CN111607268A - Outdoor weather-resistant grade antibacterial powder coating and manufacturing method thereof - Google Patents
Outdoor weather-resistant grade antibacterial powder coating and manufacturing method thereof Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- 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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
- C09D5/033—Powdery paints characterised by the additives
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/67—Particle size smaller than 100 nm
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
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- C08K2003/0806—Silver
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2201/011—Nanostructured additives
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Abstract
The invention relates to the field of coatings, in particular to an outdoor weather-resistant grade antibacterial powder coating and a manufacturing method thereof. The coating comprises the following substances in percentage by weight, namely 60-70 parts of non-branched carboxyl-terminated polyester: triglycidyl isocyanurate 4.5-5.3: 0.5-7% of auxiliary agent: 0.8-5 parts of modified zinc-type antibacterial agent: 12.7-34.2 of pigment and filler; the modified zinc-type antibacterial agent comprises the following substances in percentage by weight: ZnO having a particle diameter of 8 to 12 μm: 40 percent; ZnO with the grain diameter less than or equal to 100 nm: 40 percent; ZnO coated silver powder with the particle size of 8-12 mu m and the particle size of less than or equal to 100 nm: 20 percent. Makes up for the serious defects of using Ag + antibacterial products outdoors in the market (the defects of Ag + antibacterial such as easy oxidation, no weather resistance, narrow construction parameter range and the like).
Description
Technical Field
The invention relates to the field of coatings, in particular to an outdoor weather-resistant grade antibacterial powder coating and a manufacturing method thereof.
Background
At present, a plurality of antibacterial products appear on the market, wherein the antibacterial products are used indoors and the antibacterial products are used outdoors. The antibacterial mode is Ag+Mainly resisting bacteria. However, it is worth studying whether silver ion antibacterial is really suitable for being applied to outdoor antibacterial products. Ag+The antibacterial mechanism of (A) is that the carrier is gradually precipitated on the surface of the coating layer due to Ag+The cell membrane is charged with positive charge and negatively, the two are firmly adsorbed together by coulomb force attraction, and metal ions penetrate through the cell wall and enter cells to react with sulfo groups, carboxyl groups and hydroxyl groups, so that protein is solidified, the activity of cell synthetase is damaged, and the cells lose division and proliferation capacity and die. Due to Ag+Having the above characteristics, Ag+The antibacterial effect of (A) can indeed meet the antibacterial standard, but Ag+Is easy to be oxidized, is not alkali-resistant, and is separated out on the surface of a paint film in an antibacterial mode for sterilization, so that Ag is essentially antibacterial+Is not suitable for being applied to outdoor decoration products for antibiosis (serious discoloration and no weather resistance).
Disclosure of Invention
The purpose of the invention is as follows: in order to provide an outdoor weather-resistant grade antibacterial powder coating which is weather-resistant and antibacterial by combining a new material compounding method with a weather-resistant coating and a manufacturing method, the specific purpose is seen in a plurality of substantial technical effects of a specific implementation part.
In order to achieve the purpose, the invention adopts the following technical scheme:
the outdoor weather-resistant grade antibacterial powder coating is characterized by comprising the following substances in parts by weight, namely 60-70 parts of non-branched carboxyl-terminated polyester: triglycidyl isocyanurate 4.5-5.3: 0.5-7% of auxiliary agent: 0.8-5 parts of modified zinc-type antibacterial agent: 12.7-34.2 of pigment and filler; the modified zinc-type antibacterial agent comprises the following substances in percentage by weight: ZnO having a particle diameter of 8 to 12 μm: 40 percent; ZnO with the grain diameter less than or equal to 100 nm: 40 percent; silver powder with the grain diameter less than or equal to 100nm coated by ZnO with the grain diameter of 8-12 mu m: 20 percent.
The invention further adopts the technical scheme that the non-branched carboxyl-terminated polyester also comprises isophthalic acid; isophthalic acid accounts for 55% of the total resin composition; acid value range: 32-36 mgKOH/g; viscosity range: 4500 ℃ and 7500mPa.s/200 ℃, softening point: 110-120 ℃; tg is more than or equal to 63 ℃.
The invention further adopts the technical scheme that the melting point range of the triglycidyl isocyanurate is as follows: 95-115 ℃, the epoxy equivalent is less than or equal to 110g/eq, the total chlorine content is less than or equal to 0.44%, the volatile matter is less than or equal to 1.0%, the viscosity (120 ℃) is less than or equal to 100CP, and the residual quantity of epichlorohydrin is less than or equal to 250 ppm.
The invention further adopts the technical scheme that the auxiliary agent is determined according to the appearance of the product, and if the product is a sand-textured product, the auxiliary agent is any one or more of the following components: fluorine resin modification auxiliary agent, polyethylene wax or fluorine-containing wax, bentonite or talcum powder; if the product is a plane product, the auxiliary agent is any one or more of the following: acrylic ester flatting agent, hydroxy benzotriazole ultraviolet absorbent, benzoin, polyethylene wax, butyl acrylate and methyl methacrylate copolymer.
The invention further adopts the technical scheme that the pigment in the pigment filler is an inorganic pigment.
The further technical proposal of the invention is that the modified zinc-type antibacterial agent is prepared by mixing ZnO with the grain diameter of 8-12 μm: 40 percent; ZnO with the grain diameter less than or equal to 100 nm: 40 percent; ZnO coated silver powder with the particle size of 8-12 mu m and the particle size of less than or equal to 100 nm: weighing and mixing the three raw materials of 20 percent according to the mass ratio, stirring the mixture in a stirring tank at a low speed for 0.5 to 1 hour, discharging and sieving the mixture.
The manufacturing method of the outdoor weather-resistant grade antibacterial powder coating is characterized in that materials are weighed according to the preset mass proportion of the coating before use; mixing with a mixer, stirring, rapidly crushing for 2min, and slowly stirring for 4 min; and (2) melting and extruding the mixed material through an extruder, cooling and crushing the mixed material through a conveying belt, wherein the extrusion temperature is as follows: the first zone is 115 ℃, and the second zone is 105 ℃; crushing by a crusher to obtain corresponding particle size, wherein the particle size of the product is controlled to be 34-38 um; and sieving the powder and packaging.
1) Compared with the prior art, the invention adopting the technical scheme has the following beneficial effects: the modified zinc-type antibacterial agent is prepared by adopting ZnO with regular structure hexagonal wurtzite and particle size of 8-12 mu m: 40 percent; ZnO with the grain diameter less than or equal to 100 nm: 40 percent; ag with particle size less than or equal to 100nm and coated by ZnO with particle size of 8-12 μm2O: 20 percent of the three raw materials are mixed. ZnO with the grain diameter of 8-12 mu m is white visually, is stable, does not change color or decompose at high temperature, is low in price and rich in resources, but has low antibacterial efficiency and can achieve the antibacterial effect only by long-time contact. ZnO having a particle diameter of 100nm or less hasThree antibacterial modes, namely a photocatalytic antibacterial mechanism, a metal ion dissolution antibacterial mechanism and an active oxygen antibacterial mechanism, are not determined so far, but the real antibacterial mechanism can play an accelerating role when the antibacterial agent is mixed with ZnO with the grain diameter of 8-12 mu m, the problems of low antibacterial efficiency and the like of the ZnO with the grain diameter of 8-12 mu m can be solved, and the defects of the zinc oxide antibacterial problem are directly made up. Addition of a large amount of zinc oxide results in a strong antibacterial ability of the coating film, but leads to a reduction in the mechanical properties of the coating film, so that the addition of zinc oxide to Ag results in a decrease in the antibacterial ability of the coating film+ZnO with the grain diameter of 8-12 mu m is used for wrapping, and the ZnO is uniformly wrapped outside the silver powder with the grain diameter of less than or equal to 100 nm. The silver powder after being coated overcomes the defect of easy oxidation and discoloration, and the addition amount of zinc oxide is greatly reduced through the high-strength antibacterial effect, so that the antibacterial capability of the coating film is ensured, the addition amount of zinc oxide can be reduced to ensure the physical performance of the coating film, and the weather resistance of the coating film can be assisted to be enhanced on the premise that the addition amount of zinc oxide is not higher than 5%. Therefore, the modified zinc-type antibacterial agent is an outdoor weather-resistant antibacterial agent which is customized for outdoor antibacterial.
Detailed Description
The present invention will be further illustrated below with reference to specific embodiments, which are to be understood as merely illustrative and not limitative of the scope of the present invention. The patent provides a plurality of parallel schemes, and different expressions belong to an improved scheme based on a basic scheme or a parallel scheme. Each solution has its own unique features.
The first embodiment is as follows: the outdoor weather-resistant grade antibacterial powder coating is characterized by comprising the following components in parts by weight, namely non-branched carboxyl-terminated polyester 70; 5.3 parts of triglycidyl isocyanurate; an auxiliary agent 7; a modified zinc-type antibacterial agent 5; 12.7 of pigment and filler; the modified zinc-type antibacterial agent comprises the following substances in percentage by weight: ZnO having a particle diameter of 8 to 12 μm: 40 percent; ZnO with the grain diameter less than or equal to 100 nm: 40 percent; ZnO coated silver powder with the particle size of 8-12 mu m and the particle size of less than or equal to 100 nm: 20 percent.
Example two: the outdoor weather-resistant grade antibacterial powder coating is characterized by comprising the following substances, namely non-branched carboxyl-terminated polyester 60 in parts by weight; 4.5 parts of triglycidyl isocyanurate and 1 part of auxiliary agent; 0.5 of modified zinc-type antibacterial agent; a pigment and filler 35; the modified zinc-type antibacterial agent comprises the following substances in percentage by weight: ZnO having a particle diameter of 8 to 12 μm: 40 percent; ZnO with the grain diameter less than or equal to 100 nm: 40 percent; ZnO coated silver powder with the particle size of 8-12 mu m and the particle size of less than or equal to 100 nm: 20 percent.
Example three: the outdoor weather-resistant grade antibacterial powder coating is characterized by comprising the following substances, namely non-branched carboxyl-terminated polyester 60 in parts by weight; 4.5 parts of triglycidyl isocyanurate, 0.9 part of an auxiliary agent acrylate leveling agent, 0.3 part of benzoin, 0.2 part of polyethylene wax and 0.5 part of a copolymer of butyl acrylate and methyl methacrylate; 0.8 of modified zinc-type antibacterial agent; 32.8 of pigment and filler; the modified zinc-type antibacterial agent comprises the following substances in percentage by weight: ZnO having a particle diameter of 8 to 12 μm: 40 percent; ZnO with the grain diameter less than or equal to 100 nm: 40 percent; ZnO coated silver powder with the particle size of 8-12 mu m and the particle size of less than or equal to 100 nm: 20 percent. Has the lowest cost of the plane weather-proof antibacterial product.
Example four: the outdoor weather-resistant grade antibacterial powder coating is characterized by comprising the following substances, namely, non-branched carboxyl-terminated polyester 70 in parts by weight; 5.3 parts of triglycidyl isocyanurate, 0.4 part of auxiliary agent acrylate flatting agent, 0.4 part of benzoin, 0.4 part of polyethylene wax, 1 part of copolymer of butyl acrylate and methyl methacrylate and 3 parts of hydroxybenzotriazole ultraviolet absorbent; a modified zinc-type antibacterial agent 5; 13.9 parts of pigment and filler; the modified zinc-type antibacterial agent comprises the following substances in percentage by weight: ZnO having a particle diameter of 8 to 12 μm: 40 percent; ZnO with the grain diameter less than or equal to 100 nm: 40 percent; ZnO coated silver powder with the particle size of 8-12 mu m and the particle size of less than or equal to 100 nm: 20 percent. The weather-proof antibacterial aging time can reach 13-15 years.
Example five: the outdoor weather-resistant grade antibacterial powder coating is characterized by comprising the following substances, namely non-branched carboxyl-terminated polyester 65 in parts by weight; 4.9 parts of triglycidyl isocyanurate, 0.4 part of auxiliary agent acrylate flatting agent, 0.4 part of benzoin, 0.4 part of polyethylene wax and 1 part of copolymer of butyl acrylate and methyl methacrylate; a modified zinc-type antibacterial agent 2; 25.3 of pigment and filler; the modified zinc-type antibacterial agent comprises the following substances in percentage by weight: ZnO having a particle diameter of 8 to 12 μm: 40 percent; ZnO with the grain diameter less than or equal to 100 nm: 40 percent; ZnO coated silver powder with the particle size of 8-12 mu m and the particle size of less than or equal to 100 nm: 20 percent. Has the characteristic of resisting neutral salt fog for 1000 h.
Example six: the outdoor weather-resistant grade antibacterial powder coating is characterized by comprising the following substances, namely non-branched carboxyl-terminated polyester 60 in parts by weight; 4.5 parts of triglycidyl isocyanurate, 0.3 part of auxiliary agent acrylate flatting agent, 0.2 part of benzoin, and 0.9 part of copolymer of butyl acrylate and methyl methacrylate; a modified zinc-type antibacterial agent 3; 32.8 of pigment and filler; the modified zinc-type antibacterial agent comprises the following substances in percentage by weight: ZnO having a particle diameter of 8 to 12 μm: 40 percent; ZnO with the grain diameter less than or equal to 100 nm: 40 percent; ZnO coated silver powder with the particle size of 8-12 mu m and the particle size of less than or equal to 100 nm: 20 percent. And the cold-heat resistant change cycle test is carried out for 1000h without abnormality.
Example seven: the outdoor weather-resistant grade antibacterial powder coating is characterized by comprising the following substances, namely non-branched carboxyl-terminated polyester 63 in parts by weight; 4.8 parts of triglycidyl isocyanurate, 1.2 parts of an auxiliary agent acrylate leveling agent, 0.3 part of benzoin, 0.2 part of polyethylene wax and 0.9 part of a copolymer of butyl acrylate and methyl methacrylate; 0.8 of modified zinc-type antibacterial agent; 32.8 of pigment and filler; the modified zinc-type antibacterial agent comprises the following substances in percentage by weight: ZnO having a particle diameter of 8 to 12 μm: 40 percent; ZnO with the grain diameter less than or equal to 100 nm: 40 percent; ZnO coated silver powder with the particle size of 8-12 mu m and the particle size of less than or equal to 100 nm: 20 percent. Has the characteristic of no abnormity in the damp and hot test for 1000 h.
Example eight: the outdoor weather-resistant grade antibacterial powder coating is characterized by comprising the following substances, namely non-branched carboxyl-terminated polyester 63 in parts by weight; 4.8 parts of triglycidyl isocyanurate, 1.2 parts of an auxiliary agent acrylate leveling agent, 0.3 part of benzoin, 0.2 part of polyethylene wax and 0.9 part of a copolymer of butyl acrylate and methyl methacrylate; 0.8 of modified zinc-type antibacterial agent; 32.8 of pigment and filler; the modified zinc-type antibacterial agent comprises the following substances in percentage by weight: ZnO having a particle diameter of 8 to 12 μm: 40 percent; ZnO with the grain diameter less than or equal to 100 nm: 40 percent; ZnO coated silver powder with the particle size of 8-12 mu m and the particle size of less than or equal to 100 nm: 20 percent. Has 80 +/-2 ℃ and 50 +/-5 RH, is kept for 240 hours and recovered for 2 hours, has no abnormal change on the surface, delta E is less than or equal to 1.5, and the adhesiveness is more than or equal to 4B.
Example nine: the outdoor weather-resistant grade antibacterial powder coating is characterized by comprising the following substances, namely non-branched carboxyl-terminated polyester 65 in parts by weight; 4.9 parts of triglycidyl isocyanurate, 0.3 part of auxiliary agent acrylate flatting agent, 0.2 part of benzoin, and 0.9 part of copolymer of butyl acrylate and methyl methacrylate; a modified zinc-type antibacterial agent 2; 25.7 of pigment and filler; the modified zinc-type antibacterial agent comprises the following substances in percentage by weight: ZnO having a particle diameter of 8 to 12 μm: 40 percent; ZnO with the grain diameter less than or equal to 100 nm: 40 percent; ZnO coated silver powder with the particle size of 8-12 mu m and the particle size of less than or equal to 100 nm: 20 percent. Has the characteristic of resisting 3% HCL for 500h without abnormality.
Example ten: the outdoor weather-resistant grade antibacterial powder coating is characterized by comprising the following substances, namely, non-branched carboxyl-terminated polyester 70 in parts by weight; 5.3 parts of triglycidyl isocyanurate, 0.3 part of auxiliary agent acrylate flatting agent, 0.2 part of benzoin, 0.7 part of polyethylene wax and 0.2 part of copolymer of butyl acrylate and methyl methacrylate; 1.5 modified zinc-type antibacterial agent; a pigment and filler 21; the modified zinc-type antibacterial agent comprises the following substances in percentage by weight: ZnO having a particle diameter of 8 to 12 μm: 40 percent; ZnO with the grain diameter less than or equal to 100 nm: 40 percent; ZnO coated silver powder with the particle size of 8-12 mu m and the particle size of less than or equal to 100 nm: 20 percent. Has the characteristic of resisting 95 percent ethanol for 500 cycles without abnormality.
Example eleven: the outdoor weather-resistant grade antibacterial powder coating is characterized by comprising the following substances, namely non-branched carboxyl-terminated polyester 68 in parts by weight; 5.2 parts of triglycidyl isocyanurate, 0.3 part of auxiliary agent acrylate flatting agent, 0.2 part of benzoin, 0.7 part of polyethylene wax and 0.7 part of copolymer of butyl acrylate and methyl methacrylate; 1.5 modified zinc-type antibacterial agent; 23.1 of pigment and filler; the modified zinc-type antibacterial agent comprises the following substances in percentage by weight: ZnO having a particle diameter of 8 to 12 μm: 40 percent; ZnO with the grain diameter less than or equal to 100 nm: 40 percent; ZnO coated silver powder with the particle size of 8-12 mu m and the particle size of less than or equal to 100 nm: 20 percent. Has the characteristic of resisting 300 MEK cycles without abnormality.
Example twelve: the outdoor weather-resistant grade antibacterial powder coating is characterized by comprising the following substances, namely non-branched carboxyl-terminated polyester 65 in parts by weight; triglycidyl isocyanurate 5, an auxiliary agent acrylate leveling agent 1, benzoin 0.3, polyethylene wax 0.4 and a copolymer 1 of butyl acrylate and methyl methacrylate; a modified zinc-type antibacterial agent 4; 27.3 of pigment and filler; the modified zinc-type antibacterial agent comprises the following substances in percentage by weight: ZnO having a particle diameter of 8 to 12 μm: 40 percent; ZnO with the grain diameter less than or equal to 100 nm: 40 percent; ZnO coated silver powder with the particle size of 8-12 mu m and the particle size of less than or equal to 100 nm: 20 percent. Has the characteristic of resisting artificial sweat soaking for 48 hours without abnormality.
Example thirteen: the outdoor weather-resistant grade antibacterial powder coating is characterized by comprising the following substances, namely, non-branched carboxyl-terminated polyester 70 in parts by weight; 5.3 parts of triglycidyl isocyanurate, 0.3 part of auxiliary agent acrylate flatting agent, 0.2 part of benzoin, 0.8 part of polyethylene wax and 0.8 part of copolymer of butyl acrylate and methyl methacrylate; 1.2 of modified zinc-type antibacterial agent; 21.2 parts of pigment and filler; the modified zinc-type antibacterial agent comprises the following substances in percentage by weight: ZnO having a particle diameter of 8 to 12 μm: 40 percent; ZnO with the grain diameter less than or equal to 100 nm: 40 percent; ZnO coated silver powder with the particle size of 8-12 mu m and the particle size of less than or equal to 100 nm: 20 percent. Has the characteristic of no abnormality when the front and back 50kg.cm of the impact resistance test is carried out.
Example fourteen: the outdoor weather-resistant grade antibacterial powder coating is characterized by comprising the following substances, namely non-branched carboxyl-terminated polyester 67 in parts by weight; 5.1 parts of triglycidyl isocyanurate, 0.9 parts of an auxiliary agent acrylate leveling agent, 0.3 parts of benzoin, 0.2 parts of polyethylene wax and 0.9 parts of a copolymer of butyl acrylate and methyl methacrylate; 1.3 modified zinc-type antibacterial agent; 21.2 parts of pigment and filler; the modified zinc-type antibacterial agent comprises the following substances in percentage by weight: ZnO having a particle diameter of 8 to 12 μm: 40 percent; ZnO with the grain diameter less than or equal to 100 nm: 40 percent; ZnO coated silver powder with the particle size of 8-12 mu m and the particle size of less than or equal to 100 nm: 20 percent. The paint has the characteristics of-40 ℃, 240 hours, 2 hours of recovery, no abnormity on the surface of a paint film, less than or equal to 1.5 of delta E and more than or equal to 4B of adhesiveness.
Example fifteen: the outdoor weather-resistant grade antibacterial powder coating is characterized by comprising the following substances, namely non-branched carboxyl-terminated polyester 67 in parts by weight; 5.1 parts of triglycidyl isocyanurate, 0.9 parts of an auxiliary agent acrylate leveling agent, 0.3 parts of benzoin, 0.2 parts of polyethylene wax and 0.9 parts of a copolymer of butyl acrylate and methyl methacrylate; 1.3 modified zinc-type antibacterial agent; 21.2 parts of pigment and filler; the modified zinc-type antibacterial agent comprises the following substances in percentage by weight: ZnO having a particle diameter of 8 to 12 μm: 40 percent; ZnO with the grain diameter less than or equal to 100 nm: 40 percent; ZnO coated silver powder with the particle size of 8-12 mu m and the particle size of less than or equal to 100 nm: 20 percent. The paint has the characteristics of-40 ℃, 240 hours, 2 hours of recovery, no abnormity on the surface of a paint film, less than or equal to 1.5 of delta E and more than or equal to 4B of adhesiveness.
Example sixteen: the outdoor weather-resistant grade antibacterial powder coating is characterized by comprising the following substances, namely non-branched carboxyl-terminated polyester 65 in parts by weight; 4.9 parts of triglycidyl isocyanurate, 0.9 part of an auxiliary agent acrylate leveling agent, 0.3 part of benzoin, 0.2 part of polyethylene wax and 0.9 part of a copolymer of butyl acrylate and methyl methacrylate; 2.5 of modified zinc-type antibacterial agent; 25.3 of pigment and filler; the modified zinc-type antibacterial agent comprises the following substances in percentage by weight: ZnO having a particle diameter of 8 to 12 μm: 40 percent; ZnO with the grain diameter less than or equal to 100 nm: 40 percent; ZnO coated silver powder with the particle size of 8-12 mu m and the particle size of less than or equal to 100 nm: 20 percent. Has the characteristic of no abnormality after resisting 60 ℃ and 3h of water bath.
Example seventeen: the outdoor weather-resistant grade antibacterial powder coating is characterized by comprising the following substances, namely non-branched carboxyl-terminated polyester 66 in parts by weight; triglycidyl isocyanurate 5, an auxiliary agent acrylate leveling agent 1, benzoin 0.3, polyethylene wax 0.2 and a copolymer 1 of butyl acrylate and methyl methacrylate; 2.3 of modified zinc-type antibacterial agent; 24.2 of pigment and filler; the modified zinc-type antibacterial agent comprises the following substances in percentage by weight: ZnO having a particle diameter of 8 to 12 μm: 40 percent; ZnO with the grain diameter less than or equal to 100 nm: 40 percent; ZnO coated silver powder with the particle size of 8-12 mu m and the particle size of less than or equal to 100 nm: 20 percent. Has chemical resistance. The white cat liquid is soaked in Coffee, cocacola, tea, milk, white cat liquid detergent, 1% glacial acetic acid and edible sesame oil for 2 hours without abnormality.
Example eighteen: the outdoor weather-resistant grade antibacterial powder coating is characterized by comprising the following substances, namely, non-branched carboxyl-terminated polyester 70 in parts by weight; 5.3 parts of triglycidyl isocyanurate, 0.4 part of fluorine resin modification auxiliary agent and 0.4 part of polyethylene wax or fluorine-containing wax; 2.1 of modified zinc-type antibacterial agent; 21.8 parts of pigment and filler; the modified zinc-type antibacterial agent comprises the following substances in percentage by weight: ZnO having a particle diameter of 8 to 12 μm: 40 percent; ZnO with the grain diameter less than or equal to 100 nm: 40 percent; ZnO coated silver powder with the particle size of 8-12 mu m and the particle size of less than or equal to 100 nm: 20 percent. Has the characteristic of bending resistance of 2 mm.
Example nineteenth: the outdoor weather-resistant grade antibacterial powder coating is characterized by comprising the following substances, namely non-branched carboxyl-terminated polyester 60 in parts by weight; 4.6 parts of triglycidyl isocyanurate, 0.4 part of fluorine resin modification auxiliary agent and 0.4 part of fluorine-containing wax; a modified zinc-type antibacterial agent 3; 31.6 parts of pigment and filler; the modified zinc-type antibacterial agent comprises the following substances in percentage by weight: ZnO having a particle diameter of 8 to 12 μm: 40 percent; ZnO with the grain diameter less than or equal to 100 nm: 40 percent; ZnO coated silver powder with the particle size of 8-12 mu m and the particle size of less than or equal to 100 nm: 20 percent. The pencil hardness can reach 2H.
Example twenty: the outdoor weather-resistant grade antibacterial powder coating is characterized by comprising the following substances, namely, non-branched carboxyl-terminated polyester 70 in parts by weight; 5.3 parts of triglycidyl isocyanurate, 0.3 part of fluorine resin modification auxiliary agent and 0.4 part of polyethylene wax or fluorine-containing wax; a modified zinc-type antibacterial agent 3; a pigment and filler 21; the modified zinc-type antibacterial agent comprises the following substances in percentage by weight: ZnO having a particle diameter of 8 to 12 μm: 40 percent; ZnO with the grain diameter less than or equal to 100 nm: 40 percent; ZnO coated silver powder with the particle size of 8-12 mu m and the particle size of less than or equal to 100 nm: 20 percent. Has UVB280h resistance, light-preserving rate not less than 50 and delta E not more than 5.
Example twenty one: the outdoor weather-resistant grade antibacterial powder coating is characterized by comprising the following substances, namely, non-branched carboxyl-terminated polyester 70 in parts by weight; 5.3 parts of triglycidyl isocyanurate, 0.2 part of fluorine resin modification auxiliary agent and 0.4 part of polyethylene wax or fluorine-containing wax; a modified zinc-type antibacterial agent 2; 22.1 of pigment and filler; the modified zinc-type antibacterial agent comprises the following substances in percentage by weight: ZnO having a particle diameter of 8 to 12 μm: 40 percent; ZnO with the grain diameter less than or equal to 100 nm: 40 percent; ZnO coated silver powder with the particle size of 8-12 mu m and the particle size of less than or equal to 100 nm: 20 percent. Has a cupping resistance of 7 mm.
Example twenty two: the outdoor weather-resistant grade antibacterial powder coating is characterized by comprising the following substances, namely non-branched carboxyl-terminated polyester 68 in parts by weight; 5.2 parts of triglycidyl isocyanurate, 0.2 part of fluorine resin modification auxiliary agent and 0.4 part of polyethylene wax or fluorine-containing wax; a modified zinc-type antibacterial agent 3; 23.2 of pigment and filler; the modified zinc-type antibacterial agent comprises the following substances in percentage by weight: ZnO having a particle diameter of 8 to 12 μm: 40 percent; ZnO with the grain diameter less than or equal to 100 nm: 40 percent; ZnO coated silver powder with the particle size of 8-12 mu m and the particle size of less than or equal to 100 nm: 20 percent. Has the effects of low gloss and rough and wrinkled surface, and has no abnormality in Q-SUN resistance for 1000 h.
Example twenty three: the outdoor weather-resistant grade antibacterial powder coating is characterized by comprising the following substances, namely non-branched carboxyl-terminated polyester 66 in parts by weight; triglycidyl isocyanurate 5, fluorine resin modifying assistant 0.1 and polyethylene wax or fluorine-containing wax 0.4; a modified zinc-type antibacterial agent 3; 25.5 of pigment and filler; the modified zinc-type antibacterial agent comprises the following substances in percentage by weight: ZnO having a particle diameter of 8 to 12 μm: 40 percent; ZnO with the grain diameter less than or equal to 100 nm: 40 percent; ZnO coated silver powder with the particle size of 8-12 mu m and the particle size of less than or equal to 100 nm: 20 percent. Has low gloss, rough surface, and no abnormal UVA1000h resistance.
Example twenty-four: the outdoor weather-resistant grade antibacterial powder coating is characterized by comprising the following substances, namely non-branched carboxyl-terminated polyester 60 in parts by weight; 4.6 parts of triglycidyl isocyanurate, 0.2 part of fluorine resin modification auxiliary agent and 0.3 part of fluorine-containing wax; a modified zinc-type antibacterial agent 2; 32.9 parts of pigment and filler; the modified zinc-type antibacterial agent comprises the following substances in percentage by weight: ZnO having a particle diameter of 8 to 12 μm: 40 percent; ZnO with the grain diameter less than or equal to 100 nm: 40 percent; ZnO coated silver powder with the particle size of 8-12 mu m and the particle size of less than or equal to 100 nm: 20 percent. The dry film adhesive force is 0 grade.
60-70 parts of non-branched carboxyl-terminated polyester;
4.5-5.3 parts of triglycidyl isocyanurate;
1-3.5 of auxiliary agent (the types of the auxiliary agent are described below);
0.8-5 parts of modified zinc-type antibacterial agent;
pigment and filler 16.7-33.7
The particle size of the finished product is as follows: 34-38 um;
the raw material requirements are as follows:
1. a non-branched carboxyl-terminated polyester;
isophthalic acid accounts for 55% of the total resin composition; acid value range: 32-36 mgKOH/g; viscosity range: 4500 ℃ and 7500mPa.s/200 ℃, softening point: 110-120 ℃; the Tg is more than or equal to 63 ℃;
2. triglycidyl isocyanurate;
melting point range: 95-115 ℃;
the epoxy equivalent is less than or equal to 110 g/eq;
the total chlorine content is less than or equal to 0.44 percent;
the volatile matter is less than or equal to 1.0 percent;
the viscosity (120 ℃) is less than or equal to 100 CP;
the residual quantity of the epichlorohydrin is less than or equal to 250 ppm;
3. the auxiliary agent is determined according to the appearance of the product;
sand streak products: fluorine resin modification auxiliary agent, polyethylene wax or fluorine-containing wax, bentonite or talcum powder; a planar product: acrylate leveling agent, hydrogenated castor oil, benzoin, polyethylene wax, butyl acrylate and methyl methacrylate.
4. Pigment and filler
Inorganic pigments and fillers (forbidden CaCO)3) A mixture of (a).
5. Modified zinc-type antibacterial agent: and (4) self-preparing a modified material.
The modified zinc type antibacterial agent comprises the following components:
2) ZnO having a particle diameter of 8 to 12 μm: 40 percent; ZnO with the grain diameter less than or equal to 100 nm: 40 percent; ag with particle size less than or equal to 100nm and coated by ZnO with particle size of 8-12 μm2O: 20 percent of the three raw materials are mixed. ZnO with the grain diameter of 8-12 mu m is white visually, is stable, does not change color or decompose at high temperature, is low in price and rich in resources, but has low antibacterial efficiency and can achieve the antibacterial effect only by long-time contact. ZnO with the grain diameter less than or equal to 100nm has three antibacterial modes, namely a photocatalytic antibacterial mechanism, a metal ion dissolution antibacterial mechanism and an active oxygen antibacterial mechanism. But have not been available to dateThe real antibacterial mechanism of the zinc oxide is determined, but when the zinc oxide is mixed with ZnO with the grain diameter of 8-12 mu m, the zinc oxide can play an accelerating role, can solve the problems of low antibacterial efficiency and the like of the ZnO with the grain diameter of 8-12 mu m, and directly makes up the defects of the zinc oxide antibacterial problem. Addition of a large amount of zinc oxide results in a strong antibacterial ability of the coating film, but leads to a reduction in the mechanical properties of the coating film, so that the addition of zinc oxide to Ag results in a decrease in the antibacterial ability of the coating film+ZnO with the grain diameter of 8-12 mu m is used for wrapping, and the ZnO is uniformly wrapped outside the silver powder with the grain diameter of less than or equal to 100 nm. The silver powder after being coated overcomes the defect of easy oxidation and discoloration, and the addition amount of zinc oxide is greatly reduced through the high-strength antibacterial effect, so that the antibacterial capability of the coating film is ensured, the addition amount of zinc oxide can be reduced to ensure the physical performance of the coating film, and the weather resistance of the coating film can be assisted to be enhanced on the premise that the addition amount of zinc oxide is not higher than 5%. Therefore, the modified zinc-type antibacterial agent is an outdoor weather-resistant antibacterial agent which is customized for outdoor antibacterial.
The modified antibacterial agent comprises the following components in percentage by mass:
ZnO having a particle diameter of 8 to 12 μm: 40 percent;
ZnO with the grain diameter less than or equal to 100 nm: 40 percent;
ag with particle size less than or equal to 100nm and coated by ZnO with particle size of 8-12 μm2O：20%。
Weighing and mixing the three raw materials according to the mass ratio, stirring the mixture in a stirring tank at a low speed for 0.5 to 1 hour, discharging and sieving the mixture.
The particle size range is 2-4 um;
the production process comprises the following steps:
weighing according to a preset mass ratio before use:
1. weighing the materials;
2. mixing with a blender, and stirring (rapidly crushing for 2min, and slowly stirring for 4 min).
3. The mixture was melt extruded through an extruder and cooled and crushed through a conveyor belt (extrusion temperature: 115 ℃ in the first zone and 105 ℃ in the second zone).
4. Crushing by a crusher to obtain corresponding particle size, wherein the particle size of the product is controlled to be 34-38 um;
5. and sieving the powder and packaging.
The detection method comprises the following steps:
the weather-resistant standard of the coating film meets AAMA2603, the antibacterial effect can be generally maintained for about ten years, and the product developed at this time can meet the antibacterial requirement and reach the same quality and guarantee period.
Paint film detection AAMA 2603:
the antibacterial detection basis and the method are as follows:
JIS Z 2801:2010
the antibacterial detection data of the outdoor weather-resistant grade antibacterial powder coating are as follows:
has the advantages that:
1. antibacterial agents: by compounding the three raw materials, the three raw materials mutually offset the defects of each other, promote the performance of each unit to be extremely high, and fill the problem which needs to be solved most urgently at present in outdoor weather-resistant antibacterial agents.
2. Because of the assistant weather resistance of the antibacterial agent to the paint film and the antibacterial time of the paint film matched with the antibacterial agent. Therefore, the antibacterial coating can be used for at least 10 years under the antibacterial condition of the coating film, and meets the AAMA2603 in the weather-resistant standard.
The formula of the outdoor weather-resistant antibacterial powder coating comprises the following components:
60-70 parts of non-branched carboxyl-terminated polyester;
4.5-5.3 parts of triglycidyl isocyanurate;
1-3.5 of auxiliary agent (the types of the auxiliary agent are described below);
0.8-5 parts of modified zinc-type antibacterial agent;
pigment and filler 16.7-33.7
The particle size of the finished product is as follows: 34-38um
The production process comprises the following steps:
weighing according to a preset mass ratio before use:
1. weighing the materials;
2. mixing with a blender, and stirring (rapidly crushing for 2min, and slowly stirring for 4 min).
3. The mixture was melt extruded through an extruder and cooled and crushed through a conveyor belt (extrusion temperature: 115 ℃ in the first zone and 105 ℃ in the second zone).
4. Crushing by a crusher to obtain corresponding particle size, wherein the particle size of the product is controlled to be 34-38 um;
5. and sieving the powder and packaging.
Curing conditions are as follows: x 10-15min at 200 deg.C (actual heating temperature)
For those skilled in the art, the product has two parts to be noticed:
1. the outdoor product formulation should match the standard with the weathering rating.
2. The modified zinc-type antibacterial agent is required to be prepared according to the provided proportion strictly, the addition amount can be added according to the antibacterial age and the antibacterial requirement, and the addition amount is required to be not less than the minimum recommended addition amount.
Under the condition of not violating the principle of the invention, various colors and surface states can be changed according to actual requirements. The essence of the research and development lies in improving the outdoor decorative antibacterial powder from three aspects of antibacterial property of antibacterial raw materials, antibacterial principle of the antibacterial raw materials, weather resistance of products matched with antibacterial time and the like, and finally enabling consumers to use products processed by the outdoor weather-resistant grade antibacterial powder coating in the true sense.
It should be noted that the plurality of schemes provided in this patent include their own basic schemes, which are independent of each other and are not restricted to each other, but they may be combined with each other without conflict, so as to achieve a plurality of effects.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are intended to illustrate the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, and the invention is to be limited to the embodiments described above.
Claims (7)
1. The outdoor weather-resistant grade antibacterial powder coating is characterized by comprising the following substances in parts by weight, namely 60-70 parts of non-branched carboxyl-terminated polyester: triglycidyl isocyanurate 4.5-5.3: 0.5-7% of auxiliary agent: 0.8-5 parts of modified zinc-type antibacterial agent: 12.7-34.2 of pigment and filler; the modified zinc-type antibacterial agent comprises the following substances in percentage by weight: ZnO having a particle diameter of 8 to 12 μm: 40 percent; ZnO with the grain diameter less than or equal to 100 nm: 40 percent; silver powder with the grain diameter less than or equal to 100nm coated by ZnO with the grain diameter of 8-12 mu m: 20 percent.
2. The outdoor weatherable grade antibacterial powder coating of claim 1, wherein said unbranched carboxyl terminated polyester further comprises isophthalic acid; isophthalic acid accounts for 55% of the total resin composition; acid value range: 32-36 mgKOH/g; viscosity range: 4500 ℃ and 7500mPa.s/200 ℃, softening point: 110-120 ℃; tg is more than or equal to 63 ℃.
3. The outdoor weatherable grade antibacterial powder coating of claim 1, wherein said triglycidyl isocyanurate has a melting point range of: 95-115 ℃, the epoxy equivalent is less than or equal to 110g/eq, the total chlorine content is less than or equal to 0.44%, the volatile matter is less than or equal to 1.0%, the viscosity (120 ℃) is less than or equal to 100CP, and the residual quantity of epichlorohydrin is less than or equal to 250 ppm.
4. The outdoor weathering grade antibacterial powder coating according to claim 1, characterized in that the auxiliaries are determined by the product appearance, and if it is a sand-grained product, any one or more of the following: fluorine resin modification auxiliary agent, polyethylene wax or fluorine-containing wax, bentonite or talcum powder; if the product is a plane product, the auxiliary agent is any one or more of the following: acrylate flatting agent, hydrogenated castor oil, benzoin, polyethylene wax, copolymer of butyl acrylate and methyl methacrylate, and hydroxy benzotriazole ultraviolet absorbent.
5. The outdoor weatherable grade antibacterial powder coating of claim 1, wherein the pigment in said pigment filler is an inorganic pigment.
6. The outdoor weather-resistant grade antibacterial powder coating as claimed in claim 1, wherein the modified zinc-type antibacterial agent is prepared by mixing ZnO with a particle size of 8-12 μm: 40 percent; ZnO with the grain diameter less than or equal to 100 nm: 40 percent; silver powder with the grain diameter less than or equal to 100nm coated by ZnO with the grain diameter of 8-12 mu m: 20 percent; the three raw materials are weighed and mixed according to the mass ratio, stirred in a stirring tank at a low speed for 0.5 to 1 hour, discharged and sieved.
7. A method for manufacturing an outdoor weather-resistant grade antibacterial powder coating, which is characterized in that materials are weighed according to a preset mass proportion of the coating as claimed in any one of claims 1 to 6 before use; mixing with a mixer, stirring, rapidly crushing for 2min, and slowly stirring for 4 min; and (2) melting and extruding the mixed material through an extruder, cooling and crushing the mixed material through a conveying belt, wherein the extrusion temperature is as follows: the first zone is 115 ℃, and the second zone is 105 ℃; crushing by a crusher to obtain corresponding particle size, wherein the particle size of the product is controlled to be 34-38 um; and sieving the powder and packaging.
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