Low-rolling-angle coating and preparation method thereof

Abstract

The specific embodiment of the invention provides a low-rolling-angle coating and a preparation method thereof, and the preparation method of the low-rolling-angle coating comprises the following steps: by taking a (methyl) acrylate compound as a monomer, controlling the power density to be 20-120w / m < 3 > in a PECVD (plasma enhanced chemical vapor deposition) mode, and preparing the low-rolling-angle coating. And the plasma polymerization coating with an excellent liquid-like surface with a low rolling angle can be prepared.

Description

Technical Field

[0001] The present invention belongs to the field of coating protection, and particularly relates to a low rolling angle coating and a preparation method thereof. Background Art

[0002] Lotus leaves have a rough micro / nano structure on the surface and low surface energy plant wax, and water droplets are easy to roll off on its surface. Inspired by lotus leaves, people have prepared superhydrophobic surfaces with a water contact angle greater than 150° through rough structures and low surface energy substances, and this surface also has a low rolling angle. However, this design depends on the stability of the air cavities in the surface texture under the liquid droplet, thus generating the so-called Cassie-Baxter state. But if pressure is applied to the liquid droplet on the surface, the liquid can be forced into the surface texture, transitioning to the Wenzel state, thereby losing the superhydrophobic and low rolling angle properties. Another issue worthy of attention is the durability of this surface, because these micro / nano structures are usually very fragile and are prone to wear during use. Inspired by Nepenthes, the inner surface of Nepenthes has a thin lubricating layer / nectar layer, so it has excellent slipperiness. In 2011, the Aizenberg group first coined the term "SLIPS". A stable smooth liquid surface is obtained by filling the pores of a substrate with micro / nano pores with a lubricating liquid. Such surfaces have a very low rolling angle and liquid droplets are easy to roll off. Although this surface has excellent liquid rolling performance, the limitation of SLIPS lies in the lubricant on its surface, which may evaporate over time and be lost under shear stress during use. Superhydrophobic and SLIPS have the disadvantage of being easily worn out, so they are restricted in industrial applications. Summary of the Invention

[0003] The specific embodiment of the present invention provides a method for preparing a low rolling angle coating by (meth)acrylate compounds through PECVD (plasma enhanced chemical vapor deposition) and a low rolling angle coating with a "liquid-like" surface prepared therefrom. The specific scheme is as follows:

[0004] A method for preparing a low rolling angle coating, comprising the following steps:

[0005] Provide a substrate and place the substrate in a vacuum deposition chamber;

[0006] Introduce the vapor of the structural monomer shown in formula (1) into the reaction chamber, and turn on the plasma discharge to form a plasma polymerization coating on the surface of the substrate. The average power density of the plasma discharge is 20 - 120 w / m 3 ,

[0007]

[0008] In formula (1), R1, R2, and R3 are each independently selected from a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R4 is an alkyl group having 1 to C 20 carbon atoms.

[0009] Optionally, the average power density of the plasma discharge is 25 to 100 w / m 3 .

[0010] Optionally, R1, R2, and R3 are each independently selected from a hydrogen atom or a methyl group.

[0011] Optionally, R1 and R2 are hydrogen atoms, and R3 is a methyl group.

[0012] Optionally, the structural monomer represented by formula (1) is selected from at least one of methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, propyl methacrylate, propyl acrylate, n-butyl methacrylate, n-butyl acrylate, isobutyl methacrylate, isobutyl acrylate, isopentyl methacrylate, isopentyl acrylate, n-octyl methacrylate, n-octyl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, nonyl methacrylate, nonyl acrylate, n-octyl methacrylate, n-octyl acrylate, isooctyl methacrylate, isooctyl acrylate, decyl methacrylate, decyl acrylate, dodecyl methacrylate, dodecyl acrylate, hexadecyl methacrylate, hexadecyl acrylate, octadecyl methacrylate, and octadecyl acrylate.

[0013] Optionally, R4 is a straight-chain alkyl group having 8 to C 12 carbon atoms.

[0014] Optionally, the average power of the plasma discharge is 1 to 400 W.

[0015] Optionally, the average power of the plasma discharge is 15 to 60 W.

[0016] Optionally, the plasma discharge is a pulsed plasma discharge.

[0017] A low rolling angle coating, which is obtained by the preparation method described above.

[0018] A device, at least a part of the surface of which has the coating described above.

[0019] A low rolling angle coating, which is a plasma polymerization coating formed by plasma deposition of a structural monomer represented by the following formula (1):

[0020]

[0021] In formula (1), R1, R2, and R3 are each independently selected from a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R4 is a linear alkyl group having 8 to C 12 ; wherein, the rolling angle of the coating is below 20°.

[0022] Optionally, R1, R2, and R3 are each independently selected from a hydrogen atom or a methyl group.

[0023] Optionally, R1 and R2 are hydrogen atoms, and R3 is a methyl group.

[0024] A device, at least a part of the surface of which has the coating described above.

[0025] The preparation method of the low-rolling-angle coating in the specific embodiment of the present invention uses (meth)acrylate compounds as monomers and, in the form of PECVD (plasma-enhanced chemical vapor deposition), by controlling the power density between 20 and 120 w / m 3 A plasma polymerization coating with an excellent low-rolling-angle "liquid-like" surface can be prepared. Description of the Drawings

[0026] Figure 1 According to the relationship between the rolling angle of the coatings in Examples 1, 4, 5, 6, 8, and 10 and the number of side-chain carbon atoms of the (meth)acrylate monomers;

[0027] Figure 2 According to the relationship between the rolling angle of the coatings in Examples 1-3 and Examples 12-15 and the average power density. Specific Embodiments

[0028] The specific embodiment of the present invention provides a preparation method of a low-rolling-angle coating, including the following steps:

[0029] Provide a substrate and place the substrate in a vacuum deposition chamber;

[0030] Introduce the vapor of the structural monomer shown in formula (1) into the reaction chamber, and turn on the plasma discharge to form a plasma polymerization coating on the surface of the substrate. The average power density of the plasma discharge is 20 to 120 w / m 3 ,

[0031]

[0032] In formula (1), R1, R2, and R3 are each independently selected from a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R4 is an alkyl group having 1 to C 20 alkyl group.

[0033] The inventors of the present invention have found through research that for the monomer plasma coating with the structure shown in formula (1), at a relatively low plasma density, the crosslinking density is low, showing a "liquid-like" surface with a low rolling angle. However, when the average power is too low, the plasma density is too low, and the monomer material cannot effectively form a film on the substrate surface, damaging the integrity of the coating, so the rolling angle will instead increase. In the preparation method of the low-rolling-angle coating in the specific embodiments of the present invention, by controlling the average power density of plasma discharge to be 20-120 w / m 3 the plasma polymerization coating prepared from the monomer with the structure shown in formula (1) has more excellent low-rolling-angle performance. In some specific embodiments, the average power density of the plasma discharge is 25-100 w / m 3 specifically, for example, 25 w / m 3 30 w / m 3 35 w / m 3 40 w / m 3 45 w / m 3 50 w / m 3 55 w / m 3 60 w / m 3 65 w / m 3 70 w / m 3 75 w / m 3 80 w / m 3 85 w / m 3 90 w / m 3 95 w / m 3 or 100 w / m 3 etc.

[0034] In the preparation method of the low-rolling-angle coating in the specific embodiments of the present invention, the average power density of the plasma discharge is the plasma discharge power * duty cycle / plasma cavity volume, and for continuous plasma discharge, the duty cycle is 100%.

[0035] In the preparation method of the low-rolling-angle coating in the specific embodiments of the present invention, in some specific embodiments, R1, R2, and R3 are each independently selected from a hydrogen atom or a methyl group. In some specific embodiments, R1 and R2 are hydrogen atoms, and R3 is a methyl group.

[0036] Preparation method of low rolling angle coating in the specific embodiments of the present invention. In some specific embodiments, the structural monomer shown in formula (1) is selected from at least one of methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, propyl methacrylate, propyl acrylate, n-butyl methacrylate, n-butyl acrylate, isobutyl methacrylate, isobutyl acrylate, isoamyl methacrylate, isoamyl acrylate, n-octyl methacrylate, n-octyl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, nonyl methacrylate, nonyl acrylate, n-octyl methacrylate, n-octyl acrylate, isooctyl methacrylate, isooctyl acrylate, decyl methacrylate, decyl acrylate, dodecyl methacrylate, dodecyl acrylate, hexadecyl methacrylate, hexadecyl acrylate, octadecyl methacrylate, octadecyl acrylate.

[0037] Preparation method of low rolling angle coating in the specific embodiments of the present invention. Considering that when the carbon chain of R4 is short, the flexibility of the overall molecular chain is poor, and when the carbon chain of R4 is long, such as octadecyl chain, etc., crystallization behavior is likely to occur, reducing the flexibility of the molecular chain. In some specific embodiments, R4 is a straight-chain alkyl group of C8-C 12 , that is, R4 is n-octyl, n-nonyl, n-decyl, undecyl or dodecyl. The coating prepared in this way better exhibits a "liquid-like" surface and has more excellent low rolling angle, and its rolling angle can reach below 20°.

[0038] Preparation method of low rolling angle coating in the specific embodiments of the present invention. In some specific embodiments, the average power of the plasma discharge is 1-400 W. In some specific embodiments, the average power of the plasma discharge is 15-60 W. Specifically, for example, it can be 15 W, 20 W, 25 W, 30 W, 35 W, 40 W, 45 W, 50 W, 55 W or 60 W, etc.

[0039] The preparation method of the low rolling angle coating in the specific embodiments of the present invention. In some specific embodiments, the plasma is continuous plasma. In some specific embodiments, the plasma is pulsed plasma. In some specific embodiments, the pulse frequency of the pulsed plasma is 10 Hz - 500 kHz, specifically, for example, it can be 10 Hz, 20 Hz, 25 Hz, 30 Hz, 35 Hz, 40 Hz, 45 Hz, 50 Hz, 55 Hz, 60 Hz, 70 Hz, 80 Hz, 90 Hz, 100 Hz, 200 Hz, 300 Hz, 400 Hz or 500 Hz, etc. In some specific embodiments, the pulse duty cycle of the pulsed plasma is 0.1% - 90%, specifically, for example, it can be 0.1%, 0.5%, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85% or 90%, etc. The plasma discharge time of the pulsed plasma is 200 s - 36000 s, specifically, for example, it can be 200 s, 500 s, 1000 s, 2000 s, 3000 s, 4000 s, 5000 s, 6000 s, 7000 s, 8000 s, 9000 s, 10000 s, 15000 s, 20000 s, 25000 s, 30000 s, 36000 s, etc.

[0040] The preparation method of the low rolling angle coating in the specific embodiments of the present invention. In some specific embodiments, the monomer flow rate is 10 - 2000 μl / min, specifically, for example, it can be 10 μl / min, 50 μl / min, 100 μl / min, 200 μl / min, 300 μl / min, 400 μl / min, 500 μl / min, 600 μl / min, 700 μl / min, 800 μl / min, 900 μl / min, 1000 μl / min, 1100 μl / min or 1200 μl / min, etc.

[0041] The preparation method of the low rolling angle coating in the specific embodiments of the present invention. In some specific embodiments, the temperature in the plasma reaction chamber is controlled at 20°C - 80°C, specifically, for example, it can be 20°C, 30°C, 40°C, 50°C, 60°C, 70°C or 80°C, etc.

[0042] The preparation method of the low rolling angle coating in the specific embodiments of the present invention. In some specific embodiments, the monomer vaporization temperature is 50°C - 120°C, specifically, for example, it can be 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C or 120°C, etc., and the vaporization occurs under vacuum conditions.

[0043] The preparation method of the low rolling angle coating in the specific embodiments of the present invention. To further enhance the bonding force between the plasma coating and the substrate, in some specific embodiments, the substrate is a substrate pretreated by pulsed plasma or continuous plasma. Specific conditions are, for example, in an inert gas atmosphere, with a plasma discharge power of 100 - 500 W and a continuous discharge time of 60 - 2400 s. In some other specific embodiments, the substrate is a substrate pretreated by methods such as heat, oxygen, or high-energy radiation.

[0044] The preparation method of the low rolling angle coating in the specific embodiments of the present invention. In some specific embodiments, the plasma discharge method can be various existing discharge methods. Specifically, for example, electrodeless discharge (such as radio frequency inductively coupled discharge, microwave discharge), single electrode discharge (such as plasma jets formed by corona discharge, monopole discharge), double electrode discharge (such as dielectric barrier discharge, bare electrode radio frequency glow discharge), and multi-electrode discharge (such as discharge using a floating electrode as the third electrode).

[0045] The preparation method of the low rolling angle coating in the specific embodiments of the present invention. In some specific embodiments, the substrate is a metal, specifically, for example, iron, magnesium, aluminum, copper, or their alloys. In some other specific embodiments, the substrate is various plastics, fabrics, glass, electrical components, or optical instruments, etc. Specifically, the electrical components can be printed circuit boards (PCBs), electronic products, or semi-finished electronic assemblies, etc. When the substrate is an electronic product, examples include but are not limited to mobile phones, tablet computers, keyboards, e-readers, wearable devices, displays, etc. The substrate can also be any suitable electrical component of an electrical assembly. Specifically, the electrical component can be a resistor, capacitor, transistor, diode, amplifier, relay, transformer, battery, fuse, integrated circuit, switch, LED, LED display, piezoelectric element, optoelectronic component, or antenna, or oscillator, etc.

[0046] The specific embodiments of the present invention also provide a low rolling angle coating, which is obtained by the preparation method described above.

[0047] The specific embodiments of the present invention also provide a low rolling angle coating, which is a plasma polymerization coating formed by plasma deposition of monomers having the structure shown in the following formula (1):

[0048]

[0049] In formula (1), R1, R2, and R3 are each independently selected from a hydrogen atom or an alkyl group of C1 - C4, and R4 is C8 - C 12a linear alkyl group; wherein, the rolling angle of the coating is below 20°, and the rolling angle is measured by the following method: adjust the 0-degree scale line of the protractor to the horizontal, align the coated substrate (glass slide) with the 0-degree scale line, with one end of the substrate (glass slide) coinciding with the center point of the protractor, use a micropipette to drop about 20 μL of water at a position 5 mm away from the other end of the glass slide, fix the end of the glass slide that coincides with the center point of the protractor and keep it still, slowly lift the other end of the glass slide, measure the angle required for the liquid droplet to just start rolling (i.e., the rolling angle), measure 3 times at different positions, and take the average value.

[0050] In some specific embodiments, R1, R2, and R3 are each independently selected from a hydrogen atom or a methyl group. In some specific embodiments, R1 and R2 are hydrogen atoms, and R3 is a methyl group. In some specific embodiments, the low-rolling-angle coating can be prepared by the aforementioned preparation method.

[0051] Specific embodiments of the present invention further provide a device, at least a part of the surface of which has the above-mentioned low-rolling-angle coating. In some specific embodiments, the above-mentioned low-rolling-angle coating is deposited on a part or all of the surface of the device.

[0052] The present invention will be further described below through specific examples.

[0053] Examples

[0054] Description of the test method

[0055] Coating thickness test: Detect by coating on a silicon wafer and using a Filmetrics F20-UV thin film thickness meter from the United States.

[0056] Water contact angle test: Conduct the test according to the standard of GB / T 30447-2013.

[0057] Rolling angle test: Adjust the 0-degree scale line of the protractor to the horizontal, align the coated substrate (glass slide) with the 0-degree scale line, with one end of the substrate (glass slide) coinciding with the center point of the protractor, use a micropipette to drop about 20 μL of water at a position 5 mm away from the other end of the glass slide, fix the end of the glass slide that coincides with the center point of the protractor and keep it still, slowly lift the other end of the glass slide, measure the angle required for the liquid droplet to just start rolling (i.e., the rolling angle), measure 3 times at different positions, and take the average value.

[0058] Example 1

[0059] Place the Si wafer and the glass slide on the substrate placement bracket in a plasma chamber with a cavity volume of 0.6 m 3 Vacuum the chamber to 80 mTorr, introduce helium gas with a flow rate of 100 sccm, and the chamber temperature is 50 °C;

[0060] Keep the chamber pressure at 80 mTorr, keep the helium flow rate at 100 sccm, turn on continuous plasma discharge with a discharge power of 200 W, and discharge continuously for 600 s to pre-treat the substrate.

[0061] Then, dodecyl methacrylate monomer is introduced into the evaporator at a flow rate of 120 μL / min, vaporized at a vaporization temperature of 100 °C, and then introduced into the plasma chamber. Keep the chamber pressure at 80 mTorr, keep the helium flow rate at 100 sccm, turn on radio frequency plasma discharge, and the energy output mode of the radio frequency is pulsed. Plasma chemical vapor deposition is carried out on the substrate surface, where the pulse duty cycle is 50%, the pulse frequency is 50 Hz, the pulse discharge power is 30 W, and the reaction time is 1800 s.

[0062] After the coating is completed, fill the chamber with compressed air to restore normal pressure, take out the coated substrate, measure the film thickness on the Si wafer, and the water contact angle and rolling angle on the glass slide are listed in Table 1 below.

[0063] Example 2

[0064] Place the Si wafer and the glass slide on the substrate placement bracket in the plasma chamber with a volume of 0.6 m 3 Vacuum the chamber to 80 mTorr, introduce helium with a flow rate of 100 sccm, and the chamber temperature is 50 °C.

[0065] Keep the chamber pressure at 80 mTorr, keep the helium flow rate at 100 sccm, turn on continuous plasma discharge with a discharge power of 200 W, and discharge continuously for 600 s to pre-treat the substrate.

[0066] Then, dodecyl methacrylate monomer is introduced into the evaporator at a flow rate of 120 μL / min, vaporized at a vaporization temperature of 100 °C, and then introduced into the plasma chamber. Keep the chamber pressure at 80 mTorr, keep the helium flow rate at 100 sccm, turn on radio frequency plasma discharge, and the energy output mode of the radio frequency is pulsed. Plasma chemical vapor deposition is carried out on the substrate surface, where the pulse duty cycle is 20%, the pulse frequency is 50 Hz, the pulse discharge power is 200 W, and the reaction time is 1800 s.

[0067] After the coating is completed, fill the chamber with compressed air to restore normal pressure, take out the coated substrate, measure the film thickness on the Si wafer, and the water contact angle and rolling angle on the glass slide are listed in Table 1 below.

[0068] Example 3

[0069] Place the Si wafer and the glass slide on the substrate placement bracket in the plasma chamber with a volume of 0.6 m 3On the substrate placement bracket of the plasma chamber, evacuate the chamber to 80 mTorr, introduce helium gas with a flow rate of 100 sccm, and the chamber temperature is 50 °C;

[0070] Maintain the chamber pressure at 80 mTorr, maintain the helium gas flow rate at 100 sccm, turn on continuous plasma discharge with a discharge power of 200 W, and continuously discharge for 600 s to pre-treat the substrate;

[0071] Then, dodecyl methacrylate monomer is introduced into the evaporator at a flow rate of 120 μL / min, vaporized at a vaporization temperature of 100 °C and then introduced into the plasma chamber. Maintain the chamber pressure at 80 mTorr, maintain the helium gas flow rate at 100 sccm, turn on radio frequency plasma discharge, and the energy output mode of the radio frequency is pulse. Perform plasma chemical vapor deposition on the substrate surface, where the pulse duty cycle is 60%, the pulse frequency is 50 Hz, the pulse discharge power is 100 W, and the reaction time is 1800 s;

[0072] After the coating is completed, fill the chamber with compressed air to restore normal pressure, take out the coated substrate, measure the film thickness on the Si wafer, and the water contact angle and rolling angle on the glass slide are listed in Table 1 below.

[0073] Example 4

[0074] Place the Si wafer and the glass slide on the substrate placement bracket of the plasma chamber with a chamber volume of 0.6 m 3 On the substrate placement bracket of the plasma chamber, evacuate the chamber to 80 mTorr, introduce helium gas with a flow rate of 100 sccm, and the chamber temperature is 50 °C;

[0075] Maintain the chamber pressure at 80 mTorr, maintain the helium gas flow rate at 100 sccm, turn on continuous plasma discharge with a discharge power of 200 W, and continuously discharge for 600 s to pre-treat the substrate;

[0076] Then, decyl methacrylate monomer is introduced into the evaporator at a flow rate of 120 μL / min, vaporized at a vaporization temperature of 100 °C and then introduced into the plasma chamber. Maintain the chamber pressure at 80 mTorr, maintain the helium gas flow rate at 100 sccm, turn on radio frequency plasma discharge, and the energy output mode of the radio frequency is pulse. Perform plasma chemical vapor deposition on the substrate surface, where the pulse duty cycle is 50%, the pulse frequency is 50 Hz, the pulse discharge power is 30 W, and the reaction time is 1800 s;

[0077] After the coating is completed, fill the chamber with compressed air to restore normal pressure, take out the coated substrate, measure the film thickness on the Si wafer, and the water contact angle and rolling angle on the glass slide are listed in Table 1 below.

[0078] Example 5

[0079] Place the Si wafer and the glass slide on the substrate placement bracket in a plasma chamber with a chamber volume of 0.6 m 3 Vacuum the chamber to 80 mTorr, introduce helium gas with a flow rate of 100 sccm, and the chamber temperature is 50 °C;

[0080] Keep the chamber pressure at 80 mTorr, keep the helium gas flow rate at 100 sccm, turn on continuous plasma discharge with a discharge power of 200 W, and continuously discharge for 600 s to pre-treat the substrate;

[0081] Then, the monomer n-octyl methacrylate is introduced into the evaporator at a flow rate of 120 μL / min, vaporized at a vaporization temperature of 100 °C and then introduced into the plasma chamber. Keep the chamber pressure at 80 mTorr, keep the helium gas flow rate at 100 sccm, turn on radio frequency plasma discharge, the energy output mode of the radio frequency is pulsed, and plasma chemical vapor deposition is carried out on the substrate surface, where the pulse duty cycle is 50%, the pulse frequency is 50 Hz, the pulse discharge power is 30 W, and the reaction time is 1800 s;

[0082] After the coating is completed, fill the chamber with compressed air to restore normal pressure, take out the coated substrate, measure the film thickness on the Si wafer, and the water contact angle and rolling angle on the glass slide are listed in Table 1 below.

[0083] Example 6

[0084] Place the Si wafer and the glass slide on the substrate placement bracket in a plasma chamber with a chamber volume of 0.6 m 3 Vacuum the chamber to 80 mTorr, introduce helium gas with a flow rate of 100 sccm, and the chamber temperature is 50 °C;

[0085] Keep the chamber pressure at 80 mTorr, keep the helium gas flow rate at 100 sccm, turn on continuous plasma discharge with a discharge power of 200 W, and continuously discharge for 600 s to pre-treat the substrate;

[0086] Then, the monomer methyl methacrylate is introduced into the evaporator at a flow rate of 120 μL / min, vaporized at a vaporization temperature of 100 °C and then introduced into the plasma chamber. Keep the chamber pressure at 80 mTorr, keep the helium gas flow rate at 100 sccm, turn on radio frequency plasma discharge, the energy output mode of the radio frequency is pulsed, and plasma chemical vapor deposition is carried out on the substrate surface, where the pulse duty cycle is 50%, the pulse frequency is 50 Hz, the pulse discharge power is 30 W, and the reaction time is 1800 s;

[0087] After the coating is completed, fill the chamber with compressed air to restore normal pressure, take out the coated substrate, measure the film thickness on the Si wafer, and the water contact angle and rolling angle on the glass slide are listed in Table 1 below.

[0088] Example 7

[0089] Place the Si wafer and the glass slide on the substrate placement bracket in a plasma chamber with a chamber volume of 0.6 m 3 Vacuum the chamber to 80 mTorr, introduce helium gas with a flow rate of 100 sccm, and the chamber temperature is 50 °C;

[0090] Keep the chamber pressure at 80 mTorr, keep the helium gas flow rate at 100 sccm, turn on the continuous plasma discharge with a discharge power of 200 W, and continuously discharge for 600 s to pre-treat the substrate;

[0091] Then, the monomer methyl methacrylate is introduced into the evaporator at a flow rate of 120 μL / min, vaporized at a vaporization temperature of 100 °C and then introduced into the plasma chamber. Keep the chamber pressure at 80 mTorr, keep the helium gas flow rate at 100 sccm, turn on the radio frequency plasma discharge, the energy output mode of the radio frequency is pulse, and perform plasma chemical vapor deposition on the substrate surface, where the pulse duty cycle is 50%, the pulse frequency is 50 Hz, the pulse discharge power is 100 W, and the reaction time is 1800 s;

[0092] After the coating is completed, fill the chamber with compressed air to restore normal pressure, take out the coated substrate, measure the film thickness on the Si wafer, and list the water contact angle and rolling angle on the glass slide in Table 1 below.

[0093] Example 8

[0094] Place the Si wafer and the glass slide on the substrate placement bracket in a plasma chamber with a chamber volume of 0.6 m 3 Vacuum the chamber to 80 mTorr, introduce helium gas with a flow rate of 100 sccm, and the chamber temperature is 50 °C;

[0095] Keep the chamber pressure at 80 mTorr, keep the helium gas flow rate at 100 sccm, turn on the continuous plasma discharge with a discharge power of 200 W, and continuously discharge for 600 s to pre-treat the substrate;

[0096] Then, the monomer n-butyl methacrylate is introduced into the evaporator at a flow rate of 120 μL / min, vaporized at a vaporization temperature of 100 °C and then introduced into the plasma chamber. Keep the chamber pressure at 80 mTorr, keep the helium gas flow rate at 100 sccm, turn on the radio frequency plasma discharge, the energy output mode of the radio frequency is pulse, and perform plasma chemical vapor deposition on the substrate surface, where the pulse duty cycle is 50%, the pulse frequency is 50 Hz, the pulse discharge power is 30 W, and the reaction time is 1800 s;

[0097] After the coating is completed, compressed air is introduced to restore the normal pressure in the chamber. The coated substrate is taken out, the film thickness on the Si wafer is measured, and the water contact angle and rolling angle on the glass slide are measured and listed in Table 1 below.

[0098] Example 9

[0099] Place the Si wafer and the glass slide on the substrate placement bracket in a plasma chamber with a chamber volume of 0.6 m 3 Vacuum the chamber to 80 mTorr, introduce helium gas with a flow rate of 100 sccm, and the chamber temperature is 50 °C;

[0100] Maintain the chamber pressure at 80 mTorr, maintain the helium gas flow rate at 100 sccm, turn on the continuous plasma discharge with a discharge power of 200 W, and continuously discharge for 600 s to pre-treat the substrate;

[0101] Then, n-butyl methacrylate monomer is introduced into the evaporator at a flow rate of 120 μL / min, vaporized at a vaporization temperature of 100 °C, and then introduced into the plasma chamber. Maintain the chamber pressure at 80 mTorr, maintain the helium gas flow rate at 100 sccm, turn on the radio frequency plasma discharge, and the energy output mode of the radio frequency is pulsed. Plasma chemical vapor deposition is carried out on the substrate surface, where the pulse duty cycle is 50%, the pulse frequency is 50 Hz, the pulse discharge power is 100 W, and the reaction time is 1800 s;

[0102] After the coating is completed, compressed air is introduced to restore the normal pressure in the chamber. The coated substrate is taken out, the film thickness on the Si wafer is measured, and the water contact angle and rolling angle on the glass slide are measured and listed in Table 1 below.

[0103] Example 10

[0104] Place the Si wafer and the glass slide on the substrate placement bracket in a plasma chamber with a chamber volume of 0.6 m 3 Vacuum the chamber to 80 mTorr, introduce helium gas with a flow rate of 100 sccm, and the chamber temperature is 50 °C;

[0105] Maintain the chamber pressure at 80 mTorr, maintain the helium gas flow rate at 100 sccm, turn on the continuous plasma discharge with a discharge power of 200 W, and continuously discharge for 600 s to pre-treat the substrate;

[0106] Then, octadecyl methacrylate monomer was introduced into the evaporator at a flow rate of 120 μL / min, vaporized at a vaporization temperature of 100 °C, and then introduced into the plasma chamber. The chamber pressure was maintained at 80 mTorr, the helium flow rate was maintained at 100 sccm, and radio frequency plasma discharge was initiated. The energy output mode of the radio frequency was pulsed. Plasma chemical vapor deposition was carried out on the substrate surface, with a pulse duty cycle of 50%, a pulse frequency of 50 Hz, a pulsed discharge power of 30 W, and a reaction time of 1800 s;

[0107] After the coating was completed, compressed air was introduced to return the chamber to atmospheric pressure. The coated substrate was taken out, the film thickness on the Si wafer was measured, and the water contact angle and rolling angle on the glass slide were measured and listed in Table 1 below.

[0108] Example 11

[0109] The Si wafer and the glass slide were placed on the substrate placement bracket in the plasma chamber with a chamber volume of 0.6 m 3 The chamber was evacuated to 80 mTorr, helium was introduced at a flow rate of 100 sccm, and the chamber temperature was 50 °C;

[0110] The chamber pressure was maintained at 80 mTorr, the helium flow rate was maintained at 100 sccm, and continuous plasma discharge was initiated with a discharge power of 200 W for 600 s to pre-treat the substrate;

[0111] Then, octadecyl methacrylate monomer was introduced into the evaporator at a flow rate of 120 μL / min, vaporized at a vaporization temperature of 100 °C, and then introduced into the plasma chamber. The chamber pressure was maintained at 80 mTorr, the helium flow rate was maintained at 100 sccm, and radio frequency plasma discharge was initiated. The energy output mode of the radio frequency was pulsed. Plasma chemical vapor deposition was carried out on the substrate surface, with a pulse duty cycle of 50%, a pulse frequency of 50 Hz, a pulsed discharge power of 100 W, and a reaction time of 1800 s;

[0112] After the coating was completed, compressed air was introduced to return the chamber to atmospheric pressure. The coated substrate was taken out, the film thickness on the Si wafer was measured, and the water contact angle and rolling angle on the glass slide were measured and listed in Table 1 below.

[0113] Example 12

[0114] The Si wafer and the glass slide were placed on the substrate placement bracket in the plasma chamber with a chamber volume of 0.6 m 3 The chamber was evacuated to 80 mTorr, helium was introduced at a flow rate of 100 sccm, and the chamber temperature was 50 °C;

[0115] Maintain the chamber pressure at 80 mTorr, maintain the helium flow rate at 100 sccm, turn on continuous plasma discharge with a discharge power of 200 W for 600 s to pre-treat the substrate;

[0116] Then, dodecyl methacrylate monomer is introduced into the evaporator at a flow rate of 120 μL / min, vaporized at a vaporization temperature of 100 °C and then introduced into the plasma chamber. Maintain the chamber pressure at 80 mTorr, maintain the helium flow rate at 100 sccm, turn on radio frequency plasma discharge with the energy output mode of the radio frequency being pulsed, and perform plasma chemical vapor deposition on the substrate surface. Among them, the pulse duty cycle is 10%, the pulse frequency is 50 Hz, the pulse discharge power is 50 W, and the reaction time is 1800 s;

[0117] After the coating is completed, fill the chamber with compressed air to restore normal pressure, take out the coated substrate, measure the film thickness on the Si wafer, and the water contact angle rolling angles measured on the glass slide are listed in Table 1 below.

[0118] Example 13

[0119] Place the Si wafer and the glass slide on the substrate placement bracket in the plasma chamber with a chamber volume of 0.6 m 3 Vacuum the chamber to 80 mTorr, introduce helium with a flow rate of 100 sccm, and the chamber temperature is 50 °C;

[0120] Maintain the chamber pressure at 80 mTorr, maintain the helium flow rate at 100 sccm, turn on continuous plasma discharge with a discharge power of 200 W for 600 s to pre-treat the substrate;

[0121] Then, dodecyl methacrylate monomer is introduced into the evaporator at a flow rate of 120 μL / min, vaporized at a vaporization temperature of 100 °C and then introduced into the plasma chamber. Maintain the chamber pressure at 80 mTorr, maintain the helium flow rate at 100 sccm, turn on radio frequency plasma discharge with the energy output mode of the radio frequency being pulsed, and perform plasma chemical vapor deposition on the substrate surface. Among them, the pulse duty cycle is 80%, the pulse frequency is 50 Hz, the pulse discharge power is 120 W, and the reaction time is 1800 s;

[0122] After the coating is completed, fill the chamber with compressed air to restore normal pressure, take out the coated substrate, measure the film thickness on the Si wafer, and the water contact angle rolling angles measured on the glass slide are listed in Table 1 below.

[0123] Example 14

[0124] Place the Si wafer and the glass slide on the substrate placement bracket in the plasma chamber with a chamber volume of 0.6 m 3On the substrate placement bracket of the plasma chamber, evacuate the chamber to 80 mTorr, introduce helium gas with a flow rate of 100 sccm, and the chamber temperature is 50 °C; the volume of the plasma chamber is 0.6 cubic meters.

[0125] Keep the chamber pressure at 80 mTorr, keep the helium gas flow rate at 100 sccm, turn on continuous plasma discharge with a discharge power of 200 W, and continuously discharge for 600 s to pre-treat the substrate.

[0126] Then, dodecyl methacrylate monomer is introduced into the evaporator at a flow rate of 120 μL / min, vaporized at a vaporization temperature of 100 °C, and then introduced into the plasma chamber. Keep the chamber pressure at 80 mTorr, keep the helium gas flow rate at 100 sccm, turn on radio frequency plasma discharge, the energy output mode of the radio frequency is pulsed, and plasma chemical vapor deposition is carried out on the substrate surface, where the pulse duty cycle is 50%, the pulse frequency is 50 Hz, the pulse discharge power is 250 W, and the reaction time is 1800 s.

[0127] After the coating is completed, fill the chamber with compressed air to restore normal pressure, take out the coated substrate, measure the film thickness on the Si wafer, and the water contact angle and rolling angle on the glass slide are listed in Table 1 below.

[0128] Example 15

[0129] Place the Si wafer and the glass slide on the substrate placement bracket of the plasma chamber with a volume of 0.1 m 3 , evacuate the chamber to 80 mTorr, introduce helium gas with a flow rate of 100 sccm, and the chamber temperature is 50 °C;

[0130] Keep the chamber pressure at 80 mTorr, keep the helium gas flow rate at 100 sccm, turn on continuous plasma discharge with a discharge power of 200 W, and continuously discharge for 600 s to pre-treat the substrate.

[0131] Then, dodecyl methacrylate monomer is introduced into the evaporator at a flow rate of 120 μL / min, vaporized at a vaporization temperature of 100 °C, and then introduced into the plasma chamber. Keep the chamber pressure at 80 mTorr, keep the helium gas flow rate at 100 sccm, turn on radio frequency plasma discharge, the energy output mode of the radio frequency is pulsed, and plasma chemical vapor deposition is carried out on the substrate surface, where the pulse duty cycle is 10%, the pulse frequency is 50 Hz, the pulse discharge power is 50 W, and the reaction time is 1800 s.

[0132] After the coating is completed, fill the chamber with compressed air to restore normal pressure, take out the coated substrate, measure the film thickness on the Si wafer, and the water contact angle and rolling angle on the glass slide are listed in Table 1 below.

[0133] Table 1 Test results of Examples 1-15

[0134]

[0135] According to the results of the above examples, it can be seen that for the plasma coating with methacrylate monomers, the contact angle of the coating can be adjusted by adjusting the number of side-chain carbon atoms (R4 alkyl chain) of the methacrylate monomers and / or the average power density. According to the relationship between the contact angle of the coating and the number of side-chain carbon atoms of the methacrylate monomers in Examples 1, 4, 5, 6, 8 and 10, referring to Figure 1 , as the number of side-chain carbon atoms increases, the contact angle first decreases and then increases. When the number of side-chain carbon atoms is in the range of 8-12, the coating has better droplet rolling performance, and the contact angle < 20°. According to the relationship between the contact angle of the coating and the average power density in Examples 1-3 and Examples 12-15, referring to Figure 2 , as the average power decreases, the contact angle first decreases and then increases. When the average power density is 25-100 W / m 3 , the coating has better droplet rolling performance, and the contact angle < 20°.

[0136] Although the present invention is disclosed as above, the present invention is not limited thereto. Any person skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention should be subject to the scope defined by the claims.

Claims

1. A method for preparing a low rolling angle coating, characterized in that, Comprising the following steps: Providing a substrate and placing the substrate in a vacuum deposition chamber; Introduce the vapor of the structural monomer shown in formula (1) into the reaction chamber, and initiate plasma discharge to form a plasma polymerization coating on the surface of the substrate. The average power density of the plasma discharge is 20 to 120 w / m 3 , In formula (1), R1, R2 and R3 are each independently selected from a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R4 is an alkyl group having 1 to 20 carbon atoms.

2. The preparation method according to claim 1, characterized in that, The average power density of the plasma discharge is 25 to 100 w / m 3 .

3. The preparation method according to claim 1, characterized in that, R1, R2, and R3 are each independently selected from a hydrogen atom or a methyl group.

4. The preparation method according to claim 3, characterized in that, R1 and R2 are hydrogen atoms, and R3 is a methyl group.

5. The preparation method according to claim 1, characterized in that, The structural monomer represented by the formula (1) is selected from at least one of methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, propyl methacrylate, propyl acrylate, n-butyl methacrylate, n-butyl acrylate, isobutyl methacrylate, isobutyl acrylate, isopentyl methacrylate, isopentyl acrylate, n-octyl methacrylate, n-octyl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, nonyl methacrylate, nonyl acrylate, n-octyl methacrylate, n-octyl acrylate, isooctyl methacrylate, isooctyl acrylate, decyl methacrylate, decyl acrylate, dodecyl methacrylate, dodecyl acrylate, hexadecyl methacrylate, hexadecyl acrylate, octadecyl methacrylate, and octadecyl acrylate.

6. The preparation method according to claim 1, characterized in that, The R4 is a straight-chain alkyl group having 8 to 12 carbon atoms.

7. The preparation method according to claim 1, characterized in that, The average power of the plasma discharge is 1 to 400 W.

8. The preparation method according to claim 7, characterized in that, The average power of the plasma discharge is 15 to 60 W.

9. The preparation method according to claim 1, characterized in that, The plasma discharge is a pulsed plasma discharge.

10. A low rolling angle coating, characterized in that, The low rolling angle coating is obtained by the preparation method described in any one of claims 1-9.

11. A device, characterized in that, At least a part of the surface of the device has the coating described in claim 10.

12. A low rolling angle coating, characterized in that, The low rolling angle coating is a plasma polymerization coating formed by plasma deposition of a structural monomer represented by the following formula (1): In formula (1), R1, R2, and R3 are each independently selected from a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R4 is a straight-chain alkyl group having 8 to 12 carbon atoms; wherein the rolling angle of the coating is 20° or less.

13. The coating according to claim 12, characterized in that, R1, R2, and R3 are each independently selected from a hydrogen atom or a methyl group.

14. The coating according to claim 13, characterized in that, R1 and R2 are hydrogen atoms, and R3 is a methyl group.

15. A device, characterized in that, At least a part of the surface of the device has the coating described in any one of claims 12-14.

Images