CN113861840A - Environment-friendly spray quick-drying chromium-free fingerprint-resistant liquid and preparation method thereof - Google Patents
Environment-friendly spray quick-drying chromium-free fingerprint-resistant liquid and preparation method thereof Download PDFInfo
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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Abstract
An environment-friendly spray quick-drying chromium-free fingerprint-resistant liquid is prepared from the following components in parts by weight: 0.6-0.8 part of graphene composite antirust pigment, 41.6-69.8 parts of ethyl acetate, 20.0-25.0 parts of ethanol, 0.6-0.8 part of 3,3, 3-trifluoropropylmethyldimethoxysilane, 3.0-5.0 parts of single-component ceramic resin, 3.0-5.0 parts of double-component ceramic resin and 3.0-5.0 parts of high-hardness organic silicon resin. The environment-friendly spray quick-drying chromium-free fingerprint resistant liquid is applied to a small amount of rusted and oiled workpieces to form a uniform and compact gray or gray black chromium-free fingerprint resistant film, the adhesive force of the film layer is 0 grade, the neutral salt spray test time reaches 108h, the damp and hot resistance test time reaches 240h, the film layer does not soften and fall off at high temperature, and the environment-friendly spray quick-drying chromium-free fingerprint resistant liquid has the functions of resisting oil stains, sweat stains and fingerprints.
Description
Technical Field
The invention belongs to the technical field of metal surface treatment, and particularly relates to an environment-friendly spray quick-drying chromium-free fingerprint-resistant liquid and a preparation method thereof.
Background
The deformed steel bar is a steel product with the largest use amount in the building industry, the yield and the consumption of the deformed steel bar in 2010 are close to 1.6 hundred million tons, which account for about 1/6 of the total yield of the steel, the mechanical property of the deformed steel bar directly determines the safety and the durability of a building structure, currently, developed countries adopt 400 MPaIII-grade deformed steel bars, and China still mainly uses 335 MPaII-grade deformed steel bars.
In order to improve the building safety standard of China, the construction department has clearly stipulated that the high-strength grade III screw thread steel is used for gradually replacing the grade II screw thread steel. Compared with microalloy strengthening and controlled rolling and controlled cooling strengthening, the III-grade screw steel produced by the post-rolling water cooling strengthening technology has the remarkable characteristic of low cost, but the product is easy to rust in the storage and transportation process, so that the appearance quality is poor, the sale is difficult, and economic loss is brought to enterprises. Meanwhile, the performance of the whole concrete structure can be reduced by directly using the deformed steel bar with rust, and the cost and the working procedure are increased by removing rust before use.
The corrosion mechanism of deformed steel bar, complex reaction on the surface of the steel bar during water penetration, and the lambda-Fe generated during the heating and cooling process of the hot rolled steel bar203、Fe304FeO being cubic, especially Fe304The existence of the oxide skin leads the oxide skin to be more compact; the surface of the water-penetrating reinforcing steel bar is made of hydroxyl ferric oxide and lambda-Fe generated by decomposing the hydroxyl ferric oxide203Mainly, loose. The oxidation film of the steel bar is not completely peeled off in the process of penetrating water, so that the electrochemical nonuniformity on the surface of the steel bar is increased (the effect of corroding the battery is strengthened). A large amount of oxide skin is washed away in the water passing process, so that the protection capability is reduced and the rust is easy to generate.
Chinese patent CN202010856926.6 discloses an aqueous environment-friendly fingerprint-resistant working solution for coil steel, which comprises the following components in percentage by weight: 20 to 35 percent of organic/inorganic composite modified resin, 0.1 to 1 percent of corrosion inhibitor, 0.1 to 2 percent of auxiliary agent and the balance of water. According to the invention, graphene oxide is reacted with hydroxyl on a silane coupling agent to form a covalent bond to be tightly combined, so that the graphene oxide modified by silane and the aqueous polymer resin containing the silane coupling agent are more easily dispersed and combined due to the similar and compatible polarities; due to the structure of rich oxygen functional groups on the surface of the graphene oxide, the graphene oxide is easy to generate covalent bonds with hydroxyl functional groups of the water-based polymer resin, so that the bonding force between the graphene oxide and the water-based polymer resin is enhanced, the excellent physical and chemical properties of the graphene can be introduced, and the environment-friendly fingerprint-resistant working solution compounded by the graphene has better corrosion resistance, chemical resistance, electrical conductivity and other properties on the basis of the original material properties. The patent belongs to water-based environment-friendly fingerprint-resistant liquid, is not easy to dry when being constructed on the surface of a workpiece, and needs hot air or far infrared for baking and drying; the use is inconvenient, the water-based environment-friendly fingerprint-resistant industrial liquid needs to be coated on a workpiece, and time and labor are wasted; is not beneficial to the outdoor storage of workpieces (such as steel bars), and the water-based film layer can be washed away by heavy rain and loses the protection effect.
In order to solve the problem that the water-through steel bars are easy to rust, an environment-friendly spray quick-drying chromium-free fingerprint-resistant liquid is needed to be developed, and the agent is constructed on the steel bars in a spray manner, so that a fingerprint-resistant passive film can be formed on the surfaces of the steel bars, and the bond strength of concrete cannot be influenced.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the environment-friendly spray quick-drying chromium-free fingerprint-resistant liquid and the preparation method thereof.
The technical scheme of the invention is as follows: an environment-friendly spray quick-drying chromium-free fingerprint-resistant liquid is prepared from the following components in parts by weight: 0.6-0.8 part of graphene composite antirust pigment, 41.6-69.8 parts of ethyl acetate, 20.0-25.0 parts of ethanol, 0.6-0.8 part of 3,3, 3-trifluoropropylmethyldimethoxysilane, 3.0-5.0 parts of single-component ceramic resin, 3.0-5.0 parts of double-component ceramic resin and 3.0-5.0 parts of high-hardness organic silicon resin.
The preparation method of the graphene composite anti-rust pigment comprises the following steps: adding 2-5 parts by weight of 3-aminopropyltriethoxysilane, 1-4 parts by weight of dimethyldiethoxysilane and 3-6 parts by weight of emulsifier OP-10 into 80-90 parts by weight of water under stirring, uniformly stirring to form mixed slurry, slowly adding 3-7 parts by weight of reduced graphene oxide (the number of layers of the reduced graphene oxide is less than 10, the sheet diameter is less than 10 mu m, and the carbon content is less than 80%) into the mixed slurry under stirring, and uniformly stirring at a low speed of 60-80 ℃ for reaction for 3-7 hours to form reduced graphene oxide slurry; adding 70-90 parts by weight of graphene slurry into a dispersing charging barrel, stirring at the rotating speed of 300-700r/min, slowly adding 5-10 parts by weight of zinc oxide, uniformly stirring, transferring into a sand mill, and grinding for 1-3h to form grinding slurry; diluting 15-20 parts by weight of 80-90% industrial phosphoric acid to 15-25 wt%, heating to 20-30 ℃ in a reaction kettle, slowly adding the grinding slurry into the reaction kettle, heating to 60-70 ℃, reacting for 4-5h to generate a precipitate, centrifugally filtering the precipitate, and washing; and drying the filtered graphene composite anti-rust pigment for 0.5-1h at 110-130 ℃ in an air flow drying manner, and then crushing the dried graphene composite anti-rust pigment to 5-10 mu m to obtain a light gray graphene anti-rust pigment finished product. The dimethyldiethoxysilane is a nonpolar molecule and can uniformly disperse the reduced graphene oxide to form the reduced graphene oxide slurry.
Wherein the water is deionized water.
Wherein the single-component ceramic resin is nano ceramic resin, is a nano zirconia polymer, preferably S6000 single-component ceramic resin of New Nagu material (Hangzhou) Co., Ltd, and has the appearance: a transparent blue phase; net content: 40 percent; viscosity (coating 4 cups): 25; pH value: 7; density: 1.28.
the two-component ceramic resin is a composition of nano ceramic resin (nano zirconia polymer) and high-hardness organic silicon resin (highly-crosslinked polysiloxane with a net structure), the weight ratio of the two resins is 1:1-1.2, S6100 two-component ceramic resin of New Nagu material (Hangzhou) GmbH is preferably selected, and the appearance: a transparent blue phase; net content: 45 percent; viscosity (coating 4 cups): 15; pH value: 7; density: 1.33.
the high-hardness organic silicon resin is preferably S6300 high-hardness organic silicon resin of New Nagu material (Hangzhou) Co, and has the appearance: colorless and transparent; net content: 45 percent; viscosity (coating 4 cups): 15; pH value: 7; density: 1.25.
the preparation method of the environment-friendly spray quick-drying chromium-free fingerprint-resistant liquid comprises the following steps: adding ethyl acetate and ethanol into a reaction kettle, starting stirring, adding the graphene composite antirust pigment, stirring for 1-2 hours, adding the single-component ceramic resin, the double-component ceramic resin and the high-hardness organic silicon resin, stirring for 3-4 hours, adding 3,3, 3-trifluoropropylmethyldimethoxysilane, stirring for 20-30 minutes to obtain the environment-friendly spray quick-drying chromium-free fingerprint-resistant liquid, and packaging by using a spray filling production line to obtain a finished product.
The use method of the environment-friendly spray quick-drying chromium-free fingerprint-resistant liquid comprises the following steps: and (3) uniformly shaking the filling spray from bottom to top, uniformly spraying the filling spray on the surface of a workpiece to be constructed back and forth for 2-3 times, drying the surface of the chromium-free fingerprint-resistant film after 3-5 minutes, and completely drying the chromium-free fingerprint-resistant film after 20-30 minutes.
The formula principle of the environment-friendly spray quick-drying chromium-free fingerprint-resistant liquid is as follows: the ethyl acetate is an important solvent of other components and can volatilize automatically after construction, the ethyl acetate has excellent solubility and quick volatility, the three types of ceramic resins can be dissolved, and the quick volatility can enable the fingerprint-resistant film layer to be quickly self-dried. Ethanol is used as a solvent, is a flatting agent of the chromium-free fingerprint-resistant film layer, and is also a hydrolysis carrier of 3,3, 3-trifluoropropylmethyldimethoxysilane; if the amount of the ethyl acetate is less than that of the ethanol, the self-drying speed of the fingerprint-resistant film layer is reduced, and the fingerprint-resistant film layer has a flow mark or sagging phenomenon; the single-component ceramic resin, the double-component ceramic resin and the high-hardness organic silicon resin are main film forming substances of the chromium-free fingerprint-resistant film, and the chromium-free fingerprint-resistant film is high in hardness, fingerprint-resistant and high-temperature-resistant after film forming; the graphene composite antirust pigment is a film forming additive, and is filled in pores of a chromium-free fingerprint-resistant film, so that the adhesion and corrosion resistance of the film are greatly enhanced, zinc dihydrogen phosphate and zinc phosphate generated by zinc oxide and phosphoric acid are stronger anticorrosive materials, wherein the zinc dihydrogen phosphate reacts with a base material to form a film, and the zinc phosphate covers the surface of the base material to resist atmospheric corrosion; 3,3, 3-trifluoropropylmethyldimethoxysilane is used as a cross-linking agent, and is cross-linked with single-component ceramic resin, double-component ceramic resin and high-hardness organic silicon resin, so that the uniformity and compactness of the chromium-free fingerprint-resistant film are improved, and the damp-heat resistant time is prolonged.
The environment-friendly spray quick-drying chromium-free fingerprint-resistant liquid has the following beneficial effects: the environment-friendly spray quick-drying chromium-free fingerprint-resistant liquid is applied to a small amount of rusted and oiled workpieces to form a uniform and compact gray or gray black chromium-free fingerprint-resistant film, the adhesive force of the film layer is 0 grade, the neutral salt spray test time reaches 108h, the damp and hot resistance test time reaches 240h, the film layer does not soften and fall off at high temperature, and the environment-friendly spray quick-drying chromium-free fingerprint-resistant liquid has the functions of resisting oil stains, sweat stains and fingerprints.
Detailed Description
The preparation method of the graphene composite anti-rust pigment in the embodiment comprises the following steps:
the preparation method of the graphene composite antirust pigment comprises the following steps: adding 3g of 3-aminopropyltriethoxysilane, 2g of dimethyldiethoxysilane and 4g of OP-10 into 85g of deionized water under stirring, uniformly stirring to form mixed slurry, slowly adding 5g of reduced graphene oxide (the number of layers of the reduced graphene oxide is less than 10, the sheet diameter is less than 10 mu m, and the carbon content is less than 80%) into the mixed slurry under stirring, uniformly stirring at a low speed of 70 ℃ for 5 hours to form reduced graphene oxide slurry, adding 80g of the graphene slurry into a dispersing cylinder, stirring at a rotating speed of 500r/min, slowly adding 8g of zinc oxide with the purity of more than 99.5%, uniformly stirring, transferring into a sand mill, and grinding for 2 hours to form ground slurry; diluting 16g of 85% industrial phosphoric acid to 20 wt%, heating to 30 ℃ in a reaction kettle, slowly adding the grinding slurry into the reaction kettle, heating to 60 ℃, reacting for 3.5 hours to generate a precipitate, and centrifugally filtering and washing the precipitate; and drying the filtered graphene composite anti-rust pigment for 0.5h at 120 ℃ in an air flow drying mode, and then crushing the dried graphene composite anti-rust pigment to 5-10 mu m to obtain a light gray graphene anti-rust pigment finished product.
In the embodiment, the single-component ceramic resin is S6000 single-component ceramic resin of new nano-grain materials (hang state) limited, the two-component ceramic resin is S6100 two-component ceramic tree of new nano-grain materials (hang state) limited, and the high-hardness organic silicon resin is S6300 high-hardness organic silicon resin of new nano-grain materials (hang state) limited.
The inventive examples and comparative examples are shown in Table 1 (percent amounts), wherein comparative example 2 replaces ethyl acetate with methyl acetate, otherwise the same as example 3; comparative example 3 ethanol was methanol, and the rest was the same as in example 3.
TABLE 1
The preparation method of the graphene composite anti-rust pigment in the comparative example 4 is as follows (dimethyl diethoxysilane is replaced by 3,3, 3-trifluoropropylmethyldimethoxysilane), and the rest is the same as that in the example 2: the preparation method of the graphene composite antirust pigment comprises the following steps: adding 3g of 3-aminopropyltriethoxysilane, 2g of 3,3, 3-trifluoropropylmethyldimethoxysilane and 4g of OP-10 into 85g of deionized water under stirring, uniformly stirring to form mixed slurry, slowly adding 5g of reduced graphene oxide (the number of layers of the reduced graphene oxide is less than 10, the sheet diameter is less than 10 mu m, and the carbon content is less than 80%) into the mixed slurry under stirring, uniformly stirring at a low speed of 70 ℃ for 5 hours to react to form reduced graphene oxide slurry, adding 80g of graphene slurry into a dispersing cylinder, stirring at a rotating speed of 500r/min, slowly adding 8g of zinc oxide with the purity of more than 99.5%, uniformly stirring, transferring into a sand mill, and grinding for 2 hours to form ground slurry; diluting 16g of 85% industrial phosphoric acid to 20 wt%, heating to 30 ℃ in a reaction kettle, slowly adding the grinding slurry into the reaction kettle, heating to 60 ℃, reacting for 3.5 hours to generate a precipitate, and centrifugally filtering and washing the precipitate; and drying the filtered graphene composite anti-rust pigment for 0.5h at 120 ℃ in an air flow drying mode, and then crushing the dried graphene composite anti-rust pigment to 5-10 mu m to obtain a light gray graphene anti-rust pigment finished product.
The preparation method of the graphene composite anti-rust pigment in the comparative example 5 (the addition amount of the industrial phosphoric acid is doubled compared with the example) is as follows, and the rest is the same as the example 2: adding 3g of 3-aminopropyltriethoxysilane, 2g of dimethyldiethoxysilane and 4g of OP-10 into 85g of deionized water under stirring, uniformly stirring to form mixed slurry, slowly adding 5g of reduced graphene oxide (the number of layers of the reduced graphene oxide is less than 10, the sheet diameter is less than 10 mu m, and the carbon content is less than 80%) into the mixed slurry under stirring, uniformly stirring at a low speed of 70 ℃ for 5 hours to form reduced graphene oxide slurry, adding 80g of the graphene slurry into a dispersing cylinder, stirring at a rotating speed of 500r/min, slowly adding 8g of zinc oxide with the purity of more than 99.5%, uniformly stirring, transferring into a sand mill, and grinding for 2 hours to form ground slurry; diluting 32g of 85% industrial phosphoric acid to 20 wt%, heating to 30 ℃ in a reaction kettle, slowly adding the grinding slurry into the reaction kettle, heating to 60 ℃, reacting for 3.5 hours to generate a precipitate, and centrifugally filtering and washing the precipitate; and drying the filtered graphene composite anti-rust pigment for 0.5h at 120 ℃ in an air flow drying mode, and then crushing the dried graphene composite anti-rust pigment to 5-10 mu m to obtain a light gray graphene anti-rust pigment finished product.
The preparation method of the graphene composite anti-rust pigment in the comparative example 6 (the addition amount of the industrial phosphoric acid is reduced by half compared with the example) is as follows, and the rest is the same as the example 2: adding 3g of 3-aminopropyltriethoxysilane, 2g of dimethyldiethoxysilane and 4g of OP-10 into 85g of deionized water under stirring, uniformly stirring to form mixed slurry, slowly adding 5g of reduced graphene oxide (the number of layers of the reduced graphene oxide is less than 10, the sheet diameter is less than 10 mu m, and the carbon content is less than 80%) into the mixed slurry under stirring, uniformly stirring at a low speed of 70 ℃ for 5 hours to form reduced graphene oxide slurry, adding 80g of the graphene slurry into a dispersing cylinder, stirring at a rotating speed of 500r/min, slowly adding 8g of zinc oxide with the purity of more than 99.5%, uniformly stirring, transferring into a sand mill, and grinding for 2 hours to form ground slurry; diluting 8g of 85% industrial phosphoric acid to 20 wt%, heating to 30 ℃ in a reaction kettle, slowly adding the grinding slurry into the reaction kettle, heating to 60 ℃, reacting for 3.5 hours to generate a precipitate, and centrifugally filtering and washing the precipitate; and drying the filtered graphene composite anti-rust pigment for 0.5h at 120 ℃ in an air flow drying mode, and then crushing the dried graphene composite anti-rust pigment to 5-10 mu m to obtain a light gray graphene anti-rust pigment finished product.
The formulations of comparative examples 4-6 are shown in Table 2.
TABLE 2
The preparation method of the environment-friendly spray quick-drying chromium-free fingerprint-resistant liquid comprises the following steps:
adding ethyl acetate and ethanol into a reaction kettle, starting stirring, adding the graphene composite antirust pigment, stirring for 2 hours, adding the single-component ceramic resin, the double-component ceramic resin and the high-hardness organic silicon resin, stirring for 3 hours, adding 3,3, 3-trifluoropropylmethyldimethoxysilane, stirring for 30 minutes to obtain the environment-friendly spray quick-drying chromium-free fingerprint-resistant liquid, and packaging by using a spray filling production line to obtain a finished product.
The application method of the environment-friendly spray quick-drying chromium-free fingerprint-resistant liquid comprises the following steps:
the filling spray is uniformly shaken from bottom to top, and is uniformly sprayed to the surface of a workpiece to be constructed back and forth for 3 times, the surface of the chromium-free fingerprint-resistant film is dried after 5 minutes, and the chromium-free fingerprint-resistant film is completely dried after 20 minutes, wherein the used construction workpieces are as follows: and (4) twisted steel bars.
The performances of the above examples and comparative examples are shown in tables 3 and 4, and the bond stress between the steel bar surface and the reinforced concrete before the formation of the fingerprint-resistant passive film is 80kg/cm2。
TABLE 3
TABLE 4
The test methods for various performance indexes are shown in Table 5.
TABLE 5
It can be seen from comparative example 1 that the addition of the graphene composite anti-rust pigment plays an important role in corrosion resistance and grip strength, and from comparative examples 5 and 6, the addition of phosphoric acid in the preparation process of the graphene composite anti-rust pigment can affect the contents of generated zinc dihydrogen phosphate and zinc phosphate, and too much phosphoric acid can affect the performances of the fingerprint-resistant passive film formed by the fingerprint solution, such as corrosion resistance, grip strength and the like.
Claims (8)
1. An environment-friendly spray quick-drying chromium-free fingerprint-resistant liquid is characterized by being prepared from the following components in parts by weight: 0.6-0.8 part of graphene composite antirust pigment, 41.6-69.8 parts of ethyl acetate, 20.0-25.0 parts of ethanol, 0.6-0.8 part of 3,3, 3-trifluoropropylmethyldimethoxysilane, 3.0-5.0 parts of single-component ceramic resin, 3.0-5.0 parts of double-component ceramic resin and 3.0-5.0 parts of high-hardness organic silicon resin.
2. The environment-friendly spray quick-drying chromium-free fingerprint-resistant liquid as claimed in claim 1, wherein the preparation method of the graphene composite anti-rust pigment is as follows: adding 2-5 parts by weight of 3-aminopropyltriethoxysilane, 1-4 parts by weight of dimethyldiethoxysilane and 3-6 parts by weight of emulsifier OP-10 into 80-90 parts by weight of water under stirring, uniformly stirring to form mixed slurry, slowly adding 3-7 parts by weight of reduced graphene oxide into the mixed slurry under stirring, and uniformly stirring at a low speed of 60-80 ℃ for reaction for 3-7 hours to form reduced graphene oxide slurry; adding 70-90 parts by weight of graphene slurry into a dispersing charging barrel, stirring, then adding 5-10 parts by weight of zinc oxide, uniformly stirring, transferring into a sand mill, and grinding for 1-3 hours to form grinding slurry; diluting 80-90 wt% industrial phosphoric acid 15-20 parts by weight to 15-25 wt%, heating to 20-30 deg.C in a reaction kettle, slowly adding the ground slurry into the reaction kettle, heating to 60-70 deg.C, reacting for 4-5h, centrifuging, filtering, and washing; and drying the graphene composite anti-rust pigment obtained by filtering, and then crushing to obtain a light gray graphene anti-rust pigment finished product.
3. The environment-friendly spray quick-drying chromium-free fingerprint-resistant liquid as claimed in claim 2, wherein the water is deionized water.
4. The environment-friendly spray quick-drying chromium-free fingerprint-resistant liquid as claimed in claim 1, wherein the single-component ceramic resin is a nano ceramic resin.
5. The environment-friendly spray quick-drying chromium-free fingerprint-resistant liquid as claimed in claim 1, wherein the two-component ceramic resin is a composition of nano ceramic resin and high hardness silicone resin.
6. The environment-friendly spray quick-drying chromium-free fingerprint-resistant liquid as claimed in claim 5, wherein the weight ratio of the nano ceramic resin to the high hardness silicone resin is 1 (1-1.2).
7. The environment-friendly spray quick-drying chromium-free fingerprint-resistant liquid as claimed in claim 1, wherein the high hardness silicone resin is S6300 high hardness silicone resin from New Nagu Material Co.
8. The preparation method of the environment-friendly spray quick-drying chromium-free fingerprint-resistant liquid according to claim 1, which is characterized by sequentially comprising the following steps: adding ethyl acetate and ethanol into a reaction kettle, starting stirring, adding the graphene composite antirust pigment, stirring for 1-2 hours, adding the single-component ceramic resin, the double-component ceramic resin and the high-hardness organic silicon resin, stirring for 3-4 hours, adding 3,3, 3-trifluoropropylmethyldimethoxysilane, stirring for 20-30 minutes to obtain the environment-friendly spray quick-drying chromium-free fingerprint-resistant liquid, and packaging by using a spray filling production line to obtain a finished product.
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PCT/CN2021/127829 WO2023070644A2 (en) | 2021-10-28 | 2021-11-01 | Environmentally friendly spray quick-drying chrome-free fingerprint-resistant liquid and preparation method therefor |
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CN116410639A (en) * | 2023-04-18 | 2023-07-11 | 上海耀岩化学品有限公司 | Quick-drying chromium-free fingerprint-resistant liquid for galvanized steel sheet |
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Application publication date: 20211231 |