WO2024046127A1 - 一种长效不粘涂料及其制备和施工方法 - Google Patents

一种长效不粘涂料及其制备和施工方法 Download PDF

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WO2024046127A1
WO2024046127A1 PCT/CN2023/113326 CN2023113326W WO2024046127A1 WO 2024046127 A1 WO2024046127 A1 WO 2024046127A1 CN 2023113326 W CN2023113326 W CN 2023113326W WO 2024046127 A1 WO2024046127 A1 WO 2024046127A1
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silicone oil
long
silane
coating
primer
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English (en)
French (fr)
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赵杰
李力锋
刘扬
张亚莉
于秦阳
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上海宜瓷龙新材料股份有限公司
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Publication of WO2024046127A1 publication Critical patent/WO2024046127A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
    • B05D1/38—Successively applying liquids or other fluent materials, e.g. without intermediate treatment with intermediate treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/53—Base coat plus clear coat type
    • B05D7/534—Base coat plus clear coat type the first layer being let to dry at least partially before applying the second layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/002—Priming paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Definitions

  • the invention belongs to the technical field of coatings and relates to a long-lasting non-stick coating and its preparation and construction methods.
  • the hardness of fluorocarbon coating is only 2H at room temperature.
  • the temperature of the pot often reaches one or two hundred degrees during the cooking process. Since the fluorocarbon coating is a thermoplastic material, it will soften at high temperatures and the hardness is not yet reached. H.
  • the coating is easily scratched and worn by shovels or food, and the coating will fall off at the scratched parts. Although the coating is still non-sticky, the exposed aluminum substrate will enter people's mouth along with the food. The intestinal tract will affect your health in the long run, so although the fluorocarbon coating is non-stick and has good durability, once the coating is damaged, the cookware needs to be replaced in time.
  • the service life of the pot is generally within 1 year.
  • the hardness of the coating is as high as 9H.
  • the -CH 3 group on the surface of the coating that plays a non-stick role will break chemical bonds as the use time increases at high temperatures, especially When dry burning or scorching occurs during cooking, the non-stick properties will drop rapidly. Therefore, the service life of ceramic-coated non-stick pans is about half a year, which is far from the user's expectations. How to combine the high hardness of ceramic coating with the non-stick durability of fluorocarbon coating to prepare a long-lasting non-stick coating is a problem that needs to be solved.
  • the purpose of the present invention is to overcome the above-mentioned existing problems in the prior art regarding non-stick pan coatings. Due to low hardness, the fluorocarbon coating has lower hardness, especially at high temperatures, and is easily scratched during cooking and exposes the base material. The service life of the coating is very low. Within 1 year; although the ceramic coating has high hardness, the -CH 3 group that provides non-stickiness at high temperatures will break as the use time increases. The non-stick durability is not good, and the service life of the coating is about half a year, etc. Insufficient, long-lasting non-stick coatings and their preparation and construction methods are provided. The invention combines the advantages of fluorocarbon coating and ceramic coating to prepare a long-lasting non-stick coating.
  • the invention relates to a long-lasting non-stick double-coat coating, in which the primer is a ceramic coating and the topcoat is a fluorocarbon coating;
  • the primer is based on 100% of the total weight, including: silica sol: 26-28%, 1% NaOH solution: 4-5%, pigment: 10-12%, filler: 8-10%, dispersant: 1-1.5% , Silane: 28-30%, Isopropyl alcohol: 3-3.5%, Silicone oil microcapsules: 6-8%, 25% formic acid: 0.7-1%, deionized water: balance;
  • the topcoat includes: fluorosilane: 1-2%, acetic acid: 3-5%, deionized water and isopropyl alcohol with a mass ratio of 1:1: the balance.
  • silica sol is the main film-forming substance of ceramic coatings.
  • Common commercial products such as: AkzoNobel's Bindzil 2034DI, Nissan Chemical's ST-O-40, Grace HS-40 etc.
  • 1% NaOH solution is used as a color paste pH regulator to adjust the pH value of the color paste to 9-10.5.
  • the pH value will drop during storage.
  • the pH value drops When it is below 8.5 and close to neutral, the silica sol will gel and cause the color paste to deteriorate. Therefore, it is necessary to use an alkaline solution to adjust the pH value of the color paste to between 9-10 to ensure that the color paste will not deteriorate during storage. Go bad.
  • the pigments give the paint different colors. Common inorganic pigments should be used. Inorganic pigments have good temperature resistance and safety. Inorganic pigments should be used in high temperature resistant areas. Such as titanium dioxide, iron oxide yellow, manganese iron black, cobalt blue, iron oxide red, etc.
  • fillers play a role in reducing coating costs and increasing the solid content of coatings.
  • Commonly used fillers are selected, such as mica powder, silica powder, kaolin, alumina powder, fumed silica, etc.
  • dispersants play the role of reducing the dispersion time of pigments and fillers, stabilizing pigment dispersions, and improving pigment tinting and hiding power, such as BYK180, BYK190, BYK2010, BYK2001, etc.
  • silane is an auxiliary film-forming substance, and methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, etc. can be used.
  • 25% formic acid solution is the catalyst for the sol-gel reaction of ceramic coatings.
  • Silane hydrolyzes under acidic conditions and undergoes a polycondensation reaction with silica sol to generate ceramic coatings.
  • silicone oil microcapsules provide the non-stick component of the ceramic coating primer. They are microcapsules with a shell-core structure. When the coating is heated, the silicone oil can gradually diffuse out of the shell structure and slowly release the non-stick properties. , extending the non-stick durability of the coating.
  • fluorosilane is both a film-forming substance and a coupling agent with the primer.
  • the non-stick properties of the layer are not good, and at least seventeen-F silane is needed to achieve good non-stick properties.
  • acetic acid is the catalyst for the hydrolysis polymerization of fluorosilane. Hydrolysis of fluorosilane under acidic conditions can form a colorless and transparent solution, which is beneficial to the formation of a colorless and transparent topcoat.
  • silicone oil microcapsule formula is as follows: silicone oil: 43-45%, silane: 48-50%, surfactant: 4-4.5%, 25% formic acid solution: the balance.
  • silicone oil provides non-stickiness of ceramic coating primers, commonly used silicone oils, such as methyl silicone oil, hydroxyl silicone oil, etc.
  • silane consists of trifunctional silane and difunctional silane in 1:1-2:1.
  • the trifunctional silane is a short-chain trifunctional silane, including methyltrimethoxysilane and methyltriethoxysilane;
  • the difunctional silane is a short-chain difunctional silane, including dimethyldimethyl Oxysilane, dimethyldiethoxysilane, etc.
  • the combination of trifunctional silane and difunctional silane can form a porous structure with a regular three-dimensional cross-linked structure, and the diameter of the pores is larger, which is conducive to the diffusion of silicone oil molecules.
  • the cross-linked structure is denser and the pore size is smaller, which is not conducive to the outward diffusion of silicone oil molecules.
  • Choosing short-chain alkyl silane can avoid steric hindrance effects in the later stages of polymerization, making the shell structure more complete and regular. Long-chain alkyl silane is prone to steric hindrance effects, making it difficult to form a complete shell structure during polymerization.
  • the ratio of trifunctional silane to difunctional silane is greater than 2:1. If there is too much trifunctional silane, the cross-linked structure formed is denser and the network diameter is smaller, which is not conducive to the outward diffusion of silicone oil molecules; the ratio is less than 1:1.
  • the surfactant is a cationic surfactant, which can exist stably under weakly acidic conditions.
  • surfactants with organic quaternary ammonium salt structures such as cetyl trimethyl quaternary ammonium bromide, octadecyl dimethyl benzyl quaternary ammonium chloride, benzalkonium chloride, and benzalkonium bromide.
  • Silane can be hydrolyzed under acidic conditions to form a colorless and transparent solution.
  • the preparation of the silicone oil microcapsules includes: mixing silicone oil, silane with mixed trifunctionality and difunctionality, and surfactant evenly, and adjusting the pH value to 25% formic acid under stirring. 4.0-5.0, react for 4-6hr, and then ultrasonic for 2-2.5hr to obtain silicone oil microcapsules.
  • the microcapsule is a shell-core structure, in which the shell is a three-dimensional cross-linked network structure of Si-O-Si formed after hydrolysis and polymerization of silane under acidic conditions, and the core is silicone oil emulsified by surfactant.
  • the network shell structure allows the silicone oil molecules inside to slowly diffuse outward.
  • the silicone oil can be evenly dispersed in the coating, and can also be evenly distributed in the coating after curing.
  • the silicone oil inside the coating can slowly dissolve at high temperatures. Diffuses out, ensuring long-term non-stickiness of the coating.
  • silicone oil is added directly to ceramic coatings, the silicone oil will only float on the surface of the coating due to its low density and poor compatibility with water-based coatings. After curing to form a film, the silicone oil will also be located on the surface of the coating. Once it loses its effect, the non-stickiness will disappear, so The non-stick durability of directly added silicone oil coating is not good.
  • This step adopts the method of first stirring for 4-6 hours and then ultrasonic for 2-2.5 hours.
  • the reaction under stirring is mainly to generate a shell structure.
  • the silicone oil and surfactant are initially combined. Under ultrasound, the silicone oil and surfactant are further emulsified to form Uniform and stable silicone oil microcapsule dispersion.
  • the invention relates to a method for preparing a long-lasting non-stick double-coat coating.
  • the method includes the following steps:
  • Color paste preparation Mix the silica sol, pigment, filler, dispersant and deionized water evenly, adjust the pH value to 9.5-10.5 with 1% NaOH solution, and grind to a fineness of less than 20 ⁇ m;
  • fluorocarbon topcoat Mix fluorosilane, acetic acid, deionized water and isopropyl alcohol evenly, and react for 8-16 hours to obtain the topcoat. In this step, since the fluorosilane molecular chain is longer and the hydrolysis rate is slower, the reaction time is also longer.
  • step A1 after grinding to a fineness of less than 20 ⁇ m, test the pH value of the color paste. If it is less than 9.0, use 1% NaOH solution to adjust it to between 9.0-10.0 and set aside.
  • the invention relates to a method for applying long-lasting non-stick double-coat paint.
  • the method includes the following steps:
  • the thickness of the primer is about 20-30 ⁇ m;
  • the metal substrate includes aluminum alloy substrate, stainless steel, etc.
  • step B2 the curing temperature should not be too high, and the time should not be too long, so that the primer reaches a finger-dry state rather than a solid dry state, that is, the surface is not sticky when touched with fingers, but the interior is not completely dry.
  • the surface of the primer There is a large amount of -OH, which is beneficial to the coupling between the topcoat and the primer, ensuring strong adhesion between the two layers.
  • step B3 after spraying the topcoat, let it sit for 5-10 minutes. This process is conducive to the diffusion of molecules.
  • the coupling agent molecules migrate to the bonding interface between the primer and topcoat and produce coupling. Leave it for a period of time before curing to ensure that the coupling agent completes the migration process, so that better adhesion between the primer and topcoat can be obtained.
  • the coupling agent also contains a large amount of -OH, which can couple with the -OH on the surface of the primer and bond firmly together.
  • the coating obtained by the above method organically combines the high hardness of the ceramic coating with the non-stick durability of the fluorocarbon coating.
  • the -F contained in the topcoat has excellent long-term non-stickiness.
  • the topcoat first provides non-stickiness.
  • the silicone oil in the primer slowly diffuses out from the microcapsules at high temperature. Continuously provides non-stick properties to coatings. Due to the high hardness of the ceramic coating primer, the wear resistance of the fluorine-containing topcoat is also greatly improved, and the service life of the topcoat is effectively extended.
  • the non-stick coating prepared by this method can have a non-stick property of more than 3 years.
  • the present invention has the following beneficial effects:
  • silicone oil microcapsules with a shell-core structure were produced, in which the shell is a three-dimensional cross-linked network structure of Si-O-Si formed by the hydrolysis polymerization of silane.
  • the core is silicone oil emulsified by surfactant. This structure makes the silicone oil have good compatibility with water-based ceramic coatings, can be evenly dispersed in the entire coating, and can slowly diffuse out at high temperatures, improving the non-stick durability of the coating;
  • Embodiments 1 to 3 provide a long-lasting non-stick coating, the composition of which is shown in Table 1.
  • Preparation of color paste Mix the silica sol, pigment, filler, dispersant and deionized water evenly, adjust the pH value to 10 with 1% NaOH solution, grind it to a fineness of less than 20 ⁇ m, and then test the pH value of the color paste. If it is less than 9.0, use 1% NaOH solution to adjust to 9.5 and set aside;
  • This comparative example provides a non-stick coating, the composition of which is shown in Table 1; the construction steps are the same as in Example 1.
  • Preparation of color paste Mix the silica sol, pigment, filler, dispersant and deionized water evenly, adjust the pH value to 10 with 1% NaOH solution, grind it to a fineness of less than 20 ⁇ m, and then test the pH value of the color paste. If it is less than 9.0, use 1% NaOH solution to adjust to 9.5 and set aside;
  • Comparative Examples 2 to 7 provide a non-stick coating, the composition of which is shown in Table 1. The preparation and application steps are the same as in Example 1.
  • the hydroalcoholic solution is a mixed solution of deionized water and isopropyl alcohol with a mass ratio of 1:1;
  • Silicone oil microcapsule 1 Combine 45% methyl silicone oil, 48% silane (equal mass ratio of methyltrimethoxysilane, dimethyldimethoxysilane), 4% surfactant (octadecyldimethyl Benzyl ammonium chloride) was mixed evenly, and the pH value was adjusted to 5 with 25% formic acid under stirring. After reacting for 6 hours, it was then ultrasonicated for 2 hours to obtain silicone oil microcapsules 1;
  • Silicone oil microcapsule 2 Mix 45% methyl silicone oil, 48% silane (equal mass ratio of methyltrimethoxysilane and methyltriethoxysilane), 4% surfactant (octadecyldimethylbenzyl ammonium chloride) and mix evenly, adjust the pH value to 5 with 25% formic acid under stirring, react for 6 hours, and then ultrasonic for 2 hours to obtain silicone oil microcapsules 2;
  • Silicone oil microcapsule 3 45% methyl silicone oil, 48% silane (equal mass ratio of dimethyldimethoxysilane and dimethyldiethoxysilane), 4% surfactant (octadecyldimethoxysilane) Methyl benzyl ammonium chloride) and mix evenly, stirring Use 25% formic acid to adjust the pH value to 5 under normal conditions, react for 6 hours, and then ultrasonic for 2 hours to obtain silicone oil microcapsules 3;
  • Silicone oil microcapsule 4 45% methyl silicone oil, 48% silane (equal mass ratio of cetyltrimethoxysilane and dimethyldimethoxysilane), 4% surfactant (octadecyldimethoxysilane) Methyl benzyl ammonium chloride) was mixed evenly, and the pH value was adjusted to 5 with 25% formic acid under stirring. After reacting for 6 hours, it was then ultrasonicated for 2 hours to obtain silicone oil microcapsules 4;
  • Silicone oil microcapsule 5 45% methyl silicone oil, 48% silane (methyltrimethoxysilane, dimethyldimethoxysilane with a mass ratio of 1:3), 4% surfactant (octadecyl Dimethylbenzyl ammonium chloride) was mixed evenly, and the pH value was adjusted to 5 with 25% formic acid under stirring. After reacting for 6 hours, it was then ultrasonicated for 2 hours to obtain silicone oil microcapsules 5;
  • Silicone oil microcapsule 6 Dissolve 0.25 grams of sodium dodecyl sulfonate and 0.75 grams of alkylphenol polyoxyethylene ether in 100 grams of deionized water, then add 10 grams of dimethyl silicone oil, 10 grams of TEOS, 1.5 grams of ten The oil phase mixture composed of octalkyltrimethoxysilane was pre-emulsified and stirred in an ice-water bath environment for 15 minutes, and then ultrasonically finely emulsified using a cell crusher for 20 minutes to obtain a fine emulsion. Adjust the pH value of the miniemulsion to 7.5 and stir at high speed for 24 hours at room temperature to obtain milky white silicone oil microcapsules 6.

Abstract

一种长效不粘涂料及其制备和施工方法；该涂料为双涂层，底漆以总重100%计，包括硅溶胶26-28%，1%NaOH溶液4-5%，颜料10-12%，填料8-10%，分散剂1-1.5%，硅烷28-30%，异丙醇3-3.5%，硅油微胶囊6-8%，25%甲酸0.7-1%，去离子水余量；面漆以总重100%计，包括氟硅烷1-2%，乙酸3-5%，等质量比的去离子水和异丙醇余量。通过氟硅烷的偶联作用，将氟碳面漆的不粘性与陶瓷涂料底漆的高硬度有机的结合起来，制得了具有长效不粘性的涂层；且底漆中加入硅油微胶囊，当面漆磨损后，可以持续为涂层提供不粘性，大幅提升了不粘持久性，涂层的不粘性可保持3年以上。

Description

一种长效不粘涂料及其制备和施工方法 技术领域
本发明属于涂料技术领域，涉及一种长效不粘涂料及其制备和施工方法。
背景技术
近年来，由于陶瓷涂料健康、安全、环保的优势明显，越来越多的被应用在不粘锅的内表面，随着不粘技术的进步陶瓷涂层的不粘性也有了很明显的提升。但是由于陶瓷涂层表面的不粘性是依靠-CH3基团的低表面能来提供的，-CH3的表面自由能约为21-23mN/m，与-F的17-19mN/m表面自由能相比还是略高，所以尽管科学家们在不断探索陶瓷涂料不粘性的提高，但是与氟碳不粘涂料相比还是具有很大的差距，根本原因在于两者提供不粘性的基团不同，其表面自由能的差异导致。
氟碳涂层常温下硬度仅为2H，作为不粘锅涂层时，烹饪过程中锅子温度往往达到一两百度，由于氟碳涂层属于热塑性材料，在高温下会软化，硬度还达不到H，涂层很容易被铲子或者食材划破出现磨损等，进而出现划伤部位涂层的脱落，此时虽然涂层不粘性还在，但是裸露出的铝基材会随着食物进入人们的肠道，长此以往会影响身体健康，所以对于氟碳涂层来说虽然不粘持久性好，但是一旦涂层破损就需要及时更换炊具，锅具的使用寿命一般在1年以内。陶瓷涂层由于是Si-O-Si的无机结构，涂层硬度高达9H，但是涂层表面起不粘作用的-CH3基团在高温下会随着使用时间的延长而出现化学键断裂，特别是烹饪时出现干烧、糊锅等现象时，不粘性会急速下降，所以陶瓷涂层的不粘锅使用寿命大约在半年左右，这样的使用寿命远远达不到使用者的预期。如何将陶瓷涂层的高硬度与氟碳涂层的不粘持久性结合起来，制备出长效不粘的涂层是需要解决的问题。
通过对现有专利文献的检索发现，ZL202110120123.9的中国发明专利公开了一种石墨烯不粘涂料的技术方案，通过底漆和面漆中加入石墨烯形成互穿网络结构，将陶瓷涂层与氟碳涂层结合起来，但是该技术方案仅利用了氟碳面漆的不粘性，底漆中没有添加硅油，一般面漆涂层比较薄，氟碳面漆一旦磨损，不粘性即刻消失，所以该技术方案对于不粘持久性的提升效果不明显。
发明内容
本发明的目的在于克服上述现有技术存在的对于不粘锅涂层，氟碳涂层由于硬度低，特别是高温下硬度更低，烹饪时很容易被划伤而裸露出基材，使用寿命1年以内；陶瓷涂层虽然硬度高，但是由于高温下提供不粘性的-CH3基团会随着使用时间的延长而发生断裂，不粘持久性不好，涂层使用寿命约为半年等不足，提供长效不粘涂料及其制备和施工方法。本发明将氟碳涂层和陶瓷涂层两者的优点结合起来，制备出具有长效不粘的涂层。
本发明的目的是通过以下技术方案实现的：
<第一方面>
本发明涉及一种长效不粘双涂层涂料，底漆为陶瓷涂层，面漆为氟碳涂层；
底漆以总重100％计，包括：硅溶胶：26-28％，1％NaOH溶液：4-5％，颜料：10-12％，填料：8-10％，分散剂：1-1.5％，硅烷：28-30％，异丙醇：3-3.5％，硅油微胶囊：6-8％，25％甲酸：0.7-1％，去离子水：余量；
面漆以总重100％计，包括：氟硅烷：1-2％，乙酸：3-5％，质量比为1:1的去离子水和异丙醇：余量。
底漆中，硅溶胶为陶瓷涂料主要成膜物质，普通市售产品，例如：阿克苏诺贝尔的Bindzil 2034DI、日产化学的ST-O-40，格雷斯HS-40等。
底漆中，1％NaOH溶液为色浆pH值调节剂，将色浆部分pH值调整至9-10.5，硅溶胶研磨色浆后在储存过程中会出现pH值下降的情况，当pH值下降至8.5以下接近中性时，硅溶胶会出现凝胶化而导致色浆变质，所以需要用碱性溶液将色浆pH值调整至9-10之间，以保证色浆在保存时不会发生变质。
底漆中，颜料赋予涂料不同颜色，选用普通无机颜料，无机颜料耐温性好、安全性好，耐高温领域宜选用无机颜料。如钛白粉、氧化铁黄、锰铁黑、钴蓝、氧化铁红等。
底漆中，填料起到降低涂料成本，增加涂料固含量等作用，选用普通常用填料，例如：云母粉、硅微粉、高岭土、氧化铝粉、气相二氧化硅等。
底漆中，分散剂起到减少颜填料分散的时间，稳定颜料分散体，提高颜料着色力和遮盖力等作用，例如：BYK180、BYK190、BYK2010、BYK2001等。
底漆中，硅烷为辅助成膜物质，可选用甲基三甲氧基硅烷、甲基三乙氧基硅烷、二甲基二甲氧基硅烷等。
底漆中，25％甲酸溶液为陶瓷涂料溶胶-凝胶反应的催化剂，硅烷在酸性条件下水解后与硅溶胶发生缩聚反应生成陶瓷涂料。
底漆中，硅油微胶囊提供陶瓷涂层底漆不粘性的组分，是一种壳-芯结构的微胶囊，涂层在受热过程中硅油可逐渐从壳结构中扩散出来，缓慢释放不粘性，延长涂层的不粘持久性。
面漆中，氟硅烷既是成膜物质，又可作为与底漆的偶联剂，选用十七氟癸基三甲氧基硅烷或十七氟癸基三乙氧基硅烷，-F的数量少涂层的不粘性不好，至少要用十七个-F的硅烷才能达到良好的不粘性。
面漆中，乙酸为氟硅烷水解聚合的催化剂，氟硅烷在酸性条件下水解可形成无色透明溶液，利于形成无色透明面漆。
作为一个实施方案，硅油微胶囊配方如下：硅油：43-45％，硅烷：48-50％，表面活性剂：4-4.5％，25％甲酸溶液：余量。
硅油微胶囊中，硅油：提供陶瓷涂料底漆的不粘性，常用硅油，例如：甲基硅油、羟基硅油等。
硅油微胶囊中，硅烷：由1：1-2：1的三官能度硅烷和二官能度硅烷组成。所述三官能度硅烷为短链三官能度硅烷，包括甲基三甲氧基硅烷、甲基三乙氧基硅烷；所述二官能度硅烷为短链二官能度硅烷，包括二甲基二甲氧基硅烷、二甲基二乙氧基硅烷等。选用三官能度硅烷和二官能度硅烷搭配使用，可以形成规整的三维交联结构的多孔状结构，且孔的直径较大，利于硅油分子的扩散，如果全部选用三官能度硅烷，则形成的交联结构较致密，孔径较小，不利于硅油分子向外扩散。选用短链烷基的硅烷可以避免聚合后期的空间位阻效应，使得壳结构更加完整也更加规整，长链烷基的硅烷由于容易产生空间位阻效应，聚合时难以形成完整的壳结构。三官能度硅烷和二官能度硅烷配比大于2：1，三官能度硅烷太多，形成的交联结构较致密，网径较小，不利于硅油分子向外扩散；配比小于1：1，二官能度硅烷太多，不利于形成完整的交联结构，会有许多线型结构的链段产生，硅油释放速度太快，涂层易产生浮油，不粘持久性不好。
硅油微胶囊中，表面活性剂选用阳离子型表面活性剂，可以在弱酸性条件下稳定存在。例如：十六烷基三甲基季铵溴化物、十八烷基二甲基苄基季铵氯化物、苯扎氯铵、苯扎溴铵等有机季铵盐结构的表面活性剂。
硅油微胶囊中，25％甲酸溶液为硅烷水解的催化剂，硅烷在酸性条件下水解可形成无色透明溶液。
作为本发明的一个实施方案，所述硅油微胶囊的制备包括：将硅油、三官能度与二官能度混合的硅烷、表面活性剂混合均匀，在搅拌状态下用25％甲酸将pH值调整至 4.0-5.0，反应4-6hr后，再超声2-2.5hr，得到硅油微胶囊。该微胶囊是一种壳-芯结构，其中壳为硅烷在酸性条件下水解聚合后形成的Si-O-Si的三维交联网状结构，芯为表面活性剂乳化下的硅油。网状的壳结构可以使内部的硅油分子缓慢向外扩散。
由于表面活性剂的作用，使得硅油可均匀分散在涂料中，固化后也可均匀分布在涂层中，使用过程中当底漆上层的硅油失去作用后，涂层内部的硅油在高温下可缓慢扩散出来，保证了涂层长效的不粘性。陶瓷涂料中如果直接加入硅油，由于硅油密度小、与水性涂料相容性不好，仅浮在涂料表面，固化成膜后，硅油也位于涂层表面，一旦失去作用，不粘性即消失，所以直接添加硅油涂层的不粘持久性不好。
该步骤采用先搅拌反应4-6小时，再超声2-2.5hr的方式，搅拌下反应以生成壳结构为主，硅油与表面活性剂进行初步结合，超声下硅油与表面活性剂进一步乳化，形成均一稳定的硅油微胶囊分散液。
<第二方面>
本发明涉及一种长效不粘双涂层涂料的制备方法，所述方法包括如下步骤：
A1、色浆制备：将硅溶胶、颜料、填料、分散剂、去离子水混合均匀，用1％NaOH溶液调节pH值至9.5-10.5，研磨至细度20μm以下；
A2、陶瓷涂料底漆制备：将硅烷、异丙醇、硅油微胶囊、25％甲酸混合均匀，然后加入步骤A1制备好的色浆混合均匀，反应4-8小时后得到陶瓷涂料底漆；
A3、氟碳面漆的制备：将氟硅烷、乙酸、去离子水和异丙醇混合均匀，反应8-16小时，得到面漆。在该步骤中，由于氟硅烷分子链较长，水解速度较慢，所以其反应时间也较长。
步骤A1中，研磨至细度20μm以下后，再测试色浆的pH值，若小于9.0则用1％NaOH溶液调节至9.0-10.0之间，待用。
<第三方面>
本发明涉及一种长效不粘双涂层涂料的施用方法，所述方法包括如下步骤：
B1、金属基材喷砂至粗糙度Ra＝2.5-4μm，清洗，烘干；
B2、将金属基材预热至45-55℃，喷涂底漆后，在80-100℃下烘烤3-5分钟，取出冷却至室温，底漆厚度约为20-30μm；
B3、喷涂面漆，静置5-10分钟后，放入200-260℃烘箱中烘烤10-15分钟，取出冷却至室温即可。固化后的面漆厚度，即干膜厚度约为5-10μm。
步骤B1中，所述金属基材包括铝合金基材、不锈钢等。
步骤B2中固化温度不易过高，时间也不宜太长，使得底漆达到指干状态而非实干状态，即表面用手指触碰不粘手，但是内部没有完全干燥的状态，此时底漆表面有大量的-OH，有利于面漆与底漆之间的偶联结合，保证两层之间牢固的附着力。
步骤B3中喷涂面漆后需静置5-10分钟，此过程利于分子的扩散作用，偶联剂分子迁移到底漆和面漆粘接界面处并产生偶联作用。放置一段时间再进行固化，保证偶联剂完成迁移过程，方能获得底漆和面漆之间较好的附着力。偶联剂中也含有大量的-OH，可以与底漆表面的-OH发生偶联作用而牢固的结合在一起。
上述方法得到的涂层，将陶瓷涂层的高硬度与氟碳涂层的不粘持久性有机结合起来。面漆中所含的-F，具有优异的长效不粘性，炊具使用时，先由面漆提供不粘性，待面漆磨损，底漆中的硅油在高温下从微胶囊中缓慢扩散出来，持续为涂层提供不粘性。由于陶瓷涂料底漆具有高的硬度，使得含氟面漆的耐磨性也有了很大的提高，面漆的使用寿命得到有效延长。该方法制备的不粘涂层其不粘性可达到3年以上。
与现有技术相比，本发明具有以下有益效果：
(1)用氟硅烷水解液对陶瓷涂层表面进行涂敷修饰，通过氟硅烷的偶联作用，将氟碳面漆的不粘性与陶瓷涂料底漆的高硬度有机的结合起来，制得了具有长效不粘性的涂层；
(2)通过硅烷的水解聚合技术、表面活性剂对硅油的乳化技术，制得了具有壳-芯结构的硅油微胶囊，其中壳为硅烷水解聚合形成的Si-O-Si的三维交联网状结构，芯为表面活性剂乳化的硅油，该结构使得硅油与水性陶瓷涂料的相容性好，可以均匀分散在整个涂层中，高温下可以缓慢扩散出来，提高了涂层的不粘持久性；
(3)底漆中加入硅油微胶囊，当面漆磨损后，可以持续为涂层提供不粘性，大幅提升了不粘持久性，涂层的不粘性可保持3年以上。
具体实施方式
下面结合实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干调整和改进。这些都属于本发明的保护范围。
实施例1～3
实施例1～3提供一种长效不粘涂料，其组成如表1所示。
该长效不粘涂料的制备步骤如下：
(1)色浆制备：将硅溶胶、颜料、填料、分散剂、去离子水混合均匀，用1％NaOH溶液调节pH值至10，研磨至细度20μm以下，再测试色浆的pH值，若小于9.0则用1％NaOH溶液调节至9.5之间，待用；
(2)陶瓷涂料底漆制备：将硅烷、异丙醇、硅油微胶囊、25％甲酸混合均匀，然后加入步骤(1)制备好的色浆混合均匀，在辊架上反应6小时后得到陶瓷涂料底漆。
(3)氟碳面漆的制备：
将氟硅烷、乙酸、水醇混合液混合均匀，在辊架上反应12小时，得到面漆。
该长效不粘涂料的施工步骤如下：
(1)铝合金基材喷砂至粗糙度Ra＝3μm，自来水清洗干净，放入烘箱中烘干水分，待用；
(2)将基材预热至50℃，喷涂底漆后，在90℃下烘烤4分钟，取出冷却至室温，底漆厚度约为25μm；
(3)喷涂面漆，静置8分钟后，放入240℃烘箱中烘烤12分钟，取出冷却至室温即可；面漆厚度约为8μm。
对比例1
本对比例提供一种不粘涂料，其组成如表1所示；施工步骤同实施例1。
该长效不粘涂料的制备步骤如下：
(1)色浆制备：将硅溶胶、颜料、填料、分散剂、去离子水混合均匀，用1％NaOH溶液调节pH值至10，研磨至细度20μm以下，再测试色浆的pH值，若小于9.0则用1％NaOH溶液调节至9.5之间，待用；
(2)陶瓷涂料底漆制备：将硅烷、异丙醇、硅油、表面活性剂(十八烷基二甲基苄基氯化铵)、25％甲酸混合均匀，然后加入步骤(1)制备好的色浆混合均匀，在辊架上反应6小时后得到陶瓷涂料底漆。
(3)氟碳面漆的制备：
将氟硅烷、乙酸、水醇混合液混合均匀，在辊架上反应12小时，得到面漆。
对比例2～7
对比例2～7提供一种不粘涂料，其组成如表1所示。制备及施用步骤同实施例1。
表1实施例与对比例的涂料组成以及用量(wt.％)

表1中，水醇溶液为质量比为1:1的去离子水和异丙醇混合溶液；
硅油微胶囊1：将45％甲基硅油、48％硅烷(等质量比的甲基三甲氧基硅烷、二甲基二甲氧基硅烷)、4％表面活性剂(十八烷基二甲基苄基氯化铵)混合均匀，在搅拌状态下用25％甲酸将pH值调整至5，反应6hr后，再超声2hr，得到硅油微胶囊1；
硅油微胶囊2：将45％甲基硅油、48％硅烷(等质量比的甲基三甲氧基硅烷和甲基三乙氧基硅烷)、4％表面活性剂(十八烷基二甲基苄基氯化铵)混合均匀，在搅拌状态下用25％甲酸将pH值调整至5，反应6hr后，再超声2hr，得到硅油微胶囊2；
硅油微胶囊3：将45％甲基硅油、48％硅烷(等质量比的二甲基二甲氧基硅烷和二甲基二乙氧基硅烷)、4％表面活性剂(十八烷基二甲基苄基氯化铵)混合均匀，在搅拌状 态下用25％甲酸将pH值调整至5，反应6hr后，再超声2hr，得到硅油微胶囊3；
硅油微胶囊4：将45％甲基硅油、48％硅烷(等质量比的十六烷基三甲氧基硅烷和二甲基二甲氧基硅烷)、4％表面活性剂(十八烷基二甲基苄基氯化铵)混合均匀，在搅拌状态下用25％甲酸将pH值调整至5，反应6hr后，再超声2hr，得到硅油微胶囊4；
硅油微胶囊5：将45％甲基硅油、48％硅烷(质量比为1:3的甲基三甲氧基硅烷、二甲基二甲氧基硅烷)、4％表面活性剂(十八烷基二甲基苄基氯化铵)混合均匀，在搅拌状态下用25％甲酸将pH值调整至5，反应6hr后，再超声2hr，得到硅油微胶囊5；
硅油微胶囊6：将0.25克十二烷基磺酸钠和0.75克烷基酚聚氧乙烯醚溶解于100克去离子水中，再加入由10克二甲基硅油、10克TEOS、1.5克十八烷基三甲氧基硅烷组成的油相混合物，在冰水浴环境下预乳化搅拌15分钟，然后使用细胞粉碎机进行超声细乳化20分钟，获得细乳液。将细乳液的pH值调整至7.5，常温下高速搅拌24小时，得乳白色硅油微胶囊6。
主要性能测试
对以上实施例和对比例施工制得的涂层进行主要性能测试，检测项目以及方法见表2，检测结果如表3所示：
表2
表3

以上对本发明的具体实施例进行了描述。需要理解的是，本发明并不局限于上述特定实施方式，本领域技术人员可以在权利要求的范围内做出各种变形或修改，这并不影响本发明的实质内容。

Claims (10)

  1. 一种长效不粘双涂层涂料组合物，其特征在于，底漆为陶瓷涂层，面漆为氟碳涂层；
    底漆以总重100％计，包括：硅溶胶：26-28％，1％NaOH溶液：4-5％，颜料：10-12％，填料：8-10％，分散剂：1-1.5％，硅烷：28-30％，异丙醇：3-3.5％，硅油微胶囊：6-8％，25％甲酸：0.7-1％，去离子水：余量；
    面漆以总重100％计，包括：氟硅烷：1-2％，乙酸：3-5％，质量比为1:1的去离子水和异丙醇：余量。
  2. 根据权利要求1所述的长效不粘双涂层涂料组合物，其特征在于，所述硅溶胶选自阿克苏诺贝尔的Bindzil 2034DI、日产化学的ST-O-40，格雷斯HS-40中的一种或几种；所述硅烷选自甲基三甲氧基硅烷、甲基三乙氧基硅烷、二甲基二甲氧基硅烷中的一种或几种。
  3. 根据权利要求1所述的长效不粘双涂层涂料组合物，其特征在于，所述颜料为无机颜料；所述填料选自云母粉、硅微粉、高岭土、氧化铝粉、气相二氧化硅中的一种或几种；所述分散剂选自BYK180、BYK190、BYK2010、BYK2001中的一种或几种。
  4. 根据权利要求1所述的长效不粘双涂层涂料组合物，其特征在于，所述氟硅烷选用十七氟癸基三甲氧基硅烷或十七氟癸基三乙氧基硅烷。
  5. 根据权利要求1所述的长效不粘双涂层涂料组合物，其特征在于，以总重为100％计，所述硅油微胶囊包括硅油43-45％，硅烷48-50％，表面活性剂4-4.5％，25％甲酸溶液余量。
  6. 根据权利要求5所述的长效不粘双涂层涂料组合物，其特征在于，所述硅油为甲基硅油、羟基硅油中的一种或几种；所述硅烷由1：1-2：1的三官能度硅烷和二官能度硅烷组成。
  7. 根据权利要求5所述的长效不粘双涂层涂料组合物，其特征在于，所述表面活性剂选用有机季铵盐结构阳离子型表面活性剂，包括：十六烷基三甲基季铵溴化物、十八烷基二甲基苄基季铵氯化物、苯扎氯铵、苯扎溴铵的一种或几种。
  8. 根据权利要求5所述的长效不粘双涂层涂料组合物，其特征在于，所述硅油微胶囊的制备包括：将硅油、三官能度与二官能度混合的硅烷、表面活性剂混合均匀，在搅拌状态下用25％甲酸将pH值调整至4.0-5.0，反应4-6hr后，再超声2-2.5hr，得到 硅油微胶囊。
  9. 一种根据权利要求1所述的长效不粘双涂层涂料的制备方法，其特征在于，所述方法包括如下步骤：
    A1、色浆制备：将硅溶胶、颜料、填料、分散剂、去离子水混合均匀，用1％NaOH溶液调节pH值至9.5-10.5，研磨至细度20μm以下；
    A2、陶瓷涂料底漆制备：将硅烷、异丙醇、硅油微胶囊、25％甲酸混合均匀，然后加入步骤A1制备好的色浆混合均匀，反应4-8小时后得到陶瓷涂料底漆；
    A3、氟碳面漆的制备：将氟硅烷、乙酸、去离子水和异丙醇混合均匀，反应8-16小时，得到面漆。在该步骤中，由于氟硅烷分子链较长，水解速度较慢，所以其反应时间也较长。
  10. 一种根据权利要求1所述的长效不粘双涂层涂料的施用方法，其特征在于，所述方法包括如下步骤：
    B1、金属基材喷砂至粗糙度Ra＝2.5-4μm，清洗，烘干；
    B2、将金属基材预热至45-55℃，喷涂底漆后，在80-100℃下烘烤3-5分钟，取出冷却至室温，底漆厚度约为20-30μm；
    B3、喷涂面漆，静置5-10分钟后，放入200-260℃烘箱中烘烤10-15分钟，取出冷却至室温即可。
PCT/CN2023/113326 2022-08-30 2023-08-16 一种长效不粘涂料及其制备和施工方法 WO2024046127A1 (zh)

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