CN108727935A - A kind of casting high durable antimicrobial coating material and preparation method thereof - Google Patents
A kind of casting high durable antimicrobial coating material and preparation method thereof Download PDFInfo
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- CN108727935A CN108727935A CN201810352539.1A CN201810352539A CN108727935A CN 108727935 A CN108727935 A CN 108727935A CN 201810352539 A CN201810352539 A CN 201810352539A CN 108727935 A CN108727935 A CN 108727935A
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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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- 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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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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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
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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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
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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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
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- C08K3/22—Oxides; Hydroxides of metals
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08K2003/2241—Titanium dioxide
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The present invention provides a kind of casting high durable antimicrobial coating materials and preparation method thereof, are prepared by following raw material：40-70 parts acrylic resin modified, 8-16 parts of bismaleimide, 3-6 parts of Triallyl isocyanurate, 5-10 parts of polyvinyl alcohol, 6-12 parts of complex antimicrobials, modified 5-10 parts of mixed fillers, 2,2-5 parts of 2 '-di-2-ethylhexylphosphine oxides (4,6- DI-tert-butylphenol compounds), 3-6 parts of 2-hydroxy-4-n-octoxybenzophenone, 2-7 parts of soybean lecithin, 3-8 parts of ethylene glycol ether acetate, 4-9 parts of dimethyl silicone polymer, 10-25 parts of glycidyl neodecanoate.Coating material of the present invention has ideal mechanical strength, while weatherability is good, and 99.35% is up to the antibiotic rate of Gram-E. coli and the staphylococcic mixed cell of Gram-positive S.Therefore the present invention is with a wide range of applications as high durable antimicrobial coating material.
Description
Technical field
The invention belongs to coating material technical fields, and in particular to a kind of casting high durable antimicrobial coating material and its system
Preparation Method.
Background technology
Currently, casting generally uses the metal materials such as copper, stainless steel, alloy as base material, but since metal surface is in length
Exposure in air, due to the property of material itself, easily connects with the pollutant in air, oxygen and moisture during phase use
Touch, cause the aging of cast(ing) surface burn into, it is mouldy phenomena such as, to influence the quality of casting, shorten and use the longevity using casting
Life.It, can also be by being sprayed in cast(ing) surface outside the performance to improve casting entirety in addition to the basis material of improvement casting itself
The mode of coating achievees the purpose that protect casting.However existing coating material is prepared by base-material of macromolecule raw material mostly
It forms, therefore the long-term coating material being exposed in air is difficult the test for being subjected to environment.
With the development of society and the raising of living standards of the people, healthy living environment has become the mesh of mankind's pursuit
Mark.As people are to the research of environmental microorganism and the continuous improvement of the level of understanding, while using microorganism helpfulness,
Recognize its harmfulness as pathogen, thereby promote the exploitation of antibiotic functional material, various antibacterial products is caused to meet the tendency of
And give birth to, and rapidly developed.Currently, antibiotic plastic, anti-bacterial fibre, anti-bacteria ceramic, antibacterial steel and antimicrobial coating etc. are anti-
Bacterium material has been applied to every field.
Antimicrobial coating material is the new function metal material successfully developed in 20th century.Antimicrobial coating material is usually with cold
It is matrix to roll plate, galvanized sheet, stainless steel, titanium, aluminium, is touched light by techniques such as spraying, roller coating, colloidal sol-gel, Composite Coatings
Matchmaker's dusty material coats on, and forms the coating product with unique antimicrobial, and the object of antibacterial refers to those to human health
The microorganisms such as the harmful and bacterium made troubles to human lives.However the anti-microbial property of existing antimicrobial coating material compared with
Difference, and the weatherability of coating is poor, it is therefore necessary to the further coating material of the exploitation high antibacterial of high durable.
Invention content
The purpose of the present invention is to provide a kind of casting high durable antimicrobial coating materials and preparation method thereof, to improve
The weatherability and antibiotic property of coating material.
To achieve the goals above, the present invention provides following technical scheme：
A kind of casting high durable antimicrobial coating material, is prepared by the raw material of following parts by weight：Acrylic resin modified 40-
70 parts, 8-16 parts of bismaleimide, 3-6 parts of Triallyl isocyanurate, 5-10 parts of polyvinyl alcohol, complex antimicrobials 6-12
Part, modified 5-10 parts of mixed fillers, 2-5 parts of 2,2 '-di-2-ethylhexylphosphine oxides (4,6- DI-tert-butylphenol compounds), 2- hydroxyl -4- n-octyloxies
3-6 parts of benzophenone, 2-7 parts of soybean lecithin, 3-8 parts of ethylene glycol ether acetate, 4-9 parts of dimethyl silicone polymer, neodecanoic acid
10-25 parts of ethylene oxidic ester；
The complex antimicrobials are prepared by nano-Ag particles, hexadecylpyridinium chloride and wollastonite in powder,
The modified mixed fillers are rutile type titanium white, the pottery that γ-glycidyl ether oxygen propyl trimethoxy silicane is modified
Porcelain fiber, silicon carbide and nano Ce O2。
Preferably, a kind of casting of the present invention high durable antimicrobial coating material, by the raw material system of following parts by weight
It is standby to form：Acrylic resin modified 55 parts, 12 parts of bismaleimide, 5 parts of Triallyl isocyanurate, 8 parts of polyvinyl alcohol,
9 parts of complex antimicrobials, modified 8 parts of mixed fillers, 4 parts of 2,2 '-di-2-ethylhexylphosphine oxides (4,6- DI-tert-butylphenol compounds), 2- hydroxyls -4- are just
5 parts of octyloxybenzophenone, 5 parts of soybean lecithin, 6 parts of ethylene glycol ether acetate, 7 parts of dimethyl silicone polymer, neodecanoic acid contracting
18 parts of water glyceride.
Further, the acrylic resin modified preparation method is as follows：50 parts of addition goes in four mouthfuls of reaction bulbs
Ionized water, 8 parts of blended emulsifier heating stirrings, are added 15 parts of acrylic acid mix monomers and 6 parts of azodiisobutyronitrile initiators, rise
Temperature after emulsion polymerization 20min, then adds 15 parts of acrylic acid mix monomers and 6 parts of azodiisobutyronitrile initiators to 85 DEG C, keeps the temperature
React 1.5h；Then 20 parts of modified mix monomers and 6 parts of azodiisobutyronitrile initiators, insulation reaction 2.5h are added；Finally will
Temperature is down to 40 DEG C, and it is 7~8 to adjust pH using lye, and filtrate is collected by filtration, reactor product is dried in an oven to get changing
Property acrylic resin；
It is 1 that the acrylic acid mix monomer, which is mass ratio,:1.5:2 methyl methacrylate, hydroxyacrylamide, metering system
Sour tetrahydro furfuryl ester；
It is 1 that the modified mix monomer, which is mass ratio,:1.5 acrylic acid tetrafluoro propyl ester and dodecafluoroheptyl methacrylate；
The emulsifier is that mass ratio is 1:1 nonylphenol polyoxyethylene ether, dodecyl polyoxyethylene ether.
Further, the preparation method of the complex antimicrobials is as follows：To 15-25 parts of pH are added in 6-13 parts of silica ashes
The salpeter solution of 4-5 is stirred 1-1.5h at a temperature of 60-80 DEG C, and 3-6 parts of nano-Ag particles, hexadecane is then added
5-10 parts of base pyridinium chloride, is stirred to react 1-2h at a temperature of 30-40 DEG C, by solution cooled to room temperature, passes through suction filtration
It collects sediment, is used in combination 30% ethanol solution to washed once sediment, then place it in baking oven and dry, after grinding to obtain the final product
Complex antimicrobials.
Preferably, the granularity of the modified mixed fillers is 30-50 mesh, wherein rutile type titanium white, ceramic fibre, carbon
SiClx and nano Ce O2Mass ratio be 3:1:2:1.
The casting of the present invention preparation method of high durable antimicrobial coating material, includes the following steps：
（1）Acrylic resin modified, bismaleimide, glycidyl neodecanoate are placed in reaction kettle and are stirred, in
30-50min is stirred at a temperature of 80-90 DEG C；Then polyvinyl alcohol, soybean lecithin, ethylene glycol ethyl ether acetic acid are sequentially added
Ester, dimethyl silicone polymer the reaction was continued 40-60min；
（2）By step（1）Reaction temperature be down to 60-75 DEG C, by complex antimicrobials, modified mixed fillers, 2,2 '-di-2-ethylhexylphosphine oxides
Step is added in (4,6- DI-tert-butylphenol compounds), 2-hydroxy-4-n-octoxybenzophenone under stirring conditions（1）Reactant
20-40min is mixed in system, after being eventually adding Triallyl isocyanurate the reaction was continued 1-3h, cools the temperature to room temperature,
Up to casting high durable antimicrobial coating material.
Preferably, the speed of agitator in the preparation process is 180-320r/min.
Preferably, the step（1）Reaction temperature be 85 DEG C, the step（2）Reaction temperature be 68 DEG C.
Advantageous effect：The present invention provides a kind of casting high durable antimicrobial coating material and preparation method thereof, the present invention
Using the acrylic resin and bismaleimide of fluorine richness as base material, the acrylic resin of fluorine richness can improve viscous
The chemical stability of knot, weatherability, hydrolytic resistance, hydrophobic, oleophobic property, stain resistance greatly improve, while in air drying mistake
Good adhesive force and intensity are formed in journey；Contain vinyl-functional in blended emulsifier used, in polymerization process in addition to
It provides outside emulsification, additionally it is possible to carry out covalent bond with resin and be avoided to keep stability of the emulsifier in system
Solve the appearance of suction phenomenon；Bismaleimide has good heat resistance, electrical insulating property, wave, radiation hardness, anti-flammability, good
Good mechanical property and dimensional stability, therefore it is added to the adhesive property that coating material greatly improves material in；It is compound
Antiseptic uses the wollastonite in powder loading nano silvery particle of hexadecylpyridinium chloride intercalation, and wollastonite in powder is through cetyl chloride
After pyridine intercalation, the gap between silica ashes is increased, to improve the load capacity of nano-Ag particles；It is shunk with neodecanoic acid sweet
Grease can assign the more preferable acid-resisting of coating, high photosensitiveness, good wetability, UV stability as diluent；It is polyvinyl alcohol, big
The addition of Fabaceous Lecithin, ethylene glycol ether acetate, dimethyl silicone polymer has the film performance of coating, lubricity and caking property
There is important role；
Modified mixed fillers are filled into material, are played the role of good reinforcement, anti-aging, are improved hardness and the shock resistance of coating
Power；
2,2 '-di-2-ethylhexylphosphine oxides (4,6- DI-tert-butylphenol compounds) and 2-hydroxy-4-n-octoxybenzophenone triallyl isocyanide urea
The addition of acid esters can play an important role the antioxygenic property and uv resistance of coating；Triallyl isocyanurate is to molten
The crosslinking of liquid system improves the synergistic effect between raw material, improves the system stability of solution.
There is coating material produced by the present invention ideal mechanical strength, tensile strength to be up to 38.51MPa, and fracture is stretched
Long rate is up to 367%, and impact strength is up to 75kg cm, while resistant of high or low temperature, acid resistance are good, and is obtained by comparative example
Go out, the acrylic resin modified mechanical strength to coating plays an important role, and the wollastonite in powder through intercalation processing loads nanometer
Silver plays an important role the antibiotic property of coating material, under same experimental conditions, to Gram-E. coli and leather
The antibiotic rate of the mixed cell of Lan Shi positive staphylococcus aureus is up to 99.35%.Therefore the present invention is high as a kind of casting
Weather-proof antimicrobial coating material is with a wide range of applications.
Specific implementation mode
The invention will now be further described with reference to specific embodiments, but examples are merely exemplary, not to this hair
Bright range constitutes any restrictions.It will be understood by those skilled in the art that without departing from the spirit and scope of the invention
Can the details and form of technical solution of the present invention be modified or be replaced, but these modifications and replacement each fall within the present invention's
In protection domain.
Acrylic resin modified preparation method described in following embodiment is as follows：50 parts of addition goes in four mouthfuls of reaction bulbs
Ionized water, 8 parts of blended emulsifier heating stirrings, are added 15 parts of acrylic acid mix monomers and 6 parts of azodiisobutyronitrile initiators, rise
Temperature after emulsion polymerization 20min, then adds 15 parts of acrylic acid mix monomers and 6 parts of azodiisobutyronitrile initiators to 85 DEG C, keeps the temperature
React 1.5h；Then 20 parts of modified mix monomers and 6 parts of azodiisobutyronitrile initiators, insulation reaction 2.5h are added；Finally will
Temperature is down to 40 DEG C, and it is 7~8 to adjust pH using lye, and filtrate is collected by filtration, reactor product is dried in an oven to get changing
Property acrylic resin；
It is 1 that the acrylic acid mix monomer, which is mass ratio,:1.5:2 methyl methacrylate, hydroxyacrylamide, metering system
Sour tetrahydro furfuryl ester；
It is 1 that the modified mix monomer, which is mass ratio,:1.5 acrylic acid tetrafluoro propyl ester and dodecafluoroheptyl methacrylate；
The emulsifier is that mass ratio is 1:1 nonylphenol polyoxyethylene ether, dodecyl polyoxyethylene ether.
Embodiment 1
A kind of casting high durable antimicrobial coating material, is prepared by the raw material of following parts by weight：Acrylic resin modified 55
Part, 12 parts of bismaleimide, 5 parts of Triallyl isocyanurate, 8 parts of polyvinyl alcohol, 9 parts of complex antimicrobials, modified mixing
8 parts of filler, 4 parts of 2,2 '-di-2-ethylhexylphosphine oxides (4,6- DI-tert-butylphenol compounds), 5 parts of 2-hydroxy-4-n-octoxybenzophenone, soybean
Phosphatidase 5 part, 6 parts of ethylene glycol ether acetate, 7 parts of dimethyl silicone polymer, 18 parts of glycidyl neodecanoate.
The complex antimicrobials are prepared by nano-Ag particles, hexadecylpyridinium chloride and wollastonite in powder, described multiple
The preparation method for closing antiseptic is as follows：To the salpeter solution that 20 parts of pH 4.5 are added in 10 parts of silica ashes, in 70 DEG C of temperature
Under be stirred 1.2h, then be added 4.5 parts of nano-Ag particles, 7.5 parts of hexadecylpyridinium chloride, stirred at a temperature of 35 DEG C
Reaction 1.5h is mixed, by solution cooled to room temperature, by collected by suction sediment, is used in combination 30% ethanol solution by sediment
It washed once, then place it in baking oven and dry, up to complex antimicrobials after grinding.
The modified mixed fillers are the rutile titanium dioxide that γ-glycidyl ether oxygen propyl trimethoxy silicane is modified
Powder, ceramic fibre, silicon carbide and nano Ce O2, the granularities of the modified mixed fillers is 40 mesh, wherein rutile type titanium white,
Ceramic fibre, silicon carbide and nano Ce O2Mass ratio be 3:1:2:1.
The casting of the present invention preparation method of high durable antimicrobial coating material, includes the following steps：
（1）Acrylic resin modified, bismaleimide, glycidyl neodecanoate are placed in reaction kettle and are stirred, in
It is stirred 40min at a temperature of 85 DEG C；Then polyvinyl alcohol, soybean lecithin, ethylene glycol ether acetate, poly- two are sequentially added
Methylsiloxane the reaction was continued 50min；
（2）By step（1）Reaction temperature be down to 68 DEG C, by complex antimicrobials, modified mixed fillers, 2,2 '-di-2-ethylhexylphosphine oxides (4,
6- DI-tert-butylphenol compounds), 2-hydroxy-4-n-octoxybenzophenone step is added under stirring conditions（1）Reaction system
Middle mixing 30min cools the temperature to room temperature to get casting after being eventually adding Triallyl isocyanurate the reaction was continued 2h
Part high durable antimicrobial coating material.
Preferably, the speed of agitator in the preparation process is 250r/min.
Embodiment 2
A kind of casting high durable antimicrobial coating material, is prepared by the raw material of following parts by weight：Acrylic resin modified 40
Part, 8 parts of bismaleimide, 3 parts of Triallyl isocyanurate, 5 parts of polyvinyl alcohol, 6 parts of complex antimicrobials, modified mixing are filled out
5 parts of material, 2 parts of 2,2 '-di-2-ethylhexylphosphine oxides (4,6- DI-tert-butylphenol compounds), 3 parts of 2-hydroxy-4-n-octoxybenzophenone, soybean phosphorus
2 parts of fat, 3 parts of ethylene glycol ether acetate, 4 parts of dimethyl silicone polymer, 10 parts of glycidyl neodecanoate.
The complex antimicrobials are prepared by nano-Ag particles, hexadecylpyridinium chloride and wollastonite in powder, described multiple
The preparation method for closing antiseptic is as follows：To the salpeter solution that 15 parts of pH 4 are added in 6 parts of silica ashes, stirred at a temperature of 60 DEG C
Mixing 1h is mixed, 3 parts of nano-Ag particles, 5 parts of hexadecylpyridinium chloride is then added, 1h is stirred to react at a temperature of 30 DEG C,
It is used in combination 30% ethanol solution to washed once sediment by collected by suction sediment solution cooled to room temperature, then
It places it in baking oven and dries, up to complex antimicrobials after grinding.
The modified mixed fillers are the rutile titanium dioxide that γ-glycidyl ether oxygen propyl trimethoxy silicane is modified
Powder, ceramic fibre, silicon carbide and ceria nanopowder, the granularities of the modified mixed fillers are 30 mesh, wherein rutile type titanium white,
The mass ratio of ceramic fibre, silicon carbide and ceria nanopowder is 3:1:2:1.
The casting of the present invention preparation method of high durable antimicrobial coating material, includes the following steps：
（1）Acrylic resin modified, bismaleimide, glycidyl neodecanoate are placed in reaction kettle and are stirred, in
It is stirred 30min at a temperature of 80 DEG C；Then polyvinyl alcohol, soybean lecithin, ethylene glycol ether acetate, poly- two are sequentially added
Methylsiloxane the reaction was continued 40min；
（2）By step（1）Reaction temperature be down to 60 DEG C, by complex antimicrobials, modified mixed fillers, 2,2 '-di-2-ethylhexylphosphine oxides (4,
6- DI-tert-butylphenol compounds), 2-hydroxy-4-n-octoxybenzophenone step is added under stirring conditions（1）Reaction system
Middle mixing 20min cools the temperature to room temperature to get casting after being eventually adding Triallyl isocyanurate the reaction was continued 1h
Part high durable antimicrobial coating material.
Speed of agitator in the preparation process is 180r/min.
Embodiment 3
A kind of casting high durable antimicrobial coating material, is prepared by the raw material of following parts by weight：Acrylic resin modified 50
Part, 10 parts of bismaleimide, 4 parts of Triallyl isocyanurate, 6 parts of polyvinyl alcohol, 8 parts of complex antimicrobials, modified mixing
6 parts of filler, 3 parts of 2,2 '-di-2-ethylhexylphosphine oxides (4,6- DI-tert-butylphenol compounds), 4 parts of 2-hydroxy-4-n-octoxybenzophenone, soybean
Phosphatidase 4 part, 4 parts of ethylene glycol ether acetate, 6 parts of dimethyl silicone polymer, 15 parts of glycidyl neodecanoate.
The complex antimicrobials are prepared by nano-Ag particles, hexadecylpyridinium chloride and wollastonite in powder, described multiple
The preparation method for closing antiseptic is as follows：To the salpeter solution that 18 parts of pH 4.2 are added in 8 parts of silica ashes, at a temperature of 65 DEG C
It is stirred 1.2h, 4 parts of nano-Ag particles, 7 parts of hexadecylpyridinium chloride is then added, is stirred to react at a temperature of 33 DEG C
Solution cooled to room temperature is used in combination 30% ethanol solution that sediment is washed one by 1.2h by collected by suction sediment
It is secondary, then place it in baking oven and dry, up to complex antimicrobials after grinding.
The modified mixed fillers are the rutile titanium dioxide that γ-glycidyl ether oxygen propyl trimethoxy silicane is modified
Powder, ceramic fibre, silicon carbide and nano Ce O2, the granularities of the modified mixed fillers is 35 mesh, wherein rutile type titanium white,
Ceramic fibre, silicon carbide and nano Ce O2Mass ratio be 3:1:2:1.
The casting of the present invention preparation method of high durable antimicrobial coating material, includes the following steps：
（1）Acrylic resin modified, bismaleimide, glycidyl neodecanoate are placed in reaction kettle and are stirred, in
It is stirred 35min at a temperature of 83 DEG C；Then polyvinyl alcohol, soybean lecithin, ethylene glycol ether acetate, poly- two are sequentially added
Methylsiloxane the reaction was continued 45min；
（2）By step（1）Reaction temperature be down to 65 DEG C, by complex antimicrobials, modified mixed fillers, 2,2 '-di-2-ethylhexylphosphine oxides (4,
6- DI-tert-butylphenol compounds), 2-hydroxy-4-n-octoxybenzophenone step is added under stirring conditions（1）Reaction system
Middle mixing 25min, after being eventually adding Triallyl isocyanurate the reaction was continued 1.5h, cool the temperature to room temperature to get
Casting high durable antimicrobial coating material.
Speed of agitator in the preparation process is 200r/min.
Embodiment 4
A kind of casting high durable antimicrobial coating material, is prepared by the raw material of following parts by weight：Acrylic resin modified 70
Part, 16 parts of bismaleimide, 6 parts of Triallyl isocyanurate, 10 parts of polyvinyl alcohol, 12 parts of complex antimicrobials are modified and mix
Close 10 parts of filler, 5 parts of 2,2 '-di-2-ethylhexylphosphine oxides (4,6- DI-tert-butylphenol compounds), 6 parts of 2-hydroxy-4-n-octoxybenzophenone, big
7 parts of Fabaceous Lecithin, 8 parts of ethylene glycol ether acetate, 9 parts of dimethyl silicone polymer, 25 parts of glycidyl neodecanoate.
The complex antimicrobials are prepared by nano-Ag particles, hexadecylpyridinium chloride and wollastonite in powder, described multiple
The preparation method for closing antiseptic is as follows：To the salpeter solution that 25 parts of pH 5 are added in 13 parts of silica ashes, at a temperature of 80 DEG C
It is stirred 1.5h, 6 parts of nano-Ag particles, 10 parts of hexadecylpyridinium chloride is then added, is stirred at a temperature of 40 DEG C anti-
2h is answered, 30% ethanol solution is used in combination that sediment is washed one by collected by suction sediment solution cooled to room temperature
It is secondary, then place it in baking oven and dry, up to complex antimicrobials after grinding.
The modified mixed fillers are the rutile titanium dioxide that γ-glycidyl ether oxygen propyl trimethoxy silicane is modified
Powder, ceramic fibre, silicon carbide and nano Ce O2, the granularities of the modified mixed fillers is 50 mesh, wherein rutile type titanium white,
Ceramic fibre, silicon carbide and nano Ce O2Mass ratio be 3:1:2:1.
The casting of the present invention preparation method of high durable antimicrobial coating material, includes the following steps：
（1）Acrylic resin modified, bismaleimide, glycidyl neodecanoate are placed in reaction kettle and are stirred, in
It is stirred 50min at a temperature of 90 DEG C；Then polyvinyl alcohol, soybean lecithin, ethylene glycol ether acetate, poly- two are sequentially added
Methylsiloxane the reaction was continued 60min；
（2）By step（1）Reaction temperature be down to 75 DEG C, by complex antimicrobials, modified mixed fillers, 2,2 '-di-2-ethylhexylphosphine oxides (4,
6- DI-tert-butylphenol compounds), 2-hydroxy-4-n-octoxybenzophenone step is added under stirring conditions（1）Reaction system
Middle mixing 40min cools the temperature to room temperature to get casting after being eventually adding Triallyl isocyanurate the reaction was continued 3h
Part high durable antimicrobial coating material.
Speed of agitator in the preparation process is 320r/min.
Comparative example 1
Difference lies in the acrylic resin of comparative example 1 is not modified comparative example 1 with embodiment 1.
Comparative example 2
Difference lies in hexadecylpyridinium chloride pair is not used in the complex antimicrobials in comparative example 2 to comparative example 2 with embodiment 1
Wollastonite in powder carries out intercalation processing.
Coating material made from embodiment 1-4 and comparative example 1-2 is subjected to following performance test, measurement result such as 1 institute of table
Show.It being obtained from table 1, there is coating material produced by the present invention ideal mechanical strength, tensile strength to be up to 38.51MPa,
Elongation at break is up to 367%, and impact strength is up to 75kg cm, while resistant of high or low temperature, acid resistance are good, and by right
Ratio show that the acrylic resin modified mechanical strength to coating plays an important role, and the wollastonite in powder through intercalation processing is negative
Carrying nano silver plays an important role the antibiotic property of coating material.Using identical antibacterial delineation bacterium experimental method respectively to reality
It applies coating material made from a 1-4 and comparative example 1-2 and carries out antibacterial experiment, measure different coating material to Gram-negative large intestine
The antibiotic rate of bacillus and the staphylococcic mixed cell of Gram-positive S, under same experimental conditions, to gram-negative
The antibiotic rate of property Escherichia coli and the staphylococcic mixed cell of Gram-positive S is up to 99.35%.
Table 1
| Sample | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 | Detection method |
| Tensile strength（MPa） | 38.51 | 26.46 | 29.82 | 33.74 | 22.95 | 35.43 | GB/T528-1998 |
| Elongation at break（%） | 367 | 256 | 281 | 334 | 223 | 348 | GB/T528-1998 |
| Impact strength（kg·cm） | 75 | 58 | 66 | 72 | 47 | 65 | GB/T1732-1993 |
| Heat resistance（250±2℃）/24h | It is not blistering, do not fall off | It is not blistering, do not fall off | It is not blistering, do not fall off | It is not blistering, do not fall off | Light discolouration, paint film are tacky | It is not blistering, do not fall off | GB/T1735-2009 |
| Acid resistance immerses 30% sulfuric acid solution 72h | It is not blistering, do not fall off | It is not blistering, do not fall off | It is not blistering, do not fall off | It is not blistering, do not fall off | Light discolouration | It is not blistering, do not fall off | GB/T9274-1988 |
| Lower temperature resistance（-50±2℃）/6h | It is unchanged | It is unchanged | It is unchanged | It is unchanged | Light deformation | It is unchanged | JG/T25-1999 |
| Bacteriostasis rate（%） | 99.35 | 94.62 | 95.67 | 97.54 | 95.41 | 86.35 |
Claims (8)
1. a kind of casting high durable antimicrobial coating material, which is characterized in that be prepared by the raw material of following parts by weight：It is modified
40-70 parts of acrylic resin, 8-16 parts of bismaleimide, 3-6 parts of Triallyl isocyanurate, 5-10 parts of polyvinyl alcohol,
6-12 parts of complex antimicrobials, modified 5-10 parts of mixed fillers, 2-5 parts of 2,2 '-di-2-ethylhexylphosphine oxides (4,6- DI-tert-butylphenol compounds), 2- hydroxyls
3-6 parts of base -4- oxy-octyl benzophenones, 2-7 parts of soybean lecithin, 3-8 parts of ethylene glycol ether acetate, dimethyl silicone polymer
4-9 parts, 10-25 parts of glycidyl neodecanoate；
The complex antimicrobials are prepared by nano-Ag particles, hexadecylpyridinium chloride and wollastonite in powder,
The modified mixed fillers are rutile type titanium white, the pottery that γ-glycidyl ether oxygen propyl trimethoxy silicane is modified
Porcelain fiber, silicon carbide and nano Ce O2。
2. a kind of casting according to claim 1 high durable antimicrobial coating material, which is characterized in that by following parts by weight
Raw material be prepared：Acrylic resin modified 55 parts, 12 parts of bismaleimide, 5 parts of Triallyl isocyanurate, poly- second
8 parts of enol, 9 parts of complex antimicrobials, modified 8 parts of mixed fillers, 4 parts of 2,2 '-di-2-ethylhexylphosphine oxides (4,6- DI-tert-butylphenol compounds), 2- hydroxyls
It is 5 parts of base -4- oxy-octyl benzophenones, 5 parts of soybean lecithin, 6 parts of ethylene glycol ether acetate, 7 parts of dimethyl silicone polymer, new
18 parts of capric acid ethylene oxidic ester.
3. a kind of casting according to claim 1 high durable antimicrobial coating material, which is characterized in that the modified propylene
The preparation method of acid resin is as follows：The deionized water of 50 parts of addition, 8 parts of blended emulsifiers heating stirrings in four mouthfuls of reaction bulbs,
15 parts of acrylic acid mix monomers and 6 parts of azodiisobutyronitrile initiators are added, are warming up to 85 DEG C, after emulsion polymerization 20min, then add
Add 15 parts of acrylic acid mix monomers and 6 parts of azodiisobutyronitrile initiators, insulation reaction 1.5h；Then 20 parts of modified mixing are added
Monomer and 6 parts of azodiisobutyronitrile initiators, insulation reaction 2.5h；40 DEG C are finally cooled the temperature to, it is 7 to adjust pH using lye
~8, filtrate is collected by filtration, reactor product is dried in an oven to get acrylic resin modified；
It is 1 that the acrylic acid mix monomer, which is mass ratio,:1.5:2 methyl methacrylate, hydroxyacrylamide, metering system
Sour tetrahydro furfuryl ester；
It is 1 that the modified mix monomer, which is mass ratio,:1.5 acrylic acid tetrafluoro propyl ester and dodecafluoroheptyl methacrylate；
The emulsifier is that mass ratio is 1:1 nonylphenol polyoxyethylene ether, dodecyl polyoxyethylene ether.
4. a kind of casting according to claim 1 high durable antimicrobial coating material, which is characterized in that the composite antibacterial
The preparation method of agent is as follows：To the salpeter solution that 15-25 parts of pH 4-5 are added in 6-13 parts of silica ashes, in 60-80 DEG C of temperature
It is stirred 1-1.5h under degree, 3-6 parts of nano-Ag particles, 5-10 parts of hexadecylpyridinium chloride is then added, in 30-40 DEG C
At a temperature of be stirred to react 1-2h, 30% ethanol solution is used in combination by collected by suction sediment in solution cooled to room temperature
Sediment washed once, then place it in baking oven and dry, up to complex antimicrobials after grinding.
5. a kind of casting according to claim 1 high durable antimicrobial coating material, which is characterized in that the modified mixing
The granularity of filler is 30-50 mesh, wherein rutile type titanium white, ceramic fibre, silicon carbide and nano Ce O2Mass ratio be 3:
1:2:1。
6. the preparation method of claim 1-5 any one of them casting high durable antimicrobial coating material, which is characterized in that packet
Include following steps：
（1）Acrylic resin modified, bismaleimide, glycidyl neodecanoate are placed in reaction kettle and are stirred, in
30-50min is stirred at a temperature of 80-90 DEG C；Then polyvinyl alcohol, soybean lecithin, ethylene glycol ethyl ether acetic acid are sequentially added
Ester, dimethyl silicone polymer the reaction was continued 40-60min；
（2）By step（1）Reaction temperature be down to 60-75 DEG C, by complex antimicrobials, modified mixed fillers, 2,2 '-di-2-ethylhexylphosphine oxides
Step is added in (4,6- DI-tert-butylphenol compounds), 2-hydroxy-4-n-octoxybenzophenone under stirring conditions（1）Reactant
20-40min is mixed in system, after being eventually adding Triallyl isocyanurate the reaction was continued 1-3h, cools the temperature to room temperature,
Up to casting high durable antimicrobial coating material.
7. the casting according to claim 6 preparation method of high durable antimicrobial coating material, which is characterized in that the system
Speed of agitator during standby is 180-320r/min.
8. the casting according to claim 6 preparation method of high durable antimicrobial coating material, which is characterized in that the step
Suddenly（1）Reaction temperature be 85 DEG C, the step（2）Reaction temperature be 68 DEG C.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112406239A (en) * | 2020-10-16 | 2021-02-26 | 西南计算机有限责任公司 | Military power equipment insulator and preparation method thereof |
| CN113771447A (en) * | 2021-10-15 | 2021-12-10 | 鸿星尔克(绵阳)实业有限公司 | High-elasticity smooth antibacterial fabric and sport pants |
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| CN102585073A (en) * | 2012-01-16 | 2012-07-18 | 中山大学 | Fluorine silicon-modified acrylic ester emulsion and preparation method thereof |
| CN104226894A (en) * | 2014-08-29 | 2014-12-24 | 吴江市液铸液压件铸造有限公司 | High-temperature-resistant casting coating and preparation method thereof |
| CN104403476A (en) * | 2014-11-28 | 2015-03-11 | 安徽省金盾涂料有限责任公司 | Self-cleaning antibacterial fluorocarbon coating |
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| CN102585073A (en) * | 2012-01-16 | 2012-07-18 | 中山大学 | Fluorine silicon-modified acrylic ester emulsion and preparation method thereof |
| CN104226894A (en) * | 2014-08-29 | 2014-12-24 | 吴江市液铸液压件铸造有限公司 | High-temperature-resistant casting coating and preparation method thereof |
| CN104403476A (en) * | 2014-11-28 | 2015-03-11 | 安徽省金盾涂料有限责任公司 | Self-cleaning antibacterial fluorocarbon coating |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112406239A (en) * | 2020-10-16 | 2021-02-26 | 西南计算机有限责任公司 | Military power equipment insulator and preparation method thereof |
| CN113771447A (en) * | 2021-10-15 | 2021-12-10 | 鸿星尔克(绵阳)实业有限公司 | High-elasticity smooth antibacterial fabric and sport pants |
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