CN116515361A - Two-coating one-baking high-leveling powder and preparation method and application thereof - Google Patents
Two-coating one-baking high-leveling powder and preparation method and application thereof Download PDFInfo
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- CN116515361A CN116515361A CN202310169122.2A CN202310169122A CN116515361A CN 116515361 A CN116515361 A CN 116515361A CN 202310169122 A CN202310169122 A CN 202310169122A CN 116515361 A CN116515361 A CN 116515361A
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- powder
- coating
- powder coating
- agent
- coat
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Classifications
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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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
- B05D3/002—Pretreatement
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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
-
- 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
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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
- 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
- B05D7/542—No clear coat specified the two layers being cured or baked together
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- C—CHEMISTRY; METALLURGY
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Abstract
The two-coating one-baking high-leveling powder comprises a bottom powder coating and a surface powder coating, wherein the bottom powder coating comprises the following components in percentage by mass: topcoat powder coating = 50-80:20-50, wherein the bottom powder coating comprises the following raw materials in percentage by mass: 40-60% of base powder, 1-5% of chain extender, 5-15% of pigment, 10-20% of filler, 0.5-1.5% of degasser, 5-10% of preservative filler, 1-2% of rheological agent, 1-3% of charging auxiliary agent and 0.2-1% of coupling agent; the surface layer powder coating comprises the following raw materials in percentage by mass: 50-70% of flour, 1-5% of curing agent, 1-2% of curing accelerator, 5-25% of pigment, 5-10% of filler, 0.5-1% of rheological agent, 0.3-1% of degasifying agent and 0.2-1% of coupling agent. The coating formed by the construction of the two-coating one-baking process has high coverage rate of corners, good corrosion resistance, long service life of the sprayed product, smooth coating surface, high glossiness and better product appearance effect, and can be applied to the fields of engineering machinery and the like; after the bottom powder is sprayed, the surface powder can be directly sprayed, so that the time is saved, and the energy consumption is reduced.
Description
Technical Field
The invention belongs to the technical field of powder coatings, and particularly relates to a two-coating one-baking high-leveling powder, a preparation method and application thereof.
Background
Along with the enhancement of global environmental protection consciousness, the powder coating has the advantages of economy, high efficiency, environmental protection, energy saving (commonly called 4E) and the like, so that the powder coating is rapidly developed, more and more high VOC (volatile organic compounds) coating is replaced by powder, and good environmental protection benefit and economic benefit are brought. However, there are still many fields in which liquid paint is used in large quantities, mainly because powder coating has various technical problems, which prevent the application of powder.
In the traditional engineering machinery and household appliances fields, the surface layer of the hardware is required to be subjected to pretreatment for many times, and an oxide layer, waste residue, a corrosion layer and the like on the surface of the hardware are removed; the general pretreatment is to perform the processes of rust removal, pre-degreasing, hot water washing, cold water washing, acid washing, cold water washing, phosphating or ceramic, cold water washing, pure water washing and the like, spray powder is sprayed and dried, and the spray powder is dispersed into uniform and fine fog drops by means of pressure or centrifugal force through a spray gun or a disc atomizer to be applied to the surface of a coated object.
However, in actual production sites, parameters in a rust removing pool, a phosphating pool or a ceramic pool can continuously change, once total acid in the rust removing pool is too high, and the crystallization coating capability in the phosphating pool or the ceramic pool is insufficient, excessive acid radical ions are excessively accumulated on the surface of the hardware after rust removing, so that film forming on the surface of the hardware is difficult in the phosphating or ceramic process, single-coating powder is difficult to attach to the surface of the hardware after spraying, part of the surface of the hardware is exposed in the spraying process without covering powder, the surface is exposed and the covering powder is caused to be in a place between after the hardware is solidified, and the phenomena of surface loosening and coating falling occur in an adhesion test, so that the surface of the hardware needs to be polished again, and then the surface of the hardware is sprayed again to enable the powder to completely cover the surface of the hardware. According to the construction method, spraying and drying are needed to be carried out for one time, then the surface is polished, and then spraying and drying are carried out for one time, the process can finally cover sharp edges of a workpiece to form a regular appearance, but is complex, labor is consumed for polishing, production efficiency is reduced, production cost is increased along with the process, meanwhile, the sprayed coating is too thick, in an adhesive force test, adhesive force between the coatings is low, and the surface coating is easy to fall off and scratch.
Therefore, it is necessary to develop a powder with high adhesion, which can cover sharp corners of a workpiece, and avoid the problems of excessively thick coating and low adhesion between the coating layers, so as to improve the efficiency and quality of production and construction.
Disclosure of Invention
The invention aims to overcome the defects of poor coated workpiece and easy to cause excessive thick surface layer and poor adhesive force of the powder coating, and provides a two-coating one-baking high-leveling powder, which ensures uniform powder coating by adding an auxiliary agent for improving the overall powder chargeability, and ensures that the cured coating has excellent corner coverage by utilizing the suitability between flour and base powder, and meanwhile, the coating has proper thickness and good adhesive force between the coatings.
The invention also aims to provide a preparation method of the two-coating one-baking high-leveling powder.
Another object of the invention is to provide a two-coat one-bake high leveling powder application.
The invention adopts the following technical scheme:
the two-coating one-baking high-leveling powder comprises a bottom powder coating and a surface powder coating, wherein the bottom powder coating comprises the following components in percentage by mass: topcoat powder coating = 50-80:20-50,
the bottom powder coating comprises the following raw materials in percentage by mass:
the surface layer powder coating comprises the following raw materials in percentage by mass:
the base powder is epoxy resin, acrylic resin and polyurethane resin.
Further, the epoxy resin adopts a copolymer of bisphenol A type epoxy resin E44 and bisphenol A type epoxy resin E51, and preferably, the dosage of the bisphenol A type epoxy resin E44 and the bisphenol A type epoxy resin E51 is 1:1.
the epoxy resin contains polar groups such as epoxy groups, hydroxyl groups, ether bonds, amino groups, ester bonds and the like, has small shrinkage rate and stable size, hardly emits low-molecular products during curing, and has small expansion coefficient influenced by temperature. The epoxy resin has high cohesive force after curing, and forms chemical bond with the metal surface, thus showing high adhesive strength. The epoxy resin contains ether bonds in the molecule, the arrangement of the molecular chains is compact, the crosslinking density is high, and the cured product has excellent electrical insulation performance.
The acrylic resin adopts a copolymer of epoxy acrylate, polybutylmethacrylate and hydroxyethyl acrylate. The acrylic ester has the advantages of good water resistance, good ageing resistance, light resistance, no yellowing and the like. Epoxy group structure is introduced into epoxy acrylate to form certain steric hindrance, so that the crosslinking degree in the polymerization process is weakened, and the excessive viscosity of the system caused by excessive crosslinking of epoxy resin is avoided. The epoxy acrylate forms a polymer with a three-dimensional network structure through free radical reaction, so that the toughness and mechanical strength of the coating can be enhanced. Hydroxyl in hydroxyethyl acrylate reacts with isocyanate groups in polyurethane resin to form carbamate groups, so that graft copolymerization of polybutylmethacrylate, polyurethane resin and epoxy resin is realized, phase separation possibly occurring is reduced, and the bonding strength of the coating and metal is improved.
The polyurethane resin is polyether polyurethane resin. The polyester polyurethane resin has the advantages of good stability, hydrolysis resistance, low temperature resistance, oxidation resistance, acid resistance and alkali resistance. The polyurethane resin has excellent wear resistance and toughness, and can overcome the defects of poor toughness, high brittleness, low peel strength and no impact vibration resistance of the epoxy resin. The polyurethane adopted by the invention is a block polymer, wherein a soft segment is formed by an oligomer polyol flexible long chain, a hard segment is formed by diisocyanate and a chain extender, and the soft segment and the hard segment are alternately arranged to form a repeated structural unit which contains urea groups, ether or vinegar groups besides carbamate groups. Due to the presence of a large number of polar groups, hydrogen bonds can be formed in polyurethane molecules and among polyurethane molecules, and soft segments and hard segments can form microphase areas and generate microphase separation. Even linear polyurethanes can form physical crosslinks through hydrogen bonds.
The flour is graphene modified polyester resin, fluorine-containing acrylic resin and polyurethane resin.
The polyester resin has outstanding mechanical properties, good decoration, high ornamental value, and poor chemical corrosion resistance and weather resistance. The hardness, toughness, acid and alkali resistance, aging resistance and other performances of the graphene modified polyester resin coating are obviously improved, the corrosion resistance is obviously improved, the salt spray resistance time is improved, and the addition of the graphene improves the coating performance because the graphene has a planar structure with a large specific surface area, strength and toughness, and the labyrinth-like structure formed in the coating can effectively prolong the path of corrosion factors to a substrate.
The fluorine-containing acrylic resin contains a carbon-fluorine bond, and the organofluorine compound is protected from direct action due to the tight shielding on the main chain, thereby improving weather resistance, oxidation resistance and corrosion resistance of the organofluorine polymer. The organic fluorine compound has low intermolecular cohesive force, small interfacial force between air and molecules, low surface energy and small friction coefficient, and after the fluorine-containing acrylic resin is cured, fluorine-containing groups can be arranged at the interface between a polymer and air to provide excellent weather resistance and corrosion resistance, meanwhile, the coating has an oil stain resistance effect, and acrylate groups can be aggregated at the interface between flour and base powder and provide excellent adhesive force.
The dosage of the bisphenol A type epoxy resin E44 and the bisphenol A type epoxy resin E51 is 1:1, when bisphenol A epoxy resin E44 is too much, the hydroxyl value is larger, and hydroxyl reacts with isocyanate groups, so that the hard segment of polyurethane is increased, and the crystallinity is too high; when bisphenol A type epoxy resin E51 is too much, the epoxy value is larger, and the epoxy groups are ring-opened and crosslinked in the copolymerization modification process, so that the viscosity of the coating is increased. Through proper proportion, the initial adhesion capability of the epoxy resin and the metal surface can be improved, and the leveling effect of the surface is ensured.
The rigid benzene ring structure in the polyurethane and the epoxy resin is combined, so that the flexibility of a molecular chain is reduced, the content of the rigid structure in the molecular chain is increased, the tensile strength of the adhesive film is increased, the hardness of the adhesive film is improved, and the elongation at break is reduced.
The epoxy resin facilitates the mixing, interaction and entanglement between the polyurethane and the polyacrylate, and the interaction between the polybutylmethacrylate is also enhanced. Polyurethane can easily react synchronously or asynchronously with other monomers or polymers, and do not interfere with each other, so that interpenetrating network polymers with excellent performance are obtained. The polymer molecular chains which are crossed and penetrated can be mutually interwoven and mutually cooperated. The winding of the network can obviously improve the dispersibility of the system and the compatibility of different phases, so that the relative stability of the system is improved, and the purpose of complementation of polymer properties is achieved.
Because the epoxy resin has the characteristics of high mechanical strength, excellent adhesive property, excellent temperature resistance, excellent chemical stability and the like, the epoxy resin is utilized to carry out interpenetrating modification on polyurethane, thereby improving the adhesive strength, solvent resistance, water resistance, thermal stability and the like of the coating. The acrylic ester can improve the wettability of the coating to the adhered hardware base material, and is beneficial to improving the bonding strength of the interpenetrating network coating. The acrylic ester has crystallinity, and can improve the initial adhesion strength of the interpenetrating network coating.
Further, the filler is one or two of precipitated barium sulfate, talcum powder, mica powder and fumed silica.
The precipitated barium sulfate has the greatest melting flow distance, good leveling property and minimum oil absorption, and is beneficial to improving the melting fluidity and glossiness of the coating.
The shrinkage rate of the coating in the curing process is effectively regulated by adding the scaly mica powder and talcum powder, and the difference of the thermal expansion coefficients between the coating and the substrate is reduced. Further reduces the influence of thermal stress generated by uneven temperature distribution in the application process of the coating, and avoids stress concentration caused by shrinkage in the coating to cause cracking of the coating.
The powder coating prepared from the fumed silica and the talcum powder has high activity, and the coating film has relatively good adhesive force, impact strength, hardness and flexibility.
The gas phase silicon dioxide has extremely strong anti-sedimentation property, and can firmly pull the amphoteric compounds in the anti-corrosion coating, so that the amphoteric compounds can react with acid-base harmful substances on the surface to prevent the amphoteric compounds from further diffusing to the inside. In addition, the fumed silica is used as an inorganic substance, has extremely strong stability, does not generate chemical corrosion, and can exert a powerful anticorrosion reinforcing function in the anticorrosion paint according to the excellent performance, and meanwhile, the fumed silica also has the functions of salt mist resistance and aging resistance.
Further, the pigment is one or more of carbon black and titanium white, and the carbon black can improve the gloss of the paint, change the fluidity of the paint and improve the durability of the paint. The carbon black has fine particles, closely packed reticular chains, large specific surface area and more particles per unit mass, and is favorable for forming a conductive structure in a matrix.
Furthermore, the invention adopts the rutile type titanium dioxide as pigment, and the gelation time and the melt fluidity of the polyester resin powder coating prepared by the rutile type titanium dioxide are both 50 percent higher than those of the anatase type titanium dioxide. In terms of melt fluidity, rutile type titanium dioxide is used as pigment, and is favorable for leveling the coating due to long gelling time, and the coating can be maintained for a long time in a low melt viscosity state by prolonging the crosslinking curing reaction time of the coating, so that enough time is provided for releasing water molecules. Meanwhile, the rutile type titanium dioxide has good light and color retention, and after a period of time, the rutile type titanium dioxide can not generate yellowing phenomenon or light-loss and color-change phenomenon.
Further, the degasifying agent is one or two of benzoin and degassing wax,
the degasifying agent is benzoin, in the curing process, the hydroxyl of hydroxyalkylamide and carboxyl of polyester resin are condensed, and then byproduct water molecules are generated in the curing film forming process, the molecules are released through the coating, the compactness of a paint film can be influenced, pinholes are easy to appear in the coating, and finally the mechanical property, the high temperature resistance, the chemical resistance and the like of the coating are influenced.
Benzoin and silicone propyl ester modified polyester resin are fused at molecular level in the melting process of the powder coating, the melting viscosity of the resin can be greatly reduced after the benzoin is melted, the gas in the resin is discharged, meanwhile, the benzoin is subjected to oxidation reaction in the film forming process, oxygen in bubbles is consumed to reduce the diameters of the bubbles, so that the Laplace tension in the bubbles is increased, and the dissolution rate of nitrogen in a system is accelerated to play a degassing role.
Meanwhile, as the curing time of the triethanolamine is too short, the wettability of the coating to the hardware substrate is insufficient, and generated moisture causes loose bubble-containing adhesive layer structure after the coating is cured, so that the bonding strength is reduced. The degassing effect can be accelerated by benzoin.
The deaerated wax is of the type Craien 9615A, which has the effect of being readily dispersible. The addition of the degassing wax can increase the yield of the extrusion process section and improve the flowability of the powder, and the product has good anti-blocking property and is not easy to agglomerate.
Further, the rheological agent is sand grain agent and organic bentonite, the rheological additive, bentonite and sand grain agent are added in the formula of the primer powder coating of the two-coating one-baking powder coating, the sand grain agent is SA2072, and the special amide modified vinylidene fluoride polymer is organically synthesized and has the particle size: 80-300 meshes, provides excellent surface performance and smooth hand feeling, ensures that a paint film has excellent performances of scratch resistance, anti-sticking, wear resistance, smoothness increase and metal scratch resistance, greatly improves the water resistance and waterproof capability of the paint film, can improve the defect of poor surface performance of the paint film caused by the paint film when the paint film is blended with fumed silica and organic bentonite, can improve the distribution of powder on the surface of a coating, and ensures that the optical rotation performance of the coating is better exerted. The sand grain agent can be directly added into a coating system, is easy to disperse, does not need grinding, and is convenient to use. The melt viscosity of the primer powder coating is improved, the migration of the primer powder coating to the surface layer can be effectively reduced in the final solidification process, the corner coverage rate is improved, and the service life of the product is prolonged by matching with the anticorrosive filler in the formula.
The organic bentonite has good dispersion and thixotropic property. The organic bentonite is used as an anti-settling agent, and has the characteristics of corrosion resistance, wear resistance, brine corrosion resistance, impact resistance, uneasiness in wetting and the like.
Further, the coupling agent is a titanate coupling agent. The coupling agent is added into the polyester resin-based powder coating as a surface treatment agent to mainly realize the effect of making the inorganic filler and the surface of the organic component compatible and fully dispersed.
In the curing stage, vinyl of the gamma-methacryloxy silane coupling agent is easy to react with polyester to form a crosslinked network structure, and the gamma-methacryloxy silane coupling agent can be used as a crosslinking agent to provide reactive groups for coating resin components, improve the hardness, adhesive force and salt spray resistance of the coating, and also can be used as a coupling agent to have better surface treatment effect on pigments and fillers.
When the isopropyl tri (dioctyl phosphate acyloxy) titanate is used for treating inorganic fillers such as precipitated barium sulfate, talcum powder and the like, the isopropyl tri (dioctyl phosphate acyloxy) titanate has better compatibility with polar polymers, can improve the dispersion and adhesion of the fillers in the polymers, reduce the viscosity of the system, improve the processing fluidity, reduce the baking temperature and shorten the baking time. At the same time, the mechanical strength of the composite material can be improved,
further, the curing agent is hydroxyalkylamide, and the hydroxyalkylamide contains four hydroxyl end groups and can carry out crosslinking curing reaction with carboxyl groups on carboxyl end group polyester resin. Because the epoxy resin contains four active functional groups and has high activity, the activation energy required by the crosslinking curing reaction is low, and the hydroxyalkyl amide has the advantages of safety and no toxicity compared with triglycidyl isocyanurate.
Further, the curing accelerator is one or two of 2-phenylimidazoline and benzyl trimethyl ammonium chloride, and the 2-phenylimidazoline contains rigid groups such as phenyl, so that the glass transition temperature of the resin can be improved due to the steric effect, the gel time can be further prolonged, the leveling of the coating is facilitated, and meanwhile, the storage stability of the coating is improved.
The benzyl trimethyl ammonium chloride has good thermal stability, and has better yellowing resistance effect compared with salicylic acid modified imidazole and 2-phenyl imidazoline, and the gel time and the leveling property are between the salicylic acid modified imidazole and the 2-phenyl imidazoline.
Further, the anti-corrosion filler adopts any one or more of graphene oxide, modified zinc phosphate and aluminum tripolyphosphate.
Further, the chain extender is one of triethanolamine and dimethyl thiotoluene diamine.
The triethanolamine molecular chain has no rigid group, has certain flexibility, can increase the distance between hard segments, reduces the degree of hydrogen bonding, is beneficial to the mutual staggered aggregation of the soft and hard segments, ensures that the molecular chain in the system has better flexibility, increases the crosslinking degree of the system, limits the sliding among molecules, increases the friction force among the molecules, ensures that the flexibility of the triethanolamine molecular chain is better, reduces the crystallinity of the hard segments, reduces the phase separation degree of the soft and hard segments, ensures that the friction resistance in the molecules is larger when the external force acts on the soft and hard segments, leads to the increase of the loss factor of the material, and can be used as a damping and shock absorbing material.
The dimethyl thiotoluene diamine contains a rigid benzene ring structure, can increase the rigidity of a hard segment, is beneficial to crystallization, and reduces the compatibility between soft and hard phases. When the external force acts, the friction resistance in the molecule is small, and the loss factor is low. The dimethyl thiotoluene diamine molecular structure contains benzene ring structure, and diamine chain extender can generate ureido with isocyanate, the polarity of the ureido is stronger than that of carbamate group generated by glycol and isocyanate, and the cohesive energy is high, so that the heat resistance of the material is improved.
The heat resistance of triethanolamine is slightly reduced compared with that of dimethyl thiotoluene diamine, and although the triethanolamine does not have a heat-resistant benzene ring structure, the triethanolamine is a trihydroxy chain extender, can generate chemical crosslinking, increases the crosslinking density of a system, and improves the thermal decomposition temperature to some extent.
Further, the charge regulator is one or more of castor oil alkanolamide borate, dimethyl diallyl ammonium chloride-acrylamide copolymer, polyamide wax and gas phase alumina. The castor oil alkanolamide borates undergo charge transfer by proton exchange, changing the surface resistivity of the powder coating. The castor oil alkanolamide borate has B-O bond, good thermal stability and good compatibility with high molecular substances.
The dimethyldiallylammonium chloride polymer has the characteristics of high charge density, the acrylamide has the characteristics of strong activity and good hydrophilicity, two copolymers of dimethyldiallylammonium chloride and acrylamide are easily polymerized to form, on one hand, the copolymers of dimethyldiallylammonium chloride and acrylamide are connected with B-O bonds in castor oil alkanolamide borate, on the other hand, the winding of the stable filler is realized, and the compatibility of the filler and a polymer can be further improved. When the hardware base material is powdered, the copolymer of the dimethyldiallylammonium chloride and the acrylamide can accelerate the electrostatic charge leakage of the surface of a workpiece, reduce large corrugated orange peel caused by electrostatic repulsion and rebound, enable the surface of a coating to be smoother, and utilize hydrophilic groups to absorb water vapor in the air on the surface of a powder coating film to form a hydrophilic film or further reduce the surface resistance by means of proton transfer.
The polyamide wax is composed of a nonpolar aliphatic hydrocarbon part and a polar amide group functional group, oxygen atoms in amide groups are high in electronegativity and easy to form hydrogen bonds with hydrogen atoms of hydrocarbon groups, and the polyamide wax dispersed in a coating system forms a three-dimensional network structure through intermolecular hydrogen bond action, so that the thixotropy of the coating can be improved, wet film sagging and precipitation of solid particles in the coating in the storage process can be effectively controlled, the polyamide wax migrates to the surface of the coating in the film forming process, and the brightness of the coating can be further improved.
The expansion coefficient difference between the vapor phase aluminum oxide and the metal matrix is smaller, so that the shrinkage rate of the coating in the curing process is effectively adjusted, the difference of the thermal expansion coefficients between the coating and the substrate is reduced, and the influence of thermal stress generated by uneven temperature distribution in the application process of the coating is further reduced.
The electrified auxiliary agent plays a role of a bridge, when film formation on the surface of the hardware is not uniform enough, the connection compactness between the metal surface and the base powder is improved through the electrified auxiliary agent, and the bonding capacity of the base powder can be improved.
The charging additive can further increase the charging performance of the powder coating, reduce electrostatic shielding effect, improve corner powdering and improve powdering rate of the powder coating.
When the coating is cured, epoxy resin, acrylic resin and polyurethane resin of the base powder form a base powder interpenetrating network under the action of a chain extender, hydroxyl groups in graphene modified polyester resin and hydroxyl groups in fluorine-containing acrylic resin of the flour react with isocyanate groups in the polyurethane resin respectively to form carbamate groups, and at the same time, the graphene modified polyester resin is cured under the action of a curing agent and a curing accelerator, the epoxy resin and the acrylic resin of the base powder further form a base powder-flour interpenetrating network with the polyurethane resin in the flour, and the graphene modified polyester resin and the fluorine-containing acrylic resin in the flour form a flour-base powder interpenetrating network with the polyurethane resin in the base powder, so that the adhesive force between the base powder and the flour is enhanced.
The preparation method of the two-coating one-baking high-leveling powder comprises the following steps:
(1) Uniformly mixing all raw materials in a base powder formula, then carrying out melt extrusion, tabletting and crushing the extruded materials, crushing the crushed material sheets by a mill, and sieving to obtain a base powder coating, wherein the average particle size of the base powder coating is controlled to be 25-45 microns;
(2) All the raw materials in the flour formula are uniformly mixed, then melt extrusion is carried out, the extruded materials are crushed after being pressed into tablets, the crushed tablets are crushed by a mill, and the surface powder coating is obtained after sieving, wherein the average particle size of the surface powder coating is controlled to be 25-45 microns.
In the step (1) and the step (2), the conditions of the melt extrusion are as follows: the temperature of the feeding section is less than 40 ℃, the temperature of the melting section is 105-115 ℃, and the temperature of the discharging section is 95-105 ℃; preferably, the temperature of the feeding section is 30 ℃, the temperature of the melting section is 110 ℃, and the temperature of the discharging section is 100 ℃.
Optionally, the average particle size of the primer powder coating is 25 micrometers, so that the electrification property of the primer powder coating is reduced, the primer powder cannot effectively cover the metal surface, the primer powder can more easily cover the surface of a hardware through air flow disturbance during spraying, and the primer powder and the metal surface form connection through an electrification auxiliary agent. The grain size of the flour powder coating is 40 microns, the powder coating further improves the spraying dead angle area through the difference of grain sizes, further covers the exposed metal surface, has good chargeability, and if the average grain size is too large, the powder quality is large, and excessive coarse powder particles are accumulated to easily cause powder falling to reduce the powder loading rate.
Application of two-coating one-baking high-leveling powder, substrate pretreatment-spraying of bottom powder coating-spraying of surface powder coating-curing.
The substrate pretreatment mode comprises: chemical treatment or physical treatment.
The chemical treatment mode comprises phosphating treatment or silane treatment.
The physical treatment mode comprises sand blasting, shot blasting or polishing treatment.
The curing conditions are as follows: the temperature is kept between 160 ℃ and 220 ℃ for 15 to 20min, preferably 200 ℃ for 15min. Due to the differences of the construction workpiece structure, the size, the thickness of the hardware base material and the like, the curing temperature needs to be adjusted in the above range on site according to specific conditions so as to ensure that the coating is completely cured, but the minimum temperature is not lower than 160 ℃, and the maximum temperature is not higher than 220 ℃.
In the actual production field, parameters in a rust removing pool, a phosphating pool or a ceramic pool can be continuously changed, the total acid in the rust removing pool is too high, the crystallization coating capability in the phosphating pool or the ceramic pool is insufficient, excessive acid radical ions are excessively accumulated on the surface of hardware after rust removing, so that the surface of the hardware is difficult to form a film in the phosphating or ceramic process, and the surface of the hardware can be completely covered with powder by constructing the coating on the surface of the workpiece, and meanwhile, the coating after curing can have excellent mechanical property and corrosion resistance.
Compared with the prior art, the invention has the following advantages:
1. the coating formed by the two-coating one-baking process has high coverage rate of corners, good corrosion resistance, long service life of the sprayed product, smooth surface of the coating, high glossiness and better appearance effect, and can be applied to the fields of engineering machinery and the like; after the bottom powder is sprayed, the surface powder can be directly sprayed, so that the time is saved, and the energy consumption is reduced; compared with paint, the powder coating does not contain VOC, is environment-friendly, and has the advantages of recycling powder and high comprehensive utilization rate.
2. The deaeration wax is added into the formula of the surface layer powder coating of the two-coating one-baking powder coating provided by the invention to reduce the viscosity of the surface layer coating, so that the deaeration of the bottom layer powder coating is facilitated in final curing, meanwhile, the viscosity difference is formed between the bottom layer powder coating and the bottom layer coating, the migration of the bottom layer powder coating into the surface layer powder coating in the curing process is prevented, the appearance of the coating is improved, the rheological additive is added into the formula, the melt viscosity of the bottom layer powder coating is improved, the migration of the bottom layer powder coating into the surface layer can be effectively reduced in the final curing process, the corner coverage rate is improved, and the product service life is prolonged by matching with the anticorrosive filler in the formula.
3. According to the invention, the base powder and the flour are used for carrying out interactive penetrating interlacing in the curing process, so that the combination degree between the base powder and the flour can be improved, the adhesive force of the coating is improved, and polymer molecular chains which are subjected to cross penetration can be mutually interwoven and mutually cooperated. By winding the network among polymer molecular chains, the dispersibility of the system can be obviously improved, and the compatibility of different phases can be improved, so that the relative stability of the system can be improved, and the purpose of complementation of polymer properties can be achieved.
4. The preparation method of the invention prepares the powder coating with proper size by selecting proper temperature, and can ensure the stability and the use effect of the product.
5. The invention can be applied to the surface spraying of hardware, can ensure that the surface of the hardware is completely covered with powder, and simultaneously, the coating after curing can have excellent mechanical property and corrosion resistance.
Detailed Description
In order to make the technical solution of the present invention more apparent to those skilled in the art, the following examples are now given, and the raw materials, reagents or apparatuses used in the following embodiments are commercially available or may be obtained by known methods unless otherwise specified.
The invention is further described with reference to the following specific examples:
table 1: weight ratio of bottom powder paint formula
Table 2: weight ratio of surface powder coating formula
Examples 1-5, their preparation and use include the following steps:
according to the weight ratio of the bottom powder coating formulation in table 1 and the weight ratio of the top powder coating formulation in table 2, all the components in the bottom powder coating and the top powder coating formulation are respectively and uniformly mixed, and then are respectively melt extruded by twin screws, and the temperature is set: feed section temperature: 30 ℃, melting section temperature: 110 ℃, discharge section temperature: crushing the flaky substrate by using a crusher at the temperature of 100 ℃, crushing the substrate by using a crusher, and screening to obtain powder with a proper particle size range, wherein the average particle size of the bottom powder coating is 25 microns, and the particle size of the flour powder coating is 40 microns. The hardware is polished and ceramic, then is subjected to electrostatic spraying, the bottom powder is sprayed on the hardware, then flour is sprayed, and the ratio of the bottom powder coating to the surface powder coating is 60:40, then placing the sprayed workpiece in an oven for heating and curing, wherein the curing temperature is 200 ℃ and the temperature is kept for 15 minutes, so that the product required by the customer is obtained.
TABLE 3 Effect of Performance test of examples 1-5
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As can be seen from the performance test effects of examples 1-5 in Table 3, in examples 1-5, the deaeration wax is added into the formulation of the top powder coating of the two-coat one-bake powder coating provided by the invention to reduce the viscosity of the top powder coating, thereby facilitating deaeration of the bottom powder coating during final curing, forming a viscosity difference with the bottom powder coating, preventing migration of the bottom powder coating into the top powder coating during curing, improving the appearance of the coating, adding a rheological additive into the formulation, improving the melt viscosity of the bottom powder coating, effectively reducing migration of the bottom powder coating into the top layer during final curing, improving corner coverage, matching with the anti-corrosive filler in the formulation, prolonging the service life of the product, and using the graphene modified polyester resin with better corner coverage. According to the invention, the base powder and the flour are used for carrying out interactive penetrating interlacing in the curing process, so that the combination degree between the base powder and the flour can be improved, the adhesive force of the coating is improved, and polymer molecular chains which are subjected to cross penetration can be mutually interwoven and mutually cooperated. The winding of the network can obviously improve the dispersibility of the system and the compatibility of different phases, so that the relative stability of the system is improved, and the purpose of complementation of polymer properties is achieved.
When the coating is cured, epoxy resin, acrylic resin and polyurethane resin of the base powder form a base powder interpenetrating network under the action of a chain extender, hydroxyl groups in graphene modified polyester resin and hydroxyl groups in fluorine-containing acrylic resin of the flour react with isocyanate groups in the polyurethane resin respectively to form carbamate groups, and at the same time, the graphene modified polyester resin is cured under the action of a curing agent and a curing accelerator, the epoxy resin and the acrylic resin of the base powder further form a base powder-flour interpenetrating network with the polyurethane resin in the flour, and the graphene modified polyester resin and the fluorine-containing acrylic resin in the flour form a flour-base powder interpenetrating network with the polyurethane resin in the base powder, so that the adhesive force between the base powder and the flour is enhanced.
Comparative examples 1 to 5
Comparative example 1
Comparative example 1 compared to example 1, the ratio of primer powder coating to topcoat powder coating was 30:70, the rest components are the same as the preparation method and the application method.
Comparative example 2
Compared with the comparative example 2 and the example 1, the surface powder coating is not added with fluorine-containing acrylic resin, and the rest components are the same as the manufacturing method and the application method.
Comparative example 3
Comparative example 3 compared with example 1, bisphenol a type epoxy resin E44 and bisphenol a type epoxy resin E51 were used in an amount of 1:2, the rest components are the same as the preparation method and the application method.
Comparative example 4
In comparative example 4, as compared with example 1, no charging assistant was added to the primer powder coating, and the other components were the same as the production method and the application method.
Comparative example 5
In comparison with example 1, the bottom powder coating and the top powder coating are not added with rheological additives, and the rest components are the same as the preparation method and the application method.
TABLE 4 Performance test Effect of comparative examples 1-5
As can be seen by comparing the performance test effects of comparative examples 1 to 5 in Table 4 with the performance test effects of example 1 in Table 3:
compared with the comparative example 1, the flour powder coating further improves the dead angle area of spraying and further covers the exposed metal surface by the difference of the sizes of flour and the base powder particles, and the flour powder coating is more, so that the ratio of the rheological agent to the charging auxiliary agent is low, the flour ratio is large, the fluidity is relatively poor when the flour powder is solidified, the thickness of the powder is large due to the accumulation of excessive flour particles, the corner coverage rate is poor, the leveling is poor, and the adhesive force is relatively poor.
In comparison with example 2 and example 1, the fluorine-containing acrylic resin contains a carbon-fluorine bond, and the organofluoro compound is protected from direct damage due to the tight shielding on the main chain, thereby improving the weather resistance, oxidation resistance and corrosion resistance of the organofluoro polymer. The organic fluorine compound has low intermolecular cohesive force, small interfacial force between air and molecules, low surface energy and small friction coefficient, and after the fluorine-containing acrylic resin is cured, fluorine-containing groups can be arranged at the interface between a polymer and air to provide excellent weather resistance and corrosion resistance, meanwhile, the coating has an oil stain resistance effect, and acrylate groups can be aggregated at the interface between flour and base powder and provide excellent adhesive force. As the fluorine-containing acrylic resin is not added, the weather resistance of the surface of the coating is relatively poor, and the neutral salt fog and ageing resistance effect are poor.
When bisphenol a type epoxy resin E51 is too much, the epoxy value is large, the epoxy group is ring-opened and crosslinked during the copolymerization modification, resulting in an increase in coating viscosity, poor corner coverage, and poor leveling property, as compared with example 1.
Comparative example 4 and example 1 compare, and electrified auxiliary agent plays the bridge effect, when the film formation of hardware surface is inhomogeneous inadequately, improves the connection compactness between metal surface and the bottom powder through electrified auxiliary agent, can improve the cohesiveness of bottom powder. Because no charging auxiliary agent is added, the corner coverage of the hardware is poor, the binding capacity of the base powder and the flour is reduced, and meanwhile, the neutral salt fog is also poor.
Compared with the comparative example 5 and the example 1, the rheological additive added in the example 1 is used for improving the melt viscosity of the primary coating powder coating, can effectively reduce the migration of the primary coating powder coating to the surface layer in the final curing process, and is matched with the anti-corrosion filler in the formula to prolong the service life of the product, so that the corner coverage in the comparative example 5 is poor, and the leveling property and the neutral salt fog are also poor.
While the foregoing is directed to the preferred embodiments of the present invention, it will be apparent to those skilled in the art that various modifications and variations can be made without departing from the technical principles of the present invention, and such modifications and variations are to be regarded as being within the scope of the invention.
Claims (10)
1. The two-coating one-baking high-leveling powder is characterized by comprising a bottom powder coating and a surface powder coating, wherein the bottom powder coating comprises the following components in percentage by mass: topcoat powder coating = 50-80:20-50,
the bottom powder coating comprises the following raw materials in percentage by mass:
the surface layer powder coating comprises the following raw materials in percentage by mass:
2. a two coat one bake high leveling powder as set forth in claim 1 wherein: the base powder comprises epoxy resin, acrylic resin and polyurethane resin.
3. A two coat one bake high leveling powder as set forth in claim 1 wherein: the flour comprises graphene modified polyester resin, fluorine-containing acrylic resin and polyurethane resin.
4. A two coat one bake high leveling powder as set forth in claim 1 wherein: the filler is one or two of precipitated barium sulfate, talcum powder, mica powder and fumed silica.
5. A two coat one bake high leveling powder as set forth in claim 1 wherein: the pigment is one or more of carbon black and titanium white, the degassing agent is one or two of benzoin and degassing wax, the rheological agent is a sand grain agent and organic bentonite, and the coupling agent is one or two of gamma-methacryloyloxy silane coupling agent and isopropyl tri (dioctyl phosphate acyloxy) titanate.
6. A two coat one bake high leveling powder as set forth in claim 1 wherein: the curing agent is hydroxyalkylamide, the curing accelerator is one or two of 2-phenylimidazoline and benzyl trimethyl ammonium chloride, and the anticorrosive filler adopts any one or more of graphene oxide, modified zinc phosphate and aluminum tripolyphosphate.
7. A two coat one bake high leveling powder as set forth in claim 1 wherein: the chain extender is one of triethanolamine and dimethyl thiotoluene diamine.
8. A two coat one bake high leveling powder as set forth in claim 1 wherein: the charge regulator is one or more of castor oil alkanolamide borate, dimethyl diallyl ammonium chloride-acrylamide copolymer, polyamide wax and gas phase alumina.
9. The method for preparing the two-coating one-baking high-leveling powder according to any one of claims 1 to 8, comprising the following steps:
(1) Uniformly mixing all raw materials in a base powder formula, then carrying out melt extrusion, tabletting and crushing the extruded materials, crushing the crushed material sheets by a mill, and sieving to obtain a base powder coating, wherein the average particle size of the base powder coating is controlled to be 25-45 microns;
(2) Uniformly mixing all raw materials in a flour formula, then carrying out melt extrusion, tabletting and crushing the extruded materials, crushing the crushed material sheets by a mill, and sieving to obtain a surface layer powder coating, wherein the average particle size of the surface layer powder coating is controlled to be 25-45 microns;
in the step (1) and the step (2), the conditions of the melt extrusion are as follows: the temperature of the feeding section is less than 40 ℃, the temperature of the melting section is 105-115 ℃, and the temperature of the discharging section is 95-105 ℃.
10. The method of using a two-coat one-bake high leveling powder according to any one of claims 1 to 8, wherein the substrate pretreatment-spray primer powder coating-spray topcoat powder coating-cure;
the substrate pretreatment mode comprises: chemical treatment or physical treatment;
the chemical treatment mode comprises phosphating treatment or silane treatment;
the physical treatment mode comprises sand blasting, shot blasting or polishing treatment;
the curing conditions are as follows: preserving heat for 15-20 min at 160-220 ℃.
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| CN113667386A (en) * | 2021-09-17 | 2021-11-19 | 黄山华佳表面科技股份有限公司 | Powder coating with two coating layers and one baking layer and preparation method thereof |
| CN114507467A (en) * | 2022-01-18 | 2022-05-17 | 湘江涂料科技有限公司 | Double-coating powder coating combined bag and coating process thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113667386A (en) * | 2021-09-17 | 2021-11-19 | 黄山华佳表面科技股份有限公司 | Powder coating with two coating layers and one baking layer and preparation method thereof |
| CN114507467A (en) * | 2022-01-18 | 2022-05-17 | 湘江涂料科技有限公司 | Double-coating powder coating combined bag and coating process thereof |
| CN115558384A (en) * | 2022-11-02 | 2023-01-03 | 广东睿智环保科技有限责任公司 | Low-temperature curing high-corner-coverage powder coating and preparation method thereof |
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