CN108384453B - Water-based paint for surface of metal color steel plate and preparation method thereof - Google Patents
Water-based paint for surface of metal color steel plate and preparation method thereof Download PDFInfo
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- CN108384453B CN108384453B CN201810232771.1A CN201810232771A CN108384453B CN 108384453 B CN108384453 B CN 108384453B CN 201810232771 A CN201810232771 A CN 201810232771A CN 108384453 B CN108384453 B CN 108384453B
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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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/10—Block or graft copolymers containing polysiloxane sequences
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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
- 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
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention discloses a water-based paint for the surface of a metal color steel plate and a preparation method thereof, wherein the paint comprises the following raw materials in percentage by weight: 50-70% of modified organic silicon resin, 5-10% of epoxy resin, 5-10% of alkyd resin, 3-8% of aliphatic diisocyanate, 2-5% of isooctyl p-methoxycinnamate, 5-10% of mica powder, 0.5-2% of antioxidant, 2-4% of film-forming assistant, 0.5-1.2% of zinc stearate and 10-15% of glycerol; the method is convenient to operate and suitable for commercial production, the prepared light stability modifier contains 2 piperidine rings, the energy for capturing free radicals and transferring excited molecules is higher than that of a common light stabilizer, the light stability modifier is easy to graft with organic silicon resin, stable modified organic silicon resin is generated by polymerization, the light stabilizer is not required to be added additionally, and the phenomenon of uneven mixing of the coating is avoided.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a water-based coating for the surface of a metal color steel plate and a preparation method thereof.
Background
The metal color steel plate is also called color coated plate, also called color plate or precoated plate, and is a composite material with organic coating, and is a product prepared by using cold-rolled steel plate and galvanized steel plate as base plate, through surface pretreatment (degreasing, cleaning and chemical conversion treatment), coating by continuous method (roller coating method), baking and cooling. Because of the advantages of good decoration, energy conservation, environmental protection, easy forming, low cost and the like, the application of the novel decorative plate is gradually expanded from the building field to the household appliance field in recent years, and the novel decorative plate is commonly used for televisions, refrigerator back plates and the like.
In high-humidity and high-temperature areas, particularly under outdoor high-strength sunlight irradiation, self-oxidation of some color-coated steel plate coatings is caused by ultraviolet absorption, so that polymers are degraded, and in addition, due to the fact that all components are not uniformly mixed or are incompletely melted, the color of the coatings can fade after being irradiated by ultraviolet rays, the color-coated plate coatings which are seriously aged begin to crack, and fall off after being wrapped, so that metal plates can be exposed, corroded and rusted, the service life is greatly shortened, the exposed metal plates can be possibly electrified, and serious potential safety hazards are brought.
Disclosure of Invention
The invention aims to provide a water-based paint for the surface of a metal color steel plate and a preparation method thereof, the method is convenient to operate, is suitable for commercial production, and solves the problem that the metal color steel plate is easy to age under strong light irradiation.
The purpose of the invention can be realized by the following technical scheme:
a water-based paint for the surface of a metal color steel plate comprises the following raw materials in percentage by weight: 50-70% of modified organic silicon resin, 5-10% of epoxy resin, 5-10% of alkyd resin, 3-8% of aliphatic diisocyanate, 2-5% of isooctyl p-methoxycinnamate, 5-10% of mica powder, 0.5-2% of antioxidant, 2-4% of film-forming assistant, 0.5-1.2% of zinc stearate and 10-15% of glycerol.
Further, the Tg of the modified organic silicon resin is 50-60 ℃, and the number average molecular weight is 8000-20000; the modified organic silicon resin is obtained by polymerizing 50-60% of phenyl siloxane monomer and 15-30% of dimethyl siloxane monomer with 8-10% of polyimide block after free radical copolymerization, and finally modifying by 5-10% of modifier.
Further, the antioxidant is a composite antioxidant of an antioxidant 168 and an antioxidant TNP, and the mass ratio of the antioxidant 168 to the antioxidant TNP is 3-4.5: 1.
Further, the film forming auxiliary agent is one or two of propylene glycol methyl ether acetate, propylene glycol phenyl ether and dodecyl alcohol ester.
A preparation method of a water-based paint for the surface of a metal color steel plate specifically comprises the following steps:
s1 preparation of modified organic silicon resin
Putting all monomers of the organic silicon resin into a mixer for premixing to obtain an organic silicon resin monomer mixture; adding a polymerization solvent into a reaction kettle, heating to 120-plus-130 ℃, keeping the temperature, slowly adding an organic silicon resin monomer mixture into the reaction kettle, carrying out heat preservation reflux reaction for 2 hours, then adding polyimide and an initiator, heating to 220-plus-235 ℃, carrying out heat preservation block polymerization for 1 hour, then cooling to 140-plus-150 ℃, adding a light-stable modifier and a coupling agent, carrying out heat preservation for modification reaction for 40-60 minutes, removing the polymerization solvent after the reaction is finished, naturally cooling the material, and then adding the material into a ball mill for grinding and crushing to obtain the modified organic silicon resin with uniform particle size;
s2, preparation of the water-based paint: putting raw materials of all component amounts in the water-based paint into a mixing tank together, premixing, then carrying out melt extrusion on a screw extruder, wherein the rotating speed of a main machine of the screw extruder is 50-65Hz, the feeding rotating speed is 15-50Hz, the extrusion temperature in a first zone is 110 ℃ and the extrusion temperature in a second zone is 140 ℃, extruding sheet materials into a grinder to be crushed into powder, and sieving the powder through a 270-mesh sieve to obtain the 30-45um water-based powder paint.
Further, the initiator is one of diisopropyl peroxydicarbonate and dicyclohexyl peroxydicarbonate, and the addition amount of the initiator is 1-4% of the total weight of the monomer mixture.
Further, the coupling agent is titanate coupling agent, and the addition amount of the coupling agent is 3-5% of the total weight of the monomer mixture.
Further, the preparation method of the light stability modifier comprises the following steps: sequentially adding 2-methylpyridine 2, boron trifluoride and a solvent dioxane into a reaction bottle, putting the reaction bottle into an ice bath, slowly adding 3-acetylpyridine 1 while stirring, reacting for 2-3h, removing the solvent by reduced pressure evaporation, putting the crude product into ethanol, heating to dissolve, naturally cooling to room temperature, putting into an environment of 5-10 ℃ to quench and separate out crystals, filtering, drying under reduced pressure to obtain a yellowish crystal intermediate 3, adding the intermediate 3 and a catalyst nickel into an autoclave, introducing hydrogen when heating to 60-70 ℃, continuously heating to introduce hydrogen until heating to 180-185 ℃, stopping introducing hydrogen when the hydrogen pressure is 9-10MPa, preserving the temperature for reaction for 1h, filtering the reaction liquid, taking the filtrate for fractional distillation, and collecting the distillate to obtain a light stabilizer 4; the reaction formula is as follows:
furthermore, the molar ratio of the 3-acetylpyridine 1 to the 2-methylpyridine 2 to the boron trifluoride is 1:1.2-1.6: 1.1-1.15.
The invention has the beneficial effects that:
(1) according to the water-based paint for the surface of the metal color steel plate, the organic silicon resin is firstly modified through polyimide block polymerization, so that the rigidity and the heat resistance of the organic silicon resin are improved, the high temperature resistance of the water-based paint is improved, and then the organic silicon resin is secondarily modified through the light stability modifier, so that the prepared water-based paint has good inhibition effect on the photo-oxidative degradation reaction of polymers in the paint while the original toughness and high elasticity of the organic silicon resin are maintained, and the problem that the metal color steel plate turns yellow under high-strength irradiation is effectively avoided;
(2) the preparation method of the water-based paint for the surface of the metal color steel plate, which is provided by the invention, is convenient to operate and suitable for commercial production, the prepared light stability modifier contains 2 piperidine rings, the energy of the prepared light stability modifier for capturing free radicals and transferring excited molecules is higher than that of a common light stabilizer, the light stability modifier is easy to graft with organic silicon resin, stable modified organic silicon resin is generated by polymerization, no light stabilizer is required to be additionally added, and the phenomenon of uneven mixing of the paint is avoided.
Of course, it is not necessary for any product in which the invention is practiced to achieve all of the above-described advantages at the same time.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparation of light stability modifier: sequentially adding 1.5mol of 2-methylpyridine 2, 1.15mol of boron trifluoride and 5ml of solvent dioxane into a reaction bottle, putting the reaction bottle into an ice bath, slowly adding 1mol of 3-acetylpyridine while stirring, reacting for 2h, performing reduced pressure evaporation to remove the solvent, putting a crude product into ethanol, heating and dissolving, naturally cooling to room temperature, then putting the crude product into an environment at 6 ℃ to quench and separate out crystals, filtering, performing reduced pressure drying to obtain a yellowish crystal intermediate 3, adding the intermediate 3 and a catalyst nickel into an autoclave, introducing hydrogen when heating to 66 ℃, continuously heating and introducing hydrogen until the temperature is 185 ℃, stopping introducing hydrogen when the hydrogen pressure is 10MPa, performing heat preservation reaction for 1h, filtering the reaction liquid, taking the filtrate for fractional distillation, and collecting the distillate to obtain a light stabilizer 4; the reaction formula is as follows:
example 2
The preparation method of the water-based paint for the surface of the metal color steel plate specifically comprises the following steps:
s1 preparation of modified organic silicon resin
Putting 50g of phenyl siloxane monomer and 30g of dimethyl siloxane monomer of organic silicon resin into a mixer for premixing to obtain an organic silicon resin monomer mixture; adding a polymerization solvent xylene into a reaction kettle, heating to 120g, keeping the temperature, slowly adding an organic silicon resin monomer mixture into the reaction kettle, carrying out heat preservation reflux reaction for 2 hours, then adding 10g of polyimide and 1.6g of diisopropyl peroxydicarbonate, heating to 220g, carrying out heat preservation modification reaction for 1 hour, then cooling to 140 ℃, adding 10g of a light-stable modifier and 2.4g of a titanate coupling agent, carrying out heat preservation for secondary modification reaction for 40 minutes, removing the polymerization solvent xylene after the reaction is finished, naturally cooling the material, and then adding the material into a ball mill for grinding and crushing to obtain the modified organic silicon resin with uniform particle size; the Tg of the modified organic silicon resin is 52 ℃, and the number average molecular weight is 11150;
s2, preparation of the water-based paint: 53g of modified organic silicon resin, 5g of epoxy resin, 10g of alkyd resin, 5g of aliphatic diisocyanate, 2g of isooctyl p-methoxycinnamate, 5.5g of mica powder, 1680.8 g of antioxidant, 0.2g of antioxidant TNP, 3g of propylene glycol monomethyl ether acetate, 0.5g of zinc stearate and 15g of glycerol; putting the materials into a mixing cylinder together for premixing, then carrying out melt extrusion on a screw extruder, putting extruded sheets into a grinder for crushing into powder, and carrying out rotary screening on the powder through a 270-mesh sieve to obtain the 32-micron water-based powder coating, wherein the rotating speed of a main machine of the screw extruder is 50Hz, the feeding rotating speed is 15Hz, the extrusion temperature is 110 ℃ in a first region and 140 ℃ in a second region.
Example 3
The preparation method of the water-based paint for the surface of the metal color steel plate specifically comprises the following steps:
s1 preparation of modified organic silicon resin
60g of phenyl siloxane monomer and 27g of dimethyl siloxane monomer of the organic silicon resin are put into a mixer for premixing to obtain an organic silicon resin monomer mixture; adding a polymerization solvent xylene into a reaction kettle, heating to 130 ℃, keeping the temperature, slowly adding an organic silicon resin monomer mixture into the reaction kettle, carrying out heat preservation reflux reaction for 2 hours, then adding 8g of polyimide and 2.2g of diisopropyl peroxydicarbonate, heating to 235 ℃, carrying out heat preservation modification reaction for 1 hour, then cooling to 150 ℃, adding 5g of a light-stable modifier and 4.6g of a titanate coupling agent, carrying out heat preservation for secondary modification reaction for 60 minutes, removing the polymerization solvent xylene after the reaction is finished, naturally cooling the material, adding the material into a ball mill, and grinding to obtain the modified organic silicon resin with uniform particle size; the Tg of the modified silicone resin is 58 ℃ and the number average molecular weight is 18900;
s2, preparation of the water-based paint: 65.3g of modified organic silicon resin, 5g of epoxy resin, 5g of alkyd resin, 3g of aliphatic diisocyanate, 2g of isooctyl p-methoxycinnamate, 5g of mica powder, 1681.2g of antioxidant, 0.3g of antioxidant TNP, 2g of propylene glycol phenyl ether, 1.2g of zinc stearate and 10g of glycerol; putting the materials into a mixing cylinder together for premixing, then carrying out melt extrusion on a screw extruder, wherein the rotating speed of a main machine of the screw extruder is 65Hz, the feeding rotating speed is 50Hz, the first extrusion temperature zone is 110 ℃, the second extrusion temperature zone is 140 ℃, extruding sheet materials are put into a grinder to be crushed into powder, and the powder is sieved through a rotary sieve with 270 meshes to obtain the 42um water-based powder coating.
Example 4
The preparation method of the water-based paint for the surface of the metal color steel plate specifically comprises the following steps:
s1 preparation of modified organic silicon resin
Putting 65g of phenyl siloxane monomer and 15g of dimethyl siloxane monomer of organic silicon resin into a mixer for premixing to obtain an organic silicon resin monomer mixture; adding a polymerization solvent xylene into a reaction kettle, heating to 125 ℃, keeping the temperature, slowly adding an organic silicon resin monomer mixture into the reaction kettle, carrying out heat preservation reflux reaction for 2 hours, then adding 10g of polyimide and 2.8g of dicyclohexyl peroxydicarbonate, heating to 230 ℃, carrying out heat preservation modification reaction for 1 hour, then cooling to 145 ℃, adding 10g of a light-stable modifier and 4.5g of a titanate coupling agent, carrying out heat preservation for secondary modification reaction for 50 minutes, removing the polymerization solvent xylene after the reaction is finished, naturally cooling the material, and then adding the material into a ball mill for grinding and crushing to obtain the modified organic silicon resin with uniform particle size; the Tg of the modified silicone resin is 60 ℃, and the number average molecular weight is 150800;
s2, preparation of the water-based paint: 55g of modified organic silicon resin, 8g of epoxy resin, 8g of alkyd resin, 5g of aliphatic diisocyanate, 3g of isooctyl p-methoxycinnamate, 7g of mica powder, 1681.5 g of antioxidant, 0.4g of antioxidant TNP, 3g of dodecyl alcohol ester, 0.8g of zinc stearate and 8.3g of glycerol; putting the materials into a mixing cylinder together for premixing, then carrying out melt extrusion on a screw extruder, wherein the rotating speed of a main machine of the screw extruder is 55Hz, the feeding rotating speed is 30Hz, the first zone of the extrusion temperature is 110 ℃, the second zone is 140 ℃, the extruded sheet materials are put into a grinder to be crushed into powder, and the powder is sieved through a rotary sieve with 270 meshes to obtain the 44um water-based powder coating.
The surface of a metal steel plate is coated with a layer of coating, and the performance test method and the evaluation standard of the coating are as follows:
the leveling evaluation standard of the coating film is used for carrying out leveling rating according to a leveling effect rating standard plate of the American PCI, wherein 1 is poor, and 10 is excellent;
the glossiness test of the coating film refers to the national standard GB/T9754;
the impact strength of the coating film is according to the national standard GB/T1732;
the pencil hardness of the coating film refers to the national standard GB/T6739;
the transparency of the coating is transparent according to national standard GB/T1721, 82-100, slightly turbid 52-81 and turbid below 51;
the flexibility of the coating film is according to the national standard GB/T1731;
the UV aging resistance of the coating film is tested according to GB/T1865-;
table 1: various performance indexes of the coating films obtained in examples 1 to 3
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (7)
1. The water-based paint for the surface of the metal color steel plate is characterized in that: the weight percentages of the raw materials are as follows: 50-70% of modified organic silicon resin, 5-10% of epoxy resin, 5-10% of alkyd resin, 3-8% of aliphatic diisocyanate, 2-5% of isooctyl p-methoxycinnamate, 5-10% of mica powder, 0.5-2% of antioxidant, 2-4% of film-forming assistant, 0.5-1.2% of zinc stearate and 10-15% of glycerol;
the Tg of the modified organic silicon resin is 50-60 ℃, and the number average molecular weight is 8000-20000; the modified organic silicon resin is obtained by polymerizing 50-60% of phenyl siloxane monomer and 15-30% of dimethyl siloxane monomer with 8-10% of polyimide block after free radical copolymerization, and finally modifying by 5-10% of modifier.
2. The water-based paint for the surface of the metal color steel plate as claimed in claim 1, wherein: the antioxidant is a composite antioxidant of an antioxidant 168 and an antioxidant TNP, and the mass ratio of the antioxidant 168 to the antioxidant TNP is 3-4.5: 1.
3. The water-based paint for the surface of the metal color steel plate as claimed in claim 1, wherein: the film-forming assistant is one or two of propylene glycol methyl ether acetate, propylene glycol phenyl ether and dodecyl alcohol ester.
4. A preparation method of water-based paint for the surface of a metal color steel plate is characterized by comprising the following steps: the method specifically comprises the following steps:
s1 preparation of modified organic silicon resin
Putting all monomers of the organic silicon resin into a mixer for premixing to obtain an organic silicon resin monomer mixture; adding a polymerization solvent into a reaction kettle, heating to 120-plus-130 ℃, keeping the temperature, slowly adding an organic silicon resin monomer mixture into the reaction kettle, carrying out heat preservation reflux reaction for 2 hours, then adding polyimide and an initiator, heating to 220-plus-235 ℃, carrying out heat preservation block polymerization for 1 hour, then cooling to 140-plus-150 ℃, adding a light-stable modifier and a coupling agent, carrying out heat preservation for modification reaction for 40-60 minutes, removing the polymerization solvent after the reaction is finished, naturally cooling the material, and then adding the material into a ball mill for grinding and crushing to obtain the modified organic silicon resin with uniform particle size;
the preparation method of the light stability modifier comprises the following steps: sequentially adding 2-methylpyridine 2, boron trifluoride and a solvent dioxane into a reaction bottle, putting the reaction bottle into an ice bath, slowly adding 3-acetylpyridine 1 while stirring, reacting for 2-3h, removing the solvent by reduced pressure evaporation, putting the crude product into ethanol, heating to dissolve, naturally cooling to room temperature, putting into an environment of 5-10 ℃ to quench and separate out crystals, filtering, drying under reduced pressure to obtain a yellowish crystal intermediate 3, adding the intermediate 3 and a catalyst nickel into an autoclave, introducing hydrogen when heating to 60-70 ℃, continuously heating to introduce hydrogen until heating to 180-185 ℃, stopping introducing hydrogen when the hydrogen pressure is 9-10MPa, preserving the temperature for reaction for 1h, filtering the reaction liquid, taking the filtrate for fractional distillation, and collecting the distillate to obtain a light stabilizer 4; the reaction formula is as follows:
s2, preparation of the water-based paint: putting raw materials of all component amounts in the water-based paint into a mixing tank together, premixing, then carrying out melt extrusion on a screw extruder, wherein the rotating speed of a main machine of the screw extruder is 50-65Hz, the feeding rotating speed is 15-50Hz, the extrusion temperature in a first zone is 110 ℃ and the extrusion temperature in a second zone is 140 ℃, extruding sheet materials into a grinder to be crushed into powder, and sieving the powder through a 270-mesh sieve to obtain the 30-45um water-based powder paint.
5. The preparation method of the water-based paint for the surface of the metal color steel plate, according to claim 4, is characterized in that: the initiator is one of diisopropyl peroxydicarbonate and dicyclohexyl peroxydicarbonate, and the addition amount of the initiator is 1-4% of the total weight of the monomer mixture.
6. The preparation method of the water-based paint for the surface of the metal color steel plate, according to claim 4, is characterized in that: the coupling agent is titanate coupling agent, and the addition amount of the coupling agent is 3-5% of the total weight of the monomer mixture.
7. The preparation method of the water-based paint for the surface of the metal color steel plate, according to claim 4, is characterized in that: the molar ratio of the 3-acetylpyridine 1 to the 2-methylpyridine 2 to the boron trifluoride is 1:1.2-1.6: 1.1-1.15.
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