Anti-sticking perfluoroether rubber sealing assembly as well as preparation method and application thereof

Abstract

The invention provides an anti-sticking perfluoroether rubber sealing assembly and a preparation method and application thereof, the preparation method comprises the following steps: mixing perfluoroether rubber with a vulcanizing agent to obtain a rubber compound, and performing high-temperature vulcanization on the rubber compound to obtain a perfluoroether rubber product; carrying out surface roughening treatment on the perfluoroether rubber product; dispersing amorphous fluororesin in the fluorinated liquid to obtain coating slurry; and coating the roughened perfluoroether rubber product with the coating slurry, and carrying out segmented heating and drying to obtain the perfluoroether rubber sealing assembly. According to the anti-sticking perfluoroether rubber sealing assembly as well as the preparation method and the application thereof, the obtained perfluoroether rubber sealing assembly has relatively low friction coefficient, excellent plasma corrosion resistance and relatively small viscous force, shows excellent non-sticking performance, and can be suitable for different environments.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer membrane materials, and particularly relates to a perfluoroether rubber sealing component with anti-sticking property, its preparation method and application. Background Art

[0002] Perfluoroether rubber (FFKM) has excellent properties such as resistance to plasma corrosion, gas corrosion, acid-base corrosion and high-temperature corrosion, and can meet the requirements of high cleanliness of rubber seals, which helps to maintain the integrity of the seal, reduce the number of repairs and improve safety. It is the best sealing material for semiconductor manufacturing equipment. However, when the perfluoroether sealing component comes into contact with materials such as metal, ceramic, and quartz, adhesion problems may occur due to the interaction between materials. This adhesion may not only cause damage to the sealing ring during disassembly or replacement, thus affecting the sealing performance of the sealing ring, but also cause the semiconductor cavity to be unable to be opened or closed smoothly, thereby affecting the normal operation of the equipment. In severe cases, it may even lead to equipment downtime, causing significant losses to production.

[0003] To solve the adhesion problem between perfluoroether sealing rings and materials such as metal, ceramic, and quartz, anti-sticking coatings have emerged. Anti-sticking coatings can reduce the adhesion force between materials and improve the fluidity and separation efficiency of materials. Common anti-sticking coatings include polytetrafluoroethylene (PTFE) coatings, polyurethane coatings, and ceramic coatings, etc., but they have disadvantages such as large processing difficulty, high cost, poor adhesion, poor stability, or being harmful to the human environment. Summary of the Invention

[0004] The present invention provides a perfluoroether rubber sealing component with anti-sticking property, its preparation method and application. Through the perfluoroether rubber sealing component with anti-sticking property, its preparation method and application provided by the present invention, the obtained perfluoroether rubber sealing component has a low friction coefficient, excellent plasma corrosion resistance and small adhesion force, showing excellent non-sticking property. It can solve the adhesion problem between the sealing component and the substrate, and at the same time meet the usage environment requirements of high temperature, plasma, corrosive gas-liquid media in the semiconductor processing process, which is beneficial to extending the service life of the perfluoroether rubber sealing component in semiconductor processing equipment, etc.

[0005] To solve the above technical problems, the present invention provides a preparation method for a perfluoroether rubber sealing component with anti-sticking property, which at least includes the following steps:

[0006] Mix perfluoroether rubber with a vulcanizing agent to obtain a mixed rubber, and subject the mixed rubber to high-temperature vulcanization to obtain a perfluoroether rubber product;

[0007] Perform surface roughening treatment on the perfluoroether rubber product;

[0008] Disperse the amorphous fluororesin in a fluorinated liquid to obtain a coating slurry; and

[0009] Apply the coating slurry onto the roughened perfluoroether rubber article and conduct segmented heating and drying to obtain a perfluoroether rubber seal assembly.

[0010] In an embodiment of the present invention, the glass transition temperature of the amorphous fluororesin is greater than or equal to 150 °C.

[0011] In an embodiment of the present invention, the amorphous fluororesin is an amorphous fluororesin formed by copolymerizing tetrafluoroethylene with other monomers, and the other monomers include perfluoro-1,3-dioxolene monomers, and the perfluoro-1,3-dioxolene monomers include at least one of perfluoro-2,2-dimethyl-1,3-dioxolene or 2,2,4-trifluoro-5-trifluoromethoxy-1,3-dioxolane.

[0012] In an embodiment of the present invention, the fluorinated liquid includes one of a first fluorinated liquid or a second fluorinated liquid. The first fluorinated liquid is selected from one of commercially available hydrofluorocarbons, perfluorocarbons, hydrofluoroethers, or fluoroalkenes with a boiling point of 50 °C to 130 °C, and the second fluorinated liquid is selected from one of commercially available hydrofluorocarbons, perfluorocarbons, hydrofluoroethers, or fluoroalkenes with a boiling point of 130 °C to 200 °C.

[0013] In an embodiment of the present invention, disperse the amorphous fluororesin in the fluorinated liquid at a preset temperature. In the coating slurry, the mass ratio of the amorphous fluororesin to the fluorinated liquid is 1 to 20:80 to 99, and the preset temperature is 50 °C to 65 °C.

[0014] In an embodiment of the present invention, the segmented heating and drying includes a first drying stage. After applying the coating slurry, immediately use a hot air gun to blow dry the coating slurry. The distance between the air outlet of the hot air gun and the perfluoroether rubber article is 5 cm to 10 cm, and keep the perfluoroether rubber article rotating uniformly during the first drying stage.

[0015] In an embodiment of the present invention, the segmented heating and drying further includes:

[0016] Dry the perfluoroether rubber article that has undergone the first drying stage for a first time at a first temperature; and

[0017] Raise the temperature from the first temperature to a second temperature and dry for a second time at the second temperature.

[0018] The present invention also provides a perfluoroether rubber seal assembly with anti-sticking properties, obtained by using the above-mentioned method.

[0019] Perfluoroether rubber product; and

[0020] An anti-sticking layer is coated on the surface of the perfluoroether rubber product. The anti-sticking layer comprises an amorphous fluororesin, and the glass transition temperature of the amorphous fluororesin is greater than or equal to 150 °C.

[0021] In an embodiment of the present invention, the thickness of the anti-sticking layer is 1 μm to 3 μm.

[0022] The present invention also provides a sealing device, which is sealed by using the anti-sticking perfluoroether rubber sealing assembly obtained by the above preparation method or the anti-sticking perfluoroether rubber sealing assembly described above.

[0023] In summary, the present invention provides an anti-sticking perfluoroether rubber sealing assembly, a preparation method and an application thereof. By providing an anti-sticking layer comprising an amorphous fluororesin with a high glass transition temperature, the perfluoroether rubber sealing assembly has a low friction coefficient and excellent plasma corrosion resistance, has a small adhesive force, exhibits excellent non-stickiness, can solve the problem of adhesion between the sealing assembly and the substrate, and at the same time meets the usage environment requirements of high temperature, plasma, and corrosive gas-liquid media in the semiconductor processing process, which is beneficial to extending the service life of the perfluoroether rubber sealing assembly in semiconductor processing equipment, etc. It can ensure the comprehensiveness and uniformity of the coverage of the anti-sticking layer in the perfluoroether rubber sealing assembly, and can improve the adhesion and firmness of the coating. The perfluoroether rubber sealing assembly provided by the present application has good mechanical properties and excellent high temperature resistance, and can be used in working conditions such as high temperature compression. Description of the Drawings

[0024] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for describing the embodiments will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present invention, and for those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0025] Figure 1 It is a thermogravimetric analysis curve of the amorphous fluororesin in an embodiment of the present invention.

[0026] Figure 2 It is the perfluoroether rubber sealing assembly obtained in an embodiment of the present invention.

[0027] Figure 3 Part A in it is the appearance of the O-ring in Comparative Example 5, Figure 3 Part B in it is the appearance of the O-ring in Comparative Example 1, Figure 3 Part C in it is the appearance of the O-ring in Comparative Example 3, Figure 3 Part D in it is the appearance of the O-ring in Comparative Example 2.

[0028] Figure 4 The surface of the mold after the compression set test of the O-ring obtained in Comparative Example 2.

[0029] Figure 5 The surface of the mold after the compression set test of the O-ring obtained in Example 1. Detailed implementation manners

[0030] The following specific examples illustrate the implementation manners of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific implementation manners. Various details in this specification can also be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention.

[0031] It should be understood that the present invention can be implemented in different forms and should not be construed as limited to the embodiments presented herein. On the contrary, providing these embodiments will make the disclosure thorough and complete, and will fully convey the scope of the present invention to those skilled in the art.

[0032] The technical solutions of the present invention will be further described in detail below in conjunction with several embodiments. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts fall within the scope of protection of the present invention.

[0033] The present invention provides a method for preparing a perfluoroether rubber sealing component with anti-sticking property, which at least includes: mixing perfluoroether rubber with a vulcanizing agent to obtain a rubber compound, and subjecting the rubber compound to high-temperature vulcanization to obtain a perfluoroether rubber product; performing surface roughening treatment on the perfluoroether rubber product; dispersing amorphous fluororesin in a fluorinating liquid to obtain a coating slurry; coating the coating slurry on the roughened perfluoroether rubber product and performing segmented heating and drying to obtain a perfluoroether rubber sealing component. Through the preparation method of the present application, the obtained perfluoroether rubber sealing component with anti-sticking property can solve the problem of adhesion between the sealing ring and the substrate, and at the same time meet the usage environment requirements of high temperature, plasma, and corrosive gas-liquid media in the semiconductor processing process. The perfluoroether rubber sealing component of the present application can be widely applied to sealing equipment such as semiconductor equipment, such as etching, cleaning, and coating equipment, and can also be applied to industries such as transportation, metallurgy, electric power, electronic instruments and meters, and sealing of parts.

[0034] In an embodiment of the present invention, the perfluoroether rubber comprises hexafluoropropylene, tetrafluoroethylene, perfluoroalkoxyalkyl vinyl ether or perfluoroalkyl vinyl ether as main monomers and a small amount of crosslinking point monomers, and the perfluoroalkyl vinyl ether includes, but is not limited to, one or more of perfluoroethyl vinyl ether (PEVE), perfluoro propyl vinyl ether (PPVE), perfluoro methoxy vinyl ether (PMOVE), perfluoro methyl vinyl ether (PMVE), etc. The monomers of the crosslinking points are, for example, iodine-containing monomers, nitrile group-containing monomers, carboxyl group-containing monomers or alkoxycarbonyl group-containing monomers, etc.

[0035] In an embodiment of the present invention, the vulcanizing agent includes, but is not limited to, one or a mixture of several of 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, dibenzoyl peroxide, di-tert-butyl perbenzoate, bis[1,3-dimethyl-3-(tert-butylperoxy)butyl] carbonate, 2,5-dimethylbenzenethiol, bisphenol A, perfluorobisphenol A, triallyl isocyanurate, tris(methallyl) isocyanurate, tris(diallylamino)-s-triazine, triallyl phosphite, N,N-diallyl acrylamide, tris(5-norbornene-2-methylene) cyanurate, trivinyl isocyanurate, hexaallyl phosphoramide, N,N,N-2,4,6-trivinylmethyltrisiloxane, tetraphenyltin, N,N-dicinnamylidene, trimethylenediamine, cinnamylethylenediamine, cinnamylidenehexamethylenediamine, hexamethylenediamine carbamate, bis(4-aminocyclohexyl)methane carbamate, 2,2-bis-(3-amino-4-hydroxyphenyl)-hexafluoropropane (BOAP), 1,3-diaminopropane monourethane, ethylenediamine carbamate or trimethylenediamine diurethane, etc. Among them, by weight, the perfluoroether rubber is, for example, 90 parts to 110 parts, and the vulcanizing agent is, for example, 0.5 parts to 2 parts.

[0036] In an embodiment of the present invention, perfluoroether rubber and a vulcanizing agent are mixed uniformly, for example, by a kneading device, and the uniformly mixed kneaded rubber is extruded, and pre-vulcanized at a preset temperature, pressure, and time to obtain a preform of a preset shape. The preform is then post-vulcanized at a preset temperature and time to form a perfluoroether rubber product. Among them, during pre-vulcanization, the kneaded rubber is directly made into a preform of a specific shape. In different embodiments, the morphology of the preform is different and can be selected according to the sealing device used. In this embodiment, for example, a preform in the shape of an O-ring is made for performance testing. The pre-vulcanization is, for example, compression molding flat vulcanization, and the temperature of the pre-vulcanization is, for example, 170°C to 200°C, the pressure of the pre-vulcanization is, for example, 5 MPa to 20 MPa, and the vulcanization time is, for example, 3 min to 30 min. Pre-vulcanization under the process of this temperature, time, and pressure can improve the mechanical properties of the product while ensuring production efficiency. The temperature of the post-vulcanization is, for example, 270°C to 320°C, the time of the post-vulcanization is, for example, 10 h to 30 h, and the post-vulcanization is, for example, carried out in a vacuum oven.

[0037] In an embodiment of the present invention, the perfluoroether rubber is, for example, a commercially available product. As an example, it includes perfluoroether rubber Dyneon PFE 194T of 3M Company, etc.

[0038] In an embodiment of the present invention, the perfluoroether rubber product is, for example, an O-ring. In different embodiments, the morphology of the perfluoroether rubber product is different and can be selected according to the semiconductor device used, such as a V-ring, a Y-ring, a U-ring, or a multi-surface sealing ring, etc.

[0039] In an embodiment of the present invention, the obtained perfluoroether rubber product is subjected to surface roughening treatment. For example, the surface of the perfluoroether rubber product is roughened by methods such as sandblasting, rough grinding, water grinding, or hand grinding, the particulate matter remaining on the surface is brushed off, and the surface roughness of the perfluoroether rubber product is increased. Then, ultrasonic cleaning and drying are carried out using acetone, isopropyl alcohol, absolute ethanol, deionized water, etc. After the surface treatment, the surface roughness Ra of the perfluoroether rubber product is, for example, 1.5 μm to 3.0 μm to improve the adhesion and firmness of the coating.

[0040] Please refer to Figure 1As shown, in an embodiment of the present invention, the amorphous fluororesin is, for example, an amorphous fluororesin formed by copolymerizing tetrafluoroethylene (TFE) with other monomers, and the other monomers include, for example, perfluoro-1,3-dioxolene (PD) monomers, etc. The perfluoro-1,3-dioxolene (PD) monomers include, for example, at least one of perfluoro-2,2-dimethyl-1,3-dioxolene (PDD) or 2,2,4-trifluoro-5-trifluoromethoxy-1,3-dioxolane (TTD), etc. Among them, the content of the other monomers is 60 mol% to 90 mol%, and the glass transition temperature of the amorphous fluororesin is, for example, greater than or equal to 150 °C, or for example, 150 °C to 250 °C. In other embodiments, for example, an amorphous fluororesin selected from commercially available ones with a glass transition temperature greater than 150 °C, such as a resin with the model of Teflon AF produced by Mitsui Chemours Japan, etc. As Figure 1 As shown, in a specific embodiment of the present invention, the upper limit of the thermal stability of the amorphous fluororesin is, for example, 400 °C. After exceeding 400 °C, the amorphous fluororesin begins to decompose. By using an amorphous fluororesin with a high glass transition temperature, the high-temperature resistance of the finally obtained perfluoroether rubber sealing assembly can be improved.

[0041] In an embodiment of the present invention, the fluorination liquid includes, for example, one of a first fluorination liquid or a second fluorination liquid, etc. The first fluorination liquid is, for example, selected from commercially available hydrofluorocarbons (HFCs), perfluorocarbons (PFCs), hydrofluoroethers (HFEs), fluoroolefins (HFOs), etc. with a boiling point of 50 °C to 130 °C. Specifically, for example, HFC-43-10mee (1,1,1,2,3,4,4,5,5,5-decafluoropentane), perfluoroheptane, HFE-7200 (nonafluorobutyl ethyl ether), etc. Or, for example, a special fluorination liquid with the model of Opteon SF10 produced by Mitsui Chemours Japan, whose boiling point is 110 °C. The second fluorination liquid is, for example, selected from commercially available hydrofluorocarbons (HFCs), perfluorocarbons (PFCs), hydrofluoroethers (HFEs), fluoroolefins (HFOs), etc. with a boiling point of 130 °C to 200 °C. Specifically, for example, C5-18 perfluoroalkane, Novec 7500 (2-(trifluoromethyl)-3-ethoxydodecafluorohexane) or perfluoronaphthalene, etc. Or, for example, an electronic fluorination liquid with the model of Fluorinert FC-40 produced by 3M Company, whose boiling point is 158 °C to 173 °C. By controlling the boiling point of the fluorination liquid, improving the stability of the fluorination liquid, ensuring the concentration of the coating slurry, the film-forming quality of the coating slurry can be improved, and it is easy to remove during the drying process.

[0042] In an embodiment of the present invention, an amorphous fluororesin is dispersed in a fluorinated liquid. For example, the dispersion is carried out at a preset temperature for a preset time, for example, by stirring, and the stirring speed is, for example, 30 rpm / min to 50 rpm / min, to obtain a stable and transparent coating slurry. Among them, the preset temperature is, for example, 50 °C to 65 °C, and the preset time is, for example, 5 h to 7 h. And the mass ratio of the amorphous fluororesin to the fluorinated liquid is, for example, 1 to 20:80 to 99.

[0043] In an embodiment of the present invention, the coating slurry is coated on the roughened perfluoroether rubber product, for example, by dip coating or electrostatic spraying. Among them, when dip coating is used, the dipping time of the perfluoroether rubber product in the coating slurry is, for example, 1 min to 3 min, to ensure that each position of the perfluoroether rubber product is coated with the coating slurry and ensure the integrity of the coating.

[0044] In an embodiment of the present invention, after coating, the coated perfluoroether rubber product is dried by segmented heating to obtain a perfluoroether rubber sealing assembly. Among them, the segmented heating, for example, includes a first drying stage, a second drying stage, and a third drying stage. In the first drying stage, for example, after coating the coating slurry, a hot air gun is immediately used to blow dry the coating slurry. And in the first drying stage, the distance between the air outlet of the hot air gun and the perfluoroether rubber product is 5 cm to 10 cm, and for example, the perfluoroether rubber product is kept rotating evenly left and right during the drying process by hanging with a nickel wire. At the same time, the position / angle of the gun muzzle is continuously changed to blow air from different directions to ensure uniform drying of each part of the perfluoroether rubber product and form a uniform coating. In this embodiment, for example, an O-ring is hung with a nickel wire with a diameter of 1 mm and the O-ring is immersed in the above-prepared coating slurry. After immersion for 1 min - 3 min, the nickel wire is slowly lifted, and while lifting, the solution on the surface of the O-ring is blown dry with a hot air gun at 140 °C to 160 °C. Blowing dry the solution on the surface of the O-ring with a hot air gun at the moment of lifting can prevent the coating slurry from dripping under the action of gravity and ensure a uniform thickness of the anti-sticking layer formed.

[0045] In an embodiment of the present invention, in the second drying stage, for example, the perfluoroether rubber product that has undergone the first drying stage is dried at a first temperature for a first period of time. The drying temperature is raised from the first temperature to a second temperature, and it is dried at the second temperature for a second period of time to complete the third drying stage. Among them, the second drying stage and the third drying stage are, for example, dried in an oven such as a hot air circulation oven or an electric blast drying oven. The first temperature is, for example, 200°C to 210°C, the first period of time is, for example, 3 min to 8 min, the second temperature is, for example, 280°C to 290°C, the second period of time is, for example, 5 min to 15 min, and the heating rate from the first temperature to the second temperature is, for example, 15°C / min to 20°C / min. After drying, it is placed in a room temperature environment to cool naturally to obtain a perfluoroether rubber sealing assembly. By drying in stages with heating, the thickness uniformity of the anti-sticking layer can be improved, and the quality of the anti-sticking layer can be improved.

[0046] The present invention also provides a perfluoroether rubber sealing assembly with anti-sticking property, which is obtained by using the above preparation method, and the perfluoroether rubber sealing assembly includes a perfluoroether rubber product and an anti-sticking layer. Among them, the perfluoroether rubber product is a product with a preset shape obtained from perfluoroether rubber, the anti-sticking layer is coated on the surface of the perfluoroether rubber product, the anti-sticking layer includes an amorphous fluororesin, and the glass transition temperature of the amorphous fluororesin is greater than or equal to 150°C. In an embodiment of the present invention, the thickness of the anti-sticking layer is, for example, 1 μm to 3 μm, and the transparency of the anti-sticking layer is relatively high. By setting an anti-sticking layer including an amorphous fluororesin with a high glass transition temperature, it has a low friction coefficient and excellent plasma corrosion resistance, can solve the problem of adhesion between the sealing ring and the substrate, and at the same time meet the usage environment requirements of high temperature, plasma, and corrosive gas-liquid media in the semiconductor processing process, which is beneficial to extending the service life of the O-ring in semiconductor processing equipment, etc. When the obtained perfluoroether rubber sealing assembly is in contact with metals and other materials on semiconductor equipment, it has a small adhesion force and exhibits excellent non-sticking property.

[0047] Hereinafter, the present invention will be more specifically explained by citing embodiments, and these embodiments should not be construed as restrictive. Within the scope consistent with the gist of the present invention, appropriate modifications can be made, and they all fall within the technical scope of the present invention.

[0048] Example 1

[0049] A flask containing 99 g of the first fluorinated liquid HFO is placed in a water bath at 60°C. After the liquid temperature reaches 60°C, the magnetic stirring is turned on at a rotation speed of 50 rpm / min, and 1 g of the random copolymer of PDD and TFE is added while stirring, where the PDD content is 87 mol%. After the resin is added, stirring is continued for 6 hours, and the stirring is stopped until a stable transparent solution is formed to obtain a coating slurry, which is left standing for later use.

[0050] The black perfluoroether rubber A214 O-ring is subjected to surface roughening treatment by means of water grinding. Among them, A214 is the O-ring of the American standard AS568 - 214 model, with a roughness of 2 μm. It is ultrasonically cleaned with deionized water and dried. The O-ring is hung with a nickel wire with a diameter of 1 mm, and the O-ring is immersed in the above-prepared coating slurry for 2 minutes. Then, the nickel wire is slowly lifted, and while lifting, the surface of the O-ring is blown with a hot air gun at 150 °C, so that the O-ring rotates uniformly left and right to obtain a smooth-surface O-ring. The above smooth-surface O-ring is placed in a hot air circulation oven for baking. First, it is baked at 204 °C for 5 minutes, then quickly heated to 290 °C at a rate of 20 °C / min, and baked at 290 °C for 10 minutes. It is taken out at high temperature and placed in a room-temperature environment to cool naturally to obtain an O-ring with an anti-sticking layer.

[0051] Example 2

[0052] A flask containing 99 g of the second fluorinated liquid C5 - 18 perfluoroalkane is placed in a water bath at 60 °C. After the liquid temperature reaches 60 °C, magnetic stirring is turned on at a rotation speed of 50 rpm / min, and 1 g of the random copolymer of PDD and TFE is added while stirring, where the PDD content is 87 mol%. After the resin is added, stirring is continued for 6 hours. When a stable transparent solution is formed, stirring is stopped to obtain the coating slurry, which is left standing for later use.

[0053] The black perfluoroether rubber A214 O-ring is subjected to surface roughening treatment by means of water grinding, with a roughness of 2 μm. It is ultrasonically cleaned with deionized water and dried. The O-ring is hung with a nickel wire with a diameter of 1 mm, and the O-ring is immersed in the above-prepared coating slurry for 2 minutes. Then, the nickel wire is slowly lifted, and while lifting, the surface of the O-ring is blown with a hot air gun at 150 °C, so that the O-ring rotates uniformly left and right to obtain a smooth-surface O-ring. The above smooth-surface O-ring is placed in a hot air circulation oven for baking. First, it is baked at 204 °C for 5 minutes, then quickly heated to 290 °C at a rate of 20 °C / min, and baked at 290 °C for 10 minutes. It is taken out at high temperature and placed in a room-temperature environment to cool naturally to obtain an O-ring with an anti-sticking layer.

[0054] Example 3

[0055] A flask containing 92 g of the first fluorinated liquid HFO of brown color is placed in a water bath at 60 °C. After the liquid temperature reaches 60 °C, magnetic stirring is turned on at a rotation speed of 50 rpm / min, and 8 g of the random copolymer of PDD and TFE is added while stirring, where the PDD content is 65 mol%. After the resin is added, stirring is continued for 6 hours. When a stable transparent solution is formed, stirring is stopped to obtain the coating slurry, which is left standing for later use.

[0056] The brown perfluoroether rubber A214 O-ring was surface roughened by water milling to a roughness of 2 μm, ultrasonically cleaned with deionized water and dried. The O-ring was hung with a 1 mm diameter nickel wire and immersed in the above-prepared coating slurry for 2 min. Then, the nickel wire was slowly lifted and rotated at rpm / min. While lifting, the solution on the surface of the O-ring was dried with a 150 °C hot air gun to obtain an O-ring with a smooth surface. The above O-ring with a smooth surface was placed in a hot air circulation oven for baking. First, it was baked at 204 °C for 5 min, then quickly heated to 290 °C at 20 °C / min, baked at 290 °C for 10 min, taken out at high temperature, and placed in a room temperature environment to cool naturally to obtain an O-ring with an anti-stick layer.

[0057] Example 4

[0058] A flask containing 92 g of the second fluorinated liquid C5-18 perfluoroalkane was placed in a water bath at 60 °C. After the liquid temperature reached 60 °C, magnetic stirring was turned on at a speed of 20 rpm / min. While stirring, 8 g of a random copolymer of PDD and TFE was added, where the PDD content was 65 mol%. After the resin was added, stirring was continued for 6 hours. When a stable transparent solution was formed, stirring was stopped to obtain the coating slurry, which was allowed to stand for later use.

[0059] The black perfluoroether rubber A214 O-ring was surface roughened by water milling to a roughness of 2 μm, ultrasonically cleaned with deionized water and dried. The O-ring was hung with a 1 mm diameter nickel wire and immersed in the above-prepared coating slurry for 2 min. Then, the nickel wire was slowly lifted, and while lifting, the surface of the O-ring was blown with a 150 °C hot air gun to make the O-ring rotate uniformly left and right to obtain an O-ring with a smooth surface. The above O-ring with a smooth surface was placed in a hot air circulation oven for baking. First, it was baked at 204 °C for 5 min, then quickly heated to 290 °C at 20 °C / min, baked at 290 °C for 10 min, taken out at high temperature, and placed in a room temperature environment to cool naturally to obtain an O-ring with an anti-stick layer.

[0060] Example 5

[0061] A flask containing 84 g of the first fluorinated liquid HFO was placed in a water bath at 60 °C. After the liquid temperature reached 60 °C, magnetic stirring was turned on at a speed of 50 rpm / min. While stirring, 16 g of a random copolymer of PDD and TFE was added, where the PDD content was 65 mol%. After the resin was added, stirring was continued for 6 hours. When a stable transparent solution was formed, stirring was stopped to obtain the coating slurry, which was allowed to stand for later use.

[0062] The black perfluoroether rubber A214 O-ring is surface roughened by water milling to a roughness of 2 μm, ultrasonically cleaned with deionized water and dried. The O-ring is hung with a 1 mm diameter nickel wire and immersed in the above-prepared coating slurry for 2 min, then the nickel wire is slowly lifted, and while lifting, the surface of the O-ring is blown with a 150 °C hot air gun to make the O-ring rotate uniformly left and right to obtain a smooth-surfaced O-ring. The above smooth-surfaced O-ring is placed in a hot air circulation oven for baking, first baked at 204 °C for 5 min, then quickly heated to 290 °C at 20 °C / min, baked at 290 °C for 10 min, taken out at high temperature, and placed in a room temperature environment to cool naturally to obtain an O-ring with an anti-adhesive layer.

[0063] Example 6

[0064] A flask containing 84 g of the second fluorinated liquid C5-18 perfluoroalkane is placed in a water bath at 60 °C. After the liquid temperature reaches 60 °C, magnetic stirring is turned on at a rotation speed of 50 rpm / min, and 16 g of the random copolymer of PDD and TFE is added while stirring, where the PDD content is 65 mol%. After the resin is added, stirring is continued for 6 hours, and stirring is stopped when a stable transparent solution is formed to obtain a coating slurry, which is left standing for later use.

[0065] The black perfluoroether rubber A214 O-ring is surface roughened by water milling to a roughness of 2 μm, ultrasonically cleaned with deionized water and dried. The O-ring is hung with a 1 mm diameter nickel wire and immersed in the above-prepared coating slurry for 2 min, then the nickel wire is slowly lifted, and while lifting, the surface of the O-ring is blown with a 150 °C hot air gun to make the O-ring rotate uniformly left and right to obtain a smooth-surfaced O-ring. The above smooth-surfaced O-ring is placed in a hot air circulation oven for baking, first baked at 204 °C for 5 min, then quickly heated to 290 °C at 20 °C / min, baked at 290 °C for 10 min, taken out at high temperature, and placed in a room temperature environment to cool naturally to obtain an O-ring with an anti-adhesive layer.

[0066] Comparative Example 1

[0067] The black perfluoroether rubber A214 O-ring is surface roughened by water milling to a roughness of 2 μm, ultrasonically cleaned with deionized water and dried. The commercially available Teflon coating 1 is loaded into a spray bottle and sprayed using compressed air. The sprayed O-ring is placed in an oven at 150 °C for drying for 15 min. Among them, the manufacturer of the Teflon coating 1 is Daikin Industries, Ltd., and the model is TCW / 8879M / 6202.

[0068] Then the above O-ring is placed in a hot air circulation oven and baked at 280 °C for 30 min, taken out at high temperature, and placed in a room temperature environment to cool naturally to obtain a surface-coated O-ring.

[0069] Comparative Example 2

[0070] The black perfluoroether rubber A214 O-ring was surface roughened by water grinding to a roughness of 2 μm, ultrasonically cleaned with deionized water and dried. The O-ring was hung with a 1 mm diameter nickel wire and immersed in commercially available Teflon coating 1. After immersion for 2 min, the nickel wire was slowly lifted, and while lifting, the surface of the O-ring was blown with a 150 °C hot air gun, and the O-ring was rotated left and right at a constant speed to dry.

[0071] The above O-ring was placed in a hot air circulation oven and baked at 300 °C for 10 min, taken out at high temperature, and placed in a room temperature environment to cool naturally to obtain a surface-coated O-ring.

[0072] Comparative Example 3

[0073] The black fluoroether rubber A214 O-ring was not surface roughened. The O-ring was hung with a 1 mm diameter nickel wire and immersed in commercially available Teflon coating 1. After immersion for 2 min, the nickel wire was slowly lifted, and while lifting, the surface of the O-ring was blown with a 150 °C hot air gun, and the O-ring was rotated left and right at a constant speed to dry.

[0074] The above O-ring was placed in a hot air circulation oven and baked at 300 °C for 10 min, taken out at high temperature, and placed in a room temperature environment to cool naturally to obtain a surface-coated O-ring.

[0075] Comparative Example 4

[0076] The black perfluoroether rubber A214 O-ring was surface roughened by water grinding to a roughness of 2 μm, ultrasonically cleaned with deionized water and dried. The O-ring was hung with a 1 mm diameter nickel wire and immersed in commercially available Teflon coating 2. After immersion for 2 min, the nickel wire was slowly lifted, and while lifting, the surface of the O-ring was blown with a 150 °C hot air gun, and the O-ring was rotated left and right at a constant speed to dry. The manufacturer of Teflon coating 2 is DuPont - Chemours in the United States, and the model is Teflon 958G - 303.

[0077] The above O-ring was placed in a hot air circulation oven and baked at 280 °C for 10 min, taken out at high temperature, and placed in a room temperature environment to cool naturally to obtain a surface-coated O-ring.

[0078] Comparative Example 5

[0079] A black perfluoroether rubber A214 O-ring without surface coating treatment.

[0080] In an embodiment of the present invention, the O-rings of the perfluoroether rubber seal assemblies prepared in Examples 1-6 and Comparative Examples 1-5 were tested for their coefficient of friction in accordance with the national standard "GB T 10006-2021", and the test results are shown in Table 1.

[0081] In an embodiment of the present invention, the O-rings of the perfluoroether rubber seal assemblies prepared in Examples 1-6 and Comparative Examples 1-5 were tested for their compression set in accordance with the national standard "GB T 7759.1-2015", and the test results are shown in Table 1.

[0082] In an embodiment of the present invention, 10 O-rings of the perfluoroether rubber seal assemblies prepared in each of the examples and comparative examples were placed in a 304 stainless steel test mold with a roughness not greater than 1.0 μm. The fastening nut was tightened to make the deformation of the O-ring 25%. After being placed at 204 °C for 24 hours, it was taken out, cooled to room temperature first, and after 3 hours, the minimum tensile force required to pull the O-ring from the mold between the stainless steels was measured by a tensile testing machine at a tensile speed of 1 mm / s. The measured value was the adhesion value of the O-ring under this condition. After removing the maximum and minimum values, the average value was taken, and the test results are shown in Table 1.

[0083] In an embodiment of the present invention, the O-rings of the perfluoroether rubber seal assemblies prepared in Examples 1-6 and Comparative Examples 1-5 were placed in an inductively coupled plasma (ICP) device to test the plasma resistance performance of the O-rings of the perfluoroether rubber seal assemblies. The test conditions were: O2 and CF4 were 80 sccm and 80 sccm respectively, the power was 800 W, and when the lower electrode was 100 W, the corresponding bias voltage was 90 V. The evaluation of the plasma resistance performance was the weight loss percentage of A214 before and after the test. The smaller the weight loss percentage, the better the plasma resistance performance of the seal against this gas.

[0084] Table 1. Partial preparation conditions and properties of the perfluoroether rubber seal assemblies in Examples 1-6 and Comparative Examples 1-5

[0085]

[0086] Please refer to Figures 2 to 3 as shown Figure 2 which shows some of the perfluoroether rubber seal assemblies obtained in this application. Among them, the surface of the O-ring is smooth, the anti-adhesive layer is uniformly arranged on the perfluoroether rubber product, and the transparency of the anti-adhesive layer is relatively high. Figure 3 Part A in Figure 3 shows the appearance of the O-ring in Comparative Example 5, Figure 3 Part B in Figure 3Part D shows the appearance of the O-ring in Comparative Example 2. Combining Comparative Examples 1-3 and 5, when the spraying method is used, the coating obtained is thicker than that obtained by dip coating, and the lubricating effect on the O-ring is also slightly worse. At the same time, due to the large coating thickness, the adhesion on the surface of the O-ring is relatively poor, and more coating is lost during the compression set process, resulting in a larger compression set. That is, different coating methods result in different surfaces of the O-ring. When the surface of the O-ring is not roughened, it is difficult to be coated, and the reduction of friction and adhesion is limited.

[0087] Please refer to Figures 4 to 5 as shown in Figure 4 the surface of the mold after the O-ring obtained in Comparative Example 2 has undergone compression set, Figure 5 and the surface of the mold after the O-ring obtained in Example 1 has undergone compression set. Comparing Example 1 and Comparative Example 2, it can be seen that after the O-ring with an anti-adhesive layer obtained by this application has undergone compression set, no obvious residue is seen on the mold, indicating that the anti-adhesive layer has good high-temperature resistance and adhesion. For the O-ring prepared with a commercially available Teflon coating, there is more coating residue on the mold after compression set, and the adhesion between the coating and the O-ring is poor, which is far from the requirements for the cleanliness of equipment and molds during actual use. Therefore, the perfluoroether rubber sealing component obtained by this application can meet the usage requirements of semiconductor equipment, showing excellent non-stickiness, which is beneficial to the cleanliness requirements of semiconductor equipment and prolongs the service life of O-rings in semiconductor processing equipment, etc.

[0088] Please refer to Table 1. Comparing Examples 1-6 and Comparative Example 5, it can be seen that compared with the O-ring without surface treatment, the friction coefficient and the adhesion to metal of the O-ring obtained by this application have decreased significantly, and the plasma tolerance to CF4 and O2 has also been significantly improved. At the same time, the compression set has not changed significantly, and it has a long service life. At the same time, the low adhesion makes it easy to replace, improving the replacement efficiency of the O-ring and ensuring the product yield. Moreover, the anti-adhesive layer prepared with fluororesin 2 has better effects of reducing friction and adhesion and plasma tolerance. With the increase of the fluororesin content, the effects of reducing friction and adhesion and the plasma resistance performance also have a certain improvement. And the coating prepared with the second fluorinated liquid with a high boiling point has a more excellent lubricating effect. The commercially available coating has no significant effect on reducing friction and adhesion and increasing plasma resistance.

[0089] In summary, the present invention provides a perfluoroether rubber sealing component with anti-sticking property, its preparation method and application. By providing an anti-sticking layer including an amorphous fluororesin with a high glass transition temperature, the perfluoroether rubber sealing component has a low friction coefficient, excellent plasma corrosion resistance, a small adhesive force, exhibits excellent non-sticking property, can solve the problem of adhesion between the sealing component and the substrate, and at the same time meets the usage environment requirements of high temperature, plasma, and corrosive gas-liquid media during semiconductor processing, which is beneficial to extending the service life of the perfluoroether rubber sealing component in semiconductor processing equipment, etc. It can ensure the comprehensiveness and uniformity of the coverage of the anti-sticking layer in the perfluoroether rubber sealing component, and can improve the adhesion and firmness of the coating. The perfluoroether rubber sealing component provided in this application has good mechanical properties and excellent high temperature resistance, and can be used in working conditions such as high temperature compression.

[0090] The above description is only a preferred embodiment of the present application and an explanation of the applied technical principle. Those skilled in the art should understand that the scope of the invention involved in the present application is not limited to the technical solution formed by the specific combination of the above technical features, but should also cover other technical solutions formed by any combination of the above technical features or their equivalent features without departing from the inventive concept, such as the technical solutions formed by mutually replacing the above features with the (but not limited to) technical features with similar functions disclosed in the present application.

[0091] Except for the technical features described in the specification, the remaining technical features are well-known to those skilled in the art. To highlight the innovative features of the present invention, the remaining technical features are not described in detail herein.

Claims

1. A preparation method of a perfluoroether rubber sealing component with anti-sticking property, characterized in that, It includes at least the following steps: Mix perfluoroether rubber with a vulcanizing agent to obtain a mixed rubber, and subject the mixed rubber to high-temperature vulcanization to obtain a perfluoroether rubber product; Roughen the surface of the perfluoroether rubber product; Disperse amorphous fluororesin in a fluorinating liquid to obtain a coating slurry; And Coat the coating slurry on the roughened perfluoroether rubber product and perform segmented heating and drying to obtain a perfluoroether rubber sealing assembly.

2. The preparation method of the perfluoroether rubber sealing component with anti-sticking property according to claim 1, characterized in that, The glass transition temperature of the amorphous fluororesin is greater than or equal to 150°C.

3. The preparation method of the perfluoroether rubber sealing component with anti-sticking property according to claim 1, characterized in that, The amorphous fluororesin is an amorphous fluororesin formed by copolymerization of tetrafluoroethylene and other monomers, and the other monomers include perfluoro-1,3-dioxolene monomers, and the perfluoro-1,3-dioxolene monomers include at least one of perfluoro-2,2-dimethyl-1,3-dioxolene or 2,2,4-trifluoro-5-trifluoromethoxy-1,3-dioxole.

4. The preparation method of the perfluoroether rubber sealing assembly with anti-sticking property according to claim 1, wherein the fluorinating liquid includes one of a first fluorinating liquid or a second fluorinating liquid. The first fluorinating liquid is selected from one of commercially available hydrofluorocarbons, perfluorocarbons, hydrofluoroethers or fluoroalkenes with a boiling point of 50°C to 130°C, and the second fluorinating liquid is selected from one of commercially available hydrofluorocarbons, perfluorocarbons, hydrofluoroethers or fluoroalkenes with a boiling point of 130°C to 200°C.

5. The preparation method of the perfluoroether rubber sealing component with anti-sticking property according to claim 1, characterized in that, Disperse the amorphous fluororesin in the fluorinating liquid at a preset temperature. In the coating slurry, the mass ratio of the amorphous fluororesin to the fluorinating liquid is 1 to 20:80 to 99, and the preset temperature is 50°C to 65°C.

6. The preparation method of the perfluoroether rubber sealing assembly with anti-sticking property according to claim 1, characterized in that, The segmented heating and drying includes a first drying stage. After coating the coating slurry, immediately use a hot air gun to blow dry the coating slurry. The distance between the air outlet of the hot air gun and the perfluoroether rubber product is 5 cm to 10 cm, and keep the perfluoroether rubber product rotating evenly during the first drying stage.

7. The preparation method of the perfluoroether rubber sealing assembly with anti-sticking property according to claim 6, characterized in that, The segmented heating and drying further includes: Drying the perfluoroether rubber product that has undergone the first drying stage at a first temperature for a first time; and Raising the temperature from the first temperature to a second temperature and drying at the second temperature for a second time.

8. A perfluoroether rubber sealing assembly with anti-sticking property, characterized in that, Obtained by using the method according to any one of claims 1-7, A perfluoroether rubber product; and An anti-sticking layer coated on the surface of the perfluoroether rubber product, the anti-sticking layer includes amorphous fluororesin, and the glass transition temperature of the amorphous fluororesin is greater than or equal to 150°C.

9. The anti-sticky perfluoroether rubber sealing assembly according to claim 8, characterized in that, The thickness of the anti-sticking layer is 1 μm to 3 μm.

10. A sealing device, characterized in that, Sealing with the perfluoroether rubber sealing assembly with anti-sticking property obtained by using the preparation method according to any one of claims 1-7 or the perfluoroether rubber sealing assembly with anti-sticking property according to any one of claims 8-9.

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