on the substrate material after cleaning and drying to make the surface have more hydroxyl groups;

[0039] S2: The substrate material after hydroxyl activation treatment is placed in a dryer for vacuum treatment, and a flexible molecular chain liquid is introduced. The flexible molecular chain liquid is polydimethylsiloxane (molecular weight MW: 3000), with hydroxyl end-capping or chlorine end-capping;

[0040] S3: The polydimethylsiloxane solution is rapidly volatilized by heating in the vacuum dryer, and a layer of flexible polymer molecular chains is deposited on the surface of the activated substrate to form a stable lubricating layer;

[0041] S4: The lubricating surface and the patterned template are attached and irradiated under ultraviolet light, so that the wettability at some positions is changed to obtain the corresponding patterned lubricating coating.

[0042] The substrate material is easy to be activated and will carry more hydroxyl groups afterwards.

[0043] The activation time of the substrate material is 2 min.

[0044] The temperature range for heating the polydimethylsiloxane solution to rapidly volatilize in the dryer is 25 - 60 °C, and the reaction time is 30 - 60 min.

[0045] A photoinitiator is added between the lubricating surface and the patterned template, and the ultraviolet light irradiation time is 10 - 30 min.

[0046] II. Application Examples. To prove the creativity and technical value of the technical solution of the present invention, this part provides application examples of the technical solution of the claims on specific products or related technologies.

[0047] Apply the patterned lubricating coating of the present invention to the developed biosensor. For example, when this type of biosensor is applied to clinical medical tests, it can effectively ensure the accuracy of test results and the visualization of test results, which can effectively reduce the human and material resources of hospital tests and the economic costs of patients' medical treatment. The anti-fouling performance of this lubricating surface can improve the service life of the biosensor, extend the usage time, and save certain medical expenses, which has an important impact on the majority of patients.

[0048] Apply the patterned lubricating coating of the present invention to the test interface of the biosensor for detecting food. It can improve the detection limit of the sensor test. Because through the patterned lubricating surface constructed by the present invention, the test liquid is basically micro-liquid, which is of great significance for the detection of trace microbial toxins, additives, pesticide and veterinary drug residues, and hormones in food.

[0049] Biosensors can effectively detect food, which is quite practical. Biosensors based on patterned lubricating surfaces should also have great economic value in food testing.

[0050] III. Evidence of the Related Effects of the Embodiments. Some positive effects have been achieved during the research and development or use of the embodiments of the present invention, and it indeed has great advantages compared with the prior art. The following content will be described in combination with the data, charts, etc. of the test process.

[0051] Example 1:

[0052] Preparation of the Lubricating Layer

[0053] (1) For the substrate material, taking a silicon wafer as an example, perform surface activation treatment. Usually, put it into a coating instrument for plasma treatment for 2 minutes.

[0054] (2) Prepare a vacuum dryer, clean it, dry it with a hot air blower, and keep it dry.

[0055] (3) Put 50 μL of polydimethylsiloxane flexible polymer chains into a sample bottle and transfer the surface-activated silicon wafer into the vacuum dryer. After sealing the dryer with sealant, use a vacuum pump to evacuate it to a vacuum state.

[0056] (4) Place the above-mentioned glass vacuum dryer in an oven, set the temperature to 60 °C, and after reacting for 30 minutes, a lubricating coating with a silicon wafer as the substrate is obtained.

[0057] Preparation of the Pattern

[0058] (1) Preparation of the photoinitiator solution: Take an appropriate amount of ammonium persulfate (APS) and dissolve it in deionized water to prepare a 30 wt% photoinitiator solution;

[0059] (2) Use a pipette to drop 100 μL of the photoinitiator solution onto the surface of a clean silicon wafer;

[0060] (3) Attach the silicon wafer to the surface of the patterned template, ensuring a tight fit with no gaps between them;

[0061] (4) Place the sample in step (3) under an ultraviolet light intensity of 100 W / m 2 , and irradiate for 10 min;

[0062] (5) Ultrasonically clean with deionized water and absolute ethanol for 10 min, and dry with nitrogen to obtain a patterned lubricating surface with the silicon wafer as the substrate.

[0063] Example 2:

[0064] Preparation of the lubricating layer

[0065] (1) For the substrate material, represented by a glass slide, perform surface activation treatment. Usually, place it in a coating instrument for plasma treatment for 2 min;

[0066] (2) Prepare a vacuum desiccator, clean it, dry it with a hot air blower, and keep it dry;

[0067] (3) Put 50 μL of polydimethylsiloxane flexible polymer chains in a sample bottle and transfer the surface-activated silicon wafer into the vacuum desiccator. After sealing the desiccator with sealant, use a vacuum pump to evacuate it to a vacuum state;

[0068] (4) Place the above glass vacuum desiccator in an oven, set the temperature to 60 °C, and after reacting for 30 min, a lubricating coating with the glass slide as the substrate is obtained.

[0069] Preparation of the pattern

[0070] (1) Preparation of the photoinitiator solution: Take an appropriate amount of APS and dissolve it in deionized water to prepare a 30 wt% photoinitiator solution;

[0071] (2) Use a pipette to drop 100 μL of the photoinitiator solution onto the surface of a clean silicon wafer;

[0072] (3) Attach the glass slide to the surface of the patterned template, ensuring a tight fit with no gaps between them;

[0073] (4) Place the sample in step (3) under an ultraviolet light intensity of 100 W / m 2 , and irradiate for 10 min;

[0074] (5) The glass slides were ultrasonically cleaned with deionized water and absolute ethanol for 10 min and then dried with nitrogen to obtain a patterned lubricating surface on the glass slides as the substrate.

[0075] Figure 2 It is a representative of using silicon wafers and glass slides as the main substrate materials for biosensors. The static contact angle data of the lubricating surface with polydimethylsiloxane vapor deposited on this surface. Through Figure 2 It can be seen that lubricating coatings can be successfully modified on the substrate surfaces of glass slides and metallic silicon (Si) wafers. After modifying the surface with flexible polymer molecular chains, it has good hydrophobic properties and the static contact angles have all increased.

[0076] Figure 3 These are the data of the sliding angles of the lubricating surfaces of silicon wafers and glass slides that have been hydroxyl-activated and grafted with flexible polymer molecular chains. The sliding angles of 10 μL water droplets on the lubricating surfaces constructed on the two substrate materials are both lower than 5 degrees, showing good lubricating properties. The lubricating coatings of this invention show good lubricating effects when modified on biosensors with silicon wafers and glass slides as the representative substrate materials.

[0077] Figure 4 It is a patterned template using laser etching. The pore positions of the patterned template can be irradiated with ultraviolet light to change the wettability of the substrate material surface. The patterning of the template can be customized and the pore size can be adjusted according to the actual detection requirements to better realize the visualization effect of the test results of biosensors.

[0078] Figure 5 In Example 1, after a lubricating coating was modified on the silicon wafer surface, a lubricating surface with different wettabilities was quickly formed under the irradiation of ultraviolet light using the patterned template. Due to the different wettabilities of the surface, the displayed patterns are also different (as shown in Figure 5 A, Figure 5 B, Figure 5 C, Figure 5 D). By grafting specific bioinformation molecules such as nucleic acids, proteins, DNA and other target substances at sites with different wettabilities, it can make the detection results based on this patterned surface show visualization. At the same time, the lubricity of the surface has a certain anti-fouling effect and a very low contact angle hysteresis phenomenon, which can reduce the influence of impurities to a certain extent during the test process, improve the specific binding of biomolecules, and thus improve the accuracy and speed of the test.

[0079] Figure 6After the surface of the glass sheet in Example 2 is modified with a lubricating coating, a patterned lubricating surface with different wettabilities is rapidly formed under the irradiation of ultraviolet light using a patterning template. The different wettabilities of the surface can be seen using an optical microscope, and the distribution of micro-droplets on the lubricating surface is also different. Different patterning templates can be customized according to actual usage requirements. Different templates result in different surface wettabilities and different displayed patterns.

[0080] The above are only specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention, any modifications, equivalent substitutions, and improvements made within the spirit and principle of the present invention shall be covered by the protection scope of the present invention.

Claims

1. A preparation method for rapidly constructing a patterned lubricating coating, characterized in that, The following steps are involved: S1: Activate the surface of the cleaned and dried substrate material; S2: placing the substrate material after hydroxyl activation treatment into a dryer, performing vacuum treatment, introducing a flexible molecular chain liquid, wherein the flexible molecular chain liquid is a polydimethylsiloxane solution, and performing hydroxyl end-capping or chlorine end-capping on the flexible molecular chain liquid; S3: by heating the vacuum dryer to make the flexible molecular chain liquid evaporate quickly, a layer of flexible polymer molecular chains is deposited on the surface of the activated substrate to form a stable lubricating layer; S4: Laminating the lubricating surface and the patterned template and irradiating them under ultraviolet light, so that the wettability of some parts changes, and obtaining a corresponding patterned lubricating coating; In step S3, the temperature of heating the dryer to rapidly volatilize the polydimethylsiloxane solution is 25-60° C., and the reaction time is 30-60 min; In step S4, the lubricated surface is bonded to the patterned template by adding a photochemical initiator solution; Preparation of photochemical initiator solution: dissolve ammonium persulfate in deionized water to prepare a 30 wt% photochemical initiator solution; The irradiation time under ultraviolet light in step S4 is 10 - 30 min, and the intensity of the ultraviolet light is 100 W / m 2 .

2. The preparation method of the fast construction of a patterned lubricating coating according to claim 1, characterized in that, In step S1, the surface of the substrate material is activated by plasma.

3. The preparation method of the quickly constructed patterned lubricating coating according to claim 1, characterized in that, The time for the surface activation treatment of the substrate material is 2 min.

4. The preparation method of the patterned lubricating coating constructed quickly as described in claim 1, characterized in that, The amount of the polydimethylsiloxane solution used is 50 μL.

5. The preparation method of the rapidly constructed patterned lubricating coating according to claim 1, wherein The amount of the photochemical initiator solution used is 100 μL.

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