CN118406411A - Preparation method of amphiphobic coating, prepared amphiphobic coating and application thereof - Google Patents
Preparation method of amphiphobic coating, prepared amphiphobic coating and application thereof Download PDFInfo
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- 238000000034 method Methods 0.000 claims description 31
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
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- 239000010959 steel Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims 1
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- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 10
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to the technical field of self-cleaning materials, in particular to a preparation method of an amphiphobic coating, which comprises the following steps: mixing resin, a curing agent and a solvent to obtain a resin coating, mixing filler particles with the resin coating to obtain a mixture, coating the mixture on the surface of a substrate, curing the mixture on the surface of the substrate to obtain an amphiphobic coating, and obtaining the minimum value of the mass fraction w of the filler particles in the mixture according to the mass fraction of the resin in the resin coating, the density of the filler particles and the density of the cured resin. The water contact angle of the amphiphobic coating prepared by the invention is 128-145 degrees, and the oil contact angle of the amphiphobic coating is 120-140 degrees. The wear resistance of the amphiphobic coating reaches 500/g, the hardness reaches 3H, and the adhesive force is 1 level.
Description
Technical Field
The invention relates to the technical field of self-cleaning materials, in particular to a preparation method of an amphiphobic coating, the prepared amphiphobic coating and application thereof.
Background
Chemical Mechanical Planarization (CMP), one of the most critical techniques for achieving multi-level metallization and gate and channel material incorporation in Integrated Circuit (IC) fabrication, is the necessary planarization process in semiconductor fabrication. However, the polishing solution used in the CMP process contains a certain amount of abrasive nanoparticles (such as SiO 2、CeO2, etc.), and the polishing solution is heated to evaporate water due to mechanical grinding in the polishing process, so that the concentration of the abrasive is increased, resulting in local supersaturation of the abrasive nanoparticles, and the heating also accelerates the movement of colloid particles, resulting in agglomeration of the nanoparticles, adhesion to the surface of the polishing device, and formation of white crystals, which is difficult to clean, seriously affecting the subsequent process and production. Meanwhile, as the polishing equipment is made of metal materials, the long-term use of the polishing solution can cause corrosion to the equipment to a certain extent. However, no clear solution exists for the agglomeration problem of nano particles in a polishing solution system, so that the application of the amphiphobic coating with the anti-corrosion and self-cleaning properties on polishing equipment becomes an effective solution.
Low surface energy and surface microstructure are two prerequisites for forming an amphiphobic coating. The traditional preparation method of the amphiphobic coating is to add substances with low surface energy for modification. However, since the low surface energy substance generally has a long (fluoro) carbon chain, an alkyl group or an aromatic group, etc., the molecular structure of these groups is relatively soft, which makes the molecules thereof relatively easy to deform in the coating layer, reducing the overall rigidity of the coating layer. In addition, these low surface energy molecular structures generally do not facilitate intermolecular interactions, weakening the forces within the coating, resulting in a reduced hardness of the coating. This results in contradiction between the amphiphobic properties of the coating and the mechanical properties of the coating, and also limits the application of the super-amphiphobic coating in practical production.
In the preparation of the coating, adding a proper amount of filler particles is a common technical means, and although the addition of the filler particles can help to strengthen the hardness of the coating to a certain extent, the addition of the filler particles is difficult to grasp, and the unsuitable addition not only leads to limited hardness improvement, but also can reduce the performance of the coating itself. In addition, the filler particles have a static liquid phase effect in the curing process of the coating, so that the particles are unevenly distributed in the coating, and the performance of the coating is further influenced.
Therefore, how to prepare a coating with certain hardness and amphiphobic property in polishing equipment and keep the surface of the polishing equipment clean is a technical problem which needs to be solved at present.
Disclosure of Invention
In order to solve the above-mentioned problems of the prior art, the present invention determines the minimum amount of filler particles required to construct a continuous rough surface structure within the coating layer according to the nature of the resin and the filler particle raw material itself. Therefore, the distribution of the filler particles in the coating is regulated, so that the filler particles can construct a continuous rough surface structure in the coating, and finally the durable high-hardness amphiphobic coating is prepared.
In the process of curing the coating, under the condition that the resin and the volatile solvent can be well compatible, along with the volatilization process of the solvent, gaps are gradually formed inside the coating, the coating is subjected to an impregnation state (filler particles are completely immersed in a resin solution), a capillary state (gaps appear inside the coating, but the filler particles are still completely immersed in the resin solution), a chain state (gaps inside the coating are further increased, liquid bridges are formed among the filler particles and are connected through liquid bridge force), and a swinging state (the liquid bridge force among the filler particles tends to be balanced) are subjected to four liquid phase processes. Therefore, the liquid bridge force of the filler particles in the liquid phase process can be regulated and controlled by regulating and controlling the dosage of the solvent, the resin and the filler particles in the coating, and the filler particles are gathered and connected through the liquid bridge force, so that the filler particles form a continuous surface coarse structure in the coating curing process.
The continuous rough surface structure is similar to a Cassie-Baxter model, air is trapped in a cavity on the rough surface, and the filled air serves as a barrier layer, so that the actual contact angle of liquid drops is increased, and the construction of the amphiphobic performance of the surface of a coating is facilitated. For more convenient formation of the above-mentioned continuously roughened surface structure, the mass fraction of filler particles is critical for forming the surface structure.
In a first aspect, the invention provides a method for preparing an amphiphobic coating, comprising the following steps: mixing resin, a curing agent and a solvent to obtain a resin coating, mixing filler particles with the resin coating to obtain a mixture, coating the mixture on the surface of a substrate, curing the mixture on the surface of the substrate to obtain an amphiphobic coating, and obtaining the minimum value of the mass fraction w of the filler particles in the mixture according to the mass fraction of the resin in the resin coating, the density of the filler particles and the density of the cured resin.
As a specific embodiment of the present invention, the mass fraction w of filler particles in the mixture satisfies the following conditionsWherein
Ρ Particles is the density of the filler particles;
ρ resin composition is the density of the cured resin; the density of the resin after curing is the density of the resin after curing after adding the curing agent into the resin; specifically, the density of the cured resin is the density of the mixture after curing when no filler particles are added in the mixture;
n is the mass fraction of the resin in the resin coating, n is the sum of the mass of the resin and the curing agent/the sum of the mass of the resin, the curing agent and the solvent;
As a specific embodiment of the invention, the mass fraction w of filler particles in the mixture is less than 65%. The mass fraction w of filler particles in the mixture is not too large, otherwise the performance of the amphiphobic coating is also reduced.
The mass fraction of filler particles in the mixture is calculated as follows:
(1) Assuming that filler particles in the amphiphobic coating are spheres with the particle size of R, dividing the amphiphobic coating into M cube units, wherein the cube units are centered on single filler particles, when the filler particles construct a continuous composite coarse structure, the filler particles are in contact with each other, and each face of each cube unit is tangent to the filler particles, as shown in figure 1.
(2) The volume of the cube unit after removal of the filler particles is:
A formula I;
(3) The value of M is:
A formula II;
In the formula II, m is the total mass of the mixture, w is the mass fraction of filler particles in the mixture, and ρ Particles is the density of the filler particles;
(4) The volume V resin composition of the resin in each cube unit is
III the number of the components to be processed,
In the formula III, ρ resin composition is the density of the resin after curing; n is the mass fraction of resin in the resin coating;
The calculation of formula III is that first Bringing M in to obtain a formula III;
(5) When the cured resin is insufficient to fill the voids between the filler particles, the filler particles spontaneously aggregate to form a composite coarse structure, at which point the resin will coat the surface of the composite coarse structure formed by the filler particles.
Thus, the filler particles are allowed to build up a rough surface structure in the coating, which is required to meet: at this time, the mass fraction w of the filler particles is: 。
When the mass fraction of filler particles in the coating meets the above formula, a continuous composite coarse structure can be constructed among the particles. The above calculations indicate that the minimum value of the mass fraction of filler particles in the mix is related to the density ρ Particles of filler particles and the density ρ resin composition of the resin after curing, as well as the mass fraction n of resin in the resin coating.
In a specific embodiment of the present invention, the filler particles have a diameter of 5 to 15. Mu.m.
As a specific embodiment of the present invention, ρ resin composition is 1.0 to 1.6 g/cm.
As a specific embodiment of the present invention, the resin is at least one selected from silicone resins, polyurethane resins, epoxy resins, polyacrylic resins, polyurea resins, phenolic resins, amino resins, alkyd resins, polyvinylidene fluoride resins.
As a specific embodiment of the present invention, ρ Particles is 0.9 to 3.9 g/cm.
As a specific embodiment of the present invention, the filler particles are at least one selected from the group consisting of light calcium powder, diatomaceous earth, kaolin, silica, heavy calcium powder, silicate, talc, gypsum powder, silicon carbide, boron nitride, alumina, and titanium dioxide.
As a specific embodiment of the invention, the absolute value of the difference between ρ resin composition and ρ Particles is 0.1-2 g/cm.
During the curing of the mix, the filler particles inevitably settle to the bottom of the coating or float to the top of the coating due to gravity, resulting in inconsistent upper and lower portions of the coating. Filler particles having a density similar to that of the resin are therefore preferred.
As specific embodiments of the present invention, the solvent is selected from one or more of methanol, ethanol, acetone, ethyl acetate, dichloromethane, tetrahydrofuran, and chloroform. The type of solvent can affect the surface tension of the coating liquid film, the distribution of filler particles in the coating, and the surface morphology of the resin cured during volatilization of the solvent.
In the present invention, in the case of being well compatible with the resin, a solvent having a low boiling point and a small surface tension is preferable, so that the solvent is easily volatilized, and the volatilization process of the solvent is accompanied, thereby forming a continuous surface roughness structure of the filler particles during the curing process of the coating.
As a specific embodiment of the invention, the value of n is 30wt% to 80wt%. Preferably 40wt% to 60wt%. The value of n is chosen primarily in relation to the molecular weight, viscosity, solubility of the resin and the strength of the resulting coating. The molecular weight of the resin determines the density and chemical reactivity of the resin. Higher molecular weights generally mean higher strength and durability, but may increase viscosity and dissolution difficulty. The viscosity describes the flow characteristics of the resin and the workability of the coating. Higher viscosities may provide better filling and vertical coating capabilities, but may also lead to construction difficulties or require higher solvent levels. The solubility determines the degree of dissolution of the resin in the solvent. The selection of a suitable solvent ensures adequate dissolution of the resin and facilitates uniform application of the coating and uniformity of the coating. The strength and durability that the final coating needs to possess are one of the key factors in determining the amount of resin added. Increasing the resin content generally enhances the hardness and abrasion resistance of the coating, but excessive use may cause construction problems or increase in cost.
Therefore, in practical application, the addition amount of the resin in the resin coating needs to be determined by comprehensively considering the above factors, and the final coating meets the expected performance requirement through test and adjustment.
In a specific embodiment of the present invention, the filler particles are hydrophobically modified filler particles. In order to prevent the filler particles from agglomerating in the solution, the filler particles also need to be subjected to a hydrophobic modification treatment. Specifically, the hydrophobic modification is modification by using a silane coupling agent.
As a specific embodiment of the invention, the resin also comprises a curing agent, wherein the curing agent is one or more selected from amine curing agents, acid anhydride, isocyanate, epoxy resin, polyamide resin and polyol.
Specifically, the amine curing agent includes: aromatic amines, aliphatic amines, cyclic amines, and the like.
As a specific embodiment of the present invention, the curing conditions in step (3) include: the curing temperature is 10-20 ℃ lower than the boiling point of the solvent. The density of the filler particles is generally larger than that of the resin, and the filler particles are easily precipitated to the bottom under the action of gravity in the curing process, so that the surface of the coating and the particles of the bottom layer are unevenly distributed, the stability of the coating is damaged, and the continuous rough surface structure is influenced. The temperature affects the evaporation rate of the coating and the above problems can be avoided or alleviated by controlling the temperature.
Preferably, the curing temperature is 10-20 ℃ below the boiling point of the solvent. If the curing temperature is too high (higher than the boiling point of the organic solvent), the solvent volatilization rate is too high, and bubbles are generated by boiling the solvent, so that the surface appearance of the coating is affected; if the curing temperature is too low, the solvent volatilization rate is slow, and the capillary force in the vertical direction of the coating liquid film is small, so that the filler particles cannot be driven to move upwards, and a continuous surface roughness structure cannot be formed.
Specifically, if methanol is selected as the solvent, the boiling point of the methanol is 64.8 ℃, and the curing temperature is preferably 44.8-54.8 ℃.
As a specific embodiment of the present invention, the substrate is selected from any one of steel, glass, PVC, marble, paper, and wood.
In a second aspect, the invention provides an amphiphobic coating prepared by the preparation method provided by the first aspect of the invention. The invention makes the coating possess excellent amphiphobic performance while possessing high hardness by constructing continuous rough surface structure in the coating. The water contact angle of the amphiphobic coating is 128-145 degrees, the oil contact angle of the amphiphobic coating is 120-140 degrees, the wear resistance of the amphiphobic coating reaches 500/g, the hardness reaches 3H, and the adhesive force is 1 level.
In a third aspect, the present invention provides an amphiphobic coating prepared by the preparation method provided by the first aspect of the present invention or an amphiphobic coating provided by the second aspect of the present invention, for use in cleaning polishing equipment during chemical mechanical planarization.
Compared with the prior art, the invention has the following beneficial effects.
The present invention determines the minimum amount of filler particles required to build a continuous roughened surface structure within the coating based on the nature of the resin and filler particle raw material itself. Therefore, by regulating the addition amount of the filler particles, the filler particles can construct a continuous rough surface structure in the coating, and finally the durable high-hardness amphiphobic coating is prepared.
The water contact angle of the amphiphobic coating prepared by the invention is 128-145 degrees, and the oil contact angle of the amphiphobic coating is 120-140 degrees. The wear resistance of the amphiphobic coating reaches 500/g, the hardness reaches 3H, and the adhesive force is 1 level.
Drawings
FIG. 1 is a graph of the tangency of each face of a cube cell with filler particles in an amphiphobic coating of the invention;
FIG. 2 is an electron micrograph of the amphiphobic coating prepared in example 1;
FIG. 3 is a graph showing the water contact angle test of the amphiphobic coating prepared in example 1;
FIG. 4 is a graph of oil contact angle measurements of the amphiphobic coating prepared in example 1;
FIG. 5 is a graph showing the contact angle of the silica polishing solution of the amphiphobic coating prepared in example 1;
FIG. 6 is an electron micrograph of the amphiphobic coating prepared in comparative example 1.
Detailed Description
The invention is further illustrated below in connection with specific examples, which are not to be construed as limiting the invention in any way.
The raw materials, filler particles, resins, and silica polishing solutions used in the examples of the present invention were purchased from manufacturers.
Aluminum silicate filler (purity 99.9%, particle size 10 μm), silicon oxide filler (purity 99.9%, particle size 10 μm), aluminum oxide filler (purity 99.9%, particle size 10 μm) were purchased from Hebei Guanchuan New Material technology Co., ltd;
Heptadecafluorodecyl trimethoxysilane is purchased from Annaiji chemistry;
PVDF resin and dicumyl peroxide curing agent are purchased from Ji Peng silicon fluorine materials Co., shenzhen City;
Bisphenol A type epoxy resin (E51), polyether amine (D230) serving as a curing agent of the epoxy resin, polyurethane resin (HDI trimer) and toluene diisocyanate-trimethylolpropane (TDI-TMP) addition products serving as curing agents of the epoxy resin are purchased from Kain chemical industry;
Reagents such as ethanol, acetone, ethyl acetate, etc. were purchased from Shanghai Ala Biochemical technologies Co., ltd.
Example 1
Hydrophobic modification of aluminum silicate filler particles:
The 15g aluminum silicate filler particles with the particle size of about 10 mu m are washed by acetone, ethanol and deionized water in sequence and then dried at 60 ℃. Dispersing 30min in 100 mL 95% ethanol solution by ultrasonic, adjusting pH to 8, adding heptadecafluorodecyl trimethoxysilane accounting for 1wt% of the mass of the filler particles, carrying out suction filtration to separate the filler particles after 6h, washing the filler particles with absolute ethanol, repeatedly cleaning for 3 times, drying at 50 ℃, grinding, and sieving with a 600-mesh sieve. Hydrophobically modified aluminum silicate filler particles are obtained.
Calculating the mass fraction of aluminum silicate filler particles:
When the density ρ Particles of the aluminum silicate filler particles is 2.8x 3kg/m3 and the density ρ resin composition of the polyvinylidene fluoride (PVDF) resin is 1.6x 3kg/m3 after curing, respectively, measured by a drainage method, and the mass fraction n of the resin in the resin coating is 0.54, a continuous rough surface structure can be constructed when the minimum mass fraction of the aluminum silicate filler particles obtained by the above formula is 50.9%.
And (3) preparing a coating:
Adding 5.5 g PVDF resin into 5.2 mL ethyl acetate (density is 0.9 g/cm 3), adding 10.6 g hydrophobically modified aluminum silicate filler particles, performing ultrasonic dispersion for 30 min, adding 0.5 g dicumyl peroxide curing agent, and continuing ultrasonic dispersion for 10min to obtain the mixture. And (3) dripping the mixture on a glass substrate, placing the substrate in a drying oven, heating to 60 ℃, keeping the temperature at 30 min, solidifying the mixture, continuously heating to 80 ℃, and keeping the temperature for 5 hours to obtain the amphiphobic coating.
The invention also adopts a scanning electron microscope (TescanAMBER) to observe the morphology of the coating prepared in the example 1, and an SEM (scanning electron microscope) picture is shown in figure 2. As can be seen from fig. 2, the coating prepared in example 1 shows a continuous surface roughness structure more completely.
The prepared amphiphobic coating is tested to have a water contact angle of 145.42 degrees, an oil contact angle of 140.14 degrees and a silica polishing liquid contact angle of 139.11 degrees. The contact angle test photographs are shown in fig. 3-5.
Example 2
Calculating the mass fraction of aluminum silicate filler particles:
When the density ρ Particles of the aluminum silicate filler particles is 2.8x 3kg/m3 and the density ρ resin composition of the polyvinylidene fluoride (PVDF) resin is 1.6x 3kg/m3 after curing, respectively, measured by a drainage method, and the mass fraction n of the resin in the resin coating is 0.54, a continuous rough surface structure can be constructed when the minimum mass fraction of the aluminum silicate filler particles obtained by the above formula is 50.9%.
And (3) preparing a coating:
Adding 5 g PVDF resin into 5.2 mL ethyl acetate (density 0.9 g/cm 3), adding 10.6 g aluminum silicate filler particles, performing ultrasonic dispersion for 30 min, adding 0.5 g dicumyl peroxide curing agent, and continuing ultrasonic dispersion for 10 min to obtain the mixture. And (3) dripping the mixture on a glass substrate, placing the substrate in a drying oven, heating to 60 ℃, keeping the temperature at 30 min, solidifying the mixture, continuously heating to 80 ℃, and keeping the temperature for 5 hours to obtain the amphiphobic coating.
The prepared amphiphobic coating is tested to have a water contact angle of 128.21 degrees, an oil contact angle of 120.57 degrees and a silica polishing liquid contact angle of 121.33 degrees.
Example 3
Hydrophobic modification of aluminum silicate filler particles:
The 15g aluminum silicate filler particles with the particle size of about 10 mu m are washed by acetone, ethanol and deionized water in sequence and then dried at 60 ℃. Dispersing 30min in 100 mL 95% ethanol solution by ultrasonic, adjusting pH to 8, adding heptadecafluorodecyl trimethoxysilane accounting for 1wt% of the mass of the filler particles, carrying out suction filtration to separate the filler particles after 6h, washing the filler particles with absolute ethanol, repeatedly cleaning for 3 times, drying at 50 ℃, grinding, and sieving with a 600-mesh sieve. Hydrophobically modified aluminum silicate filler particles are obtained.
Calculating the mass fraction of aluminum silicate filler particles:
When the density ρ Particles of the aluminum silicate filler particles was 2.8X10- 3kg/m3 and the density ρ resin composition of the bisphenol A type epoxy resin (E51) was 1.5X10- 3kg/m3 after curing, respectively, by the drainage method, and the mass fraction n of the resin in the resin coating was 0.54, a continuous rough surface structure was constructed when the minimum mass fraction of the aluminum silicate filler particles obtained by the above formula was 52.5%.
And (3) preparing a coating:
Adding 5g bisphenol A epoxy resin (E51) into 5.2 mL ethyl acetate (density 0.9 g/cm 3), adding 11.3 g hydrophobically modified aluminum silicate filler particles, ultrasonically dispersing for 30 min, adding 0.5 g polyether amine (D230) curing agent, and continuously ultrasonically dispersing for 10 min to obtain a mixture. And (3) dripping the mixture on a glass substrate, placing the substrate in a drying oven, heating to 60 ℃, keeping the temperature at 30 min, solidifying the mixture, continuously heating to 80 ℃, and keeping the temperature for 5 hours to obtain the amphiphobic coating.
The prepared amphiphobic coating is tested to have a water contact angle of 140.65 degrees, an oil contact angle of 137.78 degrees and a silica polishing liquid contact angle of 139.29 degrees.
Example 4
Hydrophobic modification of aluminum silicate filler particles:
The 15g aluminum silicate filler particles with the particle size of about 10 mu m are washed by acetone, ethanol and deionized water in sequence and then dried at 60 ℃. Dispersing 30min in 100 mL 95% ethanol solution by ultrasonic, adjusting pH to 8, adding heptadecafluorodecyl trimethoxysilane accounting for 1wt% of the mass of the filler particles, carrying out suction filtration to separate the filler particles after 6h, washing the filler particles with absolute ethanol, repeatedly cleaning for 3 times, drying at 50 ℃, grinding, and sieving with a 600-mesh sieve. Hydrophobically modified aluminum silicate filler particles are obtained.
When the density ρ Particles of the aluminum silicate filler particles was 2.8x10 3kg/m3 and the density ρ resin composition of the polyurethane resin (HDI trimer) was 1.3x10 3kg/m3 after curing, respectively, using a drainage method, and the mass fraction n of the resin in the resin coating was 0.54, a continuous rough surface structure could be constructed when the minimum mass fraction of the aluminum silicate filler particles obtained by the above formula was 56.1%.
And (3) preparing a coating:
5g polyurethane resin (HDI trimer) was added to 5.2 mL ethyl acetate (density 0.9 g/cm 3), 13 g aluminum silicate filler particles were added, after ultrasonic dispersion of 30min, 0.5 g toluene diisocyanate-trimethylolpropane (TDI-TMP) adduct curing agent was added, and ultrasonic dispersion was continued for 10min to obtain a mixture. And (3) dripping the mixture on a glass substrate, placing the substrate in a drying oven, heating to 60 ℃, keeping the temperature at 30min, solidifying the mixture, continuously heating to 80 ℃, and keeping the temperature for 5 hours to obtain the amphiphobic coating.
The prepared amphiphobic coating is tested to have a water contact angle of 142.34 degrees, an oil contact angle 136.81 degrees and a silica polishing liquid contact angle of 138.66 degrees.
Example 5
Hydrophobic modification of silica filler particles:
And (3) washing 15g silicon oxide filler particles with the particle size of about 10 mu m by acetone, ethanol and deionized water in sequence, and drying at 60 ℃. Dispersing 30min in 100 mL 95% ethanol solution by ultrasonic, adjusting pH to 8, adding heptadecafluorodecyl trimethoxysilane accounting for 1wt% of the mass of the filler particles, carrying out suction filtration to separate the filler particles after 6h, washing the filler particles with absolute ethanol, repeatedly cleaning for 3 times, drying at 50 ℃, grinding, and sieving with a 600-mesh sieve. Hydrophobically modified silica filler particles are obtained.
When the densities ρ Particles and ρ resin composition of the silica filler particles were 2.6X10: 10 3kg/m3 and the polyvinylidene fluoride (PVDF) resin was 1.6X10: 10 3kg/m3, respectively, measured by a drainage method, and the mass fraction n of the resin in the resin coating was 0.54, respectively, a continuous rough surface structure was constructed when the minimum mass fraction of the silica filler particles obtained by the above formula was 49.1%.
And (3) preparing a coating:
Adding 5. 5 g PVDF resin into 5.2 mL ethyl acetate (density is 0.9 g/cm 3), adding 9.9 g hydrophobically modified silica filler particles, performing ultrasonic dispersion on the mixture for 30min, adding 0.5 g dicumyl peroxide curing agent, and continuing ultrasonic dispersion for 10min to obtain the mixture. And (3) dripping the mixture on a glass substrate, placing the substrate in a drying oven, heating to 60 ℃, keeping the temperature at 30min, solidifying the mixture, continuously heating to 80 ℃, and keeping the temperature for 5 hours to obtain the amphiphobic coating.
The water contact angle of the amphiphobic coating prepared by testing is 141.28 degrees, the oil contact angle is 134.57 degrees, and the contact angle of the silicon dioxide polishing liquid is 139.46 degrees.
Example 6
Hydrophobic modification of alumina filler particles:
Alumina filler particles with the particle size of 15g about 10 mu m are washed by acetone, ethanol and deionized water in sequence and then dried at 60 ℃. Dispersing 30min in 100 mL 95% ethanol solution by ultrasonic, adjusting pH to 8, adding heptadecafluorodecyl trimethoxysilane accounting for 1wt% of the mass of the filler particles, carrying out suction filtration to separate the filler particles after 6h, washing the filler particles with absolute ethanol, repeatedly cleaning for 3 times, drying at 50 ℃, grinding, and sieving with a 600-mesh sieve. Hydrophobically modified alumina filler particles are obtained.
The density ρ Particles of the alumina filler particles was 3.3X10 3kg/m3 and the density ρ resin composition of the polyvinylidene fluoride (PVDF) resin after curing was 1.6X10 3kg/m3, respectively, measured by the drainage method, and the mass fraction n of the resin in the resin coating was 0.54, and when the minimum mass fraction of the alumina filler particles obtained by the above formula was 55%, a continuous rough surface structure could be constructed.
And (3) preparing a coating:
Adding 5 g PVDF resin into 5.2 mL ethyl acetate (density 0.9 g/cm 3), adding 12.5 g alumina filler particles, performing ultrasonic dispersion for 30 min, adding 0.5 g dicumyl peroxide curing agent, and continuing ultrasonic dispersion for 10 min to obtain a mixture. And (3) dripping the mixture on a glass substrate, placing the substrate in a drying oven, heating to 60 ℃, keeping the temperature at 30 min, solidifying the mixture, continuously heating to 80 ℃, and keeping the temperature for 5 hours to obtain the amphiphobic coating.
The water contact angle of the amphiphobic coating prepared by testing is 143.17 degrees, the oil contact angle is 134.52 degrees, and the contact angle of the silicon dioxide polishing liquid is 137.63 degrees.
Example 7
Hydrophobic modification of aluminum silicate filler particles:
aluminum silicate filler particles with the particle size of 20 g of about 10 mu m are sequentially washed by acetone, ethanol and deionized water and then dried at 60 ℃. Dispersing 30min in 130 mL of 95% ethanol solution by ultrasonic, adjusting the pH value to 8, adding heptadecafluorodecyl trimethoxysilane accounting for 1wt% of the mass of the filler particles, carrying out suction filtration to separate the filler particles after 6h, washing the filler particles with absolute ethanol, repeatedly washing for 3 times, drying at 50 ℃, grinding and sieving with a 600-mesh sieve. Hydrophobically modified aluminum silicate filler particles are obtained.
Calculating the mass fraction of aluminum silicate filler particles:
When the density ρ Particles of the aluminum silicate filler particles is 2.8x 3kg/m3 and the density ρ resin composition of the polyvinylidene fluoride (PVDF) resin is 1.6x 3kg/m3 after curing, respectively, measured by a drainage method, and the mass fraction n of the resin in the resin coating is 0.54, a continuous rough surface structure can be constructed when the minimum mass fraction of the aluminum silicate filler particles obtained by the above formula is 50.9%.
Adding 5. 5g PVDF resin into 5.2 mL ethyl acetate (density is 0.9 g/cm 3), adding 15.27 g hydrophobically modified aluminum silicate filler particles, performing ultrasonic dispersion for 30 min, adding 0.5 g dicumyl peroxide curing agent, and continuing ultrasonic dispersion for 10 min to obtain the mixture. And (3) dripping the mixture on a glass substrate, placing the substrate in a drying oven, heating to 60 ℃, keeping the temperature at 30 min, solidifying the mixture, continuously heating to 80 ℃, and keeping the temperature for 5 hours to obtain the amphiphobic coating.
The prepared amphiphobic coating is tested to have a water contact angle of 145.76 degrees, an oil contact angle of 140.87 degrees and a silica polishing liquid contact angle of 139.23 degrees.
The slightly increased w value of this example compared to example 1 demonstrates that a slightly excessive amount of filler particles can build up a coarser surface structure by stacking, which is beneficial to enhancing the amphiphobic properties of the coating.
Comparative example 1
Hydrophobic modification of aluminum silicate filler particles:
The 15g aluminum silicate filler particles with the particle size of about 10 mu m are washed by acetone, ethanol and deionized water in sequence and then dried at 60 ℃. Dispersing 30min in 100 mL 95% ethanol solution by ultrasonic, adjusting pH to 8, adding heptadecafluorodecyl trimethoxysilane accounting for 1wt% of the mass of the filler particles, carrying out suction filtration to separate the filler particles after 6h, washing the filler particles with absolute ethanol, repeatedly cleaning for 3 times, drying at 50 ℃, grinding, and sieving with a 600-mesh sieve. Hydrophobically modified aluminum silicate filler particles are obtained.
And (3) preparing a coating:
Adding 5g PVDF resin into 5.2 mL ethyl acetate (density is 0.9 g/cm 3), adding 3g hydrophobically modified aluminum silicate filler particles, ultrasonically dispersing for 30 min, adding 0.5 g dicumyl peroxide curing agent, and continuously ultrasonically dispersing for 10min to obtain the coating. And (3) dripping the mixture on a glass substrate, placing the substrate in a drying oven, heating to 60 ℃, keeping the temperature at 30 min, solidifying the mixture, continuously heating to 80 ℃, and keeping the temperature for 5 hours to obtain the amphiphobic coating.
The morphology of the coating prepared in comparative example 1 was observed using a scanning electron microscope (TescanAMBER), and the SEM photograph is shown in fig. 6. As can be seen from fig. 6, the coating prepared in comparative example 1 shows a discontinuous surface roughness structure due to the addition amount of filler particles being too small.
The prepared coating was tested for a water contact angle of 96.7 °, an oil contact angle of 88.32 °, and a silica polishing liquid contact angle of 90.15 °.
Comparative example 2
Hydrophobic modification of aluminum silicate filler particles:
The 15g aluminum silicate filler particles with the particle size of about 10 mu m are washed by acetone, ethanol and deionized water in sequence and then dried at 60 ℃. Dispersing 30min in 100 mL 95% ethanol solution by ultrasonic, adjusting pH to 8, adding heptadecafluorodecyl trimethoxysilane accounting for 1wt% of the mass of the filler particles, carrying out suction filtration to separate the filler particles after 6h, washing the filler particles with absolute ethanol, repeatedly cleaning for 3 times, drying at 50 ℃, grinding, and sieving with a 600-mesh sieve. Hydrophobically modified aluminum silicate filler particles are obtained.
Calculation of aluminum silicate filler particles:
When the density ρ Particles of the aluminum silicate filler particles is 3×10 3kg/m3 and the density ρ resin composition of the PVDF resin after curing is 1.6x10 3kg/m3, respectively, measured by a drainage method, and the mass fraction n of the resin in the resin coating is 0.23, a continuous rough surface structure can be constructed when the minimum mass fraction of the aluminum silicate filler particles brought into the above-mentioned state is 31%.
And (3) preparing a coating:
Adding 5g PVDF resin into 20 mL ethyl acetate (density 0.9 g/cm 3), adding 10.6 g hydrophobically modified aluminum silicate filler particles, ultrasonically dispersing 30min, adding 0.5 g dicumyl peroxide curing agent, and continuously ultrasonically dispersing 10min to obtain the mixture. And then dripping the mixture on a glass substrate, placing the substrate in a drying oven, heating to 60 ℃, keeping the temperature at 30min, solidifying the mixture, continuously heating to 80 ℃, and keeping the temperature for 5 hours to obtain the amphiphobic coating.
The prepared amphiphobic coating is tested to have a water contact angle of 96.28, an oil contact angle 84.56 and a silica polishing liquid contact angle of 91.33. The solvent is added too much, so that the viscosity of the coating is small, the fluidity is large, and the filling property and uniformity of filler particles cannot be ensured, thus being unfavorable for the amphiphobic property of the coating.
Comparative example 3
Hydrophobic modification of aluminum silicate filler particles:
The 15g aluminum silicate filler particles with the particle size of about 10 mu m are washed by acetone, ethanol and deionized water in sequence and then dried at 60 ℃. Dispersing 30min in 100 mL 95% ethanol solution by ultrasonic, adjusting pH to 8, adding heptadecafluorodecyl trimethoxysilane accounting for 1wt% of the mass of the filler particles, carrying out suction filtration to separate the filler particles after 6h, washing the filler particles with absolute ethanol, repeatedly cleaning for 3 times, drying at 50 ℃, grinding, and sieving with a 600-mesh sieve. Hydrophobically modified aluminum silicate filler particles are obtained.
Calculation of aluminum silicate filler particles:
When the density ρ Particles of the aluminum silicate filler particles is 2.8x10 3kg/m3 and the density ρ resin composition of the PVDF resin after curing is 1.6x10 3kg/m3, respectively, measured by the drainage method, and the mass fraction n of the resin in the resin coating is 0.54, the minimum mass fraction of the aluminum silicate filler particles brought into the above formula is 50.9%, a continuous rough surface structure can be constructed.
And (3) preparing a coating:
Adding 5.5 g PVDF resin into 5.2 mL ethyl acetate (density is 0.9 g/cm 3), adding 10.6 g hydrophobically modified aluminum silicate filler particles, ultrasonically dispersing for 30min, adding 0.5g dicumyl peroxide curing agent, continuously ultrasonically dispersing for 10 min to obtain a mixture, dripping the mixture on a glass substrate, and curing at room temperature to obtain the coating.
The prepared amphiphobic coating is tested to have a water contact angle of 70.62, an oil contact angle of 58.36 and a silica polishing liquid contact angle of 64.78. When the mixture is solidified, the solidification temperature is low, the solvent in the coating volatilizes slowly, the capillary force can not drive the filler example to move upwards, filler particles are deposited at the bottom of the coating due to the gravity factor, and a surface roughness structure can not be constructed.
Comparative example 4
The aluminum silicate filler particles with the particle size of about 10 mu m of 50 g are washed by acetone, ethanol and deionized water in sequence and then dried at 60 ℃. Dispersing 30 min mL of 95% ethanol solution by ultrasonic method, adjusting pH to 8, adding heptadecafluorodecyl trimethoxysilane accounting for 1wt% of the mass of the filler particles, carrying out suction filtration to separate the filler particles after 6 h, washing the filler particles with absolute ethanol, repeatedly cleaning for 3 times, drying at 50 ℃, grinding, and sieving with 600 mesh sieve. Hydrophobically modified aluminum silicate filler particles are obtained.
Calculating the mass fraction of aluminum silicate filler particles:
When the density ρ Particles of the aluminum silicate filler particles is 2.8x 3kg/m3 and the density ρ resin composition of the polyvinylidene fluoride (PVDF) resin is 1.6x 3kg/m3 after curing, respectively, measured by a drainage method, and the mass fraction n of the resin in the resin coating is 0.54, a continuous rough surface structure can be constructed when the minimum mass fraction of the aluminum silicate filler particles obtained by the above formula is 50.9%.
Adding 5. 5g PVDF resin into 5.2 mL ethyl acetate (density is 0.9 g/cm 3), adding 40.72 g hydrophobically modified aluminum silicate filler particles, performing ultrasonic dispersion for 30 min, adding 0.5 g dicumyl peroxide curing agent, and continuing ultrasonic dispersion for 10 min to obtain the mixture. And (3) dripping the mixture on a glass substrate, placing the substrate in a drying oven, heating to 60 ℃, keeping the temperature at 30 min, solidifying the mixture, continuously heating to 80 ℃, and keeping the temperature for 5 hours to obtain the amphiphobic coating.
The prepared amphiphobic coating is easy to peel and crack, at the moment, the content of filler particles in the coating is too high, the viscosity of the mixture is increased, the fluidity of the mixture is poor, and a uniform coating is difficult to form. In addition, too many filler particles can cause shrinkage of the coating, especially during drying of the mix, the filler particles can impede the flow of resin, leading to concentration of shrinkage stresses and cracking of the coating.
The coatings prepared in the examples and comparative examples were subjected to mechanical property testing.
(1) Abrasion resistance test:
The substrate coated with the amphiphobic coating in the embodiment and the comparative example is horizontally placed, 320 pieces of sand paper with the area of about 1/3 of the area of the amphiphobic coating are placed on the surface of the substrate, a glass plate with the area equal to that of the sand paper is placed on the back adhesive surface of the sand paper, the sand paper and the glass plate are adhered together through back adhesive, relative sliding is avoided, finally a weight is placed on the glass plate to ensure that the amphiphobic coating is contacted with the surface of the sand paper, the sand paper is moved at the speed of v=0.5 mm/s, and the minimum weight corresponding to the scratch depth of the surface of the amphiphobic coating is recorded to be more than or equal to 1 mu m, so that the wear resistance of the coating is measured. The test results are shown in Table 1.
(2) Hardness testing:
The hardness of the surface abrasion-resistant coatings of the amphiphobic coatings prepared in examples and comparative examples was tested using a pencil hardness method. The test results are shown in Table 1.
(3) Adhesion test:
The adhesion properties between the amphiphobic coating and the substrate were tested using the GB/T9286-1998 standard. The adhesive force of the coating was tested by cutting a10 x 10 grid array on the surface of the coating with a blade, adhering the adhesive tape to the cut grid surface with a 610 tape, forcibly wiping the surface of the tape with an eraser to ensure that the adhesive tape is adhered to the grid surface, and then tearing off the adhesive tape in a 90 degree direction by grasping one end of the tape with a hand. The edges of the grid cuts were smooth and free of falling, indicating a coating adhesion of class 1. The test results are shown in Table 1.
Table 1 results of mechanical property test of coatings in examples and comparative examples
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (10)
1. A method of preparing an amphiphobic coating, the method comprising: mixing resin, a curing agent and a solvent to obtain a resin coating, mixing filler particles with the resin coating to obtain a mixture, and coating the mixture on the surface of a substrate, wherein the mixture is cured on the surface of the substrate to obtain the amphiphobic coating.
2. The process according to claim 1, wherein the mass fraction w of filler particles in the mixture is such that,Wherein
Ρ Particles is the density of the filler particles;
ρ resin composition is the density of the cured resin;
n is the mass fraction of resin in the resin coating;
And/or w is less than 65%.
3. The preparation method according to claim 2, wherein the filler particles have a particle diameter of 5 to 15 μm;
And/or, ρ resin composition is 1.0-1.6 g/cm;
And/or, ρ Particles is 0.9-3.9 g/cm;
And/or the absolute value of the difference between the rho resin composition and the rho Particles is 0.1-2 g/cm.
4. The method according to claim 1 or 2, wherein the resin is at least one selected from the group consisting of silicone resins, polyurethanes, epoxy resins, polyacrylic resins, polyurea resins, phenolic resins, amino resins, alkyd resins, polyvinylidene fluoride resins;
and/or the solvent is at least one selected from methanol, ethanol, acetone, ethyl acetate, dichloromethane, tetrahydrofuran and chloroform;
and/or the filler particles are at least one selected from light calcium powder, diatomite, kaolin, silicon dioxide, heavy calcium powder, wollastonite, talcum powder, gypsum powder, silicon carbide, boron nitride, aluminum oxide and titanium dioxide.
5. The method according to claim 2, wherein the value of n is 30wt% to 80wt%.
6. The preparation method according to claim 1 or 2, wherein the filler particles are hydrophobically modified filler particles.
7. The preparation method according to claim 1 or 2, wherein the curing agent is one or more selected from amine curing agents, acid anhydrides, isocyanates, epoxy resins, polyamide resins, polyols, peroxides.
8. The production method according to claim 1 or 2, wherein the curing conditions include: the curing temperature is 10-20 ℃ lower than the boiling point of the solvent;
And/or the substrate is selected from any one of steel, glass, PVC, marble, paper and wood.
9. An amphiphobic coating prepared by the preparation method of any one of claims 1-8, wherein the water contact angle of the amphiphobic coating is 128-145 degrees, the oil contact angle of the amphiphobic coating is 120-140 degrees, the wear resistance of the amphiphobic coating reaches 500/g, the hardness reaches 3H, and the adhesive force is 1 level.
10. Use of an amphiphobic coating prepared by the preparation method of any one of claims 1-8 or the amphiphobic coating of claim 9 for cleaning polishing equipment during chemical mechanical planarization.
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| US20220372303A1 (en) * | 2020-02-06 | 2022-11-24 | Bando Chemical Industries, Ltd. | Water-repellent structure, manufacturing method therefor, and water-repellent coating agent employed in same |
| CN114133772A (en) * | 2021-12-31 | 2022-03-04 | 武汉理工大学 | Durable super-amphiphobic thin film material with gradient structure and preparation method thereof |
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