CN110484040B - PCM plate for air conditioner outdoor unit and production process thereof - Google Patents

PCM plate for air conditioner outdoor unit and production process thereof Download PDF

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CN110484040B
CN110484040B CN201910760029.2A CN201910760029A CN110484040B CN 110484040 B CN110484040 B CN 110484040B CN 201910760029 A CN201910760029 A CN 201910760029A CN 110484040 B CN110484040 B CN 110484040B
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parts
layer
paint layer
substrate
modified
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CN110484040A (en
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龚锡华
吴少华
张金龙
何伯鑫
阎志
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Hangzhou Puluofei New Material Technology Co ltd
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Hangzhou Puluofei New Material Technology Co ltd
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    • 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
    • B05D3/0272—After-treatment with ovens
    • 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
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • 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
    • B05D7/51—One specific pretreatment, e.g. phosphatation, chromatation, in combination with one specific coating
    • 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
    • B05D7/54—No clear coat specified
    • B05D7/546—No clear coat specified each layer being cured, at least partially, separately
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • 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
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • 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
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • 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
    • 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
    • B05D2320/00—Organic additives
    • 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
    • B05D2502/00—Acrylic polymers
    • 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
    • B05D2503/00—Polyurethanes
    • 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
    • B05D2506/00—Halogenated polymers
    • B05D2506/20—Chlorinated polymers
    • B05D2506/25—PVC
    • 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
    • B05D2518/00—Other type of polymers
    • B05D2518/10—Silicon-containing polymers
    • B05D2518/12—Ceramic precursors (polysiloxanes, polysilazanes)
    • 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
    • B05D2601/00—Inorganic fillers
    • B05D2601/20—Inorganic fillers used for non-pigmentation effect
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
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    • C08K2003/3045—Sulfates
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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  • Paints Or Removers (AREA)

Abstract

The invention discloses a PCM (pulse code modulation) board for an air-conditioning outdoor unit and a production process thereof, wherein the PCM board for the air-conditioning outdoor unit comprises a finish paint layer, a primer paint layer, a passivation layer, a substrate, the passivation layer, the primer paint layer and a back paint layer which are sequentially stacked; the finishing paint layer comprises the following components: castor oil modified waterborne polyurethane, modified carbon fiber, perchloro-ethylene resin, acetone, titanium dioxide, deionized water, barium sulfate, a flatting agent, a film-forming assistant, a dispersing agent and polyether modified organic siloxane; the back paint layer comprises the following components: the coating comprises an aqueous polyurethane dispersion, modified nano zinc oxide, hexafluorobutyl acrylate, nano silicon dioxide, chlorinated paraffin, a nano lotus leaf hydrophobic agent, a flatting agent, a film-forming auxiliary agent, a dispersing agent, polyether modified organic siloxane and deionized water. The PCM plate for the outdoor unit of the air conditioner has the advantages of good coating tensile property, difficult edge crack generation and excellent temperature and salt spray corrosion resistance.

Description

PCM plate for air conditioner outdoor unit and production process thereof
Technical Field
The invention relates to the technical field of color coated sheets, in particular to a PCM (pulse code modulation) sheet for an air conditioner outdoor unit and a production process thereof.
Background
The PCM plate is a color-coated steel plate and consists of a substrate and a coating, not only has the mechanical strength and easy-forming performance of the steel plate, but also has the advantages of good decoration, corrosion resistance, attractive appearance and the like of organic materials. For point-added products or parts with higher processing and stamping requirements, such as back plates of PDP, LED and the like, an air conditioner outdoor unit and the like, because the existing color-coated plate products cannot meet the requirements, the defects of coating cracks or falling off, substrate cracking, reduced corrosion resistance of deformed parts and the like are easy to occur in the processing and forming process.
In the prior art, a chinese patent application with application number CN201811210392.9 discloses a corrosion-resistant nano-graphene color-coated plate, which includes a top coating layer, a bottom coating layer, a first corrosion-resistant layer, a substrate, a second corrosion-resistant layer and a back coating layer, which are sequentially stacked; wherein the first corrosion-resistant layer comprises the following raw materials in parts by weight: 45-55 parts of bisphenol A type epoxy resin, 5-9 parts of nano graphene, 2-6 parts of talcum powder, 3-5 parts of wax powder, 15-21 parts of titanium dioxide and 1-3 parts of a first antioxidant; the second corrosion-resistant layer comprises the following raw materials in parts by weight: 60-70 parts of propyne-polyvinylidene fluoride copolymer, 4-8 parts of nano graphene, 5-9 parts of methyl cellulose, 3-7 parts of precipitated barium sulfate, 20-30 parts of polyvinyl alcohol and 0.5-1.5 parts of second antioxidant.
The existing corrosion-resistant nano graphene color-coated plate fully utilizes the excellent mechanical property, chemical stability and hydrophobic property of graphene, and improves the overall corrosion resistance of the color-coated plate, but if the corrosion-resistant nano graphene color-coated plate is made into an air conditioner outdoor unit and is used in humid and hot climate in coastal areas, because the top coating and the bottom coating of the color-coated plate can be stretched in the processing, stamping and bending processes, the stretching properties of the top coating and the bottom coating are poor, fine gaps can be generated on the stretched rear coating and the bottom coating, and the temperature of the air conditioner outdoor unit can be increased in the using process, so that the salt spray corrosion of the color-coated plate can be caused by the fact that salt spray particles in the air permeate between the coating and the substrate.
Therefore, the development of a PCM plate for an air conditioner outdoor unit, which has excellent resistance to water and salt mist corrosion and is suitable for use in humid and hot climates in coastal areas, is a problem to be solved.
Disclosure of Invention
Aiming at the defects in the prior art, the first purpose of the invention is to provide the PCM plate for the outdoor unit of the air conditioner, which has the advantages of good coating tensile property, difficult edge crack generation, excellent temperature and salt spray corrosion resistance and suitability for being used in the humid and hot climate in the rock sea area.
The second purpose of the invention is to provide a production process of the PCM plate for the outdoor unit of the air conditioner, which has the advantages of easy operation and convenient manufacture.
In order to achieve the first object, the invention provides the following technical scheme: a PCM plate for an air conditioner outdoor unit comprises a finish paint layer, a primer layer, a passivation layer, a substrate, a passivation layer, a primer layer and a back paint layer which are sequentially stacked;
the finish paint layer comprises the following components in parts by weight: 20-30 parts of castor oil modified waterborne polyurethane, 10-15 parts of modified carbon fiber, 6-10 parts of perchloro ethylene resin, 3-7 parts of acetone, 2.6-3.0 parts of titanium dioxide, 40-50 parts of deionized water, 1.2-1.6 parts of barium sulfate, 0.2-0.4 part of flatting agent, 0.3-0.5 part of film-forming assistant, 0.6-0.8 part of dispersing agent and 0.4-0.7 part of polyether modified organic siloxane; the back paint layer comprises the following components in parts by weight: 15-25 parts of aqueous polyurethane dispersoid, 6-10 parts of modified nano zinc oxide, 3-5 parts of hexafluorobutyl acrylate, 1.2-1.6 parts of nano silicon dioxide, 0.6-1 part of chlorinated paraffin, 2.2-2.6 parts of nano lotus leaf hydrophobing agent, 0.1-0.3 part of flatting agent, 0.1-0.3 part of film forming auxiliary agent, 0.4-0.6 part of dispersing agent, 0.2-0.5 part of polyether modified organic siloxane and 20-30 parts of deionized water.
By adopting the technical scheme, as the castor oil modified waterborne polyurethane and the perchloro-ethylene resin are adopted as film forming substances, the finish paint with good stability and strong hydrophobicity can be formed on the substrate, the water resistance and the moisture resistance of the finish paint are improved, the viscosity of the castor oil modified waterborne polyurethane is increased, the tensile strength is enhanced, the mechanical property of the finish paint can be improved, and the adhesion of the finish paint is enhanced; the carbon fiber has the advantages of high strength, high modulus, high density, small linear expansion coefficient and soft and rigid outside, the modified carbon fiber and the castor oil modified waterborne polyurethane are matched with each other, so that the tensile strength, the tear resistance and the wear resistance of a finish paint layer can be enhanced, the tensile strength of the finish paint is improved, the finish paint is not easy to crack and generate gaps during bending and stamping, corrosive substances are prevented from entering the coating and generating corrosion, and the corrosion resistance effect of the finish paint can be further enhanced due to the mutual cooperation of the nano titanium dioxide, the acetone and the barium sulfate; the modified carbon fiber, barium sulfate, nano titanium dioxide and other raw materials have small heat conductivity coefficient, and when the PCM plate is manufactured into an air conditioner outdoor unit, the heat conduction is small, so that the corrosion of warm water salt mist can be relieved.
The aqueous polyurethane dispersion and hexafluorobutyl acrylate are used as film forming substances, a glue film formed by the aqueous polyurethane dispersion is firm and has high elasticity and strong adhesive force, and is matched with hexafluorobutyl acrylate, the viscosity of the back paint is increased, the tensile strength is increased, the elongation at break is increased, the hydrophobicity of the aqueous polyurethane dispersion and the hexafluorobutyl acrylate after mixing can be further improved by the nano lotus leaf water repellent agent, so that the hydrophobic effect of the back paint is improved, the tensile strength, the tear resistance and the wear resistance of the back paint layer can be improved by the nano silicon dioxide, and the corrosion resistance, the adhesive force and the flexibility of the finish paint are improved; the nano zinc oxide can improve the wear resistance, mechanical strength, ageing resistance and smoothness of a coating film, the modified nano zinc oxide has better dispersibility in the back paint, is not easy to agglomerate, and can play a role in enhancing the corrosion resistance effect of the back paint, and the nano silicon dioxide and the chlorinated paraffin can reduce the heat conduction of the back paint and reduce the corrosion of warm water salt mist.
Further, the castor oil modified waterborne polyurethane is prepared by the following method:
drying polytetrahydrofuran diol at the constant temperature of 80-90 ℃ for 1-2h, taking out, adding castor oil, dibutyl tin dilaurate, 1, 4-butanediol, isophorone diisocyanate and dimethylolpropionic acid, stirring for reaction for 2-3h, adding hydroxyethyl methacrylate for continuous reaction for 0.8-1h, cooling to 35-40 ℃, adding triethylamine for neutralization for 25-30min, adding deionized water, stirring for 25-30min, adding sodium dodecyl sulfate, potassium persulfate and 2-perfluorooctyl ethyl acrylate, and stirring for 3-4h to obtain the modified waterborne polyurethane.
By adopting the technical scheme, the castor oil is used as a modifier, the dimethylolpropionic acid is used as a hydrophilic chain extension monomer, the 1, 4-butanediol is used as a straight chain extension monomer, the waterborne polyurethane is modified, the contact angle of the waterborne polyurethane to water is improved, the tensile property and the elongation at break of the waterborne polyurethane are enhanced, and meanwhile, the 2-perfluoro octyl ethyl acrylate is added into the waterborne polyurethane to improve the heat resistance, the water resistance and the mechanical property of the coating film.
Further, the castor oil modified waterborne polyurethane comprises the following components in parts by weight: 19-21 parts of polytetrahydrofuran diol, 9-10 parts of castor oil, 0.5-0.6 part of dibutyl tin dilaurate, 3-4 parts of 1, 4-butanediol, 11-13 parts of isophorone diisocyanate, 5-6 parts of dimethylolpropionic acid, 2-3 parts of hydroxyethyl methacrylate, 5-6 parts of triethylamine, 50-60 parts of deionized water, 2.5-3 parts of sodium dodecyl sulfate, 1.1-1.5 parts of potassium persulfate and 20-30 parts of 2-perfluorooctyl ethyl acrylate.
Further, the modified carbon fiber is prepared by the following method: (1) placing the carbon fiber in a muffle furnace at 650-700 ℃ for firing for 0.5-1h, washing with deionized water for 3-5 times, placing in a dopamine solution, reacting for 24h at room temperature, filtering, washing with deionized water for 3-5 times, and vacuum drying at 50-60 ℃; the mass ratio of the carbon fiber to the dopamine solution is 1: 3-5; (2) uniformly mixing graphene oxide, aluminum tripolyphosphate and a dopamine solution, adding carbon fibers, uniformly mixing, centrifuging, placing a substance obtained by centrifuging in an epoxy resin emulsion for curing, and preparing the modified carbon fibers, wherein the mass ratio of the carbon fibers, the graphene oxide, the aluminum tripolyphosphate and the dopamine solution is (1), (0.3-0.5), (0.6-0.8), (1.5-2.5), and the mass ratio of the substance obtained by centrifuging and the epoxy resin emulsion is (1), (1.3-1.5).
Through adopting above-mentioned technical scheme, place the carbon fiber in the muffle furnace firing, get rid of the impurity on carbon fiber surface, mix carbon fiber and dopamine solution, dopamine solution forms polydopamine layer on carbon fiber surface, polydopamine layer is as oxidation graphite alkene, the connecting agent of aluminium triphosphate and carbon fiber, adsorb oxidation graphite alkene and aluminium triphosphate evenly on carbon fiber surface, thereby improve the acid and alkali corrosion resistance and the salt fog corrosion resistance ability of carbon fiber, place the carbon fiber of even adsorption oxidation graphite alkene and aluminium triphosphate in the epoxy emulsion, form the hydrophobic layer on carbon fiber surface, thereby strengthen the hydrophobic property of carbon fiber, improve the water resistance of coating, temperature-resistant water salt fog performance.
Further, the modified nano zinc oxide is prepared by the following method: mixing 3-4 parts by weight of titanate coupling agent and 5-6 parts by weight of acetone, adding 4.5-6.5 parts by weight of 1, 4-propylene glycol, uniformly stirring, adding nano zinc oxide, stirring for 30-40min, uniformly mixing, performing suction filtration, washing with acetone, dripping for 3-5 times, and drying at 80-90 ℃; adding the modified nano-zinc oxide into deionized water, stirring to prepare a suspension, adding the graphene oxide dispersion, stirring for 2-3h, performing centrifugal separation, and drying at 60-70 ℃ for 10-12h to prepare the modified nano-zinc oxide, wherein the mass ratio of the modified nano-zinc oxide to the deionized water to the graphene oxide dispersion is 1 (3-5) to 1.5-2.5.
By adopting the technical scheme, the nano zinc oxide is firstly mixed with the titanate coupling agent and the 1, 4-propylene glycol to improve the dispersibility of the nano zinc oxide in the coating and enhance the corrosion resistance of the coating, and the graphene dispersed uniformly can be uniformly mixed with the nano zinc oxide by doping the graphene oxide dispersion liquid to enhance the toughness, strength and dispersibility of the coating and improve the salt spray corrosion resistance of the coating.
Further, the leveling agent is one or two of EFKA-3777, BYK-354 and polyether modified silicone oil; the film-forming aid is prepared by mixing dipropylene glycol methyl ether and alcohol ester-12 according to the mass ratio of 1: 1-2;
the dispersing agent is prepared by mixing sodium p-toluenesulfonate, oleamide and polyethylene glycol according to the mass ratio of (3.8-4.2) to (1.8-2.2) to 4.
By adopting the technical scheme, the sodium p-toluenesulfonate can adjust the viscosity of the primer and the finish paint, improve the fluidity of the primer and the finish paint, and can reduce and increase the dispersion uniformity of the primer and the finish paint and improve the surface gloss of the primer and the finish paint by being matched with the oleamide and the polyethylene glycol.
Furthermore, the thickness of the surface paint layer is 17-20 μm, the thickness of the back paint layer is 2-12 μm, the thickness of the primer layer between the passivation layer and the surface paint layer is 6.5-10 μm, the thickness of the primer layer between the passivation layer and the back paint layer is 6-10 μm,the thickness of the passivation layer is 20-30mg/m2。
By adopting the technical scheme, the thicknesses of the finish paint, the back paint, the primer and the passivation layer are proper, and the finish paint, the back paint, the primer and the passivation layer can be matched with each other to enhance the tensile strength, the acid and alkali corrosion resistance and the salt spray corrosion resistance of the PCM plate.
Further, the substrate is a galvanized plate, and the galvanizing amount is 130-140g/m2。
By adopting the technical scheme, the zinc plating amount is 130-140g/m2The galvanized steel sheet has unqualified T-bend test due to too large galvanizing amount and poor corrosion resistance due to small galvanizing amount, so the requirement of the galvanizing amount is 130-2。
In order to achieve the second object, the invention provides the following technical scheme: a process for producing a PCM board for an outdoor unit of an air conditioner according to any one of claims 1 to 8, comprising the steps of:
s1, degreasing and cleaning the substrate: degreasing, cleaning and drying the substrate;
s2, passivation treatment: soaking the substrate in a passivation solution, passivating for 10-30min, taking out, and drying to form passivation layers on two sides of the substrate;
s3, primer coating and curing: uniformly coating priming paint with the temperature of 40-45 ℃ and the viscosity of 54-56S on the passivation layers on the two sides of the substrate, then placing the substrate into a curing furnace for curing, wherein the curing temperature is 214-220 ℃, forming the priming paint layers on the two sides of the passivation layer, and then cooling the priming paint layers on the substrate by using demineralized water;
s4, coating and curing a back paint layer: uniformly coating back finish paint with the temperature of 38-42 ℃ on the primer layer on one side of the substrate, putting the substrate into a curing furnace with the temperature of 220-230 ℃ for curing to form a back paint layer, and cooling by using demineralized water;
s5, coating and curing of the finishing paint layer: uniformly coating finish paint with the temperature of 35-40 ℃ and the viscosity of 225-229S on the primer layer on the side, far away from the back paint layer, of the substrate, putting the substrate into a curing furnace with the curing temperature of 224-235 ℃ to form a finish paint layer, cooling the finish paint layer by using desalted water, and rolling the PCM plate at the linear speed of 20-25 m/min.
By adopting the technical scheme, the curing temperature of the primer and the finish paint is proper, so that the primer and the finish paint can be completely cured, and the primer and the finish paint are not easy to crack after stamping and are not easy to crack after trimming.
Further, the cleaning liquid in the S1 is alkali liquor, the concentration is 0.5-1.5%, and the temperature of the alkali liquor is 50-70 ℃; in the step S2, the solubility of the passivation solution is 20-45%, and the drying temperature is 80-100 ℃; in the steps S3, S4 and S5, the conductivity of the desalted water is 70-80 μm/S, the cooling treatment time is 12-15S, and the temperature of the primer layer, the back paint layer and the finish paint layer after cooling is 36-42 ℃.
In conclusion, the invention has the following beneficial effects:
firstly, because the castor oil modified waterborne polyurethane and the perchloro-ethylene resin are adopted as film forming substances, a hydrophobic film can be formed on the substrate, due to the addition of the modified carbon fibers, the hydrophobic film has good tensile strength, strong elongation at break and good tensile property, and due to the doping of the barium sulfate and the nano titanium dioxide, the hydrophobic film has good corrosion resistance effect.
Secondly, the aqueous polyurethane dispersion is preferably adopted to be made into a film material, the adhesion force of the aqueous polyurethane dispersion is strong and elastic, after the aqueous polyurethane dispersion is matched with hexafluorobutyl acrylate, the tensile property of the back paint can be further enhanced, the electronegativity of fluorine atoms is extremely strong, common electron pairs in carbon-fluorine strongly deviate to the fluorine atoms, redundant negative charges are formed around the fluorine atoms, and a nucleophilic reagent is difficult to attack the carbon atoms through a negative charge protective layer, so that the back paint layer has strong corrosion resistance, the surface energy of the back paint is low due to the fluorine atoms, the contact angle of the back paint to water is more than 90 degrees, the back paint is difficult to wet, the back paint has super-strong hydrophobicity, the primer has strong corrosion resistance and hydrophobicity, and the corrosion phenomenon is prevented.
Thirdly, in the invention, as the dopamine solution is used for forming the polydopamine layer on the carbon fiber, and then the polydopamine layer is mixed with the graphene oxide and the aluminum tripolyphosphate to form the barrier structure on the carbon fiber, the corrosion resistance of the carbon fiber can be further improved, and the carbon fiber is cured in the epoxy resin to improve the tensile property, the bending property and the impact strength of the carbon fiber.
Drawings
Fig. 1 is a schematic structural view of a PCM board in embodiment 1 of the present invention.
In the figure: 1. a finish paint layer; 2. a primer layer; 3. a passivation layer; 4. a substrate; 5. and (6) backing a paint layer.
Detailed Description
The present invention will be described in further detail with reference to the following drawings and examples.
Preparation examples 1 to 3 of Castor oil-modified aqueous polyurethane
Preparation example 1: according to the raw material proportion in the table 1, 19g of polytetrahydrofuran diol is dried at the constant temperature of 80 ℃ for 2h, taken out, 9g of castor oil, 0.5g of dibutyltin dilaurate, 3g of 1, 4-butanediol, 11g of isophorone diisocyanate and 5g of dimethylolpropionic acid are added, stirring is carried out for 2h, 2g of hydroxyethyl methacrylate is added for continuous reaction for 0.8h, the temperature is reduced to 35 ℃, 5g of triethylamine is added for neutralization for 30min, 50g of deionized water is added, stirring is carried out for 30min, 2.5g of sodium dodecyl sulfate, 1.1g of potassium persulfate and 20g of 2-perfluorooctyl ethyl acrylate are added, and stirring is carried out for 3h, so that the modified waterborne polyurethane is prepared.
TABLE 1 amount of raw materials for Castor oil-modified waterborne polyurethane in preparation examples 1 to 3
Figure BDA0002169969550000061
Preparation example 2: according to the raw material proportion in Table 1, 20g of polytetrahydrofuran diol is dried at the constant temperature of 85 ℃ for 1.5h, taken out, 9.5g of castor oil, 0.55g of dibutyltin dilaurate, 3.5g of 1, 4-butanediol, 12g of isophorone diisocyanate and 5.5g of dimethylolpropionic acid are added, the stirring reaction is carried out for 2.5h, 2.5g of hydroxyethyl methacrylate is added for continuous reaction for 0.9h, the temperature is reduced to 38 ℃, 5.5g of triethylamine is added for neutralization for 28min, 55g of deionized water is added, the stirring is carried out for 28min, 2.8g of sodium dodecyl sulfate, 1.3g of potassium persulfate and 25g of 2-perfluorooctyl ethyl acrylate are added, and the stirring is carried out for 3.5h, so that the modified waterborne polyurethane is prepared.
Preparation example 3: according to the raw material proportion in Table 1, 21g of polytetrahydrofuran diol is dried at the constant temperature of 90 ℃ for 1h, taken out, 11g of castor oil, 0.6g of dibutyltin dilaurate, 6g of 1, 4-butanediol, 13g of isophorone diisocyanate and 6g of dimethylolpropionic acid are added, stirring is carried out for reaction for 3h, 3g of hydroxyethyl methacrylate is added for continuous reaction for 1h, the temperature is reduced to 40 ℃, 6g of triethylamine is added for neutralization for 25min, 50g of deionized water is added, stirring is carried out for 25min, 3g of sodium dodecyl sulfate, 1.5g of potassium persulfate and 30g of 2-perfluorooctyl ethyl acrylate are added, and stirring is carried out for 4h, so that the modified waterborne polyurethane is prepared.
Preparation examples 4 to 6 of modified carbon fibers
Preparation examples 4 to 6 the carbon fiber was selected from the carbon fiber sold by Shanghai Limo composite science and technology Co., Ltd under the Cat No. 062, the graphene oxide was selected from the graphene oxide sold by Hunan Fenghua Material development Co., Ltd under the model No. FH-661, the aluminum tripolyphosphate was selected from the aluminum tripolyphosphate sold by Changzhou Roro New chemical Material Co., Ltd under the model No. RA-8995, and the epoxy resin emulsion was selected from the epoxy resin emulsion sold by Guanguan general chemical products Co., Ltd under the model No. BH-653.
Preparation example 4: (1) placing the carbon fiber in a muffle furnace at 650 ℃ for firing for 1h, cleaning with deionized water for 3 times, placing in a dopamine solution with the concentration of 2g/L and the pH value of 8.5, reacting for 24h at room temperature, filtering, cleaning with deionized water for 3 times, and vacuum-drying at 50 ℃; the mass ratio of the carbon fiber to the dopamine solution is 1: 3;
(2) uniformly mixing graphene oxide, aluminum tripolyphosphate and a dopamine solution, adding carbon fibers, uniformly mixing, centrifuging, placing a centrifuged substance in an epoxy resin emulsion for curing, and preparing the modified carbon fibers, wherein the mass ratio of the carbon fibers, the graphene oxide, the aluminum tripolyphosphate and the dopamine solution is 1:0.3:0.6:1.5, and the mass ratio of the centrifuged substance to the epoxy resin emulsion is 1: 1.3.
Preparation example 5: (1) putting the carbon fiber in a muffle furnace at 680 ℃ for firing for 0.8h, washing with deionized water for 4 times, putting in a dopamine solution with the concentration of 2g/L and the pH value of 8.5, reacting for 24h at room temperature, filtering, washing with deionized water for 4 times, and vacuum-drying at 55 ℃; the mass ratio of the carbon fiber to the dopamine solution is 1: 4;
(2) uniformly mixing graphene oxide, aluminum tripolyphosphate and a dopamine solution, adding carbon fibers, uniformly mixing, centrifuging, placing a substance obtained by centrifuging in an epoxy resin emulsion for curing, and preparing the modified carbon fibers, wherein the mass ratio of the carbon fibers, the graphene oxide, the aluminum tripolyphosphate and the dopamine solution is 1:0.4:0.7:2, and the mass ratio of the substance obtained by centrifuging to the epoxy resin emulsion is 1: 1.4.
Preparation example 6: (1) placing the carbon fiber in a muffle furnace at 700 ℃ for firing for 0.5h, washing with deionized water for 5 times, placing in a dopamine solution with the concentration of 2g/L and the pH value of 8.5, reacting for 24h at room temperature, filtering, washing with deionized water for 5 times, and vacuum-drying at 60 ℃; the mass ratio of the carbon fiber to the dopamine solution is 1: 5;
(2) uniformly mixing graphene oxide, aluminum tripolyphosphate and a dopamine solution, adding carbon fibers, uniformly mixing, centrifuging, placing a centrifuged substance in an epoxy resin emulsion for curing, and preparing the modified carbon fibers, wherein the mass ratio of the carbon fibers, the graphene oxide, the aluminum tripolyphosphate and the dopamine solution is 1:0.5:0.8:2.5, and the mass ratio of the centrifuged substance to the epoxy resin emulsion is 1: 1.5.
Preparation examples 7 to 9 of modified Nano Zinc oxide
The titanate coupling agent in preparation examples 7 to 9 was selected from the titanate coupling agent sold under the trade name of 030 from Lvwei plastics Co.Ltd, of Dongguan city, the nano zinc oxide was selected from the nano zinc oxide sold under the trade name of PZT, which is sold under the trade name of Nanjing Baker New Material Co.Ltd, and the graphene oxide dispersion was selected from the graphene oxide dispersion sold under the trade name of RTP001, which is sold under the trade name of Jiangsutaneng nanometer Material science and technology Co.Ltd.
Preparation example 7: mixing 3kg of titanate coupling agent and 5kg of acetone, adding 4.5kg of 1, 4-propylene glycol, stirring uniformly, adding nano zinc oxide, stirring for 30min, mixing uniformly, performing suction filtration, washing with acetone, dripping for 3 times, and drying at 80 ℃; adding the modified nano-zinc oxide into deionized water, stirring to prepare a suspension, adding the graphene oxide dispersion, stirring for 2h, performing centrifugal separation, and drying at 60 ℃ for 12h to prepare the modified nano-zinc oxide, wherein the mass ratio of the modified nano-zinc oxide to the deionized water to the graphene oxide dispersion is 1:3: 1.5.
Preparation example 8: mixing 3.5kg titanate coupling agent and 5.5kg acetone, adding 5.5kg 1, 4-propylene glycol, stirring, adding nanometer zinc oxide, stirring for 35min, mixing, vacuum filtering, washing with acetone for 4 times, and drying at 85 deg.C; adding the modified nano-zinc oxide into deionized water, stirring to prepare a suspension, adding the graphene oxide dispersion, stirring for 2.5 hours, performing centrifugal separation, and drying at 65 ℃ for 11 hours to prepare the modified nano-zinc oxide, wherein the mass ratio of the modified nano-zinc oxide to the deionized water to the graphene oxide dispersion is 1:4: 2.
Preparation example 9: mixing 4kg of titanate coupling agent and 6kg of acetone, adding 6.5kg of 1, 4-propylene glycol, stirring uniformly, adding nano zinc oxide, stirring for 40min, mixing uniformly, performing suction filtration, washing with acetone, dripping for 5 times, and drying at 90 ℃; adding the modified nano-zinc oxide into deionized water, stirring to prepare a suspension, adding the graphene oxide dispersion, stirring for 3h, performing centrifugal separation, and drying at 70 ℃ for 10h to prepare the modified nano-zinc oxide, wherein the mass ratio of the modified nano-zinc oxide to the deionized water to the graphene oxide dispersion is 1:5: 2.5.
Examples
Examples 1-5 the primer was selected from the group consisting of the primer sold by Hangzhou Asian paint ink Co., Ltd under the trade designation DQ0042, the aqueous polyurethane dispersion was selected from the group consisting of the aqueous polyurethane dispersion sold by Jining HuaKai resin Co., Ltd under the trade designation HK718, the perchloroethylene resin was selected from the group consisting of the perchloroethylene resin sold by Jinan sea chemical engineering Co., Ltd under the trade designation 39871, the hexafluorobutyl acrylate was selected from the group consisting of the hexafluorobutyl acrylate sold by Guangdong Shangjiang chemical reagent Co., Ltd under the trade designation PB04350, the chlorinated paraffin was selected from the group consisting of the chlorinated paraffin sold by Jinan Lu Ying chemical Co., Ltd under the trade designation 011, the nano-hydrophobizing agent was selected from the group consisting of the nano-lotus leaf hydrophobizing agent sold by Dongguan Chengjiang chemical Co., Ltd under the trade designation SP-2405, the dipropylene glycol methyl ether was selected from the group consisting of the dipropylene glycol methyl ether sold by Tianjin Zhongsheng and Tai chemical Co., Ltd under the trade designation -12, the polyester modified organosiloxane is selected from SH-022, EFKA-3777, BYK-354 being from BYK-354 sold by seoul chemical limited, shanghai and jabi chemical limited, OFX-0400, oleamide, DH-K220, and passivation solution, Bonderite1402W, from hangao surface technology limited.
Example 1: the PCM board for the air-conditioning outdoor unit comprises a finish paint layer 1, a primer paint layer 2, a passivation layer 3, a substrate 4 layer, a passivation layer 3, a primer paint layer 2 and a back paint layer 5 which are sequentially stacked, wherein the thickness of the finish paint layer 1 is 17 mu m, the thickness of the back paint layer 5 is 2 mu m, the thickness of the primer paint layer 2 between the finish paint layer 1 and the passivation layer 3 is 6.5 mu m, the thickness of the primer paint layer 2 between the back paint layer 5 and the passivation layer 3 is 6 mu m, and the thickness of the passivation layer 3 is 20mg/m2The substrate 4 is a galvanized steel sheet having a galvanizing content of 140g/m2。
The production process of the PCM plate for the outdoor unit of the air conditioner comprises the following steps:
s1, degreasing and cleaning of the substrate 4: degreasing, cleaning and drying the substrate 4, wherein the cleaning solution is alkali liquor, the concentration of the alkali liquor is 0.5%, and the temperature of the alkali liquor is 50 ℃;
s2, passivation treatment: soaking the substrate 4 in a passivation solution for passivation for 10min, wherein the solubility of the passivation solution is 20%, the drying temperature is 80 ℃, taking out and drying, and forming passivation layers 3 on two sides of the substrate 4;
s3, primer coating and curing: uniformly coating priming paint with the temperature of 40 ℃ and the viscosity of 54S on the passivation layers 3 on the two sides of the substrate 4, then putting the substrate 4 into a curing furnace for curing, wherein the curing temperature is 214 ℃, the priming paint layers 2 are formed on the two sides of the passivation layer 3, then cooling the priming paint layers 2 on the substrate 4 by using demineralized water, the conductivity of the demineralized water is 70 mu m/S, the cooling treatment time is 12S, and the temperature of the priming paint layers 2 after cooling is 36 ℃;
s4, coating and curing of the back paint layer 5: uniformly coating back finish paint with the temperature of 38 ℃ on the primer layer 2 on one side of the substrate 4, putting the substrate 4 into a curing furnace with the temperature of 220 ℃ for curing to form a back paint layer 5, cooling by using desalted water, wherein the conductivity of the desalted water is 70 mu m/s, the cooling treatment time is 12s, and the temperature of the primer layer 2 after cooling is 36 ℃;
the back paint is prepared from the raw materials in the following table 2 according to the following method: stirring 0.1kg of film-forming auxiliary agent, 2.2kg of nano lotus leaf hydrophobing agent, 0.2kg of polyether modified organic siloxane and 0.6kg of chlorinated paraffin for 5min to prepare a premixed solution; adding 1.2kg of nano silicon dioxide, 6kg of modified nano zinc oxide, 3kg of hexafluorobutyl acrylate, 0.4kg of dispersing agent and premixed liquid into 20kg of deionized water, uniformly mixing, grinding until the fineness reaches 40 mu m, adding 15kg of aqueous polyurethane dispersion and 0.1kg of flatting agent, uniformly stirring, and standing for curing for 30 min; the leveling agent is EFKA-3777, the film-forming aid is prepared by mixing dipropylene glycol methyl ether and alcohol ester-12 according to the mass ratio of 1:1, the dispersant is prepared by mixing sodium p-toluenesulfonate, oleamide and polyethylene glycol according to the mass ratio of 3.8:2.2:4, and the modified nano zinc oxide is prepared by preparation example 7;
s5, coating and curing the finishing paint layer 1: uniformly coating finish paint with the temperature of 35 ℃ and the viscosity of 225S on the primer layer 2 on the side, far away from the back paint layer 5, of the substrate 4, putting the substrate 4 into a curing furnace, wherein the curing temperature is 224 ℃, forming a finish paint layer 1, cooling the finish paint layer 1 by using desalted water, the conductivity of the desalted water is 70 mu m/S, the cooling treatment time is 12S, the temperature of the primer layer 2 after cooling is 36 ℃, and winding the PCM plate at the linear speed of 20 m/min;
the primer is prepared from the raw materials in the following table 2 according to the following method: 20kg of castor oil modified waterborne polyurethane, 40kg of deionized water, 0.6kg of a dispersing agent, 1.2kg of barium sulfate, 10kg of modified carbon fiber and 2.6kg of titanium dioxide are uniformly mixed, the mixture is ground to the fineness of 40 micrometers, 6kg of perchloroethylene resin dissolved by 3kg of acetone is added, 0.3kg of a film forming aid, 0.2kg of a leveling agent and 0.4kg of polyether modified organosiloxane are added and uniformly mixed to prepare the finish paint, wherein the leveling agent is EFKA-3777, the film forming aid is prepared by mixing dipropylene glycol methyl ether and alcohol ester-12 according to the mass ratio of 1:1, the dispersing agent is prepared by mixing sodium p-methyl benzene sulfonate, oleamide and polyethylene glycol according to the mass ratio of 3.8:2.2:4, the castor oil modified waterborne polyurethane is prepared by preparation example 1, and the modified carbon fiber is prepared by preparation example 4.
TABLE 2 raw material ratios of top coat and back coat in examples 1-5
Figure BDA0002169969550000101
Figure BDA0002169969550000111
Example 2: the PCM board for the outdoor unit of the air conditioner comprises a finish paint layer 1, a primer paint layer 2, a passivation layer 3, a substrate 4 layer, a passivation layer 3, a primer paint layer 2 and a back paint layer 5 which are sequentially overlapped, wherein the thickness of the finish paint layer 1 is 19 mu m, the thickness of the back paint layer 5 is 7 mu m, the thickness of the primer paint layer 2 between the finish paint layer 1 and the passivation layer 3 is 8 mu m, the thickness of the primer paint layer 2 between the back paint layer 5 and the passivation layer 3 is 8 mu m, and the thickness of the passivation layer 3 is 23mg/m2The substrate 4 is a galvanized steel sheet with a galvanizing amount of 130g/m2。
The production process of the PCM plate for the outdoor unit of the air conditioner comprises the following steps:
s1, degreasing and cleaning of the substrate 4: degreasing, cleaning and drying the substrate 4, wherein the cleaning solution is alkali liquor, the concentration of the alkali liquor is 1%, and the temperature of the alkali liquor is 60 ℃;
s2, passivation treatment: soaking the substrate 4 in a passivation solution for passivation for 20min, wherein the solubility of the passivation solution is 35%, the drying temperature is 90 ℃, taking out and drying, and forming passivation layers 3 on two sides of the substrate 4;
s3, primer coating and curing: uniformly coating primers with the temperature of 43 ℃ and the viscosity of 55S on the passivation layers 3 on the two sides of the substrate 4, then putting the substrate 4 into a curing furnace for curing, wherein the curing temperature is 217 ℃, the primer layers 2 are formed on the two sides of the passivation layer 3, then cooling the primer layers 2 on the substrate 4 by using demineralized water, the conductivity of the demineralized water is 75 mu m/S, the cooling treatment time is 14S, and the temperature of the primer layers 2 after cooling is 39 ℃;
s4, coating and curing of the back paint layer 5: uniformly coating back finish paint with the temperature of 38 ℃ on the primer layer 2 on one side of the substrate 4, putting the substrate 4 into a curing furnace with the temperature of 225 ℃ for curing to form a back paint layer 5, cooling by using desalted water, wherein the conductivity of the desalted water is 75 mu m/s, the cooling treatment time is 14s, and the temperature of the primer layer 2 after cooling is 39 ℃;
the back paint is prepared from the raw materials in the following table 2 according to the following method: stirring 0.15kg of film-forming assistant, 2.3kg of nano lotus leaf hydrophobing agent, 0.3kg of polyether modified organic siloxane and 0.7kg of chlorinated paraffin for 8min to prepare a premixed solution; adding 1.3kg of nano silicon dioxide, 7kg of modified nano zinc oxide, 3.5kg of hexafluorobutyl acrylate, 0.45kg of dispersing agent and premixed liquid into 23kg of deionized water, uniformly mixing, grinding until the fineness reaches 45 micrometers, adding 18kg of aqueous polyurethane dispersion and 0.15kg of flatting agent, uniformly stirring, standing and curing for 45 min; the leveling agent is BYK-354, the film-forming aid is prepared by mixing dipropylene glycol methyl ether and alcohol ester-12 according to the mass ratio of 1:1.5, the dispersant is prepared by mixing sodium p-toluenesulfonate, oleamide and polyethylene glycol according to the mass ratio of 4:2:4, and the modified nano zinc oxide is prepared by preparation example 8;
s5, coating and curing the finishing paint layer 1: uniformly coating finish paint with the temperature of 38 ℃ and the viscosity of 227S on the primer layer 2 on the side, far away from the back paint layer 5, of the substrate 4, putting the substrate 4 into a curing furnace, wherein the curing temperature is 230 ℃, forming a finish paint layer 1, cooling the finish paint layer 1 by using demineralized water, the conductivity of the demineralized water is 75 mu m/S, the cooling treatment time is 14S, the temperature of the primer layer 2 after cooling is 39 ℃, and winding the PCM plate at the linear speed of 23 m/min;
the primer is prepared from the raw materials in the following table 2 according to the following method: 21kg of castor oil modified waterborne polyurethane, 42kg of deionized water, 0.65kg of a dispersing agent, 1.3kg of barium sulfate, 11kg of modified carbon fiber and 2.7kg of titanium dioxide are uniformly mixed, the mixture is ground to the fineness of 45 micrometers, 7kg of perchloroethylene resin dissolved by 4kg of acetone is added, 0.35kg of a film forming aid, 0.25kg of a leveling agent and 0.5kg of polyether modified organosiloxane are added and uniformly mixed to prepare the finish paint, wherein the leveling agent is BYK-354, the film forming aid is prepared by mixing dipropylene glycol methyl ether and alcohol ester-12 according to the mass ratio of 1:1.5, the dispersing agent is prepared by mixing sodium p-methyl benzene sulfonate, oleamide and polyethylene glycol according to the mass ratio of 4:2:4, the castor oil modified waterborne polyurethane is prepared by preparation example 2, and the modified carbon fiber is prepared by preparation example 5.
Example 3: the PCM board for the outdoor unit of the air conditioner comprises a finish paint layer 1, a primer paint layer 2, a passivation layer 3, a substrate 4 layer, a passivation layer 3, a primer paint layer 2 and a back paint layer 5 which are sequentially overlapped, wherein the thickness of the finish paint layer 1 is 20 mu m, the thickness of the back paint layer 5 is 12 mu m, the thickness of the primer paint layer 2 between the finish paint layer 1 and the passivation layer 3 is 10 mu m, the thickness of the primer paint layer 2 between the back paint layer 5 and the passivation layer 3 is 10 mu m, and the thickness of the passivation layer 3 is 25mg/m2The substrate 4 is a galvanized steel sheet with a galvanizing amount of 135g/m2。
The production process of the PCM plate for the outdoor unit of the air conditioner comprises the following steps:
s1, degreasing and cleaning of the substrate 4: degreasing, cleaning and drying the substrate 4, wherein the cleaning solution is alkali liquor, the concentration of the alkali liquor is 1.5%, and the temperature of the alkali liquor is 70 ℃;
s2, passivation treatment: soaking the substrate 4 in a passivation solution for passivation for 30min, wherein the solubility of the passivation solution is 45%, and the drying temperature is 100 ℃, taking out and drying to form passivation layers 3 on two sides of the substrate 4;
s3, primer coating and curing: uniformly coating primers with the temperature of 45 ℃ and the viscosity of 56S on the passivation layers 3 on the two sides of the substrate 4, then putting the substrate 4 into a curing furnace for curing, wherein the curing temperature is 220 ℃, the primer layers 2 are formed on the two sides of the passivation layer 3, then cooling the primer layers 2 on the substrate 4 by using demineralized water, the conductivity of the demineralized water is 80 mu m/S, the cooling treatment time is 15S, and the temperature of the primer layers 2 after cooling is 42 ℃;
s4, coating and curing of the back paint layer 5: uniformly coating a back finish paint with the temperature of 42 ℃ on the primer layer 2 on one side of the substrate 4, putting the substrate 4 into a curing furnace with the temperature of 230 ℃ for curing to form a back paint layer 5, cooling by using desalted water, wherein the conductivity of the desalted water is 80 mu m/s, the cooling treatment time is 15s, and the temperature of the primer layer 2 after cooling is 42 ℃;
the back paint is prepared from the raw materials in the following table 2 according to the following method: stirring 0.2kg of film-forming assistant, 2.4kg of nano lotus leaf hydrophobing agent, 0.4kg of polyether modified organic siloxane and 0.8kg of chlorinated paraffin for 10min to prepare a premixed solution; adding 1.4kg of nano silicon dioxide, 8kg of modified nano zinc oxide, 4kg of hexafluorobutyl acrylate, 0.5kg of dispersing agent and premixed liquid into 25kg of deionized water, uniformly mixing, grinding until the fineness reaches 50 micrometers, adding 20kg of aqueous polyurethane dispersion and 0.2kg of flatting agent, uniformly stirring, and standing for curing for 60 min; the leveling agent is polyether modified silicone oil, the film-forming assistant is prepared by mixing dipropylene glycol methyl ether and alcohol ester-12 according to the mass ratio of 1:2, the dispersant is prepared by mixing sodium p-toluenesulfonate, oleamide and polyethylene glycol according to the mass ratio of 4.2:1.8:4, and the modified nano zinc oxide is prepared by preparation example 9;
s5, coating and curing the finishing paint layer 1: uniformly coating finish paint with the temperature of 40 ℃ and the viscosity of 229S on the primer layer 2 on one side, far away from the back paint layer 5, of the substrate 4, putting the substrate 4 into a curing furnace, wherein the curing temperature is 235 ℃, forming a finish paint layer 1, cooling the finish paint layer 1 by using demineralized water, the conductivity of the demineralized water is 80 mu m/S, the cooling treatment time is 15S, and the temperature of the primer layer 2 after cooling is 42 ℃; winding the PCM plate at a linear speed of 25 m/min;
the primer is prepared from the raw materials in the following table 2 according to the following method: 22kg of castor oil modified waterborne polyurethane, 45kg of deionized water, 0.7kg of a dispersing agent, 1.4kg of barium sulfate, 12kg of modified carbon fiber and 2.8kg of titanium dioxide are uniformly mixed, the mixture is ground to the fineness of 50 micrometers, 5kg of acetone 8kg of perchloroethylene resin is added, 0.4kg of a film forming aid, 0.3kg of a leveling agent and 0.6kg of polyether modified organosiloxane are added, the mixture is uniformly mixed to prepare the finish paint, the leveling agent is polyether modified silicone oil, the film forming aid is prepared by mixing dipropylene glycol methyl ether and alcohol ester-12 according to the mass ratio of 1:2, the dispersing agent is prepared by mixing sodium p-toluenesulfonate, oleamide and polyethylene glycol according to the mass ratio of 4.2:1.8:4, the castor oil modified waterborne polyurethane is prepared by preparation example 4, and the modified carbon fiber is prepared by preparation example.
Examples 4 to 5: a PCM board for an outdoor unit of an air conditioner, which is different from example 1 in that the amounts of the materials for the top coating and the back coating are shown in table 2.
Comparative example
Comparative example 1: the PCM plate for the outdoor unit of the air conditioner is different from the PCM plate in the embodiment 1 in that the waterborne polyurethane in the finish paint is not modified by castor oil.
Comparative example 2: the PCM plate for the air conditioner outdoor unit is different from the PCM plate in the embodiment 1 in that 2-perfluorooctyl ethyl acrylate is not added into castor oil modified waterborne polyurethane in finish paint.
Comparative example 3: the PCM board for the outdoor unit of the air conditioner is different from the PCM board in the embodiment 1 in that modified carbon fibers are not added in finish paint.
Comparative example 4: the PCM plate for the air conditioner outdoor unit is different from the PCM plate in example 1 in that graphene oxide and aluminum tripolyphosphate are not added into finish-coat modified carbon fibers.
Comparative example 5: the PCM plate for the outdoor unit of the air conditioner is different from the PCM plate in the embodiment 1 in that modified nano zinc oxide is not added into a primer.
Comparative example 6: the PCM plate for the outdoor unit of the air conditioner is different from the PCM plate in the embodiment 1 in that graphene oxide dispersion liquid is not used in modified nano zinc oxide in primer.
Comparative example 7: the PCM plate for the outdoor unit of the air conditioner is different from the PCM plate in the embodiment 1 in that a nano lotus leaf hydrophobic agent is not added into a primer.
Comparative example 8: with the corrosion-resistant nano graphene color-coated plate prepared in example 2 of chinese invention patent application No. CN201811210392.9 as a reference, a corrosion-resistant nano graphene color-coated plate includes a top coat layer, a bottom coat layer, a reflective layer, an adhesive layer, a first corrosion-resistant layer, a substrate 4, a second corrosion-resistant layer, and a back coat layer, which are sequentially stacked, wherein the first corrosion-resistant layer includes 55 parts by weight of bisphenol a epoxy resin, 5 parts by weight of nano graphene, 6 parts by weight of talc powder, 3 parts by weight of wax powder, 15 parts by weight of titanium dioxide, 3 parts by weight of a first antioxidant, 4.4 parts by weight of a dispersant, and 0.2 part by weight of a light rare earth element; the thickness of the first corrosion-resistant layer is 30 mu m; the primer layer comprises 55 parts by weight of propyne-polyvinylidene fluoride copolymer, 4 parts by weight of pigment, 10 parts by weight of maleic anhydride low molecular weight liquid polybutadiene, 1 part by weight of diethyl toluenediamine, 3 parts by weight of cyclohexanone peroxide and 0.5 part by weight of dimethyl p-toluidine; the top coating comprises 65 parts by weight of polymethyl methacrylate, 30 parts by weight of acetylene-butyl acrylate copolymer, 3 parts by weight of poly (1, 4-butanediol), 4 parts by weight of anionic waterborne polyurethane and 8 parts by weight of diphenylmethane diisocyanate; the second corrosion-resistant layer comprises 60 parts by weight of propyne-polyvinylidene fluoride copolymer, 8 parts by weight of nano graphene, 5 parts by weight of methyl cellulose, 7 parts by weight of precipitated barium sulfate, 20 parts by weight of polyvinyl alcohol, 0.5 part by weight of second antioxidant, 3 parts by weight of dispersant and 0.4 part by weight of light rare earth element; the back coating comprises 60 parts by weight of bisphenol A epoxy resin, 8 parts by weight of graphene oxide, 2.5 parts by weight of aluminum nitride, 0.4 part by weight of beta-hydroxyalkylamide, 0.3 part by weight of fumed silica, 3 parts by weight of anionic waterborne polyurethane and 9 parts by weight of diphenylmethane diisocyanate.
Performance test
Firstly, detecting the performance of the finish paint layer 1: color-coated sheets were prepared according to the methods of examples 1 to 5, comparative examples 1 to 4 and comparative example 8, and the properties of the topcoat layer 1 in the color-coated sheets were examined according to the following methods, with the examination results of the topcoat layer 1 of the color-coated sheets in comparative examples 1 to 5 being reported in table 3, and the examination results of the topcoat layer 1 of the color-coated sheets in comparative examples 1 to 4 and comparative example 8 being reported in table 4.
TABLE 3 testing of the properties of the top coats of the color coated panels of examples 1-5
Figure BDA0002169969550000141
Figure BDA0002169969550000151
As can be seen from the data in table 3, the PCM boards prepared according to the methods of examples 1 to 5 have good gloss, firm hardness, resistance to acid and alkali corrosion, resistance to hot water and salt spray corrosion, good water and moisture resistance, and strong weather resistance and mechanical properties, and when used for preparing outdoor units of air conditioners in coastal areas, they can resist the hot water and salt spray corrosion even if the temperature of the outdoor units is increased.
TABLE 4 Performance testing of the top coats of color-coated sheets prepared in comparative examples 1 to 4 and comparative example 8
Figure BDA0002169969550000152
Figure BDA0002169969550000161
As can be seen from the comparison of the data in tables 3 and 4, the color-coated sheets prepared in comparative examples 1 to 4 show the phenomena of foaming and fading after being soaked in acid solution and alkali solution, when being sprayed with warm saline water, the corrosion widths of the cross parts and the edge parts are large, the water resistance and the corrosion resistance are reduced, the mechanical properties are reduced, the tensile properties of the color-coated sheets are reduced, and the cracking phenomenon of the coating is easy to occur when the operations such as bending, stamping and the like are performed.
Comparative example 8 is a color-coated sheet prepared in the prior art, and compared with the color-coated sheets prepared in examples 1 to 5, the mechanical properties are reduced, and the acid and alkali resistance and the resistance to hot water and salt mist corrosion are reduced.
Secondly, detecting the performance of the back paint layer 5: color coated sheets were prepared according to the methods of examples 1 to 5 and comparative examples 5 to 8, and the properties of the back paint layer 5 were measured according to the following methods, and the results of measurement of the back paint layer 5 of the color coated sheets of examples 1 to 5 are shown in table 5, and the results of measurement of the back paint layer 5 of the color coated sheets of comparative examples 5 to 8 are shown in table 6.
TABLE 5 test results of the properties of the back paint layer of the color coated sheets in examples 1-5
Figure BDA0002169969550000171
As can be seen from the data in Table 5, the PCM board backcoat layers 5 prepared according to examples 1-5 have high gloss. The coating has the advantages of firm hardness, strong acid-base corrosion resistance, strong water and salt mist corrosion resistance, excellent water resistance and moisture resistance, good mechanical property and better tensile property, and can prevent salt mist particles from entering the coating when bending, stamping and other operations are carried out, thereby enhancing the water and salt mist corrosion resistance of the PCM plate.
Table 6 performance testing of the back paint layers of color coated panels prepared in comparative examples 4-8
Figure BDA0002169969550000181
Figure BDA0002169969550000191
Comparing the data in tables 5 and 6, it can be seen that the color-coated sheets prepared by the method in comparative examples 4-8 have the phenomena of fading, bubbling and falling off when the back paint layer 5 is soaked in the acid solution and the alkali solution, and when the back paint layer 5 is corroded by spraying warm saline water, the corrosion width of the primer layer 2 is large, the corrosion is severe, the mechanical property is reduced, the flexibility of the back paint layer 5 is poor, and cracks are easy to appear during bending and stamping.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.

Claims (6)

1. The PCM plate for the air-conditioning outdoor unit is characterized by comprising a finish paint layer (1), a primer layer (2), a passivation layer (3), a substrate (4), the passivation layer (3), the primer layer (2) and a back paint layer (5) which are sequentially stacked;
the finishing paint layer (1) comprises the following components in parts by weight: 20-30 parts of castor oil modified waterborne polyurethane, 10-15 parts of modified carbon fiber, 6-10 parts of perchloro ethylene resin, 3-7 parts of acetone, 2.6-3.0 parts of titanium dioxide, 40-50 parts of deionized water, 1.2-1.6 parts of barium sulfate, 0.2-0.4 part of flatting agent, 0.3-0.5 part of film-forming assistant, 0.6-0.8 part of dispersing agent and 0.4-0.7 part of polyether modified organic siloxane;
the back paint layer (5) comprises the following components in parts by weight: 15-25 parts of aqueous polyurethane dispersion, 6-10 parts of modified nano zinc oxide, 3-5 parts of hexafluorobutyl acrylate, 1.2-1.6 parts of nano silicon dioxide, 0.6-1 part of chlorinated paraffin, 2.2-2.6 parts of nano lotus leaf hydrophobing agent, 0.1-0.3 part of flatting agent, 0.1-0.3 part of film forming auxiliary agent, 0.4-0.6 part of dispersing agent, 0.2-0.5 part of polyether modified organic siloxane and 20-30 parts of deionized water;
the castor oil modified waterborne polyurethane is prepared by the following method:
drying polytetrahydrofuran diol at the constant temperature of 80-90 ℃ for 1-2h, taking out, adding castor oil, dibutyl tin dilaurate, 1, 4-butanediol, isophorone diisocyanate and dimethylolpropionic acid, stirring for reaction for 2-3h, adding hydroxyethyl methacrylate for continuous reaction for 0.8-1h, cooling to 35-40 ℃, adding triethylamine for neutralization for 25-30min, adding deionized water, stirring for 25-30min, adding sodium dodecyl sulfate, potassium persulfate and 2-perfluorooctyl ethyl acrylate, and stirring for 3-4h to obtain modified waterborne polyurethane;
the castor oil modified waterborne polyurethane comprises the following components in parts by weight: 19-21 parts of polytetrahydrofuran diol, 9-10 parts of castor oil, 0.5-0.6 part of dibutyl tin dilaurate, 3-4 parts of 1, 4-butanediol, 11-13 parts of isophorone diisocyanate, 5-6 parts of dimethylolpropionic acid, 2-3 parts of hydroxyethyl methacrylate, 5-6 parts of triethylamine, 50-60 parts of deionized water, 2.5-3 parts of sodium dodecyl sulfate, 1.1-1.5 parts of potassium persulfate and 20-30 parts of 2-perfluorooctyl ethyl acrylate;
the modified carbon fiber is prepared by the following method: (1) placing the carbon fiber in a muffle furnace at 650-700 ℃ for firing for 0.5-1h, washing with deionized water for 3-5 times, placing in a dopamine solution, reacting for 24h at room temperature, filtering, washing with deionized water for 3-5 times, and vacuum drying at 50-60 ℃; the mass ratio of the carbon fiber to the dopamine solution is 1: 3-5; (2) uniformly mixing graphene oxide, aluminum tripolyphosphate and a dopamine solution, adding carbon fibers, uniformly mixing, centrifuging, placing a substance obtained by centrifuging in an epoxy resin emulsion for curing, and preparing modified carbon fibers, wherein the mass ratio of the carbon fibers, the graphene oxide, the aluminum tripolyphosphate and the dopamine solution is (1), (0.3-0.5), (0.6-0.8), (1.5-2.5), and the mass ratio of the substance obtained by centrifuging and the epoxy resin emulsion is (1), (1.3-1.5);
the modified nano zinc oxide is prepared by the following method: mixing 3-4 parts by weight of titanate coupling agent and 5-6 parts by weight of acetone, adding 4.5-6.5 parts by weight of 1, 4-propylene glycol, uniformly stirring, adding nano zinc oxide, stirring for 30-40min, uniformly mixing, performing suction filtration, washing with acetone, dripping for 3-5 times, and drying at 80-90 ℃; adding the modified nano-zinc oxide into deionized water, stirring to prepare a suspension, adding the graphene oxide dispersion, stirring for 2-3h, performing centrifugal separation, and drying at 60-70 ℃ for 10-12h to prepare the modified nano-zinc oxide, wherein the mass ratio of the modified nano-zinc oxide to the deionized water to the graphene oxide dispersion is 1 (3-5) to 1.5-2.5.
2. The PCM plate for the outdoor unit of an air conditioner as claimed in claim 1, wherein the leveling agent is one or two of EFKA-3777, BYK-354 and polyether modified silicone oil;
the film-forming aid is prepared by mixing dipropylene glycol methyl ether and alcohol ester-12 according to the mass ratio of 1: 1-2;
the dispersing agent is prepared by mixing sodium p-toluenesulfonate, oleamide and polyethylene glycol according to the mass ratio of (3.8-4.2) to (1.8-2.2) to 4.
3. The PCM board for an outdoor unit of an air conditioner according to claim 1, wherein the thickness of the topcoat layer (1) is 17 to 20 μm, the thickness of the topcoat layer (5) is 2 to 12 μm, the thickness of the primer layer (2) between the passivation layer (3) and the topcoat layer (1) is 6.5 to 10 μm, the thickness of the primer layer (2) between the passivation layer (3) and the topcoat layer (5) is 6 to 10 μm, and the thickness of the passivation layer (3) is 20 to 30mg/m 2.
4. The PCM plate for the outdoor unit of an air conditioner according to claim 1, wherein the substrate (4) is a galvanized plate with a galvanizing amount of 130-140g/m2。
5. A process for producing a PCM plate for an outdoor unit of an air conditioner according to any of claims 1 to 4, comprising the steps of:
s1, degreasing and cleaning the substrate (4): degreasing, cleaning and drying the substrate (4);
s2, passivation treatment: soaking the substrate (4) in a passivation solution, passivating for 10-30min, taking out, and drying to form passivation layers (3) on two sides of the substrate (4);
s3, primer coating and curing: uniformly coating priming paint with the temperature of 40-45 ℃ and the viscosity of 54-56S on the passivation layers (3) on the two sides of the substrate (4), then putting the substrate (4) into a curing furnace for curing, wherein the curing temperature is 214-;
s4, coating and curing the back paint layer (5): uniformly coating a back finish with the temperature of 38-42 ℃ on the primer layer (2) on one side of the substrate (4), putting the substrate (4) into a curing furnace with the temperature of 220-230 ℃ for curing to form a back paint layer (5), and cooling by using demineralized water;
s5, coating and curing the finishing paint layer (1): uniformly coating finish paint with the temperature of 35-40 ℃ and the viscosity of 225-229S on the primer layer (2) on the side, away from the back paint layer (5), of the substrate (4), putting the substrate (4) into a curing furnace with the curing temperature of 224-235 ℃ to form a finish paint layer (1), cooling the finish paint layer (1) by using demineralized water, and winding the PCM plate at the linear speed of 20-25 m/min.
6. The process for producing the PCM plate for the outdoor unit of the air conditioner as claimed in claim 5, wherein the cleaning solution in S1 is an alkali solution with the concentration of 0.5-1.5% and the temperature of the alkali solution is 50-70 ℃;
in the step S2, the solubility of the passivation solution is 20-45%, and the drying temperature is 80-100 ℃;
in the steps S3, S4 and S5, the conductivity of the desalted water is 70-80 μm/S, the cooling treatment time is 12-15S, and the temperature of the primer layer (2), the back paint layer (5) and the finishing paint layer (1) after cooling is 36-42 ℃.
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