CN109183053B - Flexible treatment liquid and method for treating pull ring material by using same - Google Patents
Flexible treatment liquid and method for treating pull ring material by using same Download PDFInfo
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- CN109183053B CN109183053B CN201811092692.1A CN201811092692A CN109183053B CN 109183053 B CN109183053 B CN 109183053B CN 201811092692 A CN201811092692 A CN 201811092692A CN 109183053 B CN109183053 B CN 109183053B
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- C—CHEMISTRY; METALLURGY
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- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
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- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/22—Light metals
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/56—Treatment of aluminium or alloys based thereon
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
- C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/16—Pretreatment, e.g. desmutting
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/24—Chemical after-treatment
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Abstract
The invention discloses a flexible treatment fluid and a method for treating a ring-pulling material by using the same, wherein the raw materials comprise magnesium fluoride, sodium tripolyphosphate, fluorozirconic acid, sodium fluosilicate, hydrochloric acid, nitric acid, phosphoric acid, vinyl triacetoxysilane, sulfuric acid, calcium nitrate, water, dialkyl peroxide, peroxydicarbonate, epoxypropyl acrylate, nano-silica and aluminum oxide, and the flexible treatment fluid is reasonably proportioned, so that the problem of high passivation toxicity of the traditional hexavalent chromium is solved, the problem of low chromium-free passivation toxicity but poor corrosion resistance is solved, the problems of complex treatment and poor adhesion of a liquid medicine used when an organic film is coated on the surface of an inorganic film in a composite passivation process are solved, and the flexible treatment fluid has good corrosion resistance, good fingerprint resistance, strong adhesion, safety, no toxicity and simple process, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the field of metal material surface treatment, and particularly relates to a flexible treatment liquid and a method for treating a pull ring material by using the same.
Background
The pull ring material is mainly processed by an aluminum base material, the thickness of the pull ring material is 0.26-0.46 mm, and in order to improve the corrosion resistance and the oxidation resistance of the pull ring material, the pull ring material is passivated.
At present, chromate containing hexavalent chromium is adopted for passivation of tin plates in domestic and foreign industrial production, but the hexavalent chromium has great pollution to the environment, is a highly toxic substance, has strong carcinogenic effect on human bodies, and is very harmful to human bodies and the environment, particularly, the application of the tab ring material is generally applied to pop cans of food and beverage, can cause irreversible damage to the human bodies after long-term use, trivalent chromium passivation solution appears on the market at present, although the toxicity of the trivalent chromium is much lower than that of the hexavalent chromium, the trivalent surface passivation treatment is greatly limited along with the improvement of national requirements on the environment and food safety, and the trivalent chromium is also toxic, and still has potential safety hazard when being used for food packaging; meanwhile, the traditional pull ring material adopts a chromium passivation process, the metal surface of the aluminum alloy contains chromium, an organic coating needs to be coated on the base material after the base material is passivated to isolate food from the base material, the process is complex, natural gas is needed to be heated and dried in the organic film coating process, and a large amount of carbon emission is generated. And simultaneously, a large amount of VOCS is generated to be processed in an environment-friendly way.
If the passivation process is not carried out in the processing process of the pull ring material, the damage of the toxicity of chromium to a human body can be reduced, however, the finish and the ductility of the pull ring material are not enough in the forming processing process, so that the pull ring material is extremely easy to damage after being formed to achieve the effect of protecting a base material, the processing is difficult, the adhesion force to coating is not enough, and the mechanical property of the pull ring material cannot be ensured.
Therefore, the research for searching hexavalent chromium substitutes is particularly important, and the current research in the aspects of trivalent chromium passivation and chromium-free passivation in China has made a certain progress, but no substitute which can be compared with hexavalent chromium is developed, and meanwhile, certain gap exists between the trivalent chromium passivation and the hexavalent chromium passivation in many aspects: the trivalent chromium passivation film has poor corrosion resistance, the appearance color of the film is not bright-colored than that of a hexavalent chromium passivation film, and the trivalent chromium passivation process is unstable, so that the operation difficulty is increased, and the quality of a conversion film is also influenced.
Further, in the case of using a tab material for a can lid, not only a process problem but also a safety problem are required to be considered in handling, and a precoat material coated with a polyester resin is used for some can lids, but also corrosion resistance is not high because corrosion is induced by ions due to the components of the content of the precoat material itself even though the precoat material itself of the polyester resin is not problematic because adhesion of the polyester resin is reduced in highly processed portions such as a can body portion and a can lid score line portion, or corrosion and adhesion of a crack portion due to impact such as dropping of a can are reduced.
In general, chromium-free treatment for containers or food applications is carried out on tin-plated steel sheets as a base material, and the treatment for container applications using aluminum substrates has been studied little, and if the method for treating tin-plated steel sheets is applied to aluminum substrates, the corrosion resistance is insufficient in the method for forming an organic-inorganic composite coating film containing an organic compound containing carbon as a main component, a phosphorus compound, and a zirconium or titanium compound; in the method of forming a surface treatment layer mainly composed of an inorganic substance on the surface of an aluminum substrate and forming an organic surface treatment layer mainly composed of an aqueous phenol resin thereon, the steps are complicated, and the waste liquid treatment after the use of the chemical solution is complicated; in the method using the anodic oxidation treatment, although the first adhesion is good, there is a tendency that the adhesion is lowered by the sterilization treatment after the filling of the content, and in addition, the heat exchange equipment for cooling the treatment liquid, the large-capacity power supply, and the like are costly, and the treatment requires a large amount of electric power during the operation, so that there is a problem that the cost is high; substrates such as aluminum foil are relatively thin, and it is considered that the flexibility of the aluminum substrate cannot be reduced by the treatment in consideration of not only the corrosion resistance and the adhesion but also the adverse effect due to the contact with the human body during the treatment process.
Disclosure of Invention
The invention provides a method for flexibly treating a pull ring material, which solves the problems of toxicity generated by a passivation film, poor safety, pollution caused by coating an organic layer, complex process, non-corrosion resistance of the pull ring material and high cost in the traditional pull ring material production process in the background technology.
The specific technical scheme is as follows:
a flexible treatment fluid comprises the following raw materials: magnesium fluoride, sodium tripolyphosphate, fluozirconic acid, sodium fluosilicate, hydrochloric acid, nitric acid, phosphoric acid, vinyl triacetoxysilane, sulfuric acid, calcium nitrate, water, dialkyl peroxide, peroxydicarbonate, glycidyl acrylate, nano-silica and aluminum oxide.
Preferably, the feed comprises the following raw materials in parts by weight: 98-100 parts of magnesium fluoride, 10-30 parts of sodium tripolyphosphate, 10-30 parts of fluozirconic acid, 23-25 parts of sodium fluosilicate, 45-50 parts of hydrochloric acid, 10-30 parts of nitric acid, 120 parts of phosphoric acid, 10-30 parts of vinyl triacetoxysilane, 30-40 parts of sulfuric acid, 30-50 parts of calcium nitrate, 250 parts of water 200, 15-25 parts of dialkyl peroxide, 20-25 parts of peroxydicarbonate, 35-40 parts of epoxypropyl acrylate, 40-45 parts of nano silicon dioxide and 25-30 parts of aluminum oxide.
Preferably, the method for processing the pull ring material by the flexible processing liquid comprises the following steps: carrying out alkali washing on the base material, and then washing with water for three times; mixing and stirring magnesium fluoride, fluorozirconic acid and sodium fluosilicate in corresponding parts for 30-40min to obtain a flexible treatment solution A, immersing the washed substrate in the flexible treatment solution A for 1-2h, taking out and drying; uniformly mixing sulfuric acid, dialkyl peroxide and peroxydicarbonate to obtain a flexibilized treatment solution B, coating the flexibilized treatment solution B on a dried base material, dissolving calcium nitrate in water, adding nitric acid, dissolving alumina in the pre-mixed solution, adding hydrochloric acid and phosphoric acid, adding water, uniformly stirring to obtain a flexibilized treatment solution C, and performing cathode electrolysis treatment on the base material in the flexibilized treatment solution C; stirring sodium tripolyphosphate, vinyl triacetoxysilane, epoxypropyl acrylate and nano silicon dioxide in a stirrer for 30-40min to prepare a flexible treatment solution D, and filtering with a 200-mesh filter screen for later use; setting the temperature of the flexible surface coating room at 20 ℃, adding the filtered flexible treatment liquid D into a trough of coating equipment, and coating; and after coating, air-drying and curing to obtain the treated pull ring material.
Preferably, the alkali washing operation comprises the following steps: conveying the base material to a first lye tank through a squeezing roller, carrying out normal-temperature spraying alkali washing, controlling the spraying pressure at 0.1-0.5Mpa, and washing for 9-12 minutes; and then conveying to a second alkali solution tank, heating to 45-50 ℃, and carrying out second alkali cleaning for 6-10 minutes.
Preferably, the alkali liquor used in the alkali washing comprises the following components: 9-10 parts of sodium gluconate, 6-8 parts of sodium carbonate, 7-10 parts of sodium hydroxide, 3-5 parts of fatty alcohol-polyoxyethylene ether, 6-8 parts of sodium diethylenetriamine pentaacetate, 1-3 parts of fatty alcohol-polyoxyethylene polyoxypropylene ether and 2-6 parts of sodium borate.
Preferably, the three-time water washing operation is as follows: and (3) washing the base material subjected to alkali washing by using first water, then washing by using second water, wherein the conductivity of water adopted in the second water washing is 50-80S/m, and then washing by using third ultrasonic wave, the conductivity of the adopted water is 10-50S/m, wherein the water temperature during washing is controlled at 30-40 ℃.
Preferably, the rotation speed of the belt roller is set to 60r/min, the rotation speed of the coating roller is set to 40r/min, and the rotation speed of the metering roller is set to 65r/min when the flexibilizing treatment liquid D is applied.
Preferably, the air-drying curing conditions are as follows: air and low-pressure nitrogen are mixed in a wind mixing chamber to form cooling wind with the temperature of 25-28 ℃, the humidity of 70-75% and the oxygen content of less than or equal to 8%, and the cooling wind is dried and solidified for 30-60 s.
Preferably, the thickness of the flexible film of the treated pull tab material is 15-17 μm.
Has the advantages that:
1. the flexible treatment liquid adopted by the invention is reasonably proportioned, so that the problem of high passivation toxicity of the traditional hexavalent chromium is solved, the problem of low passivation toxicity but poor corrosion resistance of the chromium-free passivation can be solved, the problems of complex treatment and poor adhesion of liquid medicine used when an organic film is coated on the surface of an inorganic film in a composite passivation process can be solved, and the flexible treatment liquid has good corrosion resistance, fingerprint resistance, strong adhesion, safety, no toxicity and simple process, and is suitable for industrial production.
2. The alkali liquor is prepared by adopting sodium gluconate, sodium carbonate, sodium hydroxide, fatty alcohol-polyoxyethylene ether, diethylenetriamine pentaacetic acid, fatty alcohol-polyoxyethylene polyoxypropylene ether and sodium borate according to a special proportion, can be subjected to saponification reaction with animal and vegetable oil adhered to the surface of a substrate and is well dissolved in a cleaning agent, the sodium carbonate softens the hardness of water, an alkaline buffer environment is provided, dirt is dispersed, and the redeposition and attachment of the dirt are prevented, and the diethylenetriamine pentaacetic acid as a chelating agent can form a coordination compound with metal ions, so that the possibility that the metal ions and fatty acid formed by saponification of grease are combined into metal soap is reduced, and the cleaning and decontamination capability is enhanced.
3. The method comprises the following steps of immersing a base material in a flexible treatment liquid A obtained by mixing and stirring magnesium fluoride, fluozirconic acid and sodium fluosilicate, quickly adsorbing the base material on the surface of the base material, and drying the base material by a drying box, wherein when the base material is extracted from a solution, an adsorption layer attached to the surface of the base material is firmer, when a sample is damaged, the newly formed surface of elemental aluminum is in a state with higher surface energy and can be regarded as an adsorbent with stronger adsorption capacity, and at the moment, the surface of the aluminum can spontaneously adsorb various adsorbents to reduce the surface energy, so that the flexible treatment liquid A is transferred to the surface of the aluminum as the adsorbent, the corrosion of the damaged part is relieved, the corrosion speed is reduced, and the slow release effect is achieved; meanwhile, the magnesium fluoride can increase the surface tension of the electrolyte, which plays an important role in reducing the redissolution loss of aluminum; in addition, the drying box uses a mechanical hand to grab the material, the material is placed on the belt, and the material is conveyed into the drying room through the belt to be dried, so that the full-automatic operation of drying the aluminum sheet is realized, manual operation is not needed, and the production cost and the amount of manual labor are effectively reduced.
4. The sulfuric acid, the dialkyl peroxide and the peroxydicarbonate are uniformly mixed to obtain a flexible treatment solution B, the peroxide group contained in the flexible treatment solution B has certain ion selectivity and can selectively exclude the adsorption of corrosive ions, meanwhile, the sulfuric acid, the dialkyl peroxide and the peroxydicarbonate are mixed to have good affinity, compatibility and complementarity, and after the flexible treatment solution A is soaked and dried, a protective film is formed on the flexible treatment solution A to improve the capability of blocking corrosive media, so that the protective performance of a film layer is improved; in addition, the flexible liquid A and the flexible liquid B act together to better cover the surface of the aluminum base material, so that the signal intensity of the aluminum is reduced, the atom percentage content is reduced, and various performance indexes including corrosion resistance of the pull ring material are improved.
5. According to the invention, fluozirconic acid, hydrochloric acid, nitric acid and phosphoric acid are used, calcium nitrate is firstly dissolved in water, nitric acid is added, alumina is then dissolved in a pre-mixed solution, hydrochloric acid and phosphoric acid are added, water is added, and the mixture is uniformly stirred to obtain a flexible treatment solution C, a calcium compound is used as a hole sealing agent, so that the gaps of organic macromolecules in the flexible treatment solution B are filled, the film is more compact, the alumina forms a compact film to cover the surfaces of the organic macromolecules, and the problem of poor performance caused by mutual dissolution of raw materials possibly caused by the simultaneous use of a plurality of acids is avoided; the flexible treatment liquid contains acid radical ions, so that the membrane has negative charges, and can react with aluminum to form insoluble compounds to be deposited on the surface.
6. Stirring sodium tripolyphosphate, vinyl triacetoxysilane, epoxypropyl acrylate and nano silicon dioxide in a stirrer for 30-40min to prepare flexible treatment liquid D, filtering with a 200-mesh filter screen to uniformly distribute the solution, and fully coating the flexible treatment liquid A, B, C with a coating layer by layer to prevent volatile substances from escaping from the coating; the nano silicon dioxide is adsorbed in the three-dimensional skeleton structure of the coating to play a role in physical isolation, and meanwhile, the interconnection of chemical bonds among silane molecules enables silane to form a compact, cross-linked and three-dimensional spatial reticular silane film with a certain thickness, so that the coagulation effect is weakened, and the corrosion resistance of the pull ring material is improved.
Drawings
FIG. 1 is a front view of a drying box;
FIG. 2 is a schematic structural view of a robot;
FIG. 3 is a schematic view of the process of applying the flexible treatment fluid D;
the reference numerals have the meanings:
1. the automatic coating machine comprises a drying room, 2. a conveying device, 3. a manipulator, 4. a driving wheel, 5. a driven wheel, 6. a belt, 7. a feeding conveying belt, 8. a feeding opening, 21. a base material, 31. a cylinder B, 32. a sliding rail, 33. a cylinder A, 34. a guide rod, 35. a linear bearing, 36. a sliding block, 37. a connecting block, 38. a mounting plate, 39. a suction cup, 9-a back backup roller, 10-a coating roller, 11-a metering roller, 12-a belt roller, 13-a belt, 14 a motor, 15-a trough and 16-a belt pulley.
Detailed Description
Example (b): the embodiments of the present invention will be described in detail with reference to the accompanying drawings.
Example 1:
the flexible treatment liquid comprises the following raw materials in parts by weight: 98 parts of magnesium fluoride, 25 parts of sodium tripolyphosphate, 30 parts of fluozirconic acid, 24 parts of sodium fluosilicate, 47 parts of hydrochloric acid, 30 parts of nitric acid, 115 parts of phosphoric acid, 15 parts of vinyl triacetoxysilane, 30 parts of sulfuric acid, 40 parts of calcium nitrate, 210 parts of water, 25 parts of dialkyl peroxide, 20 parts of peroxydicarbonate, 36 parts of epoxypropyl acrylate, 44 parts of nano-silica and 27 parts of aluminum oxide.
The method for treating the tab material by the flexible treatment liquid comprises the following steps: conveying the base material to a first lye tank through a squeezing roller, carrying out normal-temperature spraying alkali washing, controlling the spraying pressure at 0.1Mpa, and washing for 10 minutes; conveying the substrate to a second alkali solution tank, heating the substrate to 48 ℃, carrying out second alkali washing for 7 minutes, carrying out first water washing on the substrate after the alkali washing, then carrying out second water washing, wherein the conductivity of water adopted by the second water washing is 50S/m, and then carrying out third ultrasonic water washing, the conductivity of the adopted water is 20S/m, wherein the water temperature during the water washing is controlled at 30 ℃; mixing and stirring magnesium fluoride, fluorozirconic acid and sodium fluosilicate in corresponding parts for 40min to obtain a flexible treatment solution A, immersing the washed substrate in the flexible treatment solution A for 1h, taking out and drying; uniformly mixing sulfuric acid, dialkyl peroxide and peroxydicarbonate to obtain a flexibilized treatment solution B, coating the flexibilized treatment solution B on a dried base material, dissolving calcium nitrate in water, adding nitric acid, dissolving alumina in the pre-mixed solution, adding hydrochloric acid and phosphoric acid, adding water, uniformly stirring to obtain a flexibilized treatment solution C, and performing cathode electrolysis treatment on the base material in the flexibilized treatment solution C; stirring sodium tripolyphosphate, vinyl triacetoxysilane, epoxypropyl acrylate and nano silicon dioxide in a stirrer for 40min to prepare a flexible treatment solution D, and filtering with a 200-mesh filter screen for later use; setting the temperature of the flexible surface coating room at 20 ℃, adding the filtered flexible treatment liquid D into a trough of coating equipment, and coating; after coating, mixing air and low-pressure nitrogen in a wind mixing chamber to form cooling wind with the temperature of 27 ℃, the humidity of 70% and the oxygen content of 7%, and carrying out air drying and curing on the processed base material for 30s to obtain the processed pull ring material.
Wherein, the alkali liquor used in the alkali washing comprises the following components: 9 parts of sodium gluconate, 6 parts of sodium carbonate, 7 parts of sodium hydroxide, 3 parts of fatty alcohol-polyoxyethylene ether, 6 parts of diethylene triamine pentaacetic acid sodium salt, 1 part of fatty alcohol-polyoxyethylene polyoxypropylene ether and 2 parts of sodium borate; when the flexible treatment liquid D is coated, the rotating speed of the material carrying roller is set to be 60r/min, the rotating speed of the coating roller is set to be 40r/min, and the rotating speed of the metering roller is set to be 65 r/min; the thickness of the flexible film of the treated pull tab material was 15 μm.
Example 2:
the flexible treatment liquid comprises the following raw materials in parts by weight: 99 parts of magnesium fluoride, 10 parts of sodium tripolyphosphate, 25 parts of fluozirconic acid, 25 parts of sodium fluosilicate, 45 parts of hydrochloric acid, 15 parts of nitric acid, 100 parts of phosphoric acid, 30 parts of vinyl triacetoxysilane, 35 parts of sulfuric acid, 50 parts of calcium nitrate, 200 parts of water, 17 parts of dialkyl peroxide, 23 parts of peroxydicarbonate, 40 parts of glycidyl acrylate, 40 parts of nano-silica and 25 parts of aluminum oxide.
The method for treating the tab material by the flexible treatment liquid comprises the following steps: conveying the base material to a first lye tank through a squeezing roller, carrying out normal-temperature spraying alkali washing, controlling the spraying pressure at 0.2Mpa, and cleaning for 9 minutes; conveying the substrate to a second alkali solution tank, heating the substrate to 45 ℃, carrying out second alkali washing for 6 minutes, carrying out first water washing on the substrate after the alkali washing, then carrying out second water washing, wherein the conductivity of water adopted by the second water washing is 70S/m, and then carrying out third ultrasonic water washing, the conductivity of the adopted water is 50S/m, wherein the water temperature during the water washing is controlled at 35 ℃; mixing and stirring magnesium fluoride, fluorozirconic acid and sodium fluosilicate in corresponding parts for 35min to obtain a flexible treatment solution A, immersing the washed substrate in the flexible treatment solution A for 1.5h, taking out and drying; uniformly mixing sulfuric acid, dialkyl peroxide and peroxydicarbonate to obtain a flexibilized treatment solution B, coating the flexibilized treatment solution B on a dried base material, dissolving calcium nitrate in water, adding nitric acid, dissolving alumina in the pre-mixed solution, adding hydrochloric acid and phosphoric acid, adding water, uniformly stirring to obtain a flexibilized treatment solution C, and performing cathode electrolysis treatment on the base material in the flexibilized treatment solution C; stirring sodium tripolyphosphate, vinyl triacetoxysilane, epoxypropyl acrylate and nano silicon dioxide in a stirrer for 30min to prepare a flexible treatment solution D, and filtering with a 200-mesh filter screen for later use; setting the temperature of the flexible surface coating room at 20 ℃, adding the filtered flexible treatment liquid D into a trough of coating equipment, and coating; after coating, mixing air and low-pressure nitrogen in a wind mixing chamber to form cooling wind with the temperature of 28 ℃, the humidity of 75% and the oxygen content of 1%, and carrying out air drying and curing on the processed base material for 40s to obtain the processed pull ring material.
Wherein, the alkali liquor used in the alkali washing comprises the following components: 10 parts of sodium gluconate, 7 parts of sodium carbonate, 9 parts of sodium hydroxide, 4 parts of fatty alcohol-polyoxyethylene ether, 7 parts of diethylenetriamine pentaacetic acid, 2 parts of fatty alcohol-polyoxyethylene polyoxypropylene ether and 4 parts of sodium borate; when the flexible treatment liquid D is coated, the rotating speed of the material carrying roller is set to be 60r/min, the rotating speed of the coating roller is set to be 40r/min, and the rotating speed of the metering roller is set to be 65 r/min; the thickness of the flexible film of the treated pull tab material was 16 μm.
Example 3:
the flexible treatment liquid comprises the following raw materials in parts by weight: 100 parts of magnesium fluoride, 30 parts of sodium tripolyphosphate, 10 parts of fluozirconic acid, 24 parts of sodium fluosilicate, 50 parts of hydrochloric acid, 20 parts of nitric acid, 107 parts of phosphoric acid, 10 parts of vinyl triacetoxysilane, 37 parts of sulfuric acid, 30 parts of calcium nitrate, 230 parts of water, 23 parts of dialkyl peroxide, 24 parts of peroxydicarbonate, 38 parts of glycidyl acrylate, 48 parts of nano-silica and 30 parts of aluminum oxide.
The method for treating the tab material by the flexible treatment liquid comprises the following steps: conveying the base material to a first lye tank through a squeezing roller, carrying out normal-temperature spraying alkali washing, controlling the spraying pressure at 0.3Mpa, and washing for 12 minutes; conveying the substrate to a second alkali solution tank, heating the substrate to 50 ℃, carrying out second alkali washing for 9 minutes, carrying out first water washing on the substrate after the alkali washing, then carrying out second water washing, wherein the conductivity of water adopted by the second water washing is 60S/m, and then carrying out third ultrasonic water washing, the conductivity of the adopted water is 30S/m, wherein the water temperature during the water washing is controlled at 38 ℃; mixing and stirring magnesium fluoride, fluorozirconic acid and sodium fluosilicate in corresponding parts for 30min to obtain a flexible treatment solution A, immersing the washed substrate in the flexible treatment solution A for 2h, taking out and drying; uniformly mixing sulfuric acid, dialkyl peroxide and peroxydicarbonate to obtain a flexibilized treatment solution B, coating the flexibilized treatment solution B on a dried base material, dissolving calcium nitrate in water, adding nitric acid, dissolving alumina in the pre-mixed solution, adding hydrochloric acid and phosphoric acid, adding water, uniformly stirring to obtain a flexibilized treatment solution C, and performing cathode electrolysis treatment on the base material in the flexibilized treatment solution C; stirring sodium tripolyphosphate, vinyl triacetoxysilane, epoxypropyl acrylate and nano silicon dioxide in a stirrer for 35min to prepare a flexible treatment solution D, and filtering with a 200-mesh filter screen for later use; setting the temperature of the flexible surface coating room at 20 ℃, adding the filtered flexible treatment liquid D into a trough of coating equipment, and coating; after coating, mixing air and low-pressure nitrogen in a wind mixing chamber to form cooling wind with the temperature of 25 ℃, the humidity of 72% and the oxygen content of 2%, and carrying out air drying and curing on the processed base material for 50s to obtain the processed pull ring material.
Wherein, the alkali liquor used in the alkali washing comprises the following components: 10 parts of sodium gluconate, 8 parts of sodium carbonate, 10 parts of sodium hydroxide, 3 parts of fatty alcohol-polyoxyethylene ether, 6 parts of diethylenetriamine pentaacetic acid, 3 parts of fatty alcohol-polyoxyethylene polyoxypropylene ether and 5 parts of sodium borate; when the flexible treatment liquid D is coated, the rotating speed of the material carrying roller is set to be 60r/min, the rotating speed of the coating roller is set to be 40r/min, and the rotating speed of the metering roller is set to be 65 r/min; the thickness of the flexible film of the treated pull tab material was 16 μm.
Example 4:
the flexible treatment liquid comprises the following raw materials in parts by weight: 98 parts of magnesium fluoride, 17 parts of sodium tripolyphosphate, 19 parts of fluozirconic acid, 23 parts of sodium fluosilicate, 47 parts of hydrochloric acid, 17 parts of nitric acid, 120 parts of phosphoric acid, 20 parts of vinyl triacetoxysilane, 40 parts of sulfuric acid, 37 parts of calcium nitrate, 250 parts of water, 15 parts of dialkyl peroxide, 25 parts of peroxydicarbonate, 35 parts of glycidyl acrylate, 50 parts of nano-silica and 28 parts of alumina.
The method for treating the tab material by the flexible treatment liquid comprises the following steps: conveying the base material to a first lye tank through a squeezing roller, carrying out normal-temperature spraying alkali washing, controlling the spraying pressure at 0.5Mpa, and washing for 11 minutes; conveying the substrate to a second alkali solution tank, heating the substrate to 47 ℃, carrying out second alkali washing for 10 minutes, carrying out first water washing on the substrate after the alkali washing, then carrying out second water washing, wherein the conductivity of water adopted by the second water washing is 80S/m, and then carrying out third ultrasonic water washing, the conductivity of the adopted water is 30S/m, wherein the water temperature during the water washing is controlled at 40 ℃; mixing and stirring magnesium fluoride, fluorozirconic acid and sodium fluosilicate in corresponding parts for 38min to obtain a flexible treatment solution A, immersing the washed substrate in the flexible treatment solution A for 1.8h, taking out and drying; uniformly mixing sulfuric acid, dialkyl peroxide and peroxydicarbonate to obtain a flexibilized treatment solution B, coating the flexibilized treatment solution B on a dried base material, dissolving calcium nitrate in water, adding nitric acid, dissolving alumina in the pre-mixed solution, adding hydrochloric acid and phosphoric acid, adding water, uniformly stirring to obtain a flexibilized treatment solution C, and performing cathode electrolysis treatment on the base material in the flexibilized treatment solution C; stirring sodium tripolyphosphate, vinyl triacetoxysilane, epoxypropyl acrylate and nano silicon dioxide in a stirrer for 37min to prepare a flexible treatment solution D, and filtering with a 200-mesh filter screen for later use; setting the temperature of the flexible surface coating room at 20 ℃, adding the filtered flexible treatment liquid D into a trough of coating equipment, and coating; after coating, mixing air and low-pressure nitrogen in a wind mixing chamber to form cooling wind with the temperature of 26 ℃, the humidity of 73% and the oxygen content of 4%, and carrying out air drying and curing on the processed base material for 60s to obtain the processed pull ring material.
Wherein, the alkali liquor used in the alkali washing comprises the following components: 9 parts of sodium gluconate, 8 parts of sodium carbonate, 8 parts of sodium hydroxide, 4 parts of fatty alcohol-polyoxyethylene ether, 6 parts of diethylenetriamine pentaacetic acid, 2 parts of fatty alcohol-polyoxyethylene polyoxypropylene ether and 6 parts of sodium borate; when the flexible treatment liquid D is coated, the rotating speed of the material carrying roller is set to be 60r/min, the rotating speed of the coating roller is set to be 40r/min, and the rotating speed of the metering roller is set to be 65 r/min; the thickness of the flexible film of the treated pull tab material was 17 μm.
After the substrate is soaked in the softening treatment a, the substrate is dried, and a drying box used in the drying box is shown in fig. 1 and 2 and comprises: drying room 1, drying room 1 is inside to have circulating hot-blast to be used for drying to the substrate material. The place ahead in stoving room 1 is provided with material loading mouth 8, material loading mouth 8 makes inside and the external world of stoving room communicate with each other. And a conveying device 2 is arranged in the drying room 1, and the conveying device 2 is parallel to the ground. The conveying device 2 comprises a driving wheel 4, a driven wheel 5, a belt 6 and a driving device, wherein the driving wheel 4 and the driven wheel 5 are respectively arranged on the side wall of the drying room 1 and connected through a bearing. The driving wheel 4 and the driven wheel 5 can rotate around the central axis of the driving wheel and the driven wheel respectively. One end of the driving wheel 4 is connected with a driving device, the driving device is fixed on the outer side of the side wall of the drying room 1 through bolts, and the driving device is a motor. The driving wheel 4 and the driven wheel 5 are sleeved with a belt 6, and the driving device can drive the driving wheel 4 to rotate so as to drive the belt 6 to operate.
One end of the conveying device 2 extends out of the feeding opening 8, and the manipulator 3 is installed outside the feeding opening 8. The manipulator 3 comprises a slide rail 32, the slide rail 32 is fixed on the rack above the outer part of the feeding hole 8 through bolts, and the slide rail 32 is arranged along the direction parallel to the belt 6. A slide block 31 is installed below the slide rail 32, and the slide block 31 can slide on the slide rail 32. One end of the sliding block 31 is connected with an extending end of an air cylinder A33, a cylinder barrel of the air cylinder A33 is fixed on the rack, and the air cylinder A33 can push the sliding block 31 to slide on the sliding rail 32. An air cylinder B36 and two guide rods 34 are installed below the sliding block 31, the two guide rods 34 are respectively located on two sides of an air cylinder B36, and the air cylinder B36 and the two guide rods 34 are both perpendicular to the horizontal plane. The extending end of the cylinder B36 is connected with a connecting block 37, linear bearings 35 are respectively mounted on the two guide rods 34, and the linear bearings 35 can slide on the guide rods 34. The connecting block 37 and the two linear bearings 35 are simultaneously connected with the mounting plate 38, and the cylinder B36 can drive the mounting plate 38 to slide up and down along the guide rod 34. A plurality of suckers 39 are installed below the mounting plate 38, and the suckers 39 are used for sucking the aluminum sheets. The part of the conveying device 2 extending out of the feeding port 8 is located below the end part of the running stroke of the mechanical arm 3 along the direction of the sliding rail 32, a feeding conveyor belt 7 is arranged below the other end of the running stroke of the mechanical arm 3 along the direction of the sliding rail 32, the feeding conveyor belt 7 is used for feeding, and the mechanical arm 3 can grab the base material 21 onto the conveying device 2 from the feeding conveyor belt 7.
When the substrate 21 needs to be dried, the feeding conveyor 7 transports the substrate 21 to a position closest to the feeding port 8. The piston rod of the air cylinder A33 contracts to drive the slide block 31 to move towards the direction close to the cylinder barrel, so that the suction cup 39 is dragged to a position above the feeding conveyor belt 7. The piston rod of the cylinder B36 is extended downward to make the suction cup 39 contact the substrate 21, and at the same time, the suction cup 39 sucks air to make the substrate 21 sucked on the suction cup 39. The piston rod of cylinder B36 retracts upward causing the suction cup 39 to pick up the substrate 21 while the piston rod of cylinder a33 extends to pull the substrate 21 over the belt 6. The piston rod of the cylinder B36 is extended downward to bring the substrate 21 into contact with the belt 6 while the suction cup 39 is de-energized to place the substrate 21 on the belt 6. The belt 6 conveys the base material 21 to the inside of the drying room 1, and the base material 21 is dried by the circulating hot air in the drying room 1. The device can realize the full automation operation that aluminum sheet material was dried, need not manual operation, the effectual manufacturing cost and the amount of labour that has reduced.
In addition, when the flexible treatment liquid D is coated, the base material 21 is placed between the backing roller 8 and the coating roller 10, the motor 14 is started, the motor 14 drives the material carrying roller 12 in the material groove 15 to rotate through the belt 13, and the flexible treatment liquid D is coated on the base material 21 through the metering roller 11 and the coating roller 10 in sequence; wherein each roller has a pulley 16 mounted thereon.
And (3) performance testing:
the corrosion resistance test:
1. neutral salt spray experiment:
a Q-FOG salt FOG box is adopted to carry out a neutral salt FOG test, the temperature in the box is set to be 37 ℃, the concentration of a NaCl solution as a corrosion medium is set to be 45-55g/L, the pH value is set to be 6.5-7.0, the continuous spraying is carried out for 8h and the continuous spraying is stopped for 16h every day, and the change of the corrosion area of the sample along with the time is recorded.
The samples in this experiment included five groups: group A is a pull tab sample prepared by the method of examples 1-4 of the present invention; group B is an aluminum substrate without any treatment; group C is a traditional hexavalent chromium passivated pull ring material; group D is the ring pulling material treated by molybdate, the process conditions are molybdate, zirconium fluoride and additives, the temperature is 25-35 ℃, the passivation treatment time is 1min, and the PH is 4.5-5.5; group E is a pull ring material treated by silicate, and the adopted raw materials comprise: sodium silicate, sulfuric acid, peroxide, thiourea, nitric acid, phosphoric acid at pH3.0, temperature 30 °, and passivation time 90 s. The results of the experiments are shown in the following table.
Table 1: corrosion area time variation table
As can be seen from the above table, the aluminum substrate without passivation has the worst corrosion resistance, the corrosion area reaches 72% after 48h of salt spray, while the corrosion area of the sample after the traditional hexavalent chromium passivation is 9% after 72h of salt spray, the corrosion area basically shows the condition of uniform growth along with the increase of the salt spray time, and finally reaches 32% after 192 h; although the corrosion area growth rate of the samples of the group D and the group E is slightly different in the process, the final result is not greatly different and is close to 30%; the pull ring material obtained by the treatment of the invention starts to generate corrosion phenomenon after being atomized for 96 hours, the corrosion area of the pull ring material is slowly increased along with the time extension, and the corrosion area of the pull ring material is only 14-15% after being atomized for 192 hours.
And calculating the corrosion rate of the sample after 192h of salt spray test by using a weight loss method. The results of the experiments are shown in the table below.
The corrosion rates of the five groups of samples in the neutral salt spray test are shown in the table, and it can be seen from the table that the corrosion rate of the untreated aluminum substrate is maximum 0.378, the corrosion rate of the hexavalent chromium passivated sample is 0.0571, the corrosion rates of the silicate and molybdate passivated samples are not greatly different and are slightly lower than the corrosion rate of the hexavalent chromium, while the corrosion rates of the samples treated by the method are about 0.02, and are significantly reduced compared with the corrosion rates of the silicate, molybdate and hexavalent chromium passivated samples, so that the corrosion resistance of the pull tab material treated by the method can be effectively improved.
2. Damage corrosion test:
and (3) making an artificial cross-shaped scratch on the surface of the sample, immersing the sample with the scratch into a sodium chloride aqueous solution, and observing and recording the time of rusting at the scratch.
The samples in this experiment included five groups: group A is a pull tab sample prepared by the method of examples 1-4 of the present invention; group B is an aluminum substrate without any treatment; group C is a traditional hexavalent chromium passivated pull ring material; group D is the ring pulling material treated by molybdate, the process conditions are molybdate, zirconium fluoride and additives, the temperature is 25-35 ℃, the passivation treatment time is 1min, and the PH is 4.5-5.5; group E is a pull ring material treated by silicate, and the adopted raw materials comprise: sodium silicate, sulfuric acid, peroxide, thiourea, nitric acid, phosphoric acid at pH3.0, temperature 30 °, and passivation time 90 s. The results of the experiments are shown in the following table.
From the above table, it can be seen that the sample which is not passivated, i.e., the group B, after being soaked by the groined scratches, the corrosion product appears after 26 hours, the corrosion product appears after 55 hours on the sample which is passivated by the conventional hexavalent chromium, the corrosion product appears after 57 hours on the sample which is passivated by the molybdate, the corrosion product appears after 60 hours on the sample which is passivated by the silicate, and the corrosion product appears on the sample which is treated by the method of the present invention after 70 hours on the sample which is treated by the salt soaking, which indicates that the pull ring material treated by the method of the present invention has a good corrosion resistance effect. The analysis reason is that the inorganic additive in the flexible treatment liquid plays a slow release role, when a sample is damaged, the newly formed elemental aluminum surface is in a state with relatively high surface energy and can be regarded as an adsorbent with relatively strong adsorption capacity, at the moment, the aluminum surface can spontaneously adsorb various adsorbents to reduce the surface energy which is too high, and because the substrate is initially immersed in the flexible treatment liquid A obtained by mixing and stirring magnesium fluoride, fluozirconic acid and sodium fluosilicate, a layer of protective film is formed on the substrate surface, and at the moment, the flexible treatment liquid A is transferred and adsorbed to the aluminum surface as the adsorbents, so that the corrosion of the damaged part is relieved, and the corrosion speed is reduced.
Other performance tests:
1. adhesive force performance of product
The samples in the experiment included five groups: group A is a pull tab sample prepared by the method of examples 1-4 of the present invention; group B is an aluminum substrate without any treatment; group C is a traditional hexavalent chromium passivated pull ring material; group D is the ring pulling material treated by molybdate, the process conditions are molybdate, zirconium fluoride and additives, the temperature is 25-35 ℃, the passivation treatment time is 1min, and the PH is 4.5-5.5; group E is a pull ring material treated by silicate, and the adopted raw materials comprise: sodium silicate, sulfuric acid, peroxide, thiourea, nitric acid, phosphoric acid at pH3.0, temperature 30 °, and passivation time 90 s. The results of the experiments are shown in the following table. And (3) coating the paint on the sample treated by the five formulas until the paint is completely cured, and carrying out adhesion test.
The adhesion test method generally adopts a grid cutting method (GB/T9286). When the multicoat layer was cut in a grid pattern and just penetrated the coating to the substrate, the resistance of the coating to separation from the substrate, or the ability of multicoat systems to resist separation from each other, was evaluated and the results were expressed as a scale.
The test steps are as follows: the template was placed on a hard, flat object and a vertical cut was made at 90 cross-cuts, with the cutter blade forming a grid pattern of regular intervals on the coating at a uniform force and rate. And lightly brushing the lattice with a soft brush in the diagonal direction for several times to remove paint chips. Placing the center point of the 75mm transparent pressure sensitive adhesive tape on the grid, the direction is parallel to a group of cutting lines, pressing the adhesive tape on the grid with fingers, rubbing the adhesive tape with finger tips to ensure good contact between the adhesive tape and the coating, and stripping the adhesive tape stably within 0.5-1.0s at an angle close to 60 degrees within 5 min.
The rating method comprises the following steps: and under a good lighting environment, visually checking the shedding condition of the cutting surface coating.
The adhesion criteria are shown in the following table:
the experimental results are as follows:
from the experimental data in the above table, it can be seen that the adhesion of the coating of the sample prepared by the present invention is good after coating, and the adhesion grades of the 3 randomly selected parts in examples 1-4 are mostly 0, and the very few are 1, while the adhesion of the coating of the original aluminum substrate without passivation treatment is poor, generally 4 or 5, which indicates that the peeling area is large and the adhesion of the coating is poor, but the sample prepared by the present invention has not only good corrosion resistance, but also good adhesion.
2. Fingerprint resistance test
The fingerprint resistance test uses white vaseline as human body sweat simulation medium, a clean cotton ball is used for dipping a small amount of vaseline to be uniformly coated on about one half of the surface of a test piece, after one hour, the vaseline on the surface is erased by the clean cotton ball, the three-color pixel coordinate values (L, a and b) of the part of the test piece which is not coated and coated with the vaseline are measured by a color difference tester, delta L, delta a and delta b before and after the white vaseline is coated on the test piece are calculated, and the color difference formula delta E is changed into (delta L is changed into delta E)2+Δa2+Δb2)1/2Δ E is calculated and is generally considered to be an ideal matching range with very little or no chromatic aberration when Δ E is less than 0.25.
The samples in the experiment included five groups: group A is a pull tab sample prepared by the method of examples 1-4 of the present invention; group B is an aluminum substrate without any treatment; group C is a traditional hexavalent chromium passivated pull ring material; group D is the ring pulling material treated by molybdate, the process conditions are molybdate, zirconium fluoride and additives, the temperature is 25-35 ℃, the passivation treatment time is 1min, and the PH is 4.5-5.5; group E is a pull ring material treated by silicate, and the adopted raw materials comprise: sodium silicate, sulfuric acid, peroxide, thiourea, nitric acid, phosphoric acid at pH3.0, temperature 30 °, and passivation time 90 s. The results of the experiments are shown in the following table.
As can be seen from the table above, the value of delta E of the pull tab material treated by the method is not more than 0.15, while the value of delta E of the untreated sample is 1.5, and is far more than 0.25, which shows that the fingerprint resistance of the pull tab material is poor, the value of delta E of the sample treated by the traditional hexavalent chromium passivation method is 0.23, which is not much different from the value of delta E of the sample treated by the silicate and molybdate passivation method, which shows that the fingerprint resistance of the material is not much different after the traditional hexavalent chromium passivation method is used for carrying out chromium-free passivation on the silicate and molybdate, and the pull tab material treated by the method has good fingerprint resistance.
It is to be understood that the invention is not limited to the specific embodiments described above, but is intended to cover various insubstantial modifications of the inventive process concepts and solutions, or its application to other applications without modification.
Claims (8)
1. A method for treating a pull ring material by using a flexible treatment solution is characterized by comprising the following steps: comprises the following steps of (a) carrying out,
the method for treating the pull ring material by the flexible treatment liquid comprises the following steps: carrying out alkali washing on the base material, and then washing with water for three times; mixing and stirring magnesium fluoride, fluorozirconic acid and sodium fluosilicate in corresponding parts for 30-40min to obtain a flexible treatment solution A, immersing the washed substrate in the flexible treatment solution A for 1-2h, taking out and drying; uniformly mixing sulfuric acid, dialkyl peroxide and peroxydicarbonate to obtain a flexibilized treatment solution B, coating the flexibilized treatment solution B on a dried base material, dissolving calcium nitrate in water, adding nitric acid, dissolving alumina in the pre-mixed solution, adding hydrochloric acid and phosphoric acid, adding water, uniformly stirring to obtain a flexibilized treatment solution C, and performing cathode electrolysis treatment on the base material in the flexibilized treatment solution C; stirring sodium tripolyphosphate, vinyl triacetoxysilane, epoxypropyl acrylate and nano silicon dioxide in a stirrer for 30-40min to prepare a flexible treatment solution D, and filtering with a 200-mesh filter screen for later use; setting the temperature of the flexible surface coating room at 20 ℃, adding the filtered flexible treatment liquid D into a trough of coating equipment, and coating; after coating, air-drying and curing to obtain the finished pull ring material;
wherein the flexible treatment liquid comprises the following raw materials: magnesium fluoride, sodium tripolyphosphate, fluozirconic acid, sodium fluosilicate, hydrochloric acid, nitric acid, phosphoric acid, vinyl triacetoxysilane, sulfuric acid, calcium nitrate, water, dialkyl peroxide, peroxydicarbonate, glycidyl acrylate, nano-silica and aluminum oxide.
2. The method of claim 1, wherein the method comprises: the flexible treatment liquid comprises the following raw materials in parts by weight: 98-100 parts of magnesium fluoride, 10-30 parts of sodium tripolyphosphate, 10-30 parts of fluozirconic acid, 23-25 parts of sodium fluosilicate, 45-50 parts of hydrochloric acid, 10-30 parts of nitric acid, 120 parts of phosphoric acid, 10-30 parts of vinyl triacetoxysilane, 30-40 parts of sulfuric acid, 30-50 parts of calcium nitrate, 250 parts of water 200, 15-25 parts of dialkyl peroxide, 20-25 parts of peroxydicarbonate, 35-40 parts of epoxypropyl acrylate, 40-45 parts of nano silicon dioxide and 25-30 parts of aluminum oxide.
3. The method of claim 1, wherein the method comprises: the alkali washing operation steps are as follows: conveying the base material to a first lye tank through a squeezing roller, carrying out normal-temperature spraying alkali washing, controlling the spraying pressure at 0.1-0.5Mpa, and washing for 9-12 minutes; and then conveying to a second alkali solution tank, heating to 45-50 ℃, and carrying out second alkali cleaning for 6-10 minutes.
4. The method of claim 3, wherein the method comprises: the components of the alkali liquor adopted in the alkali washing are as follows: 9-10 parts of sodium gluconate, 6-8 parts of sodium carbonate, 7-10 parts of sodium hydroxide, 3-5 parts of fatty alcohol-polyoxyethylene ether, 6-8 parts of sodium diethylenetriamine pentaacetate, 1-3 parts of fatty alcohol-polyoxyethylene polyoxypropylene ether and 2-6 parts of sodium borate.
5. The method of claim 4, wherein the method comprises: the three-time water washing operation is as follows: and (3) washing the base material subjected to alkali washing by using first water, then washing by using second water, wherein the conductivity of water adopted in the second water washing is 50-80S/m, and then washing by using third ultrasonic wave, the conductivity of the adopted water is 10-50S/m, wherein the water temperature during washing is controlled at 30-40 ℃.
6. The method of claim 5, wherein the method comprises: when the flexible treatment liquid D is applied, the rotation speed of the belt roller is set to 60r/min, the rotation speed of the coating roller is set to 40r/min, and the rotation speed of the metering roller is set to 65 r/min.
7. The method of claim 1, wherein the method comprises: the air drying and curing conditions are as follows: air and low-pressure nitrogen are mixed in a wind mixing chamber to form cooling wind with the temperature of 25-28 ℃, the humidity of 70-75% and the oxygen content of less than or equal to 8%, and the cooling wind is dried and solidified for 30-60 s.
8. The method of claim 1, wherein the method comprises: the thickness of the flexible film of the treated pull tab material is 15-17 μm.
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