CN115710439B - Oil-stain-resistant scratch-resistant antibacterial coating and preparation method thereof - Google Patents
Oil-stain-resistant scratch-resistant antibacterial coating and preparation method thereof Download PDFInfo
- Publication number
- CN115710439B CN115710439B CN202211414998.0A CN202211414998A CN115710439B CN 115710439 B CN115710439 B CN 115710439B CN 202211414998 A CN202211414998 A CN 202211414998A CN 115710439 B CN115710439 B CN 115710439B
- Authority
- CN
- China
- Prior art keywords
- parts
- water
- resistant
- scratch
- modified
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention relates to the field of paint, in particular to an oil-resistant scratch-resistant antibacterial paint and a preparation method thereof, comprising the following components in parts by weight: 55-75 parts of aqueous polyester resin emulsion, 6-10 parts of amino resin, 12-18 parts of modified filler, 10-20 parts of pigment, 0.6-1.2 parts of flatting agent, 1.6-2.2 parts of wetting dispersant, 0.5-1 part of defoaming agent and 15-20 parts of water. The main raw material of the invention is water-based polyester resin emulsion, and has the advantages of water resistance, chemical corrosion resistance, high strength and good glossiness; the added auxiliary materials comprise amino resin, modified filler and other auxiliary agents, wherein the amino resin is methyl etherified amino resin capable of being cured under the low-temperature condition, has good crosslinking property, and has good hardness and weather resistance as a curing agent; the modified filler is self-made modified polyaluminosilazane, and aims to supplement the scratch resistance and the antibacterial property of the coating.
Description
Technical Field
The invention relates to the field of coatings, in particular to an oil-resistant scratch-resistant antibacterial coating and a preparation method thereof.
Background
With the development of the building decoration industry in recent years, people put forward higher requirements on decoration, and the requirements on environmental protection performance, oil stain resistance and antibacterial and mildew resistance of the building decoration industry are gradually increased. Along with the development of cities and the adjustment of industrial structures, the third industry is rapidly developed, and the catering industry belongs to an indispensable industrial chain. With the rapid development of catering industry, the problems of oil smoke and greasy dirt pollution caused by the rapid development of the catering industry are increasingly remarkable. In the chambers where food is made, especially in the kitchen, a lot of oily fumes are often generated. Besides being exhausted through the exhaust device, the volatile oil in the flue gas is easy to adhere to the surfaces of walls, tableware, electric appliances and the like in processing places. These greasy dirt are very liable to cause accumulation and grow a large number of bacteria, such as mites, escherichia coli, staphylococcus aureus, aspergillus etc., which pose a threat to human health.
At present, the problem is mainly solved by adopting a periodic cleaning mode at home and abroad. However, many dirt is difficult to thoroughly clean, and meanwhile, frequent cleaning can generate certain friction to damage the surfaces of cabinets, range hoods and the like, and the damaged surfaces are more likely to gather oil stains, so that subsequent cleaning is more difficult. This tends to reduce the life of cabinets, hoods, etc., and increase the cleaning costs of the processing site.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide an oil-stain-resistant scratch-resistant antibacterial coating and a preparation method thereof.
The aim of the invention is realized by adopting the following technical scheme:
the invention provides an oil-stain-resistant scratch-resistant antibacterial coating, which comprises the following components in parts by weight:
55-75 parts of aqueous polyester resin emulsion, 6-10 parts of amino resin, 12-18 parts of modified filler, 10-20 parts of pigment, 0.6-1.2 parts of flatting agent, 1.6-2.2 parts of wetting dispersant, 0.5-1 part of defoaming agent and 15-20 parts of water.
Preferably, the preparation method of the aqueous polyester resin emulsion comprises the following steps:
mixing water-soluble saturated polyester resin, a diluent and deionized water, and fully stirring to form water-based polyester resin emulsion;
wherein the diluent is ethylene glycol butyl ether or propylene glycol methyl ether, the addition amount of the diluent is 0.1% -0.5% of the total mass of the resin, and the prepared emulsion has a solid content of 70% +/-2%.
Preferably, the water-soluble saturated polyester resin is SK EW-370, has the solid content of more than or equal to 99%, has the molecular weight of 12000, has the intrinsic viscosity of 0.4dL/g and the hydroxyl value of 8mgKOH/g.
Preferably, the amino resin is a methyl etherified amino resin, in particular a hexamethoxymethyl melamine resin, which belongs to the group of water-soluble resins.
Preferably, the pigment is any one or a combination of more than one of titanium dioxide, iron oxide red, iron oxide yellow, phthalocyanine blue, phthalocyanine green and carbon black.
Preferably, the leveling agent is one of UNIQ FLOW 495U, UNIQ FLOW 497U, UNIQ FLOW 477U.
Preferably, the wetting dispersant is any one or more of sodium succinate sulfonate, sodium dodecyl sulfonate, dodecyl sulfate and sodium hexametaphosphate.
Preferably, the defoaming agent is a polyether type defoaming agent, and comprises any one of GP type glycerin polyether, GPE type polyoxyethylene polyoxypropylene glycerin ether and PPG type polypropylene glycol.
Preferably, the modified filler is modified polyaluminosilazane, and the preparation method comprises the following steps:
s1, dissolving water-soluble zirconium salt and water-soluble selenium salt in water to prepare a pre-reaction solution;
s2, mixing organic aluminum and polysilazane in a reaction container, heating up in a stage mode after uniformly mixing, naturally cooling, and crushing to obtain polysilazane particles;
s3, mixing the polyaluminosilazane particles with a pre-reaction liquid, performing hydrothermal reaction treatment, and then washing and drying to obtain the zirconium diselenide modified polyaluminosilazane;
s4, zinc salt and urotropine are dissolved in deionized water, zirconium diselenide modified polyaluminium silazane is added, hydrothermal reaction is carried out, and washing and drying are carried out, thus obtaining the modified polyaluminium silazane.
Preferably, in step S1, the water-soluble zirconium salt is sodium zirconate (Na 2 ZrO 3 ) The water-soluble selenium salt is ammonium selenate ((NH) 4 ) 2 SeO 4 ) The mass ratio of the sodium zirconate, the ammonium selenate and the deionized water is 1:2.04-2.1:100.
Preferably, in step S2, the organoaluminum is aluminum acetylacetonate; polysilazane is purchased from Anhui Aijia silicone oil limited company, the model is organic polysilazane IOTA 9150, the viscosity is 36cp, the purity is more than or equal to 99%, and the molecular weight is 850; the added organic aluminum accounts for 0.2 to 0.5 percent of the mass of the polysilazane.
Preferably, in the step S2, the temperature rising rate of the stepwise temperature rising is 5 ℃/min, the heat preservation treatment is carried out for 0.5h at each temperature rising temperature of 50 ℃, and the heat preservation treatment is carried out for 4-6h after the temperature rising temperature reaches 380 ℃.
Preferably, in the step S3, the mass ratio of the polyaluminosilazane particles to the pre-reaction liquid is 1:50-80, the temperature of the hydrothermal reaction is 210-260 ℃, and the heat preservation time is 10-15h.
Preferably, in the step S4, the zinc salt is zinc acetate, and the mass ratio of the zinc salt to urotropine to deionized water is 0.7-0.8:1:50-60.
Preferably, in the step S4, the mass ratio of the zirconium diselenide modified polyaluminosilane to the deionized water is 1:5-6.
Preferably, in step S4, the temperature of the hydrothermal reaction is 140-160 ℃, and the heat preservation time is 10-15h.
Preferably, the preparation method of the modified polyaluminosilazane comprises the following steps:
s1, weighing sodium zirconate and ammonium selenate, mixing in a container containing deionized water, and stirring and dispersing under the condition of room temperature to form a uniform solution, namely a pre-reaction solution;
s2, mixing organic aluminum and polysilazane in a reaction container, introducing nitrogen as a protective gas, stirring at room temperature for 0.5-1h, then gradually heating up at a heating rate of 5 ℃/min, carrying out heat preservation at 50 ℃ for 0.5h, carrying out heat preservation for 4-6h after heating up to 380 ℃, naturally cooling to obtain the polysilazane, and crushing into particles;
s3, mixing the pre-reaction liquid with polyaluminium silazane particles, fully stirring and mixing, pouring the mixture into a reaction kettle with tetrafluoroethylene as a lining, carrying out heat preservation treatment on the reaction kettle at the temperature of 210-260 ℃ for 10-15 hours, naturally cooling after the reaction is finished, filtering to remove liquid, flushing the collected solid powder with pure water for at least three times, and carrying out vacuum drying to obtain the zirconium diselenide modified polyaluminium silazane;
s4, mixing zinc acetate and urotropine in deionized water, fully dissolving, adding zirconium diselenide modified polyaluminium silazane, fully dispersing, transferring into a reaction kettle with tetrafluoroethylene as a lining, preserving heat for 10-15h at 140-160 ℃, washing with absolute ethyl alcohol and deionized water in sequence, and vacuum drying to obtain the modified polyaluminium silazane.
The second object of the invention is to provide a preparation method of the oil-stain-resistant scratch-resistant antibacterial paint, which comprises the following steps:
(1) Sequentially adding a wetting dispersant, a modified filler, a pigment and water into the aqueous polyester resin emulsion, and fully stirring and dispersing to form a mixed dispersion liquid;
(2) And sequentially adding the amino resin, the flatting agent and the defoamer into the mixed dispersion liquid, and fully stirring and dispersing again to obtain the oil-resistant scratch-resistant antibacterial coating.
Preferably, in the step (1), the stirring speed is 300-500r/min, and the stirring time is 0.5-1h; in the step (2), the stirring speed is 200-400r/min, and the stirring time is 0.2-0.5h.
The beneficial effects of the invention are as follows:
1. the invention provides an oil-stain-resistant scratch-resistant antibacterial coating, which belongs to a water-based environment-friendly coating, and is prepared by water-soluble saturated polyester resin through water-soluble compounding, wherein the main raw material is water-based polyester resin emulsion, and the water-soluble saturated polyester resin has the advantages of water resistance, chemical corrosion resistance, high strength and good glossiness; the added auxiliary materials comprise amino resin, modified filler and other auxiliary agents, wherein the amino resin is methyl etherified amino resin capable of being cured under the low-temperature condition, has good crosslinking property, and has good hardness and weather resistance as a curing agent; the modified filler is self-made modified polyaluminosilazane, and aims to supplement the scratch resistance and the antibacterial property of the coating.
2. The modified filler in the coating component takes the prepared polyaluminosilazane as a basic raw material, and zirconium diselenide and zinc oxide are sequentially grown in situ on the basis of the basic raw material, so that the modified polyaluminosilazane is prepared. The polyaluminosilane is a product obtained by crosslinking and combining polysilazane with aluminum acetylacetonate, and has mechanical properties better than those of polysilazane, but is still insufficient in terms of flexibility and scratch resistance. Therefore, the invention is innovatively further modified on the structure, the prepared polyaluminosilane is taken as a matrix, zirconium diselenide and zinc oxide are sequentially grown in situ, zirconium diselenide belongs to a substance with a two-dimensional structure, an array type coating structure can be formed in the in-situ growth process, the structural characteristics are combined with zinc oxide which is grown subsequently, the antibacterial property can be better enhanced, the specific surface area of the zinc oxide can be increased, the fusion degree with paint resin is better, and the high temperature resistance, the flexibility and the scratch resistance of the paint are improved in the aspect of the performance influence on the paint through detection.
Detailed Description
The technical features, objects and advantages of the present invention will be more clearly understood from the following detailed description of the technical aspects of the present invention, but should not be construed as limiting the scope of the invention.
Polysilazane (PSZ) is commonly called as high-temperature non-inflammable resin, has the characteristics of super strong adhesive force of organic matters and super high temperature resistance of inorganic matters, and integrates the characteristics of corrosion resistance, wear resistance, fouling resistance, water resistance and the like. However, polysilazane has a defect of excessively high brittleness, and is easily cracked and has a defect of generating cells when used as a coating additive. Therefore, the invention adds metal aluminum on the basis of polysilazane to prepare the polysilazane, and then carries out a series of modification treatment on the polysilazane to obtain the modified polysilazane material.
The invention is further described with reference to the following examples.
Example 1
The oil-stain-resistant scratch-resistant antibacterial coating comprises the following components in parts by weight:
65 parts of aqueous polyester resin emulsion, 8 parts of amino resin, 15 parts of modified filler, 15 parts of pigment, 0.8 part of flatting agent, 1.8 parts of wetting dispersant, 0.6 part of defoamer and 17 parts of water.
The preparation method of the aqueous polyester resin emulsion comprises the following steps:
mixing water-soluble saturated polyester resin, a diluent and deionized water, and fully stirring to form water-based polyester resin emulsion; wherein the diluent is ethylene glycol butyl ether or propylene glycol methyl ether, the addition amount of the diluent is 0.3% of the total mass of the resin, and the prepared emulsion has the solid content of 70% +/-2%; the model of the water-soluble saturated polyester resin is SK EW-370, the solid content is more than or equal to 99%, the molecular weight is 12000, the intrinsic viscosity is 0.4dL/g, and the hydroxyl value is 8mgKOH/g.
The amino resin is methyl etherified amino resin, in particular to hexamethoxy methyl melamine resin, and the resin belongs to water-soluble resin.
The pigment is titanium dioxide and iron oxide yellow which are mixed according to the weight ratio of 15:1; the leveling agent is UNIQ FLOW 495U; the wetting dispersant is sodium succinate sulfonate; the defoaming agent is GPE type polyoxyethylene polyoxypropylene glycerol ether.
The modified filler is modified polyaluminosilane, and the preparation method of the modified polyaluminosilane comprises the following steps:
s1, weighing sodium zirconate (Na 2 ZrO 3 ) With ammonium selenate ((NH) 4 ) 2 SeO 4 ) Mixing in a container containing deionized water, wherein the mass ratio of sodium zirconate, ammonium selenate to deionized water is 1:2.08:100, and stirring and dispersing under the condition of room temperature to form a uniform solution, namely a pre-reaction solution;
s2, mixing aluminum acetylacetonate (organic aluminum) and polysilazane in a reaction container, wherein the aluminum acetylacetonate accounts for 0.3% of the mass of the polysilazane, introducing nitrogen as a protective gas, stirring at room temperature for 0.6h, then gradually heating at a heating rate of 5 ℃/min, carrying out heat preservation treatment at 50 ℃ for 0.5h, carrying out heat preservation treatment for 5h after the temperature is raised to 380 ℃, naturally cooling to obtain the polysilazane, and crushing into particles;
s3, mixing the pre-reaction liquid with polyaluminium silazane particles, wherein the mass ratio of the polyaluminium silazane particles to the pre-reaction liquid is 1:60, pouring the mixture into a reaction kettle with tetrafluoroethylene as a lining after full stirring and mixing, carrying out heat preservation treatment on the reaction kettle at 240 ℃ for 12 hours, naturally cooling after the reaction is finished, filtering to remove liquid, flushing the collected solid powder with pure water for at least three times, and carrying out vacuum drying to obtain zirconium diselenide modified polyaluminium silazane;
s4, mixing zinc acetate and urotropine in deionized water, wherein the mass ratio of the zinc acetate to the urotropine to the deionized water is 0.7:1:55, adding zirconium diselenide modified polyaluminium silazane, wherein the mass ratio of the zirconium diselenide modified polyaluminium silazane to the deionized water is 1:5, dispersing fully, transferring into a reaction kettle with tetrafluoroethylene as a lining, preserving heat for 12 hours at 150 ℃, washing with absolute ethyl alcohol and deionized water sequentially, and drying in vacuum to obtain the modified polyaluminium silazane.
The preparation method of the oil-stain-resistant scratch-resistant antibacterial coating comprises the following steps:
(1) Sequentially adding a wetting dispersant, a modified filler, a pigment and water into the aqueous polyester resin emulsion, and fully stirring and dispersing at the stirring speed of 400r/min for 0.6h to form a mixed dispersion;
(2) And sequentially adding the amino resin, the flatting agent and the defoamer into the mixed dispersion liquid, fully stirring and dispersing again, wherein the stirring speed is 300r/min, and the stirring time is 0.3h, so as to obtain the oil-resistant scratch-resistant antibacterial coating.
Example 2
The oil-stain-resistant scratch-resistant antibacterial coating comprises the following components in parts by weight:
55 parts of aqueous polyester resin emulsion, 6 parts of amino resin, 12 parts of modified filler, 10 parts of pigment, 0.6 part of flatting agent, 1.6 parts of wetting dispersant, 0.5 part of defoamer and 15 parts of water.
The preparation method of the aqueous polyester resin emulsion comprises the following steps:
mixing water-soluble saturated polyester resin, a diluent and deionized water, and fully stirring to form water-based polyester resin emulsion; wherein the diluent is ethylene glycol butyl ether or propylene glycol methyl ether, the addition amount of the diluent is 0.1% of the total mass of the resin, and the prepared emulsion has the solid content of 70% +/-2%; the model of the water-soluble saturated polyester resin is SK EW-370, the solid content is more than or equal to 99%, the molecular weight is 12000, the intrinsic viscosity is 0.4dL/g, and the hydroxyl value is 8mgKOH/g.
The amino resin is methyl etherified amino resin, in particular to hexamethoxy methyl melamine resin, and the resin belongs to water-soluble resin.
The pigment is titanium dioxide, iron oxide red and phthalocyanine green which are mixed according to the weight ratio of 10:1.2:1.8; the leveling agent is UNIQ FLOW 497U; the wetting dispersant is sodium dodecyl sulfonate; the defoamer is GP type glycerol polyether.
The modified filler is modified polyaluminosilane, and the preparation method of the modified polyaluminosilane comprises the following steps:
s1, weighing sodium zirconate (Na 2 ZrO 3 ) With ammonium selenate ((NH) 4 ) 2 SeO 4 ) Mixing in a container containing deionized water, wherein the mass ratio of sodium zirconate, ammonium selenate to deionized water is 1:2.04:100, and stirring and dispersing under the condition of room temperature to form a uniform solution, namely a pre-reaction solution;
s2, mixing aluminum acetylacetonate (organic aluminum) and polysilazane in a reaction container, wherein the aluminum acetylacetonate accounts for 0.2% of the mass of the polysilazane, introducing nitrogen as a protective gas, stirring at room temperature for 0.5h, then gradually heating at a heating rate of 5 ℃/min, carrying out heat preservation treatment at 50 ℃ for 0.5h, carrying out heat preservation treatment for 4h after the temperature is raised to 380 ℃, naturally cooling to obtain the polysilazane, and crushing into particles;
s3, mixing the pre-reaction liquid with polyaluminium silazane particles, wherein the mass ratio of the polyaluminium silazane particles to the pre-reaction liquid is 1:50, pouring the mixture into a reaction kettle with tetrafluoroethylene as a lining after fully stirring and mixing, carrying out heat preservation treatment on the reaction kettle at 210 ℃ for 15 hours, naturally cooling after the reaction is finished, filtering to remove liquid, flushing the collected solid powder with pure water for at least three times, and carrying out vacuum drying to obtain zirconium diselenide modified polyaluminium silazane;
s4, mixing zinc acetate and urotropine in deionized water, wherein the mass ratio of the zinc acetate to the urotropine to the deionized water is 0.7:1:50, adding zirconium diselenide modified polyaluminium silazane, wherein the mass ratio of the zirconium diselenide modified polyaluminium silazane to the deionized water is 1:5, dispersing fully, transferring into a reaction kettle with tetrafluoroethylene as a lining, preserving heat at 140 ℃ for 15 hours, washing with absolute ethyl alcohol and deionized water sequentially, and drying in vacuum to obtain the modified polyaluminium silazane.
The preparation method of the oil-stain-resistant scratch-resistant antibacterial coating comprises the following steps:
(1) Sequentially adding a wetting dispersant, a modified filler, a pigment and water into the aqueous polyester resin emulsion, and fully stirring and dispersing at the stirring speed of 300r/min for 1h to form a mixed dispersion;
(2) And sequentially adding the amino resin, the flatting agent and the defoamer into the mixed dispersion liquid, fully stirring and dispersing again, wherein the stirring speed is 200r/min, and the stirring time is 0.5h, so as to obtain the oil-resistant scratch-resistant antibacterial coating.
Example 3
The oil-stain-resistant scratch-resistant antibacterial coating comprises the following components in parts by weight:
75 parts of aqueous polyester resin emulsion, 10 parts of amino resin, 18 parts of modified filler, 20 parts of pigment, 1.2 parts of flatting agent, 2.2 parts of wetting dispersant, 1 part of defoaming agent and 20 parts of water.
The preparation method of the aqueous polyester resin emulsion comprises the following steps:
mixing water-soluble saturated polyester resin, a diluent and deionized water, and fully stirring to form water-based polyester resin emulsion; wherein the diluent is ethylene glycol butyl ether or propylene glycol methyl ether, the addition amount of the diluent is 0.5% of the total mass of the resin, and the prepared emulsion has a solid content of 70% +/-2%. The model of the water-soluble saturated polyester resin is SK EW-370, the solid content is more than or equal to 99%, the molecular weight is 12000, the intrinsic viscosity is 0.4dL/g, and the hydroxyl value is 8mgKOH/g.
The amino resin is methyl etherified amino resin, in particular to hexamethoxy methyl melamine resin, and the resin belongs to water-soluble resin.
The pigment is titanium dioxide, phthalocyanine blue and carbon black which are mixed according to the weight ratio of 12:1.5:0.3; the leveling agent is UNIQ FLOW 477U; the wetting dispersant is dodecyl sulfate; the defoamer is PPG type polypropylene glycol.
The modified filler is modified polyaluminosilane, and the preparation method of the modified polyaluminosilane comprises the following steps:
s1, weighing sodium zirconate (Na 2 ZrO 3 ) With ammonium selenate ((NH) 4 ) 2 SeO 4 ) Mixing in a container containing deionized water, wherein the mass ratio of sodium zirconate, ammonium selenate to deionized water is 1:2.1:100, and stirring and dispersing under the condition of room temperature to form a uniform solution, namely a pre-reaction solution;
s2, mixing aluminum acetylacetonate (organic aluminum) and polysilazane in a reaction container, wherein the aluminum acetylacetonate accounts for 0.5% of the mass of the polysilazane, introducing nitrogen as a protective gas, stirring at room temperature for 1h, then gradually heating at a heating rate of 5 ℃/min, carrying out heat preservation treatment for 0.5h at 50 ℃ each time, carrying out heat preservation treatment for 6h after the temperature is raised to 380 ℃, naturally cooling to obtain the polysilazane, and crushing into particles;
s3, mixing the pre-reaction liquid with polyaluminium silazane particles, wherein the mass ratio of the polyaluminium silazane particles to the pre-reaction liquid is 1:80, pouring the mixture into a reaction kettle with tetrafluoroethylene as a lining after fully stirring and mixing, carrying out heat preservation treatment on the reaction kettle at 260 ℃ for 10 hours, naturally cooling after the reaction is finished, filtering to remove liquid, flushing the collected solid powder with pure water for at least three times, and carrying out vacuum drying to obtain zirconium diselenide modified polyaluminium silazane;
s4, mixing zinc acetate and urotropine in deionized water, wherein the mass ratio of the zinc acetate to the urotropine to the deionized water is 0.8:1:60, adding zirconium diselenide modified polyaluminium silazane, wherein the mass ratio of the zirconium diselenide modified polyaluminium silazane to the deionized water is 1:6, dispersing fully, transferring into a reaction kettle with tetrafluoroethylene as a lining, preserving heat at 160 ℃ for 10 hours, washing with absolute ethyl alcohol and deionized water sequentially, and drying in vacuum to obtain the modified polyaluminium silazane.
The preparation method of the oil-stain-resistant scratch-resistant antibacterial coating comprises the following steps:
(1) Sequentially adding a wetting dispersant, a modified filler, a pigment and water into the aqueous polyester resin emulsion, and fully stirring and dispersing at the stirring speed of 500r/min for 0.5h to form a mixed dispersion;
(2) Sequentially adding the amino resin, the flatting agent and the defoamer into the mixed dispersion liquid, fully stirring and dispersing again, wherein the stirring speed is 400r/min, and the stirring time is 0.2h, so as to obtain the oil-resistant scratch-resistant antibacterial coating.
Comparative example 1
The water-based paint comprises the following components in parts by weight:
65 parts of aqueous polyester resin emulsion, 8 parts of amino resin, 15 parts of modified filler, 15 parts of pigment, 0.8 part of flatting agent, 1.8 parts of wetting dispersant, 0.6 part of defoamer and 17 parts of water.
The difference from example 1 is that the modified filler is polysilazane.
Comparative example 2
The water-based paint comprises the following components in parts by weight:
65 parts of aqueous polyester resin emulsion, 8 parts of amino resin, 15 parts of modified filler, 15 parts of pigment, 0.8 part of flatting agent, 1.8 parts of wetting dispersant, 0.6 part of defoamer and 17 parts of water.
The difference from example 1 is that the modified filler is polyaluminosilazane.
The preparation method of the polyaluminosilazane comprises the following steps: mixing aluminum acetylacetonate (organic aluminum) and polysilazane in a reaction container, wherein the aluminum acetylacetonate accounts for 0.3% of the mass of the polysilazane, introducing nitrogen as a protective gas, stirring at room temperature for 0.6h, then gradually heating at a heating rate of 5 ℃/min, carrying out heat preservation treatment for 0.5h at 50 ℃ each time, carrying out heat preservation treatment for 5h after the temperature is raised to 380 ℃, and naturally cooling to obtain the polysilazane.
Comparative example 3
The water-based paint comprises the following components in parts by weight:
65 parts of aqueous polyester resin emulsion, 8 parts of amino resin, 15 parts of modified filler, 15 parts of pigment, 0.8 part of flatting agent, 1.8 parts of wetting dispersant, 0.6 part of defoamer and 17 parts of water.
The difference from example 1 is that the modified filler is zirconium diselenide modified polyaluminosilane.
The preparation method of the zirconium diselenide modified polyaluminosilane comprises the following steps:
s1, weighing sodium zirconate (Na 2 ZrO 3 ) With ammonium selenate ((NH) 4 ) 2 SeO 4 ) Mixing in a container containing deionized water, wherein the mass ratio of sodium zirconate, ammonium selenate to deionized water is 1:2.08:100, and stirring and dispersing under the condition of room temperature to form a uniform solution, namely a pre-reaction solution;
s2, mixing aluminum acetylacetonate (organic aluminum) and polysilazane in a reaction container, wherein the aluminum acetylacetonate accounts for 0.3% of the mass of the polysilazane, introducing nitrogen as a protective gas, stirring at room temperature for 0.6h, then gradually heating at a heating rate of 5 ℃/min, carrying out heat preservation treatment at 50 ℃ for 0.5h, carrying out heat preservation treatment for 5h after the temperature is raised to 380 ℃, naturally cooling to obtain the polysilazane, and crushing into particles;
s3, mixing the pre-reaction liquid with polyaluminium silazane particles, wherein the mass ratio of the polyaluminium silazane particles to the pre-reaction liquid is 1:60, pouring the mixture into a reaction kettle with tetrafluoroethylene as a lining after fully stirring and mixing, carrying out heat preservation treatment on the reaction kettle at 240 ℃ for 12 hours, naturally cooling after the reaction is finished, filtering to remove liquid, flushing the collected solid powder with pure water for at least three times, and carrying out vacuum drying to obtain the zirconium diselenide modified polyaluminium silazane.
Comparative example 4
The water-based paint comprises the following components in parts by weight:
65 parts of aqueous polyester resin emulsion, 8 parts of amino resin, 15 parts of modified filler, 15 parts of pigment, 0.8 part of flatting agent, 1.8 parts of wetting dispersant, 0.6 part of defoamer and 17 parts of water.
The difference from example 1 is that the modified filler is zinc oxide modified polyaluminosilazane.
S1, mixing aluminum acetylacetonate (organic aluminum) and polysilazane in a reaction container, wherein the aluminum acetylacetonate accounts for 0.3% of the mass of the polysilazane, introducing nitrogen as a protective gas, stirring at room temperature for 0.6h, then gradually heating at a heating rate of 5 ℃/min, carrying out heat preservation treatment at 50 ℃ for 0.5h, carrying out heat preservation treatment for 5h after the temperature is raised to 380 ℃, naturally cooling to obtain the polysilazane, and crushing into particles;
s2, mixing zinc acetate and urotropine in deionized water, wherein the mass ratio of the zinc acetate to the urotropine to the deionized water is 0.7:1:55, adding polyaluminium silazane, wherein the mass ratio of the polyaluminium silazane to the deionized water is 1:5 after the zinc acetate to the urotropine to the deionized water is fully dissolved, fully dispersing the polyaluminium silazane and the deionized water, transferring the mixture into a reaction kettle with tetrafluoroethylene as a lining, preserving heat for 12 hours at the temperature of 150 ℃, washing the mixture with absolute ethyl alcohol and the deionized water in sequence, and carrying out vacuum drying to obtain the zinc oxide modified polyaluminium silazane.
Experimental example
In order to further clearly illustrate the content of the present invention, the present invention was examined for the coatings obtained in example 1, comparative examples 1 to 4. The coatings obtained in example 1 and comparative examples 1 to 4 were each coated on a corresponding plate to a thickness of 50. Mu.m, baked in an oven at 75℃for 30 minutes, and then tested for each coating,
impact resistance: reference standard GB/T1732 (height standard, cm).
Surface hardness: reference standard GB/T6739 (pencil method).
Scratch resistance: reference standard GB/T9279 (scratch tester), load weight 150g; the test was performed in parallel for 3 times, and no scratch was recorded as "no scratch", and if there was a scratch, it was classified into "slight scratch", "moderate scratch" and "severe scratch" according to the degree of scratch.
Adhesion force: reference standard GB/T1720 (circle method, 1-7).
Water resistance: after soaking in tap water at 25℃for 96 hours, it was observed whether or not bubbling and peeling occurred.
Contact angle with water, contact angle with oil: the measurement was performed using an goniometer type contact angle measuring instrument.
Antibacterial properties: the antibacterial ratio (E.coli and Staphylococcus aureus) was calculated with reference to standard GB/T21866.
The results are shown in Table 1:
TABLE 1 Performance of different coatings
As can be seen from the test results in table 1, example 1 of the present invention was excellent in not only high impact resistance (good toughness) but also surface hardness, adhesion and water resistance, and also very bright in oil stain resistance (large contact angle with oil) and water resistance (large contact angle with water), and also had very good antibacterial performance.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (9)
1. The oil-stain-resistant scratch-resistant antibacterial coating is characterized by comprising the following components in parts by weight:
55-75 parts of aqueous polyester resin emulsion, 6-10 parts of amino resin, 12-18 parts of modified filler, 10-20 parts of pigment, 0.6-1.2 parts of flatting agent, 1.6-2.2 parts of wetting dispersant, 0.5-1 part of defoaming agent and 15-20 parts of water;
the modified filler is modified polyaluminosilazane, and the preparation method comprises the following steps:
s1, dissolving water-soluble zirconium salt and water-soluble selenium salt in water to prepare a pre-reaction solution;
s2, mixing organic aluminum and polysilazane in a reaction container, heating up in a stage mode after uniformly mixing, naturally cooling, and crushing to obtain polysilazane particles;
s3, mixing the polyaluminosilazane particles with a pre-reaction liquid, performing hydrothermal reaction treatment, and then washing and drying to obtain the zirconium diselenide modified polyaluminosilazane;
s4, zinc salt and urotropine are dissolved in deionized water, zirconium diselenide modified polyaluminium silazane is added, hydrothermal reaction is carried out, and washing and drying are carried out, thus obtaining the modified polyaluminium silazane.
2. The oil stain-resistant scratch-resistant antibacterial coating according to claim 1, wherein the preparation method of the aqueous polyester resin emulsion is as follows:
mixing water-soluble saturated polyester resin, a diluent and deionized water, and fully stirring to form water-based polyester resin emulsion;
wherein the diluent is ethylene glycol butyl ether or propylene glycol methyl ether, the addition amount of the diluent is 0.1% -0.5% of the total mass of the resin, and the prepared emulsion has a solid content of 70% +/-2%; the model of the water-soluble saturated polyester resin is SK EW-370, the solid content is more than or equal to 99%, the molecular weight is 12000, the intrinsic viscosity is 0.4dL/g, and the hydroxyl value is 8mgKOH/g.
3. An anti-oil-stain scratch-resistant antibacterial coating according to claim 1, characterized in that the amino resin is a methyl etherified amino resin, in particular a hexamethoxymethyl melamine resin, which belongs to a water-soluble resin.
4. The oil stain-resistant scratch-resistant antibacterial coating according to claim 1, wherein the pigment is any one or a combination of more of titanium dioxide, iron oxide red, iron oxide yellow, phthalocyanine blue, phthalocyanine green and carbon black.
5. The oil stain and scratch resistant antimicrobial coating according to claim 1, wherein the leveling agent is one of UNIQ FLOW 495U, UNIQ FLOW 497U, UNIQ FLOW 477U.
6. The oil stain and scratch resistant antimicrobial coating according to claim 1, wherein the wetting dispersant is any one or more of sodium succinate sulfonate, sodium dodecyl sulfonate, dodecyl sulfate, sodium hexametaphosphate.
7. The oil stain-resistant scratch-resistant antibacterial coating according to claim 1, wherein the defoamer is a polyether defoamer comprising any one of GP-type glycerol polyether, GPE-type polyoxyethylene polyoxypropylene glycerol ether and PPG-type polypropylene glycol.
8. The oil stain-resistant scratch-resistant antibacterial coating according to claim 1, wherein in the step S1, the water-soluble zirconium salt is sodium zirconate, the water-soluble selenium salt is ammonium selenate, and the mass ratio of the sodium zirconate, the ammonium selenate and deionized water is 1:2.04-2.1:100;
in the step S2, the organic aluminum is aluminum acetylacetonate; polysilazane is purchased from Anhui Aijia silicone oil limited company, the model is organic polysilazane IOTA 9150, the viscosity is 36cp, the purity is more than or equal to 99%, and the molecular weight is 850; the added organic aluminum accounts for 0.2 to 0.5 percent of the mass of the polysilazane;
in the step S2, the temperature rising rate of the stage temperature rising is 5 ℃/min, the heat preservation is carried out for 0.5h at the temperature of 50 ℃ when the temperature rises, and the heat preservation is carried out for 4-6h after the temperature rises to 380 ℃;
in the step S3, the mass ratio of the polyaluminosilazane particles to the pre-reaction liquid is 1:50-80, the temperature of the hydrothermal reaction is 210-260 ℃, and the heat preservation time is 10-15h;
in the step S4, the zinc salt is zinc acetate, and the mass ratio of the zinc salt to urotropine to deionized water is 0.7-0.8:1:50-60;
in the step S4, the temperature of the hydrothermal reaction is 140-160 ℃, and the heat preservation time is 10-15h.
9. A method for preparing the oil stain-resistant scratch-resistant antibacterial paint as claimed in any one of claims 1 to 8, which comprises the following steps:
(1) Sequentially adding a wetting dispersant, a modified filler, a pigment and water into the aqueous polyester resin emulsion, and fully stirring and dispersing to form a mixed dispersion liquid;
(2) And sequentially adding the amino resin, the flatting agent and the defoamer into the mixed dispersion liquid, and fully stirring and dispersing again to obtain the oil-resistant scratch-resistant antibacterial coating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211414998.0A CN115710439B (en) | 2022-11-10 | 2022-11-10 | Oil-stain-resistant scratch-resistant antibacterial coating and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211414998.0A CN115710439B (en) | 2022-11-10 | 2022-11-10 | Oil-stain-resistant scratch-resistant antibacterial coating and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115710439A CN115710439A (en) | 2023-02-24 |
| CN115710439B true CN115710439B (en) | 2023-07-18 |
Family
ID=85232907
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211414998.0A Active CN115710439B (en) | 2022-11-10 | 2022-11-10 | Oil-stain-resistant scratch-resistant antibacterial coating and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115710439B (en) |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4368115A (en) * | 1977-05-16 | 1983-01-11 | Exxon Research And Engineering Co. | Catalysts comprising layered chalcogenides of group IVb-group VIIb prepared by a low temperature nonaqueous precipitate technique |
| JPH085963B2 (en) * | 1986-09-26 | 1996-01-24 | 東燃株式会社 | Novel polyaluminosilazane and method for producing the same |
| CN104830230A (en) * | 2015-05-13 | 2015-08-12 | 江西科技师范大学 | Space environment damage prevention protective coating as well as preparation method and application thereof |
| CN107383376B (en) * | 2017-07-12 | 2020-04-24 | 东南大学 | Method for preparing polyaluminum carbosilane precursor by taking aluminum stearate as aluminum source and application of polyaluminum carbosilane precursor |
| CN109233578A (en) * | 2018-07-10 | 2019-01-18 | 河北晨阳工贸集团有限公司 | A kind of volume aluminium Amino-Polyester baking vanish |
| CN110894394A (en) * | 2019-11-12 | 2020-03-20 | 无锡华东锌盾科技有限公司 | Water-based polyester amino baking varnish coating and preparation method and application thereof |
-
2022
- 2022-11-10 CN CN202211414998.0A patent/CN115710439B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN115710439A (en) | 2023-02-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107987693B (en) | Durable antibacterial water-based alkyd paint | |
| US3993843A (en) | Aqueous dispersion of aromatic polysulfone resin with perfluorocarbon resin, and coated articles | |
| CN108193202B (en) | Environment-friendly metal surface treating agent and application thereof | |
| CN100447212C (en) | Water industrial paint based on organosilicon acrylic acid epoxy ester water dispersion and preparation method thereof | |
| CN103483883B (en) | A kind of High-performance silica sol inorganic exterior coating | |
| CN102719191B (en) | High-temperature-resistant anticorrosive paint and preparation method thereof | |
| CN104877484B (en) | Petrochemical industry oil tank aqueous energy-saving heat-insulating thermal insulation coatings and preparation method thereof | |
| CA2890185A1 (en) | A waterborne anticorrosion coating composition and process for providing a corrosion-resistant coating on a metal surface | |
| KR102283891B1 (en) | High thermal insulation coating composition for high-temperature surface parts | |
| KR101480105B1 (en) | Aqueous anti-corrosive and high weatherproof silicone acrylic paints using dissolved hydrogen water | |
| CN103805054A (en) | Concrete outer wall protective agent and preparation method thereof | |
| US4169117A (en) | Aromatic polysulfone resin solution having perfluorocarbon polymer particles dispersed therein | |
| CN108117835A (en) | A kind of chromium-free fingerprint-resistant environmental protection coating material and preparation method thereof | |
| CN110938350A (en) | Epoxy primer for rail transit and preparation method thereof | |
| KR101300395B1 (en) | Fluoropolymer bonding compositions | |
| CN110655855A (en) | Industrial heavy-duty corrosion-resistant long-acting weather-resistant water-based acrylic polyurethane anticorrosive paint and preparation method thereof | |
| CN104725969A (en) | Water-based anti-corrosion floating type aluminium powder paint and preparation method thereof | |
| CN115710439B (en) | Oil-stain-resistant scratch-resistant antibacterial coating and preparation method thereof | |
| US11827801B2 (en) | Primer for ethylene/tetrafluoroethylene copolymer coating materials | |
| CN106608717A (en) | Thick knife-coated sand-textured building paint and preparation method thereof | |
| CN106118302A (en) | A kind of preparation method for outdoor type water-based anticorrosive paint | |
| US4021395A (en) | Aqueous dispersion of an aryloxysulfone copolymer | |
| CN111925673A (en) | Inorganic coating and preparation method thereof | |
| CN111471376A (en) | Antibacterial clean coil coating and preparation method thereof | |
| CN110724414A (en) | Stain-resistant high-temperature-resistant water-based paint and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |