Hole sealing agent and hole sealing method using same

Abstract

The invention belongs to the technical field of ceramic coating repairing, and particularly relates to a hole sealing agent and a hole sealing method using the same. The hole sealing agent provided by the invention comprises a component A and a component B which are independently packaged, the component A comprises epoxy resin and an epoxy reactive diluent; the component B comprises an anhydride curing agent and an accelerant; the epoxy resin comprises alicyclic epoxy resin or a composition of the alicyclic epoxy resin and bisphenol epoxy resin; the alicyclic epoxy resin is one or more of 3, 4-epoxy cyclohexyl formic acid-3 ', 4'-epoxy cyclohexyl methyl ester, hydrogenated bisphenol A epoxy resin and bis ((3, 4-epoxy cyclohexyl) methyl) adipate. The hole sealing agent provided by the invention is good in flowability, high in hole sealing efficiency, capable of being cured at low temperature and good in insulating property.

Description

Technical Field

[0001] This invention belongs to the field of ceramic coating repair technology, specifically relating to a sealing agent and a method for sealing pores using the same. Background Technology

[0002] Due to their excellent high-temperature resistance, corrosion resistance, and wear resistance, ceramics have become the mainstream coating material for semiconductor equipment components. However, due to manufacturing processes, ceramic layers often contain surface pores, blind holes, and even through-holes. The porosity of the coating surface not only affects its corrosion resistance and mechanical properties but also its overall service performance, including insulation, conductivity, magnetism, and wear resistance. In the working environment, corrosive media (air, water, corrosive ions, etc.) can directly reach the substrate interface through these through-holes. Because the potential of the coating material is often higher than that of the substrate material, electrochemical corrosion with a large cathode and small anodic structure occurs at the substrate interface, causing rapid dissolution of the anodic substrate. For surface pores and closed pores, due to the different electrochemical activities of various elements in the coating, electrochemical corrosion easily occurs near the defects, slowly dissolving the pore walls. The pores expand and interconnect, ultimately leading to the rapid accumulation of corrosion products at the substrate interface, causing the coating to fail and detach. Therefore, ceramic coatings must undergo pore-sealing to reduce the porosity of the coating surface, thereby blocking corrosion channels and improving the service life of the coating. At the same time, it can improve the dielectric breakdown strength and dielectric constant of the insulating ceramic coating, thus slowing down the rapid failure of the coating under the action of an electric field.

[0003] The quality of thermal spray coatings is determined by the flight state of the sprayed particles (velocity, melting state, particle size, etc.) and the particle packing state controlled by the spraying distance. Even with high-efficiency plasma spraying technology, optimized process parameters, and spraying materials, which can produce highly dense coatings in the sprayed state, the porosity still remains at 3-8%. Therefore, scholars both domestically and internationally are focusing more on post-treatment for sealing the pores in the coating. Post-treatment for sealing involves using methods such as immersion or application to allow the liquid sealing agent to penetrate as deeply as possible into the bottom of the coating, followed by curing to reduce the coating porosity.

[0004] Sealing methods are mainly divided into organic and inorganic sealing agents. Organic sealing agents have their own advantages and are widely used, but they are volatile and flammable, polluting the environment. Some sealing agents also have relatively poor high-temperature resistance and wear resistance. Therefore, their application is somewhat limited.

[0005] A typical system of organic sealing agents uses epoxy resin or epoxy-modified silicone resin as a binder. It primarily utilizes the high insulation properties of epoxy resin and its excellent adhesion to alumina coatings. However, oxide ceramic insulating coatings prepared by plasma spraying often exhibit defects such as porosity and cracks, severely affecting their insulation performance. Typically, a layer of polymer sealing material is needed to fill these surface defects and prevent conductive media from entering the pores or cracks and forming electrical pathways. However, polymer sealing materials have poor environmental adaptability; long-term exposure to aging media easily leads to aging and failure, resulting in insufficient reliability and ultimately sealing failure, affecting the insulation properties of the ceramic layer.

[0006] To improve the corrosion resistance of ceramic coatings and expand their application range, epoxy resin and silicone resin have been used as sealing agents for pore sealing treatment, which has shown some effectiveness. However, many current sealing agents have high viscosity, complex preparation methods, and high curing temperatures, which are detrimental to the later service life of insulating coatings. To meet the pore sealing requirements of insulating ceramic coatings, it is necessary to develop a sealing material with low viscosity, long working time, good wettability, low shrinkage, and low-temperature curing properties. Summary of the Invention

[0007] The purpose of this invention is to provide a sealing agent and a method for sealing holes using the same. The sealing agent provided by this invention has good fluidity, high sealing efficiency, can be cured at low temperatures, and has good insulation properties.

[0008] To achieve the above objectives, the present invention provides the following technical solution:

[0009] This invention provides a sealing agent comprising individually packaged component A and component B;

[0010] Component A includes epoxy resin and epoxy reactive diluent;

[0011] Component B includes an acid anhydride curing agent and an accelerator; the epoxy resin includes an alicyclic epoxy resin, or a combination of an alicyclic epoxy resin and a bisphenol type epoxy resin.

[0012] The alicyclic epoxy resin is one or more of 3,4-epoxycyclohexylcarboxylic acid-3',4'-epoxycyclohexylmethyl ester, hydrogenated bisphenol A type epoxy resin, and bis((3,4-epoxycyclohexyl)methyl)adipate.

[0013] Preferably, the bisphenol type epoxy resin includes bisphenol A type epoxy resin and / or bisphenol F type epoxy resin.

[0014] Preferably, the epoxy reactive diluent is one or more of C12-14 alkyl glycidyl ether, 1,4-butanediol diglycidyl ether, phenyl glycidyl ether, and o-tolyl glycidyl ether.

[0015] Preferably, the mass ratio of the epoxy reactive diluent to the epoxy resin is 5-20:100; the epoxy value (eq / 100g) of component A is 0.40-0.56, the volatile matter is ≤0.5%, and the room temperature viscosity is ≤2000mPa.S.

[0016] Preferably, the anhydride curing agent is methyltetrahydrophthalic anhydride and / or methylhexahydrophthalic anhydride; the accelerator is an imidazole or tertiary amine accelerator, wherein the imidazole accelerator is one or more of 2-ethyl-4-methylimidazolium, dimethylimidazolium, and diethylimidazolium; and the tertiary amine accelerator is N,N-dimethylbenzylamine and / or 1,8-diazabicyclo[5.4.0]undec-7-enephenol.

[0017] Preferably, the mass ratio of accelerator to anhydride curing agent in component B is 0.1 to 5:100; the room temperature viscosity of component B is ≤50 mPa·s.

[0018] The present invention also provides a method for sealing pores using the sealing agent described above, comprising the following steps:

[0019] Mix component A and component B to obtain the prepared sealing agent;

[0020] The insulating ceramic coated workpiece is immersed in the prepared sealing agent and then dried and cured to obtain the sealed insulating ceramic coated workpiece.

[0021] Preferably, before mixing components A and B, the mixture further includes keeping components A and B at a temperature of 40–60°C for 20–30 minutes.

[0022] Preferably, the soaking time is 2 to 5 hours; the soaking temperature is 40 to 60°C.

[0023] Preferably, the drying and curing temperature is 50–80°C; and the drying and curing time is 6–24 hours.

[0024] The sealing agent of this invention has the properties of low viscosity, good fluidity, and high penetrability. It can not only deeply fill pores of different sizes, but also exhibits minimal volume shrinkage after curing, preventing cracking due to shrinkage. The sealing operation is convenient; after mixing components A and B, multiple coats are not required on the ceramic-coated workpiece (high sealing efficiency). Only soaking is needed. It features low viscosity, a long pot life, extended action time, and improved penetration, achieving excellent sealing results. Furthermore, the alicyclic epoxy resin in the sealing agent improves the aging resistance of the insulating coating, making it suitable for sealing insulating coatings under high temperature and light conditions. Data from the examples show that the sealing agent of this invention exhibits excellent insulation properties on ceramic coatings, increasing the coating impedance to over 1 GΩ·cm after sealing.2 Therefore, the insulation properties of the insulating ceramic coating are also significantly improved.

[0025] Furthermore, the epoxy resins used in this invention are all common industrial products on the market, with inexpensive and readily available raw materials, simple preparation processes, and strong applicability. Therefore, the process of this invention is simple and feasible, and easy to mass-produce. Detailed Implementation

[0026] This invention provides a sealing agent comprising individually packaged component A and component B;

[0027] Component A includes epoxy resin and epoxy reactive diluent;

[0028] Component B includes an acid anhydride curing agent and an accelerator;

[0029] The alicyclic epoxy resin is one or more of 3,4-epoxycyclohexylcarboxylic acid-3',4'-epoxycyclohexylmethyl ester, hydrogenated bisphenol A type epoxy resin, and bis((3,4-epoxycyclohexyl)methyl)adipate.

[0030] In one embodiment of the present invention, the mass ratio of component A to component B in the sealing agent can be 100:80 to 100, specifically 100:80, 100:90 or 100:100.

[0031] In one embodiment of the present invention, the epoxy resin may include an alicyclic epoxy resin or a combination of an alicyclic epoxy resin and a bisphenol type epoxy resin; the alicyclic epoxy resin may be one or more of 3,4-epoxycyclohexylcarboxylic acid-3',4'-epoxycyclohexylmethyl ester, hydrogenated bisphenol A type epoxy resin, and bis((3,4-epoxycyclohexyl)methyl)adipate; the bisphenol type epoxy resin may include bisphenol A type epoxy resin and / or bisphenol F type epoxy resin.

[0032] In one embodiment of the present invention, the epoxy reactive diluent may be one or more of C12-14 alkyl glycidyl ether, 1,4-butanediol diglycidyl ether, phenyl glycidyl ether, and o-tolyl glycidyl ether.

[0033] In one embodiment of the present invention, the mass ratio of the epoxy reactive diluent to the epoxy resin can be 5 to 20:100, specifically 10:90 or 15:85; the epoxy value of component A is 0.40 to 0.56 eq / 100g, the volatile matter is ≤0.5%, and the room temperature viscosity is ≤2000 mPa·s.

[0034] In one embodiment of the present invention, component B may include an anhydride curing agent and an accelerator; the anhydride curing agent may be methyltetrahydrophthalic anhydride and / or methylhexahydrophthalic anhydride;

[0035] In one embodiment of the present invention, the accelerator is an imidazole or tertiary amine accelerator. Specifically, the imidazole accelerator is one or more of 2-ethyl-4-methylimidazolium, dimethylimidazolium, diethylimidazolium, N,N-dimethylbenzylamine, and 1,8-diazabicyclo[5.4.0]undec-7-enephenol.

[0036] In one embodiment of the present invention, the mass ratio of accelerator to anhydride curing agent in component B can be 0.1 to 5:100, specifically 2:98 or 3:97; the room temperature viscosity of component B is ≤50 mPa·s.

[0037] The present invention also provides a method for sealing pores using the sealing agent described above, comprising the following steps:

[0038] Mix component A and component B to obtain the prepared sealing agent;

[0039] The insulating ceramic coated workpiece is immersed in the prepared sealing agent and then dried and cured to obtain the sealed insulating ceramic coated workpiece.

[0040] This invention mixes component A and component B to obtain a prepared sealing agent.

[0041] As one embodiment of the present invention, before mixing components A and B, components A and B are kept at a temperature of 40-60°C for 20-30 minutes; specifically, components A and B can be kept at a temperature of 40-60°C in water or an oven.

[0042] After obtaining the prepared sealing agent, the present invention immerses the insulating ceramic coated workpiece in the prepared sealing agent, and then dries and cures it to obtain the sealed insulating ceramic coated workpiece.

[0043] In one embodiment of the present invention, the insulating ceramic coating includes an Al2O3 ceramic insulating coating; in another embodiment of the present invention, the mixing can be stirring mixing, and the stirring mixing time is 10 to 30 minutes, specifically 10 minutes, 15 minutes, 20 minutes, 25 minutes or 30 minutes.

[0044] In one embodiment of the present invention, the soaking time can be 2 to 5 hours, specifically 2 hours, 3 hours, 4 hours or 5 hours; the soaking temperature can be 40 to 60 degrees Celsius, specifically 40 degrees Celsius, 50 degrees Celsius or 60 degrees Celsius.

[0045] In one embodiment of the present invention, the drying and curing temperature can be 50 to 80°C, specifically 50°C, 60°C, 70°C or 80°C; the drying and curing time can be 6 to 24 hours, specifically 6 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours or 24 hours.

[0046] The sealing agent provided by this invention has the properties of insulation, high voltage resistance, low viscosity, environmental protection, low temperature curing (50-80℃), and resistance to yellowing. It is suitable for sealing pores in Al2O3 ceramic insulating coatings.

[0047] To further illustrate the present invention, the following detailed description of the embodiments is provided in conjunction with the present invention, but these descriptions should not be construed as limiting the scope of protection of the present invention.

[0048] Example 1

[0049] (1) Preparation of sealing agent A: Weigh 10g of bisphenol A type epoxy resin E51, 75g of hydrogenated bisphenol A type epoxy resin, 10g of C12-14 alkyl glycidyl ether and 5g of 1,4-butanediol diglycidyl ether. Keep each weighed component in an oven at 50℃ for 30min. Then stir the above resin at a speed of 300r / min for 30min. The epoxy value of the prepared component A is 0.45eq / 100g and the viscosity at room temperature is 1800mPa.S.

[0050] (2) Preparation of sealing agent B: Weigh 98g of methyltetrahydrophthalic anhydride and 2g of 2-ethyl-4-methylimidazole, and stir the weighed components at a speed of 300r / min for 20min.

[0051] (3) Prepare sealing agent: Mix the above sealing agent A and B at a mass ratio of 1:0.8 and stir at 500 r / min for 15 min at room temperature to make it completely uniform, and obtain sealing agent with a room temperature viscosity of 600 mPa·s.

[0052] (4) Ceramic sheet soaking: Preheat the dry Al2O3 ceramic sheet to 40°C and keep it warm for 30 minutes. Then immerse the ceramic sheet in the above sealing agent for 5 hours at a temperature of 40°C.

[0053] (5) Coating curing: Take out the soaked ceramic parts, wipe off the excess sealing agent on the surface, and put them into the oven for drying and curing. The drying and curing temperature is 80℃ and the curing time is 6 hours.

[0054] Example 2

[0055] Preparation of sealing agent A: Weigh 60g of hydrogenated bisphenol A type epoxy resin, 30g of 3,4-epoxycyclohexylcarboxylic acid-3',4'-epoxycyclohexylmethyl ester, 5g of 1,4-butanediol diglycidyl ether, and 5g of o-tolyl glycidyl ether. Incubate each component in a 50℃ oven for 30min, then stir the resin at 300r / min for 30min. The prepared component A has an epoxy value of 0.56eq / 100g and a room temperature viscosity of 1500mPa·s.

[0056] (2) Preparation of sealing agent B: Weigh 97g of methylhexahydrophthalic anhydride, 1.5g of diethylimidazole and 1.5g of 1,8-diazabicyclo[5.4.0]undec-7-enephenol, and stir the weighed components at a speed of 300r / min for 20min.

[0057] (3) Prepare sealing agent: Mix the above sealing agent A and B in a mass ratio of 1:1, stir at 500 r / min for 15 min at room temperature to make it completely uniform, and obtain sealing agent with a room temperature viscosity of 400 mPa·s.

[0058] (4) Ceramic sheet soaking: Preheat the dry Al2O3 ceramic sheet to 60°C and keep it warm for 30 minutes. Then immerse the ceramic sheet in the above sealing agent for 2 hours at a temperature of 60°C.

[0059] (5) Coating curing: Take out the soaked ceramic parts, wipe off the excess sealing agent on the surface, and put them into the oven for drying and curing. The drying and curing temperature is 60℃ and the curing time is 12 hours.

[0060] Example 3

[0061] Preparation of sealing agent A: Weigh 65g of bisphenol F type epoxy resin F51, 20g of bis((3,4-epoxycyclohexyl)methyl)adipate, 10g of C12-14 alkyl glycidyl ether, and 5g of phenyl glycidyl ether. Incubate each component in a 50℃ oven for 30min, then stir the resin at 300r / min for 30min. The prepared component A has an epoxy value of 0.50eq / 100g and a room temperature viscosity of 1600mPa·s.

[0062] (2) Preparation of sealing agent B: Weigh 97g of methylhexahydrophthalic anhydride, 2g of dimethylimidazole, and 1g of N,N-dimethylbenzylamine. Stir the weighed components at a speed of 300r / min for 20min.

[0063] (3) Preparation of sealing agent: Mix the above sealing agent A and B at a mass ratio of 1:0.9 and stir at 500 r / min for 15 min at room temperature to make it completely uniform, and obtain the sealing agent with a room temperature viscosity of 500 mPa·s.

[0064] (4) Ceramic sheet soaking: Preheat the dry Al2O3 ceramic sheet to 50°C and keep it warm for 30 minutes. Then immerse the ceramic sheet in the above sealing agent for 4 hours at a temperature of 50°C.

[0065] (5) Coating curing: Take out the soaked ceramic parts, wipe off the excess sealing agent on the surface and put them into the oven for drying and curing. The drying and curing temperature is 50℃ and the curing time is 24 hours.

[0066] The present invention tested the impedance modulus of the coatings in Examples 1 to 3 in the low-frequency region (f = 0.1 Hz) under 500 V conditions. The relevant test standards and results are shown in Table 1.

[0067] Table 1 shows the impedance modulus of the coatings in Examples 1-3 in the low-frequency region (f = 0.1 Hz) under 500 V conditions.

[0068] sample Testing Reference Standards / Methods <![CDATA[Before sealing (Ω·cm 2 )]]> <![CDATA[(Ω·cm after sealing hole 2 )]]> Example 1 GB / T39482.3-2020 1.1×10^8 4.53×10^9 Example 2 GB / T39482.3-2020 1.1×10^8 1.97×10^10 Example 3 GB / T39482.3-2020 1.1×10^8 3.36×10^9

[0069] The sealing agent coatings prepared in the above embodiments were subjected to anti-aging tests. The anti-aging test was carried out in a UV aging test chamber in accordance with the standard GB / T14522-2008. After the corresponding irradiation time, the coating gloss index was tested to characterize the anti-aging performance. The results are shown in Table 2.

[0070] Table 2. Gloss of the coatings in Examples 1-3

[0071] Test time 0h 100h 200h 300h 400h 500h 600h Example 1 140.85 136.71 133.81 130.73 129.51 128.19 127.94 Example 2 141.56 137.55 134.83 131.73 130.33 129.26 129.02 Example 3 139.98 135.35 132.56 128.45 127.89 126.58 126.33

[0072] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, and not all embodiments. Other embodiments can be obtained based on these embodiments without creative effort, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A sealing agent, characterized in that, Includes individually packaged components A and B; Component A includes epoxy resin and epoxy reactive diluent; Component B includes an acid anhydride curing agent and an accelerator; the epoxy resin includes an alicyclic epoxy resin, or a combination of an alicyclic epoxy resin and a bisphenol type epoxy resin. The alicyclic epoxy resin is one or more of 3,4-epoxycyclohexylcarboxylic acid-3',4'-epoxycyclohexylmethyl ester, hydrogenated bisphenol A type epoxy resin, and bis((3,4-epoxycyclohexyl)methyl)adipate.

2. The sealing agent as described in claim 1, characterized in that, The bisphenol type epoxy resin includes bisphenol A type epoxy resin and / or bisphenol F type epoxy resin.

3. The sealing agent as described in claim 1, characterized in that, The epoxy reactive diluent is one or more of C12-14 alkyl glycidyl ether, 1,4-butanediol diglycidyl ether, phenyl glycidyl ether, and o-tolyl glycidyl ether.

4. The sealing agent as described in claim 1, characterized in that, The mass ratio of the epoxy reactive diluent to the epoxy resin is 5-20:100; the epoxy value (eq / 100g) of component A is 0.40-0.56, the volatile matter is ≤0.5%, and the room temperature viscosity is ≤2000mPa.S.

5. The sealing agent as described in claim 1, characterized in that, The anhydride curing agent is methyltetrahydrophthalic anhydride and / or methylhexahydrophthalic anhydride; the accelerator is an imidazole or tertiary amine accelerator, wherein the imidazole accelerator is one or more of 2-ethyl-4-methylimidazolium, dimethylimidazolium, and diethylimidazolium; and the tertiary amine accelerator is N,N-dimethylbenzylamine and / or 1,8-diazabicyclo[5.4.0]undec-7-enephenol.

6. The sealing agent as described in claim 1, characterized in that, The mass ratio of accelerator to anhydride curing agent in component B is 0.1 to 5:100; the room temperature viscosity of component B is ≤50 mPa·s.

7. A method for sealing pores using the sealing agent according to any one of claims 1 to 6, comprising the following steps: Mix component A and component B to obtain the prepared sealing agent; The insulating ceramic coated workpiece is immersed in the prepared sealing agent and then dried and cured to obtain the sealed insulating ceramic coated workpiece.

8. The method as described in claim 7, characterized in that, Before mixing components A and B, the mixture further includes keeping components A and B at a temperature of 40–60°C for 20–30 minutes.

9. The method as described in claim 7, characterized in that, The soaking time is 2 to 5 hours; the soaking temperature is 40 to 60°C.

10. The method as described in claim 7, characterized in that, The drying and curing temperature is 50–80°C; the drying and curing time is 6–24 hours.